WO2015162133A1 - Pyrazoles comportant un cycloalcényle en c3-c4 destinés à la lutte contre les invertébrés nuisibles - Google Patents

Pyrazoles comportant un cycloalcényle en c3-c4 destinés à la lutte contre les invertébrés nuisibles Download PDF

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WO2015162133A1
WO2015162133A1 PCT/EP2015/058608 EP2015058608W WO2015162133A1 WO 2015162133 A1 WO2015162133 A1 WO 2015162133A1 EP 2015058608 W EP2015058608 W EP 2015058608W WO 2015162133 A1 WO2015162133 A1 WO 2015162133A1
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alkyl
cycloalkenyl
cio
spp
unsubstituted
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PCT/EP2015/058608
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Daniel Saelinger
Birgit GOCKEL
Sebastian Soergel
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to novel pyrazoles of formula I. Moreover, the invention relates to processes and intermediates for preparing the pyrazoles of formula I, and also to active compound combinations comprising them, to compositions comprising them, and to their use for protecting growing plants from attack or infestation by invertebrate pests. Furthermore, the invention relates to methods of applying such compounds. The present invention also relates to seed comprising such compounds.
  • Invertebrate pests and in particular arthropods and nematodes destroy growing and harvested crops and attack wooden dwelling and commercial structures, thereby causing large economic loss to the food supply and to property.
  • There is an ongoing need for new agents for combating invertebrate pests such as insects, arachnids and nematodes.
  • WO 2009/027393, WO 2010/034737, WO 2010/034738, and WO 2010/1 12177 describe derivatives of N-arylamides, derived from pyrazole carboxylic acids. These compounds are mentioned to be useful for combating invertebrate pests.
  • the present invention relates to compounds of formula I
  • U is N or CR u ;
  • T is S, O or NR 1b , wherein R 1b is selected from H , Ci-Cio-alkyl, Ci-C 4 -haloalkyl, C3-C10- cycloalkyl, C3-Cio-cycloalkylmethyl, C3-Cio-halocycloalkyl, C2-Cio-alkenyl, C2-C10- haloalkenyl, C2-Cio-alkynyl, Ci-Cio-alkoxy-Ci-C 4 -alkyl, OR a , heterocyclyl, heterocyclyl- Ci-C 4 -alkyl, aryl, hetaryl, aryl-Ci-C 4 -alkyl and hetaryl-Ci-C 4 -alkyl, wherein the cyclic moi- eties may be unsubstituted or may carry 1 , 2, 3, 4 or 5 identical or different substituents selected from halogen,
  • R 1 is H, CN, Ci-Cio-alkyl, Ci-Cio-haloalkyl, C 3 -Cio-cycloalkyl, C 3 -Cio-halocycloalkyl, C1-C4- alkoxy-Ci-C4-alkyl, C2-Cio-alkenyl, C2-Cio-haloalkenyl, C2-Cio-alkynyl, C3-Cio-haloalkynyl, Ci-C 5 -alkylen-CN , OR a , Ci-C 5 -alkylen-OR a , C(Y)R b , Ci-C 5 -alkylen-C(Y)R b , C(Y)OR c , Ci- C 5 -alkylen-C(Y)OR c , S(0) 2 R d , NR e R f , Ci-C 5 -alkylen-NR
  • R 2 and R 3 are independently of each other selected from H, halogen, CN , NO2, Ci-Cio-alkyl, C2- Cio-alkenyl, C2-Cio-alkynyl, wherein the C-atoms may be unsubstituted, may be partially or fully halogenated, or may carry 1 , 2 or 3 identical or different substituents R x ;
  • L-C3-Cio-cycloalkenyl, L-C3-Cio-cycloalkenyloxy and L-C3-Cio-cycloalkenylthio wherein the cycloalkenyl rings may be unsubstituted, may be partially or fully halogenated, or may carry 1 , 2, 3, 4 or 5 identical or different substituents selected from the radicals Ry and R x , and wherein
  • L is Ci-Cs-alkylene, C2-Cs-alkenylene, C2-Cs-alkynylene, or C3-C6-cycloalkylene, wherein the C-atoms may be unsubstituted or may carry 1 , 2, 3, 4 or 5 identical or different substituents R x ;
  • Ci-C 5 -alkylene-OR a Ci-C 5 -alkylene-CN, Ci-C 5 -alkylene-C(Y)R , C1-C5- alkylene-C(Y)OR c , Ci-C 5 -alkylene-N R e R f , Ci-C 5 -alkylene-C(Y)NR9R h , Ci-C 5 -alkylene- S(0)mR d , Ci-C 5 -alkylene-S(0)mN R e R f , d-Cs-alkylene-NR'NR ⁇ , heterocyclyl, hetaryl, C3-Cio-cycloalkyl, C3-Cio-cycloalkenyl, heterocyclyl-Ci-Cs-alkyl, hetaryl-Ci-Cs-alkyl, C3- Cio-cycloalkenyl, heterocyclyl-Ci-Cs-alkyl,
  • L is Ci-Cs-alkylene, C2-Cs-alkenylene, C2-Cs-alkynylene, or C3-C6-cycloalkylene, wherein the C-atoms may be unsubstituted or may carry 1 , 2, 3, 4 or 5 identical or different substituents R x ;
  • R 4a , R 4b and R 4c are independently of each other selected from H, halogen, CN, NO2, Ci- Cio-alkyl, C2-Cio-alkenyl, C2-Cio-alkynyl, wherein the C-atoms may be unsubstituted, may be partially or fully halogenated or may carry 1 , 2 or 3 identical or different substituents R x ;
  • Ci-Cio-haloalkyl Ci-Cio-alkoxy, Ci-C4-alkoxy-Ci-Cio-alkyl, wherein the C-atoms may be unsubstituted, or partially or fully substituted by identical or different sub- stituents Ry;
  • heterocyclyl C3-Cio-cycloalkyl, C3-Cio-cycloalkenyl, hetaryl, aryl, heterocyclyl-Ci-
  • C5-alkyl C3-Cio-cycloalkyl-Ci-C5-alkyl, C3-Cio-cycloalkenyl-Ci-C5-alkyl, hetaryl- Ci-Cs-alkyl, and aryl-d-Cs-alkyl, wherein the cyclic moieties may be
  • unsubstituted may be partially or fully halogenated, or may carry 1 , 2, 3, 4 or 5 identical or different substituents Ry;
  • A is a 3- to 12-membered non-aromatic carbo- or heterocycle, which heterocycle may contain 1 , 2, 3, 4 or 5 heteroatoms selected from N, O, and S, wherein S may be oxidised, and which carbo- or heterocycle may be partially or fully substituted by R and/or R' radicals;
  • D is a direct bond, Ci-C6-alkylene, C2-C6-alkenylene, or C2-C6-alkynylene, which carbon chains can be partially or fully substituted R n ;
  • E is a non-aromatic 3- to 12-membered carbo- or heterocycle, which may contain 1 , 2, 3, or 4 heteroatoms selected from N, O, and S, wherein S may be oxidised, which carbo- or heterocycle may be partially or fully substituted by R N and/or R 1 radicals;
  • G is Ci-C6-alkylene, C2-C6-alkenylene, C2-C6-alkynylene, C3-C6-cycloalkylene, or C3-C6-cycloalkenylene, wherein the C-atoms may be unsubstituted, or partially or fully substituted by RP;
  • R 4D is Ci-C4-haloalkyl or C3-C6-cycloalkyl, which may be halogenated;
  • Q is a direct bond, d-Cs-alkylene, C2-Cs-alkenylene, or C2-Cs-alkynylene, which carbon chains can be partially or fully substituted by R R ;
  • R 4E is H, d-Cs-alkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -alkynyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 - cycloalkenyl, 3- to 6-membered heterocycle, which may contain 1 or 2 heteroatoms selected from N, O, and S, wherein S may be oxidised, which groups can be unsubstituted, or partially or fully substituted by R R and/or R' radicals; or R 4E and Q together may form a 3- to 6-membered carbocyclic ring or a 4- to 6- membered heterocyclic ring with a direct bond to the pyrazole moiety, which ring may contain 1 or 2 heteroatom moieties selected from N, O, and S, wherein S may be oxidized, and which ring can be partially or fully substituted by R R and/or R' radicals;
  • M is O, S, N R M , NOR M , or NSR M , wherein
  • R M is a group mentioned for R 4E , or wherein
  • R M and Q may together form a 4- to 6-membered unsaturated, non-aromatic N- containing heterocyclic ring, which ring may contain an additional heteroatom selected from O, and S, wherein S may be oxidized, and which ring can be partially or fully substituted by R R ;
  • W is Ci-Cs-alkylene, Cs-Cs-cycloalkylene, Cs-Cs-heterocycloalkylene, C2-C8- alkenylene, Cs-Cs-cycloalkenylene, Cs-Cs-heterocycloalkenylene, or C2-C8- alkynylene, wherein W may be unsubstituted or may be partially or fully substi- tuted by substituents which, independently of each other, are selected from R 1 and/or R 1 radicals;
  • V is O, S or N R 1A , wherein R 1A is selected from H, Ci-Cio-alkyl, Ci-C 4 -haloalkyl, C 3 - Cio-cycloalkyl, C3-Cio-cycloalkylmethyl, C3-Cio-halocycloalkyl, C2-Cio-alkenyl, C2- Cio-haloalkenyl, C2-Cio-alkynyl, Ci-Cio-alkoxy-Ci-C 4 -alkyl, OR A , heterocyclyl, heterocyclyl-Ci-C 4 -alkyl, aryl, hetaryl, aryl-Ci-C 4 -alkyl and hetaryl-Ci-C 4 -alkyl, wherein the cyclic moieties may be unsubstituted or may carry 1 , 2, 3, 4 or 5 identical or different substituents selected from halogen, CN, NO2,
  • R 1A and R 4 ⁇ together with the carbon atom to which R 4 9 is bonded and the nitrogen atom to which R 1A is bonded as well as the nitrogen atom between said carbon atom and said nitrogen atom form a 4- to 8-membered heterocycle, which contains the two nitrogen atoms as heteroatoms, and may further contain 1 or 2 heteroatoms which, independently of each other, are selected from N, O, and S, wherein S may be oxidized, and/or wherein the heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R 1 and/or R 1 radicals;
  • R 4 9 is H, d-Ce-alkyl, Ci-C 6 -alkyl-X, C 3 -C 6 -cycloalkyl or C 3 -C 6 -cycloalkyl-X, wherein X is selected from O, S, NH or NR', wherein the Ci-C6-alkyl or C3-C6-cycloalkyl may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R 1 ; and
  • R 4f is Ci-C6-alkyl, Ci-C6-alkyl-X, C3-C6-cycloalkyl or C3-C6-cycloalkyl-X, wherein X is selected from O, S, NH or NR', wherein the Ci-C6-alkyl or C3-C6-cycloalkyl may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R 1 ; or
  • R 4 9 and R 4f together with the carbon atom to which they are bonded form a 3- to 8- membered, saturated or unsaturated carbo- or heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from N, O, and S, wherein S may be oxidized and/or wherein the carbo- or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R 1 and/or R 1 radicals; and wherein
  • R a , R b , R c are independently of each other selected from H, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6- cycloalkyl, C3-C6-cycloalkylmethyl, C3-C6-halocycloalkyl, C3-C6-cycloalkenyl, C3-C6- cycloalkenylmethyl, C3-C6-halocycloalkenyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4- alkynyl, Ci-C4-alkoxy-Ci-C4-alkyl, heterocyclyl, heterocyclyl-Ci-C4-alkyl, aryl, hetaryl, ar- yl-Ci-C4-alkyl and hetaryl-Ci-C4-alkyl, wherein the cyclic moieties may be unsubstit
  • R d is selected from H, Ci-C4-alkoxy, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6- cycloalkylmethyl, C3-C6-halocycloalkyl, C3-C6-cycloalkenyl, C3-C6-cycloalkenylmethyl, C3- C6-halocycloalkenyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, Ci-C4-alkoxy-Ci- C4-alkyl, heterocyclyl, heterocyclyl-Ci-C4-alkyl, aryl, hetaryl, aryl-Ci-C4-alkyl and hetaryl- Ci-C4-alkyl, wherein the cyclic moieties may be unsubstituted or may carry 1 , 2,
  • R e , R f are independently of each other selected from H, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6- cycloalkyl, C3-C6-cycloalkylmethyl, C3-C6-halocycloalkyl, C3-C6-cycloalkenyl, C3-C6- cycloalkenylmethyl, C3-C6-halocycloalkenyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4- alkynyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkylcarbonyl, Ci-C4-haloalkylcarbonyl, C1-C4- alkylsulfonyl, Ci-C4-haloalkylsulfonyl, heterocyclyl, heterocyclyl-Ci-C4-alkyl,
  • R e and R f together with the nitrogen atom to which they are bonded form a 5- or 6-membered, saturated or unsaturated heterocycle, which may carry a further heteroatom being se- lected from O, S and N as a ring member atom, and wherein the heterocycle may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substituents which are independently of each other selected from halogen, CN, NO2, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci- C4-haloalkoxy;
  • R h are independently of each other selected from H, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6- cycloalkyl, C3-C6-halocycloalkyl, C3-C6-cycloalkenyl, C3-C6-cycloalkenylmethyl, C3-C6- halocycloalkenyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, Ci-C4-alkoxy-Ci-C4- alkyl, heterocyclyl, heterocyclyl-Ci-C4-alkyl, aryl, hetaryl, aryl-Ci-C4-alkyl and hetaryl-Ci- C4-alkyl, wherein the cyclic moieties may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substituents which are independently of each other selected from
  • halogen OH, CN, NO2, Ci-Cio-alkyl, Ci-Cio-haloalkyl, Ci-Cio-alkoxy, Ci- Cio-haloalkoxy, or S(0) m R k , C3-C6-cycloalkyl, or 3- to 6-membered heterocycle, which may contain 1 or 2 heteroatoms selected from N, O, and S, wherein S may be oxidized, which R j groups are unsubstituted or partially or fully substituted by R m and/or R' radicals and wherein two groups R j connected to the same or adjacent ring atoms may together form a 3- to 6-membered carbo- or heterocycle which heterocycle may contain 1 or 2 heteroatoms selected from N, O, and S, wherein S may be oxidised, which cycles may be partially or fully substituted by R m and/or R' radicals;
  • Ci-C4-alkyl is H, Ci-C4-alkyl, Ci-C4-haloalkyl, or C3-C6-cycloalkyl, which cycle may be partially or fully substituted by R';
  • Ci-C4-alkyl Ci-C4-haloalkyl, Ci-C4-alkylcarbonyl, Ci-C4-haloalkylcarbonyl, or Ci-C4-alkoxycarbonyl;
  • halogen OH, CN, N0 2 , Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, C 3 -C 6 -cycloalkyl, Ci- C4-alkoxy, Ci-C4-haloalkoxy, or S(0) m R k ;
  • Ci-C4-alkyl is H, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl, Ci-C4-alkoxy;
  • Ci-C4-alkyl Ci-C4-haloalkyl, C3-C6-cycloalkyl, Ci-C4-alkoxy, C1-C4- alkylcarbonyl, Ci-C4-haloalkylcarbonyl, or Ci-C4-alkoxycarbonyl;
  • RP is halogen, CN, NO2, Ci-C2-alkyl, Ci-C2-haloalkyl, C3-C6-cycloalkyl, Ci-C4-alkoxy, or Cr C2-haloalkoxy, or two groups RP can together form a 3- to 6-membered carbo- or hetero- cyclic ring, which heterocycle contains 1 or 2 heteroatoms selected from N, O, and S, wherein S may be oxidised, which carbo- or heterocyclic ring is unsubstituted or partly or fully substituted by groups R ⁇ ;
  • R q is halogen, CN, N0 2 , Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, C 3 -C 6 -cycloalkyl, Ci-C 4 -alkoxy, or Ci- C 4 -haloalkoxy;
  • R r bonded to C is halogen, CN, N0 2 , Ci-C 2 -alkyl, Ci-C 2 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 2 - haloalkoxy, or S(0) m R k ; or two groups R r can together form a 3- to 6-membered carbo- or heterocyclic ring, which heterocycle contains 1 or 2 heteroatoms selected from N, O, and S, wherein S may be oxidized, and which carbo- or heterocyclic ring is unsubstituted or partially or fully substituted by R s ;
  • R s is halogen, CN, N0 2 , Ci-C 2 -alkyl, Ci-C 2 -haloalkyl, C 3 -C 6 -cycloalkyl, Ci-C 4 -alkoxy, or Ci- C 2 -haloalkoxy;
  • N NSR V ; or two R 1 bonded to the same carbon atom or to adjacent carbon atoms together with the carbon atom(s) to which they are bonded form a 3- to 6-membered, saturated or unsaturated carbo- or heterocycle, which may contain 1 or 2 heteroatoms which, independently of each other, are selected from N, O, and S, wherein S may be oxidized, wherein N may be unsubstituted or substituted by R';
  • R v is Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, C3-C6-cycloalkyl, or C3-C6-halocycloalkyl;
  • R w is H, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, C3-C6-cycloalkyl, or C3-C6-halocycloalkyl, Ci-C 4 -alkoxy, or Ci-C 4 -haloalkoxy;
  • R x is selected from halogen, CN, N0 2 , Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 - haloalkoxy, S(0) m R d , S(0) m NR e R f , Ci-Cio-alkylcarbonyl, Ci-C 4 -haloalkylcarbonyl, Ci-C 4 - alkoxycarbonyl, Ci-C 4 -haloalkoxycarbonyl, C3-C6-cycloalkyl, 5- to 7-membered heterocyclyl, 5- or 6-membered hetaryl, aryl, C3-C6-cycloalkoxy, 3- to 6-membered heterocyclyloxy and phenoxy, wherein the cyclic moieties may be unsubstituted or may carry 1 , 2, 3, 4 or 5 radicals R y ; and
  • R y is selected from halogen, CN, N0 2 , Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 - haloalkoxy, S(0) m R d , S(0) m NR e R f , Ci-C 4 -alkylcarbonyl, Ci-C 4 -haloalkylcarbonyl, Ci-C 4 - alkoxycarbonyl, Ci-C 4 -haloalkoxycarbonyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C 2 -C 4 - alkenyl, C 2 -C 4 -haloalkenyl, C 2 -C 4 -alkynyl and Ci-C 4 -alkoxy-Ci-C 4 -alkyl;
  • Y is O or S
  • n 0, 1 or 2;
  • R 2 and R 3 are substituents, which comprises a C3-C 4 -cycloalkenyl group, which may be unsubstituted, may be partially or fully halogenated or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from radicals R x or R y ;
  • R 4 is any one of options (i) or (ii), which comprises a C3-C4-cycloalkenyl group, which may be unsubstituted, may be partially or fully halogenated or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from radicals R ;
  • R 4a , R 4b and R 4c comprises a C3-C4-cycloalkenyl group, which may be unsubstituted, may be partially or fully halogenated, or may carry 1 ,
  • E is a C3-C4-cycloalkenyl group, which may be partially or fully substituted by R n ;
  • G is a C3-C4-cycloalkenyl group, wherein the C-atoms may be unsubstituted, or partially or fully substituted by RP;
  • the present invention relates to a composition and to an agricultural composition for combating animal pests comprising at least one compound of formula I .
  • the present invention relates to a method for combating or controlling invertebrate pests and to a method for protecting growing plants from attack or infestation by invertebrate pests.
  • the present invention relates to seed comprising a compound of for- mula I , and in yet another aspect, the present invention relates to the use of the compounds of formula I for protecting growing plants from attack or infestation by invertebrate pests.
  • the present invention relates to compounds of formula I , wherein T is O, S or NR 1 b . These compounds correspond to formula 1.1 , formula I .2 and formula 1.3, respectively.
  • the compounds according to the invention can be prepared analogously to the synthesis routes described in WO 2009/027393 and WO 2010/034737 according to standard processes of organic chemistry.
  • Compounds of formula 1.1 wherein T is O, can be prepared e.g. by reacting activated pyrazole carboxylic acid derivatives of formula I I with a 3-aminopyridine, or 4-aminopyridazine of formula I I I (e.g. Houben-Weyl: "Methoden der organ. Chemie” [Methods of Organic Chemistry], Georg- Thieme-Verlag, Stuttgart, New York 1985, Volume E5, pp. 941 -1045).
  • Compounds of formula 1.1 wherein R 1 is different from hydrogen can also be prepared by alkylating the amides 1.1 , in which R 1 is hydrogen, using suitable alkylating agents in the presence of bases.
  • the alkylation can be effected under standard conditions known from literature.
  • X is a suitable leaving group such as halo- gen, N3, p-nitrophenoxy or pentafluorophenoxy and the like.
  • Activated pyrazole carboxylic acid derivatives of formula II are preferably halides, activated esters, anhydrides, azides, for example chlorides, fluorides, bromides, para-nitrophenyl esters, pentafluorophenyl esters, N-hydroxysuccinimides, hydroxybenzotriazol-1 -yl esters.
  • the activated pyrazole carboxylic acid derivatives of formula II al- ready contain those radicals R 2 , R 3 and R 4 , which are desired for the pyrazole compound of formula I.
  • R 4 in the pyrazole compound of formula I is any one of the following groups (iiia), (iiib), (iiic), 3 ⁇ 4 G S(0)m_R d (iiid),
  • the following activated pyrazole carboxylic acid derivatives of formula II are preferably used in the above described synthesis of the pyrazole compounds of formula 1.1 .
  • the activated pyrazole carboxylic acid derivatives of formula II including the activated pyrazole carboxylic acid derivatives of formulae ll(iiia), ll(iiib), ll(iiic), ll(iiid) and ll(iva) as well as the com- pounds of formula III are commercially available or can be prepared by methods known in the literature (cf. WO 05/040169; WO 08/074824; Journal of Fluorine chemistry 132(1 1 ), p. 995 (201 1 )).
  • the activated pyrazole carboxylic acid derivatives of formula 11 (ivb) can be prepared by methods known in the art starting from commercially available precursors.
  • the carbon nitrogen double bond of group (ivb) may be established by a reaction, which is analogous to an imine formation, starting from an aldehyde or ketone substituted by R 4 ⁇ and R 4f and a suitable pyrazole carboxylic acid derivative (see WO 2013/072882, J. Org. Chem. 48(20), p. 3531
  • the V-W-bond of group (ivb) may be established by a substitution reaction, starting from an oxime, thioxime or hydrazone substituted by R 4 9 and R 4f and a suitable pyrazole carboxylic acid derivative, which contains a leaving group at the W substituent (see J. Med. Chem, 28(7), p. 896 (1985)).
  • the pyrazole carboxylic acid derivative may be converted to an activated pyrazole carboxylic acid derivative of formula 11 (ivb).
  • Compounds of formula 1.2, wherein T is S can be prepared e.g. by reacting compounds of formula 1.1 with 2,4-bis(4-methoxyphenyl)-1 ,3,2,4-dithiadiphosphetane-2,4-disulfide or PSs according to the method described in Synthesis 2003, p. 1929.
  • the present invention relates to compounds of formula I, wherein U is CR U , preferably CH or N.
  • U is CR U , preferably CH or N.
  • R 1 is H
  • the compounds of formula I may be present in two or three tautomeric forms depending on the meaning of U. For example, if U is selected to be CH, as in the compounds of formula I.A, two tautomers T-A and T-B can be formed.
  • R 1 is different from H
  • the compounds of formula I may be present in two or three isomeric forms depending on the meaning of U. For example, if U is selected to be CH, as in the com- pounds of formula I. A, two structural isomers ISO-A and ISO-B can be formed.
  • ISO-B and ISO-C can be formed.
  • the compounds of formula I are present in the form of the structural isomers ISO-A.
  • the compounds of formula I may also be present in the form of the structural isomers ISO-B or ISO-C or in the form of mixtures of two or more of the structural isomers ISO-A, ISO-B and ISO-C.
  • the structural isomer ISO-A only throughout the specification, but its description embraces the disclosure of the other structural isomers as well.
  • Isomers ISO-C can be obtained by alkylation of compounds I.B, wherein R 1 is hydrogen.
  • the reaction can be performed by analogy to known N-alkylation of pyridazines.
  • N-Alkylation of pyridazines is known in literature and can be found in e.g.: J. Chem. Soc, Perkin Trans. Vol. 1 , p. 401 (1988), and J. Org. Chem. Vol. 46, p. 2467 (1981 ).
  • the following compound I.B. may be used as starting material.
  • the present invention relates to compounds of formula I, wherein R 4 is any one of groups (iiia), (iiib), (iiic), (iiid), (iva) or (ivb). These compounds correspond to formula l(iiia), formula l(iiib), formula l(iiic), formula l(iiid), formula l(iva) and formula l(ivb), respectively.
  • the present invention relates to compounds of formula I, wherein at least one of R 2 and R 3 is a substituent, which comprises a C3-C4-cycloalkenyl group, which may be unsubstituted, may be partially or fully halogenated or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from radicals R x or Ry.
  • R 2 is a substituent, which comprises a C3-C4-cycloalkenyl group, which may be unsubstituted, may be partially or fully halogenated or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from radicals R x or Ry, correspond to formula I.R 2c y, wherein R 2c y denotes a substituent falling under the definition of R 2 , which comprises a C3-C4- cycloalkenyl group, which may be unsubstituted, may be partially or fully halogenated or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from radicals R x or Ry.
  • R 3 is a substituent, which comprises a C3-C4-cycloalkenyl group, which may be unsubstituted, may be partially or fully halogenated or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from radicals R x or Ry, correspond to formula I.R 3c y, wherein R3cy denotes a substituent falling under the definition of R 3 , which comprises a C3-C4- cycloalkenyl group, which may be unsubstituted, may be partially or fully halogenated or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from radicals R x or Ry.
  • the present invention relates to compounds of formula I, wherein R 4 is selected as outlined in the following to give compounds of formula I.R 4c y(i), formula I.R 4c y(ii), formu- la I.R 4c (iiia), formula I.R 4c y(iiib), formula I.R 4c y(iiic), and formula I.R 4c y(iiid).
  • Ci-C 5 -alkylene-OR a Ci-C 5 -alkylene-CN, Ci-C 5 -alkylene-C(Y)R b , Ci- C 5 -alkylene-C(Y)OR c , Ci-C 5 -alkylene-NR e R f , Ci-C 5 -alkylene-C(Y)NR9R h , Ci-C 5 - alkylene-S(0) m R d , Ci-C 5 -alkylene-S(0) m NR e R f , d-Cs-alkylene-NR i NR ⁇ f , heterocyclyl, hetaryl, C3-Cio-cycloalkyl, C3-Cio-cycloalkenyl, heterocyclyl-C-i-Cs-alkyl, hetaryl-Ci-Ci-Cs-alkyl, C3-Cio-cycloalkenyl, heterocycly
  • R 4cy (i) denotes a substituent falling under the definition of R 4 according to option (i), which comprises a C3-C4-cycloalkenyl group, which may be unsubstituted, may be partially or fully halogenated or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from radicals R y .
  • R 4cy (ii) denotes a substituent falling under the definition of R 4 according to option (ii), which comprises a C3-C4-cycloalkenyl group, which may be unsubstituted, may be partially or fully halogenated or may carry 1 , 2, 3, 4, or 5 identical or different substituents selected from radicals R y .
  • R 4 is a substituent according to option (iiia), i.e. a substituent represented by the group (iiia)
  • R 4a , R 4b and R 4c comprises a C3-C4-cycloalkenyl group, which may be unsubstituted, may be partially or fully halogenated, or may carry 1 , 2, 3, 4, or 5 identical or different substituents R y , correspond to formula I.R 4cy (iiia), wherein R 4cy (iiia) denotes a substituent falling under the definition of R 4 according to option (iiia), wherein at least one of R 4a , R 4b and R 4c comprises a C3-C4-cycloalkenyl group, which may be unsubstituted, may be partially or fully halogenated, or may carry 1 , 2, 3, 4, or 5 identical or different substituents R y .
  • R 4 is a substituent according to option (iiib), i.e. a substituent represented by the group (iiib)
  • A is a C3-C4-cycloalkenyl group, which may be partially or fully substituted by Ri, corre- spond to formula I.R 4cy (iiib), wherein R 4cy (iiib) denotes a substituent falling under the definition of R 4 according to option (iiib), wherein A is a C3-C4-cycloalkenyl group, which may be partially or fully substituted by Ri.
  • R 4 is a substituent according to option (iiic), i.e. a substituent represented by the group (iiic)
  • E is a C3-C4-cycloalkenyl group, which may be partially or fully substituted by R N , correspond to formula I.
  • R 4 is a substituent according to option (iiid), i.e. a substituent represented by the group (iiid)
  • G is a C3-C4-cycloalkenyl group, wherein the C-atoms may be unsubstituted, or partially or fully substituted by RP, correspond to formula I.
  • N-oxides of the compounds of formula I can be prepared by oxidation of compounds I according to standard methods of preparing heteroaromatic N-oxides, e.g. by the method described in Journal of Organometallic Chemistry 1989, 370, 17-31 .
  • reaction mixtures are worked up in the customary manner, for example by mixing with water, separating the phases, and, if appropriate, purifying the crude products by chromatography, for example on alumina or on silica gel.
  • Some of the intermediates and end products may be obtained in the form of colorless or pale brown viscous oils which are freed or purified from volatile components under reduced pressure and at moderately elevated temperature. If the inter- mediates and end products are obtained as solids, they may be purified by recrystallization or trituration.
  • compound(s) according to the invention comprises the compound(s) as defined herein as well as a stereoisomer, salt, tautomer or N-oxide thereof.
  • compound(s) of the present invention is to be understood as equivalent to the term “compound(s) according to the invention”, therefore also comprising a stereoisomer, salt, tautomer or N-oxide thereof.
  • the radicals attached to the backbone of formula I may contain one or more centers of chirali- ty.
  • the compounds of formula I are present in the form of different enantiomers or diastereomers, depending on the substituents.
  • the present invention relates to every possible stereoisomer of the formula I, i.e. to single enantiomers or diastereomers, as well as to mixtures thereof.
  • the compounds of formula I may be present in the form of different structural isomers depending on the position of R 1 , provided that R 1 is different from H.
  • the pre- sent invention relates to every possible structural isomer as indicated in the compounds of formula I .A(R *H):ISO-A, formula I.A(R *H):ISO-B, formula I .B(R *H):ISO-A, formula
  • the compounds of formula I may also be present in the form of different tautomers depending e.g. on the selection of the radicals R 1 and R 4 .
  • the present inven- tion relates to every possible tautomer of the formula I.
  • the compounds of formula I may be present in the form of different geometric isomers depending e.g. on the selection of R 4 . If geometric isomers are possible, the present invention relates to both, the E- and Z-isomers of the compounds of formula I .
  • the compounds of formula I may be amorphous or may exist in one or more different crystal- line states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities.
  • the present invention relates to amorphous and crystalline compounds of formula I , mixtures of different crystalline states of the respective compound I , as well as amorphous or crystalline salts thereof.
  • Salts of the compounds of the formula I are preferably veterinary and/or agriculturally accepta- ble salts, preferably agriculturally acceptable salts. They can be formed in a customary manner, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality.
  • Veterinary and/or agriculturally useful salts of the compounds of formula I encompass especially the acid addition salts of those acids whose cations and anions, respectively, have no ad- verse effect on the pesticidal action of the compounds of formula I .
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting com- pounds 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 formula I which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety.
  • the organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members.
  • the prefix C n - Cm indicates in each case the possible number of carbon atoms in the group.
  • halogen denotes in each case fluorine, bromine, chlorine or iodine, in particular flu- orine, chlorine or bromine.
  • alkyl as used herein and in the alkyl moieties of alkylamino, alkylcarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl and alkoxyalkyl denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably from 1 to 3 carbon atoms.
  • Examples of an alkyl group are methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 1 - methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethyl propyl, n-hexyl, 1 ,1 - dimethylpropyl, 1 ,2-dimethylpropyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4- methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3- dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1
  • haloalkyl as used herein and in the haloalkyl moieties of haloalkylcarbonyl, haloalkoxycarbonyl, haloalkylthio, haloalkylsulfonyl, haloalkylsulfinyl, haloalkoxy and
  • haloalkoxyalkyl denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms.
  • Preferred haloalkyl moieties are selected from Ci-C4-haloalkyl, more preferably from Ci- C3-haloalkyl or Ci-C2-haloalkyl, in particular from Ci-C2-fluoroalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and the like.
  • alkoxy denotes in each case a straight-chain or branched alkyl group which is bonded via an oxygen atom and has usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
  • alkoxy group examples are methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, 2-butyloxy, iso-butyloxy, tert.-butyloxy, and the like.
  • alkoxyalkyl refers to alkyl usually comprising 1 to 10, frequently 1 to 4, preferably 1 to 2 carbon atoms, wherein 1 carbon atom carries an alkoxy radical usually comprising 1 to 4, preferably 1 or 2 carbon atoms as defined above. Examples are CH2OCH3, CH2-OC2H5, 2-(methoxy)ethyl, and 2-(ethoxy)ethyl.
  • haloalkoxy denotes in each case a straight-chain or branched alkoxy group having from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms, in particular fluorine atoms.
  • Preferred haloalkoxy moieties include C1-C4- haloalkoxy, in particular Ci-C2-fluoroalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1 -fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2- chloro-2-fluoroethoxy, 2-chloro-2,2-difluoro-ethoxy, 2,2dichloro-2-fluorethoxy, 2,2,2- trichloroethoxy, pentafluoroethoxy and the like.
  • Ci-C2-fluoroalkoxy such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1 -fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2- chloro-2-fluoroethoxy,
  • alkylthio ( alkylsulfanyl: alkyl-S-)
  • haloalkylthio refers to an alkylthio group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • haloalkylsulfinyl refers to an alkylsulfinyl group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • haloalkylsulfonyl refers to an alkylsulfonyl group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • haloalkylcarbonyl refers to an alkylcarbonyl group as mentioned above, wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • alkoxycarbonyl refers to an alkylcarbonyl group as defined above, which is bonded via an oxygen atom to the remainder of the molecule.
  • haloalkoxycarbonyl refers to an alkoxycarbonyl group as mentioned above, where- in the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • alkenyl denotes in each case a singly unsaturated hydrocarbon radical having usually 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms, e.g. vinyl, allyl (2- propen-1 -yl), 1 -propen-1 -yl, 2-propen-2-yl, methallyl (2-methylprop-2-en-1 -yl), 2-buten-1 -yl, 3- buten-1 -yl, 2-penten-1 -yl, 3-penten-1 -yl, 4-penten-1 -yl, 1 -methylbut-2-en-1 -yl, 2-ethylprop-2-en- 1 -yl and the like.
  • haloalkenyl refers to an alkenyl group as defined above, wherein the hydrogen atoms are partially or totally replaced with halogen atoms.
  • alkynyl denotes in each case a singly unsaturated hydrocarbon rad- ical having usually 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms, e.g. ethynyl, propargyl (2-propyn-1 -yl), 1 -propyn-1 -yl, 1 -methylprop-2-yn-1 -yl), 2-butyn-1 -yl, 3-butyn-1 -yl, 1 - pentyn-1 -yl, 3-pentyn-1 -yl, 4-pentyn-1 -yl, 1 -methylbut-2-yn-1 -yl, 1 -ethylprop-2-yn-1 -yl and the like.
  • haloalkynyl refers to an alkynyl group as defined above, wherein the hydrogen atoms are partially or totally replaced with halogen atoms.
  • cycloalkyl as used herein and in the cycloalkyl moieties of cycloalkoxy and cycloalkylthio denotes in each case a monocyclic cycloaliphatic radical having usually from 3 to 10 or from 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl or cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • halocycloalkyl as used herein and in the halocycloalkyl moieties of halocycloalkoxy and halocycloalkylthio denotes in each case a monocyclic cycloaliphatic radical having usually from 3 to 10 C atoms or 3 to 6 C atoms, wherein at least one, e.g. 1 , 2, 3, 4 or 5 of the hydrogen atoms, are replaced by halogen, in particular by fluorine or chlorine.
  • Examples are 1 - and 2- fluorocyclopropyl, 1 ,2-, 2,2- and 2,3-difluorocyclopropyl, 1 ,2,2-trifluorocyclopropyl, 2,2,3,3- tetrafluorocyclpropyl, 1 - and 2-chlorocyclopropyl, 1 ,2-, 2,2- and 2,3-dichlorocyclopropyl, 1 ,2,2- trichlorocyclopropyl, 2,2,3,3-tetrachlorocyclpropyl, 1 -,2- and 3-fluorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-difluorocyclopentyl, 1 -,2- and 3-chlorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-difluorocyclopentyl, 1 -,2- and 3-chlorocyclopentyl, 1
  • cycloalkoxy refers to a cycloalkyl group as defined above, which is bonded via an oxygen atom to the remainder of the molecule.
  • halocycloalkoxy refers to a halocycloalkyl group as defined above, which is bonded via an oxygen atom to the remainder of the molecule.
  • cycloalkylthio refers to a cycloalkyl group as defined above, which is bonded via a sulfur atom to the remainder of the molecule.
  • halocycloalkylthio refers to a halocycloalkyl group as defined above, which is bonded via a sulfur atom to the remainder of the molecule.
  • cycloalkenyl as used herein and in the cycloalkenyl moieties of cycloalkenyloxy and cycloalkenylthio denotes in each case a monocyclic singly unsaturated non-aromatic radical having usually from 3 to 10, e.g. 3 or 4 or from 5 to 10 carbon atoms, preferably from 3- to 8 carbon atoms.
  • exemplary cycloalkenyl groups include cyclopropenyl, cycloheptenyl or cyclooctenyl.
  • halocycloalkenyl as used herein and in the halocycloalkenyl moieties of halo- cycloalkenyloxy and halocycloalkenylthio denotes in each case a monocyclic singly unsaturated non-aromatic radical having usually from 3 to 10, e.g. 3 or 4 or from 5 to 10 carbon atoms, pref- erably from 3- to 8 carbon atoms, wherein at least one, e.g. 1 , 2, 3, 4 or 5 of the hydrogen atoms, are replaced by halogen, in particular by fluorine or chlorine. Examples are 3,3,- difluorocyclopropen-1 -yl and 3,3-dichlorocyclopropen-1 -yl.
  • cycloalkenyloxy refers to a cycloalkenyl group as defined above, which is bonded via an oxygen atom to the remainder of the molecule.
  • halocycloalkenyloxy refers to a halocycloalkenyl group as defined above, which is bonded via an oxygen atom to the remainder of the molecule.
  • cycloalkenylthio refers to a cycloalkenyl group as defined above, which is bonded via a sulfur atom to the remainder of the molecule.
  • halocycloalkenylthio refers to a halocycloalkenyl group as defined above, which is bonded via a sulfur atom to the remainder of the molecule.
  • carrier or “carbocyclyl” includes in general a 3- to 12-membered, preferably a 3- to 8-membered or a 5- to 8-membered, more preferably a 5- or 6-membered mono-cyclic, non-aromatic ring comprising 3 to 12, preferably 3 to 8 or 5 to 8, more preferably 5 or 6 carbon atoms.
  • the term “carbocycle” covers cycloalkyl and cycloalkenyl groups as defined above.
  • heterocycloalkyl includes in general 3- to 8-membered, in particular 6-membered monocyclic saturated heterocyclic non-aromatic radicals.
  • the heterocyclic non-aromatic radicals usually comprise 1 , 2, or 3 heteroatoms selected from N, O and S as ring members, where S- atoms as ring members may be present as S, SO or SO2.
  • heterocycloalkenyl includes in general 3- to 8-membered, in particular 6-membered monocyclic singly unsaturated heterocyclic non-aromatic radicals.
  • the heterocyclic non- aromatic radicals usually comprise 1 , 2, or 3 heteroatoms selected from N, O and S as ring members, where S-atoms as ring members may be present as S, SO or SO2.
  • heterocycle or “heterocyclyl” includes in general 3- to 12-membered, preferably 3- to 8-membered or 5- to 8-membered, more preferably 5- or 6-membered, in particular 6- membered monocyclic heterocyclic non-aromatic radicals.
  • the heterocyclic non-aromatic radicals usually comprise 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where S-atoms as ring members may be present as S, SO or SO2.
  • Examples of 5- or 6-membered heterocyclic radicals comprise saturated or unsaturated, non-aromatic heterocyclic rings, such as oxiranyl, oxetanyl, thietanyl, thietanyl-S-oxid (S-oxothietanyl), thietanyl-S-dioxid (S-dioxothiethanyl), pyrrolidinyl, pyrrolinyl, pyrazolinyl, tetrahydrofuranyl, dihy- drofuranyl, 1 ,3-dioxolanyl, thiolanyl, S-oxothiolanyl, S-dioxothiolanyl, dihydrothienyl, S- oxodihydrothienyl, S-dioxodihydrothienyl, oxazolidinyl, oxazolinyl, thiazoliny
  • aryl includes mono-, bi- or tricyclic aromatic radicals having usually from 6 to 14, preferably 6, 10 or 14 carbon atoms.
  • exemplary aryl groups include phenyl, naphthyl and anthracenyl. Phenyl is preferred as aryl group.
  • heteroaryl includes monocyclic 5- or 6-membered heteroaromatic radicals comprising as ring members 1 , 2, 3 or 4 heteroatoms selected from N, O and S. Examples of 5- or
  • 6-membered heteroaromatic radicals include pyridyl, i.e. 2-, 3-, or 4-pyridyl, pyrimidinyl, i.e. 2-, 4- or 5-pyrimidinyl, pyrazinyl, pyridazinyl, i.e. 3- or 4-pyridazinyl, thienyl, i.e. 2- or 3-thienyl, furyl, i.e. 2-or 3-furyl, pyrrolyl, i.e. 2- or 3-pyrrolyl, oxazolyl, i.e. 2-, 3- or 5-oxazolyl, isoxazolyl, i.e. 3-, 4- or 5-isoxazolyl, thiazolyl, i.e. 2-, 3- or 5-thiazolyl, isothiazolyl, i.e. 3-, 4- or
  • 5-isothiazolyl pyrazolyl, i.e. 1 -, 3-, 4- or 5-pyrazolyl, i.e. 1 -, 2-, 4- or 5-imidazolyl, oxadiazolyl, e.g. 2- or 5-[1 ,3,4]oxadiazolyl, 4- or 5-(1 ,2,3-oxadiazol)yl, 3- or 5-(1 ,2,4-oxadiazol)yl, 2- or
  • heteroaryl also includes bicyclic 8 to 10-membered heteroaromatic radicals comprising as ring members 1 , 2 or 3 het- eroatoms selected from N, O and S, wherein a 5- or 6-membered heteroaromatic ring is fused to a phenyl ring or to a 5- or 6-membered heteroaromatic radical.
  • Examples of a 5- or 6- membered heteroaromatic ring fused to a phenyl ring or to a 5- or 6-membered heteroaromatic radical include benzofuranyl, benzothienyl, indolyl, indazolyl, benzimidazolyl, benzoxathiazolyl, benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl, chinolinyl, isochinolinyl, purinyl, 1 ,8- naphthyridyl, pteridyl, pyrido[3,2-d]pyrimidyl or pyridoimidazolyl and the like.
  • These fused hetaryl radicals may be bonded to the remainder of the molecule via any ring atom of 5- or 6- membered heteroaromatic ring or via a carbon atom of the fused phenyl moiety.
  • heterocyclyloxy refers to heterocyclyl, hetaryl and aryl as defined above and phenyl, which are bonded via an oxygen atom to the remainder of the molecule.
  • heterocyclylsulfonyl refers to heterocycly, hetaryl and aryl as defined above, and phenyl, respectively, which are bonded via the sulfur atom of a sulfonyl group to the remainder of the molecule.
  • alkylene refers to alkyl, cycloalkyl, heterocycloalkyl, alkenyl, cycloalkenyl, heterocycloalkenyl and alkynyl as defined above, respectively, which are bonded to the remainder of the molecule, via two atoms, preferably via two carbon atoms, of the respec- tive group, so that they represent a linker between two moieties of the molecule.
  • cyclic moiety can refer to any cyclic groups, which are present in the compounds of formula I, and which are defined above, e.g. cycloalkyl, cycloalkenyl, carbocycle,
  • heterocycloalkyl heterocycloalkenyl, heterocycle, aryl, hetaryl and the like.
  • particularly preferred embodiments of the intermediates correspond to those of the compounds of the formula I.
  • variables of the compounds of the formula I have the following meanings, these meanings, both on their own and in combination with one another, being particular embodiments of the compounds of the formula I:
  • the invention relates to compounds of formula I, wherein T is O, i.e. compounds of formula 1.1 as depicted above.
  • the invention relates to compounds of formula I, wherein U is CH or N, i.e. compounds of formula I.A or I.B as depicted above.
  • Compounds of formula I, wherein U is N, i.e. compounds of formula I.B, are particularly preferred according to the invention.
  • R P1 , R P2 and R P3 are H.
  • the invention relates to compounds of formula I, wherein R 4 is any one of groups (iiia), (iiib), (iiic), (iiid), (iva) or (ivb), i.e. to compounds of formula l(iiia), l(iiib), l(iiic), l(iiid), l(iva) or l(ivb).
  • the invention relates to compounds of formula I, wherein R 2 is R 2c y as defined above or wherein R 3 is R 3c y as defined above, i.e. to compounds of formula I.R 2c y or I.R 3c y.
  • Compounds of formula I.R 2c y are preferred according to the invention.
  • the invention relates to compounds of formula I, wherein R 4 is any one of substituents R 4c y(i), R 4c y(ii), R 4c y(iiia), R 4c y(iiib), R 4c y(iiic) or R 4c y(iiid) as defined above, i.e. compounds of formula I.R 4c y(i), I.R 4c y(ii), I.R 4c y(iiia), I.R 4c y(iiib), I.R 4c y(iiic) or I.R 4c y(iiid).
  • R 1 is H, Ci-C2-alkyl, or C1-C2- alkoxy-Ci-C2-alkyl, and preferably Ci-C2-alkyl.
  • R 2 and R 3 are independently of each other selected from H, halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C4-cycloalkyl, C3- C4-cycloalkenyl, C3-C4-halocycloalkyl, C3-C4-halocycloalkenyl, OR a , and SR a , wherein R a is Ci- C4-alkyl, Ci-C4-haloalkyl, C3-C4-cycloalkyl, C3-C4-halocycloalkyl, C3-C4-cycloalkenyl, or C3-C4- halocycloalkenyl.
  • R 2 is selected from Ci-C2-alkyl, Ci-C2-haloalkyl, C3-cycloalkyl, C3- halocycloalkyl, C3-cycloalkenyl, and C3-halocycloalkenyl.
  • R 3 is selected from H, C3- cycloalkenyl, and C3-halocycloalkenyl.
  • R 2 is CH3 or halomethyl, preferably CH3 or fluoromethyl, with the proviso that either
  • R 3 is a substituent, which comprises a C3-C4-cycloalkenyl or C3-C4-halocycloalkenyl group;
  • R 4 is any one of options (i) or (ii), which comprises a C3-C4-cycloalkenyl or C3-C4- halocycloalkenyl group,
  • R 4a , R 4b and R 4c comprises a C3-C4-cycloalkenyl or C3-C4-halocycloalkenyl group
  • option (iiib) wherein A is a C3-C4-cycloalkenyl or C3-C4-halocycloalkenyl group, or option (iiic), wherein E is a C3-C4-cycloalkenyl or C3-C4-halocycloalkenyl group, or option (iiid), wherein G is a C3-C4-cycloalkenyl or C3-C4-halocycloalkenyl group.
  • R 3 is H with the proviso that either
  • R 2 is a substituent, which comprises a C3-C4-cycloalkenyl or C3-C4-halocycloalkenyl group,
  • R 4 is any one of options (i) or (ii), which comprises a C3-C4-cycloalkenyl or C3-C4- halocycloalkenyl group,
  • R 4a , R 4b and R 4c comprises a C3-C4-cycloalkenyl or C3-C4-halocycloalkenyl group
  • option (iiib) wherein A is a C3-C4-cycloalkenyl or C3-C4-halocycloalkenyl group, or option (iiic), wherein E is a C3-C4-cycloalkenyl or C3-C4-halocycloalkenyl group, or option (iiid), wherein G is a C3-C4-cycloalkenyl or C3-C4-halocycloalkenyl group.
  • At least one of R 2 and R 3 is C3-C4-cycloalkenyl or C3-C4-halocycloalkenyl, preferably C3-cycloalkenyl, or C3- halocycloalkenyl, more preferably C3-cycloalkenyl, or C3-fluorocycloalkenyl.
  • R 4 is any one of options (iiia), (iiib), (iiic), (iiid), (iva) or (ivb), i.e. is any one of groups (iiia), (iiib), (iiic), (iiid), (iva) or (ivb) as depicted bel S(0) M -R 4D ( .i.i.i.d),
  • R 4a , R 4b , R 4c , R 4d , R 4e , R 4f , R 4 9, A, D, E, G, M, Q, V, W and m are as defined above, with the proviso that at least one of R 2 and R 3 is a substituent, which comprises a C3-C4- cycloalkenyl or C3-C4-halocycloalkenyl group.
  • R 4a is CN, C 2 -C 6 -alkyl, Ci-C 2 -haloalkyl, Ci-C 2 -alkoxy-Ci-C 2 -alkyl, or C 3 -C 6 -cycloalkyl, wherein the C-atoms may be substituted as indicated above;
  • R 4b is Ci-C4-alkyl, Ci-C4-haloalkyl, or C3-C6-cycloalkyl, wherein the C-atoms may be substituted as indicated above;
  • R 4c is H or CH 3 .
  • R 4a is H, F, CN, Ci-C 2 -alkyl, or halomethyl
  • A is a cycloalkyl ring, preferably a cyclohexyl, a cyclopentyl or a cyclobutyl ring, or a
  • R 4a is CN, Ci-C 2 -alkyl, Ci-C 2 -haloalkyl, or cyclopropyl;
  • R 4b is H, CN, Ci-C 2 -alkyl, or Ci-C 2 -haloalkyl;
  • D is a direct bond or Ci-C4-alkylene
  • E is a saturated or unsaturated heterocyclic group, wherein the heterocycle may be sub- stituted as indicated above, and wherein a phenyl group may optionally be annealed to the ring.
  • G is a-branched C 2 -C 3 -alkylene, preferably CH(CH 3 ) or CH(CH 3 )CH 2 ,
  • n 0 or 1 ;
  • R 4d is Ci-C 2 -haloalkyl or C-C3H5, wherein the carbon atoms may be halogenated. Further, it is particularly preferred under the above proviso that in group (iva)
  • Q is an a-branched or straight-chain C-i-Cs-alkylene, C2-Cs-alkenylene or C2-C8- alkynylene, which carbon chains can be partially or fully substituted as indicated above, or a direct bond;
  • R 4e is H or CH 3 ;
  • Q and R 4e together form a 4- to 6-membered carbocyclic ring or a 4- to 6-membered heterocyclic ring, which contains O or S as heteroatom, and which groups may be substituted as indicated above;
  • M is O, S, NOCH3 or NSCHs;
  • W is an a-branched or straight-chain C-i-Cs-alkylene, Cs-Cs-cycloalkylene or C3-C8- heterocycloalkylene, wherein the groups W may be substituted as indicated above;
  • V is O or S;
  • R 4 9 is H, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl or C3-C6-cycloalkylmethyl, wherein the alkyl or cycloalkyl groups may be substituted as indicated above; and R 4f is Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl or C3-C6-cycloalkylmethyl, wherein the alkyl or cycloalkyl groups may be substituted as indicated above.
  • R 4 is C3-C4-cycloalkenyl, C3- C4-halocycloalkenyl, L-C3-C4-cycloalkenyl, L-C3-C4-halocycloalkenyl, L-C3-C4-cycloalkenyloxy, L-C3-C4-halocycloalkenyloxy, L-C3-C4-cycloalkenylthio, or L-C3-C4-halocycloalkenylthio, wherein L is d-Cs-alkylene, C2-Cs-alkenylene, C2-Cs-alkynylene, or C3-C6-cycloalkylene, and wherein the C-atoms may be unsubstituted or may carry 1 , 2, 3, 4 or 5 identical or different sub- stituents R x .
  • L is Ci-C2-alkylene or C3-cycloalkylene, wherein the C-atoms may be unsubstituted or may carry 1 or 2 identical or different substituents selected from Ci-C2-alkyl. More preferably, L is CH 2 , CH(CH 3 ), CH 2 CH, CH(CH 3 )CH 2 or cyclopropylene. If L is
  • the branched end is typically attached to the pyrazole moiety, whereas the CH2 group is bonded to the cycloalkenyl ring.
  • R 2 is CH3 or halomethyl
  • R 3 is H
  • L is Ci-C2-alkylene or C3-cycloalkylene, wherein the C-atoms may be unsubstituted or may carry 1 or 2 identical or different substituents selected from Ci-C2-alkyl, or
  • E is a C3-C4-cycloalkenyl or C3-C4-halocycloalkenyl group, or
  • G is a C3-C4-cycloalkenyl or C3-C4-halocycloalkenyl group;
  • R 2 is CH3 or halomethyl
  • R 3 is C3-C 4 -cycloalkenyl, C3-C 4 -halocycloalkenyl, OR a , or SR a ,
  • R a is C3-C4-cycloalkenyl, or C3-C4-halocycloalkenyl
  • L-C3-C4-cycloalkenyl is L-C3-C4-cycloalkenyl, L-C3-C4-halocycloalkenyl, L-C3-C4-cycloalkenyloxy, L-C3- C4-halocycloalkenyloxy, L-C3-C4-cycloalkenylthio, or L-C3-C4- halocycloalkenylthio,
  • L is Ci-C2-alkylene or C3-cycloalkylene, wherein the C-atoms may be unsubstituted or may carry 1 or 2 identical or different substituents selected from Ci-C2-alkyl, and
  • R 4 is an
  • R 4a , R 4b , R 4c , R 4d , R 4e , R 4f , R 4 9, A, D, E, G, M, Q, V, W and m are as defined above; or
  • R 2 is C3-C 4 -cycloalkenyl, C3-C 4 -halocycloalkenyl, OR a , or SR a ,
  • R a is C3-C4-cycloalkenyl, or C3-C4-halocycloalkenyl
  • L-C3-C4-cycloalkenyl is L-C3-C4-cycloalkenyl, L-C3-C4-halocycloalkenyl, L-C3-C4-cycloalkenyloxy, L-C3- C4-halocycloalkenyloxy, L-C3-C4-cycloalkenylthio, or L-C3-C4- halocycloalkenylthio,
  • L is Ci-C2-alkylene or C3-cycloalkylene, wherein the C-atoms may be unsubstituted or may carry 1 or 2 identical or different substituents selected from Ci-C 2 -alkyl,
  • R 3 is H
  • R 4 is any one of the following groups
  • R 4a , R 4b , R 4c , R 4d , R 4e , R 4f , R 4 9, A, D, E, G, M, Q, V, W and m are as defined above.
  • R 2 is a substituent falling under the definition of R 2c y or R 3 is a substituent falling under the definition R 3c y
  • R 4 is a substituent falling under the definition of R 4c y(i), R 4c y(ii), R 4c y(iiia), R 4c y(iiib), R 4c y(iiic) or R 4c y(iiid) provided above.
  • R 4c y(i), R 4c y(ii), R 4c y(iiia), R 4c y(iiib), R 4c y(iiic) or R 4c y(iiid) are together referred to as R 4c y in the following.
  • the invention preferably relates to compounds of formula I,
  • T O
  • U is CH
  • R P1 , R P2 and R P3 are H
  • R 2 is R 2c y, i.e. compounds of for-
  • R 4 is R 4c y(i), i.e. compounds of formula l * .1.A.R 4c y(i);
  • R 4 is R 4c y(ii), i.e. compounds of formula l * .1 .A.R 4c y(ii);
  • R 4 is R 4c y(iiia), i.e. compounds of formula l * .1 .A.R 4c y(iiia);
  • T is O
  • U is CH
  • R P1 , R P2 and R P3 are H
  • R 4 is R 4c y(iiib), i.e. compounds of formula I * .1 .A.R 4c y(iiib);
  • R 4 is R 4c y(iiic), i.e. compounds of formula l * .1 .A.R 4c y(iiic);
  • T is O
  • U is CH
  • R P1 , R P2 and R P3 are H
  • R 4 is R 4c y(iiid), i.e. compounds of formula l * .1 .A.R 4c y(iiid).
  • the invention preferably relates to compounds of formula I
  • R P1 , R P2 and R P3 are H and R 4 is R 4c y(iiia), i.e. compounds of formula I * .1 . B.R 4c y(iiia);
  • R 4 is R 4c y(iiib), i.e. compounds of formula IM . B.R 4c (iiib);
  • R 4 is R 4c y(iiic), i.e. compounds of formula IM . B.R 4c v(iiic); or
  • R 4 is R 4c y(iiid), i.e. compounds of formula IM . B.R 4c y(iiid).
  • the present invention also relates to a mixture of at least one compound of the present inven- tion with at least one mixing partner as defined herein after.
  • Preferred are binary mixtures of one compound of the present invention as component I with one mixing partner as defined herein after as component II.
  • Preferred 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 preferably 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 acaricides, fungicides, herbicides, plant growth regulators, fertilizers, and the like.
  • Preferred mixing partners are insecticides, nematicides and fungicides.
  • M.1 Acetylcholine esterase (AChE) inhibitors from the class of: M.1A carbamates, for example aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofu- ran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC
  • GABA-gated chloride channel antagonists such as: M.2A cyclodiene organochlorine compounds, as for example endosulfan or chlordane; or M.2B fiproles (phenylpyrazoles), as for example ethiprole, fipronil, flufiprole, pyrafluprole and pyriprole;
  • M.3 Sodium channel modulators from the class of M.3A pyrethroids for example acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S- cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda- cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta- cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, eto- fenprox,
  • M.4 Nicotinic acetylcholine receptor agonists from the class of M.4A neonicotinoids, for example acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thia- cloprid and thiamethoxam; or the compounds 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-hexahydroimidazo[1 ,2-a]pyridine; or from the class M.4B nicotine;
  • M.6 Chloride channel activators from the class of avermectins and milbemycins, for example abamectin, emamectin benzoate, ivermectin, lepimectin or milbemectin;
  • M.7 Juvenile hormone mimics such as M.7A juvenile hormone analogues as hydroprene, ki- noprene and methoprene; or others as M.7B fenoxycarb or M.7C pyriproxyfen;
  • M.8 miscellaneous non-specific (multi-site) inhibitors for example M.8A alkyl halides as methyl bromide and other alkyl halides, or M.8B chloropicrin, or M.8C sulfuryl fluoride, or M.8D borax, or M.8E tartar emetic;
  • M.9 Selective homopteran feeding blockers for example M.9B pymetrozine, or M.9C floni- camid;
  • M.10 Mite growth inhibitors for example M.10A clofentezine, hexythiazox and diflovidazin, or M.10B etoxazole;
  • M.1 1 Microbial disruptors of insect midgut membranes, for example bacillus thuringiensis or bacillus sphaericus and the insecticdal proteins they produce such as bacillus thuringiensis subsp. israelensis, bacillus sphaericus, bacillus thuringiensis subsp. aizawai, bacillus thur- ingiensis subsp. kurstaki and bacillus thuringiensis subsp. tenebrionis, or the Bt crop proteins: Cry-IAb, CrylAc, Cryl Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb and Cry34/35Ab1 ;
  • M.12 Inhibitors of mitochondrial ATP synthase for example M.12A diafenthiuron, or M.12B or- ganotin miticides such as azocyclotin, cyhexatin or fenbutatin oxide, or M.12C propargite, or M.12D tetrad if on;
  • Nicotinic acetylcholine receptor (nAChR) channel blockers for example nereistoxin ana- logues as bensultap, cartap hydrochloride, thiocyclam or thiosultap sodium;
  • benzoylureas as for example bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron or triflumuron;
  • M.16 Inhibitors of the chitin biosynthesis type 1 as for example buprofezin;
  • Ecdyson receptor agonists such as diacylhydrazines, for example methoxyfenozide, te- bufenozide, halofenozide, fufenozide or chromafenozide;
  • Octopamin receptor agonists as for example amitraz
  • M.20 Mitochondrial complex III electron transport inhibitors for example M.20A hydramethyl- non, or M.20B acequinocyl, or M.20C fluacrypyrim;
  • M.21 Mitochondrial complex I electron transport inhibitors for example M.21 A METI acaricides and insecticides such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad or tolfenpyrad, or M.21 B rotenone;
  • M.22 Voltage-dependent sodium channel blockers for example M.22A indoxacarb, or M.22B metaflumizone, or M.22B.1 : 2-[2-(4-Cyanophenyl)-1 -[3-(trifluoromethyl)phenyl]ethylidene]-N-[4- (difluoromethoxy)phenyl]-hydrazinecarboxamide or M.22B.2: N-(3-Chloro-2-methylphenyl)-2-[(4- chlorophenyl)[4-[methyl(methylsulfonyl)amino]phenyl]methylene]-hydrazinecarboxamide;
  • M.23 Inhibitors of the of acetyl CoA carboxylase such as Tetronic and Tetramic acid derivatives, for example spirodiclofen, spiromesifen or spirotetramat;
  • M.24 Mitochondrial complex IV electron transport inhibitors for example M.24A phosphine such as aluminium phosphide, calcium phosphide, phosphine or zinc phosphide, or M.24B cyanide;
  • Mitochondrial complex II electron transport inhibitors such as beta-ketonitrile derivatives, for example cyenopyrafen or cyflumetofen;
  • M.28 Ryanodine receptor-modulators from the class of diamides as for example flubendia- mide, chlorantraniliprole (rynaxypyr®), cyantraniliprole (cyazypyr®), tetraniliprole, or the phtha- lamide compounds
  • M.28.1 (R)-3-Chlor-N1 - ⁇ 2-methyl-4-[1 ,2,2,2 -tetrafluor-1 - (trifluormethyl)ethyl]phenyl ⁇ -N2-(1 -methyl-2-methylsulfonylethyl)phthalamid
  • M.28.3 3-bro
  • insecticidal active compounds of unknown or uncertain mode of action as for example afidopyropen, afoxolaner, azadirachtin, amidoflumet, benzoximate, bifenazate, broflanilide, bromopropylate, chinomethionat, cryolite, dicloromezotiaz, dicofol, flufenerim, flometoquin, flu- ensulfone, fluhexafon, fluopyram, flupyradifurone, fluralaner, metoxadiazone, piperonyl butox- ide, pyflubumide, pyridalyl, pyrifluquinazon, sulfoxaflor, tioxazafen, triflumezopyrim, or the compounds
  • M.29.5 1 -[2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)-1 H-1 ,2,4- triazole-5-amine, or actives on basis of bacillus firmus (Votivo, 1-1582); or
  • M.29.6a (E/Z)-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2- trifluoro-acetamide
  • M.29.6b (E/Z)-N-[1 -[(6-chloro-5-fluoro-3-pyridyl)methyl]-2-pyridylidene]- 2,2,2-trifluoro-acetamide
  • M.29.6c (E/Z)-2,2,2-trifluoro-N-[1 -[(6-fluoro-3-pyridyl)methyl]-2- pyridylidene]acetamide
  • M.29.6d (E/Z)-N-[1 -[(6-bromo-3-pyridyl)methyl]-2
  • M.29.10 5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1 H-pyrazole; or a compound selected from the group of M.29.1 1 , wherein the compound is selected from M.29.1 1 b) to M.29.1 1 p): M.29.1 1.b) 3-(benzoylmethylamino)-N-[2-bromo-4-[1 , 2,2,3,3,3- hexafluoro-1 -(trifluoromethyl)propyl]-6-(trifluoromethyl)phenyl]-2-fluoro-benzamide; M.29.1 1.c) 3-(benzoylmethylamino)-2-fluoro-N-[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]-6- (trifluoromethyl)phenyl]-benzamide; M.29.
  • M.29.14a 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.29.14b) 1 -[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro- 1 ,2,3,5,6,7-hexahydroimidazo[1 ,2-a]pyridin-5-ol; or the compounds
  • M.29.16a 1 -isopropyl-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; or M.29.16b) 1 - (1 ,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; M.29.16c) N,5- dimethyl-N-pyridazin-4-yl-1 -(2,2,2-trifluoro-1 -methyl-ethyl)pyrazole-4-carboxamide; M.29.16d) 1 - [1 -(1 -cyanocyclopropyl)ethyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide;
  • M.29.16e N-ethyl-1 -(2-fluoro-1 -methyl-propyl)-5-methyl-N-pyridazin-4-yl-pyrazole-4- carboxamide
  • M.29.16f 1 -(1 ,2-dimethylpropyl)-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4- carboxamide
  • M.29.16h N-methyl-1 -(2-fluoro-1-methyl-propyl]-5-methyl-N-pyridazin-4-yl- pyrazole-4-carboxamide
  • M.29.16i 1 -(4,4-difluorocyclohexyl)-N-ethyl-5-
  • the M.4 neonicotinoid cycloxaprid is known from WO2010/069266 and WO201 1/069456, the neonicotinoid M.4A.2, sometimes also to be named as guadipyr, is known from
  • WO2013/003977 and the neonicotinoid M.4A.3 (approved as paichongding in China) is known from WO2007/101369.
  • the metaflumizone analogue M.22B.1 is described in CN 10171577 and the analogue M.22B.2 in CN102126994.
  • the phthalamides M.28.1 and M.28.2 are both known from WO2007/101540.
  • the anthranilamide M.28.3 is described in WO2005/077934.
  • the hydrazide compound M.28.4 is described in WO2007/043677.
  • the anthranilamides M.28.5a) to M.28.5d) and M.28.5h) are described in WO 2007/006670, WO2013/024009 and
  • WO2013/024010 the anthranilamide ⁇ .28.5 ⁇ ) is described in WO201 1/085575, M.28.5j) in WO2008/134969, M.28.5k) in US201 1/046186 and M.28.5I) in WO2012/034403.
  • the diamide compounds M.28.6 and M.28.7 can be found in CN102613183.
  • the spiroketal-substituted cyclic ketoenol derivative M.29.3 is known from WO2006/089633 and the biphenyl-substituted spirocyclic ketoenol derivative M.29.4 from WO2008/06791 1.
  • the triazoylphenylsulfide M.29.5 is described in WO2006/043635, and biological control agents on the basis of bacillus firmus are described in WO2009/124707.
  • the compounds M.29.6a) to ⁇ .29.6 ⁇ ) listed under M.29.6 are described in WO2012/029672, and M.29.6j) and M.29.6k) in WO2013/129688.
  • the nematicide M.29.8 is known from WO2013/055584.
  • the isoxazoline M.29.9.a) is described in
  • WO2013/050317 The isoxazoline M.29.9.b) is described in WO2014/126208.
  • the pyridalyl- type analogue M.29.10 is known from WO2010/060379.
  • the carboxamides broflanilide and M.29.1 1.b) to M.29.1 1 .h) are described in WO2010/018714, and the carboxamides M.29.1 1 i) to M.29.1 1 .P) in WO2010/127926.
  • the pyridylthiazoles M.29.12.a) to M.29.12.c) are known from WO2010/006713, M.29.12.d) and M.29.12.e) are known from WO2012/000896, and M.29.12.f) to M.29.12.m) from WO2010/129497.
  • the compounds M.29.14a) and M.29.14b) are known from WO2007/101369.
  • the pyrazoles M.29.16.a) to M.29.16h) are described in
  • Inhibitors of complex III at Q 0 site e. g. strobilurins: azoxystrobin (A.1 .1 ), coumethoxy- strobin (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), mandestrobin (A.1.10), metominostrobin (A.1.1 1 ), orysastrobin (A.1.12), picoxy- .strobin (A.1.13), pyraclostrobin (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-methyl-acetamide (A.1.18), pyribencarb (A.1.19),
  • triclopyricarb/chlorodincarb A.1.20
  • famoxadone A.1.21
  • fenamidone A.1 .21
  • methyl-A/-[2- [(1 ,4-dimethyl-5-phenyl-pyrazol-3-yl)oxylmethyl]phenyl]-N-methoxy-carbamate A.1 .22
  • inhibitors of complex III at Qi site cyazofamid (A.2.1 ), amisulbrom (A.2.2), [(3S,6S,7R,8R)- 8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan- 7-yl] 2-methylpropanoate (A.2.3), [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy- pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate (A.2.4), [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine-2-carbony
  • inhibitors of complex II e. g. carboxamides: benodanil (A.3.1 ), benzovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.1 1 ), isopyrazam (A.3.12), mepronil (A.3.13), oxycarboxin (A.3.14), penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), tecloftalam (A.3.17), thifluzamide (A.3.18), N-(4'-trifluoromethylthiobiphenyl-2-yl)-
  • respiration inhibitors e. g. complex I, uncouplers: diflumetorim (A.4.1 ), (5,8-difluoro- quinazolin-4-yl)- ⁇ 2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl ⁇ -amine (A.4.2); nitrophenyl derivates: binapacryl (A.4.3), dinobuton (A.4.4), dinocap (A.4.5), fluazinam (A.4.6); ferimzone (A.4.7); organometal compounds: fentin salts, such as fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.1 1 ); and silthiofam (A.4.12); B) Sterol biosynthesis inhibitors (SBI fungicides)
  • SBI fungicides Sterol biosynthesis inhibitors
  • C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole (B.1 .1 ), bitertanol (B.1.2), bromuconazole (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 .1 1 ), 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)
  • 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), spiroxamine (B.2.8);
  • Inhibitors of 3-keto reductase fenhexamid (B.3.1 );
  • phenylamides or acyl amino acid fungicides benalaxyl (C.1.1 ), benalaxyl-M (C.1 .2), kiralaxyl (C.1.3), metalaxyl (C.1.4), metalaxyl-M (mefenoxam, C.1 .5), ofurace (C.1.6), oxadixyl (C.1.7);
  • 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
  • tubulin inhibitors such as benzimidazoles, thiophanates: benomyl (D1.1 ), carbendazim (D1 .2), fuberidazole (D1.3), thiabendazole (D1 .4), thiophanate-methyl (D1.5);
  • triazolopyrimidines 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine (D1 .6);
  • diethofencarb (D2.1 ), ethaboxam (D2.2), pencycuron (D2.3), fluopicolide (D2.4), zoxamide (D2.5), metrafenone (D2.6), pyriofenone (D2.7);
  • - methionine synthesis inhibitors anilino-pyrimidines: cyprodinil (E.1 .1 ), mepanipyrim (E.1.2), pyrimethanil (E.1 .3);
  • 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), polyoxine (E.2.7), validamycin A (E.2.8);
  • MAP / histidine kinase inhibitors fluoroimid (F.1.1 ), iprodione (F.1 .2), procymidone (F.1 .3), vinclozolin (F.1 .4), fenpiclonil (F.1 .5), fludioxonil (F.1.6);
  • G protein inhibitors quinoxyfen (F.2.1 );
  • 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) and N-(1 -(1 -(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4- fluorophenyl) ester (G.3.8);
  • inorganic active substances Bordeaux mixture (H.1.1 ), copper acetate (H.1 .2), copper hydroxide (H.1.3), copper oxychloride (H.1 .4), basic copper sulfate (H.1 .5), sulfur (H.1.6);
  • 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 e. g. phthalimides, sulfamides, chloronitriles: 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.3.1 1 ), N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl- benzenesulfonamide (H.3.12);
  • organochlorine compounds e. g. phthalimides, sulfamides, chloronitriles
  • 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-1 H,5H- [1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone (H.4.10);
  • inhibitors of glucan synthesis validamycin (1.1.1 ), polyoxin B (1.1 .2);
  • melanin synthesis inhibitors pyroquilon (1.2.1 ), tricyclazole (1.2.2), carpropamid (I.2.3), dicyclomet (I.2.4), fenoxanil (1.2.5);
  • bronopol K.1.1
  • chinomethionat K.1.2
  • cyflufenamid K.1 .3
  • cymoxanil K.1.4
  • dazomet K.1.5
  • debacarb K.1.6
  • diclomezine K.1 .7
  • difenzoquat K.1 .8
  • difenzoquat-methylsulfate K.1.9
  • diphenylamin K.1 .10
  • fenpyrazamine K.1 .1 1
  • flumetover K.1 .12
  • flusulfamide K.1.13
  • flutianil K.1.14)
  • methasulfocarb K.1.15), nitrapyrin (K.1.16), nitrothal-isopropyl (K.1.18), oxathiapiprolin (K.1 .19), tolprocarb (K.1 .20), oxin-copper (K.1 .
  • 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 commercially available.
  • 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, microbial 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 activators (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.
  • biopesticides in conjunction with which the compounds of the present invention can be used, is intended to illustrate the possible combinations but does not limit them:
  • Microbial pesticides with fungicidal, bactericidal, viricidal and/or plant defense activator activity Ampelomyces quisqualis, Aspergillus flavus, Aureobasidium pullulans, Bacillus altitudinis, B. amyloliquefaciens, B. megaterium, B. mojavensis, B. mycoides, B. pumilus, B. simplex, B. solisalsi, B. subtilis, B. subtilis var. amyloliquefaciens, Candida oleophila, C. saitoana,
  • Pseudozyma flocculosa Pichia anomala, Pythium oligandrum, Sphaerodes mycoparasitica, Streptomyces 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);
  • 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. aizawai, B. t. ssp. israelensis, B. t. ssp. galleriae, B. t. ssp. kurstaki, B. t. ssp. tenebrionis, Beauveria bassiana, B.
  • brongniartii brongniartii, Burkholderia spp., Chromobacterium subtsugae, Cydia pomonella granulovirus (CpGV), Cryptophlebia leucotreta granulovirus (CrleGV),
  • Flavobacterium spp. Helicoverpa armigera nucleopolyhedrovirus (HearNPV), Helicoverpa zea nucleopolyhedrovirus (HzNPV), Helicoverpa zea single capsid nucleopolyhedrovirus (HzSNPV), Heterorhabditis bacteriophora, Isaria fumosorosea, Lecanicillium longisporum, L. muscarium, Metarhizium anisopliae, Metarhizium anisopliae var. anisopliae, M. anisopliae var.
  • Microbial pesticides with plant stress reducing, plant growth regulator, plant growth promoting 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
  • leguminosarum bv. phaseoli R. I. bv. trifolii, R. I. bv. viciae, R. tropici, Sinorhizobium meliloti.
  • the biopesticides from group L1 ) and/or L2) may also have insecticidal, acaricidal,
  • 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.
  • GELFIX® Gramineas 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., Quat- tro Barras, Brazil or Simbiose-Maiz® 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. amyloliquefaciens spp. plantarum D747 isolated from air in Kikugawa-shi, Japan
  • RhizoVital® 42 from AbiTEP GmbH, Germany
  • B. amyloliquefaciens ssp. plantarum MBI600 isolated from faba bean in Sutton Bonington, Nottinghamshire, U.K. at least before 1988 (also called 1430; NRRL B-50595; US 2012/0149571 A1 ; e. g. Integral® from BASF Corp., USA)
  • NRRL B-21661 e. g. Serenade® MAX from Bayer Crop Science 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 tracheiphila (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. pumilus QST 2808 was isolated from soil collected in
  • WO 201 1/109395 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, Munsingen, Germany), B. t. ssp. /a/rsfa/ / ' 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.
  • 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.
  • SEMIA 5079 isolated from soil in Cerrados region, Brazil by Embrapa-Cerrados used in commercial 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.
  • HearNPV Helicoverpa armigera nucleopolyhedrovirus
  • HNSNPV Helicoverpa armigera nucleopolyhedrovirus
  • HzSNPV Helicoverpa zea single capsid nucleopolyhedrovirus
  • HzSNPV Helicoverpa zea nucleopolyhedrovirus ABA- NPV-U
  • Heterorhabditis bacteriophora e. g. Nemasys® G from BASF Agricultural 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-97TM or PreFeRal® from Certis LLC, USA), Metarhizium anisopliae var.
  • anisopliae 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. formerly Shemer® from Agrogreen, Israel),
  • 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
  • Streptomyces microflavus NRRL B-50550 WO 2014/124369; Bayer CropScience, Germany
  • Trichoderma asperelloides JM41 R isolated in South Africa NRRL 50759; also referred to as T. fertile; e. g. Trichoplus® from BASF Agricultural Specialities (Pty) Ltd., South Africa
  • T. fertile e. g. Trichoplus® from BASF Agricultural Specialities (Pty) Ltd., South Africa
  • T. fertile e. g. Trichoplus® from BASF Agricultural Specialities (Pty) Ltd., South Africa
  • T. fertile e. g. Trichoplus® from BASF
  • the solid material (dry matter) of the biopesticides (with the exception 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.
  • CFU may also be understood as the number of (juvenile) individual nematodes in case of (entomopathogenic) nematode biopesticides, such as
  • the application 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.
  • 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 101 1 , 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.
  • 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.
  • the concentration is about 1 x 106 to about 1 x 109 CFU/seed.
  • 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.
  • 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 customary types of agro-chemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, 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 Monograph 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, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifi- ers and binders.
  • suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, 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 fractions 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, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclo ⁇ hexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g.
  • mineral oil fractions 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, tetrahydronaphthalene, alkyl
  • 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, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammonium 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, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
  • polysaccharide powders e.g. cellulose, starch
  • 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 colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, 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- fates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylaryl- sulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkyhnaphthalenes, sulfosuccinates or sulfosuccinamates.
  • Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples 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- pies 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 alkylpolyglucosides.
  • polymeric surfactants are homo- or copolymers of
  • 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 polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines.
  • 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 invention 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), anorganic 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 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 polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
  • the agrochemical compositions generally comprise between 0.01 and 95%, preferably between 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 cormprising them as premix or, if appropriate not until immediately 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 agrochemical 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 according 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 invention 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 invention 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 invention or partially premixed components, e. g. components comprising compounds of the present 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 attack or infestation by animal pests. Therefore, the present invention also relates to a plant protection 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 infes- tation by animal pests, with a pesticidally effective amount of a compound of the present invention.
  • 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 controlling 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 pesticidally effective amount of a compound of the present invention.
  • the compounds of the present invention are effective through both contact and ingestion. Furthermore, 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 comprising 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 application, 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 pelleting.
  • furrow applications typically include the steps of making a furrow in cultivated land, seeding 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 compounds/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. habitat, 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 insect 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.
  • iceberg lettuce chicory, cabbage, asparagus, cabbages, carrots, onions, garlic, leeks, tomatoes, potatoes, cu- curbits 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, tobacco, 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.
  • plant is to be understood as including wild type plants and plants, which have been modified by either conventional breeding, or mutagenesis or genetic engineering, or by a combination thereof.
  • Plants, which have been modified by mutagenesis or genetic engineering, and are of particular commercial importance include alfalfa, rapeseed (e.g. oilseed rape), bean, carnation, chicory, cotton, eggplant, eucalyptus, flax, lentil, maize, melon, papaya, petunia, plum, poplar, potato, rice, soybean, squash, sugar beet, sugarcane, sunflower, sweet pepper, tobacco, tomato, and cereals (e.g. wheat), in particular maize, soybean, cotton, wheat, and rice.
  • one or more genes have been mutagen- ized or integrated into the genetic material of the plant.
  • the one or more mutagenized or integrated genes are preferably selected from pat, epsps, crylAb, bar, cry1 Fa2, crylAc, cry34Ab1 , cry35AB1 , cry3A, cryF, cry1 F, mcry3a, cry2Ab2, cry3Bb1 , cry1A.105, dfr, barnase, vip3Aa20, barstar, als, bxn, bp40, asnl , and ppo5.
  • the mutagenesis or integration of the one or more genes is performed in order to improve certain properties of the plant.
  • Such properties include abiotic stress tolerance, altered growth/yield, disease resistance, herbicide tolerance, insect resistance, modified product quality, and pollination control.
  • herbicide tolerance e.g. imidazolinone tolerance, glyphosate tolerance, or glufosinate tolerance
  • mutagenesis Several plants have been rendered tolerant to herbicides by mutagenesis, for example Clearfield® oilseed rape being tolerant to
  • imidazolinones e.g. imazamox.
  • genetic engineering methods have been used to render plants, such as soybean, cotton, corn, beets and oil seed rape, tolerant to herbicides, such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate).
  • herbicides such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate).
  • glyphosate and glufosinate some of which are commercially available under the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate).
  • insect resistance is of importance, in particular lepidopteran insect resistance and coleopteran insect resistance.
  • Insect resistance is typically achieved by modifying plants by integrating cry and/or vip genes, which were
  • Plants may be modified by mutagenesis or genetic engineering either in terms of one property (singular traits) or in terms of a combination of properties (stacked traits). Stacked traits, e.g. the combination of herbicide tolerance and insect resistance, are of increasing importance.
  • the pesticidal activity of the compounds of the present in- vention 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/compositions used in the invention.
  • a pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target 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 ingredients 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 hectare, 30 to 40 g per hectare, or 40 to 50 g per hectare.
  • the compounds of the present 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 present invention therefore also relates to a method for the protection of seeds from insects, in particular from soil insects, and of the seedling's roots and shoots from insects, in particular from soil and foliar insects, said method comprising treating the seeds before sowing and/or after pregermina- tion with a compound of the present 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 carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.
  • the present 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. When the said propagation product is (re)planted, it may absorb the active ingredient.
  • Suitable seed is for example seed of cereals, root crops, oil crops, vegetables, spices, ornamentals, 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, bananas, 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, pansies 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, solutions 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 latter. 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 formulation 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 present 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.
  • 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
  • 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 present invention, or an agriculturally useful salt thereof, as defined herein.
  • the amount of the compound of the present 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 present invention may also be used for improving the health of a plant. Therefore, the present 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 present 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 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 content 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 efficiency, processability).
  • yield for example increased biomass and/or increased content of valuable ingredients
  • quality for example improved content 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 efficiency, 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 methods known to a skilled person.
  • the compounds of the invention are also suitable for use against non-crop insect pests.
  • compounds of the present 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, termites, 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, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, 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.pherobase.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 present 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 stabilizers, 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 present 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 present 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 preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder.
  • the compounds of the present invention and its compositions can be used for protecting wooden materials 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 human 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.
  • the compounds of the present 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. fimbriana, 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 viridigrisea, 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 braziliensis, Caloptilis theivora, Capua reticulana, Carposina spp. such as C. niponensis, C. sasakii; Cephus spp., Chaetocnema aridula, Cheimatobia brumata, Chilo spp. such as C. Indicus, C. suppressalis, C. partellus; Choreutis pariana, Choristoneura spp. such as C. conflictana, C. fumiferana, C. longicellana, C. murinana, C. occidentalis, C.
  • kuehniella kuehniella; Epinotia aporema, Epiphyas postvittana, Erannis tiliaria, Erionota 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; Mamstra 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. idaeusalis, P.
  • insects from the order of Coleoptera for example Acalymma vittatum, Acanthoscehdes obtectus, 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, Amphimallus solstitialis, Anisandrus dispar, Anisoplia austriaca, Anobium punctatum, Anomala diverenta, Anomala rufocuprea, Anoplophora spp. such as A.
  • Anthonomus spp. such as A. eugenii, A. grandis, A. pomorum; Anthrenus spp., Aphthona euphoridae, Apion spp., Apogonia spp., Athous haemorrhoidalis, Atomaria spp. such as A. linearis; Attagenus spp., Aulacophora femoralis, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp. such as B. lentis, B. pisorum, B.
  • vespertinus Conotrachelus nenuphar, Cosmopolites spp., Costelytra zealandica, Crioceris asparagi, Cryptolestes ferrugineus, Cryptorhynchus lapathi, Ctenicera spp. such as C. destructor; Curcu- lio spp., Cylindrocopturus spp., Cyclocephala spp., Dactylispa balyi, Dectes texanus, Dermestes spp., Diabrotica spp. such as D. undecimpunctata, D. speciosa, D. longicornis, D. semipunctata, D.
  • Diaprepes abbreviates, Dichocrocis spp., Dicladispa armigera, Diloboderus abderus, Diocalandra frumenti (Diocalandra stigmaticollis), Enaphalodes rufulus, Epilachna spp. such as E. varivestis, E. vigintioctomaculata; Epitrix spp. such as E. hirtipennis, E.
  • Eutheola humilis Eutinobothrus brasiliensis, Faustinus cubae, Gibbium psylloides, Gnathocerus cornutus, Hellula undalis, Heteronychus 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
  • Maladera matrida Megaplatypus mutates, Megascelis spp., Melanotus communis, Meligethes spp. such as M. aeneus
  • M. hippocastani such as M. hippocastani, M. melolontha; Metamasius hemipterus, Microtheca spp., Migdolus spp. such as M. fryanus, Monochamus spp. such as M.
  • 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., Tanymecus spp., Tenebrio molitor, Tenebrioides mauretanicus, Tribolium spp. such as T.
  • Trogoderma spp. Tychius spp.
  • Xylotrechus spp. such as X. pyrrhoderus
  • Zabrus spp. such as Z. tenebrioides
  • insects from the order of Diptera for example Aedes spp. such as A. aegypti, A. albopictus, A. vexans; Anastrepha ludens, Anopheles spp. such as A. albimanus, A. crucians, A. freeborni, A. gambiae, A. leucosphyrus, A. maculipennis, A. minimus, A. quadrimaculatus, A. sinensis; Bactrocera invadens, Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capitata, Chrysomyia spp. such as C. bezziana, C.
  • fuscipes G. morsitans, 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 corbetti, 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 tsugae, Adelphocoris spp., such as A. rapidus, A.
  • Diaspis spp. such as D. bromeliae; Dichelops furcatus, Diconocoris hewetti, 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., Edes- sa spp., Geocoris spp., Empoasca spp. such as E.
  • Idiocerus spp. Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lecanoideus floccissimus, Lepidosaphes spp. such as L. ulmi; Leptocorisa spp., Leptoglossus phyllopus, Lipaphis erysimi, Lygus spp. such as L. hes- perus, 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., Reduvius senilis, Rhizoecus americanus, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosiphum spp. such as R. pseudobrassicas, R. insertum, R. maidis, R.
  • T. accerra, T. perditor Tibraca spp., Tomaspis spp., Toxoptera spp. such as T. aurantii; Trialeurodes spp. such as T. abutilonea, T. ricini, T. vaporariorum; Triatoma spp., Trioza spp., Typhlocyba spp., Unaspis spp. such as U. citri, U. yanonensis; and Viteus vitifolii,
  • Paravespula spp. such as P. germanica, P. pennsylvanica, P. vulgaris; Pheidole spp. such as P. megacephala; Pogonomyrmex spp. such as P. barbatus, P. californicus, Polistes rubiginosa, Prenolepis impairs, Pseudomyrmex gracilis, Schelipron spp., Sirex cyaneus, Solenopsis spp. such as S. geminata, S.invicta, S.
  • molesta S. richteri, S. xyloni, Sphecius speciosus, Sphex spp., Tapinoma spp. such as T. melanocephalum, T. sessile; Tetramorium spp. such as T. caespitum, T. bicarinatum, Vespa spp. such as V. crabro; Vespula spp. such as V.
  • 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), Argas spp. such as A. persicu), Boophilus spp. such as B. annulatus, B. decoloratus, B. microplus, Dermacentor spp. such as D.silvarum, D. andersoni, D. variabilis, Hyalomma spp. such as H. truncatum, Ixodes spp. such as /. ricinus, I.
  • Amblyomma spp. e.g. A. americanum, A. variegatum, A. maculatum
  • Argas spp. such as A. persicu
  • Boophilus spp. such as B. annul
  • rubicundus I. scapularis, I. holocyclus, I. pacificus, 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, Rhizoglyphus spp., Sarcoptes spp. such asS.
  • 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. kanzawai, T, pacificus, T. phaseulus, T. telarius and T. urticae
  • Bryobia praetiosa Panonychus spp. such as P. ulmi, P. citri; Metatetranychus spp.
  • Oligonychus spp. such as O. pratensis, O. perseae, Vasates lycopersici; Raoiella indica, Family Carpoglyphidae including Carpoglyphus spp.; Penthaleidae spp.
  • Halotydeus destructor Family Demodicidae with species such as Demodex spp.; Family Trombicidea including Trombicula spp.; Family Cellyssidae including Ornothonyssus spp.; Family Pyemotidae including Pyemotes tritici; Tyrophagus putrescentiae; 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 nematodes, Globodera spp. such as G. rostochiensis; Heterodera spp. such as H. avenae, H.
  • glycines 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. longicaudatus
  • Pine nematodes Bursaphelenchus spp.
  • B. lignicolus B. xylophilus
  • Ring nematodes Criconema spp.
  • Criconemella spp. such as C. xenoplax and C. ornata
  • Criconemoides informis 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, Hemicycliophora spp.
  • Neotermes spp. Procornitermes spp., Zootermopsis spp. such as Z. angusticollis, Z. nevadensis, Reticulitermes spp. such as R. hes- perus, 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; Blattella spp. such as B. asahinae, B. germanica; Leucophaea maderae, Panchlora nivea, Periplaneta spp. such as P. americana, P. australasiae, P. brunnea, P. fuligginosa, P.
  • 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 Pediculus 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, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp
  • Haemonchus contortus such as Haemonchus contortus; Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp.,
  • the compounds of the present invention are suitable for use in treating or protecting animals against infestation or infection by parasites.
  • the present invention also relates to the use of a compound of the present invention for the manufacture of a medicament for the treatment or protection of animals against infestation or infection by parasites. Furthermore, the present invention relates to a method of treating or protecting animals against infestation and infec- tion by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a compound of the present invention.
  • the present invention also relates to the non-therapeutic use of compounds of the present invention for treating or protecting animals against infestation and infection by parasites. Moreover, the present invention relates to a non-therapeutic method of treating or protecting animals against infestation and infection by parasites, which comprises applying to a locus a parasiticidally effective amount of a compound of the present invention.
  • the compounds of the present invention are further suitable for use in combating or controlling parasites in and on animals. Furthermore, the present invention relates to a method of combating or controlling parasites in and on animals, which comprises contacting the parasites with a parasitically effective amount of a compound of the present invention.
  • the present invention also relates to the non-therapeutic use of compounds of the present invention for controlling or combating parasites. Moreover, the present invention relates to a non- therapeutic method of combating or controlling parasites, which comprises applying to a locus a parasiticidally effective amount of a compound of the present invention.
  • the compounds of the present 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 present invention can be applied to any and all developmental stages.
  • the compounds of the present invention can be applied as such or in form of compositions comprising the compounds of the present invention.
  • the compounds of the present 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 compositions 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 compositions comprising said mixtures.
  • the compounds of the present invention and compositions comprising them can be applied orally, parenterally or topically, e.g. dermally.
  • the compounds of the present invention can be systemically or non-systemically effective.
  • the application can be carried out prophylactically, therapeutically or non-therapeutically. Furthermore, 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 contact (applying the compounds/compositions to the locus of the parasite).
  • the contact of the parasite through application to its locus is an example of a non-therapeutic use of the compounds of the present invention.
  • locus means the habitat, food supply, breeding ground, area, material or environment in which a parasite is growing or may grow outside of the animal.
  • parasites includes endo- and ectoparasites. In some embodiments of the present 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, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chig- gers, gnats, mosquitoes and fleas.
  • the compounds of the present invention are especially useful for combating parasites of the following orders and species, respectively:
  • fleas e.g. Ctenocephalides felis, Ctenocephalides cams, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus
  • cockroaches e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis
  • flies mosquitoes (Diptera), e.g.
  • Acarapis spp. Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus 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.
  • Camallanida e.g. Dracunculus medinensis (guinea worm); Spirurida, e.g. Thelazia spp., Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp. a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Habronema spp.; Thorny headed worms
  • Acanthocephala e.g. Acanthocephalus spp., Macracanthorhynchus hirudinaceus and
  • Faciola spp. Fascioloides magna
  • Paragonimus spp. Dicrocoelium spp.
  • Fasciolopsis buski Clonorchis sinensis
  • Schistosoma spp. Trichobilharzia spp., Alaria alata, Paragonimus spp., and Nanocyetes spp.; Cercomeromorpha, in particular Cestoda (Tapeworms), e.g.
  • Diphyllobothrium spp. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium caninum, Multiceps spp., Hymenolepis spp., Mesocestoides spp., Vampirolepis spp., Moniezia spp., Anoplocephala spp., Sirometra spp., Anoplocephala spp., and Hymenolepis spp..
  • animal includes warm-blooded animals (including humans) and fish.
  • 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.
  • domestic animals such as dogs or cats.
  • 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 com- pounds/compositions 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, target species, mode of application, and the like.
  • the compounds of the present 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.
  • the formula I compounds may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules.
  • the formula I compounds may be administered to the animals in their drinking water.
  • 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.
  • the formula I compounds may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection.
  • the formula I compounds may be dispersed or dissolved in a physiologically acceptable carrier for subcuta- neous injection.
  • the formula I compounds may be formulated into an implant for subcutaneous administration.
  • the formula I compound may be transdermally administered to animals.
  • 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.
  • 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.
  • dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the formula I compound.
  • the formula I compounds may be formulated as ear tags for animals, particularly 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;
  • Solid preparations such as powders, premixes or concentrates, granules, pellets, tablets, boluses, capsules; aerosols and inhalants, and active compound-containing shaped articles.
  • compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and optionally adding further auxiliaries such as acids, bases, buffer salts, pre- servatives, and solubilizers.
  • auxiliaries for injection solutions are known in the art. The solutions are filtered and filled sterile.
  • Oral solutions are administered directly. Concentrates are administered orally after prior dilution 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 necessary.
  • 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 solutions 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 compound penetrating the skin and acting systemically.
  • Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in suitable skin-compatible solvents or solvent mixtures.
  • 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 compound either in the hydrophobic or in the hydrophilic phase and homogenizing this with the solvent 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 hydrophilic 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 suspending the active compound in a suspending agent, if appropriate with addition of other auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxidants, light stabilizers. Suitable suspending agents, and suitable other auxiliaries for suspensions 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.
  • the active compound is mixed with suitable excipi- ents, if appropriate with addition of auxiliaries, and brought into the desired form.
  • auxiliaries for this purpose are known in the art.
  • compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the compound of the present invention.
  • Ready-to-use preparations contain the compounds acting against parasites, preferably ectoparasites, 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.
  • 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 collars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.
  • solid formulations which release compounds of the present 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.

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Abstract

La présente invention concerne de nouveaux pyrazoles de formule (I). La présente invention concerne également des procédés et des intermédiaires destinés à la préparation des pyrazoles de formule (I), ainsi que des combinaisons de composés actifs les comportant, des compositions les comportant, et leur utilisation pour la protection des plantes en croissance contre l'attaque ou l'infestation par des invertébrés nuisibles. De plus, l'invention concerne des procédés d'application de tels composés. La présente invention enfin des semences comportant de tels composés.
PCT/EP2015/058608 2014-04-22 2015-04-21 Pyrazoles comportant un cycloalcényle en c3-c4 destinés à la lutte contre les invertébrés nuisibles WO2015162133A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109832303A (zh) * 2017-11-28 2019-06-04 苏婷婷 一种天然草药安眠蚊香及其制备方法
US10440953B2 (en) 2015-08-07 2019-10-15 Basf Se Control of pests in maize by ginkgolides and bilobalide
US10513498B2 (en) 2014-07-31 2019-12-24 Basf Se Process for preparing pyrazoles
US10584102B2 (en) 2015-05-11 2020-03-10 Basf Se Process for preparing 4-amino-pyridazines
US11034669B2 (en) 2018-11-30 2021-06-15 Nuvation Bio Inc. Pyrrole and pyrazole compounds and methods of use thereof
EP4140986A1 (fr) * 2021-08-23 2023-03-01 Basf Se Composés de pyrazine destinés à la lutte contre les organismes nuisibles invertébrés
WO2023025602A1 (fr) * 2021-08-23 2023-03-02 Basf Se Composés pyrazines pour la lutte contre les nuisibles invertébrés

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Publication number Priority date Publication date Assignee Title
WO2009027393A2 (fr) * 2007-08-27 2009-03-05 Basf Se Composés de pyrazole permettant de lutter contre les nuisibles invertébrés
WO2010034737A1 (fr) * 2008-09-24 2010-04-01 Basf Se Composés de pyrazole pour la lutte contre des parasites invertébrés

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009027393A2 (fr) * 2007-08-27 2009-03-05 Basf Se Composés de pyrazole permettant de lutter contre les nuisibles invertébrés
WO2010034737A1 (fr) * 2008-09-24 2010-04-01 Basf Se Composés de pyrazole pour la lutte contre des parasites invertébrés

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10513498B2 (en) 2014-07-31 2019-12-24 Basf Se Process for preparing pyrazoles
US10584102B2 (en) 2015-05-11 2020-03-10 Basf Se Process for preparing 4-amino-pyridazines
US11046656B2 (en) 2015-05-11 2021-06-29 Basf Se Process for preparing 4-amino-pyridazines
US10440953B2 (en) 2015-08-07 2019-10-15 Basf Se Control of pests in maize by ginkgolides and bilobalide
CN109832303A (zh) * 2017-11-28 2019-06-04 苏婷婷 一种天然草药安眠蚊香及其制备方法
US11034669B2 (en) 2018-11-30 2021-06-15 Nuvation Bio Inc. Pyrrole and pyrazole compounds and methods of use thereof
EP4140986A1 (fr) * 2021-08-23 2023-03-01 Basf Se Composés de pyrazine destinés à la lutte contre les organismes nuisibles invertébrés
WO2023025602A1 (fr) * 2021-08-23 2023-03-02 Basf Se Composés pyrazines pour la lutte contre les nuisibles invertébrés

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