WO2019224092A1 - Pesticidally active c15-derivatives of ginkgolides - Google Patents

Pesticidally active c15-derivatives of ginkgolides Download PDF

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Publication number
WO2019224092A1
WO2019224092A1 PCT/EP2019/062565 EP2019062565W WO2019224092A1 WO 2019224092 A1 WO2019224092 A1 WO 2019224092A1 EP 2019062565 W EP2019062565 W EP 2019062565W WO 2019224092 A1 WO2019224092 A1 WO 2019224092A1
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Prior art keywords
same
heterocyclic ring
unsubstituted
substituted
alkyl
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PCT/EP2019/062565
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French (fr)
Inventor
Birgit GOCKEL
Wolfgang Von Deyn
Martin John MCLAUGHLIN
Tomoyasu Hirose
Toshiaki Sunazuka
Satoshi Omura
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Basf Se
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Publication of WO2019224092A1 publication Critical patent/WO2019224092A1/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/16—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with oxygen as the ring hetero atom

Definitions

  • Pesticidally Active C15-Derivatives of Ginkgolides Description
  • the present invention relates to the use of a compound of formula (I), or a salt, stereoisomer, tautomer, or N-oxide there of,
  • variables have a meaning as defined below, as an agrochemical pesticide. It also relates to seeds, pesticidal mixtures and compositions comprising a compound of formula (I). The invention also relates to methods of application of a compound of formula (I), or of the pes- ticidal composition. Another object is a compound of formula (I) per se, as defined below. Invertebrate pests and especially insects, arthropods and nematodes destroy growing and har- vested crops and commercial structures, thereby causing large economic loss to the food sup- ply and to property.
  • Ginkgolides are a pesticidally active group of natural products comprising the compounds ginkgolide A, ginkgolide B, ginkgolide C, ginkgolide J and ginkgolide M.
  • ginkgolides have a pesticidal activity, e.g. insecticidal activity, as described in WO2015/128338, WO2017/025454, WO2017/032580, and WO2016/059240. It is also known to admix ginkgolides to other pesticidally active compounds, as disclosed in WO2016/059240. It is further known from these documents that ginkgolide compounds are particularly effective to combat Pentatomidae pests, which are often comprehensively referred to as stink bugs, and which are extremely hard to control by other conventional pesticides.
  • variables in formula (I) have the following meaning R 1 , R 2 are independently H, halogen, OH, CN, NO2, N3, or SCN;
  • R 11 is halogen, CN, NO2, SCN;
  • heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R 112 ; or
  • R 111 is halogen, OH, CN, or NO 2 ;
  • C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, or C2-C10-alkynyl which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C 1 -C 10 -alkoxy, C 1 -C 6 -haloalkoxy, and C 1 -C 10 -alkyl- carbonyl; or a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R A ;
  • R A is halogen, OH, NO 2 , CN, C 1 -C 10 -alkyl, C 1 -C 10 -haloalkyl, C 1 -C 10 -alkoxy, C 1 -C 6 - haloalkoxy, or C1-C10-alkyl-carbonyl; or
  • R A form a 3- to 7-membered saturated, or partially unsaturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or differ- ent heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents selected from hal- ogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy;
  • R 112 is halogen, OH, CN, NO 2 ;
  • phenyl which is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, NO2, C1-C10-alkyl, C1-C10-haloalkyl, C1- C 10 -alkoxy, C 1 -C 6 -haloalkoxy, and C 1 -C 10 -alkyl-carbonyl;
  • two germinal substituents R 112 form a 3- to 7-membered saturated, or partially un- saturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents R A ;
  • R 113 is H
  • a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R 112 ;
  • R 114 is H, halogen, CN
  • a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R 112 ;
  • R 115 , R 116 , R 117 are independently H, CN;
  • heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R 112 ; or
  • R 115 , R 116 , and R 117 that are bound to the same N- atom represent a C 2 -C 6 alkylene chain forming a 3- to 7-membered saturated, par- tially unsaturated, or fully unsaturated heterocyclic ring together with the N-atom they are bonded to, wherein the alkylene chain contains none, or one or more, same or different heteroatoms O, S, or N, and is unsubstituted or substituted with one or more, same or different substituents selected from halogen, C 1 -C 4 -alkyl, C 1 -C 4 - haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy, and wherein the N-and/or S-atoms of the heterocyclic ring are oxidized or non-oxidized;
  • R 118 is H, halogen, CN, NO 2 , SCN;
  • a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R 112 ;
  • R 12 is halogen, CN, NO2, SCN;
  • a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R 122 ;
  • two germinal substituents R 12 form a 3- to 7-membered saturated, or partially un- saturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents R 122 ;
  • R 121 is halogen, OH, CN, NO2;
  • R 122 is halogen, OH, CN, NO2;
  • phenyl which is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, NO2, C1-C10-alkyl, C1-C10-haloalkyl, C1- C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl; or
  • R 122 form a 3- to 7-membered saturated, or partially un- saturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents R A ;
  • R 123 is H
  • a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R 112 ;
  • R 124 is H, halogen, CN; C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or sub- stituted with one or more, same or different substituents R 111 ; or
  • a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R 112 ;
  • R 125 , R 126 , R 127 are independently H, CN;
  • a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R 112 ; or
  • R 125 , R 126 , and R 127 substituents selected from R 125 , R 126 , and R 127 that are bound to the same N- atom represent a C2-C6 alkylene chain forming a 3- to 7-membered saturated, par- tially unsaturated, or fully unsaturated heterocyclic ring together with the N-atom they are bonded to, wherein the alkylene chain contains none, or one or more, same or different heteroatoms O, S, or N, and is unsubstituted or substituted with one or more, same or different substituents selected from halogen, C1-C4-alkyl, C1-C4- haloalkyl, C 1 -C 4 -alkoxy, and C 1 -C 4 -haloalkoxy, and wherein the N-and/or S-atoms of the heterocyclic ring are oxidized or non-oxidized;
  • R 13 is H
  • a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R 132 ;
  • R 131 is halogen, OH, CN, NO2;
  • phenyl which is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, NO 2 , C 1 -C 10 -alkyl, C 1 -C 10 -haloalkyl, C 1 - C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl;
  • R 132 form a 3- to 7-membered saturated, or partially un- saturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents R A ;
  • R 14 is H, halogen, CN
  • a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R 132 ;
  • R 15 , R 16 , R 17 are independently H, CN;
  • a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R 152 ; or
  • R 15 , R 16 , and R 17 that are bound to the same N- atom represent a C2-C6 alkylene chain forming a 3- to 7-membered saturated, par- tially unsaturated, or fully unsaturated heterocyclic ring together with the N-atom they are bonded to, wherein the alkylene chain contains none, or one or more, same or different heteroatoms O, S, or N, and is unsubstituted or substituted with one or more, same or different substituents R 152 , and wherein the N-and/or S-atoms of the heterocyclic ring are oxidized or non-oxidized;
  • R 151 is halogen, OH, CN, NO2; C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsub- stituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C 1 -C 10 -alkoxy, C 1 -C 6 -haloalkoxy, and C 1 -C 10 -alkyl-carbonyl; a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substitute
  • two germinal substituents R 151 form a 3- to 7-membered saturated, or partially un- saturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents R A ;
  • R 152 is halogen, OH, CN, NO2;
  • phenyl which is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, NO2, C1-C10-alkyl, C1-C10-haloalkyl, C1- C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl; or
  • two germinal substituents R 152 form a 3- to 7-membered saturated, or partially un- saturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents R A ;
  • R 18 is H, halogen, CN, NO2, SCN;
  • a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R 182 ;
  • R 19 is H, C 1 -C 4 -alkyl, C 1 -C 6 -cycloalkyl, C 1 -C 2 -alkoxy-C 1 -C 2 -alkyl, phenyl, benzyl; or R 18 and R 19 form a 3- to 7-membered saturated, partially unsaturated, or fully unsaturated
  • the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or differ- ent substituents R A ;
  • R 181 is halogen, OH, CN, NO2;
  • R 182 is halogen, OH, CN, NO 2 ;
  • phenyl which is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, NO 2 , C 1 -C 10 -alkyl, C 1 -C 10 -haloalkyl, C 1 - C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl; or
  • two germinal substituents R 182 form a 3- to 7-membered saturated, or partially un- saturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents R A ;
  • R 20a , R 20b are independently H, C1-C10-alkyl, C1-C6-haloalkyl, C1-C10-alkoxy, C1-C4-alkoxy-C1- C 4 -alkyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -halocycloalkyl, C 1 -C 4 -haloalkoxy-C 1 -C 4 -alkyl, or phenyl;
  • R 31 is H
  • a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R 312 ;
  • R 311 is halogen, OH, CN, or NO2;
  • C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, or C2-C10-alkynyl which groups are un- substituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl; or a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R A ;
  • R 312 is halogen, OH, CN, NO2;
  • phenyl which is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, NO 2 , C 1 -C 10 -alkyl, C 1 -C 10 -haloalkyl, C 1 - C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl;
  • two germinal substituents R 312 form a 3- to 7-membered saturated, or partially un- saturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents R A ;
  • R 32 is H, halogen, CN
  • a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R 312 ;
  • R 33 , R 34 are independently H, CN;
  • a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R 32 ; or two R 33 and R 34 that are bound to the same N-atom represent a C2-C6 alkylene chain forming a 3- to 7-membered saturated, partially unsaturated, or fully unsatu- rated heterocyclic ring together with the N-atom they are bonded to, wherein the al- kylene chain contains none, or one or more, same or different heteroatoms O, S, or N, and is unsubstituted or substituted with one or more, same or different
  • R 4 is H
  • a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R 42 ; or
  • R 41 is halogen, CN, NO 2 , SCN;
  • a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R 112 ; or
  • R 42 is halogen, CN, NO2, SCN;
  • R 43 is H
  • a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R 132 ;
  • R 44 is H, halogen, CN
  • a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R 132 ;
  • R 45 , R 46 , R 47 are independently H, CN;
  • R 45 , R 46 , and R 47 substituents selected from R 45 , R 46 , and R 47 that are bound to the same N-atom represent a C 2 -C 6 alkylene chain forming a 3- to 7-membered saturated, partially un- saturated, or fully unsaturated heterocyclic ring together with the N-atom they are bonded to, wherein the alkylene chain contains none, or one or more, same or dif- ferent heteroatoms O, S, or N, and is unsubstituted or substituted with one or more, same or different substituents R 152 , and wherein the N-and/or S-atoms of the hetero- cyclic ring are oxidized or non-oxidized; and
  • n 0, 1, or 2.
  • the invention also relates to:
  • compositions comprising at least one compound of formula (I) as defined above;
  • compositions comprising a compound of formula (I), or the pesticidal mixture, and a liquid or solid carrier;
  • invertebrate pests are insects or nematodes, more preferably insects, com- prising contacting the pests, their food supply, habitat, breeding grounds or their locus with a compound of formula (I) as defined above, or the pesticidal mixture in pesticidally effective amounts.
  • invertebrate pests preferably from insects or nematodes, more preferably from insects, comprising contacting the plant, or the soil or water in which the plant is growing, with a compound of formula (I) as defined above or the pesticidal mixture in pesticidally effective amounts.
  • non-therapeutic method method for treating animals infested or infected by parasites or pre- venting animals of getting infected or infested by parasites or protecting animals against infesta- tion or infection by parasites which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a compound of formula (I) as de- fined above or the pesticidal mixture;
  • a process for the preparation of a veterinary composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises adding a parasiticidally effective amount of a compound of formula (I) as defined above to a carrier com- position suitable for veterinary use;
  • the invention further relates to novel compounds of formula (I), wherein the variables have a meaning as defined for the uses and methods of application of compounds of formula (I), but wherein compounds are excluded that have the following definition of variables:
  • R 3 is OH; and R 4 is benzyl;
  • R 1 is H
  • R 3 is OH
  • R 4 is benzyl
  • R 3 , R 4 are H
  • R 1 , R 2 are H, or one of the variable R 1 is H, while the other variable is OH.
  • Compounds of formula (I) have several centres of chirality.
  • the term“stereoisomers of com- pounds of formula (I)” includes compounds of formula (Ia), wherein all variables have a defini- tion as in formula (I).
  • Compounds of formula (Ia) are diastereomers of compounds of formula (I) regarding the sub- stituents R 1 and R 2 , i.e. epimers of compounds of formula (I).
  • the term“stereoisomers” includes stereoisomers of compounds of formula (I), wherein each centre of chirality is independently in its (R)-, or its (S)-configuration.
  • the term“stereoisomers of compounds of formula (I)” relates to all stereoisomers in which the cen- tres of chirality at those carbon atoms to which the substituents R 1 andR 2 , R 3 , and R 4 O are di- rectly attached to by a single bond, are independently in their (R)-, or (S)-configuration.
  • the term“stereoisomers of compounds of formula (I)” relates to the diastere- omeric compounds of formula (I) and/or (Ia).
  • the invention relates to com- pounds of formula (I), their salts, tautomers, or N-oxides.
  • the invention in another embodiment, relates to compounds of formula (Ia), their salts, tautomers, or N-oxides.
  • the invention provides both the single pure diastereomers of the compounds of formula (I), and their mixtures and the use and methods of application according to the invention of the pure diastereomers of the com- pound of formula (I) or its mixtures.
  • Suitable compounds of formula (I) also include all possible geometrical stereoisomers
  • Cis/trans isomers and mixtures thereof.
  • Cis/trans isomers may be present with respect to an alkene, carbon-nitrogen double-bond or amide group.
  • stereoisomer(s) encompasses both optical isomers, such diastereomers and epimers, as well as geometrical isomers (cis/trans isomers).
  • the present invention relates to every possible stereoisomer of the compounds of for- mula (I), i.e. to single diastereomers, as well as to mixtures thereof.
  • the compounds of formula (I) may be present in the form of their tautomers.
  • the invention also relates to the tautomers of formula (I) and the stereoisomers, salts, tautomers and N-oxides of said tautomers.
  • Salts of compounds of the formula (I) are preferably agriculturally and/or veterinary acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question, if the compound of formula (I) has a basic functionality, or by reacting an acidic compound of formula (I) with a suitable base.
  • Suitable agriculturally or veterinary useful salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any ad- verse effect on the action of the compounds according to the present invention.
  • Suitable cations are especially the ions of the alkali metals, preferably lithium, sodium and potassium, of the al- kaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH4 + ) and substituted am- monium in which one to four of the hydrogen atoms are replaced by C1-C4-alkyl, C1-C4-hydroxy- alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, hydroxy-C1-C4-alkoxy-C1-C4-alkyl, phenyl or ben- zyl.
  • substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetrae- thylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl-am- monium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyltriethylammo- nium, furthermore phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compounds of formula (I) with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • N-oxide includes any compound of the present invention which has at least one ter- tiary nitrogen atom that is oxidized to an N-oxide moiety.
  • the term“compound(s) of the invention” relates to compound(s) of formula (I).
  • the organic moieties mentioned in the above definitions of the variables are - like the term hal- ogen - collective terms for individual listings of the individual group members.
  • the prefix C n -C m indicates in each case the possible number of carbon atoms in the group.
  • Halogen means F, Cl, Br, or I, preferably Cl.
  • substituted with e.g.
  • Cn-Cm-alkyl refers to a branched or unbranched saturated hydrocarbon group having n to m, e.g.1 to 10 carbon atoms, prefera- bly 1 to 6 carbon atoms, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dime- thylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2- methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-
  • C n -C m -haloalkyl refers to a straight-chain or branched alkyl group having n to m carbon atoms, e.g.1 to 10 in particular 1 to 6 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example C 1 -C 4 -haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoro- ethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl
  • C1-C10-haloal- kyl in particular comprises C1-C2-fluoroalkyl, which is synonym with methyl or ethyl, wherein 1, 2, 3, 4 or 5 hydrogen atoms are substituted with fluorine atoms, such as fluoromethyl, difluoro- methyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl and pen- tafluoromethyl.
  • Cn-Cm-alkoxy refers to straight-chain or branched alkyl groups having n to m carbon atoms, e.g.1 to 10, in particular 1 to 6 or 1 to 4 carbon atoms (as mentioned above) bonded through oxygen at any bond in the alkyl group.
  • Examples include C 1 -C 4 -alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy.
  • Cn-Cm-haloalkoxy refers to straight-chain or branched alkyl groups hav- ing n to m carbon atoms, e.g.1 to 10, in particular 1 to 6 or 1 to 4 carbon atoms (as mentioned above) bonded through oxygen linkage, at any bond in the alkyl group, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example C1-C2-haloalkoxy, such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloro- methoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoro- methoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroeth- oxy, 2,2-difluoroethoxy, 2,
  • C2-Cm-alkenyl intends a branched or unbranched unsaturated hy- drocarbon group having 2 to m, e.g.2 to 10 or 2 to 6 carbon atoms and a double bond in any position, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-bu- tenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1- pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl- 1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl- 1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl
  • C 2 -C m -alkynyl refers to a branched or unbranched unsaturated hy- drocarbon group having 2 to m, e.g.2 to 10 or 2 to 6 carbon atoms and containing at least one triple bond, such as ethynyl, propynyl, 1-butynyl, 2-butynyl, and the like.
  • C n -C m -alkoxy-C n -C m -alkyl refers to alkyl having n to m carbon at- oms, e.g. like specific examples mentioned above, wherein one hydrogen atom of the alkyl radi- cal is replaced by an Cn-Cm-alkoxy group; wherein the value of n and m of the alkoxy group are independently chosen from that of the alkyl group.
  • 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring or ring system refers to monocyclic, or fused and/or bridged bicyclic, tricyclic, or polycyclic ring systems having a total of 3- to 12 carbon atoms as ring members, preferably to monocyclic and bicyclic systems.
  • Examples of "3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring or ring systems" are cyclopropane, cyclopropane, cyclobutene, cy- clobutene, cyclobutadiene, cyclopentane, cyclopentene, cyclopentadiene, cyclohexene, cyclo- hexadiene, phenyl, cycloheptane, cycloheptene, cycloheptadiene, cycloheptatriene, cy- clooctene, cyclooctadiene, cyclooctatriene, cyclooctatetraene, decalin, naphthalene, pentalene, indane, indene, 2,3,3a,4,5,6,7,7a-octahydro-1H-indene, tetralin, azulene,
  • 3- to 12-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring or ring system refers to monocyclic, or fused bicyclic, tricyclic, or polycyclic ring systems having a total of 3- to 12 ring members, preferably to monocyclic and bicyclic sys- tems.
  • the heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member.
  • the heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxi- dized, preferably one N-atom.
  • Examples of fully saturated heterocyclic rings or ring systems include: oxiranyl, aziridinyl, azet- idinyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrroli- dinyl, 3-pyrrolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-imidazolidinyl, 4-imidazoli- dinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5- isoxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 1,2,4
  • Examples of partially unsaturated heterocyclic rings or ring systems include: 2,3-dihydrofur-2- yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihy- drothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyr- rolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin 3 yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-is
  • Examples of fully unsaturated heterocyclic rings or ring systems are: 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-ox- azolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,3-triazole-1-yl, 1,2,3-tria- zole-2-yl, 1,2,4-triazole-1-yl, 1,2,4-triazole-1-yl, 1,3,4-triazol-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridi- nyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazin
  • C3-Cm-cycloalkyl refers to a monocyclic ring of 3- to m-membered saturated cycloaliphatic radicals, e.g. cyclopropyl (cC 3 H 5 ), cyclobutyl (cC 4 H 7 ), cyclopentyl (cC5H9), cyclohexyl (cC6H11), cycloheptyl (cC7H13), cyclooctyl (cC8H15) and cyclodecyl (cC10H19).
  • C3-Cm-cycloalkenyl refers to a monocyclic ring of 3- to m-mem- bered partially unsaturated cycloaliphatic radicals.
  • a "C2-Cm-alkylene” is divalent branched or preferably unbranched aliphatic chain having 2 to m, e.g.2 to 7 carbon atoms, for example CH2CH2, -CH(CH3)-, CH2CH2CH2, CH(CH3)CH2, CH 2 CH(CH 3 ), CH 2 CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 , and
  • a C 2 -C m -alkylene chain containing one or more, same or different heteroatoms refers to such an aliphatic chain having 2 to m carbon atoms, wherein the heteroatoms replace carbon atoms as chain members, for example CH2SCH2,
  • CH 2 CH 2 SCH 2 CH 2 NHCH 2 CH 2 CH 2 , or CH 2 CH 2 OCH 2 .
  • the terms“natural product ginkgolides”,“naturally occurring ginkgolides”, and“ginkgolide nat- ural products” refer to compounds of formula (II), wherein the variables have a meaning as de- fined in a line of Table A.
  • the compounds of formula (I) can be prepared from the natural product ginkgolides A-M in Ta- ble A by standard synthetic procedures that are well-known to the skilled person in the field of organic chemistry. If individual compounds of formula (I) cannot be produced from the natural product ginkgolides A-M, they may be produced from other compounds of formula (I) by stand- ard chemical reactions.
  • condensation reactions are suitable to pro- prise ethers, thioethers, secondary-, and tertiary amines.
  • the condensation reaction usually takes place in the presence of an inert organic solvent and a catalyst, such as an acid.
  • the acid is p-toluene sulfonic acid or acetic acid.
  • the H 2 O may be removed from by distil- lation or a molecular sieve.
  • R 1 or R 2 e.g. R 13 O, R 14 , or NR 15 R 16
  • R 3 , R 4 , R 5 and R 6 are defined as for compounds of formula (I).
  • the reaction may be carried out in the presence of a base, typically in the presence of an organic base, e.g dimethylamino- pyridine, pyridine, or ((CH 3 ) 2 CH) 2 (CH 3 CH 2 )N.
  • Compounds of formula (I-D), corresponding to compounds of formula (I), wherein R 1 or R 2 is bound to C15 by a C-atom, and wherein an electron-withdrawing-group W is bound to said C- atom, may be prepared by reacting compounds of formula (I-A) with a suitable Wittig reagent, followed by an intramolecular Oxa-Michael reaction
  • the reaction may be carried out in an inert organic solvent at a temperature of 0 to 120 °C, optionally in the presence of a base.
  • Compounds of formula (I-E), corresponding to compounds of formula (I), wherein R 1 or R 2 is CN, C2-C10-alkenyl, or C2-C10-alkynyl, can be produced by reaction of compounds of formula (I- A) with the corresponding trimethylsilyl-reagent (CH 3 ) 3 Si-CN, (CH 3 ) 3 Si-(C 2 -C 10 -alkenyl), or (CH 3 ) 3 Si-(C 2 -C 10 -alkynyl) in the presence of a Lewis-acid, e.g. BF 3 .
  • the reaction may be carried out in an inert organic solvent, such as CH2Cl2, at a temperature of from -100 to -50 °C, prefera- bly at -78 °C.
  • an inert organic solvent e.g. DMF
  • Q is a carbo-, or heterocyclic ring or ring system as defined for compounds of formula (I); and R 3 , R 4 , R 5 and R 6 are defined as for compounds of formula (I).
  • Compounds of formula (I-J), wherein R 1 or R 2 is halogen may be produced by reaction of compounds of formula (I-A) with a suitable deoxygenating-halogenating agent, such as bis(2- methoxyethyl)aminosulfur trifluoride, in an inert organic solvent, such as CH 2 Cl 2 .
  • a suitable deoxygenating-halogenating agent such as bis(2- methoxyethyl)aminosulfur trifluoride
  • an inert organic solvent such as CH 2 Cl 2 .
  • deoxy- genating-halogenating agents are commercially available.
  • Compounds of formulae (I-A), (I-B), (I-C), (I-D), (I-E), (I-F), (I-G), (I-H) and (I-J) are comprised by the definition of compounds of formula (I).
  • Embodiments and preferred compounds of the present invention for use in pesticidal methods and for insecticidal application purposes are outlined in the following paragraphs.
  • the embodi- ments and preferred compounds are valid for the inventive uses and methods of application as well as for the compounds of formula (I) per se, mixtures and formulations containing them.
  • the remarks made below concerning preferred embodiments of the variables of compounds of for- mula (I) are valid both on their own and in combination with each other.
  • the variables of the compounds of formula (I) have the following meanings, these meanings, both on their own and in combination with one another, being embodiments of the compounds of the formula (I).
  • compounds of formula (I) have one substituent R 1 or R 2 that is H or OH, preferably H. At least one substituetn R 1 or R 2 is typically not H or OH.
  • At least one substituent R 1 or R 2 is H, OH, halogen, N3, or CN, preferably H, OH, N 3 or CN, more preferably CN.
  • one substituent R 1 or R 2 is H, and the other substituent is H, OH, halogen, N3, or CN, preferably H, OH, N3, or CN, more preferably CN.
  • at least one substituent R 1 or R 2 is C1-C10-alkyl, C2-C10-alkenyl, or C2-C10- alkynyl, which groups are unsubstituted, or substituted with one or more, same or different sub- stituents R 11 .
  • At least one substituent R 1 or R 2 is C1-C4-alkyl, C2-C4- alkenyl, or C 2 -C 4 -alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R 11 .
  • at least one substituent R 1 or R 2 is C1-C10-al- kyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R 11 .
  • At least one substituent R 1 or R 2 is C 1 -C 4 -al- kyl, or C2-C4-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R 11 .
  • At least one substituent R 1 or R 2 is a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or hetero- cyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R 12 .
  • At least one substituent R 1 or R 2 is a 3- to 12-membered saturated, par- tially unsaturated, or fully unsaturated carbocyclic ring or ring system, preferably a 3- to 10- membered ring or ring system, which carbocyclic ring or ring system is unsubstituted, or substi- tuted with one or more, same or different substituents R 12 .
  • At least one substituent R 1 or R 2 is phenyl, which is unsubstituted, or sub- stituted with one or more, same or different substituents R 12 .
  • at least one substituent R 1 or R 2 is phenyl.
  • at least one substituent R 1 or R 2 is phenyl, which is substituted with one or more, same or different substituents selected from halo- gen, CN, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy, preferably C1-C4- alkoxy.
  • At least one substituent R 1 or R 2 is a monocyclic or bicyclic C 3 -C 10 - cycloalkyl, or C3-C10-cycloalkenyl, which groups are substituted with one or more, same or different substituents R 12 .
  • At least one substituent R 1 or R 2 is a monocyclic or bicyclic C3-C10-cycloalkyl, or C3-C10-cycloalkenyl, which groups are substituted with one or more, same or different substituents selected from halogen, CN, C 1 -C 4 -alkyl, C 1 -C 4 - haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy.
  • At least one substituent R 1 or R 2 is a 3- to 10-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring or ring system, wherein said hetero- cyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C 1 -C 3 -alkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -haloalkyl, C 1 -C 3 -haloalkoxy, and phenyl.
  • said heterocyclic ring or ring system comprises at least one N-atom as a ring member and is bonded to the C15-atom by a direct bond to said N-atom.
  • said heteriocyclic ring or ring system comprises at least one S-atom as a ring member.
  • At least one substituent R 1 or R 2 is selected from the following:
  • heterocyclic rings and ring systems D1-D154 aziridine (D1), azetidin (D2), 1,3-diazetidine (D3), pyrrolidine (D4), 3-pyrroline (D5), 2-pyrroline (D6), pyrrole (D7), pyrazolidine (D8), imidazolidine (D9), 2-pyrrazoline (D10), 2-imidazoline (D11), pyrrazole (D12), imidazole (D13), 1,2,4-triazole (D14), 1,2,3-triazole (D15), tetrazole (D16), piperidine (D17), piperazine (D18), 1,4-morpholine (D19), 1,4-thiomorpholine (D20), 2H-1,2-oxazine (D21), 1,4-oxazine (D22), 1,4-thiazine (D23), 2H-1,2-thiazine (D24), thymine (D25),
  • At least one substituent R 1 or R 2 is selected from D1-D67, which heterocyclic rings or ring systems are unsubstituted, or substituted with one or more, same or different substituents R 12 . In one embodiment, at least one substituent R 1 or R 2 is selected from D14, D15, D16, D19, D18, D20, D28, D37, and D38, which heterocyclic rings or ring systems are unsubstituted, or substituted with one or more, same or different substituents R 12 .
  • At least one substituent R 1 or R 2 is selected from D14, D15, D16, D19, D18, D20, D28, D37, D38, and D104 which heterocyclic rings or ring systems are unsubstituted, or substituted with one or more, same or different substituents R 12 .
  • At least one substituent R 1 or R 2 is selected from phenyl, C3-C8- cycloalkyl, C 3 -C 8 -cycloalkenyl, D14, D15, D16, D18, D19, D20, D28, D37 and D38, which carbo- or heterocyclic ring or ring systems are unsubstituted, or substituted with one or more, same or different substituents R 12 .
  • At least one substituent R 1 or R 2 is selected from phenyl, C3-C8- cycloalkyl, C 3 -C 8 -cycloalkenyl, D14, D15, D16, D18, D19 D20, D28, D37, D38, and D104 which carbo- or heterocyclic ring or ring systems are unsubstituted, or substituted with one or more, same or different substituents R 12 .
  • At least one substituent R 1 or R 2 is selected from phenyl, C 3 -C 8 - cycloalkyl, C 3 -C 8 -cycloalkenyl, D14, D15, D16, D18, D19 D20, D28, D37 and D38, which carbo- or heterocyclic ring or ring systems are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4- haloalkoxy, and phenyl.
  • At least one substituent R 1 or R 2 is selected from phenyl, C3-C8- cycloalkyl, C3-C8-cycloalkenyl, D14, D15, D16, D18, D19 D20, D28, D37, D38, and D104, which carbo- or heterocyclic ring or ring systems are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy, and phenyl.
  • At least one substituent R 1 or R 2 is selected from phenyl, C 3 -C 8 - cycloalkyl, C3-C8-cycloalkenyl, D15, D16, D18, D19, D20, D37, and D38, which carbo- or heterocyclic ring or ring systems are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 1 -C 4 - haloalkoxy, and phenyl.
  • At least one substituent R 1 or R 2 is selected from phenyl, D15, D16, D18, D19, D20, D37, and D38 which carbo- or heterocyclic ring or ring systems are
  • At least one substituent R 1 or R 2 is selected from phenyl, D15, D16, D18, D19, D20, D37, D38 and D104, which carbo- or heterocyclic ring or ring systems are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy, and phenyl.
  • At least one substituent R 1 or R 2 is selected from D15, D18, D19, D20, D37, and D38 which heterocyclic rings or ring systems are unsubstituted or substituted with one or more, same or different substituents selected from halogen, phenyl, C1-C3-alkyl, or C1-C3- haloalkyl, preferably phenyl or C1-C3-alkyl.
  • At least one substituent R 1 or R 2 is selected from D15, D18, D19, D20, D37, D38 and D104 which heterocyclic rings or ring systems are unsubstituted or substituted with one or more, same or different substituents selected from halogen, phenyl, C1-C3-alkyl, or C 1 -C 3 -haloalkyl, preferably phenyl or C 1 -C 3 -alkyl.
  • R 12 is typically halogen, OH, CN, NO 2 ; or
  • R 12 is halogen, OH, CN; or
  • R 12 is C1-C3-alkyl, C1-C3-alkoxy, phenyl, which groups are unsubstituted, or halogenated.
  • R 12 is C1-C4-alkyl, C1-C4-alkoxy, or phe- nyl, preferably C 1 -C 3 -alkyl or phenyl.
  • R 13 and R 14 are independently H;
  • a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heter- ocyclic ring or ring system wherein said heterocyclic ring or ring system is selected from D1 to D154, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R A ;
  • heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R 132 .
  • R 13 and R 14 are independently H;
  • heterocyclic ring or ring system is selected from D1 to D154, and is unsubstituted, or substituted with one or more, same or different substituents se- lected from halogen, OH, CN, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, and C1-C4- haloalkoxy; or
  • a 3- to 10-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring or ring system wherein said carbocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C3-alkyl, C1-C3- haloalkyl, C 1 -C 3 -alkoxy, and C 1 -C 3 -haloalkoxy.
  • R 13 , R 14 are independently H;
  • C1-C10-alkyl C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from
  • a 3- to 8-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring or ring system wherein said carbocyclic ring or ring system is unsubstituted, or substi- tuted with one or more, same or different substituents selected from halogen, OH, CN, C 1 - C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy; or
  • R 13 and R 14 are independently H;
  • At least one substituent R 1 or R 2 is a group NR 15 NR 16 .
  • R 15 , R 16 , R 17 are independently H;
  • heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R 152 .
  • R 15 , R 16 , R 17 are independently H;
  • C 1 -C 10 -alkyl C 2 -C 10 -alkenyl, C 2 -C 10 -alkynyl, benzyl, or phenyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, CN, OH, phenyl, C1-C3-alkoxy, and C1-C3-haloalkoxy.
  • R 15 , R 16 , R 17 are independently H, C1-C3-alkyl, C2-C3-alkenyl, C2-C3- alkynyl, benzyl, or phenyl, preferably H, C 1 -C 3 -alkyl, benzyl, or phenyl.
  • R 18 is usually H;
  • heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents from halogen, CN, C 1 -C 3 -alkyl, C 1 -C 3 -alkoxy, C 1 -C 3 - haloalkyl, and C1-C3-haloalkoxy.
  • R 19 is usually H, C1-C4-alkyl, phenyl, or benzyl.
  • R 18 and R 19 form a 3- to 7-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or hetero- cyclic ring is unsubstituted or substituted with one or more, same or different substituents from halogen, CN, C 1 -C 3 -alkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -haloalkyl, and C 1 -C 3 -haloalkoxy.
  • R 18 is H
  • R 20a , R 20b are typically independently H, C 1 -C 3 -alkyl, C 1 -C 3 -haloalkyl, or phe- nyl, preferably C1-C3-alkyl or phenyl.
  • R 1 , R 2 are independently H, halogen, CN, NO 2 , N 3 , or SCN;
  • heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R 12 ;
  • R 31 is typically H;
  • heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R 312 .
  • R 31 is H, C1-C6-alkyl, C3-C6-cycloalkyl, phenyl, C2-C6-alkenyl, C2-C6-al- kynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, CN, OH, or C1-C3-alkoxy, phenoxy, or benzyloxy.
  • R 31 is H, or C1-C6-alkyl, which is unsubstituted or substituted with halogen, OH, or CN.
  • R 31 is H, or C 1 -C 3 -alkyl
  • the substituent R 32 is typically H;
  • C 1 -C 6 -alkyl C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C 1 -C 3 -alkyl, C 1 -C 3 -alkoxy, C1-C3-haloalkyl, and C1-C3-haloalkoxy; or
  • heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C 1 -C 3 -alkyl, C 1 -C 3 -alkoxy, C 1 -C 3 - haloalkyl, and C 1 -C 3 -haloalkoxy.
  • the substituents R 33 and R 34 are usually independently from another H;
  • C1-C3-alkyl which is unsubstituted, or substituted with one or more, same or different substitu- ents selected from halogen, C 1 -C 3 -alkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -haloalkyl, and C 1 -C 3 -haloalkoxy; or a 3- to 6-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkyl, and C1-C3-
  • R 4 is H
  • R 41 is usually OR 113 , preferably C1-C3-alkoxy, C1-C3-haloalkoxy, phenoxy, or benzyloxy.
  • R 43 and R 44 are independently
  • heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R 132 .
  • R 42 is typically halogen, CN;
  • R 42 is halogen, C 1 -C 3 -alkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -haloalkyl, or C 1 -C 3 -haloal- koxy.
  • R 43 and R 44 are independently
  • a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heter- ocyclic ring or ring system wherein said heterocyclic ring or ring system is selected from D1 to D154, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R A ;
  • heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R 132 .
  • R 43 and R 44 are independently
  • a 3- to 10-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring or ring system wherein said carbocyclic ring or ring system is unsubstituted, or substi- tuted with one or more, same or different substituents selected from halogen, OH, CN, C1- C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy; or
  • a 3- to 10-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring or ring system wherein said carbocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C3-alkyl, C1-C3- haloalkyl, C1-C3-alkoxy, and C1-C3-haloalkoxy.
  • R 43 and R 44 are independently
  • R 43 and R 44 are independently
  • heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R 152 .
  • substituents R 45 , R 46 , R 47 are independently H;
  • heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R 152 .
  • R A is usually halogen, OH, CN, C 1 -C 10 -alkyl, C 1 -C 10 -haloalkyl, C 1 -C 10 -alkoxy, or C 1 -C 6 -haloal- koxy, preferably halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, or C1-C4-haloalkoxy.
  • R 111 is usually halogen, OH, or CN; or a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R A .
  • R 111 is halogen, OH, CN, C1-C6-cycloalkyl, or phenyl, more preferably halogen.
  • R 112 is usually halogen, OH, CN; C1-C4-alkyl, C1-C4-alkoxy, C3-C6-cycloalkyl, C2-C6-alkenyl, C3- C 6 -cycloalkenyl, phenyl or C 2 -C 6 -alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, and CN.
  • R 112 is halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy.
  • R 113 and R 114 are independently H;
  • heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R 112 .
  • R 113 and R 114 are independently H;
  • a 3- to 6-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring or ring system which ring or ring system is unsubstituted, or substituted with one or more, same or dif- ferent substituents selected from halogen, OH, C1-C3-alkyl, C1-C3-haloalkyl, C1-C3-alkoxy, and C 1 -C 3 -haloalkoxy.
  • R 113 and R 114 are independently C1-C3-alkyl, C1-C3-haloalkyl, phenyl or benzyl.
  • R 115 , R 116 , R 117 are independently H;
  • heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R 112 .
  • R 115 , R 116 , R 117 are independently H;
  • R 115 , R 116 , R 117 are independently H;
  • C1-C6-alkyl C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, phenyl, which groups are unsubstituted, or halogenated.
  • R 118 is usually H, halogen
  • heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R 112 .
  • R 118 is H, halogen; C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cyclo- alkyl, C 3 -C 6 -cycloalkenyl, phenyl, which groups are unsubstituted, or halogenated.
  • R 119 is usually H, C1-C4-alkyl, C1-C6-cycloalkyl, C1-C2-alkoxy-C1-C2-alkyl, phenyl, benzyl, pref- erably H, C1-C4-alkyl, phenyl or benzyl, more preferably H, C1-C4-alkyl.
  • R 118 and R 119 form a 3- to 7-membered saturated, partially unsatu- rated, or fully unsaturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or hetero- cyclic ring is unsubstituted or substituted with one or more, same or different substituents se- lected from halogen, C 1 -C 3 -alkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -haloalkoxy, and C 1 -C 3 -haloalkyl.
  • R 121 is halogen, OH, CN, NO2;
  • heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R A .
  • R 121 is halogen, OH, CN, C1-C3-alkoxy, or C1-C3-haloalkoxy.
  • R 122 is halogen, OH, CN; or
  • R 122 is halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkyl, or C1-C3- haloalkoxy.
  • R 123 and R 124 are independently H, C1-C3-alkyl, C1-C3-haloalkyl, or phenyl.
  • R 125 , R 126 and R 127 may be independently from one another H;
  • R 125 , R 126 and R 127 may be independently from one another H, C 1 -C 3 -alkyl, or C1-C3-haloalkyl.
  • R 131 is typically halogen, OH, CN, C 1 -C 10 -alkoxy; or
  • heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkyl, C1-C3-haloalkoxy.
  • R 131 is halogen, CN; or
  • variable R 132 is typically halogen, OH, CN; C1-C6-alkyl, C1-C6-alkoxy, C3-C6-cycloalkyl, C2-C6-alkenyl, C3-C6-cycloalkenyl, C2-C6-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, and CN.
  • R 132 is halogen, CN, C 1 -C 3 -alkyl, C 1 - C3-alkoxy, C1-C3-haloalkyl, C1-C3-haloalkoxy.
  • R 151 is halogen, OH, CN; or
  • heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, CN, C1-C3-alkyl, C1-C3- alkoxy, C1-C3-haloalkyl, and C1-C3-haloalkoxy.
  • R 151 is phenyl, which is un- substituted, or substituted with one or more, same or different substituents selected from halo- gen, CN, C 1 -C 3 -alkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -haloalkyl, and C 1 -C 3 -haloalkoxy.
  • R 151 is phenyl.
  • variable R 152 is usually halogen, CN, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkyl, and C1- C 3 -haloalkoxy, preferably halogen, C 1 -C 3 -alkyl, or C 1 -C 3 -alkoxy.
  • R 311 is typically halogen, OH, CN;
  • heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C1-C3-alkyl, C1-C3-alkoxy, C 1 -C 3 -haloalkyl, or C 1 -C 3 -haloalkoxy.
  • R 311 is a 3- to 10-membered saturated, partially unsaturated, or fully un- saturated carbocyclic ring or ring system, which is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3- haloalkyl, or C 1 -C 3 -haloalkoxy.
  • R 312 is typically halogen, OH, CN
  • R 312 is halogen, OH, CN, C1-C3-alkyl, or C1-C3-alkoxy.
  • R 5 , R 6 are independently H, or OH. In one embodiment, R 5 is H and R 6 is OH. In one embodi- ment, R 5 is H.
  • n is 0, 1, or 2. In one embodiment, n is 0. In another embodiment, n is 1. In yet an- other embodiment, n is 2. Examples of preferred compounds of formula (I) are compiled in tables 1 to 156 below. Moreo- ver, the meanings mentioned below for the individual variables in the tables are per se, independently of the combination in which they are mentioned, a particularly preferred embodi- ment of the substituents in question. Table 1: Compounds of the formula (I) in which R 3 is H, R 4 is H, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 2 Compounds of the formula (I) in which R 3 is H, R 4 is H, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 3 Compounds of the formula (I) in which R 3 is OH, R 4 is H, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 4 Compounds of the formula (I) in which R 3 is OH, R 4 is H, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 5 Compounds of the formula (I) in which R 3 is CH3OCH2O, R 4 is H, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 6 Compounds of the formula (I) in which R 3 is CH 3 OCH 2 O, R 4 is H, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 7 Compounds of the formula (I) in which R 3 is C6H5CH2OCH2O, R 4 is H, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 8 Compounds of the formula (I) in which R 3 is C6H5CH2OCH2O, R 4 is H, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 9 Compounds of the formula (I) in which R 3 is H, R 4 is H9, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 10 Compounds of the formula (I) in which R 3 is H, R 4 is H9, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 11 Compounds of the formula (I) in which R 3 is OH, R 4 is H9, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 12 Compounds of the formula (I) in which R 3 is OH, R 4 is H9, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 13 Compounds of the formula (I) in which R 3 is CH3OCH2O, R 4 is H9, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 14 Compounds of the formula (I) in which R 3 is CH3OCH2O, R 4 is H9, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 15 Compounds of the formula (I) in which R 3 is C6H5CH2OCH2O, R 4 is H9, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 16 Compounds of the formula (I) in which R 3 is C 6 H 5 CH 2 OCH 2 O, R 4 is H9, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 42 Compounds of the formula (I) in which R 3 is H, R 4 is 4-methoxybenzylaminocar- bonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 43 Compounds of the formula (I) in which R 3 is OH, R 4 is 4-methoxybenzylaminocar- bonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 44 Compounds of the formula (I) in which R 3 is OH, R 4 is 4-methoxybenzylaminocar- bonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 45 Compounds of the formula (I) in which R 3 is CH3OCH2O, R 4 is 4-methoxybenzyla- minocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 46 Compounds of the formula (I) in which R 3 is CH 3 OCH 2 O, R 4 is 4-methoxybenzyla- minocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 47 Compounds of the formula (I) in which R 3 is C6H5CH2OCH2O, R 4 is 4-methoxyben- zylaminocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 48 Compounds of the formula (I) in which R 3 is C6H5CH2OCH2O, R 4 is 4-methoxyben- zylaminocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • R 5 is H
  • R 6 is OH
  • the combination of R 1 and R 2 is a row of Ta- ble B.
  • R 5 is H
  • R 6 is OH
  • the combination of R 1 and R 2 is a row of Ta- ble B.
  • R 5 is H
  • R 6 is OH
  • the combination of R 1 and R 2 is a row of Ta- ble C.
  • Table 65 Compounds of the formula (I) in which R 3 is H, R 4 is 4-fluorophenylaminocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 66 Compounds of the formula (I) in which R 3 is H, R 4 is4-fluorophenylaminocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 67 Compounds of the formula (I) in which R 3 is OH, R 4 is4-fluorophenylaminocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 68 Compounds of the formula (I) in which R 3 is OH, R 4 is4-fluorophenylaminocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 69 Compounds of the formula (I) in which R 3 is CH3OCH2O, R 4 is 4-fluorophenyla- minocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 70 Compounds of the formula (I) in which R 3 is CH 3 OCH 2 O, R 4 is 4-fluorophenyla- minocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 71 Compounds of the formula (I) in which R 3 is C6H5CH2OCH2O, R 4 is 4-fluorophenyla- minocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 72 Compounds of the formula (I) in which R 3 is C6H5CH2OCH2O, R 4 is 4-fluorophenyla- minocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 73 Compounds of the formula (I) in which R 3 is H, R 4 is 2-fluorophenylaminocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 74 Compounds of the formula (I) in which R 3 is H, R 4 is 2-fluorophenylaminocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 75 Compounds of the formula (I) in which R 3 is OH, R 4 is 2-fluorophenylaminocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 76 Compounds of the formula (I) in which R 3 is OH, R 4 is 2-fluorophenylaminocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 77 Compounds of the formula (I) in which R 3 is CH 3 OCH 2 O, R 4 is 2-fluorophenyla- minocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 78 Compounds of the formula (I) in which R 3 is CH3OCH2O, R 4 is 2-fluorophenyla- minocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 79 Compounds of the formula (I) in which R 3 is C6H5CH2OCH2O, R 4 is 2-fluorophenyla- minocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 80 Compounds of the formula (I) in which R 3 is C 6 H 5 CH 2 OCH 2 O, R 4 is 4-fluorophenyla- minocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 81 Compounds of the formula (I) in which R 3 is H, R 4 is naphthyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 82 Compounds of the formula (I) in which R 3 is H, R 4 is naphthyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 83 Compounds of the formula (I) in which R 3 is OH, R 4 is naphthyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 84 Compounds of the formula (I) in which R 3 is OH, R 4 is naphthyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 85 Compounds of the formula (I) in which R 3 is CH 3 OCH 2 O, R 4 is naphthyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 86 Compounds of the formula (I) in which R 3 is CH3OCH2O, R 4 is naphthyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 87 Compounds of the formula (I) in which R 3 is C 6 H 5 CH 2 OCH 2 O, R 4 is naphthyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 88 Compounds of the formula (I) in which R 3 is C6H5CH2OCH2O, R 4 is naphthyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 105 Compounds of the formula (I) in which R 3 is H, R 4 is benzylsulfanylthiocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 106 Compounds of the formula (I) in which R 3 is H, R 4 is benzylsulfanylthiocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 107 Compounds of the formula (I) in which R 3 is OH, R 4 is benzylsulfanylthiocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 108 Compounds of the formula (I) in which R 3 is OH, R 4 is benzylsulfanylthiocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 109 Compounds of the formula (I) in which R 3 is CH 3 OCH 2 O, R 4 is benzylsulfanylthio- carbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 110 Compounds of the formula (I) in which R 3 is CH3OCH2O, R 4 is benzylsulfanylthio- carbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 111 Compounds of the formula (I) in which R 3 is C6H5CH2OCH2O, R 4 is benzylsulfanyl- thiocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 112 Compounds of the formula (I) in which R 3 is C 6 H 5 CH 2 OCH 2 O, R 4 is benzylsulfanyl- thiocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 113 Compounds of the formula (I) in which R 3 is H, R 4 is 3-methoxybenzylsulfinylthio- carbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 114 Compounds of the formula (I) in which R 3 is H, R 4 is 3-methoxybenzylsulfinylthio- carbonyl,, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 115 Compounds of the formula (I) in which R 3 is OH, R 4 is 3-methoxybenzylsulfinylthio- carbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 116 Compounds of the formula (I) in which R 3 is OH, R 4 is 3-methoxybenzylsulfinylthio- carbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 118 Compounds of the formula (I) in which R 3 is CH3OCH2O, R 4 is 3-methoxybenzyl- sulfinylthiocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 119 Compounds of the formula (I) in which R 3 is C6H5CH2OCH2O, R 4 is 3-methoxyben- zylsulfinylthiocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of
  • Table 120 Compounds of the formula (I) in which R 3 is C 6 H 5 CH 2 OCH 2 O, R 4 is 3-methoxyben- zylsulfinylthiocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of
  • Table 121 Compounds of the formula (I) in which R 3 is H, R 4 is 4-fluorobenzylsulfinylthiocar- bonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 122 Compounds of the formula (I) in which R 3 is H, R 4 is 4-fluorobenzylsulfinylthiocar- bonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 123 Compounds of the formula (I) in which R 3 is OH, R 4 is 4-fluorobenzylsulfinylthiocar- bonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 124 Compounds of the formula (I) in which R 3 is OH, R 4 is 4-fluorobenzylsulfinylthiocar- bonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 125 Compounds of the formula (I) in which R 3 is CH3OCH2O, R 4 is 4-fluorobenzylsulfi- nylthiocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of
  • Table B Table 126: Compounds of the formula (I) in which R 3 is CH3OCH2O, R 4 is 4-fluorobenzylsulfi- nylthiocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 127 Compounds of the formula (I) in which R 3 is C 6 H 5 CH 2 OCH 2 O, R 4 is 4-fluorobenzyl- sulfinylthiocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 128 Compounds of the formula (I) in which R 3 is C6H5CH2OCH2O, R 4 is 4-fluorobenzyl- sulfinylthiocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 129 Compounds of the formula (I) in which R 3 is H, R 4 is naphthylmethylsulfanylthiocar- bonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 130 Compounds of the formula (I) in which R 3 is H, R 4 is naphthylmethylsulfanylthiocar- bonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 131 Compounds of the formula (I) in which R 3 is OH, R 4 is naphthylmethylsulfanylthio- carbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 132 Compounds of the formula (I) in which R 3 is OH, R 4 is naphthylmethylsulfanylthio- carbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 133 Compounds of the formula (I) in which R 3 is CH3OCH2O, R 4 is naphthylmethyl- sulfanylthiocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 134 Compounds of the formula (I) in which R 3 is CH 3 OCH 2 O, R 4 is naphthylmethyl- sulfanylthiocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 135 Compounds of the formula (I) in which R 3 is C6H5CH2OCH2O, R 4 is naphthylmethyl- sulfanylthiocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of
  • Table 136 Compounds of the formula (I) in which R 3 is C6H5CH2OCH2O, R 4 is naphthylmethyl- sulfanylthiocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of
  • Table 137 Compounds of the formula (I) in which R 3 is H, R 4 is 4-iodoobenzylsulfanylthiocar- bonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 138 Compounds of the formula (I) in which R 3 is H, R 4 is 4-iodoobenzylsulfanylthiocar- bonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 139 Compounds of the formula (I) in which R 3 is OH, R 4 is 4-iodoobenzylsulfanylthio- carbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 140 Compounds of the formula (I) in which R 3 is OH, R 4 is 4-iodoobenzylsulfanylthio- carbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 141 Compounds of the formula (I) in which R 3 is CH3OCH2O, R 4 is 4-iodoobenzyl- sulfanylthiocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 142 Compounds of the formula (I) in which R 3 is CH3OCH2O, R 4 is 4-iodoobenzyl- sulfanylthiocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 143 Compounds of the formula (I) in which R 3 is C 6 H 5 CH 2 OCH 2 O, R 4 is 4-iodoobenzyl- sulfanylthiocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 144 Compounds of the formula (I) in which R 3 is C6H5CH2OCH2O, R 4 is 4-iodoobenzyl- sulfanylthiocarbonyl, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 145 Compounds of the formula (I) in which R 3 is H, R 4 is H12, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 146 Compounds of the formula (I) in which R 3 is H, R 4 is H12, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 147 Compounds of the formula (I) in which R 3 is H, R 4 is H12, R 5 is OH, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 148 Compounds of the formula (I) in which R 3 is H, R 4 is H12, R 5 is OH, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 149 Compounds of the formula (I) in which R 3 is H, R 4 is H12, R 5 is OH, R 6 is H, and the combination of R 1 and R 2 is a row of Table B.
  • Table 150 Compounds of the formula (I) in which R 3 is H, R 4 is H12, R 5 is OH, R 6 is H, and the combination of R 1 and R 2 is a row of Table C.
  • Table 151 Compounds of the formula (I) in which R 3 is OH, R 4 is H12, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 152 Compounds of the formula (I) in which R 3 is OH, R 4 is H12, R 5 is H, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 153 Compounds of the formula (I) in which R 3 is OH, R 4 is H12, R 5 is OH, R 6 is OH, and the combination of R 1 and R 2 is a row of Table B.
  • Table 154 Compounds of the formula (I) in which R 3 is OH, R 4 is H12, R 5 is OH, R 6 is OH, and the combination of R 1 and R 2 is a row of Table C.
  • Table 155 Compounds of the formula (I) in which R 3 is OH, R 4 is H12, R 5 is OH, R 6 is H, and the combination of R 1 and R 2 is a row of Table B.
  • Table 156 Compounds of the formula (I) in which R 3 is OH, R 4 is H12, R 5 is OH, R 6 is H, and the combination of R 1 and R 2 is a row of Table C.
  • Table B Compounds of the formula (I) in which R 3 is OH, R 4 is H12, R 5 is OH, R 6 is H, and the combination of R 1 and R 2 is a row of Table C.
  • At least one variable R 1 or R 2 is selected from H, OH, halogen, CN, N3, preferably H, halogen, CN, N3; C1-C4-alkyl, C2-4-alkenyl (preferably C1-C4-alkyl), which groups are unsubstituted, or substituted with one or more, same or different substituents selected from
  • R 13 is C1-C6-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, which groups are unsubstituted, or substituted with halogen or CN, preferably Cl or CN; or
  • R 14 is C1-C8-alkyl, (preferably C2-C8-alkyl) which is unsubstituted, or halogenated;
  • phenyl, benzyl, or cyclopropyl which groups are unsubstituted or substituted with C 1 -C 4 -alkyl, or halogen;
  • R 15 is CH 3 ;
  • R 16 is benzyl
  • a carbo- or heterocyclic ring or ring system selected from phenyl, indol, indolin, morpholin, thiomorpholin, piperazin, triazol, and tetrazol, which groups are unsubstituted, or substituted with halogen, phenyl, C1-C4-alkyl, or C1-C4-alkoxy, preferably phenyl, C1-C4-alkyl, or C1-C4- alkoxy.
  • at least one variable R 1 or R 2 is selected from
  • C1-C4-alkyl C2-4-alkenyl (preferably C1-C4-alkyl), which groups are unsubstituted, or substituted with one or more, same or different substituents selected from
  • R 13 is C1-C6-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, which groups are unsubstituted, or substituted with halogen or CN, preferably Cl or CN; or
  • R 14 is C1-C8-alkyl, (preferably C2-C8-alkyl) which is unsubstituted, or halogenated;
  • phenyl, benzyl, or cyclopropyl which groups are unsubstituted or substituted with C1-C4-alkyl, or halogen;
  • R 15 is CH3
  • R 16 is benzyl
  • a carbo- or heterocyclic ring or ring system selected from phenyl, indol, indolin, 1,3-dithian, morpholin, thiomorpholin, piperazin, triazol, and tetrazol, which groups are unsubstituted, or substituted with halogen, phenyl, C1-C4-alkyl, or C1-C4-alkoxy, preferably phenyl, C1-C4-alkyl, or C 1 -C 4 -alkoxy.
  • R 3 is H or OR 31
  • R 5 is H or OH
  • R 6 is OH
  • at least one variable R 1 or R 2 is selected from H, OH, halogen, CN, N 3 , preferably H, halogen, CN, N 3 ; C1-C4-alkyl, C2-C4-alkenyl, (preferabyl C1-C4-alkyl) which groups are unsubstituted, or substituted with one or more, same or different substituents selected from
  • R 14 is C1-C8-alkyl, which is unsubstituted, or halogenated;
  • phenyl C 3 -C 8 -cycloalkyl, which groups are unsubstituted or substituted with C1-C4-alkyl, or halogen;
  • R 15 is C1-C3-alkyl
  • R 16 is C 1 -C 3 -alkyl, which is unsubstituted or substituted with one or more, same or
  • R 3 is H or OR 31
  • R 5 is H or OH
  • R 6 is OH
  • at least one variable R 1 or R 2 is selected from H, OH, halogen, CN, N3, preferably H, halogen, CN, N3;
  • R 13 is C 1 -C 6 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, C 3 -C 8 -cycloalkyl, which groups are
  • R 14 is C1-C8-alkyl, which is unsubstituted, or halogenated;
  • R 15 is C1-C3-alkyl
  • R 16 is C1-C3-alkyl, which is unsubstituted or substituted with one or more, same or
  • R 3 is H or OH;
  • R 5 is H or OH;
  • R 6 is OH; and at least one variable R 1 or R 2 is selected from
  • R 14 is C1-C8-alkyl, (preferably C2-C8-alkyl) which is unsubstituted, or halogenated;
  • phenyl, benzyl, or cyclopropyl which groups are unsubstituted or substituted with C 1 -C 4 -alkyl, or halogen;
  • R 15 is CH 3 ;
  • R 16 is benzyl
  • R 3 is H or OH
  • R 4 is H, or (3,5-ditert-butylphenyl)methylsulfanylcar- bonyl
  • R 5 is H
  • R 6 is OH
  • at least one variable R 1 or R 2 is selected from
  • R 14 is C1-C8-alkyl, (preferably C2-C8-alkyl) which is unsubstituted, or halogenated;
  • phenyl, benzyl or cyclopropyl which groups are unsubstituted or substituted with C1-C4-alkyl, or halogen;
  • R 15 is CH3
  • R 16 is benzyl
  • R 3 is H or OH
  • R 4 is H, or (3,5-ditert-butylphenyl)methylsulfanylcar- bonyl
  • R 5 is H
  • R 6 is OH
  • at least one variable R 1 or R 2 is selected from
  • R 13 is C1-C6-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, (preferably C2-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl) which groups are unsubstituted, or substituted with halogen or CN, preferably Cl or CN; or
  • R 14 is C1-C8-alkyl, (preferably C2-C8-alkyl) which is unsubstituted, or halogenated;
  • phenyl, benzyl or cyclopropyl which groups are unsubstituted or substituted with C1-C4-alkyl, or halogen;
  • R 15 is CH3
  • R 16 is benzyl
  • R 3 is H or OH;
  • R 4 is H;
  • R 5 is H;
  • R 6 is OH; and at least one variable R 1 or R 2 is selected from
  • R 13 is C 1 -C 3 -alkyl; C 2 -C 4 -alkynyl; or
  • R 14 is C1-C4-alkyl, preferably C2-C4-alkyl
  • R 15 is CH3;
  • R 16 is benzyl
  • R 3 is H or OH;
  • R 4 is H;
  • R 5 is H;
  • R 6 is OH; and at least one variable R 1 or R 2 is selected from
  • R 13 is C1-C3-alkyl; C2-C4-alkynyl; or
  • R 14 is C 1 -C 4 -alkyl, preferably C 2 -C 4 -alkyl
  • R 15 is CH3;
  • R 16 is benzyl
  • R 3 is H or OH;
  • R 4 is H;
  • R 5 is H;
  • R 6 is OH; and at least one variable R 1 or R 2 is selected from
  • R 14 is C 1 -C 4 -alkyl, preferably C 2 -C 4 -alkyl
  • R 15 is CH3;
  • R 16 is benzyl
  • R 3 is H or OH;
  • R 4 is H;
  • R 5 is H;
  • R 6 is OH; and at least one variable R 1 or R 2 is selected from
  • R 13 is C1-C3-alkyl; C2-C4-alkynyl; or
  • R 14 is C1-C4-alkyl, preferably C2-C4-alkyl
  • R 15 is CH 3 ;
  • R 16 is benzyl
  • the term“compound(s) of the present invention” or“compound(s) according to the invention” refers to the compound(s) of formula (I) as defined above, which are also referred to as“compound(s) of formula (I)” or“compound(s) I” or“formula (I) compound(s)”, and includes their salts, tautomers, stereoisomers, and N-oxides.
  • the present invention also relates to a mixture of at least one compound of the invention with at least one mixing partner as defined herein.
  • Pre- ferred weight ratios for such binary mixtures are from 5000:1 to 1:5000, preferably from 1000:1 to 1:1000, more preferably from 100:1 to 1:100, particularly from 10:1 to 1:10.
  • components I and II may be used in equal amounts, or an excess of component I, or an excess of component II may be used.
  • Mixing partners can be selected from pesticides, in particular insecticides, nematicides, and ac- aricides, fungicides, herbicides, plant growth regulators, fertilizers.
  • Preferred mixing partners are insecticides, nematicides and fungicides.
  • M.1 Acetylcholine esterase (AChE) inhibitors M.1A carbamates, e.g.
  • aldicarb aldicarb, alanycarb, bendi- ocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofen- carb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, ox- amyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate; or M.1B organophosphates, e.g.
  • GABA-gated chloride channel antagonists M.2A cyclodiene organochlorine compounds, e.g. endosulfan or chlordane; or M.2B fiproles (phenylpyrazoles), e.g. ethiprole, fipronil, flufiprole, pyrafluprole, and pyriprole;
  • M.3 Sodium channel modulators from the class of M.3A pyrethroids e.g. acrinathrin, allethrin, d- cis-trans allethrin, d-trans allethrin, bifenthrin, kappa-bifenthrin, bioallethrin, bioallethrin S-cylclo- pentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalo- thrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cyperme- thrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin,
  • M.4 Nicotinic acetylcholine receptor agonists M.4A neonicotinoids, e.g. acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or the compounds M.4A.14,5-Dihydro-N-nitro-1-(2-oxiranylmethyl)-1H-imidazol-2-amine, M.4A.2: (2E-)-1-[(6-Chloropyridin-3-yl)methyl]-N'-nitro-2-pentylidenehydrazinecarboximidamide; or M4.A.3: 1-[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro-5-propoxy-1,2,3,5,6,7-hexahydroim- idazo[1,2-a]pyridine; or M.4B nicotine
  • M.7 Juvenile hormone mimics such as M.7A juvenile hormone analogues hydroprene, kino- prene, and methoprene; or M.7B fenoxycarb, or M.7C pyriproxyfen;
  • M.8 miscellaneous non-specific (multi-site) inhibitors e.g. M.8A alkyl halides as methyl bromide and other alkyl halides, M.8B chloropicrin, M.8C sulfuryl fluoride, M.8D borax, or M.8E tartar emetic;
  • M.9 Chordotonal organ TRPV channel modulators e.g. M.9B pymetrozine; pyrifluquinazon; M.10 Mite growth inhibitors, e.g. M.10A clofentezine, hexythiazox, and diflovidazin, or M.10B etoxazole;
  • M.11 Microbial disruptors of insect midgut membranes e.g. bacillus thuringiensis or bacillus sphaericus and the insecticdal proteins they produce such as bacillus thuringiensis subsp. is- raelensis, bacillus sphaericus, bacillus thuringiensis subsp. aizawai, bacillus thuringiensis subsp. kurstaki and bacillus thuringiensis subsp. tenebrionis, or the Bt crop proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, and Cry34/35Ab1;
  • M.12 Inhibitors of mitochondrial ATP synthase e.g. M.12A diafenthiuron, or M.12B organotin miticides such as azocyclotin, cyhexatin, or fenbutatin oxide, M.12C propargite, or M.12D tetra- difon;
  • chlorfenapyr DNOC, or sulfluramid
  • Nicotinic acetylcholine receptor (nAChR) channel blockers e.g. nereistoxin analogues bensultap, cartap hydrochloride, thiocyclam, or thiosultap sodium;
  • M.15 Inhibitors of the chitin biosynthesis type 0, such as benzoylureas e.g. bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, or triflumuron;
  • benzoylureas e.g. bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, or triflumuron;
  • Ecdyson receptor agonists such as diacylhydrazines, e.g. methoxyfenozide, tebufenozide, halofenozide, fufenozide, or chromafenozide;
  • Octopamin receptor agonists e.g. amitraz
  • M.20 Mitochondrial complex III electron transport inhibitors e.g. M.20A hydramethylnon, M.20B acequinocyl, M.20C fluacrypyrim; or M.20D bifenazate;
  • M.21 Mitochondrial complex I electron transport inhibitors e.g. M.21A METI acaricides and in- secticides such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad or tolfen- pyrad, or M.21B rotenone;
  • M.22 Voltage-dependent sodium channel blockers e.g. M.22A indoxacarb, M.22B metaflumi- zone, or M.22B.1: 2-[2-(4-Cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoro- methoxy)phenyl]-hydrazinecarboxamide or M.22B.2: N-(3-Chloro-2-methylphenyl)-2-[(4-chloro- phenyl)[4-[methyl(methylsulfonyl)amino]phenyl]methylene]-hydrazinecarboxamide;
  • M.23 Inhibitors of the of acetyl CoA carboxylase such as Tetronic and Tetramic acid deriva- tives, e.g. spirodiclofen, spiromesifen, or spirotetramat; M.23.1 spiropidion;
  • M.24 Mitochondrial complex IV electron transport inhibitors e.g. M.24A phosphine such as alu- minium phosphide, calcium phosphide, phosphine or zinc phosphide, or M.24B cyanide;
  • Mitochondrial complex II electron transport inhibitors such as beta-ketonitrile derivatives, e.g. cyenopyrafen or cyflumetofen;
  • M.28 Ryanodine receptor-modulators from the class of diamides e.g. flubendiamide, chlor- antraniliprole, cyantraniliprole, tetraniliprole
  • M.28.2 (S)-3-Chloro-N1- ⁇ 2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl ⁇ -N2-(1-methyl-2- methylsulfonylethyl)phthalamid
  • M.28.4 methyl-2-[3,5-dibromo-2-( ⁇ [3- bromo-1-(
  • M.29 Chordotonal organ Modulators– undefined target site, e.g. flonicamid;
  • M.UN. insecticidal active compounds of unknown or uncertain mode of action e.g. afidopyro- pen, afoxolaner, azadirachtin, amidoflumet, benzoximate, broflanilide, bromopropylate, chino- methionat, cryolite, dicloromezotiaz, dicofol, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, fluralaner, metaldehyde, metoxadiazone, piperonyl butoxide, pyflubumide, pyridalyl, tioxazafen, M.UN.3: 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1,4-dioxa-9-aza- dispiro[4.2.4.2]-tetradec-11-en-10-one,
  • M.UN.4 3-(4’-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-1-azaspiro[4.5]dec-3-en-2-one
  • M.UN.5 1-[2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)-1H-1,2,4- triazole-5-amine, or actives on basis of bacillus firmus (Votivo, I-1582);
  • M.UN.8 fluazaindolizine
  • M.UN.9.a 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3- yl]-2-methyl-N-(1-oxothietan-3-yl)benzamide
  • M.UN.10 5-[3-[2,6-di- chloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1H-pyrazole;
  • M.UN.11.i 4-cyano-N-[2-cyano-5-[[2,6-dibromo-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)pro- pyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; M.UN.11.j) 4-cyano-3-[(4-cyano-2-methyl- benzoyl)amino]-N-[2,6-dichloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]-2- fluoro-benzamide; M.UN.11.k) N-[5-[[2-chloro-6-cyano-4-[1,2,2,3,3,3-hexafluoro-1-(trifluorome- thyl)propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; M.
  • M.UN.12.a 2-(1,3-Dioxan-2-yl)-6-[2-(3-pyridinyl)-5-thiazolyl]-pyridine; M.UN.12.b) 2-[6-[2-(5- Fluoro-3-pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine; M.UN.12.c) 2-[6-[2-(3-Pyridinyl)-5- thiazolyl]-2-pyridinyl]-pyrimidine; M.UN.12.d) N-Methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyri- dine-2-carboxamide; M.UN.12.e) N-Methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carbox- amide;
  • M.UN.14a 1-[(6-Chloro-3-pyridinyl)methyl]-1,2,3,5,6,7-hexahydro-5-methoxy-7-methyl-8-nitro- imidazo[1,2-a]pyridine; or M.UN.14b) 1-[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro- 1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-5-ol;
  • M.UN.16a 1-isopropyl-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide
  • M.UN.16b 1- (1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide
  • M.UN.16c N,5- dimethyl-N-pyridazin-4-yl-1-(2,2,2-trifluoro-1-methyl-ethyl)pyrazole-4-carboxamide
  • M.UN.16d 1-[1-(1-cyanocyclopropyl)ethyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide
  • M.UN.16e N-ethyl-1-(2-fluoro-1-methyl-propyl)-5-methyl-N-pyridazin-4-yl-pyrazole-4-car
  • M.UN.17a N-(1-methylethyl)-2-(3-pyridinyl)-2H-indazole-4-carboxamide
  • M.UN.17b N-cyclo- propyl-2-(3-pyridinyl)-2H-indazole-4-carboxamide
  • M.UN.17c N-cyclohexyl-2-(3-pyridinyl)-2H- indazole-4-carboxamide
  • M.UN.17d 2-(3-pyridinyl)-N-(2,2,2-trifluoroethyl)-2H-indazole-4-car- boxamide
  • M.UN.17e 2-(3-pyridinyl)-N-[(tetrahydro-2-furanyl)methyl]-2H-indazole-5-carbox- amide
  • M.UN.17f methyl 2-[[2-(3-pyridinyl)-2H-indazol-5-yl]carbonyl]
  • M.UN.17h N-(2,2-difluoropropyl)-2-(3-pyridinyl)-2H-indazole-5-carboxamide
  • M.UN.17i 2-(3- pyridinyl )-N-(2-pyrimidinylmethyl )-2H-indazole-5-carboxamide
  • M.UN.17j N-[(5-methyl-2-pyra- zinyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide
  • M.UN.21 N-[4-Chloro-3-[[(phenylmethyl)amino]carbonyl]phenyl]-1-methyl-3-(1,1,2,2,2-pentafluo- roethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide;
  • M.UN.22a 2-(3-ethylsulfonyl-2-pyridyl)- 3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, or M.UN.22b 2-[3-ethylsulfonyl-5-(trifluorome- thyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine;
  • M.UN.23a 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(4R)-2-ethyl-3-oxo- isoxazolidin-4-yl]-2-methyl-benzamide, or M.UN.23b) 4-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(tri- fluoromethyl)-4H-isoxazol-3-yl]-N-[(4R)-2-ethyl-3-oxo-isoxazolidin-4-yl]-2-methyl-benzamide; M.UN.24a) N-[4-chloro-3-(cyclopropylcarbamoyl)phenyl]-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)- 4-(trifluoromethyl)pyrazole-3-carboxamide or M.UN.24b)
  • M.UN.29a [(2S,3R,4R,5S,6S)-3,5-dimethoxy-6-methyl-4-propoxy-tetrahydropyran-2-yl] N-[4-[1- [4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]carbamate; M.UN.29b) [(2S,3R,4R,5S,6S)- 3,4,5-trimethoxy-6-methyl-tetrahydropyran-2-yl] N-[4-[1-[4-(trifluoromethoxy)phenyl]-1,2,4- triazol-3-yl]phenyl]carbamate; M.UN.29c) [(2S,3R,4R,5S,6S)-3,5-dimethoxy-6-methyl-4- propoxy-tetrahydropyran-2-yl] N-[4-[1-[4-(1,1,2,
  • M.UN.29.e (2Z)-3-(2-isopropylphenyl)-2-[(E)-[4-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3- yl]phenyl]methylenehydrazono]thiazolidin-4-one or M.UN.29f) (2Z)-3-(2-isopropylphenyl)-2-[(E)- [4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]methylenehydrazono]thia- zolidin-4-one.
  • M.4 cycloxaprid is known from WO2010/069266 and WO2011/069456.
  • M.4A.1 is known from CN 103814937; CN105367557, CN 105481839.
  • M.4A.2, guadipyr, is known from WO 2013/003977, and M.4A.3 (approved as paichongding in China) is known from WO
  • M.22B.1 is described in CN10171577 and M.22B.2 in CN102126994.
  • Spiropidion M.23.1 is known from WO 2014/191271.
  • M.28.1 and M.28.2 are known from WO2007/101540.
  • M.28.3 is described in WO2005/077934.
  • M.28.4 is described in WO2007/043677.
  • M.28.5a) to M.28.5d) and M.28.5h) are described in WO 2007/006670, WO2013/024009 and WO
  • M.28.5i is described in WO2011/085575, M.28.5j) in WO2008/134969, M.28.5k) in US2011/046186 and M.28.5l) in WO2012/034403.
  • M.28.6 can be found in WO2012/034472.
  • M.UN.3 is known from WO2006/089633 and M.UN.4 from WO2008/067911.
  • M.UN.5 is descri- bed in WO2006/043635, and biological control agents on the basis of bacillus firmus are de- scribed in WO2009/124707. Flupyrimin is described in WO2012/029672.
  • M.UN.8 is known from WO2013/055584.
  • M.UN.9.a is described in WO2013/050317.
  • M.UN.9.b is described in WO2014/126208.
  • M.UN.10 is known from WO2010/060379. Broflanilide and M.UN.11.b) to M.UN.11.h) are described in WO2010/018714, and M.UN.11i) to M.UN.11.p) in WO2010/018714, and M.UN.11i) to M.UN.11.p) in WO
  • M.UN.12.a) to M.UN.12.c) are known from WO2010/006713
  • M.UN.12.d) and M.UN.12.e) are known from WO2012/000896
  • M.UN.14a) and M.UN.14b) are known from WO2007/101369.
  • M.UN.16.a) to M.UN.16h) are described in WO2010/034737,
  • WO2012/084670, and WO2012/143317, resp., and M.UN.16i) and M.UN.16j) are described in WO2015/055497.
  • M.UN.17a) to M.UN.17.j) are described in WO2015/038503.
  • M.UN.18 Tyclo- prazoflor is described in US2014/0213448.
  • M.UN.19 is described in WO2014/036056.
  • M.UN.20 is known from WO2014/090918.
  • M.UN.21 is known from EP2910126.
  • M.UN.22a and M.UN.22b are known from WO2015/059039 and WO2015/190316.
  • M.UN.23a and M.UN.23b are known from WO2013/050302.
  • M.UN.24a) and M.UN.24b) are known from WO2012/126766.
  • Acyn- onapyr M.UN.25 is known from WO 2011/105506.
  • Benzpyrimoxan M.UN.26 is known from WO2016/104516.
  • M.UN.27 is known from WO2016/174049.
  • M.UN.28 Oxazosulfyl is known from WO2017/104592.
  • M.UN.29a) to M.UN.29f) are known from WO2009/102736 or
  • azoxystrobin (A.1.1), coumethoxystrobin (A.1.2), coumoxystrobin (A.1.3), dimoxystrobin (A.1.4), enestroburin (A.1.5), fenaminstrobin (A.1.6), fenoxystrobin/flufenoxystrobin (A.1.7), fluoxastrobin (A.1.8), kresoxim-methyl (A.1.9), mande- strobin (A.1.10), metominostrobin (A.1.11), orysastrobin (A.1.12), picoxystrobin (A.1.13), pyra- clostrobin (A.1.14), pyrametostrobin (A.1.15), pyraoxystrobin (A.1.16), trifloxystrobin (A.1.17), 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2
  • respiration inhibitors diflumetorim (A.4.1); nitrophenyl derivates: binapacryl (A.4.2), dinobuton (A.4.3), dinocap (A.4.4), fluazinam (A.4.5), meptyldinocap (A.4.6), ferimzone (A.4.7); organometal compounds: fentin salts, e. g. fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.11); silthiofam (A.4.12);
  • - C14 demethylase inhibitors triazoles: azaconazole (B.1.1), bitertanol (B.1.2), bromucona- zole (B.1.3), cyproconazole (B.1.4), difenoconazole (B.1.5), diniconazole (B.1.6), diniconazole- M (B.1.7), epoxiconazole (B.1.8), fenbuconazole (B.1.9), fluquinconazole (B.1.10), flusilazole (B.1.11), flutriafol (B.1.12), hexaconazole (B.1.13), imibenconazole (B.1.14), ipconazole
  • benalaxyl (C.1.1), benalaxyl-M (C.1.2), kiral- axyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (C.1.5), ofurace (C.1.6), oxadixyl (C.1.7);
  • nucleic acid synthesis inhibitors hymexazole (C.2.1), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrimidin- 4-amine (C.2.6), 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine (C.2.7), 5-fluoro- 2-(4-chlorophenylmethoxy)pyrimidin-4 amine (C.2.8);
  • tubulin inhibitors benomyl (D.1.1), carbendazim (D.1.2), fuberidazole (D1.3), thia- bendazole (D.1.4), thiophanate-methyl (D.1.5), 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phe- nyl-pyridazine (D.1.6), 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine (D.1.7), N-ethyl-2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]butanamide (D.1.8), N-ethyl-2-[(3-ethynyl-8-me- thyl-6-quinolyl)oxy]-2-methylsulfanyl-acetamide (D.1.9), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]- N-(2-(
  • diethofencarb (D.2.1), ethaboxam (D.2.2), pencycuron (D.2.3), fluopicolide (D.2.4), zoxamide (D.2.5), metrafenone (D.2.6), pyriofenone (D.2.7);
  • cyprodinil E.1.1
  • mepanipyrim E.1.2
  • pyrimethanil E.1.3
  • fluoroimid F.1.1
  • iprodione F.1.2
  • procymidone F.1.3
  • vinclozolin F.1.4
  • fludioxonil F.1.5
  • edifenphos G.1.1
  • iprobenfos G.1.2
  • pyrazophos G.1.3
  • isoprothiolane G.1.4
  • dimethomorph G.3.1
  • flumorph G.3.2
  • mandipropamid G.3.3
  • pyrimorph G.3.4
  • benthiavalicarb G.3.5
  • iprovalicarb G.3.6
  • valifenalate G.3.7
  • ferbam H.2.1
  • mancozeb H.2.2
  • maneb H.2.3
  • metam H.2.4
  • metiram H.2.5
  • propineb H.2.6
  • thiram H.2.7
  • zineb H.2.8
  • ziram H.2.9
  • organochlorine compounds anilazine (H.3.1), chlorothalonil (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.11);
  • guanidine H.4.1
  • dodine H.4.2
  • dodine free base H.4.3
  • guazatine H.4.4
  • guazatine-acetate H.4.5
  • iminoctadine H.4.6
  • iminoctadine-triacetate H.4.7
  • iminoctadine-tris(albesilate) H.4.8
  • dithianon H.4.9
  • 2,6-dimethyl-1H,5H-[1,4]di- thiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetraone H.4.10)
  • - melanin synthesis inhibitors pyroquilon (I.2.1), tricyclazole (I.2.2), carpropamid (I.2.3), di- cyclomet (I.2.4), fenoxanil (I.2.5);
  • fungicides described by common names, their preparation and their activity e.g. against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are com- briefly available.
  • Some compounds are identified by their CAS Registry Number which is separated by hyphens into three parts, the first consisting from two up to seven digits, the second consisting of two digits, and the third consisting of a single digit.
  • Biopesticides have been defined as a form of pesticides based on micro-organisms (bacteria, fungi, viruses, nematodes, etc.) or natural products (compounds, such as metabolites, proteins, or extracts from biological or other natural sources) (U.S. Environmental Protection Agency: http://www.epa.gov/pesticides/biopesticides/). Biopesticides fall into two major classes, micro- bial and biochemical pesticides:
  • Microbial pesticides consist of bacteria, fungi or viruses (and often include the metabolites that bacteria and fungi produce). Entomopathogenic nematodes are also classified as microbial pesticides, even though they are multi-cellular.
  • Biochemical pesticides are naturally occurring substances or or structurally-similar and functionally identical to a naturally-occurring substance and extracts from biological sources that control pests or provide other crop protection uses as defined below, but have non-toxic mode of actions (such as growth or developmental regulation, attractents, repellents or defence acti- vators (e.g. induced resistance) and are relatively non-toxic to mammals.
  • Biopesticides for use against crop diseases have already established themselves on a variety of crops. For example, biopesticides already play an important role in controlling downy mildew diseases. Their benefits include: a 0-Day Pre-Harvest Interval, the ability to use under moderate to severe disease pressure, and the ability to use in mixture or in a rotational program with other registered pesticides.
  • Biopesticidal seed treatments are e.g. used to control soil borne fungal pathogens that cause seed rots, damping-off, root rot and seedling blights. They can also be used to control internal seed borne fungal pathogens as well as fungal pathogens that are on the surface of the seed.
  • Many biopesticidal products also show capacities to stimulate plant host defenses and other physiological processes that can make treated crops more resistant to a variety of biotic and abiotic stresses or can regulate plant growth. Many biopesticidal products also show capacities to stimulate plant health, plant growth and/or yield enhancing activity.
  • Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudi- nis, B. amyloliquefaciens, B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, Candida oleophila, C.
  • Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity harpin protein, Reynoutria sachalinensis extract;
  • Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity Agrobacterium radiobacter, Bacillus cereus, B. firmus, B. thuringiensis, B. thuringiensis ssp. ai- zawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp. tenebrionis, Beau- veria bassiana, B.
  • Agrobacterium radiobacter Bacillus cereus, B. firmus, B. thuringiensis, B. thuringiensis ssp. ai- zawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ss
  • brongniartii Burkholderia spp., Chromobacterium subtsugae, Cydia pomo- nella granulovirus (CpGV), Cryptophlebia leucotreta granulovirus (CrleGV), Flavobacterium spp., Helicoverpa armigera nucleopolyhedrovirus (HearNPV), Helicoverpa zea nucleopolyhe- drovirus (HzNPV), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV), Heterorhab- ditis bacteriophora, Isaria fumosorosea, Lecanicillium longisporum, L.
  • HearNPV Helicoverpa armigera nucleopolyhedrovirus
  • HzNPV Helicoverpa zea nucleopolyhe- drovirus
  • HzSNPV Helicoverpa zea single
  • Microbial pesticides with plant stress reducing, plant growth regulator, plant growth pro- moting and/or yield enhancing activity Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium spp., B. elkanii, B. japonicum, B. liaoningense, B. lupini, Delftia acidovorans, Glomus intraradices, Mesorhizobium spp., Rhizobium legumi- nosarum bv. phaseoli, R. l. bv. trifolii, R. l. bv. viciae, R. tropici, Sinorhizobium meliloti.
  • the biopesticides from group L1) and/or L2) may also have insecticidal, acaricidal, molluscidal, pheromone, nematicidal, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity.
  • the biopesticides from group L3) and/or L4) may also have fungicidal, bactericidal, viricidal, plant defense activator, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity.
  • the biopesticides from group L5) may also have fungicidal, bactericidal, viricidal, plant defense activator, insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity.
  • amyloliquefaciens spp. plantarum FZB24 isolated from soil in Brandenburg, Germany also called SB3615; DSM 96-2; J. Plant Dis. Prot.105, 181–197, 1998; e. g. Taegro® from Novozyme Biologicals, Inc., USA
  • B. amyloliquefaciens ssp. plantarum MBI600 isolated from faba bean in Sutton Bon- ington, Nottinghamshire, U.K. at least before 1988 also called 1430; NRRL B-50595;
  • pumilus INR-7 otherwise referred to as BU-F22 and BU-F33 isolated at least before 1993 from cucumber infested by Erwinia tra- cheiphila (NRRL B-50185, NRRL B-50153; US 8,445,255), B. pumilus KFP9F isolated from the rhizosphere of grasses in South Africa at least before 2008 (NRRL B-50754; WO 2014/029697; e. g. BAC-UP or FUSION-P from BASF Agricultural Specialities (Pty) Ltd., South Africa), B. pu- milus QST 2808 was isolated from soil collected in Pohnpei, Federated States of Micronesia, in 1998 (NRRL B-30087; e. g.
  • B. simplex ABU 288 (NRRL B-50304; US 8,445,255), B. subtilis FB17 also called UD 1022 or UD10-22 isolated from red beet roots in North America (ATCC PTA-11857; System. Appl. Mi- crobiol.27, 372-379, 2004; US 2010/0260735; WO 2011/109395); B. thuringiensis ssp. aizawai ABTS-1857 isolated from soil taken from a lawn in Ephraim, Wisconsin, U.S.A., in 1987 (also called ABG-6346; ATCC SD-1372; e. g.
  • tenebrionis NB-176-1 a mutant of strain NB ⁇ 125, a wild type strain isolated in 1982 from a dead pupa of the beetle Tenebrio molitor (DSM 5480; EP 585215 B1; e. g. Novodor® from Valent BioSciences, Switzerland), Beauveria bassiana GHA (ATCC 74250; e. g. BotaniGard® 22WGP from Laver- lam Int. Corp., USA), B. bassiana JW-1 (ATCC 74040; e. g. Naturalis® from CBC (Europe) S.r.l., Italy), B.
  • DSM 5480 Tenebrio molitor
  • EP 585215 B1 e. g. Novodor® from Valent BioSciences, Switzerland
  • Beauveria bassiana GHA ATCC 74250; e. g. BotaniGard® 22WGP from Laver- lam Int. Corp., USA
  • bassiana PPRI 5339 isolated from the larva of the tortoise beetle Conchyloctenia punctata (NRRL 50757; e. g. BroadBand® from BASF Agricultural Specialities (Pty) Ltd., South Africa), Bradyrhizobium elkanii strains SEMIA 5019 (also called 29W) isolated in Rio de Janeiro, Brazil and SEMIA 587 isolated in 1967 in the State of Rio Grande do Sul, from an area previ- ously inoculated with a North American isolate, and used in commercial inoculants since 1968 (Appl. Environ. Microbiol.73(8), 2635, 2007; e. g. GELFIX 5 from BASF Agricultural Specialties Ltd., Brazil), B.
  • japonicum 532c isolated from Wisconsin field in U.S.A. (Nitragin 61A152; Can. J. Plant. Sci.70, 661-666, 1990; e. g. in Rhizoflo®, Histick®, Hicoat® Super from BASF
  • SEMIA 5080 obtained under lab condtions by Embrapa- Cerrados in Brazil and used in commercial inoculants since 1992, being a natural variant of SEMIA 586 (CB1809) originally isolated in U.S.A. (CPAC 7; e. g. GELFIX 5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil); Burkholderia sp. A396 isolated from soil in Nikko, Ja- pan, in 2008 (NRRL B-50319; WO 2013/032693; Marrone Bio Innovations, Inc., USA), Coni- othyrium minitans CON/M/91-08 isolated from oilseed rape (WO 1996/021358; DSM 9660; e.
  • Contans® WG Contans® WG, Intercept® WG from Bayer CropScience AG, Germany
  • harpin alpha-beta protein
  • Science 257, 85-88, 1992 e. g. MessengerTM or HARP-N-Tek from Plant Health Care plc, U.K.
  • HearNPV Helicoverpa armigera nucleopolyhedrovirus
  • HSSNPV sin- gle capsid nucleopolyhedrovirus
  • ABA-NPV-U e. g. Heligen® from AgBiTech Pty Ltd., Queensland, Australia
  • Heterorhabditis bacteriophora e. g.
  • Met52® Novozymes Biologicals BioAg Group, Canada Metschnikowia fructicola 277 isolated from grapes in the central part of Israel (US 6,994,849; NRRL Y-30752; e. g. for- merly Shemer® from Agrogreen, Israel), Paecilomyces ilacinus 251 isolated from infected nem- atode eggs in the Philippines (AGAL 89/030550; WO1991/02051; Crop Protection 27, 352-361, 2008; e. g.
  • Paenibacillus alvei NAS6G6 isolated from the rhizosphere of grasses in South Africa at least before 2008 (WO 2014/029697; NRRL B-50755; e.g. BAC-UP from BASF Agricultural Speciali- ties (Pty) Ltd., South Africa), Paenibacillus strains isolated from soil samples from a variety of European locations including Germany: P. epiphyticus Lu17015 (WO 2016/020371; DSM 26971), P. polymyxa ssp. plantarum Lu16774 (WO 2016/020371; DSM 26969), P. p. ssp.
  • WO 1995/017806 e. g. Jump Start®, Provide® from Novozymes Biologicals BioAg Group, Can- ada), Reynoutria sachalinensis extract (EP 0307510 B1; e. g. Regalia® SC from Marrone BioIn- novations, Davis, CA, USA or Milsana® from BioFa AG, Germany), Steinernema carpocapsae (e. g. Millenium® from BASF Agricultural Specialities Limited, UK), S. feltiae (e. g.
  • the solid material (dry matter) of the biopesticides (with the excep- tion of oils such as Neem oil) are considered as active components (e.g. to be obtained after drying or evaporation of the extraction or suspension medium in case of liquid formulations of the microbial pesticides).
  • the weight ratios and percentages used herein for a biological extract such as Quillay extract are based on the total weight of the dry content (solid material) of the respective extract(s).
  • the total weight ratios of compositions comprising at least one microbial pesticide in the form of viable microbial cells including dormant forms can be determined using the amount of CFU of the respective microorganism to calclulate the total weight of the respective active component with the following equation that 1 x 10 10 CFU equals one gram of total weight of the respective active component.
  • Colony forming unit is measure of viable microbial cells, in particular fungal and bacterial cells.
  • here“CFU” may also be understood as the number of (juvenile) individual nematodes in case of (entomopathogenic) nematode biopesticides, such as Stei- nernema feltiae.
  • the applica- tion rates preferably range from about 1 x 10 6 to 5 x 10 15 (or more) CFU/ha, preferably from about 1 x 10 8 to about 1 x 10 13 CFU/ha, and even more preferably from about 1 x 10 9 to about 1 x 10 12 CFU/ha.
  • (entomopathogenic) nematodes as microbial pesticides (e. g.
  • the application rates preferably range inform about 1 x 10 5 to 1 x 10 12 (or more), more preferably from 1 x 10 8 to 1 x 10 11 , even more preferably from 5 x 10 8 to 1 x 10 10 individuals (e. g. in the form of eggs, juvenile or any other live stages, preferably in an infetive juvenile stage) per ha.
  • the applica- tion rates with respect to plant propagation material preferably range from about 1 x 10 6 to 1 x 10 12 (or more) CFU/seed.
  • the concentration is about 1 x 10 6 to about 1 x 10 9 CFU/seed.
  • the application rates with respect to plant propagation material also preferably range from about 1 x 10 7 to 1 x 10 14 (or more) CFU per 100 kg of seed, preferably from 1 x 10 9 to about 1 x 10 12 CFU per 100 kg of seed.
  • the invention also relates to agrochemical compositions comprising an auxiliary and at least one compound of the present invention or a mixture thereof.
  • An agrochemical composition comprises a pesticidally effective amount of a compound of the present invention or a mixture thereof.
  • the term "pesticidally effective amount” is defined below.
  • the compounds of the present invention or the mixtures thereof can be converted into custom- ary types of agro-chemical compositions, e. g. solutions, emulsions, suspensions, dusts, pow- ders, pastes, granules, pressings, capsules, and mixtures thereof.
  • composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g.
  • compositions types are defined in the “Catalogue of pesticide formulation types and international coding system”, Technical Mono- graph No.2, 6th Ed. May 2008, CropLife International.
  • compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfac- tants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protec- tive colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimu- lants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifi- ers and binders.
  • suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfac- tants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protec- tive colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimu- lants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil frac- tions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, al- kylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g.
  • mineral oil frac- tions of medium to high boiling point e.g. kerosene, diesel oil
  • oils of vegetable or animal origin oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e. g. toluene, paraffin, tetrahydrona
  • lactates carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
  • Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, lime- stone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammo- nium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • mineral earths e.g. silicates, silica gels, talc, kaolins, lime- stone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
  • polysaccharide powders e.
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective col- loid, or adjuvant. Examples of surfactants are listed in McCutcheon’s, Vol.1: Emulsifiers & De- tergents, McCutcheon’s Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sul-fa- tes, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylaryl-sul- fonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfona- tes of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.
  • Examples of sul- fates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethox-ylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters. Exam-ples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol eth-oxylates.
  • Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • Exam- ples of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpoly- glucosides.
  • polymeric surfactants are homo- or copolymers of vinylpyrrolidone, vi- nylalcohols, or vinylacetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block pol- ymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene ox- ide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suita- ble polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of poly- acrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyeth- yleneamines.
  • Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compounds of the present in- vention on the target.
  • examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anor- ganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazoli- nones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants e.g. in red, blue, or green
  • Suitable colorants are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
  • composition types and their preparation are:
  • a compound I according to the invention 10-60 wt% of a compound I according to the invention and 5-15 wt% wetting agent (e.g. alco- hol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) up to 100 wt%.
  • the active substance dissolves upon dilution with water.
  • a compound I according to the invention 5-25 wt% of a compound I according to the invention and 1-10 wt% dispersant (e. g. polyvi- nylpyrrolidone) are dissolved in up to 100 wt% organic solvent (e.g. cyclohexanone). Dilution with water gives a dispersion.
  • dispersant e. g. polyvi- nylpyrrolidone
  • emulsifiers e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • water-insol- uble organic solvent e.g. aromatic hydrocarbon
  • Emulsions (EW, EO, ES)
  • emulsifiers e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • 20-40 wt% water-insoluble organic solvent e.g. aromatic hydrocarbon
  • a compound I according to the invention 20-60 wt% of a compound I according to the invention are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alco- hol ethoxylate), 0,1-2 wt% thickener (e.g. xanthan gum) and up to 100 wt% water to give a fine active substance suspension. Dilution with water gives a stable suspension of the active sub- stance. For FS type composition up to 40 wt% binder (e.g. polyvinylalcohol) is added.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alco- hol ethoxylate
  • 0,1-2 wt% thickener e.g. xanthan gum
  • 50-80 wt% of a compound I according to the invention are ground finely with addition of up to 100 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solu- tion of the active substance.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alcohol ethoxylate
  • wt% of a compound I according to the invention are ground in a rotor-stator mill with ad- dition of 1-5 wt% dispersants (e.g. sodium lignosulfonate), 1-3 wt% wetting agents (e.g. alcohol ethoxylate) and up to 100 wt% solid carrier, e.g. silica gel. Dilution with water gives a stable dis- persion or solution of the active substance.
  • dispersants e.g. sodium lignosulfonate
  • wetting agents e.g. alcohol ethoxylate
  • solid carrier e.g. silica gel
  • a compound I according to the invention In an agitated ball mill, 5-25 wt% of a compound I according to the invention are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1-5 wt% thickener (e.g. car- boxymethylcellulose) and up to 100 wt% water to give a fine suspension of the active sub- stance. Dilution with water gives a stable suspension of the active substance.
  • dispersants e.g. sodium lignosulfonate
  • 1-5 wt% thickener e.g. car- boxymethylcellulose
  • 5-20 wt% of a compound I according to the invention are added to 5-30 wt% organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alko- hol ethoxylate and arylphenol ethoxylate), and water up to 100 %.
  • organic solvent blend e.g. fatty acid dimethylamide and cyclohexanone
  • surfactant blend e.g. alko- hol ethoxylate and arylphenol ethoxylate
  • An oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g. methyl- methacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radi-cal initiator results in the formation of poly(meth)acrylate microcapsules.
  • an oil phase compris- ing 5-50 wt% of a compound I according to the invention, 0-40 wt% water insolu-ble organic sol- vent (e.g.
  • an isocyanate monomer e.g. diphenylme-thene-4,4’- diisocyanatae
  • a protective colloid e.g. polyvinyl alco- hol
  • the addition of a polyamine results in the for-mation of a pol- yurea microcapsule.
  • the monomers amount to 1-10 wt%. The wt% relate to the total CS com- position.
  • Dustable powders (DP, DS)
  • 1-10 wt% of a compound I according to the invention are ground finely and mixed intimately with up to 100 wt% solid carrier, e.g. finely divided kaolin.
  • 0.5-30 wt% of a compound I according to the invention is ground finely and associated with up to 100 wt% solid carrier (e.g. silicate). Granulation is achieved by extrusion, spray-drying or the fluidized bed.
  • solid carrier e.g. silicate
  • 1-50 wt% of a compound I according to the invention are dissolved in up to 100 wt% organic solvent, e.g. aromatic hydrocarbon.
  • organic solvent e.g. aromatic hydrocarbon.
  • compositions types i) to xi) may optionally comprise further auxiliaries, such as 0.1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1-1 wt% anti-foaming agents, and 0.1-1 wt% col- orants.
  • auxiliaries such as 0.1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1-1 wt% anti-foaming agents, and 0.1-1 wt% col- orants.
  • the agrochemical compositions generally comprise between 0.01 and 95%, preferably be- tween 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active sub-stance.
  • the active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immedi- ately prior to use (tank mix).
  • pesticides e.g. herbicides, insecticides, fungicides, growth regulators, safeners
  • These agents can be admixed with the compositions according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.
  • the user applies the composition according to the invention usually from a predosage de-vice, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the agrochem- ical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition ac- cording to the invention is thus obtained.
  • 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
  • composition according to the in- vention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
  • either individual components of the composition according to the in- vention or partially premixed components may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.
  • either individual components of the composition according to the in- vention or partially premixed components e. g. components comprising compounds of the pre- sent invention and/or mixing partners as defined above, can be applied jointly (e.g. after tank mix) or consecutively.
  • the compounds of the present invention are suitable for use in protecting crops, plants, plant propagation materials, such as seeds, or soil or water, in which the plants are growing, from at- tack or infestation by animal pests. Therefore, the present invention also relates to a plant pro- tection method, which comprises contacting crops, plants, plant propagation materials, such as seeds, or soil or water, in which the plants are growing, to be protected from attack or infesta- tion by animal pests, with a pesticidally effective amount of a compound of the present inven- tion.
  • the compounds of the present invention are also suitable for use in combating or controlling animal pests. Therefore, the present invention also relates to a method of combating or control- ling animal pests, which comprises contacting the animal pests, their habitat, breeding ground, or food supply, or the crops, plants, plant propagation materials, such as seeds, or soil, or the area, material or environment in which the animal pests are growing or may grow, with a pesti- cidally effective amount of a compound of the present invention.
  • the compounds of the present invention are effective through both contact and ingestion.
  • Fur- thermore the compounds of the present invention can be applied to any and all developmental stages, such as egg, larva, pupa, and adult.
  • the compounds of the present invention can be applied as such or in form of compositions comprising them as defined above. Furthermore, the compounds of the present invention can be applied together with a mixing partner as defined above or in form of compositions compris- ing said mixtures as defined above.
  • the components of said mixture can be applied simultane- ously, jointly or separately, or in succession, that is immediately one after another and thereby creating the mixture“in situ” on the desired location, e.g. the plant, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.
  • the application can be carried out both before and after the infestation of the crops, plants, plant propagation materials, such as seeds, soil, or the area, material or environment by the pests.
  • Suitable application methods include inter alia soil treatment, seed treatment, in furrow appli- cation, and foliar application.
  • Soil treatment methods include drenching the soil, drip irrigation (drip application onto the soil), dipping roots, tubers or bulbs, or soil injection.
  • Seed treatment techniques include seed dressing, seed coating, seed dusting, seed soaking, and seed pellet- ing.
  • furrow applications typically include the steps of making a furrow in cultivated land, seed- ing the furrow with seeds, applying the pesticidally active compound to the furrow, and closing the furrow.
  • Foliar application refers to the application of the pesticidally active compound to plant foliage, e.g. through spray equipment.
  • pheromones for specific crops and pests are known to a skilled person and publicly available from databases of pheromones and semiochemicals, such as http://www.pherobase.com.
  • the term "contacting” includes both direct contact (applying the com- pounds/compositions directly on the animal pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus, i.e. habi- tat, breeding ground, plant, seed, soil, area, material or environment in which a pest is growing or may grow, of the animal pest or plant).
  • animal pest includes arthropods, gastropods, and nematodes.
  • Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, in particular insects.
  • Insects, which are of particular relevance for crops, are typically referred to as crop in- sect pests.
  • crop refers to both, growing and harvested crops.
  • plant includes cereals, e.g. durum and other wheat, rye, barley, triticale, oats, rice, or maize (fodder maize and sugar maize / sweet and field corn); beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g.
  • iceb33erg lettuce chic- ory, cabbage, asparagus, cabbages, carrots, onions, garlic, leeks, tomatoes, potatoes, cucurbits or sweet peppers; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rapeseed, sugar cane or oil palm; tobacco; nuts, e.g. walnuts; pistachios; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers (e.g.
  • Preferred plants include potatoes sugar beets, to- bacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rapeseed, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • cultivagenesis includes techniques of random mutagenesis using X-rays or mutagenic chemicals, but also techniques of targeted mutagenesis, in order to create mutations at a specific locus of a plant genome.
  • Targeted mutagenesis techniques frequently use oligonucleotides or proteins like CRISPR/Cas, zinc-finger nucleases, TALENs or meganucleases to achieve the targeting effect.
  • Genetic engineering usually uses recombinant DNA techniques to create modifications in a plant genome which under natural circumstances cannot readily be obtained by cross breeding, mutagenesis or natural recombination.
  • one or more genes are integrated into the ge- nome of a plant in order to add a trait or improve a trait. These integrated genes are also re- ferred to as transgenes in the art, while plant comprising such transgenes are referred to as transgenic plants.
  • the process of plant transformation usually produces several transformation events, wich differ in the genomic locus in which a transgene has been integrated. Plants com- prising a specific transgene on a specific genomic locus are usually described as comprising a specific“event”, which is referred to by a specific event name. Traits which have been intro- prised in plants or hae been modified include in particular herbicide tolerance, insect resistance, increased yield and tolerance to abiotic conditions, like drought.
  • Herbicide tolerance has been created by using mutagenesis as well as using genetic engineer- ing. Plants which have been rendered tolerant to acetolactate synthase (ALS) inhibitor herbi- cides by conventional methods of mutagenesis and breeding comprise plant varieties commer- cially available under the name Clearfield ® . However, most of the herbicide tolerance traits have been created via the use of transgenes.
  • ALS acetolactate synthase
  • Herbicide tolerance has been created to glyphosate, glufosinate, 2,4-D, dicamba, oxynil herbi- cides, like bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitor herbicides and 4-hy- droxyphenylpyruvate dioxygenase (HPPD) inhibitors, like isoxaflutole and mesotrione.
  • HPPD 4-hy- droxyphenylpyruvate dioxygenase
  • Transgenes wich have been used to provide herbicide tolerance traits comprise: for tolerance to glyphosate: cp4 epsps, epsps grg23ace5, mepsps, 2mepsps, gat4601, gat4621 and goxv247, for tolerance to glufosinate: pat and bar, for tolerance to 2,4-D: aad-1 and aad-12, for tolerance to dicamba: dmo, for tolerance to oxynil herbicies: bxn, for tolerance to sulfonylurea herbicides: zm-hra, csr1-2, gm-hra, S4-HrA, for tolerance to ALS inhibitor herbicides: csr1-2, for tolerance to HPPD inhibitor herbicides: hppdPF, W336 and avhppd-03.
  • Transgenic corn events comprising herbicide tolerance genes are for example, but not exclud- ing others, DAS40278, MON801, MON802, MON809, MON810, MON832, MON87411, MON87419, MON87427, MON88017, MON89034, NK603, GA21, MZHG0JG, HCEM485, VCO- ⁇ 1981-5, 676, 678, 680, 33121, 4114, 59122, 98140, Bt10, Bt176, CBH-351, DBT418, DLL25, MS3, MS6, MZIR098, T25, TC1507 and TC6275.
  • Transgenic soybean events comprising herbicide tolerance genes are for example, but not ex- cluding others, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21, A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS- 81419-2, GU262, SYHT ⁇ H2, W62, W98, FG72 and CV127.
  • Transgenic cotton events comprising herbicide tolerance genes are for example, but not exclud- ing others, 19-51a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN10211, BXN10215, BXN10222, BXN10224, MON1445, MON1698, MON88701, MON88913, GHB119, GHB614, LLCotton25, T303-3 and T304-40.
  • Transgenic canola events comprising herbicide tolerance genes are for example, but not ex- cluding others, MON88302, HCR-1, HCN10, HCN28, HCN92, MS1, MS8, PHY14, PHY23, PHY35, PHY36, RF1, RF2 and RF3.
  • Insect resistance has mainly been created by transferring bacterial genes for insecticidal pro- teins to plants.
  • Transgenes which have most frequently been used are toxin genes of Bacillus spec. and synthetic variants thereof, like cry1A, cry1Ab, cry1Ab-Ac, cry1Ac, cry1A.105, cry1F, cry1Fa2, cry2Ab2, cry2Ae, mcry3A, ecry3.1Ab, cry3Bb1, cry34Ab1, cry35Ab1, cry9C, vip3A(a), vip3Aa20.
  • genes of plant origin have been transferred to other plants.
  • In particu- lar genes coding for protease inhibitors like CpTI and pinII.
  • a further approach uses transgenes in order to produce double stranded RNA in plants to target and downregulate insect genes.
  • An example for such a transgene is dvsnf7.
  • Transgenic corn events comprising genes for insecticidal proteins or double stranded RNA are for example, but not excluding others, Bt10, Bt11, Bt176, MON801, MON802, MON809, MON810, MON863, MON87411, MON88017, MON89034, 33121, 4114, 5307, 59122, TC1507, TC6275, CBH-351, MIR162, DBT418 and MZIR098.
  • Transgenic soybean events comprising genes for insecticidal proteins are for example, but not excluding others, MON87701, MON87751 and DAS-81419.
  • Transgenic cotton events comprising genes for insecticidal proteins are for example, but not ex- cluding others, SGK321, MON531, MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317, BNLA-601, Event1, COT67B, COT102, T303-3, T304-40, GFM Cry1A, GK12, MLS 9124, 281-24-236, 3006-210-23, GHB119 and SGK321.
  • Increased yield has been created by increasing ear biomass using the transgene athb17, being present in corn event MON87403, or by enhancing photosynthesis using the transgene bbx32, being present in the soybean event MON87712.
  • Cultivated plants comprising a modified oil content have been created by using the transgenes: gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A and fatb1-A. Soybean events comprising at least one of these genes are: 260-05, MON87705 and MON87769.
  • Tolerance to abiotic conditions, in particular to tolerance to drought, has been created by using the transgene cspB, comprised by the corn event MON87460 and by using the transgene Hahb- 4, comprised by soybean event IND- ⁇ 41 ⁇ -5.
  • Traits are frequently combined by combining genes in a transformation event or by combining different events during the breeding process.
  • Preferred combination of traits are herbicide toler- ance to different groups of herbicides, insect tolerance to different kind of insects, in particular tolerance to lepidopteran and coleopteran insects, herbicide tolerance with one or several types of insect resistance, herbicide tolerance with increased yield as well as a combination of herbi- cide tolerance and tolerance to abiotic conditions.
  • Plants comprising singular or stacked traits as well as the genes and events providing these traits are well known in the art.
  • detailed information as to the mutagenized or inte- grated genes and the respective events are available from websites of the organizations“Inter- national Service for the Acquisition of Agri-biotech Applications (ISAAA)”
  • compositions according to the invention on cultivated plants may result in effects which are specific to a cultivated plant comprising a certain gene or event. These effects might involve changes in growth behavior or changed resistance to biotic or abiotic stress factors. Such effects may in particular comprise enhanced yield, enhanced resistance or tolerance to insects, nematodes, fungal, bacterial, mycoplasma, viral or viroid pathogens as well as early vigour, early or delayed ripening, cold or heat tolerance as well as changed amino acid or fatty acid spectrum or content.
  • the pesticidal activity of the compounds of the present inven- tion may be enhanced by the insecticidal trait of a modified plant. Furthermore, it has been found that the compounds of the present invention are suitable for preventing insects to become resistant to the insecticidal trait or for combating pests, which already have become resistant to the insecticidal trait of a modified plant. Moreover, the compounds of the present invention are suitable for combating pests, against which the insecticidal trait is not effective, so that a com- plementary insecticidal activity can advantageously be used.
  • plant propagation material refers to all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e.g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhi- zomes, shoots, sprouts and other parts of plants. Seedlings and young plants, which are to be transplanted after germination or after emergence from soil, may also be included. These plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting.
  • vegetative plant material such as cuttings and tubers (e.g. potatoes)
  • seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like, and means in a preferred embodiment true seeds.
  • pesticidally effective amount means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism.
  • the pesticidally effective amount can vary for the various compounds/composi- tions used in the invention.
  • a pesticidally effective amount of the compositions will also vary ac- cording to the prevailing conditions such as desired pesticidal effect and duration, weather, tar- get species, locus, mode of application, and the like.
  • the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m 2 , preferably from 0.001 to 20 g per 100 m 2 .
  • the rate of application of the active in- gredients of this invention may be in the range of 0.0001 g to 4000 g per hectare, e.g. from 1 g to 2 kg per hectare or from 1 g to 750 g per hectare, desirably from 1 g to 100 g per hectare, more desirably from 10 g to 50 g per hectare, e.g., 10 to 20 g per hectare, 20 to 30 g per hec- tare, 30 to 40 g per hectare, or 40 to 50 g per hectare.
  • the compounds of the invention are particularly suitable for use in the treatment of seeds in order to protect the seeds from insect pests, in particular from soil-living insect pests, and the resulting seedling’s roots and shoots against soil pests and foliar insects.
  • the invention there- fore also relates to a method for the protection of seeds from insects, in particular from soil in- sects, and of the seedling's roots and shoots from insects, in particular from soil and foliar in- sects, said method comprising treating the seeds before sowing and/or after pregermination with a compound of the invention.
  • the protection of the seedling's roots and shoots is preferred. More preferred is the protection of seedling’s shoots from piercing and sucking insects, chewing insects and nematodes.
  • seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking, seed pelleting, and in-furrow application methods.
  • seed treatment application of the active compound is car- ried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.
  • the invention also comprises seeds coated with or containing the active compound.
  • coated with and/or containing generally signifies that the active ingredient is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application.
  • the said propagation product When the said propagation product is (re)planted, it may absorb the active ingredi- ent.
  • Suitable seed is for example seed of cereals, root crops, oil crops, vegetables, spices, orna- mentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, ba- nanas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pan- sies and impatiens.
  • the active compound may also be used for the treatment of seeds from plants, which have been modified by mutagenisis or genetic engineering, and which e.g. tolerate the action of herbicides or fungicides or insecticides. Such modified plants have been described in detail above.
  • Conventional seed treatment formulations include for example flowable concentrates FS, solu- tions LS, suspoemulsions (SE), powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the lat- ter. Preferably, the formulations are applied such that germination is not included.
  • the active substance concentrations in ready-to-use formulations are preferably from 0.01 to 60% by weight, more preferably from 0.1 to 40 % by weight.
  • a FS formulation is used for seed treatment.
  • a FS formu- lation may comprise 1-800 g/l of active ingredient, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
  • Especially preferred FS formulations of the compounds of the invention for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/l) of the active ingredient, from 0.1 to 20 % by weight (1 to 200 g/l) of at least one surfactant, e.g.0.05 to 5 % by weight of a wetter and from 0.5 to 15 % by weight of a dispersing agent, up to 20 % by weight, e.g.
  • an anti-freeze agent from 5 to 20 % of an anti-freeze agent, from 0 to 15 % by weight, e.g.1 to 15 % by weight of a pigment and/or a dye, from 0 to 40 % by weight, e.g.1 to 40 % by weight of a binder (sticker /adhesion agent), optionally up to 5 % by weight, e.g. from 0.1 to 5 % by weight of a thickener, optionally from 0.1 to 2 % of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1 % by weight and a filler/vehicle up to 100 % by weight.
  • a binder sticker /adhesion agent
  • a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1 % by weight and a filler/
  • the application rates of the compounds of the invention are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, more preferably from 1 g to 1000 g per 100 kg of seed and in particular from 1 g to 200 g per 100 kg of seed, e.g. from 1 g to 100 g or from 5 g to 100 g per 100 kg of seed.
  • the invention therefore also relates to seed comprising a compound of the invention, or an ag- riculturally useful salt thereof, as defined herein.
  • the amount of the compound of the invention or the agriculturally useful salt thereof will in general vary from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed. For specific crops such as lettuce the rate can be higher.
  • the compounds of the invention may also be used for improving the health of a plant.
  • the invention also relates to a method for improving plant health by treating a plant, plant propagation material and/or the locus where the plant is growing or is to grow with an effective and non-phytotoxic amount of a compound of the invention.
  • an effective and non-phytotoxic amount means that the compound is used in a quantity which allows to obtain the desired effect but which does not give rise to any phyto- toxic symptom on the treated plant or on the plant grown from the treated propagule or treated soil.
  • Plant health is defined as a condition of the plant and/or its products which is determined by several aspects alone or in combination with each other such as yield (for example increased biomass and/or increased content of valuable ingredients), quality (for example improved con- tent or composition of certain ingredients or shelf life), plant vigour (for example improved plant growth and/or greener leaves (“greening effect”), tolerance to abiotic (for example drought) and/or biotic stress (for example disease) and production efficiency (for example, harvesting ef- ficiency, processability).
  • yield for example increased biomass and/or increased content of valuable ingredients
  • quality for example improved con- tent or composition of certain ingredients or shelf life
  • plant vigour for example improved plant growth and/or greener leaves (“greening effect”)
  • tolerance to abiotic for example drought
  • biotic stress for example disease
  • production efficiency for example, harvesting ef- ficiency, processability
  • the above identified indicators for the health condition of a plant may be interdependent and may result from each other.
  • Each indicator is defined in the art and can be determined by meth- ods known to a skilled person.
  • the compounds of the invention are also suitable for use against non-crop insect pests.
  • compounds of the invention can be used as bait composition, gel, general insect spray, aerosol, as ultra-low volume application and bed net (impregnated or surface applied).
  • drenching and rodding methods can be used.
  • non-crop insect pest refers to pests, which are particularly relevant for non-crop targets, such as ants, termites, wasps, flies, ticks, mosquitos, crickets, or cock- roaches.
  • the bait can be a liquid, a solid or a semisolid preparation (e.g. a gel).
  • the bait employed in the composition is a product, which is sufficiently attractive to incite insects such as ants, ter- mites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it.
  • the attractiveness can be manipulated by using feeding stimulants or sex pheromones.
  • Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, in- sect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyor- ganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature (e.g. http://www.phero- base.com), and are known to those skilled in the art.
  • the typical content of active ingredient is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compound.
  • Formulations of the compounds of the invention as aerosols are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches.
  • Aerosol recipes are preferably composed of the active compound, solvents, furthermore auxiliaries such as emulsifiers, perfume oils, if appropriate sta- bilizers, and, if required, propellants.
  • the oil spray formulations differ from the aerosol recipes in that no propellants are used.
  • the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.
  • the compounds of the invention and its respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems.
  • Methods to control infectious diseases transmitted by insects e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis
  • compounds of the invention and its respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like.
  • Insecticidal compositions for application to fibers, fabric, knitgoods, nonwovens, netting material or foils and tarpaulins prefer- ably comprise a mixture including the insecticide, optionally a repellent and at least one binder.
  • the compounds of the invention and its compositions can be used for protecting wooden ma- terials such as trees, board fences, sleepers, frames, artistic artifacts, etc. and buildings, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or hu- man being (e.g. when the pests invade into houses and public facilities).
  • Customary application rates in the protection of materials are, for example, from 0.001 g to 2000 g or from 0.01 g to 1000 g of active compound per m 2 treated material, desirably from 0.1 g to 50 g per m 2 .
  • Insecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and/or insecticide. Pests
  • the compounds of the the invention are especially suitable for efficiently combating animal pests such as arthropods, gastropods and nematodes including but not limited to:
  • insects from the order of Lepidoptera for example Achroia grisella, Acleris spp. such as A. fim- briana, A. gloverana, A. variana; Acrolepiopsis assectella, Acronicta major, Adoxophyes spp. such as A. cyrtosema, A. orana; Aedia leucomelas, Agrotis spp. such as A. exclamationis, A. fucosa, A. ipsilon, A. orthogoma, A. segetum, A.
  • Argyresthia conjugella Argyroploce spp., Argyrotaenia spp.
  • A. velutinana Athetis mindara, Austroasca viridi- grisea, Autographa gamma, Autographa nigrisigna, Barathra brassicae, Bedellia spp., Bonagota salubricola, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp. such as C. murinana, C.
  • Cactoblastis cactorum Cadra cautella, Calingo brazilien- sis, Caloptilis theivora, Capua reticulana, Carposina spp. such as C. niponensis, C. sasakii; Ce- phus spp., Chaetocnema aridula, Cheimatobia brumata, Chilo spp. such as C. Indicus, C. sup- pressalis, C. partellus; Choreutis pariana, Choristoneura spp. such as C. conflictana, C. fumife- rana, C. longicellana, C. murinana, C.
  • kuehniella kuehniella; Epinotia aporema, Epiphyas postvittana, Erannis tiliaria, Erio- nota thrax, Etiella spp., Eulia spp., Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Faronta albilinea, Feltia spp. such as F. subterranean; Galleria mellonella, Gracillaria spp., Grapholita spp. such as G. funebrana, G. molesta, G.
  • H. armigera Heliothis armigera
  • H. zea Heliothis zea
  • Heliothis spp. such as H. assulta, H. subflexa, H. virescens
  • Hellula spp. such as H. undalis, H.
  • Mamestra spp. such as M. brassicae, M. configurata; Mam- stra brassicae, Manduca spp. such as M. quinquemaculata, M. sexta; Marasmia spp, Marmara spp., Maruca testulalis, Megalopyge lanata, Melanchra picta, Melanitis leda, Mocis spp. such as M. lapites, M.
  • operculella Phyllocnistis citrella, Phyllonorycter spp. such as P. blancardella, P. crataegella, P. issikii, P. ringoniella; Pieris spp. such as P. brassicae, P. rapae, P. napi; Pilocrocis tripunctata, Plathypena scabra, Platynota spp. such as P. flavedana, P. idae- usalis, P.
  • insects from the order of Coleoptera for example Acalymma vittatum, Acanthoscehdes obtec- tus, Adoretus spp., Agelastica alni, Agrilus spp. such as A. anxius, A. planipennis, A. sinuatus; Agriotes spp. such as A. fuscicollis, A. lineatus, A. obscurus; Alphitobius diaperinus, Amphimal- lus solstitialis, Anisandrus dispar, Anisoplia austriaca, Anobium punctatum, Anomala diveren- ta, Anomala rufocuprea, Anoplophora spp. such as A.
  • Anthonomus spp. such as A. eugenii, A. grandis, A. pomorum; Anthrenus spp., Aphthona euphoridae, Apion spp., Apogo- nia spp., Athous haemorrhoidalis, Atomaria spp. such as A. linearis; Attagenus spp., Aulaco- phora femoralis, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp. such as B. lentis, B. pisorum, B.
  • vespertinus Conotrachelus nenuphar, Cos- mopolites spp., Costelytra zealandica, Crioceris asparagi, Cryptolestes ferrugineus, Cryptorhyn- chus lapathi, Ctenicera spp. such as C. destructor; Curculio spp., Cylindrocopturus spp., Cyclo- cephala spp., Dactylispa balyi, Dectes texanus, Dermestes spp., Diabrotica spp. such as D. un- decimpunctata, D. speciosa, D. longicornis, D. semipunctata, D.
  • Diaprepes abbrevi- ates Dichocrocis spp., Dicladispa armigera, Diloboderus abderus, Diocalandra frumenti (Diocal- andra stigmaticollis), Enaphalodes rufulus, Epilachna spp. such as E. varivestis, E. vigintioc- tomaculata; Epitrix spp. such as E. hirtipennis, E.
  • Eutheola humilis Eutinobothrus bra- siliensis, Faustinus cubae, Gibbium psylloides, Gnathocerus cornutus, Hellula undalis, Heter- onychus arator, Hylamorpha elegans, Hylobius abietis, Hylotrupes bajulus, Hypera spp. such as H. brunneipennis, H. postica; Hypomeces squamosus, Hypothenemus spp., Ips typographus, Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lema spp.
  • L. bilineata L. melanopus
  • Leptinotarsa spp. such as L. decemlineata
  • Leptispa pygmaea Limonius californicus, Lissorhoptrus oryzophilus, Lixus spp., Luperodes spp., Lyctus spp. such as L. bruneus
  • Mala- dera matrida Megaplatypus mutates, Megascelis spp., Melanotus communis, Meligethes spp. such as M. aeneus
  • M. hippocastani such as M. hippocastani, M. melolontha; Metamasius he- mipterus, Microtheca spp., Migdolus spp. such as M. fryanus, Monochamus spp. such as M.
  • al- ternatus Naupactus xanthographus, Niptus hololeucus, Oberia brevis, Oemona hirta, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorrhynchus sulcatus, Otior- rhynchus ovatus, Otiorrhynchus sulcatus, Oulema melanopus, Oulema oryzae, Oxycetonia ju- cunda, Phaedon spp. such as P. brassicae, P.
  • vulneratus Saperda candida, Scolytus schevyrewi, Scyphophorus acupunctatus, Sitona lineatus, Sitophilus spp. such as S. granaria, S. oryzae, S. zeamais; Sphenophorus spp. such as S. levis; Stegobium paniceum, Sternechus spp. such as S. subsignatus; Strophomorphus ctenotus, Symphyletes spp., Tany- mecus spp., Tenebrio molitor, Tenebrioides mauretanicus, Tribolium spp. such as T.
  • insects from the order of Diptera e.g. Aedes spp. such as A. aegypti, A. albopictus, A. vexans; Anastrepha ludens, Anopheles spp. such as A. albimanus, A. crucians, A. freeborni, A. gam- biae, A. leucosphyrus, A. maculipennis, A. minimus, A. quadrimaculatus, A. sinensis; Bactro- cera invadens, Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capitata, Chrysomyia spp.
  • Aedes spp. such as A. aegypti, A. albopictus, A. vexans
  • Anastrepha ludens Anopheles spp.
  • A. albimanus A.
  • C. bezziana such as C. bezziana, C. hominivorax, C. macellaria; Chrysops atlanticus, Chrysops discalis, Chrysops silacea, Cochliomyia spp. such as C. hominivorax; Contarinia spp. such as C. sorghicola; Cordylobia anthropophaga, Culex spp. such as C. nigripalpus, C. pipi- ens, C. quinquefasciatus, C. tarsalis, C.
  • Geomyza tipunctata, Glossina spp. such as G. fuscipes, G. mor- sitans, G. palpalis, G. tachinoides; Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia spp. such as H. platura; Hypoderma spp. such as H. lineata; Hyppobosca spp., Hydrellia philippina, Leptoconops torrens, Liriomyza spp. such as L. sativae, L. trifolii; Lucilia spp. such as L. caprina, L. cuprina, L.
  • insects from the order of Thysanoptera for example, Basothrips biformis, Dichromothrips cor- betti, Dichromothrips ssp., Echinothrips americanus, Enneothrips flavens, Frankliniella spp. such as F. fusca, F. occidentalis, F. tritici; Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Microcephalothrips abdominalis, Neohydatothrips samayunkur, Pezothrips kellyanus, Rhipiphorothrips cruentatus, Scirtothrips spp. such as S.
  • insects from the order of Hemiptera for example, Acizzia jamatonica, Acrosternum spp. such as A. hilare; Acyrthosipon spp. such as A. onobrychis, A. pisum; Adelges laricis, Adelges tsu- gae, Adelphocoris spp., such as A. rapidus, A.
  • Brachycolus spp. Brachycorynella asparagi, Brevicoryne brassicae, Cacopsylla spp. such as C. fulguralis, C. pyricola (Psylla piri); Calligypona marginata, Calocoris spp., Campylomma livida, Capitophorus horni, Carneocephala fulgida, Cavelerius spp., Ceraplastes spp., Ceratovacuna lanigera, Ceroplastes ceriferus, Cerosipha gossypii, Chaetosiphon fragaefolii, Chionaspis tega- lensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Cimex spp.
  • C. fulguralis C. pyricola (
  • Diaspis spp. such as D. bromeliae; Dichelops furcatus, Diconocoris he- wetti, Doralis spp., Dreyfusia nordmannianae, Dreyfusia piceae, Drosicha spp., Dysaphis spp. such as D. plantaginea, D. pyri, D. radicola; Dysaulacorthum pseudosolani, Dysdercus spp. such as D. cingulatus, D. intermedius; Dysmicoccus spp., Edessa spp., Geocoris spp., Empo- asca spp. such as E.
  • Idiocerus spp. Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lecanoideus floccissimus, Lepidosaphes spp. such as L. ulmi; Leptocorisa spp., Lepto- glossus phyllopus, Lipaphis erysimi, Lygus spp. such as L. hesperus, L. lineolaris, L.
  • Nezara spp. such as N. viridula; Nilaparvata lugens, Nysius huttoni, Oebalus spp. such as O.
  • Pteromalus spp. Pulvinaria amygdali, Pyrilla spp., Quadraspidiotus spp., such as Q. perniciosus; Quesada gigas, Rastrococcus spp., Redu- vius senilis, Rhizoecus americanus, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosi- phum spp. such as R. pseudobrassicas, R. insertum, R. maidis, R.
  • Sagatodes spp., Sahl- bergella singularis, Saissetia spp., Sappaphis mala, Sappaphis mali, Scaptocoris spp., Scaph- oides titanus, Schizaphis graminum, Schizoneura lanuginosa, Scotinophora spp., Selenaspidus articulatus, Sitobion avenae, Sogata spp., Sogatella furcifera, Solubea insularis, Spissistilus festinus ( Stictocephala festina), Stephanitis nashi, Stephanitis pyrioides, Stephanitis takeyai, Tenalaphara malayensis, Tetraleurodes perseae, Therioaphis maculate, Thyanta spp.
  • T. accerra, T. perditor Tibraca spp., Tomaspis spp., Toxoptera spp. such as T. aurantii; Trialeu- rodes spp. such as T. abutilonea, T. ricini, T. vaporariorum; Triatoma spp., Trioza spp., Typhlo- cyba spp., Unaspis spp. such as U. citri, U. yanonensis; and Viteus vitifolii,
  • Paravespula spp. such as P. germanica, P. pennsylvanica, P. vulgaris; Phei- dole spp. such as P. megacephala; Pogonomyrmex spp. such as P. barbatus, P. californicus, Polistes rubiginosa, Prenolepis impairs, Pseudomyrmex gracilis, Schelipron spp., Sirex cya- neus, Solenopsis spp. such as S.
  • Insects from the order Orthoptera for example Acheta domesticus, Calliptamus italicus, Chor- toicetes terminifera, Ceuthophilus spp., Diastrammena asynamora, Dociostaurus maroccanus, Gryllotalpa spp. such as G. africana, G. gryllotalpa; Gryllus spp., Hieroglyphus daganensis, Kraussaria angulifera, Locusta spp. such as L. migratoria, L. pardalina; Melanoplus spp. such as M. bivittatus, M. femurrubrum, M. mexicanus, M. sanguinipes, M.
  • Boophilus spp. such as B. annulatus, B. decoloratus, B. micro- plus, Dermacentor spp. such as D.silvarum, D. andersoni, D. variabilis, Hyalomma spp. such as H. truncatum, Ixodes spp. such as I. ricinus, I. rubicundus, I. scapularis, I. holocyclus, I. pacifi- cus, Rhipicephalus sanguineus, Ornithodorus spp. such as O. moubata, O. hermsi, O.
  • Aculus spp. such as A.
  • A. Dermata spp.
  • Colomerus vitis Epitrimerus pyri, Phyllocoptruta oleivora; Eriophytes ribis and Eriophyes spp. such as Eriophyes sheldoni
  • Family Tarsonemidae including Hemitarsonemus spp., Phytonemus pallidus and Polyphagotarsonemus latus, Steno- tarsonemus spp. Steneotarsonemus spinki
  • Family Tenuipalpidae including Brevipalpus spp. such as B.
  • Tetranychidae including Eotetranychus spp., Eutetranychus spp., Oligonychus spp., Petrobia latens, Tetranychus spp. such as T. cinnabarinus, T. evansi, T. kan- zawai, T, pacificus, T. phaseulus, T. telarius and T. urticae; Bryobia praetiosa; Panonychus spp. such as P. ulmi, P. citri; Metatetranychus spp. and Oligonychus spp. such as O. pratensis, O.
  • Pests from the Phylum Nematoda for example, plant parasitic nematodes such as root-knot nematodes, Meloidogyne spp. such as M. hapla, M. incognita, M. javanica; cyst-forming nema- todes, Globodera spp. such as G. rostochiensis; Heterodera spp. such as H. avenae, H. glyci- nes, H. schachtii, H. trifolii; Seed gall nematodes, Anguina spp.; Stem and foliar nematodes, Aphelenchoides spp. such as A.
  • plant parasitic nematodes such as root-knot nematodes, Meloidogyne spp. such as M. hapla, M. incognita, M. javanica; cyst-forming nema- todes, Globodera spp. such
  • Criconemoides spp. such as Criconemoides informis; Mesocriconema spp.; Stem and bulb nematodes, Ditylenchus spp. such as D. destructor, D.
  • Awl nematodes Dolichodorus spp.
  • Spiral nematodes Heliocotylenchus multicinctus
  • Sheath and sheathoid nematodes Hem- icycliophora spp. and Hemicriconemoides spp.
  • Hirshmanniella spp. Lance nematodes, Hop- loaimus spp.
  • False rootknot nematodes Nacobbus spp.
  • Needle nematodes Longidorus spp. such as L. elongatus
  • Lesion nematodes Pratylenchus spp. such as P.
  • brachyurus P. neglec- tus, P. penetrans, P. curvitatus, P. goodeyi; Burrowing nematodes, Radopholus spp. such as R. similis; Rhadopholus spp.; Rhodopholus spp.; Reniform nematodes, Rotylenchus spp. such as R. robustus, R. reniformis; Scutellonema spp.; Stubby-root nematode, Trichodorus spp. such as T. obtusus, T. primitivus; Paratrichodorus spp. such as P.
  • Stunt nematodes Tylencho- rhynchus spp. such as T. claytoni, T. dubius
  • Citrus nematodes Tylenchulus spp. such as T. semipenetrans
  • Dagger nematodes Xiphinema spp.
  • other plant parasitic nematode spe- cies Stunt nematodes, Tylencho- rhynchus spp. such as T. claytoni, T. dubius
  • Citrus nematodes Tylenchulus spp.
  • Dagger nematodes Xiphinema spp.
  • Insects from the order Isoptera for example Calotermes flavicollis, Coptotermes spp. such as C. formosanus, C. gestroi, C. acinaciformis; Cornitermes cumulans, Cryptotermes spp. such as C. brevis, C. cavifrons; Globitermes sulfureus, Heterotermes spp. such as H. aureus, H. longi- ceps, H. tenuis; Leucotermes flavipes, Odontotermes spp., Incisitermes spp. such as I. minor, I. Snyder; Marginitermes hubbardi, Mastotermes spp. such as M. darwiniensis Neocapritermes spp. such as N.
  • Neotermes spp. Procornitermes spp., Zootermopsis spp. such as Z. angusticollis, Z. nevadensis, Reticulitermes spp. such as R. hesperus, R. tibialis, R. speratus, R. flavipes, R. grassei, R. lucifugus, R. santonensis, R. virginicus; Termes natalensis, Insects from the order Blattaria for example Blatta spp. such as B. orientalis, B. lateralis; Blat- tella spp. such as B. asahinae, B.
  • Thysanura for example Lepisma saccharina , Ctenolepisma urbana, and Thermobia domestica
  • Pests from the class Chilopoda for example Geophilus spp., Scutigera spp. such as Scutigera coleoptrata;
  • Pests from the class Diplopoda for example Blaniulus guttulatus, Julus spp., Narceus spp.
  • Pests from the class Symphyla for example Scutigerella immaculata
  • Insects from the order Collembola for example Onychiurus spp., such as Onychiurus armatus, Pests from the order Isopoda for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber,
  • Insects from the order Phthiraptera for example Damalinia spp., Pediculus spp. such as Pe- diculus humanus capitis, Pediculus humanus corporis, Pediculus humanus humanus; Pthirus pubis, Haematopinus spp. such as Haematopinus eurysternus, Haematopinus suis;
  • Linognathus spp. such as Linognathus vituli; Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus, Trichodectes spp.,
  • Examples of further pest species which may be controlled by compounds of fomula (I) include: from the Phylum Mollusca, class Bivalvia, for example, Dreissena spp.; class Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea canaliclata, Succinea spp.; from the class of the helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancy- lostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis s
  • Haemonchus contortus such as Haemonchus contortus; Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesoph- agostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp., Strongyloides fuelleborni, Strongyloides stercora lis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichi- nella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti.
  • Compounds of formula (I) including their stereoisomers, their tautomers, their salts or their N- oxides as well as compositions thereof are particularly useful for controlling invertebrate pests, preferably for controlling arthropods and nematodes, more preferably insects, and in particular Pentatomidae pests.
  • Pentatomidae pests include Acrosternum spp., Euschistus spp., Halyo- morpha spp., Nezara spp., Megacopta spp., Piezodorus spp., preferably Acrosternum hilare, Euschistus servus, Euschistus heros, Halyomorpha halys, Megacopta cribraria, Nezara viridula, and Piezodorus viridula. Animal health The compounds of the invention are suitable for use in treating or protecting animals against infestation or infection by parasites.
  • the invention also relates to the use of a com- pound of the invention for the manufacture of a medicament for the treatment or protection of animals against infestation or infection by parasites. Furthermore, the invention relates to a method of treating or protecting animals against infestation and infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiti- cidally effective amount of a compound of the invention.
  • the present invention also relates to the non-therapeutic use of compounds of the invention for treating or protecting animals against infestation and infection by parasites. Moreover, the invention relates to a non-therapeutic method of treating or protecting animals against infesta- tion and infection by parasites, which comprises applying to a locus a parasiticidally effective amount of a compound of the invention.
  • the compounds of the invention are further suitable for use in combating or controlling para- sites in and on animals. Furthermore, the invention relates to a method of combating or control- ling parasites in and on animals, which comprises contacting the parasites with a parasitically effective amount of a compound of the invention.
  • the invention also relates to the non-therapeutic use of compounds of the invention for con- trolling or combating parasites. Moreover, the invention relates to a non-therapeutic method of combating or controlling parasites, which comprises applying to a locus a parasiticidally effec- tive amount of a compound of the invention.
  • the compounds of the invention can be effective through both contact (via soil, glass, wall, bed net, carpet, blankets or animal parts) and ingestion (e.g. baits). Furthermore, the compounds of the invention can be applied to any and all developmental stages.
  • the compounds of the invention can be applied as such or in form of compositions comprising the compounds of the invention.
  • the compounds of the invention can also be applied together with a mixing partner, which acts against pathogenic parasites, e.g. with synthetic coccidiosis compounds, polyetherantibiotics such as Amprolium, Robenidin, Toltrazuril, Monensin, Salinomycin, Maduramicin, Lasalocid, Narasin or Semduramicin, or with other mixing partners as defined above, or in form of compo- sitions comprising said mixtures.
  • a mixing partner which acts against pathogenic parasites, e.g. with synthetic coccidiosis compounds, polyetherantibiotics such as Amprolium, Robenidin, Toltrazuril, Monensin, Salinomycin, Maduramicin, Lasalocid, Narasin or Semduramicin, or with other mixing partners as defined above, or in form of compo- sitions comprising said mixtures.
  • the compounds of the invention and compositions comprising them can be applied orally, par- enterally or topically, e.g. dermally.
  • the compounds of the invention can be systemically or non- systemically effective.
  • the application can be carried out prophylactically, therapeutically or non-therapeutically. Fur- thermore, the application can be carried out preventively to places at which occurrence of the parasites is expected.
  • the term "contacting" includes both direct contact (applying the com- pounds/compositions directly on the parasite, including the application directly on the animal or excluding the application directly on the animal, e.g. at it's locus for the latter) and indirect con- tact (applying the compounds/compositions to the locus of the parasite).
  • the contact of the par- asite through application to its locus is an example of a non-therapeutic use of the compounds of the invention.

Abstract

The invention relates to the use of ginkgolide derivatives of formula (I), wherein the variables are defined in the specification; as agrochemical pesticide. It also relates to certain comppounds of formula (I); to mixtures, agrochemical and veterinary compositions, and seed containing the compounds, and to methods of application for combating pests.

Description

Pesticidally Active C15-Derivatives of Ginkgolides Description The present invention relates to the use of a compound of formula (I), or a salt, stereoisomer, tautomer, or N-oxide there
Figure imgf000002_0002
of,
Figure imgf000002_0003
wherein the variables have a meaning as defined below, as an agrochemical pesticide. It also relates to seeds, pesticidal mixtures and compositions comprising a compound of formula (I). The invention also relates to methods of application of a compound of formula (I), or of the pes- ticidal composition. Another object is a compound of formula (I) per se, as defined below. Invertebrate pests and especially insects, arthropods and nematodes destroy growing and har- vested crops and commercial structures, thereby causing large economic loss to the food sup- ply and to property. While a high number of pesticidal agents are known, due to the ability of tar- get pests to develop resistance to said agents, there is an ongoing need for new agents for combating invertebrate pests such as insects, arachnids and nematodes. There is also a need to find pesticides with favorable ecotoxicological profile, that are safe for the applicant, and which require low application rates as compared to other pestiides. It is desirable that such novel pesticides have a high target specificity, thereby leaving desired species unaffected. Ginkgolides are a pesticidally active group of natural products comprising the compounds ginkgolide A, ginkgolide B, ginkgolide C, ginkgolide J and ginkgolide M. They are commercially available, or can be isolated from extracts of the Ginkgo biloba tree. Table A and formula (II) summarize the chemical identity of the naturally occurring ginkgolides. The asterisk indicates the position of the C15 atom in the ginkgolide scaffold.
Figure imgf000002_0001
Figure imgf000002_0004
Figure imgf000003_0002
Table A: definitions of substituents for naturally occurring ginkgolides of formula (II) It is known that ginkgolides have a pesticidal activity, e.g. insecticidal activity, as described in WO2015/128338, WO2017/025454, WO2017/032580, and WO2016/059240. It is also known to admix ginkgolides to other pesticidally active compounds, as disclosed in WO2016/059240. It is further known from these documents that ginkgolide compounds are particularly effective to combat Pentatomidae pests, which are often comprehensively referred to as stink bugs, and which are extremely hard to control by other conventional pesticides. Natural ginkgolide com- pounds of formula (II) do not fall under the definition of ginkgolide derivatives of formula (I). Certain ginkgolide derivatives have been published inter alia in Ishi et al., Org. Biomol. Chem. (2005), vol.3, p.3471-3472; in Jensen et al., J. Med. Chem. (2007), vol.50, p.1610-1617; in He et al., Spectrochimica Acta Part A (2008), vol.69, p.1213-1222; in Kato et al., Org. Biomol. Chem. (2007), vol.5, p.3758-3761(and its Supplementary Information); in Kawamura et al. (2017), vol.89, p.475-481 (and its Supplementary Information), and in WO2007/002410. How- ever, none of the cited prior art documents on ginkgolide derivatives discloses their use as an agrochemical pesticide.
There remains a need to find compounds, as well as their uses and methods of application, which have an increased pesticidal effect as compared with the ginkgolide natural products, which reduce their necessary application rates, and display pesticidal activity against difficult to control insects, arachnids and nematodes. Other objectives are reduced off-target effect, an in- creased chemical and physical stability, and/or an improved compatibility with other agrochemi- cally active compounds. It is desirable that such compounds improve or maintain the favorable ecotoxicological profile of ginkgolide natural products, are safe for the applicant, and have a high target specificity, thereby leaving desired species (e.g. bees) unaffected. It has been found that these objectives can be achieved by using certain ginkgolide derivatives that are chemically modified at the C15 atom, i.e. derivatives of ginkgolides that have substitu- ents R1 and R2 at the position as indicated in formula (I) instead of a carbonyl group. Accordingly, there is provided the use of compounds of formula (I), or a salt, stereoisomer, tautomer, or N-oxide thereof
Figure imgf000003_0001
as an agrochemical pesticide, wherein the variables in formula (I) have the following meaning R1, R2 are independently H, halogen, OH, CN, NO2, N3, or SCN;
C1-C10-alkyl, C2-C10-alkenyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R11; a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or differ- ent substituents R12;
OR13, OC(=O)R14, OC(=O)OR13, OC(=O)NR15R16, OC(=O)SR13, OC(=S)NR15R16, OC(=S)SR13, OS(O)nR14, OS(=O)nNR15R16, ONR15R16, ON=CR18R19, NR15C(=O)R14, NR15C(=O)SR13, NR15C(=O)OR13, NR15C(=O)NR16R17, NR15R16, N=CR18R19, NNR15R16, NNR15, S(O)nR14, NR15S(=O)nR14, SC(=O)SR13, SC(=O)OR13, SC(=O)NR15R16, S(O)nNR15R16, C(=O)R14, C(=S)R14, C(=O)NR15R16, C(=O)OR13, C(=S)NR15R16, C(=S)OR13, SC(=O)SR13,SC(=O)OR13, C(=S)SR13, C(=NR15)R16, C(=NR15)NR16R17, or Si(R20a)2R20b; or
R1 and R2 form together with the carbon atom they are bonded to a group C=NR15R16, or C=NOR13;
R11 is halogen, CN, NO2, SCN;
C1-C10-alkyl, C2-C10-alkenyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R111;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R112; or
OR113, SR113, OC(=O)R114, OC(=O)OR113, OC(=O)NR115R116, OC(=O)SR113, OC(=S)NR115R116, OS(O)nR114, OS(=O)nNR115R116, ONR115R116, ON=CR118R119, NR115C(=O)R114, NR115R116, N=CR118R119, NNR115R116, NNR115, S(O)nR114, SC(=O)SR113, SC(=O)NR115R116, S(O)nNR115R116, C(=O)R114, C(=O)NR115R116, C(=O)OR113, C(=O)SR113, C(=S)R114, C(=S)NR115R116, C(=S)OR113, C(=S)SR113, C(=NR115)R113, C(=NR115)NR116R117, or Si(R20a)2R20b;
R111 is halogen, OH, CN, or NO2;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl- carbonyl; or a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents RA;
RA is halogen, OH, NO2, CN, C1-C10-alkyl, C1-C10-haloalkyl, C1-C10-alkoxy, C1-C6- haloalkoxy, or C1-C10-alkyl-carbonyl; or
two germinal substituents RA form a 3- to 7-membered saturated, or partially unsaturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or differ- ent heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents selected from hal- ogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy;
R112 is halogen, OH, CN, NO2;
C1-C10-alkyl, C1-C10-alkoxy, C3-C8-cycloalkyl, C2-C10-alkenyl, C3-C8-cycloalkenyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, C1-C6- haloalkoxy, and C1-C10-alkyl-carbonyl;
phenyl, which is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, NO2, C1-C10-alkyl, C1-C10-haloalkyl, C1- C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl;
two geminal substituents R112 form together with the atom to which they are bound a group =O, =S, or =NR111; or
two germinal substituents R112 form a 3- to 7-membered saturated, or partially un- saturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents RA;
R113 is H;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or sub- stituted with one or more, same or different substituents R111;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R112;
R114 is H, halogen, CN;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or sub- stituted with one or more, same or different substituents R111;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R112;
R115, R116, R117 are independently H, CN;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsub- stituted, or substituted with one or more, same or different substituents R111;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R112; or
two substituents selected from R115, R116, and R117 that are bound to the same N- atom represent a C2-C6 alkylene chain forming a 3- to 7-membered saturated, par- tially unsaturated, or fully unsaturated heterocyclic ring together with the N-atom they are bonded to, wherein the alkylene chain contains none, or one or more, same or different heteroatoms O, S, or N, and is unsubstituted or substituted with one or more, same or different substituents selected from halogen, C1-C4-alkyl, C1-C4- haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy, and wherein the N-and/or S-atoms of the heterocyclic ring are oxidized or non-oxidized;
R118 is H, halogen, CN, NO2, SCN;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or sub- stituted with one or more, same or different substituents R111; or
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R112;
R119 H, C1-C4-alkyl, C1-C6-cycloalkyl, C1-C2-alkoxy-C1-C2-alkyl, phenyl, benzyl; or R118 and R119 form a 3- to 7-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or differ- ent substituents RA;
R12 is halogen, CN, NO2, SCN;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or sub- stituted with one or more, same or different substituents R121;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R122;
OR123, SR123, OC(=O)R124, OC(=O)OR123, OC(=O)NR125R126, OC(=O)SR123,
OC(=S)NR125R126, OS(O)nR124, OS(=O)nNR125R126, ONR125R126, ON=CR118R119, NR125C(=O)R124, NR125R126, N=CR118R119, NNR125R126, NNR125, S(O)nR124, SC(=O)SR123, SC(=O)NR125R126, S(O)nNR125R126, C(=O)R124, C(=O)NR125R126, C(=O)OR123, C(=O)SR123, C(=S)R124, C(=S)NR125R126, C(=S)OR123, C(=S)SR123, C(=NR125)R124, C(=NR125)NR126R127, Si(R20a)2R20b; two geminal substituents R12 form together with the atom to which they are bound a group =O, =S, or =NR121; or
two germinal substituents R12 form a 3- to 7-membered saturated, or partially un- saturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents R122;
R121 is halogen, OH, CN, NO2;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsub- stituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl; or a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents RA;
R122 is halogen, OH, CN, NO2;
C1-C10-alkyl, C1-C10-alkoxy, C3-C8-cycloalkyl, C2-C10-alkenyl, C3-C8-cycloalkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, C1-C6- haloalkoxy, and C1-C10-alkyl-carbonyl;
phenyl, which is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, NO2, C1-C10-alkyl, C1-C10-haloalkyl, C1- C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl; or
two geminal substituents R122 form together with the atom to which they are bound a group =O, =S, or =NR121; or
two germinal substituents R122 form a 3- to 7-membered saturated, or partially un- saturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents RA;
R123 is H;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or sub- stituted with one or more, same or different substituents R111; or
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R112;
R124 is H, halogen, CN; C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or sub- stituted with one or more, same or different substituents R111; or
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R112;
R125, R126, R127 are independently H, CN;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsub- stituted, or substituted with one or more, same or different substituents R111;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R112; or
two substituents selected from R125, R126, and R127 that are bound to the same N- atom represent a C2-C6 alkylene chain forming a 3- to 7-membered saturated, par- tially unsaturated, or fully unsaturated heterocyclic ring together with the N-atom they are bonded to, wherein the alkylene chain contains none, or one or more, same or different heteroatoms O, S, or N, and is unsubstituted or substituted with one or more, same or different substituents selected from halogen, C1-C4-alkyl, C1-C4- haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy, and wherein the N-and/or S-atoms of the heterocyclic ring are oxidized or non-oxidized;
R13 is H;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or sub- stituted with one or more, same or different substituents R131;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R132;
R131 is halogen, OH, CN, NO2;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsub- stituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl; or a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents RA; R132 is halogen, OH, CN, NO2;
C1-C10-alkyl, C1-C10-alkoxy, C3-C8-cycloalkyl, C2-C10-alkenyl, C3-C8-cycloalkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, and C1-C6-haloalkoxy;
phenyl, which is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, NO2, C1-C10-alkyl, C1-C10-haloalkyl, C1- C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl;
two geminal substituents R132 form together with the atom to which they are bound a group =O, =S, or =NR131; or
two germinal substituents R132 form a 3- to 7-membered saturated, or partially un- saturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents RA;
R14 is H, halogen, CN;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or sub- stituted with one or more, same or different substituents R131;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R132;
R15, R16, R17 are independently H, CN;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsub- stituted, or substituted with one or more, same or different substituents R151;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R152; or
or two substituents selected from R15, R16, and R17 that are bound to the same N- atom represent a C2-C6 alkylene chain forming a 3- to 7-membered saturated, par- tially unsaturated, or fully unsaturated heterocyclic ring together with the N-atom they are bonded to, wherein the alkylene chain contains none, or one or more, same or different heteroatoms O, S, or N, and is unsubstituted or substituted with one or more, same or different substituents R152, and wherein the N-and/or S-atoms of the heterocyclic ring are oxidized or non-oxidized;
R151 is halogen, OH, CN, NO2; C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsub- stituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl; a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents RA; or
two germinal substituents R151 form a 3- to 7-membered saturated, or partially un- saturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents RA;
R152 is halogen, OH, CN, NO2;
C1-C10-alkyl, C1-C10-alkoxy, C3-C8-cycloalkyl, C2-C10-alkenyl, C3-C8-cycloalkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, and C1-C6-haloalkoxy;
phenyl, which is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, NO2, C1-C10-alkyl, C1-C10-haloalkyl, C1- C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl; or
two geminal substituents R152 form together with the atom to which they are bound a group =O, =S, or =NR151; or
two germinal substituents R152 form a 3- to 7-membered saturated, or partially un- saturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents RA;
R18 is H, halogen, CN, NO2, SCN;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or sub- stituted with one or more, same or different substituents R181; or
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R182;
R19 is H, C1-C4-alkyl, C1-C6-cycloalkyl, C1-C2-alkoxy-C1-C2-alkyl, phenyl, benzyl; or R18 and R19 form a 3- to 7-membered saturated, partially unsaturated, or fully unsaturated
carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or differ- ent substituents RA;
R181 is halogen, OH, CN, NO2;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsub- stituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl; or a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, wherein said N- and S-atoms are independently oxidized, or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents RA;
R182 is halogen, OH, CN, NO2;
C1-C10-alkyl, C1-C10-alkoxy, C3-C8-cycloalkyl, C2-C10-alkenyl, C3-C8-cycloalkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, and C1-C6-haloalkoxy;
phenyl, which is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, NO2, C1-C10-alkyl, C1-C10-haloalkyl, C1- C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl; or
two geminal substituents R182 form together with the atom to which they are bound a group =O, =S, or =NR181; or
two germinal substituents R182 form a 3- to 7-membered saturated, or partially un- saturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents RA;
R20a, R20b are independently H, C1-C10-alkyl, C1-C6-haloalkyl, C1-C10-alkoxy, C1-C4-alkoxy-C1- C4-alkyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C1-C4-haloalkoxy-C1-C4-alkyl, or phenyl;
R3 is H, OR31, OC(=O)R32, OC(=O)OR31, OC(=O)NR33R34, OC(=O)SR31,
OC(=S)NR33R34, OC(=S)SR31, OS(O)nR31, OS(=O)nNR33R34, ONR33R34, or ON=CR18R19;
R31 is H;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or sub- stituted with one or more, same or different substituents R311;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R312; R311 is halogen, OH, CN, or NO2;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, or C2-C10-alkynyl, which groups are un- substituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl; or a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents RA;
R312 is halogen, OH, CN, NO2;
C1-C10-alkyl, C1-C10-alkoxy, C3-C8-cycloalkyl, C2-C10-alkenyl, C3-C8-cycloalkenyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, C1-C6- haloalkoxy, and C1-C10-alkyl-carbonyl;
phenyl, which is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, NO2, C1-C10-alkyl, C1-C10-haloalkyl, C1- C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl;
two geminal substituents R312 form together with the atom to which they are bound a group =O, =S, or =NR311; or
two germinal substituents R312 form a 3- to 7-membered saturated, or partially un- saturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents RA;
R32 is H, halogen, CN;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or sub- stituted with one or more, same or different substituents R311;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R312;
R33, R34 are independently H, CN;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsub- stituted, or substituted with one or more, same or different substituents R31;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R32; or two R33 and R34 that are bound to the same N-atom represent a C2-C6 alkylene chain forming a 3- to 7-membered saturated, partially unsaturated, or fully unsatu- rated heterocyclic ring together with the N-atom they are bonded to, wherein the al- kylene chain contains none, or one or more, same or different heteroatoms O, S, or N, and is unsubstituted or substituted with one or more, same or different substitu- ents selected from halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, and C1-C4- haloalkoxy, and wherein the N-and/or S-atoms of the heterocyclic ring are oxidized or non-oxidized;
R4 is H;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or sub- stituted with one or more, same or different substituents R41;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R42; or
C(=S)OR43, C(=S)SR43, C(=O)OR43, C(=O)R44, S(O)nR44, C(=S)R44, C(=O)NR45R46, C(=O)SR43, C(=S)NR45R46, C(=NR45)R46, or C(=NR45)NR46R47;
R41 is halogen, CN, NO2, SCN;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or sub- stituted with one or more, same or different substituents R111;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R112; or
OR113, SR113, OC(=O)R114, OC(=O)OR113, OC(=O)NR115R116, OC(=O)SR113, OC(=S)NR115R116, OS(O)nR113, OS(=O)nNR115R116, ONR115R116, ON=CR118R119, NR115R116, NR115C(=O)R114, N=CR118R119, NNR115R116, NNR115, S(O)nR113, SC(=O)SR113, SC(=O)NR115R116, S(O)nNR115R116, C(=O)R114, C(=O)NR115R116, C(=O)OR113, C(=O)SR113, C(=S)R114, C(=S)NR115R116, C(=S)OR113, C(=S)SR113, C(=NR115)R113, C(=NR115)NR116R117, Si(R20a)2R20b;
R42 is halogen, CN, NO2, SCN;
C1-C10-alkyl, C3-C8-cycloalkyl, C2-C10-alkenyl, C3-C8-cycloalkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R121;
phenyl, which is unsubstituted, or substituted with one or more, same or different substituents R122; or
OR123, SR123, OC(=O)R124, OC(=O)OR123, OC(=O)NR125R126, OC(=O)SR123, OC(=S)NR125R126, OS(O)nR124, OS(=O)nNR125R126, ONR125R126, ON=CR118R119, NR125R126, NR125C(=O)R124, N=CR118R119, NNR125R126, NNR125, S(O)nR124, SC(=O)SR123, SC(=O)NR125R126, S(O)nNR125R126, C(=O)R124, C(=O)NR125R126, C(=O)OR123, C(=O)SR123, C(=S)R124, C(=S)NR125R126, C(=S)OR123, C(=S)SR123, C(=NR125)R124, C(=NR125)NR126R127, Si(R20a)2R20b; or two geminal substituents R42 form together with the atom to which they are bound a group =O, =S, or =NR121; or two germinal substituents R42 form a 3- to 7-membered saturated, or partially un- saturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents R122;
R43 is H;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or sub- stituted with one or more, same or different substituents R131;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R132;
R44 is H, halogen, CN;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or sub- stituted with one or more, same or different substituents R131;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R132;
R45, R46, R47 are independently H, CN;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, C2-C10-alkynyl, acetyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R151; a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system com- prises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different sub- stituents R152; or
two substituents selected from R45, R46, and R47 that are bound to the same N-atom represent a C2-C6 alkylene chain forming a 3- to 7-membered saturated, partially un- saturated, or fully unsaturated heterocyclic ring together with the N-atom they are bonded to, wherein the alkylene chain contains none, or one or more, same or dif- ferent heteroatoms O, S, or N, and is unsubstituted or substituted with one or more, same or different substituents R152, and wherein the N-and/or S-atoms of the hetero- cyclic ring are oxidized or non-oxidized; and
n is 0, 1, or 2. The invention also relates to:
- pesticidal mixtures comprising at least one compound of formula (I) as defined above and an- other agrochemically active ingredient.
- compositions comprising at least one compound of formula (I) as defined above;
- agricultural or veterinary compositions comprising a compound of formula (I), or the pesticidal mixture, and a liquid or solid carrier;
- a method for controlling invertebrate pests, infestation, or infection by invertebrate pests, pref- erably wherein the invertebrate pests are insects or nematodes, more preferably insects, com- prising contacting the pests, their food supply, habitat, breeding grounds or their locus with a compound of formula (I) as defined above, or the pesticidal mixture in pesticidally effective amounts.
- a method for preventing or protecting against invertebrate pests, preferably against insects or nematodes, more preferably against insects, comprising contacting the invertebrate pests, or their food supply, habitat or breeding grounds with a compound of formula (I) as defined above or the pesticidal mixture in pesticidally effective amounts;
- a method of protecting plants from attack or infestation by invertebrate pests, preferably from insects or nematodes, more preferably from insects, comprising contacting the plant, or the soil or water in which the plant is growing, with a compound of formula (I) as defined above or the pesticidal mixture in pesticidally effective amounts.
- a method for protection of plant propagation material comprising contacting the plant propaga- tion material with a compound of formula (I) as defined above or the pesticidal mixture in pesti- cidally effective amounts.
- seed comprising a compound of formula (I) as defined above, or the pesticidal mixture in an amount of from 0.1 g to 10 kg per 100 kg of seed;
- The use of compounds of formula (I) as defined above, or of the pesticidal mixture, for combat- ing invertebrate pests, preferably for combating insects and nematodes, more preferably for combating insects.
- a non-therapeutic method method for treating animals infested or infected by parasites or pre- venting animals of getting infected or infested by parasites or protecting animals against infesta- tion or infection by parasites which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a compound of formula (I) as de- fined above or the pesticidal mixture;
- a method for treating, controlling, preventing or protecting animals against infestation or infec- tion by parasites by administering or applying orally, topically or parenterally to the animals a compound of formula (I) as defined above or the pesticidal mixture;
- the use of the compounds of formula (I) as defined above for protecting growing plants or plant propagation material from attack or infestation by invertebrate pests, preferably by insects or nematodes, more preferably from insects;
- the use of compounds of formula (I) as defined above for combating parasites in and on ani- mals;
- a process for the preparation of a veterinary composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises adding a parasiticidally effective amount of a compound of formula (I) as defined above to a carrier com- position suitable for veterinary use;
- the use of a compound of formula (I) or the enantiomers, diastereomers and/or veterinary ac- ceptable salt thereof for the preparation of a medicament for treating, controlling, preventing or protecting animals against infestation or infection by parasites. The invention further relates to novel compounds of formula (I), wherein the variables have a meaning as defined for the uses and methods of application of compounds of formula (I), but wherein compounds are excluded that have the following definition of variables:
a) One of the variables R1 or R2 is H, while the other variable is CH3C(=O)O;
R3 is OH; and R4 is benzyl;
b) R1 is H;
R2 is CH2CH=CH2;
R3 is OH; and
R4 is benzyl;
c) One of the variables R1 or R2 is H, while the other variable is CH2CH=CH2;
R3, R4 are H;
d) R1, R2 are H, or one of the variable R1 is H, while the other variable is OH. Combinations of embodiments with other embodiments, regardless of their respective level of preference, are within the scope of the invention. Compounds of formula (I) have several centres of chirality. The term“stereoisomers of com- pounds of formula (I)” includes compounds of formula (Ia), wherein all variables have a defini- tion as in formula (I).
Figure imgf000016_0001
Compounds of formula (Ia) are diastereomers of compounds of formula (I) regarding the sub- stituents R1 and R2, i.e. epimers of compounds of formula (I). The term“stereoisomers” includes stereoisomers of compounds of formula (I), wherein each centre of chirality is independently in its (R)-, or its (S)-configuration. In one embodiment, the term“stereoisomers of compounds of formula (I)” relates to all stereoisomers in which the cen- tres of chirality at those carbon atoms to which the substituents R1 andR2, R3, and R4O are di- rectly attached to by a single bond, are independently in their (R)-, or (S)-configuration. In an- other embodiment, the term“stereoisomers of compounds of formula (I)” relates to the diastere- omeric compounds of formula (I) and/or (Ia). In one embodiment, the invention relates to com- pounds of formula (I), their salts, tautomers, or N-oxides. In another embodiment, the invention relates to compounds of formula (Ia), their salts, tautomers, or N-oxides. The invention provides both the single pure diastereomers of the compounds of formula (I), and their mixtures and the use and methods of application according to the invention of the pure diastereomers of the com- pound of formula (I) or its mixtures.
Suitable compounds of formula (I) also include all possible geometrical stereoisomers
(cis/trans isomers) and mixtures thereof. Cis/trans isomers may be present with respect to an alkene, carbon-nitrogen double-bond or amide group. The term "stereoisomer(s)" encompasses both optical isomers, such diastereomers and epimers, as well as geometrical isomers (cis/trans isomers). The present invention relates to every possible stereoisomer of the compounds of for- mula (I), i.e. to single diastereomers, as well as to mixtures thereof.
Depending on the substitution pattern, the compounds of formula (I) may be present in the form of their tautomers. Hence the invention also relates to the tautomers of formula (I) and the stereoisomers, salts, tautomers and N-oxides of said tautomers.
Salts of compounds of the formula (I) are preferably agriculturally and/or veterinary acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question, if the compound of formula (I) has a basic functionality, or by reacting an acidic compound of formula (I) with a suitable base.
Suitable agriculturally or veterinary useful salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any ad- verse effect on the action of the compounds according to the present invention. Suitable cations are especially the ions of the alkali metals, preferably lithium, sodium and potassium, of the al- kaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH4+) and substituted am- monium in which one to four of the hydrogen atoms are replaced by C1-C4-alkyl, C1-C4-hydroxy- alkyl, C1-C4-alkoxy, C1-C4-alkoxy-C1-C4-alkyl, hydroxy-C1-C4-alkoxy-C1-C4-alkyl, phenyl or ben- zyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetrae- thylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl-am- monium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyltriethylammo- nium, furthermore phosphonium ions, sulfonium ions, preferably tri(C1-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(C1-C4-alkyl)sulfoxonium.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C1-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting the compounds of formula (I) with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
The term“N-oxide” includes any compound of the present invention which has at least one ter- tiary nitrogen atom that is oxidized to an N-oxide moiety.
The term“compound(s) of the invention” relates to compound(s) of formula (I). The organic moieties mentioned in the above definitions of the variables are - like the term hal- ogen - collective terms for individual listings of the individual group members. The prefix Cn-Cm indicates in each case the possible number of carbon atoms in the group. "Halogen" means F, Cl, Br, or I, preferably Cl. The term“substituted with”, e.g. as used in "partially, or fully substituted with" means that one or more, e.g.1, 2, 3, 4 or 5 or all of the hydrogen atoms of a given radical have been replaced by one or more, same or different substituents, such as a halogen, in particular F or Cl.
The term "Cn-Cm-alkyl" as used herein (and also in Cn-Cm-alkyl-carbonyl) refers to a branched or unbranched saturated hydrocarbon group having n to m, e.g.1 to 10 carbon atoms, prefera- bly 1 to 6 carbon atoms, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dime- thylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2- methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethyl- butyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2- trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, heptyl, oc- tyl, 2-ethylhexyl, nonyl and decyl and their isomers. C1-C4-alkyl means for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl.
The term "Cn-Cm-haloalkyl" as used herein refers to a straight-chain or branched alkyl group having n to m carbon atoms, e.g.1 to 10 in particular 1 to 6 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example C1-C4-haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoro- ethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2- dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and the like. The term C1-C10-haloal- kyl in particular comprises C1-C2-fluoroalkyl, which is synonym with methyl or ethyl, wherein 1, 2, 3, 4 or 5 hydrogen atoms are substituted with fluorine atoms, such as fluoromethyl, difluoro- methyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl and pen- tafluoromethyl. Similarly, "Cn-Cm-alkoxy" refers to straight-chain or branched alkyl groups having n to m carbon atoms, e.g.1 to 10, in particular 1 to 6 or 1 to 4 carbon atoms (as mentioned above) bonded through oxygen at any bond in the alkyl group. Examples include C1-C4-alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy and tert-butoxy. Accordingly, the term "Cn-Cm-haloalkoxy" refers to straight-chain or branched alkyl groups hav- ing n to m carbon atoms, e.g.1 to 10, in particular 1 to 6 or 1 to 4 carbon atoms (as mentioned above) bonded through oxygen linkage, at any bond in the alkyl group, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example C1-C2-haloalkoxy, such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloro- methoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoro- methoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroeth- oxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroeth- oxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy and pentafluoroethoxy. Similarly, the term C1-C2-fluoroalkoxy refers to C1-C2-fluoroalkyl which is bound to the remainder of the molecule via an oxygen atom or a sulfur atom, respectively.
The term "C2-Cm-alkenyl" as used herein intends a branched or unbranched unsaturated hy- drocarbon group having 2 to m, e.g.2 to 10 or 2 to 6 carbon atoms and a double bond in any position, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-bu- tenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1- pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl- 1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2- methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-di- methyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4- hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1- pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl- 4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-bu- tenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-bu- tenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2,2-dimethyl-3-bu- tenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-bu- tenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1- butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-pro- penyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl.
The term "C2-Cm-alkynyl" as used herein refers to a branched or unbranched unsaturated hy- drocarbon group having 2 to m, e.g.2 to 10 or 2 to 6 carbon atoms and containing at least one triple bond, such as ethynyl, propynyl, 1-butynyl, 2-butynyl, and the like.
The term "Cn-Cm-alkoxy-Cn-Cm-alkyl" as used herein refers to alkyl having n to m carbon at- oms, e.g. like specific examples mentioned above, wherein one hydrogen atom of the alkyl radi- cal is replaced by an Cn-Cm-alkoxy group; wherein the value of n and m of the alkoxy group are independently chosen from that of the alkyl group.
The suffix“-carbonyl” in a group or“C(=O)” denotes in each case that the group is bound to the remainder of the molecule via a carbonyl C=O group.
The term "3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring or ring system" refers to monocyclic, or fused and/or bridged bicyclic, tricyclic, or polycyclic ring systems having a total of 3- to 12 carbon atoms as ring members, preferably to monocyclic and bicyclic systems. Examples of "3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring or ring systems" are cyclopropane, cyclopropane, cyclobutene, cy- clobutene, cyclobutadiene, cyclopentane, cyclopentene, cyclopentadiene, cyclohexene, cyclo- hexadiene, phenyl, cycloheptane, cycloheptene, cycloheptadiene, cycloheptatriene, cy- clooctene, cyclooctadiene, cyclooctatriene, cyclooctatetraene, decalin, naphthalene, pentalene, indane, indene, 2,3,3a,4,5,6,7,7a-octahydro-1H-indene, tetralin, azulene, 1,2,3,3a,4,5,6,7,8,8a- decahydroazulene, 1,2,3,3a,4,5,6,6a-octahydropentalene, bicyclo[3.1.0]hexane.
Accordingly, the term "3- to 12-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring or ring system" refers to monocyclic, or fused bicyclic, tricyclic, or polycyclic ring systems having a total of 3- to 12 ring members, preferably to monocyclic and bicyclic sys- tems.
The heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member. The heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxi- dized, preferably one N-atom.
Examples of fully saturated heterocyclic rings or ring systems include: oxiranyl, aziridinyl, azet- idinyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 2-pyrroli- dinyl, 3-pyrrolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-imidazolidinyl, 4-imidazoli- dinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5- isoxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 1,2,4-oxadiazolidin-3-yl, 1,2,4-oxadiazolidin 5 yl, 1,2,4-thiadiazolidin-3-yl, 1,2,4-thiadiazolidin-5-yl, 1,2,4-triazolidin-3-yl,-1,3,4-oxadiazolidin-2-yl, 1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-2-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 1,3-dioxan-5-yl, 1,4-dioxan-2-yl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 3-hexahydropyridazinyl, 4-hexahydropyridazinyl, 2-hex- ahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 1-piperazyl, 2-piperazinyl, 1,3,5-hexahydrotriazin-2-yl and 1,2,4-hexahydrotriazin-3-yl, 2-morpholinyl, 3-morpholinyl, 4-mor- pholinyl, 2-thiomorpholinyl, 3-thiomorpholinyl, 4-thiomorpholinyl, 1-oxothiomorpholin-2-yl, 1-ox- othiomorpholin-3-yl, 1,1-dioxothiomorpholin-2-yl, 1,1-dioxothiomorpholin-3-yl, hexahydroazepin- 1-, -2-, -3- or -4-yl, hexahydrooxepinyl, hexahydro-1,3-diazepinyl, hexahydro-1,4-diazepinyl, hexahydro-1,3-oxazepinyl, hexahydro-1,4-oxazepinyl, hexahydro-1,3-dioxepinyl, and hexahy- dro-1,4-dioxepinyl.
Examples of partially unsaturated heterocyclic rings or ring systems include: 2,3-dihydrofur-2- yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihy- drothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyr- rolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin 3 yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2-isothi- azolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothi- azolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3 dihydropyrazol-1-yl, 2,3- dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4-dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4-dihydropyrazol-5- yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol- 5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5- yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5- yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-, 3-, 4-, 5- or 6-di- or tetrahydropyridinyl, 3-di- or tetrahydropyridazinyl, 4-di- or tetrahydropyridazinyl, 2-di- or tetrahy- dropyrimidinyl, 4-di- or tetrahydropyrimidinyl, 5-di- or tetrahydropyrimidinyl, di- or tetrahydropyra- zinyl, 1,3,5-di- or tetrahydrotriazin-2-yl, 1,2,4-di- or tetrahydrotriazin-3-yl, 2,3,4,5-tetrahy- dro[1H]azepin-1-, -2-, -3-, -4-, -5-, -6- or -7-yl, 3,4,5,6-tetrahydro[2H]azepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,4,7 tetrahydro[1H]azepin-1-, -2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,6,7 tetrahydro[1H]azepin- 1-, -2-, -3-, -4-, -5-, -6- or -7-yl, tetrahydrooxepinyl, such as 2,3,4,5-tetrahydro[1H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,4,7 tetrahydro[1H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,6,7 tetrahy- dro[1H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, tetrahydro-1,3-diazepinyl, tetrahydro-1,4-diazepinyl, tetrahydro-1,3-oxazepinyl, tetrahydro-1,4-oxazepinyl, tetrahydro-1,3-dioxepinyl, tetrahydro-1,4- dioxepinyl, indoline-1-yl, isoindoline-2-yl.
Examples of fully unsaturated heterocyclic rings or ring systems are: 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-ox- azolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,3-triazole-1-yl, 1,2,3-tria- zole-2-yl, 1,2,4-triazole-1-yl, 1,2,4-triazole-1-yl, 1,3,4-triazol-2-yl, 2-pyridinyl, 3-pyridinyl, 4-pyridi- nyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl, in- dole-1-yl, 1H-indole-2-yl, 1H-indole-3-yl, Isoindole-2-yl, 2H-isoindole-1-yl, 2-quinolyl, 3-quinolyl, 4-quinolyl, 1-isoquinolinyl, 3-isoquinolinyl, 4-isoquinolinyl, benzimidazole-1-yl, purine-1-yl, car- bazole-9-yl, and benzo[b]azepine-1-yl,
The following abbreviations are used throughout the text:
Figure imgf000021_0002
Figure imgf000021_0003
The term "C3-Cm-cycloalkyl" as used herein refers to a monocyclic ring of 3- to m-membered saturated cycloaliphatic radicals, e.g. cyclopropyl (cC3H5), cyclobutyl (cC4H7), cyclopentyl (cC5H9), cyclohexyl (cC6H11), cycloheptyl (cC7H13), cyclooctyl (cC8H15) and cyclodecyl (cC10H19). The term " C3-Cm-cycloalkenyl" as used herein refers to a monocyclic ring of 3- to m-mem- bered partially unsaturated cycloaliphatic radicals.
A "C2-Cm-alkylene" is divalent branched or preferably unbranched aliphatic chain having 2 to m, e.g.2 to 7 carbon atoms, for example CH2CH2, -CH(CH3)-, CH2CH2CH2, CH(CH3)CH2, CH2CH(CH3), CH2CH2CH2CH2, CH2CH2CH2CH2CH2, CH2CH2CH2CH2CH2CH2, and
CH2CH2CH2CH2CH2CH2CH2.Accordingly, a C2-Cm-alkylene chain containing one or more, same or different heteroatoms refers to such an aliphatic chain having 2 to m carbon atoms, wherein the heteroatoms replace carbon atoms as chain members, for example CH2SCH2,
CH2CH2SCH2, CH2NHCH2CH2CH2, or CH2CH2OCH2.
The terms“natural product ginkgolides”,“naturally occurring ginkgolides”, and“ginkgolide nat- ural products” refer to compounds of formula (II), wherein the variables have a meaning as de- fined in a line of Table A. The compounds of formula (I) can be prepared from the natural product ginkgolides A-M in Ta- ble A by standard synthetic procedures that are well-known to the skilled person in the field of organic chemistry. If individual compounds of formula (I) cannot be produced from the natural product ginkgolides A-M, they may be produced from other compounds of formula (I) by stand- ard chemical reactions.
Compounds of formula (II) may be reduced by the addition of a suitable reducing agent to yield compounds of formula (I-A), having an OH-group attached to C15
Figure imgf000021_0001
, wherein all variables are defined as for compounds of formula (II). Compounds of formula (I-A) are comprised by the definition of compounds of formula (I) and may serve as a basis to gener- ate other compounds of formula (I) by standard methods of organic chemistry. The reduction typically produces a racemic mixture of the (S)-, and the (R)-enantiomeric compound of formula (I-A). Reactions of this kind have been described by Kato et al., Org. Biomol. Chem. (2007), vol. 5, p.3758-3761 and Nakanish et al, Org. Biomol. Chem. (2005), vol.3, p.3471-3472. Typically, the reducing agent is diisobutylaluminiumhydride (DIBAL-H) and the reaction is carried out in an inert organic solvent at a temperature below 0 °C, preferably below -50 °C.
Compounds of formula (I-B), corresponding to compounds of formula (I), wherein R1 or R2 is attached to C15 by an ether group, a thioether group, a secondary, or primary amine group, can be produced by reaction of compounds of formula (I-A) with the corresponding amine, hydroxyl, or thiol compound A-XH in a condensation reaction
Figure imgf000022_0003
wherein X is O, S, N, or NH; A is the remaining part of R1 or R2, e.g. R13; and R3, R4, R5, and R6 are defined as for compounds of formula (I). These condensation reactions are suitable to pro- duce ethers, thioethers, secondary-, and tertiary amines. The condensation reaction usually takes place in the presence of an inert organic solvent and a catalyst, such as an acid. Typi- cally, the acid is p-toluene sulfonic acid or acetic acid. The H2O may be removed from by distil- lation or a molecular sieve.
Compounds of formula (I-C), corresponding to compounds of formula (I), wherein R1 or R2 is attached to C15 by an O-atom via a group -C(=O)O-, -S(O)2O-, or -S(=O)O-, can be produced by reaction of compounds of formula (I-A) with an acid chloride B-Y(=O)Cl
Figure imgf000022_0002
, wherein Y is C, S, or SO; B is the remaining part of R1 or R2, e.g. R13O, R14, or NR15R16; and R3, R4, R5 and R6 are defined as for compounds of formula (I). Alternative to the reaction with an acid chloride, compounds of formula (I-A) may be reacted with an anhydride [B-Y(=O)]2O or an- other suitable activated form of the carbonic acid B-Y(=O)OH. The reaction may be carried out in the presence of a base, typically in the presence of an organic base, e.g dimethylamino- pyridine, pyridine, or ((CH3)2CH)2(CH3CH2)N.
Compounds of formula (I-D), corresponding to compounds of formula (I), wherein R1 or R2 is bound to C15 by a C-atom, and wherein an electron-withdrawing-group W is bound to said C- atom, may be prepared by reacting compounds of formula (I-A) with a suitable Wittig reagent, followed by an intramolecular Oxa-Michael reaction
Figure imgf000022_0001
wherein W is an electron-withdrawing-group, such as CN, C(=O)R14, or C(=O)OR13; and R3, R4, R5, and R6 are defined as for compounds of formula (I). The reaction may be carried out in an inert organic solvent at a temperature of 0 to 120 °C, optionally in the presence of a base.
Compounds of formula (I-E), corresponding to compounds of formula (I), wherein R1 or R2 is CN, C2-C10-alkenyl, or C2-C10-alkynyl, can be produced by reaction of compounds of formula (I- A) with the corresponding trimethylsilyl-reagent (CH3)3Si-CN, (CH3)3Si-(C2-C10-alkenyl), or (CH3)3Si-(C2-C10-alkynyl) in the presence of a Lewis-acid, e.g. BF3. The reaction may be carried out in an inert organic solvent, such as CH2Cl2, at a temperature of from -100 to -50 °C, prefera- bly at -78 °C.
Compounds of formula (I-F), corresponding to compounds of formula (I), wherein R1 or R2 is N3, may be produced by reaction of compounds of formula (I-C), wherein the group B-Y(=O) is benzoyl, with NaN3 in an inert organic solvent, e.g. DMF, at a temperature of -50 to 120 °C, preferably at a temperature of 0 to 100 °C.
Compounds of formula (I-G), corresponding to compounds of formula (I), wherein R1 or R2 is a carbo-, or heterocyclic ring or ring system Q that is attached to C15 via a C-atom, may be pro- duced by reacting compounds of formula (I-C), wherein the group B-Y(=O) is benzoyl (Bz), with said carbo-, or heterocyclic ring or ring system in the presence of a Lewis-acid, e.g. BF3, in an inert solvent, e.g. CH2Cl2, at a temperature of from 0 to 100 °C, preferably from 20 to 40 °C
Figure imgf000023_0001
,
wherein Q is a carbo-, or heterocyclic ring or ring system as defined for compounds of formula (I); and R3, R4, R5 and R6 are defined as for compounds of formula (I).
Compounds of formula (I-H), corresponding to compounds of formula (I), wherein one substituent R1 or R2 is OH and the other one is not H, can be produced from compounds of formula (I), wherein only one substituent R1 or R2 is H and the other is not H or OH, by reaction with a suitable oxidizing agent, such as 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) in an inert organic solvent at a temperature of from 0 to 100 °C
Figure imgf000023_0002
, wherein all variables have a meaning as defined for compounds of formula (I). Compounds of formula (I-H) may be used as starting compounds for all compounds of formula (I), wherein both R1 and R2 are not H.
Compounds of formula (I-J), wherein R1 or R2 is halogen, may be produced by reaction of compounds of formula (I-A) with a suitable deoxygenating-halogenating agent, such as bis(2- methoxyethyl)aminosulfur trifluoride, in an inert organic solvent, such as CH2Cl2. Such deoxy- genating-halogenating agents are commercially available. Compounds of formulae (I-A), (I-B), (I-C), (I-D), (I-E), (I-F), (I-G), (I-H) and (I-J) are comprised by the definition of compounds of formula (I). They may serve as educts for the preparation of other compounds of formula (I) in standard synthesis methods, particularly for generating sub- stituents R3, R4, R5 and/or R6 different from the definitions in the natural product ginkgolides of formula (II) in Table A, e.g. by reactions described in WO2007/002410A2. Alternatively, com- pounds of formula (II) may in a first step be modified to generate substituents R3, R4, R5 and/or R6 that are different from the natural product ginkgolides of formula (II) in Table A, followed by generating substituents R1 and/or R2 as described above. Preferences:
Embodiments and preferred compounds of the present invention for use in pesticidal methods and for insecticidal application purposes are outlined in the following paragraphs. The embodi- ments and preferred compounds are valid for the inventive uses and methods of application as well as for the compounds of formula (I) per se, mixtures and formulations containing them. The remarks made below concerning preferred embodiments of the variables of compounds of for- mula (I) are valid both on their own and in combination with each other. In one embodiment, the variables of the compounds of formula (I) have the following meanings, these meanings, both on their own and in combination with one another, being embodiments of the compounds of the formula (I). Typically, compounds of formula (I) have one substituent R1 or R2 that is H or OH, preferably H. At least one substituetn R1 or R2 is typically not H or OH.
In one embodiment, at least one substituent R1 or R2 is H, OH, halogen, N3, or CN, preferably H, OH, N3 or CN, more preferably CN. In another embodiment, one substituent R1 or R2 is H, and the other substituent is H, OH, halogen, N3, or CN, preferably H, OH, N3, or CN, more preferably CN. In one embodiment, at least one substituent R1 or R2 is C1-C10-alkyl, C2-C10-alkenyl, or C2-C10- alkynyl, which groups are unsubstituted, or substituted with one or more, same or different sub- stituents R11. In another embodiment, at least one substituent R1 or R2 is C1-C4-alkyl, C2-C4- alkenyl, or C2-C4-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R11. In one embodiment, at least one substituent R1 or R2 is C1-C10-al- kyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R11. In another embodiment, at least one substituent R1 or R2 is C1-C4-al- kyl, or C2-C4-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R11. R11 is usually halogen, CN, NO2, S(O)nR114, S(O)nNR115R116, C(=O)R114, C(=O)NR115R116, C(=O)OR113, C(=O)SR113, C(=S)R114, C(=S)NR115R116, C(=S)OR113, C(=S)SR113, C(=NR115)R113, or C(=NR115)NR116R117, preferably CN, or C(=O)OR113. In another embodiment, R11 is CN, NO2, C(=O)R114, C(=O)NR115R116, C(=O)OR113, C(=O)SR113. In another embodiment, R11 is CN, or C(=O)OR113. Accordingly, in one embodiment at least one substituent R1 or R2 is C1-C4-alkyl, C2-C4-alkenyl, or C2-C4-alkynyl, which groups are unsubstituted, or substituted with one or more, same or dif- ferent substituents selected from halogen, CN, NO2, S(O)nR114, S(O)nNR115R116, C(=O)R114, C(=O)NR115R116, C(=O)OR113, C(=O)SR113, C(=S)R114, C(=S)NR115R116, C(=S)OR113,
C(=S)SR113, C(=NR115)R113, and C(=NR115)NR116R117, preferably from CN and C(=O)OR113. In another embodiment at least one substituent R1 or R2 is CH3, which is substituted with a substituent selected from halogen, CN, NO2, S(O)nR114, S(O)nNR115R116, C(=O)R114,
C(=O)NR115R116, C(=O)OR113, C(=O)SR113, C(=S)R114, C(=S)NR115R116, C(=S)OR113,
C(=S)SR113, C(=NR115)R113, and C(=NR115)NR116R117, preferably from CN and C(=O)OR113. In another embodiment, at least one substituent R1 or R2 is a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or hetero- cyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R12.
In one embodiment, at least one substituent R1 or R2 is a 3- to 12-membered saturated, par- tially unsaturated, or fully unsaturated carbocyclic ring or ring system, preferably a 3- to 10- membered ring or ring system, which carbocyclic ring or ring system is unsubstituted, or substi- tuted with one or more, same or different substituents R12.
In one embodiment, at least one substituent R1 or R2 is phenyl, which is unsubstituted, or sub- stituted with one or more, same or different substituents R12. In another embodiment, at least one substituent R1 or R2 is phenyl. In another embodiment, at least one substituent R1 or R2 is phenyl, which is substituted with one or more, same or different substituents selected from halo- gen, CN, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy, preferably C1-C4- alkoxy.
In one embodiment, at least one substituent R1 or R2 is a monocyclic or bicyclic C3-C10- cycloalkyl, or C3-C10-cycloalkenyl, which groups are substituted with one or more, same or different substituents R12. In another embodiment, at least one substituent R1 or R2 is a monocyclic or bicyclic C3-C10-cycloalkyl, or C3-C10-cycloalkenyl, which groups are substituted with one or more, same or different substituents selected from halogen, CN, C1-C4-alkyl, C1-C4- haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy.
In another embodiment, at least one substituent R1 or R2 is a 3- to 10-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring or ring system, wherein said hetero- cyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkyl, C1-C3-haloalkoxy, and phenyl. Preferably, said heterocyclic ring or ring system comprises at least one N-atom as a ring member and is bonded to the C15-atom by a direct bond to said N-atom. In another
embodiment, said heteriocyclic ring or ring system comprises at least one S-atom as a ring member.
In one embodiment, at least one substituent R1 or R2 is selected from the following
heterocyclic rings and ring systems D1-D154: aziridine (D1), azetidin (D2), 1,3-diazetidine (D3), pyrrolidine (D4), 3-pyrroline (D5), 2-pyrroline (D6), pyrrole (D7), pyrazolidine (D8), imidazolidine (D9), 2-pyrrazoline (D10), 2-imidazoline (D11), pyrrazole (D12), imidazole (D13), 1,2,4-triazole (D14), 1,2,3-triazole (D15), tetrazole (D16), piperidine (D17), piperazine (D18), 1,4-morpholine (D19), 1,4-thiomorpholine (D20), 2H-1,2-oxazine (D21), 1,4-oxazine (D22), 1,4-thiazine (D23), 2H-1,2-thiazine (D24), thymine (D25), cytosine (D26), uracil (D27), thiomorpholinedioxide (D28), 1,4,5,6-tetrahydrocyclopenta[b]pyrrole (D29), 1,3a-4,6a-tetrahydropyrrolo[3,2-b]pyrrole (D30), 1,4-dihydropyrrolo[3,2-b]pyrrole (D31), 1,6-dihydropyrrolo[2,3-b]pyrrole (D32), 6H-furo[2,3- b]pyrrole (D33), 4H-furo[3,2-b]pyrrole (D34), 4H-thieno[3,2-b]pyrrole (D35), 6H-thieno[2,3- b]pyrrole (D36), indoline (D37), 1H-indole (D38), 2H-isoindole (D39), 1H-indazole (D40), benzimidazole (D41), 7-azaindazole (D42), 4-azaindazole (D43), 5-azaindazole (D44), 5- azaindole (D45), succinimide (D46), hydantoin (D47), 2-oxazolidone (D48), adenine (D49), guanine (D50), 1,2-benzisothiazole-3(2H)-one (D51), decahydroisoquinoline (D52),
decahydroquinoline (D53), 1,2,3,4-tetrahydroquinoline (D54), 1,2-dihydroquinoline (D55), 1,2- dihydroisoquinoline (D56), 2H-benzo[e][1,2]oxazine (D57), quinolin-2(1H)-one (D58), 2- azaadamantane (D59), 2,3-dihydroazepine (D60), 2,5-dihydroazepine (D61), azepine (D62), 1,2-diazepine (D63), 1,3-diazepine (D64), 1,4-diazepine (D65), azocane (D66), azonane (D67), oxirane (D68), thiirane (D69), 2,3-dihydroazete (D70), azete (D71), oxetane (D72), 2H-oxete (D73), thietane (D74), 2H-thiete (D75), 2H-pyrrole (D76), tetrahydrofuran (D77), furan (D78), 1,3-dioxolane (D79), tetrahydrothiophene (D80), thiophene (D81), oxazole (D82), isoxazole (D83), isothiazole (D84), thiazole (D85), 1,2-oxathiolane (D84), 1,3-oxathiolane (D85), 1,2,5- oxadiazole (D86), 1,2,3-oxadiazole (D87), 1,3,4-thiadiazole (D88), 1,2,5-thiadiazole (D89), sulfolane (D90), pyridazine (D91), pyrimidine (D92), pyrazine (D93), 1,2,4-triazine (D94), 1,3,5- triazine (D95), tetrahydrofuran (D96), 2H-pyran (D97), 4H-pyran (D98), dioxane (D99), 1,4- dioxine (D100), thiane (D101), 2H-thiopyran (D102), 4H-thiopyran (D103), 1,3-dithiane (D104), 1,4-dithiane (D105), 1,3,5-trithiane (D106), 4H-1,2-oxazine (D107), 6H-1,2-oxazine (D108), 4H- 1,3-oxazine (D109), 2H-1,3-oxazine (D110), 6H-1,3-oxazine (D110), 2H-1,4-oxazine (D111), 6H-1,2-thiazine (D112), 2H-1,4-thiazine (D113), hexahydro-1-H-pyrrolizine (D114), indolizine (D115), pyrazolo[1,5-a]pyrimidine (D115), benzofuran (D116), isobenzofuran (D117), benzo[c]thiophene (D118), benzo[b]thiophene (D119), benzo[d]isoxazole (D120),
benzo[c]isoxazole (D121), benzo[d]isothiazole D122), benzo[c]isothiazole (D123),
benzo[d]oxazole (D124), benzo[d]thiazole (D125), benzo[c][1,2,5]thiadiazole (D126), quinoline (D127), isoquinoline (D128), 4H-quinolizine (D129), quinoxaline (D130), phthalazine (D131), quinazoline (D132), cinnoline (D133), 1,8-naththyridine (D134), pyrido[3,2-d]pyrimidine (D135), pyrido[4,3-d]pyrimidine (D136), pyrido[3,4-b]pyrazine (D137), pyrido[2,3-b]pyrazine (D138), pteridine (D139), 2H-chromene (D140), 1H-isochromene (D141), 3H-isochromene (D142), 2H- benzo[e][1,3]oxazine (D143), 2H-benzo[b][1,4]oxazine (D144), 4,5-dihydroazepine (D145), 2H- azepine (D146), 3H-azepine (D147), 4H-azepine (D148), oxepane (D149), thiepine (D150), 1,4- thiazepine (D151), azocine (D152), thiocane (D153), azecine (D154), which heterocyclic rings or ring systems are unsubstituted, or substituted with one or more, same or different
substituents R12.
In one embodiment, at least one substituent R1 or R2 is selected from D1-D67, which heterocyclic rings or ring systems are unsubstituted, or substituted with one or more, same or different substituents R12. In one embodiment, at least one substituent R1 or R2 is selected from D14, D15, D16, D19, D18, D20, D28, D37, and D38, which heterocyclic rings or ring systems are unsubstituted, or substituted with one or more, same or different substituents R12. In one embodiment, at least one substituent R1 or R2 is selected from D14, D15, D16, D19, D18, D20, D28, D37, D38, and D104 which heterocyclic rings or ring systems are unsubstituted, or substituted with one or more, same or different substituents R12.
In another embodiment, at least one substituent R1 or R2 is selected from phenyl, C3-C8- cycloalkyl, C3-C8-cycloalkenyl, D14, D15, D16, D18, D19, D20, D28, D37 and D38, which carbo- or heterocyclic ring or ring systems are unsubstituted, or substituted with one or more, same or different substituents R12.
In another embodiment, at least one substituent R1 or R2 is selected from phenyl, C3-C8- cycloalkyl, C3-C8-cycloalkenyl, D14, D15, D16, D18, D19 D20, D28, D37, D38, and D104 which carbo- or heterocyclic ring or ring systems are unsubstituted, or substituted with one or more, same or different substituents R12.
In another embodiment, at least one substituent R1 or R2 is selected from phenyl, C3-C8- cycloalkyl, C3-C8-cycloalkenyl, D14, D15, D16, D18, D19 D20, D28, D37 and D38, which carbo- or heterocyclic ring or ring systems are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4- haloalkoxy, and phenyl.
In another embodiment, at least one substituent R1 or R2 is selected from phenyl, C3-C8- cycloalkyl, C3-C8-cycloalkenyl, D14, D15, D16, D18, D19 D20, D28, D37, D38, and D104, which carbo- or heterocyclic ring or ring systems are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy, and phenyl. In another embodiment, at least one substituent R1 or R2 is selected from phenyl, C3-C8- cycloalkyl, C3-C8-cycloalkenyl, D15, D16, D18, D19, D20, D37, and D38, which carbo- or heterocyclic ring or ring systems are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4- haloalkoxy, and phenyl.
In another embodiment, at least one substituent R1 or R2 is selected from phenyl, D15, D16, D18, D19, D20, D37, and D38 which carbo- or heterocyclic ring or ring systems are
unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy, and phenyl.
In another embodiment, at least one substituent R1 or R2 is selected from phenyl, D15, D16, D18, D19, D20, D37, D38 and D104, which carbo- or heterocyclic ring or ring systems are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy, and phenyl.
In another embodiment, at least one substituent R1 or R2 is selected from D15, D18, D19, D20, D37, and D38 which heterocyclic rings or ring systems are unsubstituted or substituted with one or more, same or different substituents selected from halogen, phenyl, C1-C3-alkyl, or C1-C3- haloalkyl, preferably phenyl or C1-C3-alkyl.
In another embodiment, at least one substituent R1 or R2 is selected from D15, D18, D19, D20, D37, D38 and D104 which heterocyclic rings or ring systems are unsubstituted or substituted with one or more, same or different substituents selected from halogen, phenyl, C1-C3-alkyl, or C1-C3-haloalkyl, preferably phenyl or C1-C3-alkyl. R12 is typically halogen, OH, CN, NO2; or
C1-C4-alkyl, C1-C4-alkoxy, C3-C8-cycloalkyl, C3-C8-cycloalkoxy, C2-C4-alkenyl, C3-C8-cycloal- kenyl, C3-C8-cycloalkenoxy, C2-C4-alkenoxy, C2-C4-alkynyl, C2-C4-alkynoxy, phenyl, which groups are unsubstituted, or substituted with one or more, same or different substituents se- lected from halogen, CN, and OH.
In another embodiment, R12 is halogen, OH, CN; or
C1-C4-alkyl, C1-C4-alkoxy, C3-C5-cycloalkyl, C2-C4-alkenyl, or phenyl which groups are unsubsti- tuted, or substituted with one or more, same or different substituents selected from halogen, CN, and OH. In another embodiment, R12 is C1-C3-alkyl, C1-C3-alkoxy, phenyl, which groups are unsubstituted, or halogenated. In another embodiment, R12 is C1-C4-alkyl, C1-C4-alkoxy, or phe- nyl, preferably C1-C3-alkyl or phenyl. In another embodiment, at least one substituent R1 or R2 is a group OR13, OC(=O)R14, OC(=O)OR13, OC(=O)NR15R16, OC(=O)SR13, OC(=S)NR15R16, OC(=S)SR13, OS(O)nR14, OS(=O)nNR15R16, ONR15R16, ON=CR18R19, NR15C(=O)R14, NR15C(=O)SR13, NR15C(=O)OR13, NR15C(=O)NR16R17, NR15R16, N=CR18R19, NNR15R16, NNR15, S(O)nR14, NR15S(=O)nR14,
SC(=O)SR13, SC(=O)OR13, SC(=O)NR15R16, S(O)nNR15R16, C(=O)R14, C(=S)R14, C(=O)NR15R16, C(=O)OR13, C(=S)NR15R16, C(=S)OR13, SC(=O)SR13 ,SC(=O)OR13, C(=S)SR13, C(=NR15)R16, C(=NR15)NR16R17, or Si(R20a)2R20b. In another embodiment, at least one substituent R1 or R2 is a group OR13, OC(=O)R14, NR15C(=O)R14, OS(O)nR13, NR15S(=O)nR13, OC(=O)OR14,
OC(=O)SR13, SC(=O)OR13, SC(=O)SR13, SC(=O)NR15R16, OC(=O)NR15R16, NR15C(=O)NR16R17, NR15C(=O)OR13, NR15C(=O)SR13, or NR15R16. In another embodiment, at least one substituent R1 or R2 is a group OR13, OC(=O)R14, OC(=O)OR13, OC(=O)NR15R16, OC(=O)SR13,
OC(=S)NR15R16, OC(=S)SR13, OS(O)nR14, OS(=O)nNR15R16. In another embodiment, at least one substituent R1 or R2 is a group OR13, OC(=O)R14, OC(=O)OR13, OC(=O)NR15R16,
OC(=O)SR13, OC(=S)NR15R16, OC(=S)SR13, OS(O)nR14, OS(=O)nNR15R16, or S(O)nR14. In another embodiment, at least one substituent R1 or R2 is a group OR13, OC(=O)R14, SC(=O)SR13, or NR15R16. In another embodiment, at least one substituent R1 or R2 is a group OR13, OC(=O)R14, or SC(=O)SR13. In another embodiment, at least one substituent R1 or R2 is a group OR13, OC(=O)R14, SC(=O)SR13, NR15R16, or S(O)nR14. In another embodiment, at least one substituent R1 or R2 is a group OR13, OC(=O)OR13, OC(=O)NR15R16, OC(=O)SR13,
OC(=S)NR15R16, OC(=S)SR13, OS(O)nR14, OS(=O)nNR15R16. In another embodiment, at least one substituent R1 or R2 is a group OR13, SC(=O)SR13, or NR15R16. In another embodiment, at least one substituent R1 or R2 is a group OR13, SC(=O)SR13, NR15R16, or S(O)nR14. In another embodiment, at least one substituent R1 or R2 is a group OR13, or SC(=O)SR13. In another em- bodiment, at least one substituent R1 or R2 is a group OR13, SC(=O)SR13, or S(O)nR14. Typically, R13 and R14 are independently H;
C1-C10-alkyl, C2-C10-alkenyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R131; or a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocy- clic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R132.
In another embodiment, R13 and R14 are independently H;
C1-C10-alkyl, C2-C10-alkenyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from
halogen, OH, CN, NO2, C1-C3-haloalkoxy; or
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heter- ocyclic ring or ring system, wherein said heterocyclic ring or ring system is selected from D1 to D154, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents RA;
or a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or hetero- cyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R132.
In another embodiment, R13 and R14 are independently H;
C1-C10-alkyl, C2-C10-alkenyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from
halogen, OH, CN; or
a 3- to 10-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring or ring system, wherein said heterocyclic ring or ring system is selected from D1 to D154, and is unsubstituted, or substituted with one or more, same or different substituents se- lected from halogen, OH, CN, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, and C1-C4- haloalkoxy; or
a 3- to 10-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring or ring system, wherein said carbocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C3-alkyl, C1-C3- haloalkyl, C1-C3-alkoxy, and C1-C3-haloalkoxy.
In another embodiment, R13, R14 are independently H;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from
halogen, OH, CN; and
a 3- to 8-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring or ring system, wherein said carbocyclic ring or ring system is unsubstituted, or substi- tuted with one or more, same or different substituents selected from halogen, OH, CN, C1- C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy; or
a 3- to 8-membered saturated, partially saturated, or fully unsaturated carbocycle, which is un- substituted, or substituted with one or more, same or different substituents selected from halo- gen, OH, CN; and C1-C4-alkyl, C1-C4-alkoxy, C3-C5-cycloalkyl, C2-C4-alkenyl, C3-C5-cycloalkenyl, C2-C4-al- kynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, and CN. In another embodiment, R13 and R14 are independently H;
C1-C10-alkyl, C2-C10-alkenyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from
halogen, CN; or
a 3- to 8-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring or ring system, wherein said carbocyclic ring or ring system is unsubstituted, or substi- tuted with one or more, same or different substituents selected from halogen, and C1-C4- alkyl; or
a 3- to 8-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring or ring system, wherein said carbocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, and C1-C4-alkyl. In another embodiment, at least one substituent R1 or R2 is a group NR15NR16.
Typically, R15, R16, R17 are independently H;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R151; or
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocy- clic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R152.
In one embodiment, R15, R16, R17 are independently H;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, benzyl, or phenyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, CN, OH, phenyl, C1-C3-alkoxy, and C1-C3-haloalkoxy.
In another embodiment, R15, R16, R17 are independently H, C1-C3-alkyl, C2-C3-alkenyl, C2-C3- alkynyl, benzyl, or phenyl, preferably H, C1-C3-alkyl, benzyl, or phenyl. R18 is usually H;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, CN, C1-C3-alkyl, C1-C3- alkoxy, C1-C3-haloalkyl, and C1-C3-haloalkoxy; or
a 3- to 6-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents from halogen, CN, C1-C3-alkyl, C1-C3-alkoxy, C1-C3- haloalkyl, and C1-C3-haloalkoxy.
R19 is usually H, C1-C4-alkyl, phenyl, or benzyl. In another embodiment, R18 and R19 form a 3- to 7-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or hetero- cyclic ring is unsubstituted or substituted with one or more, same or different substituents from halogen, CN, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkyl, and C1-C3-haloalkoxy.
In one embodiment, R18 is H;
C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, which groups are unsubstituted, or halogenated;
a 3- to 6-membered saturated, partially unsaturated, or fully unsaturated carbocycle.
The substituents R20a, R20b are typically independently H, C1-C3-alkyl, C1-C3-haloalkyl, or phe- nyl, preferably C1-C3-alkyl or phenyl. In one embodiment, R1, R2 are independently H, halogen, CN, NO2, N3, or SCN;
C1-C10-alkyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R11;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocy- clic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R12;
OR13, OC(=O)R14, OC(=O)NR15R16, OC(=O)SR13, OC(=S)NR15R16, OC(=S)SR13, OS(O)nR14, OS(=O)nNR15R16, ONR15R16, ON=CR18R19, NR15C(=O)R14, NR15C(=O)SR13, NR15C(=O)OR13, NR15C(=O)NR16R17, NR15R16, N=CR18R19, NNR15R16, NNR15, S(O)nR14, NR15S(=O)nR14,
SC(=O)SR13, SC(=O)OR13, SC(=O)NR15R16, S(O)nNR15R16, C(=O)R14, C(=S)R14, C(=O)NR15R16, C(=O)OR13, C(=S)NR15R16, C(=S)OR13, SC(=O)SR13,SC(=O)OR13, C(=S)SR13, C(=NR15)R16, C(=NR15)NR16R17, or Si(R20a)2R20b; or
R1 and R2 form together with the carbon atom they are bonded to a group C=NR15R16, or C=NOR13;
with the proviso that if one variable R1 or R2 is H, the other variable is not H. R3 is H, OR31, OC(=O)R32, OC(=O)OR31, OC(=O)NR33R34, OC(=O)SR31, OC(=S)NR33R34, OC(=S)SR31, OS(O)nR31, OS(=O)nNR33R34, ONR33R34, or ON=CR18R19, preferably R3 is H, or OR31. R31 is typically H;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R311; or
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocy- clic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R312.
In one embodiment, R31 is H, C1-C6-alkyl, C3-C6-cycloalkyl, phenyl, C2-C6-alkenyl, C2-C6-al- kynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, CN, OH, or C1-C3-alkoxy, phenoxy, or benzyloxy. In another embodiment, R31 is H, or C1-C6-alkyl, which is unsubstituted or substituted with halogen, OH, or CN. In another embodiment, R31 is H, or C1-C3-alkyl The substituent R32 is typically H;
C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkyl, and C1-C3-haloalkoxy; or
a 3- to 6-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3- haloalkyl, and C1-C3-haloalkoxy.
The substituents R33 and R34 are usually independently from another H;
C1-C3-alkyl, which is unsubstituted, or substituted with one or more, same or different substitu- ents selected from halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkyl, and C1-C3-haloalkoxy; or a 3- to 6-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkyl, and C1-C3-haloalkoxy. R4 is typically H;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R41;
C(=S)OR43, C(=S)SR43, C(=O)OR43, C(=O)R44, S(O)nR44, C(=S)R44, C(=O)NR45R46, C(=O)SR43, C(=S)NR45R46, C(=NR45)R46, or C(=NR45)NR46R47.
In one embodiment, R4 is H;
C(=S)OR43, C(=S)SR43, C(=O)OR43, C(=O)R44, S(O)nR44, C(=S)R44, C(=O)NR45R46, C(=O)SR43, C(=S)NR45R46, C(=NR45)R46, or C(=NR45)NR46R47.
In another embodiment, R4 is H; C(=O)OR43, C(=O)SR43, C(=S)OR43, or C(=S)SR43
In another embodiment, R4 is H, or C(=S)SR43. R41 is usually OR113, preferably C1-C3-alkoxy, C1-C3-haloalkoxy, phenoxy, or benzyloxy.
Typically, R43 and R44 are independently
C1-C10-alkyl, C2-C10-alkenyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R131; or
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocy- clic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R132. R42 is typically halogen, CN;
C1-C6-alkyl, C3-C6-cycloalkyl, C2-C6-alkenyl, C3-C6-cycloalkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R121; or OR123, OC(=O)R124, NR125R126, NR125C(=O)R124; or
or two geminal substituents R42 form together with the atom to which they are bound a group =O, =S, or =NR121.
In one embodiment, R42 is halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkyl, or C1-C3-haloal- koxy.
In one embodiment, R43 and R44 are independently
C1-C10-alkyl, C2-C10-alkenyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from
halogen, OH, CN, NO2, C1-C3-haloalkoxy; or
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heter- ocyclic ring or ring system, wherein said heterocyclic ring or ring system is selected from D1 to D154, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents RA;
or a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or hetero- cyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R132.
In another embodiment, R43 and R44 are independently
C1-C10-alkyl, C2-C10-alkenyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from
halogen, OH, CN; or
a 3- to 10-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring or ring system, wherein said carbocyclic ring or ring system is unsubstituted, or substi- tuted with one or more, same or different substituents selected from halogen, OH, CN, C1- C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy; or
a 3- to 10-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring or ring system, wherein said carbocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C3-alkyl, C1-C3- haloalkyl, C1-C3-alkoxy, and C1-C3-haloalkoxy.
In another embodiment, R43 and R44 are independently
C1-C4-alkyl, C2-C4-alkenyl, or C2-C4-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from
halogen, CN; or
a 3- to 8-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring or ring system, wherein said carbocyclic ring or ring system is unsubstituted, or substi- tuted with one or more, same or different substituents selected from halogen, and C1-C4- alkyl; or
a 3- to 8-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring or ring system, wherein said carbocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, and C1-C4-alkyl. In another embodiment, R43 and R44 are independently
C1-C4-alkyl, C2-C4-alkenyl, or C2-C4-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from
halogen, CN; or
a 3- to 8-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring or ring system, wherein said carbocyclic ring or ring system is unsubstituted, or substi- tuted with one or more, same or different substituents selected from halogen, and C1-C4- alkyl. The substituents R45, R46, R47 are usually independently H;
C1-C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, acetyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R151;
a 3- to 6-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R152.
In one embodiment, the substituents R45, R46, R47 are independently H;
C1-C3-alkyl, acetyl, which groups are unsubstituted, or substituted with one or more, same or dif- ferent substituents R151;
a 3- to 10-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocy- clic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R152. RA is usually halogen, OH, CN, C1-C10-alkyl, C1-C10-haloalkyl, C1-C10-alkoxy, or C1-C6-haloal- koxy, preferably halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, or C1-C4-haloalkoxy. R111 is usually halogen, OH, or CN; or a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are inde- pendently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents RA. Preferably, R111 is halogen, OH, CN, C1-C6-cycloalkyl, or phenyl, more preferably halogen.
R112 is usually halogen, OH, CN; C1-C4-alkyl, C1-C4-alkoxy, C3-C6-cycloalkyl, C2-C6-alkenyl, C3- C6-cycloalkenyl, phenyl or C2-C6-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, and CN. In one embodi- ment, R112 is halogen, C1-C4-alkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-haloalkoxy.
Typically, R113 and R114 are independently H;
C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R111; or
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocy- clic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R112.
In one embodiment, R113 and R114 are independently H;
C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, benzyl, which groups are unsubstituted, or halogen- ated; or
a 3- to 6-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring or ring system, which ring or ring system is unsubstituted, or substituted with one or more, same or dif- ferent substituents selected from halogen, OH, C1-C3-alkyl, C1-C3-haloalkyl, C1-C3-alkoxy, and C1-C3-haloalkoxy.
In another embodiment, R113 and R114 are independently C1-C3-alkyl, C1-C3-haloalkyl, phenyl or benzyl.
Typically, R115, R116, R117 are independently H;
C1-C6-alkyl, C1-C6-alkoxy, C2-C6-alkenyl, C2-C6-alkynyl, which groups are unsubstituted, or sub- stituted with one or more, same or different substituents R111;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocy- clic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R112.
In one embodiment, R115, R116, R117 are independently H;
C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, which groups are unsubstituted, or halogenated; or a 3- to 6-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, CN, C1-C3-alkyl, C1-C3-haloalkyl, C1-C3-alkoxy, and C1-C3-haloalkoxy.
In one embodiment, R115, R116, R117 are independently H;
C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, phenyl, which groups are unsubstituted, or halogenated.
R118 is usually H, halogen;
C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R111; or
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocy- clic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R112.
In one embodiment, R118 is H, halogen; C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C6-cyclo- alkyl, C3-C6-cycloalkenyl, phenyl, which groups are unsubstituted, or halogenated.
R119 is usually H, C1-C4-alkyl, C1-C6-cycloalkyl, C1-C2-alkoxy-C1-C2-alkyl, phenyl, benzyl, pref- erably H, C1-C4-alkyl, phenyl or benzyl, more preferably H, C1-C4-alkyl. In another embodiment, R118 and R119 form a 3- to 7-membered saturated, partially unsatu- rated, or fully unsaturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or hetero- cyclic ring is unsubstituted or substituted with one or more, same or different substituents se- lected from halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkoxy, and C1-C3-haloalkyl. Typically, R121 is halogen, OH, CN, NO2;
C1-C10-alkoxy, C1-C10-haloalkoxy, C1-C10-alkyl-carbonyl; or
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocy- clic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents RA.
In one embodiment, R121 is halogen, OH, CN, C1-C3-alkoxy, or C1-C3-haloalkoxy.
Typically, R122 is halogen, OH, CN; or
C1-C3-alkyl, C1-C3-alkoxy, C2-C4-alkenyl, C2-C4-alkynyl, which groups are unsubstituted, or sub- stituted with one or more, same or different substituents selected from halogen, and CN.
In one embodiment, R122 is halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkyl, or C1-C3- haloalkoxy.
Typically, R123 and R124 are independently H, C1-C3-alkyl, C1-C3-haloalkyl, or phenyl.
R125, R126 and R127 may be independently from one another H;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen and CN; or a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocy- clic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkyl, and C1-C3-haloalkoxy.
In one embodiment, R125, R126 and R127 may be independently from one another H, C1-C3-alkyl, or C1-C3-haloalkyl. R131 is typically halogen, OH, CN, C1-C10-alkoxy; or
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocy- clic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkyl, C1-C3-haloalkoxy.
In one embodiment, R131 is halogen, CN; or
a 3- to 6-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring.
The variable R132 is typically halogen, OH, CN; C1-C6-alkyl, C1-C6-alkoxy, C3-C6-cycloalkyl, C2-C6-alkenyl, C3-C6-cycloalkenyl, C2-C6-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, and CN. In one embodiment, R132 is halogen, CN, C1-C3-alkyl, C1- C3-alkoxy, C1-C3-haloalkyl, C1-C3-haloalkoxy. Typically, R151 is halogen, OH, CN; or
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocy- clic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, CN, C1-C3-alkyl, C1-C3- alkoxy, C1-C3-haloalkyl, and C1-C3-haloalkoxy. In one embodiment, R151 is phenyl, which is un- substituted, or substituted with one or more, same or different substituents selected from halo- gen, CN, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkyl, and C1-C3-haloalkoxy. In another embodi- ment, R151 is phenyl.
The variable R152 is usually halogen, CN, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkyl, and C1- C3-haloalkoxy, preferably halogen, C1-C3-alkyl, or C1-C3-alkoxy. R311 is typically halogen, OH, CN;
C1-C10-alkoxy, which is unsubstituted, or substituted with one or more, same or different substit- uents selected from halogen, OH, CN; or
a 3- to 10-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocy- clic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3-haloalkyl, or C1-C3-haloalkoxy.
In one embodiment, R311 is a 3- to 10-membered saturated, partially unsaturated, or fully un- saturated carbocyclic ring or ring system, which is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3- haloalkyl, or C1-C3-haloalkoxy.
R312 is typically halogen, OH, CN;
C1-C3-alkyl, C1-C3-alkoxy, C3-C8-cycloalkyl, C2-C10-alkenyl, C3-C8-cycloalkenyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl. In one embodiment, R312 is halogen, OH, CN, C1-C3-alkyl, or C1-C3-alkoxy. R5, R6 are independently H, or OH. In one embodiment, R5 is H and R6 is OH. In one embodi- ment, R5 is H.
The index n is 0, 1, or 2. In one embodiment, n is 0. In another embodiment, n is 1. In yet an- other embodiment, n is 2. Examples of preferred compounds of formula (I) are compiled in tables 1 to 156 below. Moreo- ver, the meanings mentioned below for the individual variables in the tables are per se, independently of the combination in which they are mentioned, a particularly preferred embodi- ment of the substituents in question. Table 1: Compounds of the formula (I) in which R3 is H, R4 is H, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 2: Compounds of the formula (I) in which R3 is H, R4 is H, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 3: Compounds of the formula (I) in which R3 is OH, R4 is H, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 4: Compounds of the formula (I) in which R3 is OH, R4 is H, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 5: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is H, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 6: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is H, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 7: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is H, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 8: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is H, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 9: Compounds of the formula (I) in which R3 is H, R4 is H9, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 10: Compounds of the formula (I) in which R3 is H, R4 is H9, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 11: Compounds of the formula (I) in which R3 is OH, R4 is H9, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 12: Compounds of the formula (I) in which R3 is OH, R4 is H9, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 13: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is H9, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 14: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is H9, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 15: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is H9, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 16: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is H9, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 17: Compounds of the formula (I) in which R3 is H, R4 is C6H5NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 18: Compounds of the formula (I) in which R3 is H, R4 is C6H5NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 19: Compounds of the formula (I) in which R3 is OH, R4 is C6H5NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 20: Compounds of the formula (I) in which R3 is OH, R4 is C6H5NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C. Table 21: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is C6H5NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 22: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is C6H5NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 23: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is C6H5NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 24: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is C6H5NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 25: Compounds of the formula (I) in which R3 is H, R4 is C6H5NHC(=S)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 26: Compounds of the formula (I) in which R3 is H, R4 is C6H5NHC(=S)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 27: Compounds of the formula (I) in which R3 is OH, R4 is C6H5NHC(=S)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 28: Compounds of the formula (I) in which R3 is OH, R4 is C6H5NHC(=S)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 29: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is C6H5NHC(=S)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 30: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is C6H5NHC(=S)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 31: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is C6H5NHC(=S)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 32: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is C6H5NHC(=S)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 33: Compounds of the formula (I) in which R3 is H, R4 is C6H5CH2NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 34: Compounds of the formula (I) in which R3 is H, R4 is C6H5CH2NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 35: Compounds of the formula (I) in which R3 is OH, R4 is C6H5CH2NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 36: Compounds of the formula (I) in which R3 is OH, R4 is C6H5CH2NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 37: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is C6H5CH2NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 38: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is C6H5CH2NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 39: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is
C6H5CH2NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B. Table 40: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is
C6H5CH2NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C. Table 41: Compounds of the formula (I) in which R3 is H, R4 is 4-methoxybenzylaminocar- bonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 42: Compounds of the formula (I) in which R3 is H, R4 is 4-methoxybenzylaminocar- bonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C. Table 43: Compounds of the formula (I) in which R3 is OH, R4 is 4-methoxybenzylaminocar- bonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 44: Compounds of the formula (I) in which R3 is OH, R4 is 4-methoxybenzylaminocar- bonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 45: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is 4-methoxybenzyla- minocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 46: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is 4-methoxybenzyla- minocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 47: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is 4-methoxyben- zylaminocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B. Table 48: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is 4-methoxyben- zylaminocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C. Table 49: Compounds of the formula (I) in which R3 is H, R4 is C6H13NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 50: Compounds of the formula (I) in which R3 is H, R4 is C6H13NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 51: Compounds of the formula (I) in which R3 is OH, R4 is C6H13NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 52: Compounds of the formula (I) in which R3 is OH, R4 is C6H13NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 53: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is C6H13NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 54: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is C6H13NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 55: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is C6H13NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 56: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is C6H13NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 57: Compounds of the formula (I) in which R3 is H, R4 is CHCCH2CH2CH2NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 58: Compounds of the formula (I) in which R3 is H, R4 is CHCCH2CH2CH2NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 59: Compounds of the formula (I) in which R3 is OH, R4 is CHCCH2CH2CH2NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 60: Compounds of the formula (I) in which R3 is OH, R4 is CHCCH2CH2CH2NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 61: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is
CHCCH2CH2CH2NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Ta- ble B.
Table 62: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is
CHCCH2CH2CH2NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Ta- ble C. Table 63: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is
CHCCH2CH2CH2NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Ta- ble B.
Table 64: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is
CHCCH2CH2CH2NHC(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Ta- ble C.
Table 65: Compounds of the formula (I) in which R3 is H, R4 is 4-fluorophenylaminocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 66: Compounds of the formula (I) in which R3 is H, R4 is4-fluorophenylaminocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 67: Compounds of the formula (I) in which R3 is OH, R4 is4-fluorophenylaminocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 68: Compounds of the formula (I) in which R3 is OH, R4 is4-fluorophenylaminocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 69: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is 4-fluorophenyla- minocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 70: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is 4-fluorophenyla- minocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 71: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is 4-fluorophenyla- minocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 72: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is 4-fluorophenyla- minocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 73: Compounds of the formula (I) in which R3 is H, R4 is 2-fluorophenylaminocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 74: Compounds of the formula (I) in which R3 is H, R4 is 2-fluorophenylaminocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 75: Compounds of the formula (I) in which R3 is OH, R4 is 2-fluorophenylaminocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 76: Compounds of the formula (I) in which R3 is OH, R4 is 2-fluorophenylaminocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 77: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is 2-fluorophenyla- minocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 78: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is 2-fluorophenyla- minocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 79: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is 2-fluorophenyla- minocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 80: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is 4-fluorophenyla- minocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 81: Compounds of the formula (I) in which R3 is H, R4 is naphthyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 82: Compounds of the formula (I) in which R3 is H, R4 is naphthyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 83: Compounds of the formula (I) in which R3 is OH, R4 is naphthyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B. Table 84: Compounds of the formula (I) in which R3 is OH, R4 is naphthyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 85: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is naphthyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 86: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is naphthyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 87: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is naphthyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 88: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is naphthyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 89: Compounds of the formula (I) in which R3 is H, R4 is CH3C(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 90: Compounds of the formula (I) in which R3 is H, R4 is CH3C(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 91: Compounds of the formula (I) in which R3 is OH, R4 is CH3C(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 92: Compounds of the formula (I) in which R3 is OH, R4 is CH3C(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 93: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is CH3C(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 94: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is CH3C(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 95: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is CH3C(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 96: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is CH3C(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 97: Compounds of the formula (I) in which R3 is H, R4 is C6H5(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 98: Compounds of the formula (I) in which R3 is H, R4 is C6H5(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 99: Compounds of the formula (I) in which R3 is OH, R4 is C6H5(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 100: Compounds of the formula (I) in which R3 is OH, R4 is C6H5(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 101: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is C6H5(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 102: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is C6H5(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 103: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is C6H5(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 104: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is C6H5(=O)-, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 105: Compounds of the formula (I) in which R3 is H, R4 is benzylsulfanylthiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B. Table 106: Compounds of the formula (I) in which R3 is H, R4 is benzylsulfanylthiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 107: Compounds of the formula (I) in which R3 is OH, R4 is benzylsulfanylthiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 108: Compounds of the formula (I) in which R3 is OH, R4 is benzylsulfanylthiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 109: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is benzylsulfanylthio- carbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 110: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is benzylsulfanylthio- carbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 111: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is benzylsulfanyl- thiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 112: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is benzylsulfanyl- thiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 113: Compounds of the formula (I) in which R3 is H, R4 is 3-methoxybenzylsulfinylthio- carbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 114: Compounds of the formula (I) in which R3 is H, R4 is 3-methoxybenzylsulfinylthio- carbonyl,, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 115: Compounds of the formula (I) in which R3 is OH, R4 is 3-methoxybenzylsulfinylthio- carbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 116: Compounds of the formula (I) in which R3 is OH, R4 is 3-methoxybenzylsulfinylthio- carbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 117: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is 3-methoxybenzyl- sulfinylthiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of
Table B.
Table 118: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is 3-methoxybenzyl- sulfinylthiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C. Table 119: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is 3-methoxyben- zylsulfinylthiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of
Table B.
Table 120: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is 3-methoxyben- zylsulfinylthiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of
Table C.
Table 121: Compounds of the formula (I) in which R3 is H, R4 is 4-fluorobenzylsulfinylthiocar- bonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 122: Compounds of the formula (I) in which R3 is H, R4 is 4-fluorobenzylsulfinylthiocar- bonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 123: Compounds of the formula (I) in which R3 is OH, R4 is 4-fluorobenzylsulfinylthiocar- bonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 124: Compounds of the formula (I) in which R3 is OH, R4 is 4-fluorobenzylsulfinylthiocar- bonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 125: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is 4-fluorobenzylsulfi- nylthiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of
Table B. Table 126: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is 4-fluorobenzylsulfi- nylthiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 127: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is 4-fluorobenzyl- sulfinylthiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B. Table 128: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is 4-fluorobenzyl- sulfinylthiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C. Table 129: Compounds of the formula (I) in which R3 is H, R4 is naphthylmethylsulfanylthiocar- bonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 130: Compounds of the formula (I) in which R3 is H, R4 is naphthylmethylsulfanylthiocar- bonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 131: Compounds of the formula (I) in which R3 is OH, R4 is naphthylmethylsulfanylthio- carbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 132: Compounds of the formula (I) in which R3 is OH, R4 is naphthylmethylsulfanylthio- carbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 133: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is naphthylmethyl- sulfanylthiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B. Table 134: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is naphthylmethyl- sulfanylthiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C. Table 135: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is naphthylmethyl- sulfanylthiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of
Table B.
Table 136: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is naphthylmethyl- sulfanylthiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of
Table C.
Table 137: Compounds of the formula (I) in which R3 is H, R4 is 4-iodoobenzylsulfanylthiocar- bonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 138: Compounds of the formula (I) in which R3 is H, R4 is 4-iodoobenzylsulfanylthiocar- bonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 139: Compounds of the formula (I) in which R3 is OH, R4 is 4-iodoobenzylsulfanylthio- carbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 140: Compounds of the formula (I) in which R3 is OH, R4 is 4-iodoobenzylsulfanylthio- carbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 141: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is 4-iodoobenzyl- sulfanylthiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B. Table 142: Compounds of the formula (I) in which R3 is CH3OCH2O, R4 is 4-iodoobenzyl- sulfanylthiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C. Table 143: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is 4-iodoobenzyl- sulfanylthiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B. Table 144: Compounds of the formula (I) in which R3 is C6H5CH2OCH2O, R4 is 4-iodoobenzyl- sulfanylthiocarbonyl, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C. Table 145: Compounds of the formula (I) in which R3 is H, R4 is H12, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 146: Compounds of the formula (I) in which R3 is H, R4 is H12, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C. Table 147: Compounds of the formula (I) in which R3 is H, R4 is H12, R5 is OH, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 148: Compounds of the formula (I) in which R3 is H, R4 is H12, R5 is OH, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 149: Compounds of the formula (I) in which R3 is H, R4 is H12, R5 is OH, R6 is H, and the combination of R1 and R2 is a row of Table B.
Table 150: Compounds of the formula (I) in which R3 is H, R4 is H12, R5 is OH, R6 is H, and the combination of R1 and R2 is a row of Table C.
Table 151: Compounds of the formula (I) in which R3 is OH, R4 is H12, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 152: Compounds of the formula (I) in which R3 is OH, R4 is H12, R5 is H, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 153: Compounds of the formula (I) in which R3 is OH, R4 is H12, R5 is OH, R6 is OH, and the combination of R1 and R2 is a row of Table B.
Table 154: Compounds of the formula (I) in which R3 is OH, R4 is H12, R5 is OH, R6 is OH, and the combination of R1 and R2 is a row of Table C.
Table 155: Compounds of the formula (I) in which R3 is OH, R4 is H12, R5 is OH, R6 is H, and the combination of R1 and R2 is a row of Table B.
Table 156: Compounds of the formula (I) in which R3 is OH, R4 is H12, R5 is OH, R6 is H, and the combination of R1 and R2 is a row of Table C. Table B
Figure imgf000045_0001
Figure imgf000045_0002
Figure imgf000046_0001
Figure imgf000046_0003
Table C
Figure imgf000046_0002
Figure imgf000046_0004
Figure imgf000047_0003
Figure imgf000047_0001
Figure imgf000047_0002
In one embodiment, at least one variable R1 or R2 is selected from H, OH, halogen, CN, N3, preferably H, halogen, CN, N3; C1-C4-alkyl, C2-4-alkenyl (preferably C1-C4-alkyl), which groups are unsubstituted, or substituted with one or more, same or different substituents selected from
CN, NO2, C(=O)R114, C(=O)NR115R116, C(=O)OR113, C(=O)SR113, C(=S)R114,
C(=S)NR115R116, C(=S)OR113, C(=S)SR113, C(=NR115)R113, and C(=NR115)NR116R117, preferably from CN, C(=O)R114, and C(=O)OR113;
OR13, OC(=O)R14, S(C(=O)SR14, or NR15R16, (preferably OR13, S(C(=O)SR14, or NR15R16), wherein
R13 is C1-C6-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, which groups are unsubstituted, or substituted with halogen or CN, preferably Cl or CN; or
benzyl, (cC3H5)CH2, C5-C7-cycloalkyl;
R14 is C1-C8-alkyl, (preferably C2-C8-alkyl) which is unsubstituted, or halogenated;
phenyl, benzyl, or cyclopropyl, which groups are unsubstituted or substituted with C1-C4-alkyl, or halogen;
R15 is CH3;
R16 is benzyl;
a carbo- or heterocyclic ring or ring system selected from phenyl, indol, indolin, morpholin, thiomorpholin, piperazin, triazol, and tetrazol, which groups are unsubstituted, or substituted with halogen, phenyl, C1-C4-alkyl, or C1-C4-alkoxy, preferably phenyl, C1-C4-alkyl, or C1-C4- alkoxy. In one embodiment, at least one variable R1 or R2 is selected from
H, OH, halogen, CN, N3, preferably H, halogen, CN, N3;
C1-C4-alkyl, C2-4-alkenyl (preferably C1-C4-alkyl), which groups are unsubstituted, or substituted with one or more, same or different substituents selected from
CN, NO2, C(=O)R114, C(=O)NR115R116, C(=O)OR113, C(=O)SR113, C(=S)R114,
C(=S)NR115R116, C(=S)OR113, C(=S)SR113, C(=NR115)R113, and C(=NR115)NR116R117, preferably from CN, C(=O)R114, and C(=O)OR113;
OR13, OC(=O)R14, S(C(=O)SR14, S(O)nR14, or NR15R16, (preferably OR13, S(C(=O)SR14, or NR15R16), wherein
R13 is C1-C6-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, which groups are unsubstituted, or substituted with halogen or CN, preferably Cl or CN; or
benzyl, (cC3H5)CH2, C5-C7-cycloalkyl;
R14 is C1-C8-alkyl, (preferably C2-C8-alkyl) which is unsubstituted, or halogenated;
phenyl, benzyl, or cyclopropyl, which groups are unsubstituted or substituted with C1-C4-alkyl, or halogen;
R15 is CH3;
R16 is benzyl;
a carbo- or heterocyclic ring or ring system selected from phenyl, indol, indolin, 1,3-dithian, morpholin, thiomorpholin, piperazin, triazol, and tetrazol, which groups are unsubstituted, or substituted with halogen, phenyl, C1-C4-alkyl, or C1-C4-alkoxy, preferably phenyl, C1-C4-alkyl, or C1-C4-alkoxy. In another embodiment, R3 is H or OR31, R5 is H or OH; R6 is OH; and at least one variable R1 or R2 is selected from H, OH, halogen, CN, N3, preferably H, halogen, CN, N3; C1-C4-alkyl, C2-C4-alkenyl, (preferabyl C1-C4-alkyl) which groups are unsubstituted, or substituted with one or more, same or different substituents selected from
CN, NO2, C(=O)R114, C(=O)NR115R116, C(=O)OR113, C(=O)SR113, C(=S)R114,
C(=S)NR115R116, C(=S)OR113, C(=S)SR113, C(=NR115)R113, and C(=NR115)NR116R117, preferably from CN, C(=O)R114, and C(=O)OR113;
OR13, OC(=O)R14, S(C(=O)SR14, or NR15R16, preferably OR13, S(C(=O)SR14, or NR15R16 wherein R13 is C1-C6-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C3-C8-cycloalkyl, which groups are
unsubstituted, or substituted with halogen, CN, phenyl, or C3-C8-cycloalkyl; R14 is C1-C8-alkyl, which is unsubstituted, or halogenated;
phenyl, C3-C8-cycloalkyl, which groups are unsubstituted or substituted with C1-C4-alkyl, or halogen;
R15 is C1-C3-alkyl;
R16 is C1-C3-alkyl, which is unsubstituted or substituted with one or more, same or
different subtituents selected from halogen, CN, and phenyl;
phenyl or a 3- to 10-membered heterocyclic ring or ring system, which groups are unsubstituted, or substituted with halogen, phenyl, C1-C4-alkyl, or C1-C4-alkoxy. In another embodiment, R3 is H or OR31, R5 is H or OH; R6 is OH; and at least one variable R1 or R2 is selected from H, OH, halogen, CN, N3, preferably H, halogen, CN, N3;
C1-C4-alkyl, C2-C4-alkenyl, (preferabyl C1-C4-alkyl) which groups are unsubstituted, or substituted with one or more, same or different substituents selected from
CN, NO2, C(=O)R114, C(=O)NR115R116, C(=O)OR113, C(=O)SR113, C(=S)R114,
C(=S)NR115R116, C(=S)OR113, C(=S)SR113, C(=NR115)R113, and C(=NR115)NR116R117, preferably from CN, C(=O)R114, and C(=O)OR113;
OR13, OC(=O)R14, S(O)nR14, S(C(=O)SR14, or NR15R16, preferably OR13, S(C(=O)SR14, or NR15R16 wherein
R13 is C1-C6-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C3-C8-cycloalkyl, which groups are
unsubstituted, or substituted with halogen, CN, phenyl, or C3-C8-cycloalkyl; R14 is C1-C8-alkyl, which is unsubstituted, or halogenated;
phenyl, C3-C8-cycloalkyl, which groups are unsubstituted or substituted with C1-C4-alkyl, or halogen;
R15 is C1-C3-alkyl;
R16 is C1-C3-alkyl, which is unsubstituted or substituted with one or more, same or
different subtituents selected from halogen, CN, and phenyl;
phenyl or a 3- to 10-membered heterocyclic ring or ring system, which groups are unsubstituted, or substituted with halogen, phenyl, C1-C4-alkyl, or C1-C4-alkoxy. In another embodiment, R3 is H or OH; R5 is H or OH; R6 is OH; and at least one variable R1 or R2 is selected from
H, OH, CN, N3, preferably H, halogen, CN, N3;
C1-C4-alkyl, C2-C4-alkenyl, (preferabyl C1-C4-alkyl) which groups are unsubstituted, or substituted with one or more, same or different substituents selected from CN, and C(=O)OCH3; OR13, OC(=O)R14, S(C(=O)SR14, or NR15R16, preferably OR13, S(C(=O)SR14, or NR15R16 wherein R13 is C1-C6-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, which groups are unsubstituted, or substituted with halogen or CN, preferably Cl or CN; or
benzyl, (cC3H5)CH2, C5-C7-cycloalkyl;
R14 is C1-C8-alkyl, (preferably C2-C8-alkyl) which is unsubstituted, or halogenated;
phenyl, benzyl, or cyclopropyl, which groups are unsubstituted or substituted with C1-C4-alkyl, or halogen;
R15 is CH3;
R16 is benzyl; or
a carbo- or heterocyclic ring or ring system selected from phenyl, indol, indolin, morpholin, thiomorpholin, piperazin, triazol, tetrazol, which groups are unsubstituted, or substituted with halogen, phenyl, C1-C4-alkyl, or C1-C4-alkoxy. In another embodiment, R3 is H or OH; R4 is H, or (3,5-ditert-butylphenyl)methylsulfanylcar- bonyl; R5 is H; R6 is OH; and at least one variable R1 or R2 is selected from
H, OH, halogen, CN, N3, preferably H, halogen, CN, N3;
C1-C4-alkyl, C2-C4-alkenyl, (preferably C1-C4-alkyl) which groups are unsubstituted, or substituted with one or more, same or different substituents selected from CN, and C(=O)OCH3; OR13, OC(=O)R14, S(C(=O)SR14, or NR15R16, preferably OR13, S(C(=O)SR14, or NR15R16 wherein R13 is C1-C6-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, (preferably C2-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl) which groups are unsubstituted, or substituted with halogen or CN, preferably Cl or CN; or
benzyl, (cC3H5)CH2, C5-C7-cycloalkyl;
R14 is C1-C8-alkyl, (preferably C2-C8-alkyl) which is unsubstituted, or halogenated;
phenyl, benzyl or cyclopropyl, which groups are unsubstituted or substituted with C1-C4-alkyl, or halogen;
R15 is CH3;
R16 is benzyl;
a carbo- or heterocyclic ring or ring system selected from phenyl, indol, indolin, morpholin, thiomorpholin, piperazin, triazol, tetrazol, which groups are unsubstituted, or substituted with phenyl, C1-C4-alkyl, or C1-C4-alkoxy. In another embodiment, R3 is H or OH; R4 is H, or (3,5-ditert-butylphenyl)methylsulfanylcar- bonyl; R5 is H; R6 is OH; and at least one variable R1 or R2 is selected from
H, OH, halogen, CN, N3, preferably H, halogen, CN, N3;
C1-C4-alkyl, C2-C4-alkenyl, (preferably C1-C4-alkyl) which groups are unsubstituted, or substituted with one or more, same or different substituents selected from CN, and C(=O)OCH3; OR13, OC(=O)R14, S(O)nR14, S(C(=O)SR14, or NR15R16, preferably OR13, S(C(=O)SR14, or NR15R16 wherein
R13 is C1-C6-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, (preferably C2-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl) which groups are unsubstituted, or substituted with halogen or CN, preferably Cl or CN; or
benzyl, (cC3H5)CH2, C5-C7-cycloalkyl;
R14 is C1-C8-alkyl, (preferably C2-C8-alkyl) which is unsubstituted, or halogenated;
phenyl, benzyl or cyclopropyl, which groups are unsubstituted or substituted with C1-C4-alkyl, or halogen;
R15 is CH3;
R16 is benzyl;
a carbo- or heterocyclic ring or ring system selected from phenyl, indol, indolin, morpholin, thiomorpholin, piperazin, triazol, tetrazol, or 1,3-dithian, which groups are unsubstituted, or substituted with phenyl, C1-C4-alkyl, or C1-C4-alkoxy. In another embodiment, R3 is H or OH; R4 is H; R5 is H; R6 is OH; and at least one variable R1 or R2 is selected from
H, OH, CN, N3, preferably H, CN, N3;
C1-C4-alkyl, C2-C4-alkenyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from CN, and C(=O)OCH3;
OR13, OC(=O)R14, or NR15R16, preferably OR13 or NR15R16 wherein
R13 is C1-C3-alkyl; C2-C4-alkynyl; or
benzyl, (cC3H5)CH2, cyclopentyl;
R14 is C1-C4-alkyl, preferably C2-C4-alkyl;
phenyl, which is unsubstituted or substituted with C1-C4-alkyl, or halogen; R15 is CH3;
R16 is benzyl;
a heterocyclic ring or ring system selected from indol, indolin, morpholin, thiomorpholin, piperazin, triazol, which groups are unsubstituted, or substituted with phenyl, or C1-C3-alkyl. In another embodiment, R3 is H or OH; R4 is H; R5 is H; R6 is OH; and at least one variable R1 or R2 is selected from
H, OH, CN, N3, preferably H, CN, N3;
C1-C4-alkyl, C2-C4-alkenyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from CN, and C(=O)OCH3;
OR13, OC(=O)R14, S(O)nR14, or NR15R16, preferably OR13 or NR15R16 wherein
R13 is C1-C3-alkyl; C2-C4-alkynyl; or
benzyl, (cC3H5)CH2, cyclopentyl;
R14 is C1-C4-alkyl, preferably C2-C4-alkyl;
phenyl, which is unsubstituted or substituted with C1-C4-alkyl, or halogen; R15 is CH3;
R16 is benzyl;
a heterocyclic ring or ring system selected from indol, indolin, morpholin, thiomorpholin, piperazin, triazol, or 1,3-dithian, which groups are unsubstituted, or substituted with phenyl, or C1-C3-alkyl. In another embodiment, R3 is H or OH; R4 is H; R5 is H; R6 is OH; and at least one variable R1 or R2 is selected from
H, OH, CN, N3, preferably H, CN, N3;
C1-C4-alkyl, C2-C4-alkenyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from CN, and C(=O)OCH3;
OR13, OC(=O)R14, or NR15R16, preferably OR13 or NR15R16 wherein R13 is C1-C3-alkyl; C2-C4-alkynyl; or
benzyl, (cC3H5)CH2, cyclopentyl;
R14 is C1-C4-alkyl, preferably C2-C4-alkyl;
phenyl, which is unsubstituted or substituted with C1-C4-alkyl, or halogen; R15 is CH3;
R16 is benzyl;
a heterocyclic ring or ring system selected from indol, indolin, morpholin, thiomorpholin, piperazin, triazol, which groups are unsubstituted, or substituted with phenyl. In another embodiment, R3 is H or OH; R4 is H; R5 is H; R6 is OH; and at least one variable R1 or R2 is selected from
H, OH, CN, N3, preferably H, CN, N3;
C1-C4-alkyl, C2-C4-alkenyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from CN, and C(=O)OCH3;
OR13, OC(=O)R14, S(O)nR14, or NR15R16, preferably OR13 or NR15R16 wherein
R13 is C1-C3-alkyl; C2-C4-alkynyl; or
benzyl, (cC3H5)CH2, cyclopentyl;
R14 is C1-C4-alkyl, preferably C2-C4-alkyl;
phenyl, which is unsubstituted or substituted with C1-C4-alkyl, or halogen; R15 is CH3;
R16 is benzyl;
a heterocyclic ring or ring system selected from indol, indolin, morpholin, thiomorpholin, piperazin, triazol, 1,3-dithian, which groups are unsubstituted, or substituted with phenyl. As used herein, the term“compound(s) of the present invention” or“compound(s) according to the invention” refers to the compound(s) of formula (I) as defined above, which are also referred to as“compound(s) of formula (I)” or“compound(s) I” or“formula (I) compound(s)”, and includes their salts, tautomers, stereoisomers, and N-oxides. Mixtures
The present invention also relates to a mixture of at least one compound of the invention with at least one mixing partner as defined herein. Preferred are binary mixtures of one compound of the invention as component I with one mixing partner as defined herein as component II. Pre- ferred weight ratios for such binary mixtures are from 5000:1 to 1:5000, preferably from 1000:1 to 1:1000, more preferably from 100:1 to 1:100, particularly from 10:1 to 1:10. In such binary mixtures, components I and II may be used in equal amounts, or an excess of component I, or an excess of component II may be used.
Mixing partners can be selected from pesticides, in particular insecticides, nematicides, and ac- aricides, fungicides, herbicides, plant growth regulators, fertilizers. Preferred mixing partners are insecticides, nematicides and fungicides.
The following list M of pesticides, grouped and numbered according the Mode of Action Classifi- cation of the Insecticide Resistance Action Committee (IRAC), together with which the com- pounds of the invention can be used and with which potential synergistic effects might be pro- duced, is intended to illustrate the possible combinations, but not to impose any limitation: M.1 Acetylcholine esterase (AChE) inhibitors: M.1A carbamates, e.g. aldicarb, alanycarb, bendi- ocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofen- carb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, ox- amyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate; or M.1B organophosphates, e.g. acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, ca- dusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimetho- ate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O-(methoxyaminothio- phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-me- thyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos- methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupi- rimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, and vami- dothion;
M.2. GABA-gated chloride channel antagonists: M.2A cyclodiene organochlorine compounds, e.g. endosulfan or chlordane; or M.2B fiproles (phenylpyrazoles), e.g. ethiprole, fipronil, flufiprole, pyrafluprole, and pyriprole;
M.3 Sodium channel modulators from the class of M.3A pyrethroids, e.g. acrinathrin, allethrin, d- cis-trans allethrin, d-trans allethrin, bifenthrin, kappa-bifenthrin, bioallethrin, bioallethrin S-cylclo- pentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalo- thrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cyperme- thrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, heptafluthrin, im- iprothrin, meperfluthrin,metofluthrin, momfluorothrin, epsilon-momfluorothrin, permethrin, phe- nothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, kappa- tefluthrin, tetramethylfluthrin, tetramethrin, tralomethrin, and transfluthrin; or M.3B sodium chan- nel modulators such as DDT or methoxychlor;
M.4 Nicotinic acetylcholine receptor agonists (nAChR): M.4A neonicotinoids, e.g. acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or the compounds M.4A.14,5-Dihydro-N-nitro-1-(2-oxiranylmethyl)-1H-imidazol-2-amine, M.4A.2: (2E-)-1-[(6-Chloropyridin-3-yl)methyl]-N'-nitro-2-pentylidenehydrazinecarboximidamide; or M4.A.3: 1-[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro-5-propoxy-1,2,3,5,6,7-hexahydroim- idazo[1,2-a]pyridine; or M.4B nicotine; M.4C sulfoxaflor; M.4D flupyradifurone; M.4E triflume- zopyrim;
M.5 Nicotinic acetylcholine receptor allosteric activators:spinosyns, e.g. spinosad or spinetoram; M.6 Chloride channel activators from the class of avermectins and milbemycins, e.g. abamectin, emamectin benzoate, ivermectin, lepimectin, or milbemectin;
M.7 Juvenile hormone mimics, such as M.7A juvenile hormone analogues hydroprene, kino- prene, and methoprene; or M.7B fenoxycarb, or M.7C pyriproxyfen;
M.8 miscellaneous non-specific (multi-site) inhibitors, e.g. M.8A alkyl halides as methyl bromide and other alkyl halides, M.8B chloropicrin, M.8C sulfuryl fluoride, M.8D borax, or M.8E tartar emetic;
M.9 Chordotonal organ TRPV channel modulators, e.g. M.9B pymetrozine; pyrifluquinazon; M.10 Mite growth inhibitors, e.g. M.10A clofentezine, hexythiazox, and diflovidazin, or M.10B etoxazole;
M.11 Microbial disruptors of insect midgut membranes, e.g. bacillus thuringiensis or bacillus sphaericus and the insecticdal proteins they produce such as bacillus thuringiensis subsp. is- raelensis, bacillus sphaericus, bacillus thuringiensis subsp. aizawai, bacillus thuringiensis subsp. kurstaki and bacillus thuringiensis subsp. tenebrionis, or the Bt crop proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, and Cry34/35Ab1;
M.12 Inhibitors of mitochondrial ATP synthase, e.g. M.12A diafenthiuron, or M.12B organotin miticides such as azocyclotin, cyhexatin, or fenbutatin oxide, M.12C propargite, or M.12D tetra- difon;
M.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient, e.g.
chlorfenapyr, DNOC, or sulfluramid;
M.14 Nicotinic acetylcholine receptor (nAChR) channel blockers, e.g. nereistoxin analogues bensultap, cartap hydrochloride, thiocyclam, or thiosultap sodium;
M.15 Inhibitors of the chitin biosynthesis type 0, such as benzoylureas e.g. bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, or triflumuron;
M.16 Inhibitors of the chitin biosynthesis type 1, e.g. buprofezin;
M.17 Moulting disruptors, Dipteran, e.g. cyromazine;
M.18 Ecdyson receptor agonists such as diacylhydrazines, e.g. methoxyfenozide, tebufenozide, halofenozide, fufenozide, or chromafenozide;
M.19 Octopamin receptor agonists, e.g. amitraz;
M.20 Mitochondrial complex III electron transport inhibitors, e.g. M.20A hydramethylnon, M.20B acequinocyl, M.20C fluacrypyrim; or M.20D bifenazate;
M.21 Mitochondrial complex I electron transport inhibitors, e.g. M.21A METI acaricides and in- secticides such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad or tolfen- pyrad, or M.21B rotenone;
M.22 Voltage-dependent sodium channel blockers, e.g. M.22A indoxacarb, M.22B metaflumi- zone, or M.22B.1: 2-[2-(4-Cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoro- methoxy)phenyl]-hydrazinecarboxamide or M.22B.2: N-(3-Chloro-2-methylphenyl)-2-[(4-chloro- phenyl)[4-[methyl(methylsulfonyl)amino]phenyl]methylene]-hydrazinecarboxamide;
M.23 Inhibitors of the of acetyl CoA carboxylase, such as Tetronic and Tetramic acid deriva- tives, e.g. spirodiclofen, spiromesifen, or spirotetramat; M.23.1 spiropidion;
M.24 Mitochondrial complex IV electron transport inhibitors, e.g. M.24A phosphine such as alu- minium phosphide, calcium phosphide, phosphine or zinc phosphide, or M.24B cyanide;
M.25 Mitochondrial complex II electron transport inhibitors, such as beta-ketonitrile derivatives, e.g. cyenopyrafen or cyflumetofen;
M.28 Ryanodine receptor-modulators from the class of diamides, e.g. flubendiamide, chlor- antraniliprole, cyantraniliprole, tetraniliprole, M.28.1: (R)-3-Chlor-N1-{2-methyl-4-[1,2,2,2–tetra- fluoro-1-(trifluoromethyl)ethyl]phenyl}-N2-(1-methyl-2-methylsulfonylethyl)phthalamid, M.28.2: (S)-3-Chloro-N1-{2-methyl-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl}-N2-(1-methyl-2- methylsulfonylethyl)phthalamid, M.28.3: cyclaniliprole, or M.28.4: methyl-2-[3,5-dibromo-2-({[3- bromo-1-(3-chlorpyridin-2-yl)-1H-pyrazol-5-yl]carbonyl}amino)benzoyl]-1,2-dimethylhydrazine- carboxylate; or M.28.5a) N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]- 2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; M.28.5b) N-[4-chloro-2-[(di- ethyl-lambda-4-sulfanylidene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluorome- thyl)pyrazole-3-carboxamide; M.28.5c) N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene)car- bamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; M.28.5d) N-[4,6-dichloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro- 2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; M.28.5h) N-[4,6-dibromo-2-[(diethyl- lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3- carboxamide; M.28.5i) N-[2-(5-Amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1- (3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide; M.28.5j) 3-Chloro-1-(3-chloro-2-pyridinyl)-N- [2,4-dichloro-6-[[(1-cyano-1-methylethyl)amino]carbonyl]phenyl]-1H-pyrazole-5-carboxamide; M.28.5k) 3-Bromo-N-[2,4-dichloro-6-(methylcarbamoyl)phenyl]-1-(3,5-dichloro-2-pyridyl)-1H-py- razole-5-carboxamide; M.28.5l) N-[4-Chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methyl- phenyl]-1-(3-chloro-2-pyridinyl)-3-(fluoromethoxy)-1H-pyrazole-5-carboxamide; or
M.28.6: cyhalodiamide; or
M.29: Chordotonal organ Modulators– undefined target site, e.g. flonicamid;
M.UN. insecticidal active compounds of unknown or uncertain mode of action, e.g. afidopyro- pen, afoxolaner, azadirachtin, amidoflumet, benzoximate, broflanilide, bromopropylate, chino- methionat, cryolite, dicloromezotiaz, dicofol, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, fluralaner, metaldehyde, metoxadiazone, piperonyl butoxide, pyflubumide, pyridalyl, tioxazafen, M.UN.3: 11-(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1,4-dioxa-9-aza- dispiro[4.2.4.2]-tetradec-11-en-10-one,
M.UN.4: 3-(4’-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-1-azaspiro[4.5]dec-3-en-2-one, M.UN.5: 1-[2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)-1H-1,2,4- triazole-5-amine, or actives on basis of bacillus firmus (Votivo, I-1582);
M.UN.6: flupyrimin;
M.UN.8: fluazaindolizine; M.UN.9.a): 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3- yl]-2-methyl-N-(1-oxothietan-3-yl)benzamide; M.UN.9.b): fluxametamide; M.UN.10: 5-[3-[2,6-di- chloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1H-pyrazole;
M.UN.11.i) 4-cyano-N-[2-cyano-5-[[2,6-dibromo-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)pro- pyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; M.UN.11.j) 4-cyano-3-[(4-cyano-2-methyl- benzoyl)amino]-N-[2,6-dichloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]-2- fluoro-benzamide; M.UN.11.k) N-[5-[[2-chloro-6-cyano-4-[1,2,2,3,3,3-hexafluoro-1-(trifluorome- thyl)propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; M.UN.11.l) N-[5- [[2-bromo-6-chloro-4-[2,2,2-trifluoro-1-hydroxy-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cy- ano-phenyl]-4-cyano-2-methyl-benzamide; M.UN.11.m) N-[5-[[2-bromo-6-chloro-4-[1,2,2,3,3,3- hexafluoro-1-(trifluoromethyl)propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-ben- zamide; M.UN.11.n) 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1,2,2,3,3,3-hexafluoro-1-(trifluoro- methyl)propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; M.UN.11.o) 4-cyano-N-[2-cyano- 5-[[2,6-dichloro-4-[1,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]phenyl]-2-methyl- benzamide; M.UN.11.p) N-[5-[[2-bromo-6-chloro-4-[1,2,2,2-tetrafluoro-1-(trifluorome- thyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; or
M.UN.12.a) 2-(1,3-Dioxan-2-yl)-6-[2-(3-pyridinyl)-5-thiazolyl]-pyridine; M.UN.12.b) 2-[6-[2-(5- Fluoro-3-pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine; M.UN.12.c) 2-[6-[2-(3-Pyridinyl)-5- thiazolyl]-2-pyridinyl]-pyrimidine; M.UN.12.d) N-Methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyri- dine-2-carboxamide; M.UN.12.e) N-Methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carbox- amide;
M.UN.14a) 1-[(6-Chloro-3-pyridinyl)methyl]-1,2,3,5,6,7-hexahydro-5-methoxy-7-methyl-8-nitro- imidazo[1,2-a]pyridine; or M.UN.14b) 1-[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro- 1,2,3,5,6,7-hexahydroimidazo[1,2-a]pyridin-5-ol;
M.UN.16a) 1-isopropyl-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; or M.UN.16b) 1- (1,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; M.UN.16c) N,5- dimethyl-N-pyridazin-4-yl-1-(2,2,2-trifluoro-1-methyl-ethyl)pyrazole-4-carboxamide; M.UN.16d) 1-[1-(1-cyanocyclopropyl)ethyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; M.UN.16e) N-ethyl-1-(2-fluoro-1-methyl-propyl)-5-methyl-N-pyridazin-4-yl-pyrazole-4-carbox- amide; M.UN.16f) 1-(1,2-dimethylpropyl)-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; M.UN.16g) 1-[1-(1-cyanocyclopropyl)ethyl]-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carbox- amide; M.UN.16h) N-methyl-1-(2-fluoro-1-methyl-propyl]-5-methyl-N-pyridazin-4-yl-pyrazole-4- carboxamide; M.UN.16i) 1-(4,4-difluorocyclohexyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole- 4-carboxamide; or M.UN.16j) 1-(4,4-difluorocyclohexyl)-N,5-dimethyl-N-pyridazin-4-yl-pyrazole- 4-carboxamide,
M.UN.17a) N-(1-methylethyl)-2-(3-pyridinyl)-2H-indazole-4-carboxamide; M.UN.17b) N-cyclo- propyl-2-(3-pyridinyl)-2H-indazole-4-carboxamide; M.UN.17c) N-cyclohexyl-2-(3-pyridinyl)-2H- indazole-4-carboxamide; M.UN.17d) 2-(3-pyridinyl)-N-(2,2,2-trifluoroethyl)-2H-indazole-4-car- boxamide; M.UN.17e) 2-(3-pyridinyl)-N-[(tetrahydro-2-furanyl)methyl]-2H-indazole-5-carbox- amide; M.UN.17f) methyl 2-[[2-(3-pyridinyl)-2H-indazol-5-yl]carbonyl]hydrazinecarboxylate; M.UN.17g) N-[(2,2-difluorocyclopropyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide;
M.UN.17h) N-(2,2-difluoropropyl)-2-(3-pyridinyl)-2H-indazole-5-carboxamide; M.UN.17i) 2-(3- pyridinyl )-N-(2-pyrimidinylmethyl )-2H-indazole-5-carboxamide; M.UN.17j) N-[(5-methyl-2-pyra- zinyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide,
M.UN.18. tyclopyrazoflor;
M.UN.19 sarolaner, M.UN.20 lotilaner;
M.UN.21 N-[4-Chloro-3-[[(phenylmethyl)amino]carbonyl]phenyl]-1-methyl-3-(1,1,2,2,2-pentafluo- roethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide; M.UN.22a 2-(3-ethylsulfonyl-2-pyridyl)- 3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine, or M.UN.22b 2-[3-ethylsulfonyl-5-(trifluorome- thyl)-2-pyridyl]-3-methyl-6-(trifluoromethyl)imidazo[4,5-b]pyridine;
M.UN.23a) 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-N-[(4R)-2-ethyl-3-oxo- isoxazolidin-4-yl]-2-methyl-benzamide, or M.UN.23b) 4-[5-(3,5-dichloro-4-fluoro-phenyl)-5-(tri- fluoromethyl)-4H-isoxazol-3-yl]-N-[(4R)-2-ethyl-3-oxo-isoxazolidin-4-yl]-2-methyl-benzamide; M.UN.24a) N-[4-chloro-3-(cyclopropylcarbamoyl)phenyl]-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)- 4-(trifluoromethyl)pyrazole-3-carboxamide or M.UN.24b) N-[4-chloro-3-[(1-cyanocyclopropyl)car- bamoyl]phenyl]-2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-carbox- amide; M.UN.25 acynonapyr; M.UN.26 benzpyrimoxan; M.UN.272-chloro-N-(1-cyanocyclopro- pyl)-5-[1-[2-methyl-5-(1,1,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazol-3-yl]pyrazol-4-yl]ben- zamide; M.UN.28 Oxazosulfyl;
M.UN.29a) [(2S,3R,4R,5S,6S)-3,5-dimethoxy-6-methyl-4-propoxy-tetrahydropyran-2-yl] N-[4-[1- [4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]carbamate; M.UN.29b) [(2S,3R,4R,5S,6S)- 3,4,5-trimethoxy-6-methyl-tetrahydropyran-2-yl] N-[4-[1-[4-(trifluoromethoxy)phenyl]-1,2,4- triazol-3-yl]phenyl]carbamate; M.UN.29c) [(2S,3R,4R,5S,6S)-3,5-dimethoxy-6-methyl-4- propoxy-tetrahydropyran-2-yl] N-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1,2,4-triazol-3- yl]phenyl]carbamate; M.UN.29d) [(2S,3R,4R,5S,6S)-3,4,5-trimethoxy-6-methyl-tetrahydropyran- 2-yl] N-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]carbamate;
M.UN.29.e) (2Z)-3-(2-isopropylphenyl)-2-[(E)-[4-[1-[4-(trifluoromethoxy)phenyl]-1,2,4-triazol-3- yl]phenyl]methylenehydrazono]thiazolidin-4-one or M.UN.29f) (2Z)-3-(2-isopropylphenyl)-2-[(E)- [4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1,2,4-triazol-3-yl]phenyl]methylenehydrazono]thia- zolidin-4-one.
The commercially available compounds of the group M listed above may be found in The Pesti- cide Manual, 17th Edition, C. MacBean, British Crop Protection Council (2015) among other publications. The online Pesticide Manual is updated regularly and is accessible through http://bcpcdata.com/pesticide-manual.html.
Another online data base for pesticides providing the ISO common names is http://www.alan- wood.net/pesticides.
The M.4 cycloxaprid is known from WO2010/069266 and WO2011/069456. M.4A.1 is known from CN 103814937; CN105367557, CN 105481839. M.4A.2, guadipyr, is known from WO 2013/003977, and M.4A.3 (approved as paichongding in China) is known from WO
2007/101369. M.22B.1 is described in CN10171577 and M.22B.2 in CN102126994. Spiropidion M.23.1 is known from WO 2014/191271. M.28.1 and M.28.2 are known from WO2007/101540. M.28.3 is described in WO2005/077934. M.28.4 is described in WO2007/043677. M.28.5a) to M.28.5d) and M.28.5h) are described in WO 2007/006670, WO2013/024009 and WO
2013/024010, M.28.5i) is described in WO2011/085575, M.28.5j) in WO2008/134969, M.28.5k) in US2011/046186 and M.28.5l) in WO2012/034403. M.28.6 can be found in WO2012/034472. M.UN.3 is known from WO2006/089633 and M.UN.4 from WO2008/067911. M.UN.5 is descri- bed in WO2006/043635, and biological control agents on the basis of bacillus firmus are de- scribed in WO2009/124707. Flupyrimin is described in WO2012/029672. M.UN.8 is known from WO2013/055584. M.UN.9.a) is described in WO2013/050317. M.UN.9.b) is described in WO2014/126208. M.UN.10 is known from WO2010/060379. Broflanilide and M.UN.11.b) to M.UN.11.h) are described in WO2010/018714, and M.UN.11i) to M.UN.11.p) in WO
2010/127926. M.UN.12.a) to M.UN.12.c) are known from WO2010/006713, M.UN.12.d) and M.UN.12.e) are known from WO2012/000896. M.UN.14a) and M.UN.14b) are known from WO2007/101369. M.UN.16.a) to M.UN.16h) are described in WO2010/034737,
WO2012/084670, and WO2012/143317, resp., and M.UN.16i) and M.UN.16j) are described in WO2015/055497. M.UN.17a) to M.UN.17.j) are described in WO2015/038503. M.UN.18 Tyclo- prazoflor is described in US2014/0213448. M.UN.19 is described in WO2014/036056. M.UN.20 is known from WO2014/090918. M.UN.21 is known from EP2910126. M.UN.22a and M.UN.22b are known from WO2015/059039 and WO2015/190316. M.UN.23a and M.UN.23b are known from WO2013/050302. M.UN.24a) and M.UN.24b) are known from WO2012/126766. Acyn- onapyr M.UN.25 is known from WO 2011/105506. Benzpyrimoxan M.UN.26 is known from WO2016/104516. M.UN.27 is known from WO2016/174049. M.UN.28 Oxazosulfyl is known from WO2017/104592. M.UN.29a) to M.UN.29f) are known from WO2009/102736 or
WO2013116053.
The following list of fungicides, in conjunction with which the compounds of the present inven- tion can be used, is intended to illustrate the possible combinations but does not limit them: A) Respiration inhibitors
- Inhibitors of complex III at Qo site: azoxystrobin (A.1.1), coumethoxystrobin (A.1.2), coumoxystrobin (A.1.3), dimoxystrobin (A.1.4), enestroburin (A.1.5), fenaminstrobin (A.1.6), fenoxystrobin/flufenoxystrobin (A.1.7), fluoxastrobin (A.1.8), kresoxim-methyl (A.1.9), mande- strobin (A.1.10), metominostrobin (A.1.11), orysastrobin (A.1.12), picoxystrobin (A.1.13), pyra- clostrobin (A.1.14), pyrametostrobin (A.1.15), pyraoxystrobin (A.1.16), trifloxystrobin (A.1.17), 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N-me- thyl-acetamide (A.1.18), pyribencarb (A.1.19), triclopyricarb/chlorodincarb (A.1.20), famoxadone (A.1.21), fenamidone (A.1.21), methyl-N-[2-[(1,4-dimethyl-5-phenyl-pyrazol-3-yl)oxylmethyl]phe- nyl]-N-methoxy-carbamate (A.1.22), 1-[2-[[1-(4-chlorophenyl)pyrazol-3-yl]oxymethyl]-3-methyl- phenyl]-4-methyl-tetrazol-5-one (A.1.25), (Z,2E)-5-[1-(2,4-dichlorophenyl)pyrazol-3-yl]­oxy-2- methoxyimino-N,3-dimethyl-pent-3-enamide (A.1.34), (Z,2E)-5-[1-(4-chlorophenyl)pyrazol-3- yl]oxy-2-methoxyimino-N,3-dimethyl-pent-3-enamide (A.1.35), pyriminostrobin (A.1.36), bifujun- zhi (A.1.37), 2-(ortho-((2,5-dimethylphenyl-oxymethylen)phenyl)-3-methoxy-acrylic acid meth- ylester (A.1.38);
- inhibitors of complex III at Qi site: cyazofamid (A.2.1), amisulbrom (A.2.2),
[(6S,7R,8R)-8-benzyl-3-[(3-hydroxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo- 1,5-dioxonan-7-yl] 2-methylpropanoate (A.2.3), fenpicoxamid (A.2.4);
- inhibitors of complex II: benodanil (A.3.1), benzovindiflupyr (A.3.2), bixafen (A.3.3), bos- calid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapy- roxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.11), isopyrazam (A.3.12), mepronil (A.3.13), oxycarboxin (A.3.14), penflufen (A.3.15), penthiopyrad (A.3.16), pydiflumetofen (A.3.17), pyrazi- flumid (A.3.18), sedaxane (A.3.19), tecloftalam (A.3.20), thifluzamide (A.3.21), inpyrfluxam (A.3.22), pyrapropoyne (A.3.23), fluindapyr (A.3.28), methyl (E)-2-[2-[(5-cyano-2-methyl-phe- noxy)methyl]phenyl]-3-methoxy-prop-2-enoate (A.3.30), isoflucypram (A.3.31), 2-(difluorome- thyl)-N-(1,1,3-trimethyl-indan-4-yl)pyridine-3-carboxamide (A.3.32), 2-(difluoromethyl)-N-[(3R)- 1,1,3-trimethylindan-4-yl]pyridine-3-carboxamide (A.3.33), 2-(difluoromethyl)-N-(3-ethyl-1,1-di- methyl-indan-4-yl)pyridine-3-carboxamide (A.3.34), 2-(difluoromethyl)-N-[(3R)-3-ethyl-1,1-dime- thyl-indan-4-yl]pyridine-3-carboxamide (A.3.35), 2-(difluoromethyl)-N-(1,1-dimethyl-3-propyl-in- dan-4-yl)pyridine-3-carboxamide (A.3.36), 2-(difluoromethyl)-N-[(3R)-1,1-dimethyl-3-propyl-in- dan-4-yl]pyridine-3-carboxamide (A.3.37), 2-(difluoromethyl)-N-(3-isobutyl-1,1-dimethyl-indan-4- yl)pyridine-3-carboxamide (A.3.38), 2-(difluoromethyl)-N-[(3R)-3-isobutyl-1,1-dimethyl-indan- 4-yl]pyridine-3-carboxamide (A.3.39);
- other respiration inhibitors: diflumetorim (A.4.1); nitrophenyl derivates: binapacryl (A.4.2), dinobuton (A.4.3), dinocap (A.4.4), fluazinam (A.4.5), meptyldinocap (A.4.6), ferimzone (A.4.7); organometal compounds: fentin salts, e. g. fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.11); silthiofam (A.4.12);
B) Sterol biosynthesis inhibitors (SBI fungicides)
- C14 demethylase inhibitors: triazoles: azaconazole (B.1.1), bitertanol (B.1.2), bromucona- zole (B.1.3), cyproconazole (B.1.4), difenoconazole (B.1.5), diniconazole (B.1.6), diniconazole- M (B.1.7), epoxiconazole (B.1.8), fenbuconazole (B.1.9), fluquinconazole (B.1.10), flusilazole (B.1.11), flutriafol (B.1.12), hexaconazole (B.1.13), imibenconazole (B.1.14), ipconazole
(B.1.15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1.19), paclobutrazole (B.1.20), penconazole (B.1.21), propiconazole (B.1.22), prothioconazole (B.1.23), simeconazole (B.1.24), tebuconazole (B.1.25), tetraconazole (B.1.26), triadimefon (B.1.27), triadimenol (B.1.28), triticonazole (B.1.29), uniconazole (B.1.30), 2-(2,4-difluorophenyl)-1,1-difluoro-3-(te- trazol-1-yl)-1-[5-[4-(2,2,2-trifluoroethoxy)phenyl]-2-pyridyl]propan-2-ol (B.1.31), 2-(2,4-difluoro- phenyl)-1,1-difluoro-3-(tetrazol-1-yl)-1-[5-[4-(trifluoromethoxy)phenyl]-2-pyridyl]propan-2-ol (B.1.32), ipfentrifluconazole (B.1.37), mefentrifluconazole (B.1.38), 2-(chloromethyl)-2-methyl-5- (p-tolylmethyl)-1-(1,2,4-triazol-1-ylmethyl)cyclopentanol (B.1.43); imidazoles: imazalil (B.1.44), pefurazoate (B.1.45), prochloraz (B.1.46), triflumizol (B.1.47); pyrimidines, pyridines, pipera- zines: fenarimol (B.1.49), pyrifenox (B.1.50), triforine (B.1.51), [3-(4-chloro-2-fluoro-phenyl)-5- (2,4-difluorophenyl)isoxazol-4-yl]-(3-pyridyl)methanol (B.1.52);
- Delta14-reductase inhibitors: aldimorph (B.2.1), dodemorph (B.2.2), dodemorph-acetate (B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7), spirox- amine (B.2.8);
- Inhibitors of 3-keto reductase: fenhexamid (B.3.1);
- Other Sterol biosynthesis inhibitors: chlorphenomizole (B.4.1);
C) Nucleic acid synthesis inhibitors
- phenylamides or acyl amino acid fungicides: benalaxyl (C.1.1), benalaxyl-M (C.1.2), kiral- axyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (C.1.5), ofurace (C.1.6), oxadixyl (C.1.7);
- other nucleic acid synthesis inhibitors: hymexazole (C.2.1), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrimidin- 4-amine (C.2.6), 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine (C.2.7), 5-fluoro- 2-(4-chlorophenylmethoxy)pyrimidin-4 amine (C.2.8);
D) Inhibitors of cell division and cytoskeleton
- tubulin inhibitors: benomyl (D.1.1), carbendazim (D.1.2), fuberidazole (D1.3), thia- bendazole (D.1.4), thiophanate-methyl (D.1.5), 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phe- nyl-pyridazine (D.1.6), 3-chloro-6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine (D.1.7), N-ethyl-2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]butanamide (D.1.8), N-ethyl-2-[(3-ethynyl-8-me- thyl-6-quinolyl)oxy]-2-methylsulfanyl-acetamide (D.1.9), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]- N-(2-fluoroethyl)butanamide (D.1.10), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-(2-fluoroethyl)-2- methoxy-acetamide (D.1.11), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-propyl-butanamide (D.1.12), 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methoxy-N-propyl-acetamide (D.1.13), 2-[(3- ethynyl-8-methyl-6-quinolyl)oxy]-2-methylsulfanyl-N-propyl-acetamide (D.1.14), 2-[(3-ethynyl-8- methyl-6-quinolyl)oxy]-N-(2-fluoroethyl)-2-methylsulfanyl-acetamide (D.1.15), 4-(2-bromo-4- fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl-pyrazol-3-amine (D.1.16);
- other cell division inhibitors: diethofencarb (D.2.1), ethaboxam (D.2.2), pencycuron (D.2.3), fluopicolide (D.2.4), zoxamide (D.2.5), metrafenone (D.2.6), pyriofenone (D.2.7);
E) Inhibitors of amino acid and protein synthesis
- methionine synthesis inhibitors: cyprodinil (E.1.1), mepanipyrim (E.1.2), pyrimethanil (E.1.3);
- protein synthesis inhibitors: blasticidin-S (E.2.1), kasugamycin (E.2.2), kasugamycin hy- drochloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6); F) Signal transduction inhibitors
- MAP / histidine kinase inhibitors: fluoroimid (F.1.1), iprodione (F.1.2), procymidone (F.1.3), vinclozolin (F.1.4), fludioxonil (F.1.5);
- G protein inhibitors: quinoxyfen (F.2.1); G) Lipid and membrane synthesis inhibitors
- Phospholipid biosynthesis inhibitors: edifenphos (G.1.1), iprobenfos (G.1.2), pyrazophos (G.1.3), isoprothiolane (G.1.4);
- lipid peroxidation: dicloran (G.2.1), quintozene (G.2.2), tecnazene (G.2.3), tolclofos-methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), etridiazole (G.2.7);
- phospholipid biosynthesis and cell wall deposition: dimethomorph (G.3.1), flumorph (G.3.2), mandipropamid (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7);
- compounds affecting cell membrane permeability and fatty acides: propamocarb (G.4.1); - inhibitors of oxysterol binding protein: oxathiapiprolin (G.5.1), 2-{3-[2-(1-{[3,5-bis(difluoro- methyl-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}phenyl methanesulfonate (G.5.2), 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4- yl) 1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate (G.5.3), 4-[1- [2-[3-(difluoromethyl)-5-methyl-pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carbox- amide (G.5.4), 4-[1-[2-[3,5-bis(difluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyri- dine-2-carboxamide (G.5.5), 4-[1-[2-[3-(difluoromethyl)-5-(trifluoromethyl)pyrazol-1-yl]acetyl]-4- piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.6), 4-[1-[2-[5-cyclopropyl-3-(difluorome- thyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.7), 4-[1-[2-[5- methyl-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.8), 4-[1-[2-[5-(difluoromethyl)-3-(trifluoromethyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1- yl-pyridine-2-carboxamide (G.5.9), 4-[1-[2-[3,5-bis(trifluoromethyl)pyrazol-1-yl]acetyl]-4-pi- peridyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.10), (4-[1-[2-[5-cyclopropyl-3-(trifluorome- thyl)pyrazol-1-yl]acetyl]-4-piperidyl]-N-tetralin-1-yl-pyridine-2-carboxamide (G.5.11);
H) Inhibitors with Multi Site Action
- inorganic active substances: Bordeaux mixture (H.1.1), copper (H.1.2), copper acetate (H.1.3), copper hydroxide (H.1.4), copper oxychloride (H.1.5), basic copper sulfate (H.1.6), sul- fur (H.1.7);
- thio- and dithiocarbamates: ferbam (H.2.1), mancozeb (H.2.2), maneb (H.2.3), metam (H.2.4), metiram (H.2.5), propineb (H.2.6), thiram (H.2.7), zineb (H.2.8), ziram (H.2.9);
- organochlorine compounds: anilazine (H.3.1), chlorothalonil (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.11);
- guanidines and others: guanidine (H.4.1), dodine (H.4.2), dodine free base (H.4.3), guazatine (H.4.4), guazatine-acetate (H.4.5), iminoctadine (H.4.6), iminoctadine-triacetate (H.4.7), iminoctadine-tris(albesilate) (H.4.8), dithianon (H.4.9), 2,6-dimethyl-1H,5H-[1,4]di- thiino[2,3-c:5,6-c']dipyrrole-1,3,5,7(2H,6H)-tetraone (H.4.10);
I) Cell wall synthesis inhibitors
- inhibitors of glucan synthesis: validamycin (I.1.1), polyoxin B (I.1.2);
- melanin synthesis inhibitors: pyroquilon (I.2.1), tricyclazole (I.2.2), carpropamid (I.2.3), di- cyclomet (I.2.4), fenoxanil (I.2.5);
J) Plant defence inducers
- acibenzolar-S-methyl (J.1.1), probenazole (J.1.2), isotianil (J.1.3), tiadinil (J.1.4), prohexa- dione-calcium (J.1.5); phosphonates: fosetyl (J.1.6), fosetyl-aluminum (J.1.7), phosphorous acid and its salts (J.1.8), calcium phosphonate (J.1.11), potassium phosphonate (J.1.12), potassium or sodium bicarbonate (J.1.9), 4-cyclopropyl-N-(2,4-dimethoxyphenyl)thiadiazole-5-carboxamide (J.1.10);
K) Unknown mode of action
- bronopol (K.1.1), chinomethionat (K.1.2), cyflufenamid (K.1.3), cymoxanil (K.1.4), dazomet (K.1.5), debacarb (K.1.6), diclocymet (K.1.7), diclomezine (K.1.8), difenzoquat (K.1.9), difen- zoquat-methylsulfate (K.1.10), diphenylamin (K.1.11), fenitropan (K.1.12), fenpyrazamine (K.1.13), flumetover (K.1.14), flusulfamide (K.1.15), flutianil (K.1.16), harpin (K.1.17), methasul- focarb (K.1.18), nitrapyrin (K.1.19), nitrothal-isopropyl (K.1.20), tolprocarb (K.1.21), oxin-copper (K.1.22), proquinazid (K.1.23), tebufloquin (K.1.24), tecloftalam (K.1.25), triazoxide (K.1.26), N’- (4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine (K.1.27), N’-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine (K.1.28), N’-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethyl- phenyl]-N-ethyl-N-methyl-formamidine (K.1.29), N’-(5-bromo-6-indan-2-yloxy-2-methyl-3- pyridyl)-N-ethyl-N-methyl-formamidine (K.1.30), N’-[5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2- methyl-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.31), N’-[5-bromo-6-(4-isopropylcyclo- hexoxy)-2-methyl-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.32), N’-[5-bromo-2-methyl-6-(1- phenylethoxy)-3-pyridyl]-N-ethyl-N-methyl-formamidine (K.1.33), N’-(2-methyl-5-trifluoromethyl- 4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine (K.1.34), N’-(5-difluorome- thyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine (K.1.35), 2- (4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide (K.1.36), 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (pyrisoxazole) (K.1.37), 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3 yl]-pyridine (K.1.38), 5-chloro-1-(4,6-di- methoxy-pyrimidin-2-yl)-2-methyl-1H-benzoimidazole (K.1.39), ethyl (Z)-3-amino-2-cyano-3- phenyl-prop-2-enoate (K.1.40), picarbutrazox (K.1.41), pentyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)- phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate (K.1.42), but-3-ynyl N-[6-[[(Z)-[(1-me- thyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate (K.1.43), 2-[2-[(7,8- difluoro-2-methyl-3-quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol (K.1.44), 2-[2-fluoro-6-[(8-fluoro-2- methyl-3-quinolyl)oxy]phen-yl]propan-2-ol (K.1.45), quinofumelin (K.1.47), 9-fluoro-2,2-dimethyl- 5-(3-quinolyl)-3H-1,4-benzoxazepine (K.1.49), 2-(6-benzyl-2-pyridyl)quinazoline (K.1.50), 2-[6- (3-fluoro-4-methoxy-phenyl)-5-methyl-2-pyridyl]quinazoline (K.1.51), dichlobentiazox (K.1.52), N’-(2,5-dimethyl-4-phenoxy-phenyl)-N-ethyl-N-methyl-formamidine (K.1.53), pyrifenamine (K.1.54).
The fungicides described by common names, their preparation and their activity e.g. against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are com- mercially available.
The active substances mentioned above, their preparation and their activity e. g. against harm- ful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available. The compounds described by IUPAC nomenclature, their preparation and their pesti- cidal activity are also known (cf. Can. J. Plant Sci.48(6), 587-94, 1968; EP-A 141317; EP- A 152031; EP-A 226917; EP-A 243970; EP-A 256503; EP-A 428941; EP-A 532022; EP-A 1028125; EP-A 1035122; EP-A 1201648; EP-A 1122244, JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; US 3,296,272; US 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501; WO 01/56358; WO 02/22583; WO 02/40431; WO 03/10149; WO 03/11853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624, WO 10/139271, WO 11/028657, WO 12/168188, WO 07/006670, WO 11/77514;
WO 13/047749, WO 10/069882, WO 13/047441, WO 03/16303, WO 09/90181, WO 13/007767, WO 13/010862, WO 13/127704, WO 13/024009, WO 13/24010, WO 13/047441,
WO 13/162072, WO 13/092224, WO 11/135833, CN 1907024, CN 1456054, CN 103387541, CN 1309897, WO 12/84812, CN 1907024, WO 09094442, WO 14/60177, WO 13/116251, WO 08/013622, WO 15/65922, WO 94/01546, EP 2865265, WO 07/129454, WO 12/165511, WO 11/081174, WO 13/47441). Some compounds are identified by their CAS Registry Number which is separated by hyphens into three parts, the first consisting from two up to seven digits, the second consisting of two digits, and the third consisting of a single digit.
Biopesticides
Suitable mixing partners for the compounds of the present invention also include biopesticides. Biopesticides have been defined as a form of pesticides based on micro-organisms (bacteria, fungi, viruses, nematodes, etc.) or natural products (compounds, such as metabolites, proteins, or extracts from biological or other natural sources) (U.S. Environmental Protection Agency: http://www.epa.gov/pesticides/biopesticides/). Biopesticides fall into two major classes, micro- bial and biochemical pesticides:
(1) Microbial pesticides consist of bacteria, fungi or viruses (and often include the metabolites that bacteria and fungi produce). Entomopathogenic nematodes are also classified as microbial pesticides, even though they are multi-cellular.
(2) Biochemical pesticides are naturally occurring substances or or structurally-similar and functionally identical to a naturally-occurring substance and extracts from biological sources that control pests or provide other crop protection uses as defined below, but have non-toxic mode of actions (such as growth or developmental regulation, attractents, repellents or defence acti- vators (e.g. induced resistance) and are relatively non-toxic to mammals.
Biopesticides for use against crop diseases have already established themselves on a variety of crops. For example, biopesticides already play an important role in controlling downy mildew diseases. Their benefits include: a 0-Day Pre-Harvest Interval, the ability to use under moderate to severe disease pressure, and the ability to use in mixture or in a rotational program with other registered pesticides.
A major growth area for biopesticides is in the area of seed treatments and soil amendments. Biopesticidal seed treatments are e.g. used to control soil borne fungal pathogens that cause seed rots, damping-off, root rot and seedling blights. They can also be used to control internal seed borne fungal pathogens as well as fungal pathogens that are on the surface of the seed. Many biopesticidal products also show capacities to stimulate plant host defenses and other physiological processes that can make treated crops more resistant to a variety of biotic and abiotic stresses or can regulate plant growth. Many biopesticidal products also show capacities to stimulate plant health, plant growth and/or yield enhancing activity.
The following list of biopesticides, in conjunction with which the compounds of the present in- vention can be used, is intended to illustrate the possible combinations but does not limit them: L) Biopesticides
L1) Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudi- nis, B. amyloliquefaciens, B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, Candida oleophila, C. saitoana, Clavi- bacter michiganensis (bacteriophages), Coniothyrium minitans, Cryphonectria parasitica, Cryp- tococcus albidus, Dilophosphora alopecuri, Fusarium oxysporum, Clonostachys rosea f. catenu- late (also named Gliocladium catenulatum), Gliocladium roseum, Lysobacter antibioticus, L. en- zymogenes, Metschnikowia fructicola, Microdochium dimerum, Microsphaeropsis ochracea, Muscodor albus, Paenibacillus alvei, Paenibacillus epiphyticus, P. polymyxa, Pantoea vagans, Penicillium bilaiae, Phlebiopsis gigantea, Pseudomonas sp., Pseudomonas chloraphis, Pseudo- zyma flocculosa, Pichia anomala, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomy- ces griseoviridis, S. lydicus, S. violaceusniger, Talaromyces flavus, Trichoderma asperelloides, T. asperellum, T. atroviride, T. fertile, T. gamsii, T. harmatum, T. harzianum, T. polysporum, T. stromaticum, T. virens, T. viride, Typhula phacorrhiza, Ulocladium oudemansii, Verticillium dahlia, zucchini yellow mosaic virus (avirulent strain);
L2) Biochemical pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity: harpin protein, Reynoutria sachalinensis extract;
L3) Microbial pesticides with insecticidal, acaricidal, molluscidal and/or nematicidal activity: Agrobacterium radiobacter, Bacillus cereus, B. firmus, B. thuringiensis, B. thuringiensis ssp. ai- zawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp. tenebrionis, Beau- veria bassiana, B. brongniartii, Burkholderia spp., Chromobacterium subtsugae, Cydia pomo- nella granulovirus (CpGV), Cryptophlebia leucotreta granulovirus (CrleGV), Flavobacterium spp., Helicoverpa armigera nucleopolyhedrovirus (HearNPV), Helicoverpa zea nucleopolyhe- drovirus (HzNPV), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV), Heterorhab- ditis bacteriophora, Isaria fumosorosea, Lecanicillium longisporum, L. muscarium, Metarhizium anisopliae, M. anisopliae var. anisopliae, M. anisopliae var. acridum, Nomuraea rileyi, Paeci- lomyces fumosoroseus, P. lilacinus, Paenibacillus popilliae, Pasteuria spp., P. nishizawae, P. penetrans, P. ramosa, P. thornea, P. usgae, Pseudomonas fluorescens, Spodoptera littoralis nucleopolyhedrovirus (SpliNPV), Steinernema carpocapsae, S. feltiae, S. kraussei, Streptomy- ces galbus, S. microflavus;
L4) Biochemical pesticides with insecticidal, acaricidal, molluscidal, pheromone and/or nemat- icidal activity: L-carvone, citral, (E,Z)-7,9-dodecadien-1-yl acetate, ethyl formate, (E,Z)-2,4-ethyl decadienoate (pear ester), (Z,Z,E)-7,11,13-hexadecatrienal, heptyl butyrate, isopropyl myristate, lavanulyl senecioate, cis-jasmone, 2-methyl 1-butanol, methyl eugenol, methyl jasmonate, (E,Z)-2,13-octadecadien-1-ol, (E,Z)-2,13-octadecadien-1-ol acetate, (E,Z)-3,13-octadecadien-1- ol, (R)-1-octen-3-ol, pentatermanone, (E,Z,Z)-3,8,11-tetradecatrienyl acetate, (Z,E)-9,12- tetradecadien-1-yl acetate, (Z)-7-tetradecen-2-one, (Z)-9-tetradecen-1-yl acetate, (Z)-11- tetradecenal, (Z)-11-tetradecen-1-ol, extract of Chenopodium ambrosiodes, Neem oil, Quillay extract;
L5) Microbial pesticides with plant stress reducing, plant growth regulator, plant growth pro- moting and/or yield enhancing activity: Azospirillum amazonense, A. brasilense, A. lipoferum, A. irakense, A. halopraeferens, Bradyrhizobium spp., B. elkanii, B. japonicum, B. liaoningense, B. lupini, Delftia acidovorans, Glomus intraradices, Mesorhizobium spp., Rhizobium legumi- nosarum bv. phaseoli, R. l. bv. trifolii, R. l. bv. viciae, R. tropici, Sinorhizobium meliloti.
The biopesticides from group L1) and/or L2) may also have insecticidal, acaricidal, molluscidal, pheromone, nematicidal, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity. The biopesticides from group L3) and/or L4) may also have fungicidal, bactericidal, viricidal, plant defense activator, plant stress reducing, plant growth regulator, plant growth promoting and/or yield enhancing activity. The biopesticides from group L5) may also have fungicidal, bactericidal, viricidal, plant defense activator, insecticidal, acaricidal, molluscidal, pheromone and/or nematicidal activity.
Many of these biopesticides have been deposited under deposition numbers mentioned herein (the prefices such as ATCC or DSM refer to the acronym of the respective culture collection, for details see e. g. here: http://www. wfcc.info/ccinfo/collection/by_acronym/), are referred to in lit- erature, registered and/or are commercially available: mixtures of Aureobasidium pullulans DSM 14940 and DSM 14941 isolated in 1989 in Konstanz, Germany (e. g. blastospores in Blos- somProtect® from bio-ferm GmbH, Austria), Azospirillum brasilense Sp245 originally isolated in wheat reagion of South Brazil (Passo Fundo) at least prior to 1980 (BR 11005; e. g. GELFIX® Gramíneas from BASF Agricultural Specialties Ltd., Brazil), A. brasilense strains Ab-V5 and Ab- V6 (e. g. in AzoMax from Novozymes BioAg Produtos papra Agricultura Ltda., Quattro Barras, Brazil or Simbiose-Maíz® from Simbiose-Agro, Brazil; Plant Soil 331, 413-425, 2010), Bacillus amyloliquefaciens strain AP-188 (NRRL B-50615 and B-50331; US 8,445,255); B. amyloliquefa- ciens spp. plantarum D747 isolated from air in Kikugawa-shi, Japan (US 20130236522 A1; FERM BP-8234; e. g. Double Nickel™ 55 WDG from Certis LLC, USA), B. amyloliquefaciens spp. plantarum FZB24 isolated from soil in Brandenburg, Germany (also called SB3615; DSM 96-2; J. Plant Dis. Prot.105, 181–197, 1998; e. g. Taegro® from Novozyme Biologicals, Inc., USA), B. amyloliquefaciens ssp. plantarum FZB42 isolated from soil in Brandenburg, Germany (DSM 23117; J. Plant Dis. Prot.105, 181–197, 1998; e. g. RhizoVital® 42 from AbiTEP GmbH, Germany), B. amyloliquefaciens ssp. plantarum MBI600 isolated from faba bean in Sutton Bon- ington, Nottinghamshire, U.K. at least before 1988 (also called 1430; NRRL B-50595;
US 2012/0149571 A1; e. g. Integral® from BASF Corp., USA), B. amyloliquefaciens spp. planta- rum QST-713 isolated from peach orchard in 1995 in California, U.S.A. (NRRL B-21661; e. g. Serenade® MAX from Bayer Crop Science LP, USA), B. amyloliquefaciens spp. plantarum TJ1000 isolated in 1992 in South Dakoda, U.S.A. (also called 1BE; ATCC BAA-390; CA
2471555 A1; e. g. QuickRoots™ from TJ Technologies, Watertown, SD, USA), B. firmus CNCM I-1582, a variant of parental strain EIP-N1 (CNCM I-1556) isolated from soil of central plain area of Israel (WO 2009/126473, US 6,406,690; e. g. Votivo® from Bayer CropScience LP, USA), B. pumilus GHA 180 isolated from apple tree rhizosphere in Mexico (IDAC 260707-01; e. g. PRO- MIX® BX from Premier Horticulture, Quebec, Canada), B. pumilus INR-7 otherwise referred to as BU-F22 and BU-F33 isolated at least before 1993 from cucumber infested by Erwinia tra- cheiphila (NRRL B-50185, NRRL B-50153; US 8,445,255), B. pumilus KFP9F isolated from the rhizosphere of grasses in South Africa at least before 2008 (NRRL B-50754; WO 2014/029697; e. g. BAC-UP or FUSION-P from BASF Agricultural Specialities (Pty) Ltd., South Africa), B. pu- milus QST 2808 was isolated from soil collected in Pohnpei, Federated States of Micronesia, in 1998 (NRRL B-30087; e. g. Sonata® or Ballad® Plus from Bayer Crop Science LP, USA), B. simplex ABU 288 (NRRL B-50304; US 8,445,255), B. subtilis FB17 also called UD 1022 or UD10-22 isolated from red beet roots in North America (ATCC PTA-11857; System. Appl. Mi- crobiol.27, 372-379, 2004; US 2010/0260735; WO 2011/109395); B. thuringiensis ssp. aizawai ABTS-1857 isolated from soil taken from a lawn in Ephraim, Wisconsin, U.S.A., in 1987 (also called ABG-6346; ATCC SD-1372; e. g. XenTari® from BioFa AG, Münsingen, Germany), B. t. ssp. kurstaki ABTS-351 identical to HD-1 isolated in 1967 from diseased Pink Bollworm black larvae in Brownsville, Texas, U.S.A. (ATCC SD-1275; e. g. Dipel® DF from Valent BioSciences, IL, USA), B. t. ssp. kurstaki SB4 isolated from E. saccharina larval cadavers (NRRL B-50753; e. g. Beta Pro® from BASF Agricultural Specialities (Pty) Ltd., South Africa), B. t. ssp. tenebrionis NB-176-1, a mutant of strain NB‑125, a wild type strain isolated in 1982 from a dead pupa of the beetle Tenebrio molitor (DSM 5480; EP 585215 B1; e. g. Novodor® from Valent BioSciences, Switzerland), Beauveria bassiana GHA (ATCC 74250; e. g. BotaniGard® 22WGP from Laver- lam Int. Corp., USA), B. bassiana JW-1 (ATCC 74040; e. g. Naturalis® from CBC (Europe) S.r.l., Italy), B. bassiana PPRI 5339 isolated from the larva of the tortoise beetle Conchyloctenia punctata (NRRL 50757; e. g. BroadBand® from BASF Agricultural Specialities (Pty) Ltd., South Africa), Bradyrhizobium elkanii strains SEMIA 5019 (also called 29W) isolated in Rio de Janeiro, Brazil and SEMIA 587 isolated in 1967 in the State of Rio Grande do Sul, from an area previ- ously inoculated with a North American isolate, and used in commercial inoculants since 1968 (Appl. Environ. Microbiol.73(8), 2635, 2007; e. g. GELFIX 5 from BASF Agricultural Specialties Ltd., Brazil), B. japonicum 532c isolated from Wisconsin field in U.S.A. (Nitragin 61A152; Can. J. Plant. Sci.70, 661-666, 1990; e. g. in Rhizoflo®, Histick®, Hicoat® Super from BASF
Agricultural Specialties Ltd., Canada), B. japonicum E-109 variant of strain USDA 138 (INTA E109, SEMIA 5085; Eur. J. Soil Biol.45, 28–35, 2009; Biol. Fertil. Soils 47, 81–89, 2011); B. ja- ponicum strains deposited at SEMIA known from Appl. Environ. Microbiol.73(8), 2635, 2007: SEMIA 5079 isolated from soil in Cerrados region, Brazil by Embrapa-Cerrados used in com- mercial inoculants since 1992 (CPAC 15; e. g. GELFIX 5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil), B. japonicum SEMIA 5080 obtained under lab condtions by Embrapa- Cerrados in Brazil and used in commercial inoculants since 1992, being a natural variant of SEMIA 586 (CB1809) originally isolated in U.S.A. (CPAC 7; e. g. GELFIX 5 or ADHERE 60 from BASF Agricultural Specialties Ltd., Brazil); Burkholderia sp. A396 isolated from soil in Nikko, Ja- pan, in 2008 (NRRL B-50319; WO 2013/032693; Marrone Bio Innovations, Inc., USA), Coni- othyrium minitans CON/M/91-08 isolated from oilseed rape (WO 1996/021358; DSM 9660; e. g. Contans® WG, Intercept® WG from Bayer CropScience AG, Germany), harpin (alpha-beta) protein (Science 257, 85-88, 1992; e. g. Messenger™ or HARP-N-Tek from Plant Health Care plc, U.K.), Helicoverpa armigera nucleopolyhedrovirus (HearNPV) (J. Invertebrate Pathol.107, 112–126, 2011; e. g. Helicovex® from Adermatt Biocontrol, Switzerland; Diplomata® from Kop- pert, Brazil; Vivus® Max from AgBiTech Pty Ltd., Queensland, Australia), Helicoverpa zea sin- gle capsid nucleopolyhedrovirus (HzSNPV) (e. g. Gemstar® from Certis LLC, USA), Heli- coverpa zea nucleopolyhedrovirus ABA-NPV-U (e. g. Heligen® from AgBiTech Pty Ltd., Queensland, Australia), Heterorhabditis bacteriophora (e. g. Nemasys® G from BASF Agricul- tural Specialities Limited, UK), Isaria fumosorosea Apopka-97 isolated from mealy bug on gynura in Apopka, Florida, U.S.A. (ATCC 20874; Biocontrol Science Technol.22(7), 747-761, 2012; e. g. PFR-97™ or PreFeRal® from Certis LLC, USA), Metarhizium anisopliae var. an- isopliae F52 also called 275 or V275 isolated from codling moth in Austria (DSM 3884, ATCC 90448; e. g. Met52® Novozymes Biologicals BioAg Group, Canada), Metschnikowia fructicola 277 isolated from grapes in the central part of Israel (US 6,994,849; NRRL Y-30752; e. g. for- merly Shemer® from Agrogreen, Israel), Paecilomyces ilacinus 251 isolated from infected nem- atode eggs in the Philippines (AGAL 89/030550; WO1991/02051; Crop Protection 27, 352-361, 2008; e. g. BioAct®from Bayer CropScience AG, Germany and MeloCon® from Certis, USA), Paenibacillus alvei NAS6G6 isolated from the rhizosphere of grasses in South Africa at least before 2008 (WO 2014/029697; NRRL B-50755; e.g. BAC-UP from BASF Agricultural Speciali- ties (Pty) Ltd., South Africa), Paenibacillus strains isolated from soil samples from a variety of European locations including Germany: P. epiphyticus Lu17015 (WO 2016/020371; DSM 26971), P. polymyxa ssp. plantarum Lu16774 (WO 2016/020371; DSM 26969), P. p. ssp.
plantarum strain Lu17007 (WO 2016/020371; DSM 26970); Pasteuria nishizawae Pn1 isolated from a soybean field in the mid-2000s in Illinois, U.S.A. (ATCC SD-5833; Federal Register 76(22), 5808, February 2, 2011; e.g. Clariva™ PN from Syngenta Crop Protection, LLC, USA), Penicillium bilaiae (also called P. bilaii) strains ATCC 18309 (= ATCC 74319), ATCC 20851 and/or ATCC 22348 (= ATCC 74318) originally isolated from soil in Alberta, Canada (Fertilizer Res.39, 97-103, 1994; Can. J. Plant Sci.78(1), 91-102, 1998; US 5,026,417,
WO 1995/017806; e. g. Jump Start®, Provide® from Novozymes Biologicals BioAg Group, Can- ada), Reynoutria sachalinensis extract (EP 0307510 B1; e. g. Regalia® SC from Marrone BioIn- novations, Davis, CA, USA or Milsana® from BioFa AG, Germany), Steinernema carpocapsae (e. g. Millenium® from BASF Agricultural Specialities Limited, UK), S. feltiae (e. g. Nemashield® from BioWorks, Inc., USA; Nemasys® from BASF Agricultural Specialities Limited, UK), Strepto- myces microflavus NRRL B-50550 (WO 2014/124369; Bayer CropScience, Germany), Tricho- derma asperelloides JM41R isolated in South Africa (NRRL 50759; also referred to as T. fertile; e. g. Trichoplus® from BASF Agricultural Specialities (Pty) Ltd., South Africa), T. harzianum T- 22 also called KRL-AG2 (ATCC 20847; BioControl 57, 687-696, 2012; e. g. Plantshield® from BioWorks Inc., USA or SabrEx™ from Advanced Biological Marketing Inc., Van Wert, OH, USA).
According to the invention, the solid material (dry matter) of the biopesticides (with the excep- tion of oils such as Neem oil) are considered as active components (e.g. to be obtained after drying or evaporation of the extraction or suspension medium in case of liquid formulations of the microbial pesticides).
In accordance with the present invention, the weight ratios and percentages used herein for a biological extract such as Quillay extract are based on the total weight of the dry content (solid material) of the respective extract(s).
The total weight ratios of compositions comprising at least one microbial pesticide in the form of viable microbial cells including dormant forms, can be determined using the amount of CFU of the respective microorganism to calclulate the total weight of the respective active component with the following equation that 1 x 1010 CFU equals one gram of total weight of the respective active component. Colony forming unit is measure of viable microbial cells, in particular fungal and bacterial cells. In addition, here“CFU” may also be understood as the number of (juvenile) individual nematodes in case of (entomopathogenic) nematode biopesticides, such as Stei- nernema feltiae.
When mixtures comprising microbial pesticides are employed in crop protection, the applica- tion rates preferably range from about 1 x 106 to 5 x 1015 (or more) CFU/ha, preferably from about 1 x 108 to about 1 x 1013 CFU/ha, and even more preferably from about 1 x 109 to about 1 x 1012 CFU/ha. In the case of (entomopathogenic) nematodes as microbial pesticides (e. g. Stei- nernema feltiae), the application rates preferably range inform about 1 x 105 to 1 x 1012 (or more), more preferably from 1 x 108 to 1 x 1011, even more preferably from 5 x 108 to 1 x 1010 individuals (e. g. in the form of eggs, juvenile or any other live stages, preferably in an infetive juvenile stage) per ha.
When mixtures comprising microbial pesticides are employed in seed treatment, the applica- tion rates with respect to plant propagation material preferably range from about 1 x 106 to 1 x 1012 (or more) CFU/seed. Preferably, the concentration is about 1 x 106 to about 1 x 109 CFU/seed. In the case of the microbial pesticides II, the application rates with respect to plant propagation material also preferably range from about 1 x 107 to 1 x 1014 (or more) CFU per 100 kg of seed, preferably from 1 x 109 to about 1 x 1012 CFU per 100 kg of seed. Formulations
The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound of the present invention or a mixture thereof.
An agrochemical composition comprises a pesticidally effective amount of a compound of the present invention or a mixture thereof. The term "pesticidally effective amount" is defined below. The compounds of the present invention or the mixtures thereof can be converted into custom- ary types of agro-chemical compositions, e. g. solutions, emulsions, suspensions, dusts, pow- ders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the “Catalogue of pesticide formulation types and international coding system”, Technical Mono- graph No.2, 6th Ed. May 2008, CropLife International.
The compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Examples for suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfac- tants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protec- tive colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimu- lants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifi- ers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil frac- tions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, al- kylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, lime- stone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammo- nium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof. Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective col- loid, or adjuvant. Examples of surfactants are listed in McCutcheon’s, Vol.1: Emulsifiers & De- tergents, McCutcheon’s Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sul-fa- tes, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl-sul- fonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfona- tes of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sul- fates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethox-ylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Exam-ples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol eth-oxylates.
Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Exam- ples of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Ex- amples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpoly- glucosides. Examples of polymeric surfactants are homo- or copolymers of vinylpyrrolidone, vi- nylalcohols, or vinylacetate.
Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block pol- ymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene ox- ide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suita- ble polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of poly- acrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyeth- yleneamines.
Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compounds of the present in- vention on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anor- ganic clays (organically modified or unmodified), polycarboxylates, and silicates.
Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazoli- nones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids. Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
Examples for composition types and their preparation are:
i) Water-soluble concentrates (SL, LS)
10-60 wt% of a compound I according to the invention and 5-15 wt% wetting agent (e.g. alco- hol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) up to 100 wt%. The active substance dissolves upon dilution with water.
ii) Dispersible concentrates (DC)
5-25 wt% of a compound I according to the invention and 1-10 wt% dispersant (e. g. polyvi- nylpyrrolidone) are dissolved in up to 100 wt% organic solvent (e.g. cyclohexanone). Dilution with water gives a dispersion.
iii) Emulsifiable concentrates (EC)
15-70 wt% of a compound I according to the invention and 5-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in up to 100 wt% water-insol- uble organic solvent (e.g. aromatic hydrocarbon). Dilution with water gives an emulsion.
iv) Emulsions (EW, EO, ES)
5-40 wt% of a compound I according to the invention and 1-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% water-insoluble organic solvent (e.g. aromatic hydrocarbon). This mixture is introduced into up to 100 wt% water by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with wa- ter gives an emulsion.
v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20-60 wt% of a compound I according to the invention are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alco- hol ethoxylate), 0,1-2 wt% thickener (e.g. xanthan gum) and up to 100 wt% water to give a fine active substance suspension. Dilution with water gives a stable suspension of the active sub- stance. For FS type composition up to 40 wt% binder (e.g. polyvinylalcohol) is added.
vi) Water-dispersible granules and water-soluble granules (WG, SG)
50-80 wt% of a compound I according to the invention are ground finely with addition of up to 100 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solu- tion of the active substance.
vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)
50-80 wt% of a compound I according to the invention are ground in a rotor-stator mill with ad- dition of 1-5 wt% dispersants (e.g. sodium lignosulfonate), 1-3 wt% wetting agents (e.g. alcohol ethoxylate) and up to 100 wt% solid carrier, e.g. silica gel. Dilution with water gives a stable dis- persion or solution of the active substance.
viii) Gel (GW, GF)
In an agitated ball mill, 5-25 wt% of a compound I according to the invention are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1-5 wt% thickener (e.g. car- boxymethylcellulose) and up to 100 wt% water to give a fine suspension of the active sub- stance. Dilution with water gives a stable suspension of the active substance.
ix) Microemulsion (ME)
5-20 wt% of a compound I according to the invention are added to 5-30 wt% organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alko- hol ethoxylate and arylphenol ethoxylate), and water up to 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
x) Microcapsules (CS)
An oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g. methyl- methacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radi-cal initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase compris- ing 5-50 wt% of a compound I according to the invention, 0-40 wt% water insolu-ble organic sol- vent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylme-thene-4,4’- diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alco- hol). The addition of a polyamine (e.g. hexamethylenediamine) results in the for-mation of a pol- yurea microcapsule. The monomers amount to 1-10 wt%. The wt% relate to the total CS com- position.
xi) Dustable powders (DP, DS)
1-10 wt% of a compound I according to the invention are ground finely and mixed intimately with up to 100 wt% solid carrier, e.g. finely divided kaolin.
xii) Granules (GR, FG)
0.5-30 wt% of a compound I according to the invention is ground finely and associated with up to 100 wt% solid carrier (e.g. silicate). Granulation is achieved by extrusion, spray-drying or the fluidized bed.
xiii) Ultra-low volume liquids (UL)
1-50 wt% of a compound I according to the invention are dissolved in up to 100 wt% organic solvent, e.g. aromatic hydrocarbon.
The compositions types i) to xi) may optionally comprise further auxiliaries, such as 0.1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1-1 wt% anti-foaming agents, and 0.1-1 wt% col- orants.
The agrochemical compositions generally comprise between 0.01 and 95%, preferably be- tween 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active sub-stance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immedi- ately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:10 to 10:1.
The user applies the composition according to the invention usually from a predosage de-vice, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochem- ical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition ac- cording to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
According to one embodiment, individual components of the composition according to the in- vention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
In a further embodiment, either individual components of the composition according to the in- vention or partially premixed components, e. g. components comprising compounds of the pre- sent invention and/or mixing partners as defined above, may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.
In a further embodiment, either individual components of the composition according to the in- vention or partially premixed components, e. g. components comprising compounds of the pre- sent invention and/or mixing partners as defined above, can be applied jointly (e.g. after tank mix) or consecutively. Application methods
The compounds of the present invention are suitable for use in protecting crops, plants, plant propagation materials, such as seeds, or soil or water, in which the plants are growing, from at- tack or infestation by animal pests. Therefore, the present invention also relates to a plant pro- tection method, which comprises contacting crops, plants, plant propagation materials, such as seeds, or soil or water, in which the plants are growing, to be protected from attack or infesta- tion by animal pests, with a pesticidally effective amount of a compound of the present inven- tion.
The compounds of the present invention are also suitable for use in combating or controlling animal pests. Therefore, the present invention also relates to a method of combating or control- ling animal pests, which comprises contacting the animal pests, their habitat, breeding ground, or food supply, or the crops, plants, plant propagation materials, such as seeds, or soil, or the area, material or environment in which the animal pests are growing or may grow, with a pesti- cidally effective amount of a compound of the present invention.
The compounds of the present invention are effective through both contact and ingestion. Fur- thermore, the compounds of the present invention can be applied to any and all developmental stages, such as egg, larva, pupa, and adult.
The compounds of the present invention can be applied as such or in form of compositions comprising them as defined above. Furthermore, the compounds of the present invention can be applied together with a mixing partner as defined above or in form of compositions compris- ing said mixtures as defined above. The components of said mixture can be applied simultane- ously, jointly or separately, or in succession, that is immediately one after another and thereby creating the mixture“in situ” on the desired location, e.g. the plant, the sequence, in the case of separate application, generally not having any effect on the result of the control measures. The application can be carried out both before and after the infestation of the crops, plants, plant propagation materials, such as seeds, soil, or the area, material or environment by the pests.
Suitable application methods include inter alia soil treatment, seed treatment, in furrow appli- cation, and foliar application. Soil treatment methods include drenching the soil, drip irrigation (drip application onto the soil), dipping roots, tubers or bulbs, or soil injection. Seed treatment techniques include seed dressing, seed coating, seed dusting, seed soaking, and seed pellet- ing. In furrow applications typically include the steps of making a furrow in cultivated land, seed- ing the furrow with seeds, applying the pesticidally active compound to the furrow, and closing the furrow. Foliar application refers to the application of the pesticidally active compound to plant foliage, e.g. through spray equipment. For foliar applications, it can be advantageous to modify the behavior of the pests by use of pheromones in combination with the compounds of the present invention. Suitable pheromones for specific crops and pests are known to a skilled person and publicly available from databases of pheromones and semiochemicals, such as http://www.pherobase.com.
As used herein, the term "contacting" includes both direct contact (applying the com- pounds/compositions directly on the animal pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus, i.e. habi- tat, breeding ground, plant, seed, soil, area, material or environment in which a pest is growing or may grow, of the animal pest or plant).
The term“animal pest” includes arthropods, gastropods, and nematodes. Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, in particular insects. Insects, which are of particular relevance for crops, are typically referred to as crop in- sect pests.
The term "crop" refers to both, growing and harvested crops.
The term“plant” includes cereals, e.g. durum and other wheat, rye, barley, triticale, oats, rice, or maize (fodder maize and sugar maize / sweet and field corn); beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, nec- tarines, almonds, cherries, papayas, strawberries, raspberries, blackberries or gooseberries; le- guminous plants, such as beans, lentils, peas, alfalfa or soybeans; oil plants, such as rapeseed (oilseed rape), turnip rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, pumpkins, cucumber or mel- ons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grape- fruits or mandarins; vegetables, such as eggplant, spinach, lettuce (e.g. iceb33erg lettuce), chic- ory, cabbage, asparagus, cabbages, carrots, onions, garlic, leeks, tomatoes, potatoes, cucurbits or sweet peppers; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rapeseed, sugar cane or oil palm; tobacco; nuts, e.g. walnuts; pistachios; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers (e.g. carnation, petunias, geranium/pelargoniums, pansies and impatiens), shrubs, broad-leaved trees (e.g. poplar) or evergreens, e.g. conifers; eucalyptus; turf; lawn; grass such as grass for animal feed or ornamental uses. Preferred plants include potatoes sugar beets, to- bacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rapeseed, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
The term "cultivated plants" is to be understood as including plants which have been modified by mutagenesis or genetic engineering in order to provide a new trait to a plant or to modify an already present trait. Mutagenesis includes techniques of random mutagenesis using X-rays or mutagenic chemicals, but also techniques of targeted mutagenesis, in order to create mutations at a specific locus of a plant genome. Targeted mutagenesis techniques frequently use oligonucleotides or proteins like CRISPR/Cas, zinc-finger nucleases, TALENs or meganucleases to achieve the targeting effect. Genetic engineering usually uses recombinant DNA techniques to create modifications in a plant genome which under natural circumstances cannot readily be obtained by cross breeding, mutagenesis or natural recombination. Typically, one or more genes are integrated into the ge- nome of a plant in order to add a trait or improve a trait. These integrated genes are also re- ferred to as transgenes in the art, while plant comprising such transgenes are referred to as transgenic plants. The process of plant transformation usually produces several transformation events, wich differ in the genomic locus in which a transgene has been integrated. Plants com- prising a specific transgene on a specific genomic locus are usually described as comprising a specific“event”, which is referred to by a specific event name. Traits which have been intro- duced in plants or hae been modified include in particular herbicide tolerance, insect resistance, increased yield and tolerance to abiotic conditions, like drought.
Herbicide tolerance has been created by using mutagenesis as well as using genetic engineer- ing. Plants which have been rendered tolerant to acetolactate synthase (ALS) inhibitor herbi- cides by conventional methods of mutagenesis and breeding comprise plant varieties commer- cially available under the name Clearfield®. However, most of the herbicide tolerance traits have been created via the use of transgenes.
Herbicide tolerance has been created to glyphosate, glufosinate, 2,4-D, dicamba, oxynil herbi- cides, like bromoxynil and ioxynil, sulfonylurea herbicides, ALS inhibitor herbicides and 4-hy- droxyphenylpyruvate dioxygenase (HPPD) inhibitors, like isoxaflutole and mesotrione.
Transgenes wich have been used to provide herbicide tolerance traits comprise: for tolerance to glyphosate: cp4 epsps, epsps grg23ace5, mepsps, 2mepsps, gat4601, gat4621 and goxv247, for tolerance to glufosinate: pat and bar, for tolerance to 2,4-D: aad-1 and aad-12, for tolerance to dicamba: dmo, for tolerance to oxynil herbicies: bxn, for tolerance to sulfonylurea herbicides: zm-hra, csr1-2, gm-hra, S4-HrA, for tolerance to ALS inhibitor herbicides: csr1-2, for tolerance to HPPD inhibitor herbicides: hppdPF, W336 and avhppd-03.
Transgenic corn events comprising herbicide tolerance genes are for example, but not exclud- ing others, DAS40278, MON801, MON802, MON809, MON810, MON832, MON87411, MON87419, MON87427, MON88017, MON89034, NK603, GA21, MZHG0JG, HCEM485, VCO- Ø1981-5, 676, 678, 680, 33121, 4114, 59122, 98140, Bt10, Bt176, CBH-351, DBT418, DLL25, MS3, MS6, MZIR098, T25, TC1507 and TC6275.
Transgenic soybean events comprising herbicide tolerance genes are for example, but not ex- cluding others, GTS 40-3-2, MON87705, MON87708, MON87712, MON87769, MON89788, A2704-12, A2704-21, A5547-127, A5547-35, DP356043, DAS44406-6, DAS68416-4, DAS- 81419-2, GU262, SYHTØH2, W62, W98, FG72 and CV127.
Transgenic cotton events comprising herbicide tolerance genes are for example, but not exclud- ing others, 19-51a, 31707, 42317, 81910, 281-24-236, 3006-210-23, BXN10211, BXN10215, BXN10222, BXN10224, MON1445, MON1698, MON88701, MON88913, GHB119, GHB614, LLCotton25, T303-3 and T304-40. Transgenic canola events comprising herbicide tolerance genes are for example, but not ex- cluding others, MON88302, HCR-1, HCN10, HCN28, HCN92, MS1, MS8, PHY14, PHY23, PHY35, PHY36, RF1, RF2 and RF3.
Insect resistance has mainly been created by transferring bacterial genes for insecticidal pro- teins to plants. Transgenes which have most frequently been used are toxin genes of Bacillus spec. and synthetic variants thereof, like cry1A, cry1Ab, cry1Ab-Ac, cry1Ac, cry1A.105, cry1F, cry1Fa2, cry2Ab2, cry2Ae, mcry3A, ecry3.1Ab, cry3Bb1, cry34Ab1, cry35Ab1, cry9C, vip3A(a), vip3Aa20. However, also genes of plant origin have been transferred to other plants. In particu- lar genes coding for protease inhibitors, like CpTI and pinII. A further approach uses transgenes in order to produce double stranded RNA in plants to target and downregulate insect genes. An example for such a transgene is dvsnf7.
Transgenic corn events comprising genes for insecticidal proteins or double stranded RNA are for example, but not excluding others, Bt10, Bt11, Bt176, MON801, MON802, MON809, MON810, MON863, MON87411, MON88017, MON89034, 33121, 4114, 5307, 59122, TC1507, TC6275, CBH-351, MIR162, DBT418 and MZIR098.
Transgenic soybean events comprising genes for insecticidal proteins are for example, but not excluding others, MON87701, MON87751 and DAS-81419.
Transgenic cotton events comprising genes for insecticidal proteins are for example, but not ex- cluding others, SGK321, MON531, MON757, MON1076, MON15985, 31707, 31803, 31807, 31808, 42317, BNLA-601, Event1, COT67B, COT102, T303-3, T304-40, GFM Cry1A, GK12, MLS 9124, 281-24-236, 3006-210-23, GHB119 and SGK321.
Increased yield has been created by increasing ear biomass using the transgene athb17, being present in corn event MON87403, or by enhancing photosynthesis using the transgene bbx32, being present in the soybean event MON87712.
Cultivated plants comprising a modified oil content have been created by using the transgenes: gm-fad2-1, Pj.D6D, Nc.Fad3, fad2-1A and fatb1-A. Soybean events comprising at least one of these genes are: 260-05, MON87705 and MON87769.
Tolerance to abiotic conditions, in particular to tolerance to drought, has been created by using the transgene cspB, comprised by the corn event MON87460 and by using the transgene Hahb- 4, comprised by soybean event IND-ØØ41Ø-5.
Traits are frequently combined by combining genes in a transformation event or by combining different events during the breeding process. Preferred combination of traits are herbicide toler- ance to different groups of herbicides, insect tolerance to different kind of insects, in particular tolerance to lepidopteran and coleopteran insects, herbicide tolerance with one or several types of insect resistance, herbicide tolerance with increased yield as well as a combination of herbi- cide tolerance and tolerance to abiotic conditions.
Plants comprising singular or stacked traits as well as the genes and events providing these traits are well known in the art. For example, detailed information as to the mutagenized or inte- grated genes and the respective events are available from websites of the organizations“Inter- national Service for the Acquisition of Agri-biotech Applications (ISAAA)”
(http://www.isaaa.org/gmapprovaldatabase) and the“Center for Environmental Risk Assess- ment (CERA)” (http://cera-gmc.org/GMCropDatabase), Further information on specific events and methods to detect them can be found for canola events MS1, MS8, RF3, GT73,
MON88302, KK179 in WO01/031042, WO01/041558, WO01/041558, WO02/036831, WO11/153186, WO13/003558, for cotton events MON1445, MON15985,
MON531(MON15985), LLCotton25, MON88913, COT102, 281-24-236, 3006-210-23, COT67B, GHB614, T304-40, GHB119, MON88701, 81910 in WO02/034946, WO02/100163,
WO02/100163, WO03/013224, WO04/072235, WO04/039986, WO05/103266, WO05/103266, WO06/128573, WO07/017186, WO08/122406, WO08/151780, WO12/134808, WO13/112527, for corn events GA21, MON810, DLL25, TC1507, MON863, MIR604, LY038, MON88017, 3272, 59122, NK603, MIR162, MON89034, 98140, 32138, MON87460, 5307, 4114, MON87427, DAS40278, MON87411, 33121, MON87403, MON87419 in WO98/044140, US02/102582, US03/126634, WO04/099447, WO04/011601, WO05/103301, WO05/061720, WO05/059103, WO06/098952, WO06/039376, US2007/292854, WO07/142840, WO07/140256,
WO08/112019, WO09/103049, WO09/111263, WO10/077816, WO11/084621, WO11/062904, WO11/022469, WO13/169923, WO14/116854, WO15/053998, WO15/142571, for potato events E12, F10, J3, J55, V11, X17, Y9 in WO14/178910, WO14/178913, WO14/178941,
WO14/179276, WO16/183445, WO17/062831, WO17/062825, for rice events LLRICE06, LLRICE601, LLRICE62 in WO00/026345, WO00/026356, WO00/026345 for soybean events H7-1, MON89788, A2704-12, A5547-127, DP305423, DP356043, MON87701, MON87769, CV127, MON87705, DAS68416-4, MON87708, MON87712, SYHT0H2, DAS81419, DAS81419 x DAS44406-6, MON87751 in WO04/074492, WO06/130436, WO06/108674, WO06/108675, WO08/054747, WO08/002872, WO09/064652, WO09/102873, WO10/080829, WO10/037016, WO11/066384, WO11/034704, WO12/051199, WO12/082548, WO13/016527, WO13/016516, WO14/201235.
The use of compositions according to the invention on cultivated plants may result in effects which are specific to a cultivated plant comprising a certain gene or event. These effects might involve changes in growth behavior or changed resistance to biotic or abiotic stress factors. Such effects may in particular comprise enhanced yield, enhanced resistance or tolerance to insects, nematodes, fungal, bacterial, mycoplasma, viral or viroid pathogens as well as early vigour, early or delayed ripening, cold or heat tolerance as well as changed amino acid or fatty acid spectrum or content.
It has surprisingly been found that the pesticidal activity of the compounds of the present inven- tion may be enhanced by the insecticidal trait of a modified plant. Furthermore, it has been found that the compounds of the present invention are suitable for preventing insects to become resistant to the insecticidal trait or for combating pests, which already have become resistant to the insecticidal trait of a modified plant. Moreover, the compounds of the present invention are suitable for combating pests, against which the insecticidal trait is not effective, so that a com- plementary insecticidal activity can advantageously be used.
The term "plant propagation material" refers to all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e.g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhi- zomes, shoots, sprouts and other parts of plants. Seedlings and young plants, which are to be transplanted after germination or after emergence from soil, may also be included. These plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting. The term“seed” embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like, and means in a preferred embodiment true seeds.
In general, "pesticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various compounds/composi- tions used in the invention. A pesticidally effective amount of the compositions will also vary ac- cording to the prevailing conditions such as desired pesticidal effect and duration, weather, tar- get species, locus, mode of application, and the like.
In the case of soil treatment, in furrow application or of application to the pests dwelling place or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m2, preferably from 0.001 to 20 g per 100 m2.
For use in treating crop plants, e.g. by foliar application, the rate of application of the active in- gredients of this invention may be in the range of 0.0001 g to 4000 g per hectare, e.g. from 1 g to 2 kg per hectare or from 1 g to 750 g per hectare, desirably from 1 g to 100 g per hectare, more desirably from 10 g to 50 g per hectare, e.g., 10 to 20 g per hectare, 20 to 30 g per hec- tare, 30 to 40 g per hectare, or 40 to 50 g per hectare. The compounds of the invention are particularly suitable for use in the treatment of seeds in order to protect the seeds from insect pests, in particular from soil-living insect pests, and the resulting seedling’s roots and shoots against soil pests and foliar insects. The invention there- fore also relates to a method for the protection of seeds from insects, in particular from soil in- sects, and of the seedling's roots and shoots from insects, in particular from soil and foliar in- sects, said method comprising treating the seeds before sowing and/or after pregermination with a compound of the invention. The protection of the seedling's roots and shoots is preferred. More preferred is the protection of seedling’s shoots from piercing and sucking insects, chewing insects and nematodes.
The term“seed treatment” comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking, seed pelleting, and in-furrow application methods. Preferably, the seed treatment application of the active compound is car- ried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.
The invention also comprises seeds coated with or containing the active compound. The term "coated with and/or containing" generally signifies that the active ingredient is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application. When the said propagation product is (re)planted, it may absorb the active ingredi- ent.
Suitable seed is for example seed of cereals, root crops, oil crops, vegetables, spices, orna- mentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, ba- nanas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pan- sies and impatiens.
In addition, the active compound may also be used for the treatment of seeds from plants, which have been modified by mutagenisis or genetic engineering, and which e.g. tolerate the action of herbicides or fungicides or insecticides. Such modified plants have been described in detail above.
Conventional seed treatment formulations include for example flowable concentrates FS, solu- tions LS, suspoemulsions (SE), powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the lat- ter. Preferably, the formulations are applied such that germination is not included.
The active substance concentrations in ready-to-use formulations, which may be obtained af- ter two-to-tenfold dilution, are preferably from 0.01 to 60% by weight, more preferably from 0.1 to 40 % by weight.
In a preferred embodiment a FS formulation is used for seed treatment. Typically, a FS formu- lation may comprise 1-800 g/l of active ingredient, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
Especially preferred FS formulations of the compounds of the invention for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/l) of the active ingredient, from 0.1 to 20 % by weight (1 to 200 g/l) of at least one surfactant, e.g.0.05 to 5 % by weight of a wetter and from 0.5 to 15 % by weight of a dispersing agent, up to 20 % by weight, e.g. from 5 to 20 % of an anti-freeze agent, from 0 to 15 % by weight, e.g.1 to 15 % by weight of a pigment and/or a dye, from 0 to 40 % by weight, e.g.1 to 40 % by weight of a binder (sticker /adhesion agent), optionally up to 5 % by weight, e.g. from 0.1 to 5 % by weight of a thickener, optionally from 0.1 to 2 % of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1 % by weight and a filler/vehicle up to 100 % by weight. In the treatment of seed, the application rates of the compounds of the invention are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, more preferably from 1 g to 1000 g per 100 kg of seed and in particular from 1 g to 200 g per 100 kg of seed, e.g. from 1 g to 100 g or from 5 g to 100 g per 100 kg of seed.
The invention therefore also relates to seed comprising a compound of the invention, or an ag- riculturally useful salt thereof, as defined herein. The amount of the compound of the invention or the agriculturally useful salt thereof will in general vary from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed. For specific crops such as lettuce the rate can be higher. The compounds of the invention may also be used for improving the health of a plant. There- fore, the invention also relates to a method for improving plant health by treating a plant, plant propagation material and/or the locus where the plant is growing or is to grow with an effective and non-phytotoxic amount of a compound of the invention. As used herein“an effective and non-phytotoxic amount” means that the compound is used in a quantity which allows to obtain the desired effect but which does not give rise to any phyto- toxic symptom on the treated plant or on the plant grown from the treated propagule or treated soil.
The terms“plant” and“plant propagation material” are defined above.
"Plant health" is defined as a condition of the plant and/or its products which is determined by several aspects alone or in combination with each other such as yield (for example increased biomass and/or increased content of valuable ingredients), quality (for example improved con- tent or composition of certain ingredients or shelf life), plant vigour (for example improved plant growth and/or greener leaves (“greening effect”), tolerance to abiotic (for example drought) and/or biotic stress (for example disease) and production efficiency (for example, harvesting ef- ficiency, processability).
The above identified indicators for the health condition of a plant may be interdependent and may result from each other. Each indicator is defined in the art and can be determined by meth- ods known to a skilled person. The compounds of the invention are also suitable for use against non-crop insect pests. For use against said non-crop pests, compounds of the invention can be used as bait composition, gel, general insect spray, aerosol, as ultra-low volume application and bed net (impregnated or surface applied). Furthermore, drenching and rodding methods can be used.
As used herein, the term“non-crop insect pest” refers to pests, which are particularly relevant for non-crop targets, such as ants, termites, wasps, flies, ticks, mosquitos, crickets, or cock- roaches.
The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). The bait employed in the composition is a product, which is sufficiently attractive to incite insects such as ants, ter- mites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it. The attractiveness can be manipulated by using feeding stimulants or sex pheromones. Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, in- sect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyor- ganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature (e.g. http://www.phero- base.com), and are known to those skilled in the art.
For use in bait compositions, the typical content of active ingredient is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compound.
Formulations of the compounds of the invention as aerosols (e.g in spray cans), oil sprays or pump sprays are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are preferably composed of the active compound, solvents, furthermore auxiliaries such as emulsifiers, perfume oils, if appropriate sta- bilizers, and, if required, propellants.
The oil spray formulations differ from the aerosol recipes in that no propellants are used.
For use in spray compositions, the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %. The compounds of the invention and its respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems.
Methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with compounds of the invention and its respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like. Insecticidal compositions for application to fibers, fabric, knitgoods, nonwovens, netting material or foils and tarpaulins prefer- ably comprise a mixture including the insecticide, optionally a repellent and at least one binder. The compounds of the invention and its compositions can be used for protecting wooden ma- terials such as trees, board fences, sleepers, frames, artistic artifacts, etc. and buildings, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or hu- man being (e.g. when the pests invade into houses and public facilities).
Customary application rates in the protection of materials are, for example, from 0.001 g to 2000 g or from 0.01 g to 1000 g of active compound per m2 treated material, desirably from 0.1 g to 50 g per m2.
Insecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and/or insecticide. Pests
The compounds of the the invention are especially suitable for efficiently combating animal pests such as arthropods, gastropods and nematodes including but not limited to:
insects from the order of Lepidoptera, for example Achroia grisella, Acleris spp. such as A. fim- briana, A. gloverana, A. variana; Acrolepiopsis assectella, Acronicta major, Adoxophyes spp. such as A. cyrtosema, A. orana; Aedia leucomelas, Agrotis spp. such as A. exclamationis, A. fucosa, A. ipsilon, A. orthogoma, A. segetum, A. subterranea; Alabama argillacea, Aleurodicus dispersus, Alsophila pometaria, Ampelophaga rubiginosa, Amyelois transitella, Anacampsis sar- citella, Anagasta kuehniella, Anarsia lineatella, Anisota senatoria, Antheraea pernyi, Anticarsia (=Thermesia) spp. such as A. gemmatalis; Apamea spp., Aproaerema modicella, Archips spp. such as A. argyrospila, A. fuscocupreanus, A. rosana, A. xyloseanus; Argyresthia conjugella, Argyroploce spp., Argyrotaenia spp. such as A. velutinana; Athetis mindara, Austroasca viridi- grisea, Autographa gamma, Autographa nigrisigna, Barathra brassicae, Bedellia spp., Bonagota salubricola, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp. such as C. murinana, C. podana; Cactoblastis cactorum, Cadra cautella, Calingo brazilien- sis, Caloptilis theivora, Capua reticulana, Carposina spp. such as C. niponensis, C. sasakii; Ce- phus spp., Chaetocnema aridula, Cheimatobia brumata, Chilo spp. such as C. Indicus, C. sup- pressalis, C. partellus; Choreutis pariana, Choristoneura spp. such as C. conflictana, C. fumife- rana, C. longicellana, C. murinana, C. occidentalis, C. rosaceana; Chrysodeixis (=Pseudoplusia) spp. such as C. eriosoma, C. includens; Cirphis unipuncta, Clysia ambiguella, Cnaphalocerus spp., Cnaphalocrocis medinalis, Cnephasia spp., Cochylis hospes, Coleophora spp., Colias eu- rytheme, Conopomorpha spp., Conotrachelus spp., Copitarsia spp., Corcyra cephalonica, Crambus caliginosellus, Crambus teterrellus, Crocidosema (=Epinotia) aporema, Cydalima (=Diaphania) perspectalis, Cydia (=Carpocapsa) spp. such as C. pomonella, C. latiferreana; Da- laca noctuides, Datana integerrima, Dasychira pinicola, Dendrolimus spp. such as D. pini, D. spectabilis, D. sibiricus; Desmia funeralis, Diaphania spp. such as D. nitidalis, D. hyalinata; Di- atraea grandiosella, Diatraea saccharalis, Diphthera festiva, Earias spp. such as E. insulana, E. vittella; Ecdytolopha aurantianu, Egira (=Xylomyges) curialis, Elasmopalpus lignosellus, Eldana saccharina, Endopiza viteana, Ennomos subsignaria, Eoreuma loftini, Ephestia spp. such as E. cautella, E. elutella, E. kuehniella; Epinotia aporema, Epiphyas postvittana, Erannis tiliaria, Erio- nota thrax, Etiella spp., Eulia spp., Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Faronta albilinea, Feltia spp. such as F. subterranean; Galleria mellonella, Gracillaria spp., Grapholita spp. such as G. funebrana, G. molesta, G. inopinata; Halysidota spp., Harrisina americana, Hedylepta spp., Helicoverpa spp. such as H. armigera (=Heliothis armigera), H. zea (=Heliothis zea); Heliothis spp. such as H. assulta, H. subflexa, H. virescens; Hellula spp. such as H. undalis, H. rogatalis; Helocoverpa gelotopoeon, Hemileuca oliviae, Her- petogramma licarsisalis, Hibernia defoliaria, Hofmannophila pseudospretella, Homoeosoma electellum, Homona magnanima, Hypena scabra, Hyphantria cunea, Hyponomeuta padella, Hyponomeuta malinellus, Kakivoria flavofasciata, Keiferia lycopersicella, Lambdina fiscellaria fiscellaria, Lambdina fiscellaria lugubrosa, Lamprosema indicata, Laspeyresia molesta, Legumi- nivora glycinivorella, Lerodea eufala, Leucinodes orbonalis, Leucoma salicis, Leucoptera spp. such as L. coffeella, L. scitella; Leuminivora lycinivorella, Lithocolletis blancardella, Lithophane antennata, Llattia octo (=Amyna axis), Lobesia botrana, Lophocampa spp., Loxagrotis albicosta, Loxostege spp. such as L. sticticalis, L. cereralis; Lymantria spp. such as L. dispar, L. monacha; Lyonetia clerkella, Lyonetia prunifoliella, Malacosoma spp. such as M. americanum, M. californi- cum, M. constrictum, M. neustria; Mamestra spp. such as M. brassicae, M. configurata; Mam- stra brassicae, Manduca spp. such as M. quinquemaculata, M. sexta; Marasmia spp, Marmara spp., Maruca testulalis, Megalopyge lanata, Melanchra picta, Melanitis leda, Mocis spp. such as M. lapites, M. repanda; Mocis latipes, Monochroa fragariae, Mythimna separata, Nemapogon cloacella, Neoleucinodes elegantalis, Nepytia spp., Nymphula spp., Oiketicus spp., Omiodes in- dicata, Omphisa anastomosalis, Operophtera brumata, Orgyia pseudotsugata, Oria spp., Ortha- ga thyrisalis, Ostrinia spp. such as O. nubilalis; Oulema oryzae, Paleacrita vernata, Panolis flammea, Parnara spp., Papaipema nebris, Papilio cresphontes, Paramyelois transitella, Paran- threne regalis, Paysandisia archon, Pectinophora spp. such as P. gossypiella; Peridroma sau- cia, Perileucoptera spp., such as P. coffeella; Phalera bucephala, Phryganidia californica, Phthorimaea spp. such as P. operculella; Phyllocnistis citrella, Phyllonorycter spp. such as P. blancardella, P. crataegella, P. issikii, P. ringoniella; Pieris spp. such as P. brassicae, P. rapae, P. napi; Pilocrocis tripunctata, Plathypena scabra, Platynota spp. such as P. flavedana, P. idae- usalis, P. stultana; Platyptilia carduidactyla, Plebejus argus, Plodia interpunctella, Plusia spp, Plutella maculipennis, Plutella xylostella, Pontia protodica, Prays spp., Prodenia spp., Proxenus lepigone, Pseudaletia spp. such as P. sequax, P. unipuncta; Pyrausta nubilalis, Rachiplusia nu, Richia albicosta, Rhizobius ventralis, Rhyacionia frustrana, Sabulodes aegrotata, Schizura con- cinna, Schoenobius spp., Schreckensteinia festaliella, Scirpophaga spp. such as S. incertulas, S. innotata; Scotia segetum, Sesamia spp. such as S. inferens, Seudyra subflava, Sitotroga ce- realella, Sparganothis pilleriana, Spilonota lechriaspis, S. ocellana, Spodoptera (=Lamphygma) spp. such as S. cosmoides, S. eridania, S. exigua, S. frugiperda, S. latisfascia, S. littoralis, S. litura, S. omithogalli; Stigmella spp., Stomopteryx subsecivella, Strymon bazochii, Sylepta dero- gata, Synanthedon spp. such as S. exitiosa, Tecia solanivora, Telehin licus, Thaumatopoea pityocampa, Thaumatotibia (=Cryptophlebia) leucotreta, Thaumetopoea pityocampa, Thecla spp., Theresimima ampelophaga, Thyrinteina spp, Tildenia inconspicuella, Tinea spp. such as T. cloacella, T. pellionella; Tineola bisselliella, Tortrix spp. such as T. viridana; Trichophaga ta- petzella, Trichoplusia spp. such as T. ni; Tuta (=Scrobipalpula) absoluta, Udea spp. such as U. rubigalis, U. rubigalis; Virachola spp., Yponomeuta padella, and Zeiraphera canadensis;
insects from the order of Coleoptera, for example Acalymma vittatum, Acanthoscehdes obtec- tus, Adoretus spp., Agelastica alni, Agrilus spp. such as A. anxius, A. planipennis, A. sinuatus; Agriotes spp. such as A. fuscicollis, A. lineatus, A. obscurus; Alphitobius diaperinus, Amphimal- lus solstitialis, Anisandrus dispar, Anisoplia austriaca, Anobium punctatum, Anomala corpulen- ta, Anomala rufocuprea, Anoplophora spp. such as A. glabripennis; Anthonomus spp. such as A. eugenii, A. grandis, A. pomorum; Anthrenus spp., Aphthona euphoridae, Apion spp., Apogo- nia spp., Athous haemorrhoidalis, Atomaria spp. such as A. linearis; Attagenus spp., Aulaco- phora femoralis, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp. such as B. lentis, B. pisorum, B. rufimanus; Byctiscus betulae, Callidiellum rufipenne, Callopis- tria floridensis, Callosobruchus chinensis, Cameraria ohridella, Cassida nebulosa, Cerotoma tri- furcata, Cetonia aurata, Ceuthorhynchus spp. such as C. assimilis, C. napi; Chaetocnema tibi- alis, Cleonus mendicus, Conoderus spp. such as C. vespertinus; Conotrachelus nenuphar, Cos- mopolites spp., Costelytra zealandica, Crioceris asparagi, Cryptolestes ferrugineus, Cryptorhyn- chus lapathi, Ctenicera spp. such as C. destructor; Curculio spp., Cylindrocopturus spp., Cyclo- cephala spp., Dactylispa balyi, Dectes texanus, Dermestes spp., Diabrotica spp. such as D. un- decimpunctata, D. speciosa, D. longicornis, D. semipunctata, D. virgifera; Diaprepes abbrevi- ates, Dichocrocis spp., Dicladispa armigera, Diloboderus abderus, Diocalandra frumenti (Diocal- andra stigmaticollis), Enaphalodes rufulus, Epilachna spp. such as E. varivestis, E. vigintioc- tomaculata; Epitrix spp. such as E. hirtipennis, E. similaris; Eutheola humilis, Eutinobothrus bra- siliensis, Faustinus cubae, Gibbium psylloides, Gnathocerus cornutus, Hellula undalis, Heter- onychus arator, Hylamorpha elegans, Hylobius abietis, Hylotrupes bajulus, Hypera spp. such as H. brunneipennis, H. postica; Hypomeces squamosus, Hypothenemus spp., Ips typographus, Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lema spp. such as L. bilineata, L. melanopus; Leptinotarsa spp. such as L. decemlineata; Leptispa pygmaea, Limonius californicus, Lissorhoptrus oryzophilus, Lixus spp., Luperodes spp., Lyctus spp. such as L. bruneus; Liogenys fuscus, Macrodactylus spp. such as M. subspinosus; Mala- dera matrida, Megaplatypus mutates, Megascelis spp., Melanotus communis, Meligethes spp. such as M. aeneus; Melolontha spp. such as M. hippocastani, M. melolontha; Metamasius he- mipterus, Microtheca spp., Migdolus spp. such as M. fryanus, Monochamus spp. such as M. al- ternatus; Naupactus xanthographus, Niptus hololeucus, Oberia brevis, Oemona hirta, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorrhynchus sulcatus, Otior- rhynchus ovatus, Otiorrhynchus sulcatus, Oulema melanopus, Oulema oryzae, Oxycetonia ju- cunda, Phaedon spp. such as P. brassicae, P. cochleariae; Phoracantha recurva, Phyllobius pyri, Phyllopertha horticola, Phyllophaga spp. such as P. helleri; Phyllotreta spp. such as P. chrysocephala, P. nemorum, P. striolata, P. vittula; Phyllopertha horticola, Popillia japonica, Premnotrypes spp., Psacothea hilaris, Psylliodes chrysocephala, Prostephanus truncates, Psyl- liodes spp., Ptinus spp., Pulga saltona, Rhizopertha dominica, Rhynchophorus spp. such as R. billineatus, R. ferrugineus, R. palmarum, R. phoenicis, R. vulneratus; Saperda candida, Scolytus schevyrewi, Scyphophorus acupunctatus, Sitona lineatus, Sitophilus spp. such as S. granaria, S. oryzae, S. zeamais; Sphenophorus spp. such as S. levis; Stegobium paniceum, Sternechus spp. such as S. subsignatus; Strophomorphus ctenotus, Symphyletes spp., Tany- mecus spp., Tenebrio molitor, Tenebrioides mauretanicus, Tribolium spp. such as T. casta- neum; Trogoderma spp., Tychius spp., Xylotrechus spp. such as X. pyrrhoderus; and, Zabrus spp. such as Z. tenebrioides;
insects from the order of Diptera e.g. Aedes spp. such as A. aegypti, A. albopictus, A. vexans; Anastrepha ludens, Anopheles spp. such as A. albimanus, A. crucians, A. freeborni, A. gam- biae, A. leucosphyrus, A. maculipennis, A. minimus, A. quadrimaculatus, A. sinensis; Bactro- cera invadens, Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capitata, Chrysomyia spp. such as C. bezziana, C. hominivorax, C. macellaria; Chrysops atlanticus, Chrysops discalis, Chrysops silacea, Cochliomyia spp. such as C. hominivorax; Contarinia spp. such as C. sorghicola; Cordylobia anthropophaga, Culex spp. such as C. nigripalpus, C. pipi- ens, C. quinquefasciatus, C. tarsalis, C. tritaeniorhynchus; Culicoides furens, Culiseta inornata, Culiseta melanura, Cuterebra spp., Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Dasi- neura oxycoccana, Delia spp. such as D. antique, D. coarctata, D. platura, D. radicum; Dermat- obia hominis, Drosophila spp. such as D. suzukii, Fannia spp. such as F. canicularis; Gastraphi- lus spp. such as G. intestinalis; Geomyza tipunctata, Glossina spp. such as G. fuscipes, G. mor- sitans, G. palpalis, G. tachinoides; Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia spp. such as H. platura; Hypoderma spp. such as H. lineata; Hyppobosca spp., Hydrellia philippina, Leptoconops torrens, Liriomyza spp. such as L. sativae, L. trifolii; Lucilia spp. such as L. caprina, L. cuprina, L. sericata; Lycoria pectoralis, Mansonia titillanus, Mayetiola spp. such as M. destructor; Musca spp. such as M. autumnalis, M. domestica; Muscina stabu- lans, Oestrus spp. such as O. ovis; Opomyza florum, Oscinella spp. such as O. frit; Orseolia oryzae, Pegomya hysocyami, Phlebotomus argentipes, Phorbia spp. such as P. antiqua, P. brassicae, P. coarctata; Phytomyza gymnostoma, Prosimulium mixtum, Psila rosae, Psorophora columbiae, Psorophora discolor, Rhagoletis spp. such as R. cerasi, R. cingulate, R. indifferens, R. mendax, R. pomonella; Rivellia quadrifasciata, Sarcophaga spp. such as S. haemorrhoidalis; Simulium vittatum, Sitodiplosis mosellana, Stomoxys spp. such as S. calcitrans; Tabanus spp. such as T. atratus, T. bovinus, T. lineola, T. similis; Tannia spp., Thecodiplosis japonensis, Tip- ula oleracea, Tipula paludosa, and Wohlfahrtia spp;
insects from the order of Thysanoptera for example, Baliothrips biformis, Dichromothrips cor- betti, Dichromothrips ssp., Echinothrips americanus, Enneothrips flavens, Frankliniella spp. such as F. fusca, F. occidentalis, F. tritici; Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Microcephalothrips abdominalis, Neohydatothrips samayunkur, Pezothrips kellyanus, Rhipiphorothrips cruentatus, Scirtothrips spp. such as S. citri, S. dorsalis, S. perseae; Stenchae- tothrips spp, Taeniothrips cardamoni, Taeniothrips inconsequens, Thrips spp. such as T. imagi- nes, T. hawaiiensis, T. oryzae, T. palmi, T. parvispinus, T. tabaci;
insects from the order of Hemiptera for example, Acizzia jamatonica, Acrosternum spp. such as A. hilare; Acyrthosipon spp. such as A. onobrychis, A. pisum; Adelges laricis, Adelges tsu- gae, Adelphocoris spp., such as A. rapidus, A. superbus; Aeneolamia spp., Agonoscena spp., Aulacorthum solani, Aleurocanthus woglumi, Aleurodes spp., Aleurodicus disperses, Aleurolo- bus barodensis, Aleurothrixus spp., Amrasca spp., Anasa tristis, Antestiopsis spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphidula nasturtii, Aphis spp. such as A. craccivora, A. fabae, A. forbesi, A. gossypii, A. grossulariae, A. maidiradicis, A. pomi, A. sambuci, A.
schneideri, A. spiraecola; Arboridia apicalis, Arilus critatus, Aspidiella spp., Aspidiotus spp., Ata- nus spp., Aulacaspis yasumatsui, Aulacorthum solani, Bactericera cockerelli (Paratrioza cocker- elli), Bemisia spp. such as B. argentifolii, B. tabaci (Aleurodes tabaci); Blissus spp. such as B. leucopterus; Brachycaudus spp. such as B. cardui, B. helichrysi, B. persicae, B. prunicola;
Brachycolus spp., Brachycorynella asparagi, Brevicoryne brassicae, Cacopsylla spp. such as C. fulguralis, C. pyricola (Psylla piri); Calligypona marginata, Calocoris spp., Campylomma livida, Capitophorus horni, Carneocephala fulgida, Cavelerius spp., Ceraplastes spp., Ceratovacuna lanigera, Ceroplastes ceriferus, Cerosipha gossypii, Chaetosiphon fragaefolii, Chionaspis tega- lensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Cimex spp. such as C. hemipterus, C. lectularius; Coccomytilus halli, Coccus spp. such as C. hesperi- dum, C. pseudomagnoliarum; Corythucha arcuata, Creontiades dilutus, Cryptomyzus ribis, Chrysomphalus aonidum, Cryptomyzus ribis, Ctenarytaina spatulata, Cyrtopeltis notatus, Dalbu- lus spp., Dasynus piperis, Dialeurodes spp. such as D. citrifolii; Dalbulus maidis, Diaphorina spp. such as D. citri; Diaspis spp. such as D. bromeliae; Dichelops furcatus, Diconocoris he- wetti, Doralis spp., Dreyfusia nordmannianae, Dreyfusia piceae, Drosicha spp., Dysaphis spp. such as D. plantaginea, D. pyri, D. radicola; Dysaulacorthum pseudosolani, Dysdercus spp. such as D. cingulatus, D. intermedius; Dysmicoccus spp., Edessa spp., Geocoris spp., Empo- asca spp. such as E. fabae, E. solana; Epidiaspis leperii, Eriosoma spp. such as E. lanigerum, E. pyricola; Erythroneura spp., Eurygaster spp. such as E. integriceps; Euscelis bilobatus, Eu- schistus spp. such as E. heros, E. impictiventris, E. servus; Fiorinia theae, Geococcus coffeae, Glycaspis brimblecombei, Halyomorpha spp. such as H. halys; Heliopeltis spp., Homalodisca vitripennis (=H. coagulata), Horcias nobilellus, Hyalopterus pruni, Hyperomyzus lactucae, Icerya spp. such as I. purchase; Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lecanoideus floccissimus, Lepidosaphes spp. such as L. ulmi; Leptocorisa spp., Lepto- glossus phyllopus, Lipaphis erysimi, Lygus spp. such as L. hesperus, L. lineolaris, L. pratensis; Maconellicoccus hirsutus, Marchalina hellenica, Macropes excavatus, Macrosiphum spp. such as M. rosae, M. avenae, M. euphorbiae; Macrosteles quadrilineatus, Mahanarva fimbriolata, Megacopta cribraria, Megoura viciae, Melanaphis pyrarius, Melanaphis sacchari, Melanocallis (=Tinocallis) caryaefoliae, Metcafiella spp., Metopolophium dirhodum, Monellia costalis, Monel- liopsis pecanis, Myzocallis coryli, Murgantia spp., Myzus spp. such as M. ascalonicus, M. cera- si, M. nicotianae, M. persicae, M. varians; Nasonovia ribis-nigri, Neotoxoptera formosana, Neo- megalotomus spp, Nephotettix spp. such as N. malayanus, N. nigropictus, N. parvus, N. vires- cens; Nezara spp. such as N. viridula; Nilaparvata lugens, Nysius huttoni, Oebalus spp. such as O. pugnax; Oncometopia spp., Orthezia praelonga, Oxycaraenus hyalinipennis, Parabemisia myricae, Parlatoria spp., Parthenolecanium spp. such as P. corni, P. persicae; Pemphigus spp. such as P. bursarius, P. populivenae; Peregrinus maidis, Perkinsiella saccharicida, Phenacoc- cus spp. such as P. aceris, P. gossypii; Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp. such as P. devastatrix, Piesma quadrata, Piezodorus spp. such as P. guildinii; Pinnaspis aspidistrae, Planococcus spp. such as P. citri, P. ficus; Prosapia bicincta, Protopulvinaria pyri- formis, Psallus seriatus, Pseudacysta persea, Pseudaulacaspis pentagona, Pseudococcus spp. such as P. comstocki; Psylla spp. such as P. mali; Pteromalus spp., Pulvinaria amygdali, Pyrilla spp., Quadraspidiotus spp., such as Q. perniciosus; Quesada gigas, Rastrococcus spp., Redu- vius senilis, Rhizoecus americanus, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosi- phum spp. such as R. pseudobrassicas, R. insertum, R. maidis, R. padi; Sagatodes spp., Sahl- bergella singularis, Saissetia spp., Sappaphis mala, Sappaphis mali, Scaptocoris spp., Scaph- oides titanus, Schizaphis graminum, Schizoneura lanuginosa, Scotinophora spp., Selenaspidus articulatus, Sitobion avenae, Sogata spp., Sogatella furcifera, Solubea insularis, Spissistilus festinus (=Stictocephala festina), Stephanitis nashi, Stephanitis pyrioides, Stephanitis takeyai, Tenalaphara malayensis, Tetraleurodes perseae, Therioaphis maculate, Thyanta spp. such as T. accerra, T. perditor; Tibraca spp., Tomaspis spp., Toxoptera spp. such as T. aurantii; Trialeu- rodes spp. such as T. abutilonea, T. ricini, T. vaporariorum; Triatoma spp., Trioza spp., Typhlo- cyba spp., Unaspis spp. such as U. citri, U. yanonensis; and Viteus vitifolii,
Insects from the order Hymenoptera for example Acanthomyops interjectus, Athalia rosae, Atta spp. such as A. capiguara, A. cephalotes, A. cephalotes, A. laevigata, A. robusta, A. sex- dens, A. texana, Bombus spp., Brachymyrmex spp., Camponotus spp. such as C. floridanus, C. pennsylvanicus, C. modoc; Cardiocondyla nuda, Chalibion sp, Crematogaster spp., Dasymutilla occidentalis, Diprion spp., Dolichovespula maculata, Dorymyrmex spp., Dryocosmus kuriphilus, Formica spp., Hoplocampa spp. such as H. minuta, H. testudinea; Iridomyrmex humilis, Lasius spp. such as L. niger, Linepithema humile, Liometopum spp., Leptocybe invasa, Monomorium spp. such as M. pharaonis, Monomorium, Nylandria fulva, Pachycondyla chinensis, Paratre- china longicornis, Paravespula spp., such as P. germanica, P. pennsylvanica, P. vulgaris; Phei- dole spp. such as P. megacephala; Pogonomyrmex spp. such as P. barbatus, P. californicus, Polistes rubiginosa, Prenolepis impairs, Pseudomyrmex gracilis, Schelipron spp., Sirex cya- neus, Solenopsis spp. such as S. geminata, S.invicta, S. molesta, S. richteri, S. xyloni, Sphe- cius speciosus, Sphex spp., Tapinoma spp. such as T. melanocephalum, T. sessile; Tetramo- rium spp. such as T. caespitum, T. bicarinatum, Vespa spp. such as V. crabro; Vespula spp. such as V. squamosal; Wasmannia auropunctata, Xylocopa sp;
Insects from the order Orthoptera for example Acheta domesticus, Calliptamus italicus, Chor- toicetes terminifera, Ceuthophilus spp., Diastrammena asynamora, Dociostaurus maroccanus, Gryllotalpa spp. such as G. africana, G. gryllotalpa; Gryllus spp., Hieroglyphus daganensis, Kraussaria angulifera, Locusta spp. such as L. migratoria, L. pardalina; Melanoplus spp. such as M. bivittatus, M. femurrubrum, M. mexicanus, M. sanguinipes, M. spretus; Nomadacris sep- temfasciata, Oedaleus senegalensis, Scapteriscus spp., Schistocerca spp. such as S. ameri- cana, S. gregaria, Stemopelmatus spp., Tachycines asynamorus, and Zonozerus variegatus; Pests from the Class Arachnida for example Acari,e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma spp. (e.g. A. americanum, A. variegatum, A. maculatum), Ar- gas spp. such as A. persicu), Boophilus spp. such as B. annulatus, B. decoloratus, B. micro- plus, Dermacentor spp. such as D.silvarum, D. andersoni, D. variabilis, Hyalomma spp. such as H. truncatum, Ixodes spp. such as I. ricinus, I. rubicundus, I. scapularis, I. holocyclus, I. pacifi- cus, Rhipicephalus sanguineus, Ornithodorus spp. such as O. moubata, O. hermsi, O. turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes spp. such as P. ovis, Rhipicephalus spp. such as R. sanguineus, R. appendiculatus, Rhipicephalus evertsi, Rhizogly- phus spp., Sarcoptes spp. such asS. Scabiei; and Family Eriophyidae including Aceria spp. such as A. sheldoni, A. anthocoptes, Acallitus spp., Aculops spp. such as A. lycopersici, A. pel- ekassi; Aculus spp. such as A. schlechtendali; Colomerus vitis, Epitrimerus pyri, Phyllocoptruta oleivora; Eriophytes ribis and Eriophyes spp. such as Eriophyes sheldoni; Family Tarsonemidae including Hemitarsonemus spp., Phytonemus pallidus and Polyphagotarsonemus latus, Steno- tarsonemus spp. Steneotarsonemus spinki; Family Tenuipalpidae including Brevipalpus spp. such as B. phoenicis; Family Tetranychidae including Eotetranychus spp., Eutetranychus spp., Oligonychus spp., Petrobia latens, Tetranychus spp. such as T. cinnabarinus, T. evansi, T. kan- zawai, T, pacificus, T. phaseulus, T. telarius and T. urticae; Bryobia praetiosa; Panonychus spp. such as P. ulmi, P. citri; Metatetranychus spp. and Oligonychus spp. such as O. pratensis, O. perseae, Vasates lycopersici; Raoiella indica, Family Carpoglyphidae including Carpoglyphus spp.; Penthaleidae spp. such as Halotydeus destructor; Family Demodicidae with species such as Demodex spp.; Family Trombicidea including Trombicula spp.; Family Macronyssidae includ- ing Ornothonyssus spp.; Family Pyemotidae including Pyemotes tritici; Tyrophagus putrescen- tiae; Family Acaridae including Acarus siro; Family Araneida including Latrodectus mactans, Tegenaria agrestis, Chiracanthium sp, Lycosa sp Achaearanea tepidariorum and Loxosceles reclusa;
Pests from the Phylum Nematoda, for example, plant parasitic nematodes such as root-knot nematodes, Meloidogyne spp. such as M. hapla, M. incognita, M. javanica; cyst-forming nema- todes, Globodera spp. such as G. rostochiensis; Heterodera spp. such as H. avenae, H. glyci- nes, H. schachtii, H. trifolii; Seed gall nematodes, Anguina spp.; Stem and foliar nematodes, Aphelenchoides spp. such as A. besseyi; Sting nematodes, Belonolaimus spp. such as B. longi- caudatus; Pine nematodes, Bursaphelenchus spp. such as B. lignicolus, B. xylophilus; Ring nematodes, Criconema spp., Criconemella spp. such as C. xenoplax and C. ornata; and, Criconemoides spp. such as Criconemoides informis; Mesocriconema spp.; Stem and bulb nematodes, Ditylenchus spp. such as D. destructor, D. dipsaci; Awl nematodes, Dolichodorus spp.; Spiral nematodes, Heliocotylenchus multicinctus; Sheath and sheathoid nematodes, Hem- icycliophora spp. and Hemicriconemoides spp.; Hirshmanniella spp.; Lance nematodes, Hop- loaimus spp.; False rootknot nematodes, Nacobbus spp.; Needle nematodes, Longidorus spp. such as L. elongatus; Lesion nematodes, Pratylenchus spp. such as P. brachyurus, P. neglec- tus, P. penetrans, P. curvitatus, P. goodeyi; Burrowing nematodes, Radopholus spp. such as R. similis; Rhadopholus spp.; Rhodopholus spp.; Reniform nematodes, Rotylenchus spp. such as R. robustus, R. reniformis; Scutellonema spp.; Stubby-root nematode, Trichodorus spp. such as T. obtusus, T. primitivus; Paratrichodorus spp. such as P. minor; Stunt nematodes, Tylencho- rhynchus spp. such as T. claytoni, T. dubius; Citrus nematodes, Tylenchulus spp. such as T. semipenetrans; Dagger nematodes, Xiphinema spp.; and other plant parasitic nematode spe- cies;
Insects from the order Isoptera for example Calotermes flavicollis, Coptotermes spp. such as C. formosanus, C. gestroi, C. acinaciformis; Cornitermes cumulans, Cryptotermes spp. such as C. brevis, C. cavifrons; Globitermes sulfureus, Heterotermes spp. such as H. aureus, H. longi- ceps, H. tenuis; Leucotermes flavipes, Odontotermes spp., Incisitermes spp. such as I. minor, I. Snyder; Marginitermes hubbardi, Mastotermes spp. such as M. darwiniensis Neocapritermes spp. such as N. opacus, N. parvus; Neotermes spp., Procornitermes spp., Zootermopsis spp. such as Z. angusticollis, Z. nevadensis, Reticulitermes spp. such as R. hesperus, R. tibialis, R. speratus, R. flavipes, R. grassei, R. lucifugus, R. santonensis, R. virginicus; Termes natalensis, Insects from the order Blattaria for example Blatta spp. such as B. orientalis, B. lateralis; Blat- tella spp. such as B. asahinae, B. germanica; Leucophaea maderae, Panchlora nivea, Peri- planeta spp. such as P. americana, P. australasiae, P. brunnea, P. fuligginosa, P. japonica; Su- pella longipalpa, Parcoblatta pennsylvanica, Eurycotis floridana, Pycnoscelus surinamensis, Insects from the order Siphonoptera for example Cediopsylla simples, Ceratophyllus spp., Ctenocephalides spp. such as C. felis, C. canis, Xenopsylla cheopis, Pulex irritans, Tricho- dectes canis, Tunga penetrans, and Nosopsyllus fasciatus,
Insects from the order Thysanura for example Lepisma saccharina , Ctenolepisma urbana, and Thermobia domestica,
Pests from the class Chilopoda for example Geophilus spp., Scutigera spp. such as Scutigera coleoptrata;
Pests from the class Diplopoda for example Blaniulus guttulatus, Julus spp., Narceus spp., Pests from the class Symphyla for example Scutigerella immaculata,
Insects from the order Dermaptera, for example Forficula auricularia,
Insects from the order Collembola, for example Onychiurus spp., such as Onychiurus armatus, Pests from the order Isopoda for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber,
Insects from the order Phthiraptera, for example Damalinia spp., Pediculus spp. such as Pe- diculus humanus capitis, Pediculus humanus corporis, Pediculus humanus humanus; Pthirus pubis, Haematopinus spp. such as Haematopinus eurysternus, Haematopinus suis;
Linognathus spp. such as Linognathus vituli; Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus, Trichodectes spp.,
Examples of further pest species which may be controlled by compounds of fomula (I) include: from the Phylum Mollusca, class Bivalvia, for example, Dreissena spp.; class Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea canaliclata, Succinea spp.; from the class of the helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancy- lostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp., Dictyocaulus filaria, Diphyl- lobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocu- laris, Enterobius vermicularis, Faciola spp., Haemonchus spp. such as Haemonchus contortus; Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesoph- agostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp., Strongyloides fuelleborni, Strongyloides stercora lis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichi- nella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti. Compounds of formula (I) including their stereoisomers, their tautomers, their salts or their N- oxides as well as compositions thereof are particularly useful for controlling invertebrate pests, preferably for controlling arthropods and nematodes, more preferably insects, and in particular Pentatomidae pests. Pentatomidae pests include Acrosternum spp., Euschistus spp., Halyo- morpha spp., Nezara spp., Megacopta spp., Piezodorus spp., preferably Acrosternum hilare, Euschistus servus, Euschistus heros, Halyomorpha halys, Megacopta cribraria, Nezara viridula, and Piezodorus viridula. Animal health The compounds of the invention are suitable for use in treating or protecting animals against infestation or infection by parasites. Therefore, the invention also relates to the use of a com- pound of the invention for the manufacture of a medicament for the treatment or protection of animals against infestation or infection by parasites. Furthermore, the invention relates to a method of treating or protecting animals against infestation and infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiti- cidally effective amount of a compound of the invention.
The present invention also relates to the non-therapeutic use of compounds of the invention for treating or protecting animals against infestation and infection by parasites. Moreover, the invention relates to a non-therapeutic method of treating or protecting animals against infesta- tion and infection by parasites, which comprises applying to a locus a parasiticidally effective amount of a compound of the invention.
The compounds of the invention are further suitable for use in combating or controlling para- sites in and on animals. Furthermore, the invention relates to a method of combating or control- ling parasites in and on animals, which comprises contacting the parasites with a parasitically effective amount of a compound of the invention.
The invention also relates to the non-therapeutic use of compounds of the invention for con- trolling or combating parasites. Moreover, the invention relates to a non-therapeutic method of combating or controlling parasites, which comprises applying to a locus a parasiticidally effec- tive amount of a compound of the invention.
The compounds of the invention can be effective through both contact (via soil, glass, wall, bed net, carpet, blankets or animal parts) and ingestion (e.g. baits). Furthermore, the compounds of the invention can be applied to any and all developmental stages.
The compounds of the invention can be applied as such or in form of compositions comprising the compounds of the invention.
The compounds of the invention can also be applied together with a mixing partner, which acts against pathogenic parasites, e.g. with synthetic coccidiosis compounds, polyetherantibiotics such as Amprolium, Robenidin, Toltrazuril, Monensin, Salinomycin, Maduramicin, Lasalocid, Narasin or Semduramicin, or with other mixing partners as defined above, or in form of compo- sitions comprising said mixtures.
The compounds of the invention and compositions comprising them can be applied orally, par- enterally or topically, e.g. dermally. The compounds of the invention can be systemically or non- systemically effective.
The application can be carried out prophylactically, therapeutically or non-therapeutically. Fur- thermore, the application can be carried out preventively to places at which occurrence of the parasites is expected.
As used herein, the term "contacting" includes both direct contact (applying the com- pounds/compositions directly on the parasite, including the application directly on the animal or excluding the application directly on the animal, e.g. at it's locus for the latter) and indirect con- tact (applying the compounds/compositions to the locus of the parasite). The contact of the par- asite through application to its locus is an example of a non-therapeutic use of the compounds of the invention.
The term "locus" means the habitat, food supply, breeding ground, area, material or environ- ment in which a parasite is growing or may grow outside of the animal. As used herein, the term“parasites” includes endo- and ectoparasites. In some embodiments of the invention, endoparasites can be preferred. In other embodiments, ectoparasites can be preferred. Infestations in warm-blooded animals and fish include, but are not limited to, lice, bit- ing lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chiggers, gnats, mosquitoes and fleas.
The compounds of the invention are especially useful for combating parasites of the following orders and species, respectively:
fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus; cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Peri- planeta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis; flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimacula- tus, Calliphora vicina, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dermatobia hominis, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Leptoconops torrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Manso- nia spp., Musca domestica, Muscina stabulans, Oestrus ovis, Phlebotomus argentipes, Psoro- phora columbiae, Psorophora discolor, Prosimulium mixtum, Sarcophaga haemorrhoidalis, Sar- cophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Taba- nus lineola, and Tabanus similis; lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus; ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocy- clus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor varia- bilis, Amblyomma americanum, Ambryomma maculatum, Ornithodorus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Ornithonyssus bacoti and Dermanyssus galli- nae; Actinedida (Prostigmata) und Acaridida (Astigmata), e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp.,
Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterol- ichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., and Laminosioptes spp; Bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp., and Arilus critatus; Anoplurida, e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp.; Mallophagida (suborders Arnblycerina and Ischnocerina), e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp.,
Lepikentron spp., Trichodectes spp., and Felicola spp.; Roundworms Nematoda: Wipeworms and Trichinosis (Trichosyringida), e.g. Trichinellidae (Trichinella spp.), (Trichuridae) Trichuris spp., Capillaria spp.; Rhabditida, e.g. Rhabditis spp., Strongyloides spp., Helicephalobus spp.; Strongylida, e.g. Strongylus spp., Ancylostoma spp., Necator americanus, Bunostomum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus, Ostertagia spp., Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oesophagostomum spp., Stepha- nurus dentatus, Ollulanus spp., Chabertia spp., Stephanurus dentatus, Syngamus trachea, An- cylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp., Parelaphostrongylus spp., Al- eurostrongylus abstrusus, and Dioctophyma renale; Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicu- laris (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi; Camallanida, e.g. Dracunculus medinensis (guinea worm); Spirurida, e.g. Thelazia spp., Wu- chereria spp., Brugia spp., Onchocerca spp., Dirofilari spp.a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Habronema spp.; Thorny headed worms (Acanthoceph- ala), e.g. Acanthocephalus spp., Macracanthorhynchus hirudinaceus and Oncicola spp.; Planar- ians (Plathelminthes): Flukes (Trematoda), e.g. Faciola spp., Fascioloides magna, Paragonimus spp., Dicrocoelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobil- harzia spp., Alaria alata, Paragonimus spp., and Nanocyetes spp.; Cercomeromorpha, in partic- ular Cestoda (Tapeworms), e.g. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylid- ium caninum, Multiceps spp., Hymenolepis spp., Mesocestoides spp., Vampirolepis spp., Mon- iezia spp., Anoplocephala spp., Sirometra spp., Anoplocephala spp., and Hymenolepis spp.. As used herein, the term“animal” includes warm-blooded animals (including humans) and fish. Preferred are mammals, such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rab- bits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur- bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels. Particularly pre- ferred are domestic animals, such as dogs or cats.
In general, "parasiticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The parasiticidally effective amount can vary for the various compounds/com- positions used in the invention. A parasiticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired parasiticidal effect and duration, tar- get species, mode of application, and the like.
Generally, it is favorable to apply the compounds of the invention in total amounts of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50 mg/kg per day.
For oral administration to warm-blooded animals, the formula (I) compounds may be formu- lated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. In addition, the formula (I) com- pounds may be administered to the animals in their drinking water. For oral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula (I) compound, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
Alternatively, the formula (I) compounds may be administered to animals parenterally, for ex- ample, by intraruminal, intramuscular, intravenous or subcutaneous injection. The formula (I) compounds may be dispersed or dissolved in a physiologically acceptable carrier for subcutane- ous injection. Alternatively, the formula (I) compounds may be formulated into an implant for subcutaneous administration. In addition the formula (I) compound may be transdermally ad- ministered to animals. For parenteral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula (I) com- pound.
The formula (I) compounds may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or water-in-oil emulsions. For topical application, dips and sprays usu- ally contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the formula (I) com- pound. In addition, the formula (I) compounds may be formulated as ear tags for animals, partic- ularly quadrupeds such as cattle and sheep.
Suitable preparations are:
- Solutions such as oral solutions, concentrates for oral administration after dilution, solutions for use on the skin or in body cavities, pouring-on formulations, gels;
- Emulsions and suspensions for oral or dermal administration; semi-solid preparations;
- Formulations in which the active compound is processed in an ointment base or in an oil-in- water or water-in-oil emulsion base;
- Solid preparations such as powders, premixes or concentrates, granules, pellets, tablets, bo- luses, capsules; aerosols and inhalants, and active compound-containing shaped articles.
Compositions suitable for injection are prepared by dissolving the active ingredient in a suita- ble solvent and optionally adding further auxiliaries such as acids, bases, buffer salts, preserva- tives, and solubilizers. Suitable auxiliaries for injection solutions are known in the art. The solu- tions are filtered and filled sterile.
Oral solutions are administered directly. Concentrates are administered orally after prior dilu- tion to the use concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being nec- essary.
Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on. Solutions for use on the skin are prepared according to the state of the art and according to what is described above for injection solutions, sterile procedures not being necessary.
Gels are applied to or spread on the skin or introduced into body cavities. Gels are prepared by treating solutions which have been prepared as described in the case of the injection solu- tions with sufficient thickener that a clear material having an ointment-like consistency results. Suitable thickeners are known in the art.
Pour-on formulations are poured or sprayed onto limited areas of the skin, the active com- pound penetrating the skin and acting systemically. Pour-on formulations are prepared by dis- solving, suspending or emulsifying the active compound in suitable skin-compatible solvents or solvent mixtures. If appropriate, other auxiliaries such as colorants, bioabsorption-promoting substances, antioxidants, light stabilizers, adhesives are added. Suitable such auxiliaries are known in the art.
Emulsions can be administered orally, dermally or as injections. Emulsions are either of the water-in-oil type or of the oil-in-water type. They are prepared by dissolving the active com- pound either in the hydrophobic or in the hydrophilic phase and homogenizing this with the sol- vent of the other phase with the aid of suitable emulsifiers and, if appropriate, other auxiliaries such as colorants, absorption-promoting substances, preservatives, antioxidants, light stabilizers, viscosity-enhancing substances. Suitable hydrophobic phases (oils), suitable hydro- philic phases, suitable emulsifiers, and suitable further auxiliaries for emulsions are known in the art.
Suspensions can be administered orally or topically/dermally. They are prepared by suspend- ing the active compound in a suspending agent, if appropriate with addition of other auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxi- dants, light stabilizers. Suitable suspending agents, and suitable other auxiliaries for suspen- sions including wetting agents are known in the art.
Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions described above only by their higher viscosity.
For the production of solid preparations, the active compound is mixed with suitable excipi- ents, if appropriate with addition of auxiliaries, and brought into the desired form. Suitable auxil- iaries for this purpose are known in the art.
The compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the compound of the invention.
Ready-to-use preparations contain the compounds acting against parasites, preferably ecto- parasites, in concentrations of 10 ppm to 80 per cent by weight, preferably from 0.1 to 65 per cent by weight, more preferably from 1 to 50 per cent by weight, most preferably from 5 to 40 per cent by weight.
Preparations which are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 per cent by weight, preferably of 1 to 50 per cent by weight.
Furthermore, the preparations comprise the compounds of formula (I) against endoparasites in concentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to 0.9 per cent by weight, very particularly preferably of 0.005 to 0.25 per cent by weight.
Topical application may be conducted with compound-containing shaped articles such as col- lars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.
Generally it is favorable to apply solid formulations which release compounds of the invention in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks. The following examples illustrate the invention. Examples:
Materials: Unless otherwise noted, reagents and solvents were purchased at highest commer- cial quality and used without further purification. Dry tetrahydrofuran (THF), dimethylsulfoxide (DMSO), acetone, ethanol (EtOH), benzene, dimethylformamide (DMF), pyridine, and CH2Cl2 were purchased from Kanto Chemical Co., Inc. All reactions were monitored by thin-layer chro- matography (TLC) using Merck silica gel 60 F254 pre-coated plates (0.25 mm). Flash chroma- tography was carried out with Kanto Chemical silica gel (Kanto Chemical, silica gel 60N, spheri- cal neutral, 0.040–0.050 mm, Cat.-No.37563–84).1H NMR spectra were recorded on JEOL JNM-ECA-500 (500 MHz). Chemical shifts are expressed in ppm downfield from the internal sol- vent peaks for acetone-d6 (1H; d = 2.05 ppm) and CD3OD (1H; d = 3.30 ppm), and J values are given in Hertz. The following abbreviations were used to explain the multiplicities: s = singlet, d = doublet, t = triplet, q = quartet, dd = double doublet, dt = double triplet, m = multiplet, br = broad. High-resolution mass spectra were measured on a JEOL JMS-T100LP. Characterization: The compounds were characterized by coupled High Performance Liquid Chromatography with mass spectrometry (HPLC/MS).
Method 1: Analytical UPLC column: Phenomenex Kinetex 1,7 µm XB-C18100A; 50 x 2.1 mm; mobile phase: A: water + 0.1% TFA; B: acetonitrile; gradient: 5-100% B in 1.50 minutes; 100% B 0.20 min; flow: 0,8-1,0mL/min in 1,50 minutes at 60°C. MS-method: ESI positive.
Method 2: Analytical UPLC column: Phenomenex Kinetex 1,7 µm XB-C18100A; 50 x 2.1 mm; mobile phase: A: water + 0.1% formic acid; B: acetonitrile; gradient: 5-100% B in 1.50 minutes; 100% B 0.25 min; flow: 0,8-1,0mL/min in 1,50 minutes at 60°C. MS-method: ESI negative. Abbreviations: HPLC is High Performance Liquid Chromatography; MS is mass spectrometry; min is minutes; M is mol/liter; h is hour; mL is milliliter; TFA is trifluoroacetic acid; MeCN is CH3CN; DMSO is dimethylsulfoxide; EtOH is CH3CH2OH; acetone-d6 is CD3C(=O)CD3; EtOAc is ethylacetate; DBU is 1,8-Diazabicyclo[5.4.0]undec-7-en; HRMS is high-resolution mass spec- troscopy. A: Preparation Examples
With appropriate modification of the starting materials, the procedures as described in the syn- thesis examples below were used to obtain further compounds of formula (I). The compounds obtained in this manner are listed in Table D that follow, together with physical data. A1: Preparation of 15-hydro-ginkgolide A (compound I-51)
To a solution of gingkolide A (3.1 g) in dry THF (190 mL) was added diisobutylaluminium hy- dride (1.0 M in CH2Cl2, 26.6 mL) dropwise over 20 min at–78 ˚C under N2 atmosphere. After stirring at the same temperature for 1 h, the reaction mixture was heated up to 20 to 25 °C and stirred for further 25 min. Then the reaction was quenched by the dropwise addition of EtOAc (60 mL) and stirred for 5 min at 20 to 25 °C, followed by addition of H2O (100 mL), EtOAc (100 mL) and 1M HCl aq. (50 mL). The mixture was separated and extracted with EtOAc. The combined organic layers were dried, filtered and concentrated. The residue was submitted to flash column chromatography to afford compound I-51 as a mixture of C15-epimers with a yield of 61%; (76% yield based on recovered starting material). Gingkolide A was recovered in an amount of 0.63 g. Compound I-51 was a ca.2:1 mixture of epimers at C15: All physical data for compound I-51 matched with the data of 15-hydro-ginkgolide A reported previously by K.
Nakanish et al. (Org. Biomol. Chem., 2005, 3, 3471-3472). A2: Preparation of a (15S)-15-deoxy-15-hydro-15-(N-indolinyl)-ginkgolide A (compound I-1) To a solution of compound I-51 (119 mg) as obtained in Preparation Example A1 in EtOH (5.8 mL) was added indoline (65.2 µl) and CH3C(O)OH (99.5 µl) at a temperature of 20 to 25 °C. The reaction mixture was heated to 90 °C. After stirring for 24 h, the reaction mixture was then cooled to a temperature of 20 to 25 °C and concentrated. The residue was purified by recrystal- lization from acetone/hexane solution. The collected brown solid was subjected to flash column chromatography to give the (15S)-15-deoxy-15-hydro-15-(N-indolinyl)-ginkgolide A (compound I-1) with a yield of 74% as a light brown solid. 1H NMR (500 MHz, acetone-d6, d) 7.05 (d, J = 7.4 Hz, 1H), 6.99 (t, J = 7.4 Hz, 1H), 6.64 (t, J = 7.4 Hz, 1H), 6.63 (d, J = 7.4 Hz, 1H), 6.05 (s, 1H), 5.68 (d, J = 4.6 Hz, 1H), 5.59 (d, J = 10.3 Hz, 1H), 5.16 (d, J = 4.0 Hz, 1H), 4.81 (d, J = 4.0 Hz, 1H), 4.52 (s, 1H), 4.45 (dd, J = 7.4, 8.6 Hz, 1H), 3.59 (m, 1H), 3.47 (m, 1H), 3.01-2.97 (complex m, 2H), 2.87-2.81 (complex m, 2H), 2.54 (dd, J = 6.9, 14.9 Hz, 1H), 2.22-2.10 (complex m, 2H), 1.99-1.88 (complex m, 2H), 1.14 (s, 9H), 1.12 (d, J = 6.9 Hz, 3H); HRMS (ESI) m/z 512.2279 [M+Na]+. A3: Preparation of a (15S)-15-deoxy-15-hydro-15-(N-indolyl)-ginkgolide A (compound I-2) A solution of compound I-1 (70.0 mg) as obtained in Preparation Example A2 in THF (2.7 ml) was treated with MnO2 (476 mg) at a temperature of 20 to 25 °C, and the resulting reaction mix- ture was stirred for 24 h. Subsequently, the reaction mixture was filtered and concentrated. The residue was purified by the recrystallization from acetone/hexane solution. The collected solid was subjected to flash column chromatography to give compound I-2 at a yield of 62% as a col- orless solid.
1H NMR (500 MHz, acetone-d6, d) 7.58 (d, J = 8.0 Hz, 1H), 7.53 (d, J = 8.0 Hz, 1H), 7.52 (d, J = 4.0 Hz, 1H), 7.19 (dd, J = 7.4, 8.0 Hz, 1H), 7.08 (dd, J = 7.4, 8.0 Hz, 1H), 6.64 (d, J = 4.0 Hz, 1H), 6.19 (d, J = 10.3 Hz, 1H), 6.12 (s, 1H), 5.81 (d, J=4.6 Hz, 1H), 5.26 (d, J = 4.0 Hz, 1H), 4.91 (d, J = 4.0 Hz, 1H), 4.82 (s, 1H), 4.64 (dd, J = 8.6, 8.6 Hz, 1H), 3.27 (m, 1H), 2.73 (dd, J = 7.4, 14.3 Hz, 1H), 2.28-2.14 (complex m, 3H), 1.95 (dd, J = 4.6, 14.3 Hz, 1H), 1.17 (s, 9H), 1.06 (d, J = 6.9 Hz, 3H); HRMS (ESI) m/z 532.1932 [M+Na]+. A4: Preparation of (15S)-15-deoxy-15-hydro-15- methoxycarbonylmethylginkgolide A (com- pound I-5)
To a solution of the compound I-51 (74.6 mg) in benzene (3.6 mL) was added methyl(triphenyl- phosphoranylidene)acetate (122 mg) at a temperature of 20 to 25 °C. The reaction mixture was heated to 90 °C and stirred for 42 h. The reaction mixture was then cooled to 20 to 25 °C, and DBU (100 mL) was added to the reaction mixture with stirring. After 10 min, the reaction mixture was concentrated in vacuo, and the residue was subjected to flash column chromatography to afford compound I-5 with a yield of 58% as a colorless solid.
1H NMR (500 MHz, acetone-d6, d) 6.00 (s, 1H), 5.66 (d, J = 4.6 Hz, 1H), 5.13 (d, J = 4.0 Hz, 1H), 4.80 (d J = 4.0 Hz, 1H), 4.45 (apparently t, J = 7.5 Hz, 1H), 4.42 (s, 1H), 4.23 (dt, J = 3.4, 10.3 Hz, 1H), 3.63 (s, 3H), 2.71 (dd, J = 2.3, 14.9 Hz, 1H), 2.54 (dd, J = 7.5, 14.9 Hz, 1H), 2.43 (m, 1H), 2.38 (dd, J = 9.2, 15.5 Hz, 1H), 2.21-2.09 (complex m, 2H), 1.92 (dd, J = 8.6, 14.3 Hz, 1H), 1.88 (dd, J = 5.2, 14.3 Hz, 1H), 1.14 (s, 9H), 1.07 (d, J = 6.3 Hz, 3H); HRMS (ESI) m/z 489.1723 [M+Na]+. A5: Preparation of 15-deoxy-15-hydro-15-benzoyloxy-ginkgolide A (compound I-10) To a solution of compound I-51 (246 mg) in pyridine (3.0 mL) was added dimethylaminopyridine (DMAP) (14.6 mg) and benzoyl chloride (138 µl) at a temperature of 20 to 25 °C. The reaction mixture was stirred for 2.5 h and then diluted with excess amount of EtOAc. The mixture was washed, dried, and concentrated. The residue was purified by the recrystallization from ace- tone/hexane solution. The collected colorless solid was subjected to flash column chromatog- raphy to afford compound I-10 with a yield of 96% as an inseparable mixture of C15-epimers with an approximate ratio of (S)- to (R)-epimer of 2:1.
1H NMR (500 MHz, acetone-d6, d) major isomer: 8.20 (d, J = 8.0 Hz, 2H), 7.54-7.48 (complex m, 3H), 6.30 (d, J = 6.3 Hz, 1H), 6.10 (s, 1H), 5.73 (d, J = 4.6 Hz, 1H), 5.21 (d, J = 4.6 Hz, 1H), 4.87 (d, J = 4.0 Hz, 1H), 4.78 (s, 1H), 4.64 (dd, J = 6.9, 9.7 Hz, 1H), 3.27 (m, 1H), 2.59 (dd, J = 6.9, 14.3 Hz, 1H), 2.26-2.14 (complex m, 3H), 1.94 (m, 1H), 1.26 (d, J = 6.9 Hz, 3H), 1.16 (s, 9H); minor isomer: 8.08 (d, J = 8.0 Hz, 2H), 7.68-7.62 (complex m, 3H), 6.59 (d, J = 5.2 Hz, 1H), 6.05 (s, 1H), 5.72 (d, J = 4.6 Hz, 1H), 5.16 (d, J = 4.6 Hz, 1H), 4.89 (apparently t, J = 9.2 Hz, 1H), 4.88 (d, J = 4.0 Hz, 1H), 4.56 (s, 1H), 3.08 (m, 1H), 2.71 (dd, J = 7.4, 15.5 Hz, 1H), 2.26- 2.14 (complex m, 3H), 1.91 (m, 1H), 1.24 (d, J = 6.9 Hz, 3H), 1.15 (s, 9H).
HRMS (ESI) m/z 537.1740 [M+Na]+. A6: Preparation of 15-deoxy-15-hydro-15-azido-ginkgolide A (compound I-8)
To a solution of compound I-10 (204 mg) as obtained in Preparation Example A5 in DMF (4.0 mL) was added NaN3 (38.7 mg) at at a temperature of 20 to 25 °C. The reaction mixture was warmed to 80 °C, stirred for 42 h and then diluted with excess amount of EtOAc. The mixture was washed, dried, filtrated and concentrated. The residue was submitted to flash column chro- matography to afford the desired product with some impurities, which was further purified by the recrystallization from acetone/hexane solution to give compound I-8 with a yield of 76% as an inseparable mixture of C15-epimers with a ratio of (S)- to (R)-epimer of 3:2.
1H NMR (500 MHz, acetone-d6, d) 6.00 (s, 2/5H), 6.00 (s, 3/5H), 5.68 (d, J = 4.0 Hz, 3/5H), 5.66 (d, J = 4.0 Hz, 2/5H), 5.61 (d, J = 5.7 Hz, 3/5H), 5.13-5.11 (complex m, 7/5H), 4.86-4.84 (com- plex m, 1H), 4.81 (apparently t, J = 8.0 Hz, 3/5H), 4.65 (s, 2/5H), 4.58 (dd, J = 6.9, 9.2 Hz, 2/5H), 4.33 (s, 3/5H), 2.86 (m, 3/5H), 2.67 (dd, J = 7.5, 15.5 Hz, 3/5H), 2.63-2.58 (complex m, 4/5H), 2.23-1.97 (complex m, 3H), 1.90-1.85 (complex m, 1H), 1.13 (s, 9H), 1.10 (d, J = 6.9 Hz, 3H); HRMS (ESI) m/z 458.1535 [M+Na]+. A7: Preparation of 15-deoxy-15-hydro-15-(4-phenyl-1H-1,2,3-triazol-1-yl)-ginkgolide A (com- pound I-11)
To a solution of compound I-8 (40.6 mg) as obtained in Preparation Example A6 and
ethynylbenzene (0.373 mmol) in acetone (1.9 mL) was added a piece of Cu(0) turning and (MeCN)4CuPF6 (7.0 mg) at a temperature of 20 to 25 °C. The reaction mixture was stirred for 40 h and then quenched by the addition of saturated aqueous Rochelle salt solution. The mixture was extracted, and the organic extracts were dried, filtrated and concentrated. The residue was purified by the recrystallization from CHCl3/hexane solution. The collected solid was subjected to flash column chromatography to afford compound I-11 with a yield of 100% as a an insepara- ble mixture of C15-epimers with a ratio of (S)- to (R)-epimers of 3:2. 1H NMR (500 MHz, acetone-d6, d) 8.55 (s, 3/5H), 8.41 (s, 2/5H), 8.02 (d, J = 7.4 Hz, 4/5H), 7.90 (d, J = 7.4 Hz, 6/5H), 7.45 (m, 2H), 7.35 (m, 1H), 6.67 (d, J = 7.4 Hz, 3/5H), 6.19 (d, J = 9.2 Hz, 2/5H), 6.16 (s, 2/5H), 6.09 (s, 3/5H), 5.92 (d, J = 4.6 Hz, 2/5H), 5.81 (d, J = 4.6 Hz, 3/5H), 5.48 (s, 3/5H), 5.33 (d, J = 4.6 Hz, 2/5H), 5.20 (d, J = 4.6 Hz, 3/5H), 5.07 (apparently t, J = 8.0 Hz, 3/5H), 5.07 (s, 2/5H), 4.95 (d, J = 4.6 Hz, 1H), 4.79 (apparently t, J = 8.0 Hz, 2/5H), 3.42 (m, 3/5H), 3.31 (m, 2/5H), 2.82 (dd, J = 7.4, 14.9 Hz, 2/5H), 2.78 (dd, J = 7.4, 14.9 Hz, 3/5H), 2.29- 2.07 (complex m, 3H), 1.98-1.92 (complex m, 1H), 1.18 (d, J = 6.9 Hz, 6/5H), 1.17 (s, 18/5H), 1.15 (s, 27/5H), 0.90 (d, J = 6.9 Hz, 9/5H); HRMS (ESI) m/z 560.2006 [M+Na]+. A8: Preparation of 15-deoxy-15-hydro-15-cyano-ginkgolide A (compound I-14)
To a solution of the compound I-51 (623 mg) as obtained in Preparation Example A1 in CH2Cl2 (38 mL) at–78 °C was added (CH3)3SiCN (941 mL) and BF3•Et2O (667 mL). After stirring for 3 min at–78 °C, the reaction mixture was heated to a temperature of 20 to 25 °C and further stirred for 21 h. The reaction was then quenched, extracted, and the organic phases were dried, filtrated and concentrated. The crude product was subjected to flash column chromatography to afford compound I-14 with a yield of 52% (67% yield based on recovered starting material) as an inseparable mixture of C15-epimers with a ratio of (S)- to (R)-epimer of 2:3. Compound I-51 was recovered in an amount of 134 mg.
1H NMR (500 MHz, acetone-d6, d) 6.05 (s, 3/5H), 6.02 (s, 2/5H), 5.74 (d, J = 4.6 Hz, 3/5H), 5.73 (d, J = 4.6 Hz, 2/5H), 5.30 (d, J = 8.0 Hz, 2/5H), 5.17 (d, J = 4.0 Hz, 3/5H), 5.14 (d, J = 4.0 Hz, 2/5H), 4.88-4.85 (complex m, 2H), 4.77 (apparently, t, J = 7.4 Hz, 2/5H), 4.64 (dd, J = 7.5, 9.2 Hz, 3/5H), 4.61 (d, J = 10.9 Hz, 3/5H), 3.11-3.04 (complex m, 1H), 2.66-2.58 (complex m, 1H), 2.24-2.02 (complex m, 3H), 1.89 (dd, J = 4.6, 13.7 Hz, 1H), 1.30 (d, J = 6.9 Hz, 6/5H), 1.23 (d, J = 6.9 Hz, 9/5H), 1.14 (s, 27/5H), 1.14 (s, 18/5H); HRMS (ESI) m/z 442.1470 [M+Na]+. A9: Preparation of 15-deoxy-15-hydro-15-cyano-ginkgolide A (compound I-14)
To a solution of compound I-10 as obtained in Preparation Example A5 (92.8 mg) in CH2Cl2 (6.0 mL) at at a temperature of 20 to 25 °C was added (CH3)3SiCN (112 µL) and BF3•Et2O (57 µL). After stirring for 10 min, the reaction was quenched, extracted, and the combined organic phases were washed, dried, filtrated and concentrated. The residue was subjected to flash col- umn chromatography to afford compound I-14 with a yield of 76% as an inseparable mixture of epimers with a ratio of (S)- to (R)-epimer of 2:1.
NMR data of each epimer of compound I-14 matched with the data collected in Preparation Ex- ample A8. A10: Preparation of (15R)-15-deoxy-15-hydro-15-ethoxy-ginkgolide A (compounds I-12 and I-16)
To a solution of compound I-51 (89.2 mg) as obtained in Preparation Example A1 in EtOH (2.2 mL) was added p-toluene sulfonic acid (4.1 mg) at a temperature of 20 to 25 °C. The reaction mixture was heated to 80 °C, stirred for 30 min, then cooled to a temperature of 20 to 25 °C, di- luted with EtOAc and quenched by the addition of saturated aqueous NaHCO3 solution. The two layers were separated, and the aqueous layer was extracted with EtOAc. The combined organic layers were dried, filtrated and concentrated. The residue was submitted to flash column chro- matography to give compound I-12 with a yield of 55% and compound I-16 with a yield of 33%. I-12: 1H NMR (500 MHz, acetone-d6, d) 5.99 (s, 1H), 5.65 (d, J = 4.6 Hz, 1H), 5.11 (d, J = 4.0 Hz, 1H), 5.10 (d, J = 4.6 Hz, 1H), 4.81 (d, J = 4.0 Hz, 1H), 4.62 (apparently t, J = 8.0 Hz, 1H), 3.74 (m, 1H), 3.68 (s, 1H), 3.42 (m, 1H), 2.64 (m, 2H), 2.22-2.10 (complex m, 2H), 1.94 (dd, J = 8.6, 14.9 Hz, 1H), 1.88 (dd, J = 4.6, 14.3 Hz, 1H), 1.15 (t, J = 6.9 Hz, 3H), 1.13 (s, 9H), 1.07 (d, J = 6.9 Hz, 3H); HRMS (ESI) m/z 461.1777 [M+Na]+.
I-16: 1H NMR (500 MHz, acetone-d6, d) 5.99 (s, 1H), 5.61 (d, J = 4.0 Hz, 1H), 5.11 (d, J = 4.0 Hz, 1H), 4.92 (d, J = 7.4 Hz, 1H), 4.79 (d, J = 4.0 Hz, 1H), 4.46 (dd, J = 6.9, 9.7 Hz, 1H), 4.39 (s, 1H), 3.71 (m, 1H), 3.46 (m, 1H), 2.71 (m, 1H), 2.51 (dd, J = 6.9, 14.3 Hz, 1H), 2.22-2.06 (complex m, 3H), 1.87 (dd, J = 5.2, 14.3 Hz, 1H), 1.15 (t, J = 7.4 Hz, 3H), 1.13 (s, 9H), 1.10 (d, J = 6.9 Hz, 3H); HRMS (ESI) m/z 461.1792 [M+Na]+. A11: Preparation of 15-deoxy-15-hydro-15-(3-chloropropyl-1-oxy)-ginkgolide A (compound I-48) In analogy to the procedure of the preparation of compounds I-12 and I-16 in Preparation Exam- ple A10, compound I-51 (219 mg) was reacted with 3-chloro-1-propanol (5.3 mL) to afford com- pound I-48 with a yield of 99%), which was obtained as an inseparable mixture of epimers with a ratio of (S)- to (R)-epimer of 3:2.
1H NMR (500 MHz, acetone-d6, d) 6.00 (s, 2/5H), 5.99 (s, 3/5H), 5.72 (d, J = 4.6 Hz, 3/5H), 5.69 (d, J = 4.6 Hz, 2/5H), 5.13-5.10 (complex m, 8/5H), 4.91 (d, J = 6.9 Hz, 2/5H), 4.82 (d, J = 4.0 Hz, 3/5H), 4.80 (d, J = 4.0 Hz, 2/5H), 4.64 (apparently t, J = 8.0 Hz, 3/5H), 4.48 (dd, J = 6.9, 9.7 Hz, 2/5H), 4.46 (s, 2/5H), 3.86-3.78 (complex m, 1H), 3.74 (s, 3/5H), 3.74-3.66 (complex m, 2H), 3.60-3.50 (complex m, 1H), 2.77 (m, 2/5H), 2.71-2.60 (complex m, 6/5H, 2.51 (dd, J = 6.9, 14.3 Hz, 2/5H), 2.23-1.94 (complex m, 5H), 1.88 (dd, J = 4.6, 14.3 Hz, 1H), 1.13 (s, 9H), 1.12 (d, J = 6.9 Hz, 6/5H), 1.09 (d, J = 6.9 Hz, 9/5H); HRMS (ESI) m/z 509.1547 [M+Na]+. A12: Preparation of 15-Deoxy-15-hydro-15-(3-cyanopropyl-1-oxy)-ginkgolide A (compound I-49) To a solution of compound I-48 (75.0 mg) as obtained in Preparation Example A11 in DMSO (1.5 mL) was added NaCN (15.1 mg) at a temperature of 20 to 25 °C. The reaction mixture was heated to 70 °C and stirred. After 16 h, the mixture was then cooled to at a temperature of 20 to 25 °C, diluted with EtOAc, washed, dried, filtrated and concentrated. The residue was subjected to flash column chromatography to give compound I-49 with a yield of 41% as d an inseparable mixture of epimers with a ratio of (S)- to (R)-epimer of approximately 1:1.
1H NMR (500 MHz, acetone-d6, d) 6.01 (s, 1/2H), 5.99 (s, 1/2H), 5.67 (d, J = 4.0 Hz, 1H), 5.14- 5.10 (complex m, 3/2H), 4.91 (d, J = 6.9 Hz, 1/2H), 4.82 (d, J = 4.0 Hz, 1/2H), 4.80 (d, J = 4.0 Hz, 1/2H), 4.65 (apparently t, J = 8.0 Hz, 1/2H), 4.49 (dd, J = 7.4, 9.7 Hz, 1/2H), 4.44 (s, 1/2H), 3.83-3.74 (complex m, 1H), 3.75 (s, 1/2H), 3.54 (m, 1/2H), 3.49 (m, 1/2H), 2.80 (m, 1/2H), 2.70 (m, 1/2H), 2.67-2.49 (complex m, 2H), 2.23-2.09 (complex m, 3H), 1.99-1.86 (complex m, 4H), 1.34 (s, 9/2H), 1.13 (s, 9/2H), 1.13 (d, J = 6.9 Hz, 3/2H), 1.09 (d, J = 6.9 Hz, 3/2H); HRMS (ESI) m/z 500.1883 [M+Na]+. A13: Preparation of (15S)-15-deoxy-15-hydro-15-allyl-ginkgolide A (compound I-53)
To a solution of compound I-10 as obtained in Preparation Example A5 (105 mg) in CH2Cl2 (6.8 mL) at a temperature of 20 to 25 °C was added allyltrimethylsilane (161 mL) and BF3•Et2O (64 mL). After stirring for 3.5 h, the reaction mixture was quenched, extracted, dried, filtrated and concentrated. The residue was purified by the recrystallization from an acetone/hexane solution. The collected solid product was subjected to flash column chromatography to afford compound I-53 with a yield of 32% as a colorless solid.
1H NMR (500 MHz, acetone-d6, d) 6.00 (s, 1H), 5.85 (m, 1H), 5.64 (d, J = 4.0 Hz, 1H), 5.11 (d, J = 4.6 Hz, 1H), 5.03 (dd, J = 1.7, 17.2 Hz, 1H), 4.95 (d, J = 10.3 Hz, 1H), 4.79 (d, J = 4.0 Hz, 1H), 4.54 (apparently t, J = 7.4 Hz, 1H), 4.30 (m, 1H), 4.26 (s, 1H), 2.94 (m, 1H), 2.47 (dd, J = 7.4, 14.9 Hz, 1H), 2.42 (m, 1H), 2.22-2.10 (complex m, 3H), 1.98 (dd, J = 8.0, 14.9 Hz, 1H), 1.88 (dd, J = 4.6, 14.3 Hz, 1H), 1.14 (s, 9H), 1.09 (d, J = 6.9 Hz, 3H); HRMS (ESI) m/z 457.1856 [M+Na]+. A14: Preparation of (15S)-15-Deoxy-15-hydro-15-(2,4,6-trimethoxyphenyl)-ginkgolide A (com- pound I-20)
To a solution of compound I-10 obtained in Preparation Example A5 (33.6 mg) in CH2Cl2 (2.2 mL) at a temperature of 20 to 25 °C was added 1,3,5-trimethoxybenzene (54.9 mg) and BF3•Et2O (20.5 mL). After stirring for 5 min, the reaction mixture was quenched, extracted and the combined organic layers were dried, filtrated and concentrated. The crude product was sub- jected to flash column chromatography to afford compound I-20 with a yield of 86% as a color- less solid.
1H NMR (500 MHz, acetone-d6, d) 6.22 (s, 2H), 5.98 (s, 1H), 5.62 (d, J = 4.6 Hz, 1H), 5.51 (d, J = 11.5 Hz, 1H), 5.11 (d, J = 4.6 Hz, 1H), 4.83 (d, J = 4.0 Hz, 1H), 4.46 (dd, J = 6.9, 9.2 Hz, 1H), 4.16 (s, 1H), 3.81 (s, 9H), 3.30 (m, 1H), 2.50 (dd, J = 6.9, 14.3 Hz, 1H), 2.33 (dd, J = 9.7, 14.3 Hz, 1H), 2.23 (apparently dt, J = 4.0, 13.7 Hz, 1H), 2.14 (dd, J = 4.6, 13.7 Hz, 1H), 1.90 (dd, J = 5.2, 14.3 Hz, 1H), 1.15 (s, 9H), 0.87 (d, J = 6.9 Hz, 3H); HRMS (ESI) m/z 583.2149 [M+Na]+. A15: Preparation of (15S)-15-Deoxy-15-hydro-15-(2,4,6-trimethoxyphenyl)-ginkgolide A (com- pound I-20)
To a solution of compound I-10 as obtained in Preparation Example A5 (33.6 mg) in CH2Cl2 (2.2 mL) at a temperature of 20 to 25 °C was added 1,3,5-trimethoxybenzene (54.9 mg) and BF3•Et2O (20.5 mL). After stirring for 5 min, the reaction mixture was quenched by the dropwise addition of saturated aqueous NaHCO3, extracted, and the combined organic layers were dried, filtrated and concentrated. The residue was subjected to flash column chromatography to afford compound I-20 with a yield of (86%) as a colorless solid.
1H NMR (500 MHz, acetone-d6, d) 6.22 (s, 2H), 5.98 (s, 1H), 5.62 (d, J = 4.6 Hz, 1H), 5.51 (d, J = 11.5 Hz, 1H), 5.11 (d, J = 4.6 Hz, 1H), 4.83 (d, J = 4.0 Hz, 1H), 4.46 (dd, J = 6.9, 9.2 Hz, 1H), 4.16 (s, 1H), 3.81 (s, 9H), 3.30 (m, 1H), 2.50 (dd, J = 6.9, 14.3 Hz, 1H), 2.33 (dd, J = 9.7, 14.3 Hz, 1H), 2.23 (apparently dt, J = 4.0, 13.7 Hz, 1H), 2.14 (dd, J = 4.6, 13.7 Hz, 1H), 1.90 (dd, J = 5.2, 14.3 Hz, 1H), 1.15 (s, 9H), 0.87 (d, J = 6.9 Hz, 3H); HRMS (ESI) m/z 583.2149 [M+Na]+. A16: Preparation of (15S)-15-Deoxy-15-hydro-15-(3,4-dimethoxyphenyl)-ginkgolide A (com- pound I-22)
In analogy to the procedure of the preparation of compound I-20 in Preparation Example A15, compound I-10 as obtained from Preparation Example A5 (144 mg) was reacted with 1,2-di- methoxybenzene (179 mL) to afford compound I-22 with a yield of 54% as a colorless solid 1H NMR (500 MHz, acetone-d6, d) 7.04 (d, J = 1.7 Hz, 1H), 6.88 (d, J = 8.0 Hz, 1H), 6.83 (dd, J = 1.7, 8.0 Hz, 1H), 6.02 (s, 1H), 5.72 (d, J = 4.6 Hz, 1H), 5.18 (d, J = 4.6 Hz, 1H), 4.88 (d, J = 4.0 Hz, 1H), 4.68 (d, J = 10.9 Hz, 1H), 4.58 (t, J = 8.0 Hz, 1H), 4.38 (s, 1H), 3.89 (s, 3H), 3.80 (s, 3H), 2.70 (dd, J = 7.4, 14.9 Hz, 1H), 2.60 (m, 1H), 2.28-2.20 (complex m, 2H), 2.15 (dd, J = 4.6, 13.7 Hz, 1H), 1.91 (dd, J = 4.6, 13.7 Hz, 1H), 1.15 (s, 9H), 0.94 (d, J = 6.9 Hz, 3H); HRMS (ESI) m/z 553.2039 [M+Na]+. A17: Preparation of (15S)-15-deoxy-15-hydroxy-15-(3,4-dimethoxyphenyl)-ginkgolide A (com- pound I-24
To a solution of compound I-22 (77.8 mg) in MeCN/H2O (10/1 v/v) (4.9 mL) at a temperature of 20 to 25 °C was added DDQ (99.8 mg). After stirring for 41 h, the reaction mixture was diluted with saturated aqueous NaHCO3, extracted, and the combined organic layers were dried, fil- trated and concentrated. The residue was purified by the recrystallization from CHCl3/hexane solution. The collected solid was subjected to flash column chromatography to afford compound I-24 (64.2 mg, 80%) as a colorless solid.
1H NMR (500 MHz, acetone-d6, d) 7.08 (d, J = 2.3 Hz, 1H), 7.02 (dd, J = 2.3, 8.6 Hz, 1H), 6.91 (d, J = 8.6 Hz, 1H), 6.00 (s, 1H), 5.74 (d, J = 4.0 Hz, 1H), 5.51 (s, 1H), 5.17 (d, J = 4.0 Hz, 1H), 4.90 (d, J = 4.0 Hz, 1H), 4.80 (t, J = 7.4 Hz, 1H), 4.51 (s, 1H), 3.86 (s, 3H), 3.81 (s, 3H), 2.79 (dd, J = 7.4, 14.9 Hz, 1H), 2.60 (dd, J = 6.9, 13.7 Hz, 1H), 2.27-2.21 (complex m, 2H), 2.15 (dd, J = 4.6, 13.7 Hz, 1H), 1.90 (dd, J = 4.6, 13.7 Hz, 1H), 1.14 (s, 9H), 1.00 (d, J = 6.9 Hz, 3H); HRMS (ESI) m/z 569.1987 [M+Na]+. A17: Preparation of 10,15-bis-(p-fluorobenzylxanthate)-ginkgolide A (compound I-26)
To a solution of compound I-51 as obtained in Preparation Example A1 (117 mg) in
CH3C(=O)CH3 (5.7 mL) at 0 oC was added powdered Cs2CO3 (279 mg), CS2 (337 µL) and 4- fluorobenzyl bromide (88.0 µL). After stirring for 10 min, the reaction mixture was heated to at a temperature of 20 to 25 °C and further stiired for 3 days, then neutralized by the addition of sat- urated aqueous NH4Cl. The mixture was extracted, and the combined organic layers were dried, filtrated and concentrated. The residue was purified by the recrystallization from CHCl3/hexane solution. The collected solid was subjected to flash column chromatography to afford compound I-26 with a yield of 31% as an inseparable mixture of C15-epimers with an (S)- to (R)-ratio of ap- proximately 1:1.
1H NMR (500 MHz, acetone-d6, d) 7.52-7.38 (comp,ex m, 4H), 7.15-7.06 (complex m, 4H), 7.01 (s, 1/2H), 6.96 (s, 1/2H), 6.57 (d, J = 6.9 Hz, 1/2H), 6.38 (s, 1/2H), 6.29 (s, 1/2H), 5.97 (d, J = 4.6 Hz, 1/2H), 5.37 (apparently t, J = 8.6 Hz, 1/2H), 5.15 (d, J = 2.9 Hz, 1/2H), 4.99 (d, J = 2.9 Hz, 1/2H), 4.81 (s, 1/2H), 4.78 (apparently t, J = 8.0 Hz, 1/2H), 4.55 (s, 3H), 4.27 (s, 1H), 4.27 (s, 2/3H), 3.24 (m, 1/2H), 3.07 (m, 1/2H), 2.94 (dd, J = 8.0, 14.3 Hz, 1/2H), 2.74 (dd, J = 7.4, 14.3 Hz, 1/2H), 2.27-2.19 (complex m, 1H), 2.02-1.91 (complex m, 2H), 1.34 (d, J = 6.9 Hz, 3/2H), 1.18 (d, J = 6.9 Hz, 3/2H), 1.13 (s, 9/2H), 1.11 (s, 9/2H); HRMS (ESI) m/z 801.1113
[M+Na]+. A18: Preparation of 15-Deoxy-15-hydro-15-(5-tetrazolyl)-ginkgolide A (compound I-55)
To a solution of compound I-51 (125 mg) in CH2Cl2 (6.1 mL) at 0 °C was added a 50 wt% solu- tion of bis(2-methoxyethyl)aminosulfur trifluoride in THF (224 mL). After stirring for 10 min, the reaction mixture was quenched by the addition of saturated aqueous NaHCO3, extracted, and the combined organic layers were dried, filtrated and concentrated. The residue was subjected to flash column chromatography to afford compound I-55 with a yield of 21% as an inseparable mixture of epimers with an (S)- to (R)-ration of approximately 3 : 2.
1H NMR (500 MHz, acetone-d6, d) 6.03 (s, 2/5H), 6.01 (s, 3/5H), 5.87 (d, J = 4.0 Hz, 2/5H), 5.74 (d, J = 4.0 Hz, 3/5H), 5.69 (d, J = 4.6 Hz, 3/5H), 5.55 (d, J = 4.6 Hz, 2/5H), 5.14 (d, J = 2.3 Hz, 2/5H), 5.13 (d, J = 2.3 Hz, 3/5H), 4.91-4.85 (complex m, 8/5H), 4.71 (s, 2/5H), 4.65 (m, 2/5H), 4.39 (s, 3/5H), 3.07 (m, 2/5H), 2.82 (m, 3/5H), 2.71 (dd, J = 8.0, 15.5 Hz, 3/5H), 2.61 (dd, J = 8.0, 14.3 Hz, 2/5H), 2.24-2.11 (complex m, 12/5H), 1.99 (dd, J = 8.0, 15.5 Hz, 3/5H), 1.89 (dd, J = 4.6, 14.3 Hz, 1H), 1.21 (d, J = 7.4 Hz, 6/5H), 1.17 d, J = 6.9 Hz, 9/5H), 1.14 (s, 18/5H), 1.14 (s, 27/5H). A19: Preparation of 15-Deoxy-15-hydro-15-(5-tetrazolyl)-ginkgolide A (compound I-56)
To a solution of compound I-14 (73.6 mg) in DMF (3.5 mL) at 20 to 25 °C was added NH4Cl (28.2 mg) and NaN3 (34.2 mg). The reaction mixture was heated to 100 oC and stirred for 22 h. The reaction was then cooled to 20 to 25 °C and quenched by the addition of saturated aque- ous NH4Cl, extracted, dried, filtrated and concentrated. The residue was purified by the recrys- tallization from acetone/hexane solution to afford compound I-56 with a yield of 32% as an in- separable mixture of epimers with an (S)- to (R)-ratio of approximately 3 : 1.
1H NMR (500 MHz, acetone-d6, d) 6.05 (s, 3/4H), 5.99 (s, 1/4H), 5.82 (d, J = 8.6 Hz, 1H), 5.21- 5.14 (complex m, 7/4H), 4.93-4.87 (complex m, 3H), 4.73 (apparently t, J = 7.4 Hz, 1/4H), 3.32 (m, 3/4H), 2.86 (m, 1/4H), 2.70-2.60 (complex m, 1H), 2.25-2.11 (complex m, 3H), 1.94-1.88 (complex m, 1H), 1.28 (d, J = 6.9 Hz, 3/4H), 1.15 (s, 27/4H), 1.13 (s, 9/4H), 0.93 (d, J = 6.9 Hz, 9/4H). A20: Preparation of 15-Deoxy-15-hydro-15-isopropylthio-ginkgolide A (compound I-57)
To a solution of the compound I-51 (104 mg) in CH2Cl2 (6.3 mL) at 20 to 25 °C was added 2- propanethiol (118 µL) and BF3•Et2O (111 µL). After stirring for 25 min, the reaction mixture was diluted with EtOAc (5 mL), and then quenched by the addition of H2O (1 mL) and saturated aqueous NaHCO3 (5 mL). The two layers were separated, and the aqueous layer was extracted with EtOAc. The combined organic layers were dried, filtrated and concentrated. The residue was subjected to flash column chromatography and to afford compound I-57 with a yield of 85% as a colorless amorphous and an inseparable mixture of epimers with an (S)- to (R)-ration of approximately 9 : 1.
1H NMR (500 MHz, acetone-d6, d) (major isomer) 5.99 (s, 1H), 5.60 (d, J = 4.1 Hz, 1H), 5.11 (d, J = 4.0 Hz, 1H), 5.01 (d, J = 10.9 Hz, 1H), 4.80 (d, J = 4.0 Hz, 1H), 4.49 (dd, J = 7.5, 9.7 Hz, 1H), 4.45 (s, 1H), 3.08 (m, 1H), 2.63 (m, 1H), 2.52 (dd, J = 7.5, 14.9 Hz, 1H), 2.20-2.10 (com- plex m, 2H), 2.00 (dd, J = 9.7, 14.4 Hz, 1H), 1.87 (dd, J = 5.2, 14.4 Hz, 1H), 1.29 (d, J = 6.9 Hz, 3H), 1.25 (d, J = 6.9 Hz, 3H), 1.13 (s, 9H), 1.13 (d, J = 6.9 Hz, 3H). HRMS (ESI) m/z 491.1702 [M+Na]+. A21: Preparation of 15-Deoxy-15-hydro-15-n-butylthio-ginkgolide A (compound I-58)
In analogy to the procedure of the preparation of compound I-57 in Preparation Example A20, compound I-51 as obtained from Preparation Example A1 (94.2 mg) was reacted with 1-bu- tanethiol (123 µL) to afford compound I-58 with a yield of 83% as a colorless amorphous and an inseparable mixture of epimers with an an (R) to (S) ratio of 7 : 1. 1H NMR (500 MHz, acetone-d6, d) (major isomer) 6.00 (s, 1H), 5.62 (d, J = 4.0 Hz, 1H), 5.12 (d, J = 4.0 Hz, 1H), 4.89 (d, J = 10.9 Hz, 1H), 4.81 (d, J = 4.0 Hz, 1H), 4.49 (dd, J = 7.5, 9.2 Hz, 1H), 4.44 (s, 1H), 2.68-2.52 (complex m, 4H), 2.26-2.09 (complex m, 2H), 1.98 (dd, J = 9.2, 14.3 Hz, 1H), 1.87 (dd, J = 5.2, 14.3 Hz, 1H), 1.58 (m, 2H), 1.44 (m, 2H), 1.14 (s, 9H), 1.11 (d, J = 6.3 Hz, 3H), 0.91 (t, J = 7.5 Hz, 3H); HRMS (ESI) m/z 505.1864 [M+Na]+. A22: Preparation of 15-Deoxy-15-hydro-15-n-butylthio-ginkgolide A (compound I-59)
To a solution of the compound I-51 (70.0 mg) in CH2Cl2 (4.3 mL) at 20 to 25 °C was added 1,3- propanedithiol (59.8 µL) and BF3•Et2O (75.0 µL). After stirring for 15 min, the reaction mixture was diluted with EtOAc (5 mL), and then quenched by the addition of saturated aqueous Na- HCO3 (5 mL). The two layers were separated, and the aqueous layer was extracted with EtOAc. The combined organic layers were dried, filtrated and concentrated. The residue was submitted to flash column chromatography to afford compound I-59 with a yield of 60%.
1H NMR (500 MHz, acetone-d6, d) 5.93 (s, 1H), 5.69 (d, J = 4.6 Hz, 1H), 5.11 (d, J = 4.0 Hz, 1H), 4.88 (d, J = 2.3 Hz, 1H), 4.56 (d, J = 4.0 Hz, 1H), 4.43 (apparently t, J = 6.3 Hz, 1H), 3.65 (d, J = 6.3 Hz, 1H), 3.39 (s, 1H), 3.12-3.00 (complex m, 3H), 2.84 (complex m, 2H) 2.73 (m, 2H), 2.18 (dd, J = 4.0, 13.2 Hz, 1H), 2.12 (m, 1H), 2.04 (m, 1H), 1.94 (dd, J = 4.6, 14.3 Hz, 1H), 1.73 (m, 1H), 1.39 (d, J = 6.9 Hz, 3H), 1.14 (s, 9H); HRMS (ESI) m/z 523.1435 [M+Na]+.
1
17 2 50 R2, R3, and R4 have a meaning as defined n] m/z [M±H]± Method mode
512.2 1 positive
510.2 1 positive
480.2 1 positive
514.2 1 positive
467.1 1 positive
493.2 1 positive
496.2 1 positive
01 0 538.2 1 positive
434 1 positive
513.1 2 negative
538.2 1 positive
437 1 positive
451.1 2 negative
418 2 negative
531 2 negative
437 2 negative
451.1 2 negative
418 2 negative
569.1 2 negative
559.4 2 negative
Figure imgf000101_0001
1
17 2 n] m/z [M±H]± Method mode 05
529.1 2 negative
529.1 2 negative
554.1 2 negative
545 2 negative
499 2 negative
776.9 2 negative
522.1 2 negative
465.2 2 negative
499.2 2 negative
463.2 2 negative
477.2 2 negative 10 505.2 2 negative 1 465.2 2 negative
463.2 2 negative
505.3 2 negative
477.2 2 negative
461.1 2 negative
493.1 2 negative
477.1 2 negative
549.2 2 negative
493.1 2 negative
521.2 2 negative
447.1 2 negative
493.2 2 negative
493.2 2 negative
Figure imgf000102_0001
1
17 2 m/z [M±H]± Method mode 05 484.9 2 negative
476 2 negative
513.1 2 negative
409.0 2 negative
393.1 2 negative
433.0 2 negative
1 20
Figure imgf000103_0001
B. Biological examples
The activity of the compounds of formula (I) of the present invention could be demonstrated and evaluated in biological tests described in the following. B.1: Boll weevil (Anthonomus grandis)
For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of 96-well-mi- crotiter plates containing an insect diet and 5-10 A. grandis eggs.
The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 5 µl, using a custom built micro atomizer, at two replications.
After application, microtiter plates were incubated at about 25 + 1°C and about 75 + 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed.
In this test, compounds I‑1, I‑2, I‑3, I‑4, I‑5, I‑6, I‑7, I‑8, I‑9, I‑10, I‑11, I‑12, I‑13, I‑14, I‑15, I‑16, I‑17, I‑18, I-51, I-52, I-53 at 2500 ppm showed at least 75% mortality in comparison with un- treated controls. B.2 Vetch aphid (Megoura viciae)
For evaluating control of vetch aphid (Megoura viciae) through contact or systemic means the test unit consisted of 24-well-microtiter plates containing broad bean leaf disks.
The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the leaf disks at 2.5 µl, using a custom built micro atomizer, at two replications.
After application, the leaf disks were air-dried and 5– 8 adult aphids placed on the leaf disks in- side the microtiter plate wells. The aphids were then allowed to suck on the treated leaf disks and incubated at about 23 ± 1°C and about 50 ± 5 % relative humidity for 5 days. Aphid mortal- ity and fecundity was then visually assessed.
In this test, compounds I‑1, I‑3, I‑4, I‑5, I‑6, I‑7, I‑8, I‑9, I‑10, I‑11, I‑12, I‑13, I‑14, I‑15, I‑16, I‑17, and I‑18, I-51, I-52, I-53 at 2500 ppm showed at least 75% mortality in comparison with un- treated controls. B.3 Green Peach Aphid (Myzus persicae)
For evaluating control of green peach aphid (Myzus persicae) through systemic means the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial mem- brane. The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were pipetted into the aphid diet, us- ing a custom built pipetter, at two replications.
After application, 5– 8 adult aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at about 23 ± 1°C and about 50 ± 5 % relative humidity for 3 days. Aphid mortality and fecundity was then visually assessed.
In this test, compounds I‑3, I‑4, I‑5, I‑6, I‑7, I‑8, I‑9, I‑10, I‑11, I‑12, I‑13, I‑14, I‑16, I‑17, I‑18, I- 51, I-52, and I-53 at 2500 ppm showed at least 75% mortality in comparison with untreated con- trols. B.4 Green Soldier Stink Bug (Nezara viridula)
The active compound is dissolved at the desired concentration in a mixture of 1:1 (vol:vol) dis- tilled water : acetone. Fresh green bean pods are dipped into treatment solution, and allowed to air dry. Dried treated beans are placed in plastic cups and inoculated with four 4th instar nymph, which have been dipped into treatment solution before. Cups were kept at about 27°C. Percent mortality was recorded after 5 days.
In this test, compounds I-8, I-10, I-11, I-12, I-13, I-14, I-15, I-16, I-17, I-18, I-19, I-31, I-32, I-33, I-36, I-38, I-39, I-40, I-51, and I-52 at 100 ppm showed at least 75% mortality in comparison with untreated controls. B.5 Brown Stink Bug (Euschistus heros)
The active compound is dissolved at the desired concentration in a mixture of 1:1 (vol:vol) dis- tilled water : acetone. Fresh bean pods were placed in a transparent plastic cup and inoculated with ten adult stage individuals. Insects, food and inside of container are sprayed with 1mL solu- tion using an air brush. Treated cups were kept at about 25°C. Percent mortality was recorded after 5 days.
In this test, compounds I-12, I-13, I-14, I-15, I-17, and I-18 at 100 ppm showed at least 75% mortality in comparison with untreated controls.aims

Claims

Claims: 1) Use of a compound of formula (I), or a salt, stereoisomer, tautomer, or N-oxide thereof
Figure imgf000106_0001
as an agrochemical pesticide,
wherein the variables in formula (I) have the following meaning
R1, R2 are independently H, halogen, OH, CN, NO2, N3, or SCN;
C1-C10-alkyl, C2-C10-alkenyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R11;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R12;
OR13, OC(=O)R14, OC(=O)OR13, OC(=O)NR15R16, OC(=O)SR13,
OC(=S)NR15R16, OC(=S)SR13, OS(O)nR14, OS(=O)nNR15R16, ONR15R16, ON=CR18R19, NR15C(=O)R14, NR15C(=O)SR13, NR15C(=O)OR13,
NR15C(=O)NR16R17, NR15R16, N=CR18R19, NNR15R16, NNR15, S(O)nR14, NR15S(=O)nR14, SC(=O)SR13, SC(=O)OR13, SC(=O)NR15R16, S(O)nNR15R16, C(=O)R14, C(=S)R14, C(=O)NR15R16, C(=O)OR13, C(=S)NR15R16, C(=S)OR13, SC(=O)SR13,SC(=O)OR13, C(=S)SR13, C(=NR15)R16, C(=NR15)NR16R17, or Si(R20a)2R20b; or
R1 and R2 form together with the carbon atom they are bonded to a group C=NR15R16, or C=NOR13;
R11 is halogen, CN, NO2, SCN;
C1-C10-alkyl, C2-C10-alkenyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R111;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R112; or
OR113, SR113, OC(=O)R114, OC(=O)OR113, OC(=O)NR115R116, OC(=O)SR113, OC(=S)NR115R116, OS(O)nR114, OS(=O)nNR115R116, ONR115R116, ON=CR118R119, NR115C(=O)R114, NR115R116, N=CR118R119, NNR115R116, NNR115, S(O)nR114, SC(=O)SR113, SC(=O)NR115R116, S(O)nNR115R116, C(=O)R114, C(=O)NR115R116, C(=O)OR113, C(=O)SR113, C(=S)R114, C(=S)NR115R116, C(=S)OR113, C(=S)SR113, C(=NR115)R113, C(=NR115)NR116R117, or Si(R20a)2R20b; R111 is halogen, OH, CN, or NO2;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10- alkyl-carbonyl; or
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents RA;
RA is halogen, OH, NO2, CN, C1-C10-alkyl, C1-C10-haloalkyl, C1-C10-alkoxy, C1-C6-haloalkoxy, or C1-C10-alkyl-carbonyl; or
two germinal substituents RA form a 3- to 7-membered saturated, or par- tially unsaturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substitu- ents selected from halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy;
R112 is halogen, OH, CN, NO2;
C1-C10-alkyl, C1-C10-alkoxy, C3-C8-cycloalkyl, C2-C10-alkenyl, C3-C8-cycloal- kenyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl;
phenyl, which is unsubstituted, or substituted with one or more, same or differ- ent substituents selected from halogen, OH, CN, NO2, C1-C10-alkyl, C1-C10- haloalkyl, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl;
two geminal substituents R112 form together with the atom to which they are bound a group =O, =S, or =NR111; or
two germinal substituents R112 form a 3- to 7-membered saturated, or partially unsaturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or differ- ent heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents RA;
R113 is H;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R111; a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R112;
R114 is H, halogen, CN;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R111; a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R112;
R115, R116, R117 are independently H, CN;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R111;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R112; or
two substituents selected from R115, R116, and R117 that are bound to the same N-atom represent a C2-C6 alkylene chain forming a 3- to 7-membered satu- rated, partially unsaturated, or fully unsaturated heterocyclic ring together with the N-atom they are bonded to, wherein the alkylene chain contains none, or one or more, same or different heteroatoms O, S, or N, and is unsubstituted or substituted with one or more, same or different substituents selected from hal- ogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy, and wherein the N-and/or S-atoms of the heterocyclic ring are oxidized or non-oxi- dized;
R118 is H, halogen, CN, NO2, SCN;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R111; or a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R112;
R119 H, C1-C4-alkyl, C1-C6-cycloalkyl, C1-C2-alkoxy-C1-C2-alkyl, phenyl, benzyl; or R118 and R119 form a 3- to 7-membered saturated, partially unsaturated, or fully unsatu- rated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroa- toms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents RA;
R12 is halogen, CN, NO2, SCN;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R121; a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R122;
OR123, SR123, OC(=O)R124, OC(=O)OR123, OC(=O)NR125R126, OC(=O)SR123, OC(=S)NR125R126, OS(O)nR124, OS(=O)nNR125R126, ONR125R126,
ON=CR118R119, NR125C(=O)R124, NR125R126, N=CR118R119, NNR125R126, NNR125, S(O)nR124, SC(=O)SR123, SC(=O)NR125R126, S(O)nNR125R126, C(=O)R124, C(=O)NR125R126, C(=O)OR123, C(=O)SR123, C(=S)R124, C(=S)NR125R126, C(=S)OR123, C(=S)SR123, C(=NR125)R124, C(=NR125)NR126R127, Si(R20a)2R20b; two geminal substituents R12 form together with the atom to which they are bound a group =O, =S, or =NR121; or
two germinal substituents R12 form a 3- to 7-membered saturated, or partially unsaturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or differ- ent heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents R122; R121 is halogen, OH, CN, NO2;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10- alkyl-carbonyl; or
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents RA;
R122 is halogen, OH, CN, NO2;
C1-C10-alkyl, C1-C10-alkoxy, C3-C8-cycloalkyl, C2-C10-alkenyl, C3-C8-cycloal- kenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1- C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl; phenyl, which is unsubstituted, or substituted with one or more, same or differ- ent substituents selected from halogen, OH, CN, NO2, C1-C10-alkyl, C1-C10- haloalkyl, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl; or two geminal substituents R122 form together with the atom to which they are bound a group =O, =S, or =NR121; or
two germinal substituents R122 form a 3- to 7-membered saturated, or partially unsaturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or differ- ent heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents RA;
R123 is H;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R111; or a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R112;
R124 is H, halogen, CN;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R111; or a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R112;
R125, R126, R127 are independently H, CN;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R111;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R112; or
two substituents selected from R125, R126, and R127 that are bound to the same N-atom represent a C2-C6 alkylene chain forming a 3- to 7-membered satu- rated, partially unsaturated, or fully unsaturated heterocyclic ring together with the N-atom they are bonded to, wherein the alkylene chain contains none, or one or more, same or different heteroatoms O, S, or N, and is unsubstituted or substituted with one or more, same or different substituents selected from hal- ogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy, and wherein the N-and/or S-atoms of the heterocyclic ring are oxidized or non-oxi- dized;
R13 is H;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R131; a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R132;
R131 is halogen, OH, CN, NO2;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10- alkyl-carbonyl; or
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents RA;
R132 is halogen, OH, CN, NO2;
C1-C10-alkyl, C1-C10-alkoxy, C3-C8-cycloalkyl, C2-C10-alkenyl, C3-C8-cycloal- kenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1- C10-alkoxy, and C1-C6-haloalkoxy;
phenyl, which is unsubstituted, or substituted with one or more, same or differ- ent substituents selected from halogen, OH, CN, NO2, C1-C10-alkyl, C1-C10- haloalkyl, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl;
two geminal substituents R132 form together with the atom to which they are bound a group =O, =S, or =NR131; or
two germinal substituents R132 form a 3- to 7-membered saturated, or partially unsaturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or differ- ent heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents RA;
R14 is H, halogen, CN;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R131; a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R132;
R15, R16, R17 are independently H, CN;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R151;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R152; or
or two substituents selected from R15, R16, and R17 that are bound to the same N-atom represent a C2-C6 alkylene chain forming a 3- to 7-membered satu- rated, partially unsaturated, or fully unsaturated heterocyclic ring together with the N-atom they are bonded to, wherein the alkylene chain contains none, or one or more, same or different heteroatoms O, S, or N, and is unsubstituted or substituted with one or more, same or different substituents R152, and wherein the N-and/or S-atoms of the heterocyclic ring are oxidized or non-oxidized; R151 is halogen, OH, CN, NO2;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10- alkyl-carbonyl;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents RA; or
two germinal substituents R151 form a 3- to 7-membered saturated, or partially unsaturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or differ- ent heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents RA;
R152 is halogen, OH, CN, NO2;
C1-C10-alkyl, C1-C10-alkoxy, C3-C8-cycloalkyl, C2-C10-alkenyl, C3-C8-cycloal- kenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1- C10-alkoxy, and C1-C6-haloalkoxy;
phenyl, which is unsubstituted, or substituted with one or more, same or differ- ent substituents selected from halogen, OH, CN, NO2, C1-C10-alkyl, C1-C10- haloalkyl, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl; or two geminal substituents R152 form together with the atom to which they are bound a group =O, =S, or =NR151; or
two germinal substituents R152 form a 3- to 7-membered saturated, or partially unsaturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or differ- ent heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents RA;
R18 is H, halogen, CN, NO2, SCN;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R181; or a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R182;
R19 is H, C1-C4-alkyl, C1-C6-cycloalkyl, C1-C2-alkoxy-C1-C2-alkyl, phenyl, benzyl; or R18 and R19 form a 3- to 7-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or different heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents RA;
R181 is halogen, OH, CN, NO2;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10- alkyl-carbonyl; or
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, wherein said N- and S-atoms are independently oxidized, or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents RA;
R182 is halogen, OH, CN, NO2;
C1-C10-alkyl, C1-C10-alkoxy, C3-C8-cycloalkyl, C2-C10-alkenyl, C3-C8-cycloal- kenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1- C10-alkoxy, and C1-C6-haloalkoxy;
phenyl, which is unsubstituted, or substituted with one or more, same or differ- ent substituents selected from halogen, OH, CN, NO2, C1-C10-alkyl, C1-C10- haloalkyl, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl; or two geminal substituents R182 form together with the atom to which they are bound a group =O, =S, or =NR181; or
two germinal substituents R182 form a 3- to 7-membered saturated, or partially unsaturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or differ- ent heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents RA;
R20a, R20b are independently H, C1-C10-alkyl, C1-C6-haloalkyl, C1-C10-alkoxy, C1-C4- alkoxy-C1-C4-alkyl, C3-C8-cycloalkyl, C3-C8-halocycloalkyl, C1-C4-haloalkoxy- C1-C4-alkyl, or phenyl;
R3 is H, OR31, OC(=O)R32, OC(=O)OR31, OC(=O)NR33R34, OC(=O)SR31,
OC(=S)NR33R34, OC(=S)SR31, OS(O)nR31, OS(=O)nNR33R34, ONR33R34, or ON=CR18R19;
R31 is H;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R311; a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R312;
R311 is halogen, OH, CN, or NO2;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10- alkyl-carbonyl; or
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents RA;
R312 is halogen, OH, CN, NO2;
C1-C10-alkyl, C1-C10-alkoxy, C3-C8-cycloalkyl, C2-C10-alkenyl, C3-C8-cycloal- kenyl, or C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl; phenyl, which is unsubstituted, or substituted with one or more, same or differ- ent substituents selected from halogen, OH, CN, NO2, C1-C10-alkyl, C1-C10- haloalkyl, C1-C10-alkoxy, C1-C6-haloalkoxy, and C1-C10-alkyl-carbonyl;
two geminal substituents R312 form together with the atom to which they are bound a group =O, =S, or =NR311; or
two germinal substituents R312 form a 3- to 7-membered saturated, or partially unsaturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or differ- ent heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents RA;
R32 is H, halogen, CN;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R311; a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R312;
R33, R34 are independently H, CN;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R31;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R32; or
or two R33 and R34 that are bound to the same N-atom represent a C2-C6 al- kylene chain forming a 3- to 7-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring together with the N-atom they are bonded to, wherein the alkylene chain contains none, or one or more, same or differ- ent heteroatoms O, S, or N, and is unsubstituted or substituted with one or more, same or different substituents selected from halogen, C1-C4-alkyl, C1- C4-haloalkyl, C1-C4-alkoxy, and C1-C4-haloalkoxy, and wherein the N-and/or S- atoms of the heterocyclic ring are oxidized or non-oxidized;
R4 is H;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R41;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R42; or
C(=S)OR43, C(=S)SR43, C(=O)OR43, C(=O)R44, S(O)nR44, C(=S)R44, C(=O)NR45R46, C(=O)SR43, C(=S)NR45R46, C(=NR45)R46, C(=NR45)NR46R47; R41 is halogen, CN, NO2, SCN;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R111; a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R112; or
OR113, SR113, OC(=O)R114, OC(=O)OR113, OC(=O)NR115R116, OC(=O)SR113, OC(=S)NR115R116, OS(O)nR113, OS(=O)nNR115R116, ONR115R116,
ON=CR118R119, NR115R116, NR115C(=O)R114, N=CR118R119, NNR115R116, NNR115, S(O)nR113, SC(=O)SR113, SC(=O)NR115R116, S(O)nNR115R116, C(=O)R114, C(=O)NR115R116, C(=O)OR113, C(=O)SR113, C(=S)R114, C(=S)NR115R116, C(=S)OR113, C(=S)SR113, C(=NR115)R113, C(=NR115)NR116R117, Si(R20a)2R20b; R42 is halogen, CN, NO2, SCN;
C1-C10-alkyl, C3-C8-cycloalkyl, C2-C10-alkenyl, C3-C8-cycloalkenyl, C2-C10-al- kynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R121;
phenyl, which is unsubstituted, or substituted with one or more, same or differ- ent substituents R122; or
OR123, SR123, OC(=O)R124, OC(=O)OR123, OC(=O)NR125R126, OC(=O)SR123, OC(=S)NR125R126, OS(O)nR124, OS(=O)nNR125R126, ONR125R126,
ON=CR118R119, NR125R126, NR125C(=O)R124, N=CR118R119, NNR125R126, NNR125, S(O)nR124, SC(=O)SR123, SC(=O)NR125R126, S(O)nNR125R126, C(=O)R124, C(=O)NR125R126, C(=O)OR123, C(=O)SR123, C(=S)R124, C(=S)NR125R126, C(=S)OR123, C(=S)SR123, C(=NR125)R124, C(=NR125)NR126R127, Si(R20a)2R20b; or two geminal substituents R42 form together with the atom to which they are bound a group =O, =S, or =NR121; or
two germinal substituents R42 form a 3- to 7-membered saturated, or partially unsaturated carbo-, or heterocyclic ring together with the atom they are bonded to, wherein the heterocyclic ring contains one or more, same or differ- ent heteroatoms O, S, or N, wherein the N-and/or S-atoms are oxidized or non-oxidized, and wherein the carbo-, or heterocyclic ring is unsubstituted or substituted with one or more, same or different substituents R122; R43 is H;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R131; a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R132;
R44 is H, halogen, CN;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R131;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R132;
R45, R46, R47 are independently H, CN;
C1-C10-alkyl, C1-C10-alkoxy, C2-C10-alkenyl, C2-C10-alkynyl, acetyl, which groups are unsubstituted, or substituted with one or more, same or different substituents R151;
a 3- to 12-membered saturated, partially unsaturated, or fully unsaturated carbo-, or heterocyclic ring or ring system, wherein said heterocyclic ring or ring system comprises one or more, same or different heteroatoms O, N, or S, which are independently oxidized or non-oxidized, and wherein said carbo-, or heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents R152; or
two substituents selected from R45, R46, and R47 that are bound to the same N- atom represent a C2-C6 alkylene chain forming a 3- to 7-membered saturated, partially unsaturated, or fully unsaturated heterocyclic ring together with the N- atom they are bonded to, wherein the alkylene chain contains none, or one or more, same or different heteroatoms O, S, or N, and is unsubstituted or substi- tuted with one or more, same or different substituents R152, and wherein the N- and/or S-atoms of the heterocyclic ring are oxidized or non-oxidized;
R5, R6 are independently H, or OH;
n is 0, 1, or 2. 2) Use according to claim 1, wherein the at least one substituent R1 or R2 is OR13,
OC(=O)R14, SC(=O)SR14, NR15R16, or S(O)nR14. 3) Use according to any of claims 1 or 2, wherein
R13, R14 are independently H;
C1-C10-alkyl, C2-C10-alkenyl, C2-C10-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from
halogen, OH, CN; and a 3- to 8-membered saturated, partially unsaturated, or fully unsaturated carbocyclic ring or ring system, wherein said carbocyclic ring or ring sys- tem is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, CN, C1-C4-alkyl, C1-C4-haloal- kyl, C1-C4-alkoxy, and C1-C4-haloalkoxy; or
a 3- to 8-membered saturated, partially saturated, or fully unsaturated carbo- cycle, which is unsubstituted, or substituted with one or more, same or differ- ent substituents selected from
halogen, OH, CN; and
C1-C4-alkyl, C1-C4-alkoxy, C3-C5-cycloalkyl, C2-C4-alkenyl, C3-C5-cycloal- kenyl, C2-C4-alkynyl, which groups are unsubstituted, or substituted with one or more, same or different substituents selected from halogen, OH, and CN. 4) Use according to claim 1, wherein at least one substituent R1 or R2 is a 3- to 10-me- mebered saturated, partially unsaturated, or fully unsaturated heterocyclic ring or ring sys- tem, wherein said heterocyclic ring or ring system comprises one or more, same or differ- ent heteroatoms O, N, or S, which are independently oxidized or non-oxidized, wherein said heterocyclic ring or ring system is unsubstituted, or substituted with one or more, same or different substituents selected from halogen, C1-C3-alkyl, C1-C3-alkoxy, C1-C3- haloalkyl, C1-C3-haloalkoxy, and phenyl. 5) Use according to claim 1, wherein at least one substituent R1 or R2 is H, halogen, OH, CN, or N3, preferably H, OH, F, N3 or CN, more preferably CN. 6) Use according to any of claims 1 to 5, wherein R3 is H, or OR31. 7) Use according to any of claims 1 to 6, wherein R31 is C1-C6-alkyl, which is unsubstituted, or substituted with halogen, OH, or CN. 8) Use according to any of claims 1 to 7, wherein R4 is H, C(=O)OR43, C(=O)SR43,
C(=S)OR43, or C(=S)SR43. 9) Use according to any of claims 1 to 8, for combating Pentatomidae pests. 10) A compound of formula (I) as defined in any of claims 1 to 8, wherein compounds are excluded that have the following definition of variables in formula (I)
a) One of the variables R1 or R2 is H, while the other variable is CH3C(=O)O;
R3 is OH; and
R4 is benzyl;
b) R1 is H;
R2 is CH2CH=CH2;
R3 is OH; and
R4 is benzyl; c) One of the variables R1 or R2 is H, while the other variable is CH2CH=CH2;
R3, R4 are H;
d) R1, R2 are H, or one of the variable R1 is H, while the other variable is OH. 11) Pesticidal mixtures comprising the compound of formula (I) as defined in any of claims 1 to 8, and another agrochemically active ingredient, preferably a pesticide, more preferably an insecticide and/or fungicide. 12) Agrochemical or veterinary compositions comprising a compound of formula (I) as defined in any of claims 1 to 8, or a pesticidal mixture as defined in claim 11, and a liquid or solid carrier. 13) Methods for controlling invertebrate pests, infestation, or infection by invertebrate pests, comprising contacting a the pests, their food supply, habitat, breeding grounds or their lo- cus with a compound of formula (I) as defined in any of claims 1 to 8 or a pesticidal mix- ture as defined in claim 11 in pesticidally effective amounts. 14) Seed, comprising a compound of formula (I) as defined in any of claims 1 to 8, or a pesti- cidal mixture as defined in claim 11 in an amount of from 0.1 g to 10 kg per 100 kg of seeds.
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