WO2014060381A1 - Heterocyclic compounds as pesticides - Google Patents

Heterocyclic compounds as pesticides Download PDF

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Publication number
WO2014060381A1
WO2014060381A1 PCT/EP2013/071469 EP2013071469W WO2014060381A1 WO 2014060381 A1 WO2014060381 A1 WO 2014060381A1 EP 2013071469 W EP2013071469 W EP 2013071469W WO 2014060381 A1 WO2014060381 A1 WO 2014060381A1
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spp
alkyl
optionally substituted
group
radical
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PCT/EP2013/071469
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German (de)
French (fr)
Inventor
Peter Jeschke
Thomas Bretschneider
Adeline KÖHLER
Reiner Fischer
Martin FÜSSLEIN
Olga Malsam
Kerstin Ilg
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Bayer Cropscience Ag
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Publication of WO2014060381A1 publication Critical patent/WO2014060381A1/en

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    • 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
    • C07D403/04—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 directly linked by a ring-member-to-ring-member bond

Definitions

  • the present application relates to novel heterocyclic compounds, to processes for their preparation and their use for controlling animal pests, which include arthropods and in particular insects, as well as intermediates for the preparation of the heterocyclic compounds.
  • Plant protection products including pesticides, must meet many requirements, for example, in terms of the level, duration and breadth of their effect and possible use. Issues of toxicity, of the ability to be combined with other active substances or formulation auxiliaries play a role, as well as the question of the effort that has to be spent on the synthesis of an active substance. Furthermore, resistances can occur. For all these reasons, the search for new pesticides can not be considered complete and there is a constant need for new compounds with improved properties over the known compounds, at least with respect to individual aspects.
  • the object of the present invention was to provide compounds which broaden the spectrum of pesticides from various aspects.
  • R is a radical from the group consisting of hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl and halogenocycloalkyl
  • R 1 is a radical from the series halogen, cyano, nitro, alkyl, haloalkyl, alkenyl, haloalkenyl, alkoxy, haloalkoxy, cycloalkyl, Halocycloalkyl, alkylthio, haloalkylthio, alkylsulfinyl, haloalylsulfinyl, alkylsulfonyl, haloalkylsulfonyl,
  • R 2 is a radical selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, alkylthioalkyl, alkenylthioalkyl, cyanoalkyl, alkoxyalkyl,
  • R 3 is a radical of the formula in which one radical is selected from the group consisting of alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyalkyloxy, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, alkylthioalkyloxy, alkylsulfinylalkyloxy, alkylsulfonylalkyloxy, haloalkylthioalkyl, haloalkylsulfinylalkyl, haloalkylsulfonylalkyl, alkylthioalkenyl , Alkylsulfinylalkenyl,
  • R 5 is a radical from the group consisting of hydrogen (only in the radicals C-33, C-36 and C-42), halogen, cyano, nitro, amino, hydroxyl and in each case optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, Alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, cycloalkylcarbonyloxy, alkoxycarbonyloxy, alkylsulfonyloxy, alkylamino, alkenylamino, alkynylamino, cycloalkylamino, alkylthio, haloalkylthio, alkenylthio, alkynylthio, cycloalkylthio, alkylsulfinyl, alkylsulf
  • Alkylthiocarbonylamino, bicycloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy, where the substituents are independently selected from halogen, cyano, nitro, hydroxy and amino, is a radical from the series consisting of hydrogen, alkyl, cycloalkyl, haloalkyl, alkenyl, alkynyl, cycloalkylalkyl, cyanoalkyl, alkylcarbonyl, alkenylcarbonyl, haloalkylcarbonyl, haloalkenylcarbonyl, alkoxyalkyl, alkoxycarbonyl, alkylsulfonyl and haloalkylsulfonyl, or a radical from the series
  • X is oxygen or sulfur
  • n is 1 or 2 .
  • R 8 is a radical from the group consisting of hydrogen, alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, alkenyl, alkoxyalkyl, in each case optionally halogen-substituted alkylcarbonyl and alkylsulfonyl, optionally halogen-substituted alkoxycarbonyl, if appropriate by halogen, alkyl, alkoxy, haloalkyl and cyano substituted cycloalkylcarbonyl, or a cation, such as a mono- or divalent metal ion (for example, alkali metal ions such as Li + , Na + , Cs + and K + and alkaline earth metal ions such as
  • R 15 and R 9 independently of one another from the series each optionally substituted amino, alkyl, alkenyl and alkynyl, each optionally substituted cycloalkyl, cycloalkylalkyl and cycloalkenyl, in which the rings at least one heteroatom selected from the group sulfur, oxygen (oxygen atoms not may be immediately adjacent) and contain nitrogen, each optionally substituted aryl, heteroaryl, arylalkyl and heteroarylalkyl and an optionally substituted amino group,
  • R 8 and R 15 together with the NS (0) n group to which they are attached, may also form a saturated or unsaturated and optionally substituted 4- to 8-membered ring containing one or more further heteroatoms selected from the group consisting of sulfur, Oxygen (where oxygen atoms are not allowed to be immediately adjacent) and nitrogen and / or at least one carbonyl group,
  • R 17 is a radical from the series in each case optionally substituted alkyl, alkoxy, alkenyl and alkynyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl and cycloalkenyl, in which the rings are at least one heteroatom from the series sulfur, oxygen (oxygen atoms may not be immediately adjacent) and each may contain nitrogen, each optionally substituted aryl, heteroaryl, arylalkyl and heteroarylalkyl and an optionally substituted amino group,
  • R 16 is a radical from the group consisting of hydrogen, in each case optionally substituted alkyl, alkoxy, alkenyl and alkynyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl and cycloalkenyl, in which the rings are at least one heteroatom selected from the group consisting of sulfur, oxygen (oxygen atoms not being directly adjacent may each contain) and nitrogen, each optionally substituted aryl, heteroaryl, arylalkyl and heteroarylalkyl and an optionally substituted amino group,
  • R 8 and R 17 may also together with the NC (X) group to which they are attached form a saturated or unsaturated and optionally substituted 4- to 8-membered ring containing one or more further heteroatoms selected from sulfur, oxygen (where oxygen atoms not immediately adjacent) and may contain nitrogen and / or at least one carbonyl group,
  • R 10 is hydrogen or alkyl
  • R 8 and R 10 together with the N atoms to which they are attached, may represent a saturated or unsaturated and optionally substituted 4- to 8-membered ring containing at least one further heteroatom selected from the group consisting of sulfur, oxygen (where Sauers toffatome not be immediately adjacent) and may contain nitrogen and / or at least one carbonyl group,
  • R and R in the radical (Dl) together with the NS (0) n group to which they are attached can form a saturated or unsaturated and optionally substituted 4- to 8-membered ring which comprises one or more further heteroatoms the series sulfur, oxygen (oxygen atoms may not be immediately adjacent) and nitrogen and / or at least one carbonyl group,
  • R and R may also together with the NS (0) n group to which they are attached form a saturated or unsaturated and optionally substituted 4- to 8-membered ring containing one or more further heteroatoms selected from the group consisting of sulfur, oxygen (where oxygen atoms are not allowed to be immediately adjacent) and may contain nitrogen and / or at least one carbonyl group,
  • R 8 and R 16 may also together with the N-atom to which they are attached form a saturated or unsaturated and optionally substituted 4- to 8-membered ring containing one or more further heteroatoms selected from the group consisting of sulfur and oxygen (where Oxygen atoms may not be immediately adjacent) and may contain nitrogen and / or at least one carbonyl group,
  • L is oxygen or sulfur
  • R and R independently of one another are each an optionally substituted radical from the series alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkyloxy, cycloalkenyloxy, cycloalkylalkoxy, alkylthio, alkenylthio, phenoxy, phenylthio, benzyloxy, benzylthio, heteroaryloxy, heteroarylthio, Heteroarylalkoxy and heteroarylalkylthio,
  • R and R may also together with the phosphorus atom to which they are attached form a saturated or unsaturated and optionally substituted 5- to 7-membered ring, the or two heteroatoms from the series oxygen (oxygen atoms may not be immediately adjacent) and sulfur may contain and
  • R and R are each independently an optionally substituted radical from the series alkyl, alkenyl, alkynyl, phenyl and phenylalkyl
  • R 18 and R 19 are independently hydrogen or each optionally substituted radical from the series alkyl, alkenyl, alkynyl, phenyl and phenylalkyl
  • novel compounds of the formula (I) have a good activity as pest control agents, for example against arthropods and in particular insects, moreover, in general, especially against crop plants are very well plant tolerated and / or favorable toxicological and / or environmental properties feature.
  • B-1 B-2 wherein the dashed line represents the bond to A and the arrow represents the bond to the group NR 2 R 3 .
  • Ci-C6-alkyl stands for a radical from the series halogen, cyano, nitro, Ci-C6-alkyl, Ci-C6-haloalkyl, C 2 - C 6 alkenyl, C 2 -C 6 haloalkenyl, Ci-C6-alkoxy, Ci-C6-halogenoalkoxy , C 3 -C 6 -cycloalkyl, C 3 -C 6 -halocycloalkyl, C 1 -C 6 -alkylthio, C 1 -C 6 -haloalkylthio, C 1 -C 6 -alkylsulfinyl, C 1 -C 6 -halogenoylsulfinyl, C 1 -C 6 -alkylsulfonyl, C 1 -C 6 -haloalkylsulfonyl.
  • C 1 -C 6 -alkyl is a radical from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkenyl, C 1 -C 6 -alkoxy, C 2 - C6-alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 6 cycloalkyloxy, Ci-C6 alkylthio-Ci-C 6 alkyl, C 2 -C 6 alkenylthio-Ci-C 6 alkyl, cyano C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl.
  • Ci-C6-alkyl stands for the rest of the formula is a radical from the series Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-Ce-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyloxy, Ci-C6-alkylthio, Ci C6-alkylsulfinyl, CI-C ⁇ - alkylsulfonyl, Ci-C6-haloalkylthio, Ci-C6 haloalkylsulfinyl, Ci-Ce
  • Ci-Ce-alkylthio-Ci-Ce-alkyl Ci-C 6 alkylsulfinyl-Ci-C 6 alkyl, C 6 - alkylsulphonyl-Ci-Ce-alkyl, Ci-C 6 -alkylthio-C 6 alkyloxy, Ci-C 6 alkylsulfinyl-Ci-C 6 - alkyloxy, Ci-C6-alkylsulfonyl-Ci-C6-alkyloxy, Ci-C6-halogenoalkylthio-Ci-C6-alkyl, Ci-Ce-haloalkylsulfinyl-Ci C6-alkyl, Ci-C6-haloalkylsulfonyl-Ci-C6-alkyl, Ci-C6-alkylthio, C 2 -C 6 alkenyl, Ci-C 6 alkyl
  • Alkylaminocarbonyl di- (C 1 -C 6 -alkyl) aminocarbonyl, aminothiocarbonyl, C 1 -C 5
  • R 5 is a radical from the series hydrogen (only in the radicals C-33, C-36 and C-42), halogen, cyano, nitro, amino, hydroxy, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, cyano-Ci-C6-alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl-Ci-C 6 alkyl, C 6 alkoxy, Ci-C6-haloalkoxy, C3-C6-alkenyloxy, C 3 -C 6 alkynyloxy, C 3 -C 6 cycloalkyloxy, C ⁇ -
  • Ci-C6-alkoxycarbonyl aminocarbonyl, Ci-C6-alkylaminocarbonyl, di (Ci-C6) alkylaminocarbonyl, aminothiocarbonyl, Ci-C6-alkylaminosulfonyl, Cl-C ⁇ - alkylsulfonylamino, Ci-C6 Alkylcarbonylamino, C 1 -C 6 -alkylthiocarbonylamino, aryl, aryloxy, heteroaryl and heteroaryloxy.
  • R 6 is a radical selected from hydrogen, Ci-C6-alkyl, C3-C6-cycloalkyl, CI-C ⁇ - haloalkyl, C 3 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 - C 6 -cycloalkyl-C 1 -C 6 -alkyl, cyano-C 1 -C 6 -alkyl, C 1 -C 6 -alkylcarbonyl, C 2 -C 6 -alkenylcarbonyl, C 1 -C 6 -haloalkylcarbonyl,
  • Haloalkenylcarbonyl C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 1 -C 6 -alkoxycarbonyl,
  • Alkylsulfonyl and Ci-C6-Halogengenalkylsufonyl is synonymous for a rest of the series
  • X is oxygen or sulfur, n is 1 or 2.
  • R 8 is a radical selected from hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, cyano-C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy , Ci-C6-haloalkoxy, C 2 -C 6 -alkenyl, Ci-C6-alkoxy-Ci-C6-alkyl, in each case optionally substituted by halogen Ci-C6-alkylcarbonyl and Ci-C6-alkylsulfonyl, optionally substituted by halogen Ci-C6 Alkoxycarbonyl, optionally substituted by halogen, Ci-C6-alkyl, Ci-C6-alkoxy, Ci-C6-haloalky
  • R 9 is a radical from the series in each case optionally substituted by halogen, Ci-C6-alkoxy, Ci-Ce- haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfinyl, CI-C ⁇ - haloalkylsulfinyl , Ci-C6-alkylsulfonyl, and Ci-C6-haloalkylsulfonyl-substituted CI-C ⁇ - alkyl, C 2 -C 6 alkenyl and C 2 -C 6 alkynyl, each optionally substituted by halogen, Ci-C6-alkyl, Ci-
  • halogen is a radical from the series in each case optionally substituted by halogen, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 1 -C 6 -alkylthio, C 1 -C 6 -haloalkylthio, C 1 -C 6 -alkylsulfinyl, C 1 -C 8 -haloalkylsulfinyl, C6-alkylsulfonyl or Ci-C6-haloalkylsulfonyl-substituted CI-C ⁇ - alkyl, Ci-C6 alkoxy, C 2 -C 6 alkenyl and C 2 -C 6 alkynyl, each optionally substituted by halogen, Ci-COE-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy or Ci-C6-haloalkoxy-substituted C3-C6
  • R 8 and R 17 can also be used together with the NC (X) group to which they are attached, a saturated or unsaturated and optionally halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, CI-C ⁇ - alkoxy, Ci-C6-haloalkoxy-substituted 5- to 7-membered ring form, which may contain one or two further heteroatoms from the series sulfur, oxygen (oxygen atoms may not be immediately adjacent) and nitrogen and / or a carbonyl group, in particular R 8 and R 17, together with the NC (X) group to which they are attached, are out of line for a remainder
  • R independently of one another represent hydrogen or an optionally substituted radical from the group consisting of C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, phenyl and phenylalkyl.
  • B-1 wherein the dashed line represents the bond to A and the arrow represents the bond to the group NR 2 R 3 .
  • Ci-C4-alkyl stands for a radical from the series halogen, cyano, nitro, Ci-C4-alkyl, Ci-C 4 haloalkyl, C 2 - C 4 alkenyl, C 2 -C 4 haloalkenyl, Ci-C 4 alkoxy, Ci-C 4 haloalkoxy, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, Ci-C 4 alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylsulfinyl, Ci- C 4 -Halogenalylsulfinyl, C -C 4 alkylsulfonyl, Ci-C4-haloalkylsulfonyl.
  • C 1 -C 4 -alkyl is a radical from the series consisting of hydrogen, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkenyl, C 1 -C 4 - alkoxy, C 2 -C 4 alkenyloxy, C 2 -C 4 alkynyloxy, C 3 -C 6 cycloalkyloxy, Ci-C4-alkylthio-Ci-C 4 alkyl, C 2 -C 4 alkenylthio-Ci C 4 -alkyl, cyano-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl.
  • R 3 is a radical of the formula stands for a radical from the group Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkylthio-Ci-C4-alkyl, Ci-C4-alkylsulfinyl-Ci-C4-alkyl, Ci-C 4 - alkylsulfonyl-Ci-C4-alkyl, Ci-C 4 haloalkyl thio-Ci-C4-alkyl, Ci-C4-haloalkylsulfinyl-Ci-C4-alkyl, Ci-C4-haloalkylsulfonyl-Ci-C4-alkyl, Ci- C 4 -alkylthio-C 2 -C 4 alkenyl, C 4 alkylsulfinyl-C 2 -C 4 alkenyl, Ci-C 4 alkylsulfonyl C 2 -C 4 alken
  • halogen is also optionally substituted by halogen, cyano, nitro, amino, hydroxy, C 1 -C 6 -alkyl, ce-Ce-haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkyl , C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 3 -C 6 -alkenyloxy, C 3 -C 6 -alkynyloxy, C 1 -C 6 -alkoxycarbonyloxy, C 1 -C 6 -alkylamino, C 3 -C 6 -alkenylamino, C 3 -C 6 -alkynylamino, C3-C6-cycloalkylamino, CI-C ⁇ - alkylthio, Ci-C 6 haloalkylthio, C 3 -C 6
  • R 3 is also out of line for a rest
  • R 5 is (only in the radical B-36), halogen, cyano, nitro, hydroxy, Ci-C4-alkyl, Ci-C alkyl 4 haloalkyl, cyano-Ci-C 4 is a radical selected from hydrogen, C 2 -C 4 alkenyl, C 2 -C alkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl-Ci-C4-alkyl, Ci-C 4 alkoxy, Ci-C 4 - haloalkoxy, C 3 -C 4 - alkenyloxy, C 3 -C alkynyloxy, C 3 -C 6 cycloalkyloxy, Ci-C alkylsulfinyl, Ci-C alkylthio, Ci- C4-haloalkylthio, Ci-C 4 alkylsulfonyl, C 1 -C 4 -alkoxyimino-C 1 -C
  • ⁇ is a radical selected from the group consisting of hydrogen, C 1 -C 4 -alkyl, C 3 -C 6 -cycloalkyl and C 1 -C 4 -haloalkyl.
  • halogen is a radical from the series in each case optionally substituted by halogen, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -haloalkylthio, C 1 -C 4 -alkylsulfinyl, C 1 -C 4 - haloalkylsulfinyl, Ci-C4-alkylsulfonyl and Ci-C4-haloalkylsulfonyl-substituted C 1 -C 4 - alkyl, C 2 -C 4 alkenyl and C 2 -C 4 alkynyl each optionally substituted by halogen, Ci-C 4 alkyl, C - C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy-substituted C3-C6-cycloalkyl
  • 4 -alkoxy represents a radical from the series in each case optionally substituted by halogen, Ci-C, C 1 -C 4 - haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylsulfinyl, C1-C4 haloalkylsulfinyl , Ci-C4-alkylsulfonyl and Ci-C4-haloalkylsulfonyl-substituted C 1 -C 4 - alkyl, C 2 -C 4 alkenyl and C 2 -C 4 alkynyl each optionally substituted by halogen, Ci-C 4 alkyl , C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, substituted C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkyl-
  • R 2 is hydrogen
  • R 3 represents the remainder of the formula R 4 stands for Ci-C4-alkylthio-Ci-C 4 -alkyl or optionally substituted by one or two radicals from the series halogen, nitro and Ci-C4-haloalkyl substituted phenyl.
  • N-alkyl especially N-Ci-C6-alkyl
  • Halogen selected from the group fluorine, chlorine, bromine and iodine, preferably again from the series fluorine, chlorine and bromine,
  • Aryl also as part of a larger unit, such as arylalkyl selected from the group phenyl, naphthyl, anthryl, phenanthrenyl and in turn preferably represents phenyl, hetaryl (equivalent to heteroaryl, also as part of a larger unit, such as hetarylalkyl) selected from the series furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1, 2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1, 2,4- Oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1, 2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, Pyridyl,
  • Halogen selected from the group fluorine, chlorine, bromine and iodine, preferably in turn from the series fluorine, chlorine and bromine,
  • Aryl also as part of a larger unit, such as, for example, arylalkyl selected from among phenyl, naphthyl, anthryl, phenanthrenyl and in turn preferably represents phenyl, hetaryl (also as part of a larger unit, such as, for example, hetarylalkyl) selected from the series furyl, Thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1, 2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1, 2,4-oxadiazolyl, 1, 3,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1, 2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, pyridyl
  • Halogen stands for fluorine, chlorine, bromine and iodine, in particular fluorine, chlorine and bromine.
  • Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl
  • heteroatoms e.g. in alkoxy, as far as possible, in each case straight-chain or branched.
  • Optionally substituted radicals may be monosubstituted or polysubstituted, with multiple substituents the substituents may be the same or different.
  • Suitable metal ions in the radical R 8 are, for example, alkali metal ions such as Li + , Na + , Cs + and K + and alkaline earth metal ions such as Mg ++ and Ca ++ .
  • alkali metal ions such as Li + , Na + , Cs + and K +
  • alkaline earth metal ions such as Mg ++ and Ca ++ .
  • the abovementioned general or preferred radical definitions or explanations apply to the end products (also for the compounds of the formulas (IA) to (IM) listed below) and correspondingly to the starting materials and intermediates. These remainder definitions can be combined with one another as desired, ie also between the respective preferred ranges. Preference according to the invention is given to compounds of the formula (I) which contain a combination of the meanings listed above as being preferred.
  • the invention relates to compounds of the formula (IB)
  • the invention relates to compounds of the formula (IC)
  • the invention relates to compounds of the formula (ID)
  • the invention relates to compounds of the formula (IE)
  • the invention relates to compounds of the formula (IF)
  • the invention relates to compounds of the formula (IG)
  • the invention relates to compounds of the formula (IH)
  • the invention relates to compounds of the formula (I-J)
  • the invention relates to compounds of the formula (I-K)
  • the invention relates to compounds of the formula (I-L)
  • the invention relates to compounds of the formula (III)
  • the compounds of the formula (I) according to the invention and their acid addition salts and metal salt complexes have good activity, in particular for controlling animal pests, which include arthropods and in particular insects.
  • the compounds of formula (I) may also be optionally substituted as stereoisomers, i.e., depending on the nature of the substituents. as geometric and / or as optical isomers or mixtures of isomers are present in different compositions. Both the pure stereoisomers and any mixtures of these isomers are the subject of this invention, although in general only compounds of the formula (I) are mentioned here.
  • the compounds of the formula (I) according to the invention can be present in different polymorphic forms or as a mixture of different polymorphic forms. Both the pure polymorphs and the polymorph mixtures are the subject of the invention and can be used according to the invention.
  • the optically active stereoisomeric forms of the compounds of the formula (I) and salts thereof are used according to the invention.
  • the invention therefore relates to both the pure enantiomers and diastereomers, as well as their mixtures for controlling animal pests, which include arthropods and in particular insects.
  • Suitable salts of the compounds of general formula (I) may be conventional non-toxic salts, i. H. Salts with corresponding bases and salts with added acids.
  • salts with inorganic bases such as alkali metal salts, for example sodium, potassium or cesium salts, alkaline earth metal salts, for example calcium or magnesium salts, ammonium salts, salts with organic bases and with inorganic amines, for example triethylammonium, dicyclohexylammonium, ⁇ , ⁇ '- Dibenzylethylenediammonium, pyridinium, picolinium or ethanolammonium salts, salts with inorganic acids, for example hydrochlorides, hydrobromides, dihydrosulfates, trihydrosulfates, or phosphates, salts with organic carboxylic acids or organic sulfonic acid, for example formates, acetates, trifluoroacetates, maleates, tartrates, methanesul
  • N-pyrazol-1-yl is B
  • LG is an in situ generated nucleofuge leaving group
  • Nitrations can be carried out by customary processes, as described, for example, in Houben-Weyl, Methods of Organic Chemistry, Volume XI / 2 (Georg Thieme Verlag Stuttgart 1958), pages 99-116.
  • Suitable nitrating reagents are fuming or 100% nitric acid, optionally in the presence of sulfuric acid (MJ Middleton et al., / Heterocyclic Chem. 1970, 7, pp. 1045-1049, LW Deady et al., Aust. J. Chem. 10), pp 2025-2034; EP 0192060) or the use of nitric acid esters, acyl nitrate or nitronium tetrafluoroborate.
  • Suitable catalysts for carrying out the catalytic hydrogenation are all customary hydrogenation catalysts, for example platinum catalysts (platinum plate, platinum sponge, platinum black, colloidal platinum, platinum oxide, platinum wire, etc.), palladium catalysts (for example palladium sponge, Palladium black, palladium oxide, palladium-carbon, colloidal palladium, palladium-barium sulfate, palladium-barium carbonate, palladium hydroxide, etc.), ruthenium catalysts, cobalt catalysts (e.g., reduced cobalt, Raney cobalt, etc.), copper catalysts (for example, reduced copper, Raney copper, Ullman copper, etc.).
  • noble metal catalysts for example platinum and palladium or ruthenium catalysts, if appropriate on a suitable support such as carbon or silicon.
  • the hydrogenation catalysts used are preferably palladium or platinum catalysts, in particular palladium-hydroxide-carbon or platinum oxide (cf., Preparation Example 1, Step 3).
  • the heterocyclic compounds of the formula (Al) with 3-substituted pyrazoles of the formula (A-6) according to method B in a first reaction step to compounds of formula (A-7) are reacted, which then either in a second reaction step Removal of the protective group PG to compounds of formula (A-5) or equal to compounds of formula (IA to ID) can be implemented.
  • the compounds of the formula (A1) are known in some cases or can be obtained by production processes known in principle, cf.
  • LG Br
  • LG 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -isoxazole
  • LG B [-OC (CH 3 ) 2 C (CH 3 ) 2 O-], J. Velcicky et al., Amer. Chem.
  • heterocycle A is, for example, optionally substituted by an R radical substituted pyrazol-4-yl (Aa), isothiazol-4-yl (Ab), isoxazol-4-yl (Ac) or pyrazine -yl (Ah), and the heterocycle B is l, 3-thiazol-2-yl, which is substituted in the 4-position by a radical R 1 , for example, by Method C according to Reaction Scheme II are shown.
  • Hal halogen, preferably bromine or iodine
  • PG tertiarybutyloxacarbonyl
  • halogen-substituted heteroaryl compounds for example halogen-substituted 1,3-thiazoles of the formula (A-8)
  • known methods such as Chem Rev. 1995, 95, 2457-2483, Tetrahedron 2002, 58, 9633-9695, Metal-Catalyzed Cross-Coupling Reactions (Eds .: A. de Meijere , F. Diederich), 2 nd ed., Wiley-VCH, Weinheim, 2004
  • suitable catalysts from the series of transition metal salts to give compounds of formula (A-9).
  • Halogen iodine
  • R 1 ethoxycarbonyl
  • R 2 hydrogen
  • PG tert- Butyloxycarbonyl (Boc)
  • heterocycle A is substituted, for example, by pyrazol-4-yl optionally substituted by one R (see IA), isothiazol-4-yl (see IB), isoxazol-4-yl (cf. IC) or pyrazine-2-yl (see ID), and the heterocycle B is l, 3,4-thiadiazol-2-yl (B-3), for example, by the method C according to Reaction Scheme III.
  • Hal halogen, preferably chlorine, bromine or iodine
  • LG stands for an in-situ generated nucleofuge leaving group
  • Hai stands for halogen (preferably bromine or iodine)
  • PG means protection group.
  • PG tertiarybutyloxacarbonyl
  • halogen-substituted heteroaryl compounds for example halogen-substituted 1,3-thiadiazoles of the formula (A-10), according to the method mentioned in Reaction Scheme III C in the presence of suitable catalysts from the series of transition metal salts to give compounds of formula (A-11).
  • Compounds of the formula (A-1) are known in some cases or can be obtained by the production processes mentioned above.
  • N-alkylation j N-alkylation / N-acylation / N-sulfonation
  • PG ferf-butyloxycarbonyl (Boc) AB-NR 2 NR 3
  • PG means Protection Group.
  • Amides, N-alkylamines, N-arylamines, imine derivatives, enamine derivatives, N-sulfenyl derivatives, N-sulfonyl derivatives or N-diarylphosphinyl derivatives can be used (see Greene TW, Wuts PGW in Protective Croups in Organic Synthesis, John Wiley & Sons, Inc 1999, "Protection for the Amino Group", p. 494).
  • carbamate-type protecting groups are used. _
  • Compounds of formulas (1-2) and (1-4) can be prepared from the compounds of formula (1-1) and (1-3) by deprotection, respectively.
  • acidic or basic reaction auxiliaries can be used according to the literature procedure for the removal of the protective group.
  • carbamate-type protecting groups preference is given to using acidic reaction auxiliaries.
  • the tert-butylcarbamate protecting group (Boc group) is used, for example, mixtures of mineral acids such as hydrochloric, hydrobromic, nitric, sulfuric, phosphoric or organic acids such as benzoic, formic, acetic, trifluoroacetic, methanesulfonic, benzenesulfonic or toluenesulfonic acid in a suitable diluent such as water and / or an organic solvent such as tetrahydrofuran, dioxane, dichloromethane, chloroform, ethyl acetate, ethanol or methanol.
  • a suitable diluent such as water and / or an organic solvent
  • the compounds of the formulas (1-1), (1-2) and (1-4) can be prepared by methods known in principle with suitable reactants and in the presence of diluents and basic reaction auxiliaries to give compounds of the formulas (1-3), (1-4) and (I) N-alkylated, N-acylated or N-sulfonylated (see Preparation Examples, Examples 1 and 2).
  • Diluents are advantageously used in such an amount that the reaction mixture remains easy to stir throughout the process.
  • Suitable diluents for carrying out the process according to the invention are all organic solvents which are inert under the reaction conditions.
  • halogenated hydrocarbons especially chlorinated hydrocarbons such as tetraethylene, tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, carbon tetrachloride, trichloroethane, trichlorethylene, pentachloroethane, difluorobenzene, 1, 2-dichloroethane, chlorobenzene, bromobenzene, dichlorobenzene, chlorotoluene, trichlorobenzene; Alcohols such as methanol, ethanol, isopropanol, butanol; Ethers such as ethyl propyl ether, methyl tert-butyl ether, n-butyl ether, anisole, phenetole, cyclohexylmethyl ether, dimethyl ether, diethyl ether, dipropl ether, diisopropyl ether
  • Preferred diluents for carrying out the process according to the invention are halogenated hydrocarbons, in particular chlorohydrocarbons, such as tetraethylene, tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, carbon tetrachloride, trichloroethane, trichlorethylene, pentachloroethane, difluorobenzene, 1, 2-dichloroethane, chlorobenzene, bromobenzene, dichlorobenzene, chlorotoluene and trichlorobenzene.
  • chlorohydrocarbons such as tetraethylene, tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, carbon tetrachloride, trichloroethane, trichlorethylene, pentachloroethane, difluoro
  • Activation reagents which may be used are all reagents which are suitable for the preparation of an amide or hydrazide bond (cf., for example, Houbel-Weyl, Methods of Organic Chemistry, Volume 15/2, Bodansky et al., Peptide Synthesis 2 nd ed. (Wiley & Sons, New York 1976) or Gross, Meienhofer, The Peptides: Analysis, Synthesis, Biology (Academy Press, New York 1979).
  • the coupling with phosphonium reagents such as bis (2-oxo-3-oxazolidinyl) phosphonium chloride ( BOP-Cl), benzotriazole-1-yl-oxy-tris (dimethylamino-phosphonium) hexafluorophosphate (BOP), benzotriazol-l-yl-tris-pyrrolidino-phosphonium hexafluorophosphate (PyBOB ®), bromo-tris- pyrrolidino-phosphonium -hexafluorophospha (PyBroP ®) or Phosphonklarreagenzien such as diethyl cyanophosphonate (DEPC) and diphenylphosphoryl azide (DPPA).
  • BOP-Cl bis (2-oxo-3-oxazolidinyl) phosphonium chloride
  • BOP benzotriazole-1-yl-oxy-tris (dimethylamino-phosphon
  • Preferred activating agents for the (thio) carboxylic acids or sulfonic acids are, for example, phosphonium reagents such as bis (2-oxo-3-oxazolidinyl) phosphonium chloride (BOP-Cl) (compare also Preparation Examples, Example 1, Step 4 and Example 2).
  • reaction auxiliaries for carrying out the process according to the invention in Reaction Scheme IV it is possible to use all suitable acid binders, for example amines, in particular tertiary amines, and also alkali metal and alkaline earth metal compounds.
  • suitable acid binders for example amines, in particular tertiary amines, and also alkali metal and alkaline earth metal compounds.
  • Examples include the hydroxides, hydrides, oxides and carbonates of lithium, sodium, potassium, magnesium, calcium and barium, further basic compounds such as amidine bases or guanidine bases such as 7-methyl-l, 5,7-triaza-bicyclo (4.4.0 ) dec-5-ene (MTBD); Diazabicyclo (4.3.0) nonene (DBN), diazabicyclo (2.2.2) octane (DABCO), 1,8-diazabicyclo (5.4.0) undecene (DBU), cyclohexyltetrabutyl-guanidine (CyTBG), cyclohexyltetramethylguanidine (CyTMG), ⁇ , ⁇ , ⁇ , ⁇ -tetramethyl-l, 8-naphthalenediamine, pentamethylpiperidine, tertiary amines such as triethylamine, trimethylamine, tribenzylamine, triisopropylamine, tributyl
  • hydroxides of lithium potassium or sodium are used.
  • tertiary amines such as N-propyl-diisopropylamine or N-ethyl-diisopropylamine (Hünig's base) are preferably used.
  • R 2 is an acceptor radical such as acyl, sulfonyl, etc.
  • tertiary amines such as N-propyl-diisopropylamine or N, depending on R 2 Ethyl-diisopropylamine (Hünig's base)
  • R 2 is optionally substituted alkyl, alkenyl, alkynyl, etc.
  • the active compounds according to the invention or to be used in accordance with the invention are suitable for plant tolerance, favorable warm-blooded toxicity and good environmental compatibility for protecting plants and plant organs, for increasing crop yields, improving the quality of the crop and for controlling animal pests, in particular insects, arachnids, helminths, Nematodes and molluscs found in agriculture, horticulture, livestock, forestry, gardens and recreational facilities, in the protection of materials and materials and in the hygiene sector. They can preferably be used as crop protection agents. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.
  • the above mentioned pests include:
  • Pests of the genus Arthropoda in particular of the class Arachnida eg Acarus spp., Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Amphitetranychus viennensis, Argas spp., Boophilus spp., Brevipalpus spp., Bryobia graminum , Bryobia praetiosa, Centruroides spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermacentor spp., Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Glycyphagus domesticus, Halotydeus destructor, Hemitarsonemus spp
  • Curculio spp. Cryptolestes ferruginus, Cryptorhynchus lapathi, Cylindrocopturus spp., Dermestes spp., Diabrotica spp., Dichocrocis spp., Dicladispa armigera, Diloboderus spp., Epilachna spp., Epitrix spp., Faustinus spp., Gibbium psylloides, Gnathocerus cornutus , Hellula and alis, Heteronychus arator, Heteronyx spp., Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypomeces squamosus, Hypothenemus spp., Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lema spp., Leptinotarsa decem
  • Phormia spp. Piophila casei, Prodiplosis spp., Psila rosae, Rhagoletis spp., Sarcophaga spp., Simulium spp., Stomoxys spp., Tabanus spp., Tetanops spp., Tipula spp .; from the order of the Heteroptera eg Anasa tristis, Antestiopsis spp., Boisea spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Collaria spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Eushtus spp., Eurygaster spp., Heli
  • Pentomidae Piesma quadrata, Piezodorus spp., Psallus spp., Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp.
  • Tinocallis caryaefoliae Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes vaporariorum, Trioza spp., Typhlocyba spp., Unaspis spp., Viteus vitifolii, Zygina spp .; from the order of Hymenoptera eg Acromyrmex spp., Athalia spp., Atta spp., Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Sirex spp., Solenopsis invicta, Tapinoma spp., Urocerus spp., Vespa spp ., Xeris spp .; from the order of Isopoda, for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber
  • Protoparce spp. Pseudaletia spp., Pseudaletia unipuncta, Pseudoplusia includens, Pyrausta nubilalis, Rachiplusia nu, Schoenobius spp., Scirpophaga spp., Scirpophaga innotata, Ontario segetum, Sesamia spp., Sesamia inferens, Sparganothis spp. , Spodoptera spp., Spodoptera praefica, Stathmopoda spp., Stomopteryx subsecivella, ""
  • Synanthedon spp. Tecia solanivora, Thermesia gemmatalis, Tinea cloacella, Tinea pellionella, Tineola bisselliella, Tortrix spp., Trichophaga tapetzella, Trichoplusia spp., Tryporyza incertulas, Tuta absolutea, Virachola spp .; from the order of Orthoptera or Saltatoria e.g.
  • Thysanoptera e.g. Anaphothrips obscurus, Baliothrips biformis, Drepanothrips reuteri, Enneothrips hevens
  • Ctenolepisma spp. Lepisma saccharina, Lepismodes inquilinus, Thermobia domestica; from the class of Symphyla e.g. Scutigerella spp .;
  • Pests from the strain of Mollusca in particular from the class of bivalvia, eg Dreissena spp., And from the class of Gastropoda eg Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea spp., Succinea spp .; Animal parasites from the strains of Plathelminthes and Nematoda, eg Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp.,
  • Opisthorchis spp. Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosome spp., Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis , Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti; Plant pests from the Nematoda strain, ie plant parasitic nematodes, in particular Aphelenchoides spp., Bursaphelenchus spp., Ditylenchus spp., Globodera spp., Heterodera spp., Longidorus spp., Meloidogy
  • Hemicycliophora spp. Anguina spp., Subanguina spp., Hemicriconemoides spp., Psilenchus spp., Pseudohalenchus spp., Criconemoides spp., Cacopaurus spp.
  • the order of coccidia can be determined, e.g. Eimeria spp. fight.
  • the present invention further relates to formulations and application forms prepared therefrom as crop protection agents and / or pesticides such. B. drench, drip and spray, comprising at least one of the active compounds according to the invention. If appropriate, the use forms contain other crop protection agents and / or pesticides and / or the effect of improving adjuvants such as penetration enhancers, eg.
  • vegetative oils such as rapeseed oil, sunflower oil, mineral oils such as paraffin oils, alkyl esters of vegetal fatty acids such as rapeseed oil or soybean oil methyl ester or alkanol alkoxylates and / or spreading agents such as alkyl siloxanes and / or salts, e.g. organic or inorganic ammonium or phosphonium salts such as ammonium sulfate or diammonium hydrogen phosphate and / or retention-promoting agents such.
  • Typical formulations are, for example, water-soluble liquids (SL), emulsion concentrates (EC), emulsions in water (EW), suspension concentrates (SC, SE, FS, OD), water-dispersible granules (WG), granules (GR) and capsule concentrates (CS). ;
  • SL water-soluble liquids
  • EC emulsion concentrates
  • EW emulsions in water
  • SC suspension concentrates
  • SC SE, SE, FS, OD
  • WG water-dispersible granules
  • GR granules
  • capsule concentrates CS
  • the formulations contain, in addition to one or more active compounds according to the invention, further agrochemical active substances.
  • auxiliaries such as extenders, solvents, spontaneity promoters, carriers, emulsifiers, dispersants, antifreeze agents, biocides, thickeners and / or further auxiliaries, for example adjuvants.
  • An adjuvant in this context is a component that enhances the biological effect of the formulation without the component itself having a biological effect.
  • Examples of adjuvants are agents which enhance retention, spreading behavior, adherence to the Promote leaf surface or penetration.
  • formulations are prepared in a known manner, e.g. by mixing the active ingredients with excipients such as extenders, solvents and / or solid carriers and / or other excipients such as surfactants.
  • excipients such as extenders, solvents and / or solid carriers and / or other excipients such as surfactants.
  • the preparation of the formulations is carried out either in suitable systems or before or during use.
  • Excipients which can be used are those which are suitable for imparting special properties, such as physical, technical and / or biological properties, to the formulation of the active substance or to the forms of use prepared from these formulations (for example usable plant protection agents such as spray mixtures or seed dressing).
  • extender e.g. Water, polar and non-polar organic chemical liquids e.g.
  • aromatic and non-aromatic hydrocarbons such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes
  • alcohols and polyols which may also be substituted, etherified and / or esterified
  • ketones such as acetone, cyclohexanone
  • Esters including fats and oils
  • poly) ethers simple and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, sulfones and sulfoxides (such as methyl sulfoxide).
  • Suitable liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g.
  • Petroleum fractions mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide and water.
  • alcohols such as butanol or glycol and their ethers and esters
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone
  • strongly polar solvents such as dimethylformamide and dimethyl sulfoxide and water.
  • Suitable solvents are, for example, aromatic hydrocarbons, e.g. Xylene, toluene or alkylnaphthalenes, chlorinated aromatic or aliphatic hydrocarbons, e.g. Chlorobenzene, chloroethylene, or methylene chloride, aliphatic hydrocarbons, e.g. Cyclohexane, paraffins, petroleum fractions, mineral and vegetable oils, alcohols such as e.g. Methanol, ethanol, iso-propanol, butanol or glycol and their ethers and esters, ketones such as e.g. Acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strong polar solvents such as dimethyl sulfoxide and water.
  • aromatic hydrocarbons e.g. Xylene, toluene or alkylnaphthalenes
  • chlorinated aromatic or aliphatic hydrocarbons e
  • Suitable carriers are in particular: for example, ammonium salts and ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock flour, such as finely divided silica, alumina and natural or synthetic silicates, resins, waxes and ""
  • Suitable carriers for granules are: e.g. Cracked and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, paper, coconut shells, corn cobs and tobacco stems.
  • liquefied gaseous diluents or solvents can be used.
  • Examples of emulsifying and / or foaming agents, dispersants or wetting agents having ionic or non-ionic properties or mixtures of these surfactants are salts of polyacrylic acid, salts of lignosulphonic acid, salts of phenolsulphonic acid or naphthalenesulphonic acid, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, with substituted phenols (preferably alkylphenols or arylphenols), salts of sulphosuccinic acid esters, taurine derivatives (preferably alkyl taurates), phosphoric acid esters of polyethoxylated alcohols or phenols, fatty acid esters of polyols and derivatives of the compounds containing sulphates, sulphonates and phosphates, eg Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, arylsulfonates, protein hydro
  • dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes, and nutrient and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • Stabilizers such as cold stabilizers, preservatives, antioxidants, light stabilizers or other chemical and / or physical stability-improving agents may also be present. It may also contain foam-forming agents or defoamers.
  • formulations and the use forms derived therefrom may also contain, as additional auxiliaries, adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-containing polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate and natural phospholipids such as cephalins and lecithins and synthetic phospholipids.
  • additional auxiliaries may be mineral and vegetable oils.
  • auxiliaries may be present in the formulations and in the use forms derived therefrom.
  • additives are, for example, perfumes, protective "
  • the active ingredients can be combined with any solid or liquid additive commonly used for formulation purposes.
  • retention promoters are all those substances which reduce the dynamic surface tension such as dioctylsulfosuccinate or increase the visco-elasticity such as hydroxypropyl guar polymers.
  • Suitable penetration promoters in the present context are all those substances which are usually used to improve the penetration of agrochemical active substances into plants.
  • Penetration promoters are in this context defined by the fact that they can penetrate from the (usually aqueous) application broth and / or from the spray coating into the cuticle of the plant and thereby increase the material mobility (mobility) of the active ingredients in the cuticle.
  • the method described in the literature can be used to determine this property.
  • Examples include alcohol alkoxylates such as coconut oil ethoxylate (10) or Isotridecylethoxylat (12), fatty acid esters such as rapeseed oil or soybean oil, fatty amine alkoxylates such as Tallowamine ethoxylate (15) or ammonium and / or phosphonium salts such as ammonium sulfate or diammonium hydrogen phosphate.
  • alcohol alkoxylates such as coconut oil ethoxylate (10) or Isotridecylethoxylat (12)
  • fatty acid esters such as rapeseed oil or soybean oil
  • fatty amine alkoxylates such as Tallowamine ethoxylate (15) or ammonium and / or phosphonium salts such as ammonium sulfate or diammonium hydrogen phosphate.
  • the formulations preferably contain between 0.00000001 and 98% by weight of active ingredient or, more preferably, between 0.01 and 95% by weight of active compound, more preferably between 0.5 and 90% by weight of active ingredient, based on the weight of the formulation.
  • the active substance content of the application forms (pesticides) prepared from the formulations can vary within wide ranges.
  • the active ingredient concentration of the use forms can usually be between 0.00000001 and 95% by weight of active ingredient, preferably between 0.00001 and 1% by weight, based on the weight of the application form.
  • the application is done in a custom forms adapted to the application.
  • the active substances to be used according to the invention or according to the invention can also be used as such or in their formulations as a mixture with one or more suitable fungicides, bactericides, acaricides, molluscicides, nematicides, insecticides, microbiologicals, beneficials, fertilizers, bird repellents, phytotonics, sterilants, synergists, Safeners, semiochemicals and / or plant growth regulators can be used, for example, to broaden the spectrum of action, to extend the duration of action, to increase the rate of action, to prevent repellence or to prevent the development of resistance. Furthermore, such drug combinations plant growth and / or tolerance to abiotic factors such. B. high or t rn
  • Acetylcholinesterase (AChE) inhibitors such as carbamates, e.g. Alanycarb, Aldicarb, Bendiocarb, Benfuracarb, Butocarboxime, Butoxycarboxime, Carbaryl, Carbofuran, Carbosulfan, Ethiofencarb, Fenobucarb, Formetanate, Furathiocarb, Isoprocarb, Methiocarb, Methomyl, Metolcarb, Oxamyl, Pirimicarb, Propoxur, Thiodicarb, Thiofanox, Triazamate, Trimethacarb, XMC and xylylcarb; or
  • AChE Acetylcholinesterase
  • Organophosphates e.g. Acephate, Azamethiphos, Azinophos-ethyl, Azinophos-methyl, Cadusafos, Chloroethoxyfos, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos-methyl, Coumaphos, Cyanophos, Demeton-S-methyl, Diazinone, Dichlorvos / DDVP, Dicrotophos, Dimethoates, Dimethylvinphos, Disulfone, EPN, Ethion, Ethoprophos, Famphur, Fenamiphos, Fenitrothion, Fenthion, Fosthiazate, Heptenophos, Imicyafos, Isofenphos, Isopropyl O- (methoxyaminothio-phosphoryl) salicylate, Isoxathione, Malathion, Mecarbam, Methamidophos, Methida
  • GABA-controlled chloride channel antagonists such as cyclodiene organochlorines, e.g. Chlordane and endosulfan; or
  • Phenylpyrazoles e.g. Ethiprole and fipronil.
  • Sodium channel modulators / voltage dependent sodium channel blockers such as Pyrethroids, eg acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin [(lR) trans isomers], deltamethrin, empenthrin [(EZ) (lR) isomers], e
  • nicotinergic acetylcholine receptor (nAChR) agonists such as
  • Neonicotinoids e.g. Acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or
  • nicotinergic acetylcholine receptor (nAChR) allosteric activators such as spinosines, e.g. Spinetoram and spinosad.
  • Avermectins / milbemycins e.g. Abamectin, Emamectin benzoate, Lepimectin and Milbemectin.
  • Juvenile hormone mimics such as juvenile hormone analogs, e.g. Hydroprene, kinoprene and methoprene; or fenoxycarb; or pyriproxyfen.
  • agents with unknown or nonspecific modes of action such as alkyl halides, e.g. Methyl bromide and other alkyl halides; or
  • mite growth inhibitors eg clofentezine, hexythiazox and diflovidazine; or Etoxazole.
  • Insect intestinal membrane microbial disruptors e.g. Bacillus thuringiensis subspecies israelensis, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis and B.t.
  • Plural proteins CrylAb, CrylAc, CrylFa, CrylA.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, Cry34 From 1/35 From 1; or
  • Bacillus sphaericus Bacillus sphaericus.
  • inhibitors of oxidative phosphorylation, ATP disruptors such as diafenthiuron; or
  • Organotin Compounds e.g. Azocyclotine, cyhexatin and fenbutatin oxide; or propargite; or tetradifon.
  • Nicotinergic acetylcholine receptor antagonists such as Bensultap, Cartap hydrochloride, thiocyclam and thiosultap sodium.
  • Type 0 inhibitors of chitin biosynthesis such as bistrilluron, chloraluazuron, dillubenzuron, flucycloxuron, flufenoxuron, hexallumuron, lufenuron, novaluron, novillumuron, tellubenzuron, and triilumuron.
  • inhibitors of chitin biosynthesis type 1, such as buprofezin.
  • Moulting agents dipteran, such as cyromazine.
  • ecdysone receptor agonists such as chromafenozides, halofenozides, methoxyfenozides, and tebufenozides.
  • Octopaminergic agonists such as amitraz.
  • complex III electron transport inhibitors such as hydramethylnone; or acequinocyl; or fluacrypyrim.
  • complex I electron transport inhibitors for example
  • METI acaricides eg fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad; or Rotenone (Derris).
  • Tetronic and tetramic acid derivatives e.g. Spirodiclofen, spiromesifen and spirotetramat.
  • complex IV electron transport inhibitors such as
  • Phosphines e.g. Aluminum phosphide, calcium phosphide, phosphine and zinc phosphide; or cyanide.
  • ryanodine receptor effectors such as diamides, e.g. Chlorantraniliprole, Cyantraniliprole and Flubendiamide.
  • agents such as amidoflumet, azadirachtin, benclothiaz, benzoximate, bifenazate, bromopropylate, quinomethionate, cryolite, dicofol, diflovidazine, fluensulfone, flufenerim, flufiprole, fluopyram, fufenocide, imidaclothiz, iprodione, meperfluthrin, pyralidyl, pyrifluquinazone, tetramethylfluthrin and iodomethane; furthermore preparations based on Bacillus firmus (in particular strain CNCM 1-1582, for example VOTiVO TM, BioNem) and the following compounds:
  • 2-yl ⁇ pyrimidine (known from WO2010 / 006713), 1- (3-chloropyridin-2-yl) -N- [4-cyano-2-methyl-6- (methylcarbamoyl) phenyl] -3 - ⁇ [5-10] (trifluoromethyl) -1 H -tetrazol-1-yl] methyl ⁇ -1 H -pyrazole-5-carboxamide (known from WO2010 / 069502), 1- (3-chloropyridin-2-yl) -N- [4-cyano 2-methyl-6- (methylcarbamoyl) phenyl] -3 - ⁇ [5- (trifluoromethyl) -2H-tetrazol-2-yl] methyl ⁇ -1H-pyrazole-5-carboxamide (known from WO2010 / 069502 ), N- [2- (tert -butylcarbamoyl) -4-cyano-6-methylphenyl] -1-
  • Fungicides suitable as mixing partners are:
  • inhibitors of ergosterol biosynthesis such as aldimorph, azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-M, dodemorph, dodemorph acetate, epoxiconazole, etaconazole, fenarimol, fenbuconazole, fenhexamide, fenpropidin, fenpropimorph, Fluquinconazole, flurprimidol, flusilazole, flutriafol, furconazole, furconazole cis, hexaconazole, imazalil, imazalil sulfate, imibenconazole, ipconazole, metconazole, myclobutanil, naftifine, nuarimol, oxpoconazole, paclobutrazole, pe
  • inhibitors of respiration such as bixafen, boscalid, carboxin, diflumetorim, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, furmecyclox, isopyrazam mixture of the syn-epimeric racemate 1RS, 4SR, 9RS and the anti- more reactive racemate 1RS, 4SR, 9SR, isopyrazam (anti-epimeric racemate), isopyrazam (anti-epimeric enantiomer 1R, 4S, 9S), isopyrazam (anti-epimeric enantiomer 1S, 4R, 9R), isopyrazam (syn-epimeric racemate 1RS, 4SR, 9RS), isopyrazam (syn-epimeric enantiomer 1R, 4S, 9R), isopyrazam (syn-epimeric enantiomer 1S, 4S, 9R), iso
  • inhibitors of respiration at the complex III of the respiratory chain, such as ametoctradine, amisulbrom, azoxystrobin, cyazofamide, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, famoxadone, fenamidone, fenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin , Picoxystrobin, Pyraclostrobin, Pyrametostrobin, Pyraoxystrobin, Pyribencarb, Triclopyricarb, Trilloxystrobin, (2E) -2- (2- ⁇ [6- (3-chloro-2-methylphenoxy) -5-fluoro-imidin-4-yl] oxy ⁇ phenyl ) -2- (methoxyimino) -N-methylethaneamide, (2E) -2- (methoxyimino) -N-
  • Mitosis and cell division inhibitors such as benomyl, carbendazim, chlorfenazole, diethofencarb, ethaboxam, fluopicolide, fuberidazole, pencycuron, thiabendazole, thiophanate-methyl, " ⁇
  • Compounds with multisite activity such as Bordeaux mixture, captafol, captan, chlorothalonil, copper preparations such as copper hydroxide, copper naphthenate, copper oxide, copper oxychloride, copper sulfate, dichlofiuanide, dithianone, dodine, dodine free base, Ferbam, Fluorofolpet, Folpet, guazatine, guazatin acetate , Ininoctadine, ininoctadinalesilate, iminoctadine triacetate, mancopper, mancozeb, maneb, metiram, zinc metiram, copper oxine, propamidine, propineb, sulfur and sulfur preparations such as calcium polysulide, thiram, tolylfluanid, zineb and ziram.
  • resistance inducers such as acibenzolar-S-methyl, isotianil, probenazole and tiadinil.
  • Inhibitors of amino acid and protein biosynthesis such as andoprim, blasticidin-S, cyprodinil, kasugamycin, kasugamycin hydrochloride hydrate, mepanipyrim, pyrimethanil, and 3- (5-fluoro-3, 3,4,4-tetramethyl-3 , 4-dihydroisoquinolin-1-yl) quinoline.
  • inhibitors of ATP production such as fentin acetate, fentin chloride, fentin hydroxide and silthiofam.
  • inhibitors of cell wall synthesis such as benthiavalicarb, dimethomorph, flumorph, iprovalicarb, mandipropamide, polyoxins, polyoxorim, validamycin A, and valifenalate.
  • inhibitors of lipid and membrane synthesis such as biphenyl, chloroneb, dicloran, edifenphos, etridiazole, iodocarb, Iprobenfos, isoprothiolane, propamocarb, propamocarb hydrochloride, prothiocarb, pyrazophos, quintozene, tecnazene and tolclofos-methyl.
  • Inhibitors of melanin biosynthesis such as carpropamide, diclocymet, fenoxanil, fthalide, pyroquilone, tricyclazole and 2,2,2-trifluoroethyl ⁇ 3-methyl-1 - [(4-methylbenzoyl) amino] butan-2-yl carbamate ,
  • Inhibitors of nucleic acid synthesis such as benalaxyl, benalaxyl-M (kiralaxyl), bupirimate, clozylacon, dimethirimol, ethirimol, furalaxyl, hymexazole, metalaxyl, metalaxyl-M
  • signal transduction inhibitors such as chlozolinate, fenpiclonil, fludioxonil, iprodione, procymidone, quinoxyfen and vinclozolin.
  • Decouplers such as binapacryl, dinocap, ferimzone, fluazinam and meptyldinocap.
  • Other compounds such as benthiazole, bethoxazine, capsimycin, carvone, quinomethionate, pyriofenone (Chlazafenone), Cufraneb, cyilufenamide, cymoxanil, cyprosulfamide, dazomet, debacarb, dichlorophen, diclomethine, difenzoquat, difenzoquat methylsulphate, diphenylamine, ecomat, fenpyrazamine, Flumetover, fluoromide, flusulfamide, flutianil, fosetyl-aluminum, fosetyl-calcium, fosetyl-sodium, hexachlorobenzene, irumamycin, methasulfocarb, methylisothiocyanate, me
  • plants are understood as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • crops may be plants which may be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering techniques or combinations of these methods, including transgenic plants and including plant varieties that are protectable or unprotectable by plant variety rights.
  • Plant parts are understood to mean all aboveground and subterranean parts and organs of plants such as shoot, leaf, flower and root, examples of which include leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, and roots, tubers and rhizomes.
  • the plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.
  • crops and vegetative and generative propagation material such as cuttings, tubers, rhizomes, offshoots and seeds.
  • all plants and their parts can be treated.
  • wild plant species or varieties of plants obtained by conventional biological breeding methods such as crossing or protoplast fusion and their parts are treated.
  • transgenic plants and varieties of plants which have been obtained by genetic engineering methods, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated.
  • Parts or “parts of plants” or “Pfianzenmaschine” has been explained above.Particular plants according to the invention are treated according to the invention of the respective commercially available or in use plant varieties.Piezian cultivars are understood as meaning plants with new properties (“traits”) have been bred either by conventional breeding, by mutagenesis or by recombinant DNA techniques. These may be varieties, breeds, biotypes and genotypes.
  • the treatment of the plants and plant parts with the active substances or active compound combinations or agents to be used according to the invention or according to the invention is carried out directly or by acting on their environment, habitat or storage space according to the usual treatment methods, e.g. by dipping, spraying, spraying, sprinkling, evaporating, atomising, atomizing, sprinkling, foaming, brushing, spreading, injecting, pouring, drip irrigation and propagating material, in particular in the case of seeds Furthermore, by dry pickling, wet pickling, slurry pickling, encrusting, single or multi-layer wrapping, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient itself into the soil.
  • a preferred direct treatment of the plants is foliar application, i. the active compounds, active ingredient combinations or agents are applied to the foliage, wherein the treatment frequency and the application rate can be adapted to the infestation pressure of the respective pathogen, pest or weed.
  • the active ingredients, active ingredient combinations or agents reach the plants via the root system.
  • the treatment of the plants is then carried out by the action of Active ingredients, active ingredient combinations or agents on the habitat of the plant.
  • This can be, for example, by drenching, mixing into the soil or the nutrient solution, ie the location of the plant (eg soil or hydroponic systems) is impregnated with a liquid form of the active ingredients, active ingredient combinations or compositions, or by the soil application, ie the active compounds according to the invention , Active ingredient combinations or agents are introduced in solid form, (eg in the form of granules) in the location of the plants. In water rice crops, this may also be by metered addition of the invention in a solid form (eg as granules) into a flooded paddy field.
  • seed treatment methods should also include the intrinsic insecticidal or nematicidal properties of pest-resistant transgenic plants in order to achieve optimum protection of the seed and of the germinating plant with a minimum of pesticide use.
  • the present invention therefore also relates in particular to a method for protecting seed and germinating plants from attack by pests by treating the seed with an active substance according to the invention or to be used according to the invention.
  • the method according to the invention for the protection of seeds and germinating plants from infestation by pests comprises a method in which the seed is treated simultaneously in one operation with an active compound of the formula (I) and mixing partner. It also includes a method in which the seed is treated at different times with an active ingredient of formula (I) and mixing partner.
  • the invention also relates to the use of the active ingredients according to the invention for the treatment of seed for the protection of the seed and the resulting plant from animal pests.
  • the invention relates to seed which has been treated with an active ingredient according to the invention for protection against animal pests.
  • the invention also relates to seed treated at the same time with an active ingredient of formula (I) and mixing partner.
  • the invention further relates to seed which has been treated at different times with an active compound of the formula (I) and mixing partner.
  • the individual active substances of the agent according to the invention may be present in different layers on the seed. In this case, the layers which contain an active ingredient of the formula (I) and mixing partners may optionally be separated by an intermediate layer.
  • the invention also relates to seed in which an active compound of the formula (I) and mixing partner are applied as a constituent of a coating or as a further layer or further layers in addition to a coating. Furthermore, the invention relates to seed, which after the treatment with the active ingredient of the formula (I) or an active ingredient combination containing it has been subjected to a film coating process in order to avoid dust abrasion on the seed.
  • One of the advantages of the present invention is that because of the particular systemic properties of the agents of the invention, the treatment of the seed with these agents not only protects the seed itself, but also the resulting plants after emergence from animal pests. In this way, the immediate treatment of the culture at the time of sowing or shortly afterwards can be omitted.
  • Another advantage is the fact that by the treatment of the seed with active ingredient of the formula (I) or combination of active substances containing germination and emergence of the treated seed can be promoted.
  • active compounds of the formula (I) and the named active substance combinations can be used in particular also in the case of transgenic seed.
  • active compounds of the formula (I) can be used in combination with signal technology agents, by way of example a better colonization with symbionts, such as rhizobia, mycorrhiza and / or endophytic bacteria, taking place and / or optimizing them Nitrogen fixation is coming.
  • compositions according to the invention are suitable for the protection of seeds of any plant variety used in agriculture, in the greenhouse, in forests or in horticulture.
  • these are seeds of cereals (eg wheat, barley, rye, millet and oats), maize, cotton, soy, rice, potatoes, sunflower, coffee, tobacco, canola, rapeseed, turnip (eg Sugar beet and fodder beet), peanut, vegetables (eg tomato, cucumber, bean, cabbage, onions and lettuce), fruit plants, turf and ornamental plants.
  • cereals eg wheat, barley, rye and oats
  • corn, soya, cotton, canola, oilseed rape and rice are examples of seeds of cereals (such as wheat, barley, rye and oats), corn, soya, cotton, canola, oilseed rape and rice.
  • transgenic seed with active ingredients of the formula (I) or a combination of active substances is of particular importance.
  • active ingredients of the formula (I) or a combination of active substances are of particular importance.
  • the heterologous genes in transgenic seed can come from microorganisms such as Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium.
  • the present invention is particularly useful for the treatment of transgenic seed containing at least one heterologous gene derived from Bacillus sp. comes.
  • the active ingredient of the formula (I) is applied to the seed alone (or as active ingredient combination) or in a suitable formulation.
  • the seed is treated in a state where it is so stable that no damage occurs during the treatment.
  • the treatment of the seed can be done at any time between harvesting and sowing.
  • seed is used which has been separated from the plant and freed from flasks, shells, stems, hull, wool or pulp.
  • seeds may be used which have been harvested, cleaned and dried to a moisture content of less than 15% by weight.
  • seed may also be used which, after drying, e.g. treated with water and then dried again.
  • the agents according to the invention can be applied directly, ie without containing further components and without being diluted.
  • suitable formulations and methods for seed treatment are known to those skilled in the art and are described e.g. in the following documents: US 4,272,417 A, US 4,245,432 A, US 4,808,430 A, US 5,876,739 A, US 2003/0176428 AI, WO 2002/080675 AI, WO 2002/028186 A2.
  • the active compounds / active substance combinations that can be used according to the invention can be converted into the customary seed dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other seed coating compositions, as well as ULV formulations.
  • formulations are prepared in a known manner by mixing the active ingredients / drug combinations with conventional additives, such as conventional extenders and - 61 -
  • Solvents or diluents dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and also water.
  • Dyes which may be present in the seed dressing formulations which can be used according to the invention are all dyes customary for such purposes. Both water-insoluble pigments and water-soluble dyes are useful in this case. Examples which may be mentioned under the names rhodamine B, C.I. Pigment Red 112 and C.I. Solvent Red 1 known dyes.
  • Suitable wetting agents which may be present in the seed dressing formulations which can be used according to the invention are all wetting-promoting substances customary for the formulation of agrochemical active compounds.
  • Preferably used are alkylnaphthalene sulfonates, such as diisopropyl or diisobutyl naphthalene sulfonates.
  • Suitable dispersants and / or emulsifiers which may be present in the seed dressing formulations which can be used according to the invention are all nonionic, anionic and cationic dispersants customary for the formulation of agrochemical active compounds.
  • Preferably usable are nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants.
  • Particularly suitable nonionic dispersants are, in particular, ethylene oxide-propylene oxide block polymers, alkylphenol polyglycol ethers and tristryrylphenol polyglycol ethers and their phosphated or sulfated derivatives.
  • Suitable anionic dispersants are in particular lignosulfonates, polyacrylic acid salts and arylsulfonate-formaldehyde condensates.
  • Defoamers which may be present in the seed dressing formulations which can be used according to the invention are all foam-inhibiting substances customary for the formulation of agrochemical active compounds.
  • Preferably usable are silicone defoamers and magnesium stearate.
  • Preservatives which may be present in the seed dressing formulations which can be used according to the invention are all substances which can be used for such purposes in agrochemical compositions. Examples include dichlorophen and Benzylalkoholhemiformal.
  • Suitable secondary thickeners which may be present in the seed dressing formulations which can be used according to the invention are all substances which can be used for such purposes in agrochemical compositions. Preference is given to cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica.
  • Suitable adhesives which may be present in the seed dressing formulations which can be used according to the invention are all customary binders which can be used in pickling agents. Preferably mentioned are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and Tylose. n
  • the gibberellins are known (see R. Wegler "Chemie der convinced- und Swdlingsbekungsstoff", Vol. 2, Springer Verlag, 1970, pp. 401-412).
  • the seed dressing formulations which can be used according to the invention can be used either directly or after prior dilution with water for the treatment of seed of various kinds.
  • the concentrates or the preparations obtainable therefrom by dilution with water can be used for dressing the seeds of cereals such as wheat, barley, rye, oats and triticale, as well as the seeds of corn, rice, rape, peas, beans, cotton, sunflowers and beets or even vegetable seeds of various nature.
  • the seed dressing formulations which can be used according to the invention or their diluted preparations can also be used for pickling seeds of transgenic plants. In this case, additional synergistic effects may occur in interaction with the substances formed by expression.
  • the seed dressing formulations which can be used according to the invention or the preparations prepared therefrom by the addition of water
  • all mixing devices customarily usable for the dressing can be considered.
  • the seed is placed in a mixer which adds either desired amount of seed dressing formulations either as such or after prior dilution with water and mixes until evenly distributed the formulation on the seed.
  • a drying process follows.
  • the application rate of the seed dressing formulations which can be used according to the invention can be varied within a relatively wide range. It depends on the respective content $ of the active substance (s) in the formulations and on the seed.
  • the application rates for active compounds / active substance combinations are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 15 g per kilogram of seed.
  • the active compounds of the formula (I) have an effect against biotic stress factors and / or abiotic stress of plants or with regard to plant growth. It has now been found that the active compounds of the formula (I) according to the invention are suitable for increasing the plant's own defenses (pathogen defense in plants).
  • plants react to natural stress conditions, such as, for example, cold, heat, dryness, wounding, pathogen infestation (viruses, bacteria, fungi), insects, etc., but also to herbicides with specific or nonspecific defense mechanisms (plant biochemistry, - 63 -
  • enzymatic proteins such as chitinases, glucanases, or (d) specific inhibitors of essential proteins, such as protease inhibitors, xylanase inhibitors attack the pathogen directly or impede its proliferation (Dangl and Jones, Nature 411, 826-833, 2001; Kessler and Baldwin, Annual Review of Plant Biology, 53, 299-328, 2003).
  • HR hypersensitive reaction
  • a known synthetic product, which one of the salicylic acid similar function is performed and can provide a protective effect against phytopathogenic fungi, bacteria and viruses, is benzothiadiazole (CGA 245704; Common name: acibenzolar-5-methyl; trade name: Bion ®) (Achuo et al. , Plant Pathology 53 (1), 65-72, 2004, Tamblyn et al., Pesticide Science 55 (6), 676-677, 1999, EP-OS 0 313 512).
  • CGA 245704 Common name: acibenzolar-5-methyl
  • Bion ® Bion ®
  • pathogenesis-related proteins which primarily support plants in the defense against biotic stressors, such as phytopathogens Fungi, Bacteria and Viruses (DE 10 2005 045 174 A; DE 10 2005 022 994 A and WO 2006/122662 A; Thielert Maischutz-Nachzin Bayer, 59 (1), 73-86, 2006; Francis et al., European Journal of Plant Pathology, publ. online 23.1.2009).
  • plants have a number of endogenous reaction mechanisms that can effect effective defense against various harmful organisms (biotic stress) and / or abiotic stress.
  • the cultivation of healthy and uniformly grown seedlings is an essential prerequisite for the large-scale cultivation and economic management of agricultural, horticultural and forestry crops.
  • Styrofoam perforated trays seeded in a special potting soil based on peat culture substrate and then cultivated in containers with suitable nutrient solution until the desired transplant size is reached (Figure 1).
  • the containers are allowed to run on the nutrient solution, from which the name of the growing method is derived (Leal, 2001, supra).
  • Floating processes have been using insecticides from the class of neonicotiniodes (chlornicotinyls) for the control of sucking pests for several years.
  • the plants are sprayed with neonicotinoid (chloronicotinyl) insecticides in the float process shortly before transplanting or are infused with neonicotinoid (chloronicotinyl) insecticides immediately before or during transplantation, which is termed "drenching" (Leal, 2001, supra; and Rogers, 2001, supra) Both methods of application are technically relatively complex.
  • Fungicides and insecticides are used to protect the crops of seed or plant material from fungal pathogens and pests until they are transplanted.
  • the choice of pesticides, the place and time of application and the application rate of the funds depend here mainly on the type of fungal diseases and pests occurring, the specific mode of action and duration of action of the agents and their plant compatibility, and thus directly to the specific requirements of different Adapted to crops and regions.
  • the active compounds of the formula (I) lead, regardless of insect control, to good protection of the plant from damage by fungal, bacterial or viral pathogens.
  • the active compounds of the formula (I) not only increase the pathogen defense in plants, but also improve plant growth and / or increase the resistance of plants to plant diseases caused by fungi, bacteria, viruses, MLO (Mycoplasma -like organisms) and / or RLO (Rickettsia-like organisms) are caused, especially against soil-borne fungal diseases, and / or are suitable for increasing the resistance of plants to abiotic stress factors.
  • Abiotic stress conditions may include, for example, drought, cold and heat conditions, osmotic stress, waterlogging, increased soil salinity, increased exposure to minerals, ozone conditions, high light conditions, limited availability of nitrogen nutrients, limited availability of phosphorous nutrients, or avoidance of shade.
  • the present invention therefore relates firstly to the use of at least one active substance of the formula (I) for increasing plant-specific defense forces and / or for improving plant growth and / or for increasing the resistance of plants to plant diseases caused by fungi, bacteria, viruses, MLO (mycoplasma-like organisms) and / or RLO (Rickettsia-like organisms) are caused, in particular against soil-borne fungal diseases, and / or to increase the resistance of plants to abiotic stress factors.
  • the term plant growth is understood to mean various advantages for plants which are not directly related to the known pesticidal activity, preferably to the insecticidal activity of the active compounds of the formula (I).
  • Such advantageous properties are, for example, the following improved plant characteristics: accelerated germination and emergence of the seed and planting material, improved surface and depth root growth, increased runners or stocking, stronger and more productive shoots and tillers, improvement in shoot growth, increased stability, increased shoot base diameter, increased leaf area, greener leaf color, higher yields of nutrients and ingredients, such as carbohydrates, fats, oils, proteins, vitamins, minerals, essential oils, dyes, fibers, better fiber quality, earlier flowering, increased number of flowers, reduced content of toxic products such as Mycotoxins, reduced content of residues or unfavorable components of any kind or better digestibility, improved storage stability of the crop, improved tolerance to unfavorable temperature improved tolerance to drought and dryness as well as oxygen deficiency due to excess water, improved tolerance to increased salt levels in soils and water, increased tolerance to UV radiation, increased tolerance to ozone stress, improved ⁇
  • Soche terms are, for example, the following: phytotonic effect, resistance to stressors, less plant stress, plant health, healthy plants, Plant Fitness, Plant Wellness, Plant Concept, Vigor Effect, Stress Shield "Crop Health Properties”, “Crop Health Products”, “Crop Health Management”, “Crop Health Therapy”, “Plant Health”, “Plant Health Properties”, “Plant Health Products”, “Plant Health Management”, “Plant Health Therapy”, “Greening Effect” or “Re-greening Effect”), “Freshness” or other terms that are well known to a person skilled in the art.
  • Fertilizers which can be used according to the invention together with the above-described active agents or agents are generally organic and inorganic nitrogen-containing compounds such as ureas, urea-formaldehyde condensation products, amino acids, ammonium salts and nitrates, potassium salts (preferably chlorides, sulfates, nitrates ), Phosphoric acid salts and / or salts of phosphorous acid (preferably potassium salts and ammonium salts).
  • NPK fertilizers ie fertilizers containing nitrogen, phosphorus and potassium, calcium ammonium nitrate, ie fertilizers that still contain calcium, ammonium sulfate nitrate (General formula NH4NO3), ammonium phosphate and ammonium sulfate.
  • These fertilizers are well known to those skilled in the art, see also, for example, Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 10, pages 323 to 431, Verlagsgesellschaft, Weinheim, 1987.
  • the fertilizers may also contain salts of micronutrients (preferably calcium, sulfur, boron, manganese, magnesium, iron, boron, copper, zinc, molybdenum and cobalt) and phytohormones (eg, vitamin B1 and indol-3-ylacetic acid (IAA)). or mixtures thereof.
  • Fertilizers used according to the invention may also contain other salts such as monoammonium phosphate (MAP), diammonium phosphate (DAP), potassium sulfate, potassium chloride or magnesium sulfate.
  • Suitable amounts for the secondary nutrients or trace elements are amounts of from 0.5 to 5% by weight, based on the total fertilizer.
  • fertilizers can be used, for example, in the form of powders, granules, prills or compactates. However, the fertilizers can also be used in liquid form dissolved in an aqueous medium. In this case, dilute aqueous ammonia can be used as nitrogen fertilizer. Further possible ingredients for fertilizers are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, 1987, Volume A 10, pages 363 to 401, DE-A 41 28 828, DE-A 19 05 834 and DE-A 196 31 764 ,
  • the general composition of the fertilizers which in the context of the present invention may be single nutrient and / or multi-nutrient fertilizers, for example nitrogen, potassium or phosphorus, may vary within a wide range.
  • a content of 1 to 30% by weight of nitrogen preferably 5 to 20% by weight
  • of 1 to 20% by weight of potassium preferably 3 to 15% by weight
  • Phosphorus preferably 3 to 10 parts by weight
  • the content of microelements is usually in the ppm range, preferably in the range of 1 to 1000 ppm.
  • the fertilizer and the active ingredient of the formula (I) at the same time, i. synchronously, administered.
  • the application takes place in a functional context, in particular within a period of generally 24 hours, preferably 18 hours, more preferably 12 hours, especially 6 hours, even more specifically 4 hours, more specifically within 2 hours.
  • the active compounds of the general formula (I) and of the fertilizer according to the invention are used in a time frame of less than 1 hour, preferably less than 30 minutes, more preferably less than 15 minutes.
  • the corresponding constituents can be mixed with one another and optionally extruded or the at least one active compound of the formula (I) to be used according to the invention can be applied to the fertilizer.
  • formulation aids may also be used in the dimensionally stable mixtures, such as extenders or pressure-sensitive adhesives, to achieve dimensional stability of the resulting mixture. Due to the corresponding dimensional stability, corresponding mixtures are suitable, in particular for use in the "Home & Garden" sector, ie for a private user or home gardener, who can use the dimensionally stable mixture or the constituents contained therein with a predetermined, clearly defined amount and without special aids ,
  • the mixtures of at least one of the active ingredients to be used according to the invention and the at least one fertilizer may also be liquid, so that-for example, in the case of a professional user in the field of agriculture-the resulting mixture can be applied as a so-called tank solution.
  • the active compounds to be used according to the invention can, if appropriate in combination with fertilizers, preferably be applied to the following plants, the following listing not being restrictive.
  • the forest stock includes trees for the production of wood, pulp, paper and products made from parts of the trees.
  • crops as used herein refers to crops used as plants for the production of food, feed, fuel or for technical purposes.
  • the crops include, for example, the following plant species: turf, vines, cereals, for example wheat, barley, rye, oats, triticale, rice, corn and millet; Beets, for example sugar beets and fodder beets; Fruits, such as pome fruit, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries and berries, eg. Strawberries, raspberries, blackberries; Legumes, such as beans, lentils, peas and soybeans; Oil crops such as rapeseed, mustard, poppy, olive, sunflower, coconut, castor oil, cocoa beans and peanuts; Cucurbits, for example squash, cucumbers and melons; Fiber plants, for example 7Q
  • Vegetables such as spinach, (headj salad, asparagus, cabbage, carrots, onions, tomatoes, potatoes and peppers, laurel family, such as avocado, cinnamomum, camphor, or even plants such as tobacco, nuts, coffee, eggplant, sugarcane, tea, pepper , Vines, hops, bananas, natural rubber plants and ornamental plants, such as flowers, shrubs, deciduous trees and conifers, this list is not limiting.
  • Particularly suitable target crops are the following plants: bamboo wool, eggplant, turf, pome fruit, stone fruit, berry fruit, corn, wheat, barley, cucumber, tobacco, vines, rice, cereals, pear, beans, soybeans, oilseed rape, tomatoes, peppers, melons , Cabbage, potato and apple.
  • trees are: Abies sp., Eucalyptus sp., Picea sp., Pinus sp., Aesculus sp., Platanus sp., Tilia sp., Acer sp., Tsuga sp., Fraxinus sp., Sorbus sp., Betula sp., Crataegus sp., Ulmus sp., Quercus sp., Fagus sp., Salix sp., Populus sp.
  • trees From the tree species Aesculus: A. hippocastanum, A. pariflora, A. carnea; from the tree species Platanus: P. aceriflora, P. occidentalis, P. racemosa; from the tree species Picea: P. abies; from the species Pinus: P. radiate, P. ponderosa, P. contorta, P. sylvestre, P. elliottii, P. montecola, P. albicaulis, P. resinosa, P. palustris, P. taeda, P. flexilis, P jeffregi, P. baksiana, P. strobes; from the tree species Eucalyptus: E. grandis, E. globulus, E. camadentis, E. nitens, E. obliqua, E. regnans, E. pilularus.
  • Particularly preferred trees can be called: horse chestnut, sycamore, linden, maple tree.
  • the present invention may also be practiced on any type of "turigrass", including "cool season turigrasses” and "warm season turigrasses.”
  • cold season lawn species are blue grasses (Poa spp “Kentucky bluegrass” (Poa pratensis L.), “rough bluegrass” (Poa trivialis L.), “Canada bluegrass” (Poa compressa L.), “annual bluegrass” (Poa annua L.), “upland bluegrass” (Poa glaucantha Gaudin), “wood bluegrass” (Poa nemoralis L.) and “bulbous bluegrass” (Poa bulbosa L.); ostrich grasses ("Bentgrass”, Agrostis spp.), such as “creeping bentgrass” (Agrostis palustris Huds.), “ colonial bentgrass “(Agrostis tenuis sib.),” velvet bentgrass “(Agrostis canina L.),” South
  • Examples of other "cool season turfgrasses” are “beachgrass” (Ammophila breviligulata Fern.), “Smooth bromegrass” (Bromus inermis leyss.), Reeds ("cattails") such as “Timothy” (Phleum pratense L.), “sand cattail “(Phleum subulatum L.),” orchardgrass “(Dactylis glomerata L.),” weeping alkaligrass “(Puccinellia distans (L.) Pari.) And” crested dog's-tail “(Cynosurus cristatus L.).
  • Examples of “warm season turfgrasses” are “Bermudagrass” (Cynodon spp., LC Rieh), “zoysiagrass” (Zoysia spp. Willd.), “St. Augustine grass” (Stenotaphrum secundatum Walt Kuntze), “centipedegrass” (Eremochloa ophiuroides Munrohack.), “Carpetgrass” (Axonopus afflnis Chase), “Bahia grass” (Paspalum notatum flügge), “Kikuyugrass” (Pennisetum clandestinum detergent, ex Chiov.), “Buffalo grass” (Buchloe daetyloids (Nutt.) Engelm.) , “Blue gramma” (Bouteloua gracilis (HBK) lag.
  • the active compounds of the formula (I) and their compositions are suitable for controlling animal pests in the hygiene sector.
  • the invention can be used in household, hygiene and storage protection, especially for controlling insects, arachnids and mites, which occur in enclosed spaces, such as apartments, factories, offices, vehicle cabins.
  • the active compounds or compositions are used alone or in combination with other active ingredients and / or adjuvants.
  • they are used in household insecticide products.
  • the active compounds according to the invention are active against sensitive and resistant species as well as against all stages of development.
  • pests of the class Arachnida from the orders Scorpiones, Araneae and Opiliones, from the classes Chilopoda and Diplopoda, from the class Insecta the order Blattodea, from the orders Coleoptera, Dermaptera, Diptera, Heteroptera, Hymenoptera, Isoptera, Lepidoptera, Phthiraptera, Psocoptera, Saltatoria or Orthoptera, Siphonaptera and Zygentoma and from the class Malacostraca the order Isopoda.
  • Application is for example in aerosols, non-pressurized sprays, e.g. Pump and atomizer sprays, fog machines, foggers, foams, gels, evaporator products with cellulose or plastic evaporator plates, liquid evaporators, gel and membrane evaporators, propeller-driven evaporators, energy-less or passive evaporation systems, moth papers, moth cushions and moth gels, as granules or dusts, in litter or bait stations.
  • Pump and atomizer sprays e.g. Pump and atomizer sprays, fog machines, foggers, foams, gels, evaporator products with cellulose or plastic evaporator plates, liquid evaporators, gel and membrane evaporators, propeller-driven evaporators, energy-less or passive evaporation systems, moth papers, moth cushions and moth gels, as granules or dusts, in litter or bait stations.
  • the active ingredients of formula (I) may be used to combat a variety of pests including, for example, noxious sucking insects, biting insects and other plant parasitic pests, storage pests, pests that destroy industrial materials, and use and include sanitary pests including animal health parasites combat such as their extinction and eradication.
  • the present invention thus also includes a method of controlling pests.
  • the active compounds according to the invention are active against animal parasites, in particular ectoparasites or endoparasites.
  • the term endoparasite includes in particular helminths and protozoa such as coccidia.
  • Ectoparasites are typically and preferably arthropods, especially insects and acarids.
  • the compounds of the present invention having favorable toxicity to warm-blooded animals are useful in the control of parasites found in livestock and livestock in livestock, breeding animals, zoo animals, laboratory animals, experimental animals and domestic animals. They are effective against all or individual stages of parasite development.
  • Farm animals include, for example, mammals such as sheep, goats, horses, donkeys, camels, buffaloes, rabbits, reindeer, fallow deer, and especially cattle and pigs; or poultry such as turkeys, ducks, geese and, in particular, chickens; or fish or crustaceans, e.g. in aquaculture; or possibly insects such as bees.
  • the domestic animals include, for example, mammals such as hamsters, guinea pigs, rats, mice, chinchillas, ferrets or, in particular, dogs, cats; Caged birds; reptiles; Amphibians or aquarium fish.
  • mammals such as hamsters, guinea pigs, rats, mice, chinchillas, ferrets or, in particular, dogs, cats; Caged birds; reptiles; Amphibians or aquarium fish.
  • the compounds of the invention are administered to mammals.
  • the compounds according to the invention are administered to birds, namely caged birds or, in particular, poultry.
  • control means that the agents can effectively reduce the incidence of the particular parasite in an animal infected with such parasites to a harmless extent. More specifically, “combat” in the present context means that the active ingredient can kill the respective parasite, prevent its growth or prevent its replication.
  • arthropods include, but are not limited to, the order Anoplurida, for example Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp .; from the order Mallophagida and the suborders Amblycerina and Ischnocerina, for example Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp .; from the order Diptera and the suborders Nematocerina and Brachycerina, for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus
  • the following Akari are exemplary, but without limitation, from the subclass Akari (Acarina) and the order Metastigmata, for example, from the family Argasidae, such as Argas spp., Ornithodorus spp., Otobius spp., From the family Ixodidae, such as Ixodes spp., Amblyomma spp., Rhipicephalus (Boophilus) spp. Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp.
  • Argasidae such as Argas spp., Ornithodorus spp., Otobius spp.
  • Ixodidae such as Ixodes spp., Amblyomma spp., Rhipicephalus (Boophilus) spp. Dermacentor spp., Haem
  • parasitic protozoa examples include, but are not limited to:
  • Mastigophora such as Trypanosomatidae, for example Trypanosoma b. brucei, T.b. gambiense, T.b. rhodesiense, T. congolense, T. cruzi, T. evansi, T. equinum, T. lewisi, T. percae, T. simiae, T. vivax, Leishmania brasiliensis, L. donovani, L. tropica, such as Trichomonadidae, for example Giardia lamblia, G. canis.
  • Trypanosomatidae for example Trypanosoma b. brucei, T.b. gambiense, T.b. rhodesiense, T. congolense, T. cruzi, T. evansi, T. equinum, T. lewisi, T. percae, T. simiae, T. vivax
  • Sarcomastigophora such as Entamoebidae, for example Entamoeba histolytica, Hartmanellidae, for example Acanthamoeba sp., Harmanella sp.
  • Apicomplexa such as Eimeridae, for example Eimeria acervulina, E. adenoides, E. alabamensis, E. anatis, E. anserina, E. arloingi, E. ashata, E. auburnensis, E. bovis, E. brunetti, E canis, E. chinchillae, E. clupearum, E. columbae, E. contorta, E. crandalis, E. debliecki, E. dispersa, E. ellipsoidales, E. falciformis, E. faurei, E. flavescens, E.
  • Eimeridae for example Eimeria acervulina, E. adenoides, E. alabamensis, E. anatis, E. anserina, E. arloingi, E. ashata, E. auburnensis, E. bovis, E.
  • gallopavonis E. hagani, E. intestinalis, E. iroquoina, E. irresidua, E. labbeana, E. leucarti, E. magna, E. maxima, E.media, E. meleagridis, E. meleagrimitis, E. mitis, E necatrix, E. ninakohlyakimovae, E.ovis, E.parva, E.pavonis, E. perforans, E. phasani, E. piriformis, E. praecox, E. residua, E. scabra, E.spec, E. sitesdai E. suis, E. tenella, E.
  • S. suihominis such as Leucozoidae, for example Leucocytozoon simondi, such as Plasmodiidae, for example Plasmodium berghei, P. falciparum, P. malariae, P. ovale, P.vivax, P.spec, such as piroplasmea, for example Babesia argentina, B.bovis, B.canis, B.spec, Theileriaparva, Theileria spec, such as Adeleina, for example Hepatozoon canis, H. spec.
  • pathogenic endoparasites examples include flatworms (e.g., Monogenea, Cestodes, and Trematodes), roundworms, Acanthocephala, and Pentastoma.
  • flatworms e.g., Monogenea, Cestodes, and Trematodes
  • roundworms e.g., Acanthocephala
  • Pentastoma e.g., Pentastoma.
  • Other helminths include, but are not limited to:
  • Monogenea e.g., Gyrodactylus spp., Dactylogyrus spp., Polystoma spp.
  • Cestodes from the order Pseudophyllidea for example: Diphyllobothrium spp., Spirometra spp., Schistocephalus spp., Ligula spp., Bothridium spp., Diplogonoporus spp.
  • Taenia spp. Echinococcus spp., Hydatigera spp., Davainea spp., Raillietina spp., Hymenolepis spp., Echinolepis spp., Echinocotyle spp., Diorchis spp., Dipylidium spp., Joyeuxiella spp., Diplopylidium spp.
  • Trematodes from the genus Digenea, for example: Diplostomum spp., Posthodiplostomum spp., Schistosoma spp., Trichobilharzia spp., Ornithobilharzia spp., Austrobilharzia spp., Gigantobilharzia spp., Leucochloridium spp., Brachylaima spp., Echinostoma spp., Echinoparyphium spp., Echinochasmus spp., Hypoderaeum spp., Fasciola spp., Fasciolides spp., Fasciolopsis spp., Cyclocoelum spp., Typhlocoelum spp., Paramphistomum spp., Calicophoron spp., Cotylophoron spp., Gigantocoty
  • Stephanurus spp. Ancylostoma spp., Uncinaria spp., Bunostomum spp., Globocephalus spp., Syngamus spp., Cyathostoma spp., Metastrongylus spp., Dictyocaulus spp., Muellerius spp., Protostrongylus spp., Neostrongylus spp., Cystocaulus spp., Pneumostrongylus spp., Spicocaulus spp., Elaphostrongylus spp.
  • Parelaphostrongylus spp. Crenosoma spp., Paracrenosoma spp., Angiostrongylus spp., Aelurostrongylus spp., Filaroides spp., Parafilaroides spp., Trichostrongylus spp., Haemonchus spp., Ostertagia spp., Marshallagia spp., Cooperia spp., Nematodirus spp , Hyostrongylus spp., Obeliscoides spp., Amidostomum spp., Ollulanus spp.
  • Acanthocephala from the order Oligacanthorhynchida eg: Macracanthorhynchus spp., Prosthenorchis spp .; from the order Polymorphida for example: Filicollis spp .; from the order Moniliformida for example: Moniliformis spp.,
  • Echinorhynchida for example Acanthocephalus spp.
  • Echinorhynchus spp. Echinorhynchus spp.
  • Pentastoma from the order Porocephalida for example Linguatula spp.
  • the administration of the active compounds according to the invention is carried out by methods well known in the art, such as enteral, parenteral, dermal or nasal in the form of suitable preparations.
  • the administration can be prophylactic or therapeutic.
  • one embodiment of the present invention relates to compounds of the invention for use as a medicament.
  • Another aspect relates to compounds of the invention for use as antiendoparasitic agents, in particular a helminthicide or antiprotozoal agent.
  • compounds of the invention for use as antiendoparasitic agents in particular a helminthicide or antiprotozoal agents, e.g. in animal husbandry, animal husbandry, stables and in the hygiene sector.
  • Another aspect relates to compounds of the invention for use as an antiectica, in particular an arthropodicide such as an insecticide or an acaricide.
  • compounds according to the invention for use as anti-topazarasitic, in particular an arthropodicide such as an insecticide or acaricide for example in animal husbandry, in animal husbandry, in stables, in the hygiene sector.
  • the active compounds of the formula (I) and compositions containing them are suitable for the protection of industrial materials against attack or destruction by insects, e.g. from the order Coleoptera, Hymenoptera, Isoptera, Lepidoptera, Psocoptera and Zygentoma.
  • compositions or compositions according to the invention contain at least one further insecticide and / or at least one fungicide.
  • this composition according to the invention is a ready-to-use composition, that is, it can be applied without further changes to the _
  • the active compounds and compositions according to the invention can be used to protect against fouling of objects, in particular hulls, sieves, nets, structures, quays and signal systems, which come into contact with seawater or brackish water.
  • the active compounds and compositions according to the invention can be used alone or in combinations with other active substances as antifouling agents.
  • N-acylation reaction was carried out analogously to the procedure of Example 1 using: 84.0 mg (0.42 mmol) of 2- (3-chloro-4-amino-1H-pyrazol-1-yl) -pyrazine 77.4 mg (0.64 mmol) of 3-methylthio-propionic acid 4.2 ml of dichloromethane
  • reaction mixture was stirred for about 18 hours at room temperature.
  • reaction mixture was concentrated in vacuo and the remaining residue purified by silica gel chromatography (cyclohexane-acetone gradient).
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Bean leaf discs Phaseolus vulgaris infected by all stages of the common spider mite (Tetranychus urticae) are sprayed with an active compound preparation of the desired concentration.
  • Emulsifier 0.5 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration. 0 "
  • Chinese cabbage leaf discs (Brassica pekinensis) are sprayed with a preparation of active compound of the desired concentration and, after drying, are populated with larvae of the horseradish leaf beetle (Phaedon cochleariae).

Abstract

The present application relates to novel heterocyclic compounds, to processes for preparation thereof and to the use thereof for control of animal pests, which include arthropods and especially insects, and intermediates for preparation of the heterocyclic compounds.

Description

Heterocvclische Verbindungen als Schädlingsbekämpfungsmittel  Heterocyclic compounds as pesticides
Die vorliegende Anmeldung betrifft neue heterocyclische Verbindungen, Verfahren zu Ihrer Herstellung und ihre Verwendung zur Bekämpfung von tierischen Schädlingen, zu denen Arthropoden und insbesondere Insekten zählen, sowie Zwischenprodukte zur Herstellung der heterocyclischen Verbindungen. The present application relates to novel heterocyclic compounds, to processes for their preparation and their use for controlling animal pests, which include arthropods and in particular insects, as well as intermediates for the preparation of the heterocyclic compounds.
Verschiedene heterocyclische Verbindungen, zu denen Thiazolyl-, Thiadiazolyl- und Pyrazolylverbindungen zählen, sind bereits bekannt geworden (vgl. DE 2704288, US 2012/0053146, WO 2004/029053, WO 2010/006713, WO 2009/149858, WO 2011/045240, WO 2011/128304, WO 2012/007500, WO 2010/129497, WO 2011/049150, WO2012/030681, WO 2012/011701, WO 2012/011702, WO 2011/089132, WO 2003/044020, Anais de Associacao Brasileira de Quimica (2001) 50(4), 162-165, Journal of Chemical Research (2011), 35(12), 703-706, Nucleosides, Nucleotides & Nucleic Acids (2011), 30(4), 280-292, CN 101723943, Youji Huaxue (2005), 25(12), 1587-1590, Phosphorus, Sulfur and Silicon and the Related Elements (2006) 181(4), 737-744, Indian Journal of Heterocyclic Chemistry (2002), 11(4), 337-338), wobei einige dieser Verbindungen Insektizide Eigenschaften besitzen. Various heterocyclic compounds, including thiazolyl, thiadiazolyl and pyrazolyl compounds, have already become known (cf., DE 2704288, US 2012/0053146, WO 2004/029053, WO 2010/006713, WO 2009/149858, WO 2011/045240, WO 2011/128304, WO 2012/007500, WO 2010/129497, WO 2011/049150, WO2012 / 030681, WO 2012/011701, WO 2012/011702, WO 2011/089132, WO 2003/044020, Anais de Associacao Brasileira de Quimica (2001) 50 (4), 162-165, Journal of Chemical Research (2011), 35 (12), 703-706, Nucleosides, Nucleotides & Nucleic Acids (2011), 30 (4), 280-292, CN 101723943 , Youji Huaxue (2005), 25 (12), 1587-1590, Phosphorus, Sulfur and Silicon and the Related Elements (2006) 181 (4), 737-744, Indian Journal of Heterocyclic Chemistry (2002), 11 (4) , 337-338), some of these compounds having insecticidal properties.
Planzenschutzmittel, zu denen auch Schädlingsbekämpfungsmittel gehören, müssen vielen Anforderungen genügen, beispielsweise in Bezug auf Höhe, Dauer und Breite ihrer Wirkung und möglichen Verwendung. Es spielen Fragen der Toxizität, der Kombinierbarkeit mit anderen Wirkstoffen oder Formulierhilfsmitteln eine Rolle sowie die Frage des Aufwands, der für die Synthese eines Wirkstoffs betrieben werden muss. Ferner können Resistenzen auftreten. Aus all diesen Gründen kann die Suche nach neuen Pflanzenschutzmitteln nicht als abgeschlossen betrachtet werden und es besteht ständig Bedarf an neuen Verbindungen mit gegenüber den bekannten Verbindungen zumindest in Bezug auf einzelne Aspekte verbesserten Eigenschaften. Plant protection products, including pesticides, must meet many requirements, for example, in terms of the level, duration and breadth of their effect and possible use. Issues of toxicity, of the ability to be combined with other active substances or formulation auxiliaries play a role, as well as the question of the effort that has to be spent on the synthesis of an active substance. Furthermore, resistances can occur. For all these reasons, the search for new pesticides can not be considered complete and there is a constant need for new compounds with improved properties over the known compounds, at least with respect to individual aspects.
Aufgabe der vorliegenden Erfindung war es, Verbindungen bereitzustellen, durch die das Spektrum der Schädlingsbekämpfungsmittel unter verschiedenen Aspekten verbreitert wird. The object of the present invention was to provide compounds which broaden the spectrum of pesticides from various aspects.
Gelöst wird die Aufgabe, sowie weitere nicht explizit genannte Aufgaben, die aus den hierin diskutierten Zusammenhängen ableitbar oder erschließbar sind, durch neue Verbindungen der Formel (I) The problem is solved, as well as other tasks not explicitly mentioned, which can be deduced or deduced from the relationships discussed herein, by novel compounds of the formula (I)
Figure imgf000002_0001
worin
Figure imgf000002_0001
wherein
A für einen Rest aus der Reihe
Figure imgf000003_0001
A for a rest of the series
Figure imgf000003_0001
A-a A-b A-c A-d
Figure imgf000003_0002
Aa From Ac Ad
Figure imgf000003_0002
A-e A-f A-g A-h steht, worin die gestrichelte Linie die Bindung zu B bedeutet, A-e A-f A-g A-h, wherein the dotted line denotes the bond to B,
B für einen Rest aus der Reihe B for a rest of the series
Figure imgf000003_0003
Figure imgf000003_0003
B-1 B-2 B-3 B-4 steht, worin die gestrichelte Linie die Bindung zu A bedeutet und der Pfeil die Bindung zur Gruppe NR2R3 bedeutet, mit der Maßgabe, dass die Reste A-f und A-g nicht mit dem Rest B-3 kombiniert werden, B-1 B-2 B-3 B-4 wherein the dotted line represents the bond to A and the arrow represents the bond to the group NR 2 R 3 , with the proviso that the radicals Af and Ag do not react with the rest B-3 combined,
R für einen Rest aus der Reihe Wasserstoff, Alkyl, Halogenalkyl, Alkenyl, Alkinyl, Cycloalkyl und Halogencycloalkyl steht, R1 für einen Rest aus der Reihe Halogen, Cyano, Nitro, Alkyl, Halogenalkyl, Alkenyl, Halogenalkenyl, Alkoxy, Halogenalkoxy, Cycloalkyl, Halogencycloalkyl, Alkylthio, Halogenalkylthio, Alkylsulfinyl, Halogenalylsulfinyl, Alkylsulfonyl, Halogenalkylsulfonyl steht, R is a radical from the group consisting of hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl and halogenocycloalkyl, R 1 is a radical from the series halogen, cyano, nitro, alkyl, haloalkyl, alkenyl, haloalkenyl, alkoxy, haloalkoxy, cycloalkyl, Halocycloalkyl, alkylthio, haloalkylthio, alkylsulfinyl, haloalylsulfinyl, alkylsulfonyl, haloalkylsulfonyl,
R2 für einen Rest aus der Reihe Wasserstoff, Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkenyl, Alkoxy, Alkenyloxy, Alkinyloxy, Cycloalkyloxy, Alkylthioalkyl, Alkenylthioalkyl, Cyanoalkyl, Alkoxyalkyl steht, R 2 is a radical selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, alkylthioalkyl, alkenylthioalkyl, cyanoalkyl, alkoxyalkyl,
R3 für einen Rest der Formel
Figure imgf000004_0001
steht, worin für einen Rest aus der Reihe Alkyl, Halogenalkyl, Alkoxy, Halogenalkoxy, Alkoxyalkyloxy, Alkylthio, Alkylsulfinyl, Alkylsulfonyl, Halogenalkylthio, Halogenalkylsulfinyl, Halogenalkylsulfonyl, Alkylthioalkyl, Alkylsulfinylalkyl, Alkylsulfonylalkyl, Alkylthioalkyloxy, Alkylsulfinylalkyloxy, Alkylsulfonylalkyloxy, Halogenalkylthioalkyl, Halogenalkylsulfinylalkyl, Halogenalkylsulfonylalkyl, Alkylthioalkenyl, Alkylsulfinylalkenyl, Alkylsulfonylalkenyl, Alkenylthioalkyl, Alkenylsulfinylalkyl, Alkenylsulfonylalkyl, Alkylcarbonylalkyl, Halogenalkylcarbonylalkyl, Alkoxyalkyl, Halogenalkoxyalkyl, Alkoxycarbonylalkyl, Halogenalkoxycarbonylalkyl steht, oder für gegebenenfalls substituiertes Aryl oder für einen Rest aus der Reihe C-1 bis C-51 R 3 is a radical of the formula
Figure imgf000004_0001
in which one radical is selected from the group consisting of alkyl, haloalkyl, alkoxy, haloalkoxy, alkoxyalkyloxy, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, alkylthioalkyloxy, alkylsulfinylalkyloxy, alkylsulfonylalkyloxy, haloalkylthioalkyl, haloalkylsulfinylalkyl, haloalkylsulfonylalkyl, alkylthioalkenyl , Alkylsulfinylalkenyl, alkylsulfonylalkenyl, alkenylthioalkyl, alkenylsulfinylalkyl, alkenylsulfonylalkyl, alkylcarbonylalkyl, haloalkylcarbonylalkyl, alkoxyalkyl, haloalkoxyalkyl, alkoxycarbonylalkyl, haloalkoxycarbonylalkyl, or optionally substituted aryl or a radical from the series C-1 to C-51
-4- -4-
Figure imgf000005_0001
Figure imgf000005_0001
Figure imgf000006_0001
Figure imgf000007_0001
Figure imgf000006_0001
Figure imgf000007_0001
C-37 C-38 C-39  C-37 C-38 C-39
Figure imgf000007_0002
Figure imgf000007_0002
Figure imgf000007_0003
Figure imgf000007_0003
C-44 C-45 C-46 C-47  C-44 C-45 C-46 C-47
Figure imgf000007_0004
Figure imgf000007_0004
C-48 C-49 C-50 C-51 steht, worin  C-48 C-49 C-50 C-51 wherein
R5 für einen Rest aus der Reihe Wasserstoff (nur in den Resten C-33, C-36 und C-42), Halogen, Cyano, Nitro, Amino, Hydroxy und jeweils gegebenenfalls substituiertes Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkylalkyl, Alkoxy, Alkenyloxy, Alkinyloxy, Cycloalkyloxy, Alkylcarbonyloxy, Alkenylcarbonyloxy, Alkinylcarbonyloxy, Cycloalkylcarbonyloxy, Alkoxycarbonyloxy, Alkylsulfonyloxy, Alkylamino, Alkenylamino, Alkinylamino, Cycloalkylamino, Alkylthio, Halogenalkylthio, Alkenylthio, Alkinylthio, Cycloalkylthio, Alkylsulfinyl, Alkylsulfonyl, Alkylcarbonyl, Alkoxyiminoalkyl, Alkoxycarbonyl, Aminocarbonyl, Alkylaminocarbonyl, Dialkylaminocarbonyl, Aminothiocarbonyl, Alkylaminosulfonyl, Alkylsulfonylamino, Alkylcarbonylamino, Alkenylcarbonylamino, Alkinylcarbonylamino, Cycloalkylcarbonylamino, Alkoxycarbonylamino,R 5 is a radical from the group consisting of hydrogen (only in the radicals C-33, C-36 and C-42), halogen, cyano, nitro, amino, hydroxyl and in each case optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, Alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, cycloalkylcarbonyloxy, alkoxycarbonyloxy, alkylsulfonyloxy, alkylamino, alkenylamino, alkynylamino, cycloalkylamino, alkylthio, haloalkylthio, alkenylthio, alkynylthio, cycloalkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl, alkoxyiminoalkyl, alkoxycarbonyl, aminocarbonyl, Alkylaminocarbonyl, dialkylaminocarbonyl, aminothiocarbonyl, alkylaminosulfonyl, alkylsulfonylamino, alkylcarbonylamino, alkenylcarbonylamino, alkynylcarbonylamino, cycloalkylcarbonylamino, alkoxycarbonylamino,
Alkylthiocarbonylamino, Bicycloalkyl, Aryl, Aryloxy, Heteroaryl und Heteroaryloxy steht, wobei die Substituenten unabhängig voneinander ausgewählt sind aus Halogen, Cyano, Nitro, Hydroxy und Amino, für einen Rest aus der Reihe Wasserstoff, Alkyl, Cycloalkyl, Halogenalkyl, Alkenyl, Alkinyl, Cycloalkylalkyl, Cyanoalkyl, Alkylcarbonyl, Alkenylcarbonyl, Halogenalkylcarbonyl, Halogenalkenylcarbonyl, Alkoxyalkyl, Alkoxycarbonyl, Alkylsulfonyl und Halogengenalkylsufonyl steht, oder für einen Rest aus der Reihe Alkylthiocarbonylamino, bicycloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy, where the substituents are independently selected from halogen, cyano, nitro, hydroxy and amino, is a radical from the series consisting of hydrogen, alkyl, cycloalkyl, haloalkyl, alkenyl, alkynyl, cycloalkylalkyl, cyanoalkyl, alkylcarbonyl, alkenylcarbonyl, haloalkylcarbonyl, haloalkenylcarbonyl, alkoxyalkyl, alkoxycarbonyl, alkylsulfonyl and haloalkylsulfonyl, or a radical from the series
Figure imgf000008_0001
Figure imgf000008_0001
(0)„ (D-7) ,0) v (D-8) X (D-9) (0) " (D - 7) , 0) v (D-8) X (D-9)
R8 ^ R R 8 ^ R
Figure imgf000008_0002
steht, worin die gestrichelte Linie die Bindung zum Stickstoffatom in der Formel (I) bedeutet, V-Z für eine Gruppe R18CH-CHR19 oder R18C=CR19 steht, X für Sauerstoff oder Schwefel steht, n für 1 oder 2 steht, R8 für einen Rest aus der Reihe Wasserstoff, Alkyl, Halogenalkyl, Cyanoalkyl, Alkoxy, Halogenalkoxy, Alkenyl, Alkoxyalkyl, jeweils gegebenenfalls durch Halogen substituiertes Alkylcarbonyl und Alkylsulfonyl, gegebenenfalls durch Halogen substituiertes Alkoxycarbonyl, gegebenenfalls durch Halogen, Alkyl, Alkoxy, Halogenalkyl und Cyano substituiertes Cycloalkylcarbonyl steht, oder für ein Kation, wie beispielsweise ein ein- oder zweiwertiges Metallion (beispielsweise Alkalimetallionen wie Li+, Na+, Cs+ und K+ und Erdalkalimetallionen wie Mg++ und Ca++) oder ein gegebenenfalls durch Alkyl oder Arylalkyl substituiertes Ammonium-Ion steht,
Figure imgf000008_0002
wherein the dotted line represents the bond to the nitrogen atom in formula (I), VZ is a group R 18 CH-CHR 19 or R 18 C = CR 19 , X is oxygen or sulfur, n is 1 or 2 . R 8 is a radical from the group consisting of hydrogen, alkyl, haloalkyl, cyanoalkyl, alkoxy, haloalkoxy, alkenyl, alkoxyalkyl, in each case optionally halogen-substituted alkylcarbonyl and alkylsulfonyl, optionally halogen-substituted alkoxycarbonyl, if appropriate by halogen, alkyl, alkoxy, haloalkyl and cyano substituted cycloalkylcarbonyl, or a cation, such as a mono- or divalent metal ion (for example, alkali metal ions such as Li + , Na + , Cs + and K + and alkaline earth metal ions such as Mg ++ and Ca ++ ) or optionally by alkyl or arylalkyl substituted ammonium ion is,
R15 und R9 unabhängig voneinander für einen Rest aus der Reihe jeweils gegebenenfalls substituiertes Amino, Alkyl, Alkenyl und Alkinyl, jeweils gegebenenfalls substituiertes Cycloalkyl, Cycloalkylalkyl und Cycloalkenyl, in welchen die Ringe mindestens ein Heteroatom aus der Reihe Schwefel, Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff enthalten können, jeweils gegebenenfalls substituiertes Aryl, Heteroaryl, Arylalkyl und Heteroarylalkyl und eine gegebenenfalls substituierte Aminogruppe stehen, R 15 and R 9 independently of one another from the series each optionally substituted amino, alkyl, alkenyl and alkynyl, each optionally substituted cycloalkyl, cycloalkylalkyl and cycloalkenyl, in which the rings at least one heteroatom selected from the group sulfur, oxygen (oxygen atoms not may be immediately adjacent) and contain nitrogen, each optionally substituted aryl, heteroaryl, arylalkyl and heteroarylalkyl and an optionally substituted amino group,
R8 und R15 auch zusammen mit der N-S(0)n Gruppe, an die sie gebunden sind, einen gesättigten oder ungesättigten und gegebenenfalls substituierten 4- bis 8-gliedrigen Ring bilden können, der ein oder mehrere weitere Heteroatome aus der Reihe Schwefel, Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff und/oder mindestens eine Carbonylgruppe enthalten kann, R 8 and R 15 , together with the NS (0) n group to which they are attached, may also form a saturated or unsaturated and optionally substituted 4- to 8-membered ring containing one or more further heteroatoms selected from the group consisting of sulfur, Oxygen (where oxygen atoms are not allowed to be immediately adjacent) and nitrogen and / or at least one carbonyl group,
R17 für einen Rest aus der Reihe jeweils gegebenenfalls substituiertes Alkyl, Alkoxy, Alkenyl und Alkinyl, jeweils gegebenenfalls substituiertes Cycloalkyl, Cycloalkylalkyl und Cycloalkenyl, in welchen die Ringe mindestens ein Heteroatom aus der Reihe Schwefel, Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff enthalten können, jeweils gegebenenfalls substituiertes Aryl, Heteroaryl, Arylalkyl und Heteroarylalkyl und eine gegebenenfalls substituierte Aminogruppe steht, R 17 is a radical from the series in each case optionally substituted alkyl, alkoxy, alkenyl and alkynyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl and cycloalkenyl, in which the rings are at least one heteroatom from the series sulfur, oxygen (oxygen atoms may not be immediately adjacent) and each may contain nitrogen, each optionally substituted aryl, heteroaryl, arylalkyl and heteroarylalkyl and an optionally substituted amino group,
R16 für einen Rest aus der Reihe Wasserstoff, jeweils gegebenenfalls substituiertes Alkyl, Alkoxy, Alkenyl und Alkinyl, jeweils gegebenenfalls substituiertes Cycloalkyl, Cycloalkylalkyl und Cycloalkenyl, in welchen die Ringe mindestens ein Heteroatom aus der Reihe Schwefel, Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff enthalten können, jeweils gegebenenfalls substituiertes Aryl, Heteroaryl, Arylalkyl und Heteroarylalkyl und eine gegebenenfalls substituierte Aminogruppe steht, R 16 is a radical from the group consisting of hydrogen, in each case optionally substituted alkyl, alkoxy, alkenyl and alkynyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl and cycloalkenyl, in which the rings are at least one heteroatom selected from the group consisting of sulfur, oxygen (oxygen atoms not being directly adjacent may each contain) and nitrogen, each optionally substituted aryl, heteroaryl, arylalkyl and heteroarylalkyl and an optionally substituted amino group,
R8 und R17 auch zusammen mit der N-C(X) Gruppe, an die sie gebunden sind, einen gesättigten oder ungesättigten und gegebenenfalls substituierten 4- bis 8-gliedrigen Ring bilden können, der ein oder mehrere weitere Heteroatome aus der Reihe Schwefel, Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff und/oder mindestens eine Carbonylgruppe enthalten kann, R 8 and R 17 may also together with the NC (X) group to which they are attached form a saturated or unsaturated and optionally substituted 4- to 8-membered ring containing one or more further heteroatoms selected from sulfur, oxygen (where oxygen atoms not immediately adjacent) and may contain nitrogen and / or at least one carbonyl group,
R10 für Wasserstoff oder Alkyl steht, R 10 is hydrogen or alkyl,
R8 und R10 auch gemeinsam mit den N-Atomen an die sie gebunden sind, für einen gesättigten oder ungesättigten und gegebenenfalls substituierten 4- bis 8-gliedrigen Ring stehen können, der mindestens ein weiteres Heteroatom aus der Reihe Schwefel, Sauerstoff (wobei Sauers toffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff und/oder mindestens eine Carbonylgruppe enthalten kann, R 8 and R 10 , together with the N atoms to which they are attached, may represent a saturated or unsaturated and optionally substituted 4- to 8-membered ring containing at least one further heteroatom selected from the group consisting of sulfur, oxygen (where Sauers toffatome not be immediately adjacent) and may contain nitrogen and / or at least one carbonyl group,
8 9 8 9
R und R im Rest (D-l) auch zusammen mit der N-S(0)n-Gruppe, an die sie gebunden sind, einen gesättigten oder ungesättigten und gegebenenfalls substituierten 4- bis 8-gliedrigen Ring bilden können, der ein oder mehrere weitere Heteroatome aus der Reihe Schwefel, Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff und/oder mindestens eine Carbonylgruppe enthalten kann, R and R in the radical (Dl) together with the NS (0) n group to which they are attached can form a saturated or unsaturated and optionally substituted 4- to 8-membered ring which comprises one or more further heteroatoms the series sulfur, oxygen (oxygen atoms may not be immediately adjacent) and nitrogen and / or at least one carbonyl group,
9 10 9 10
R und R auch zusammen mit der N-S(0)n Gruppe, an die sie gebunden sind, einen gesättigten oder ungesättigten und gegebenenfalls substituierten 4- bis 8-gliedrigen Ring bilden können, der ein oder mehrere weitere Heteroatome aus der Reihe Schwefel, Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff und/oder mindestens eine Carbonylgruppe enthalten kann, R and R may also together with the NS (0) n group to which they are attached form a saturated or unsaturated and optionally substituted 4- to 8-membered ring containing one or more further heteroatoms selected from the group consisting of sulfur, oxygen ( where oxygen atoms are not allowed to be immediately adjacent) and may contain nitrogen and / or at least one carbonyl group,
R8 und R16 auch zusammen mit dem N-Atom, an das sie gebunden sind, einen gesättigten oder ungesättigten und gegebenenfalls substituierten 4- bis 8-gliedrigen Ring bilden können, der ein oder mehrere weitere Heteroatome aus der Reihe Schwefel, Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff und/oder mindestens eine Carbonylgruppe enthalten kann, R 8 and R 16 may also together with the N-atom to which they are attached form a saturated or unsaturated and optionally substituted 4- to 8-membered ring containing one or more further heteroatoms selected from the group consisting of sulfur and oxygen (where Oxygen atoms may not be immediately adjacent) and may contain nitrogen and / or at least one carbonyl group,
L für Sauerstoff oder Schwefel steht, L is oxygen or sulfur,
11 12 11 12
R und R unabhängig voneinander für einen jeweils gegebenenfalls substituierten Rest aus der Reihe Alkyl, Alkenyl, Alkinyl, Alkoxy, Alkenyloxy, Alkinyloxy, Cycloalkyl, Cycloalkyloxy, Cycloalkenyloxy, Cycloalkylalkoxy, Alkylthio, Alkenylthio, Phenoxy, Phenylthio, Benzyloxy, Benzylthio, Heteroaryloxy, Heteroarylthio, Heteroarylalkoxy und Heteroarylalkylthio stehen, R and R independently of one another are each an optionally substituted radical from the series alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkyloxy, cycloalkenyloxy, cycloalkylalkoxy, alkylthio, alkenylthio, phenoxy, phenylthio, benzyloxy, benzylthio, heteroaryloxy, heteroarylthio, Heteroarylalkoxy and heteroarylalkylthio,
11 12 11 12
R und R auch gemeinsam mit dem Phosphoratom, an das sie gebunden sind, einen gesättigten oder ungesättigten und gegebenenfalls substituierten 5- bis 7-gliedrigen Ring bilden können, der ein oder zwei Heteroatome aus der Reihe Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Schwefel enthalten kann und R and R may also together with the phosphorus atom to which they are attached form a saturated or unsaturated and optionally substituted 5- to 7-membered ring, the or two heteroatoms from the series oxygen (oxygen atoms may not be immediately adjacent) and sulfur may contain and
R und R unabhängig voneinander für einen jeweils gegebenenfalls substituierten Rest aus der Reihe Alkyl, Alkenyl, Alkinyl, Phenyl und Phenylalkyl stehen, R18 und R19 unabhängig voneinander für Wasserstoff oder einen jeweils gegebenenfalls substituierten Rest aus der Reihe Alkyl, Alkenyl, Alkinyl, Phenyl und Phenylalkyl stehen, R and R are each independently an optionally substituted radical from the series alkyl, alkenyl, alkynyl, phenyl and phenylalkyl, R 18 and R 19 are independently hydrogen or each optionally substituted radical from the series alkyl, alkenyl, alkynyl, phenyl and phenylalkyl,
Y1 und Y2 unabhängig voneinander für C=0 oder S(0)2 stehen und m für 1, 2, 3 oder 4 steht. Y 1 and Y 2 are independently C = 0 or S (0) 2 and m is 1, 2, 3 or 4.
Weiterhin wurde gefunden, dass die neuen Verbindungen der Formel (I) eine gute Wirksamkeit als Schädlingsbekämpfungsmittel aufweisen, beispielsweise gegen Arthropoden und insbesondere Insekten, darüber hinaus in der Regel insbesondere gegenüber Kulturpflanzen sehr gut pflanzenverträglich sind und/oder über günstige toxikologische und/oder umweltrelevante Eigenschaften verfügen. Furthermore, it has been found that the novel compounds of the formula (I) have a good activity as pest control agents, for example against arthropods and in particular insects, moreover, in general, especially against crop plants are very well plant tolerated and / or favorable toxicological and / or environmental properties feature.
Bevorzugte Substituenten bzw. Bereiche der in den Verbindungen der Formel (I) aufgeführten Reste werden im Folgenden erläutert. A steht für einen Rest aus der Reihe Preferred substituents or ranges of the radicals listed in the compounds of the formula (I) are explained below. A stands out for the rest
Figure imgf000011_0001
Figure imgf000011_0001
A-a A-b A-d A-h worin die gestrichelte Linie die Bindung zu B bedeutet.  A-a A-b A-d A-h wherein the dotted line represents the bond to B.
B steht für einen Rest aus der Reihe B stands for a rest of the series
Figure imgf000011_0002
Figure imgf000011_0002
B-1 B-2 worin die gestrichelte Linie die Bindung zu A bedeutet und der Pfeil die Bindung zur Gruppe NR2R3 bedeutet. steht für einen Rest aus der Reihe Wasserstoff, Ci-C6-Alkyl, Ci-C6-Halogenalkyl, C2-C6- Alkenyl, C2-C6-Alkinyl, C3-C6-Cycloalkyl und C3-C6-Halogencycloalkyl. steht für einen Rest aus der Reihe Halogen, Cyano, Nitro, Ci-C6-Alkyl, Ci-C6-Halogenalkyl, C2- C6-Alkenyl, C2-C6-Halogenalkenyl, Ci-C6-Alkoxy, Ci-C6-Halogenalkoxy, C3-C6-Cycloalkyl, C3-C6-Halogencycloalkyl, Ci-C6-Alkylthio, Ci-C6-Halogenalkylthio, Ci-C6-Alkylsulfinyl, Ci- C6-Halogenalylsulfinyl, Ci-C6-Alkylsulfonyl, Ci-C6-Halogenalkylsulfonyl. steht für einen Rest aus der Reihe Wasserstoff, Ci-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C3- C6-Cycloalkyl, C3-C6-Cycloalkenyl, Ci-C6-Alkoxy, C2-C6-Alkenyloxy, C2-C6-Alkinyloxy, C3-C6-Cycloalkyloxy, Ci-C6-Alkylthio-Ci-C6-alkyl, C2-C6-Alkenylthio-Ci-C6-alkyl, Cyano-Ci- Ce-alkyl, Ci-C6-Alkoxy-Ci-C6-alkyl. steht für den Rest der Formel
Figure imgf000012_0001
steht für einen Rest aus der Reihe Ci-C6-Alkyl, Ci-C6-Halogenalkyl, Ci-C6-Alkoxy, Ci-Ce- Halogenalkoxy, Ci-C6-Alkoxy-Ci-C6-alkyloxy, Ci-C6-Alkylthio, Ci-C6-Alkylsulfinyl, CI-CÖ- Alkylsulfonyl, Ci-C6-Halogenalkylthio, Ci-C6-Halogenalkylsulfinyl, Ci-Ce-B-1 B-2 wherein the dashed line represents the bond to A and the arrow represents the bond to the group NR 2 R 3 . is a radical selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkyl and C 3 -C 6 -halocycloalkyl. stands for a radical from the series halogen, cyano, nitro, Ci-C6-alkyl, Ci-C6-haloalkyl, C 2 - C 6 alkenyl, C 2 -C 6 haloalkenyl, Ci-C6-alkoxy, Ci-C6-halogenoalkoxy , C 3 -C 6 -cycloalkyl, C 3 -C 6 -halocycloalkyl, C 1 -C 6 -alkylthio, C 1 -C 6 -haloalkylthio, C 1 -C 6 -alkylsulfinyl, C 1 -C 6 -halogenoylsulfinyl, C 1 -C 6 -alkylsulfonyl, C 1 -C 6 -haloalkylsulfonyl. is a radical from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkenyl, C 1 -C 6 -alkoxy, C 2 - C6-alkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 6 cycloalkyloxy, Ci-C6 alkylthio-Ci-C 6 alkyl, C 2 -C 6 alkenylthio-Ci-C 6 alkyl, cyano C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl. stands for the rest of the formula
Figure imgf000012_0001
is a radical from the series Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkoxy, Ci-Ce-haloalkoxy, Ci-C6-alkoxy-Ci-C6-alkyloxy, Ci-C6-alkylthio, Ci C6-alkylsulfinyl, CI-C Ö - alkylsulfonyl, Ci-C6-haloalkylthio, Ci-C6 haloalkylsulfinyl, Ci-Ce
Halogenalkylsulfonyl Ci-Ce-Alkylthio-Ci-Ce-alkyl, Ci-C6-Alkylsulfinyl-Ci-C6-alkyl, Ci-C6- Alkylsulfonyl-Ci-Ce-alkyl, Ci-C6-Alkylthio-Ci-C6-alkyloxy, Ci-C6-Alkylsulfinyl-Ci-C6- alkyloxy, Ci-C6-Alkylsulfonyl-Ci-C6-alkyloxy, Ci-C6-Halogenalkylthio-Ci-C6-alkyl, Ci-Ce- Halogenalkylsulfinyl-Ci-C6-alkyl, Ci-C6-Halogenalkylsulfonyl-Ci-C6-alkyl, Ci-C6-Alkylthio- C2-C6-alkenyl, Ci-C6-Alkylsulfinyl-C2-C6-alkenyl, Ci-C6-Alkylsulfonyl-C2-C6-alkenyl, C2-C6- Alkenylthio-Ci-Ce-alkyl, C2-C6-Alkenylsulfinyl-Ci-C6-alkyl, C2-C6-Alkenylsulfonyl-Ci-C6- alkyl, Ci-C6-Alkylcarbonyl-Ci-C6-alkyl, Ci-C6-Halogenalkylcarbonyl-Ci-C6-alkyl, Ci-Ce- Alkoxy-Ci-C6-alkyl, Ci-C6-Halogenalkoxy-Ci-C6-alkyl, Ci-C6-Alkoxycarbonyl-Ci-C6-alkyl, Ci- C6-Halogenalkoxycarbonyl-Ci-C6-alkyl. steht auch für gegebenenfalls durch Halogen, Cyano, Nitro, Amino, Hydroxy, Ci-C6-Alkyl, Ci- Ce-Halogenalkyl, Cyano-Ci-C6-alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C3-C6-Cycloalkyl, C3-C6- Cycloalkyl-Ci-C6-alkyl, Ci-C6-Alkoxy, Ci-C6-Halogenalkoxy, C3-C6-Alkenyloxy, C3-C6- Alkinyloxy, C3-C6-Cycloalkyloxy, Ci-C6-Alkylcarbonyloxy, C2-C6-Alkenylcarbonyloxy, C2-C6- Alkinylcarbonyloxy, C3-C6-Cycloalkylcarbonyloxy, Ci-C6-Alkoxycarbonyloxy, CI-CÖ- Alkylsulfonyloxy, Ci-C6-Alkylamino, C3-C6-Alkenylamino, C3-C6-Alkinylamino, C3-C6-Haloalkylsulfonyl Ci-Ce-alkylthio-Ci-Ce-alkyl, Ci-C 6 alkylsulfinyl-Ci-C 6 alkyl, C 6 - alkylsulphonyl-Ci-Ce-alkyl, Ci-C 6 -alkylthio-C 6 alkyloxy, Ci-C 6 alkylsulfinyl-Ci-C 6 - alkyloxy, Ci-C6-alkylsulfonyl-Ci-C6-alkyloxy, Ci-C6-halogenoalkylthio-Ci-C6-alkyl, Ci-Ce-haloalkylsulfinyl-Ci C6-alkyl, Ci-C6-haloalkylsulfonyl-Ci-C6-alkyl, Ci-C6-alkylthio, C 2 -C 6 alkenyl, Ci-C 6 alkylsulfinyl-C 2 -C 6 alkenyl, C 6 - alkylsulfonyl-C 2 -C 6 alkenyl, C 2 -C 6 - alkenylthio-Ci-Ce-alkyl, C 2 -C 6 alkenylsulfinyl-Ci-C 6 alkyl, C 2 -C 6 alkenylsulfonyl-Ci-C 6 -alkyl, C 1 -C 6 -alkylcarbonyl-C 1 -C 6 -alkyl, C 1 -C 6 -haloalkylcarbonyl-C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 1 -C 6 -haloalkoxy-C 1 -C 6 -alkyl alkyl, C 1 -C 6 -alkoxycarbonyl-C 1 -C 6 -alkyl, C 1 -C 6 -haloalkoxycarbonyl-C 1 -C 6 -alkyl. is also optionally substituted by halogen, cyano, nitro, amino, hydroxy, C 1 -C 6 -alkyl, cis-C 1 -haloalkyl, cyano-C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 - alkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 - cycloalkyl-Ci-C6-alkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, C 3 -C 6 alkenyloxy, C 3 -C6- alkynyloxy, C 3 -C 6 cycloalkyloxy, Ci-C6 alkylcarbonyloxy, C 2 -C 6 alkenylcarbonyloxy, C 2 -C6- Alkinylcarbonyloxy, C 3 -C 6 cycloalkylcarbonyloxy, Ci-C6-alkoxycarbonyloxy, CI-C Ö - Alkylsulfonyloxy, Ci-C6-alkylamino, C3-C6-alkenylamino, C3-C6-alkynylamino, C3-C6-
Cycloalkylamino, Ci-C6-Alkylthio, Ci-C6-Halogenalkylthio, C3-C6-Alkenylthio, C3-C6-Cycloalkylamino, C 1 -C 6 -alkylthio, C 1 -C 6 -haloalkylthio, C 3 -C 6 -alkenylthio, C 3 -C 6 -cycloalkylamino
Alkinylthio, C3-C6-Cycloalkylthio, Ci-C6-Alkylsulfinyl, Ci-Ce-Alkylsulfonyl, Ci-Cs- Alkylcarbonyl, Ci-C6-Alkoxyimino-Ci-C6-alkyl, Ci-C6-Alkoxycarbonyl, Aminocarbonyl, Ci-Ce-Alkynylthio, C 3 -C 6 cycloalkylthio, Ci-C 6 alkylsulfinyl, Ci-Ce-alkylsulfonyl, Ci-Cs-alkylcarbonyl, Ci-C6-alkoxyimino-Ci-C6-alkyl, Ci-C6-alkoxycarbonyl, aminocarbonyl, Ci -Ce-
Alkylaminocarbonyl, Di-(Ci-C6-alkyl)-aminocarbonyl, Aminothiocarbonyl, C1-C5-Alkylaminocarbonyl, di- (C 1 -C 6 -alkyl) aminocarbonyl, aminothiocarbonyl, C 1 -C 5
Alkylaminosulfonyl, Ci-C6-Alkylsulfonylamino, Ci-C6-Alkylcarbonylamino, C1-C5- Alkylthiocarbonylamino substituiertes Phenyl oder für einen Rest aus der Reihe Alkylaminosulfonyl, C 1 -C 6 -alkylsulfonylamino, C 1 -C 6 -alkylcarbonylamino, C 1 -C 5 -alkylthiocarbonylamino-substituted phenyl or a radical from the series
Figure imgf000013_0001
Figure imgf000013_0001
C-8 C-10 C-1 1 C-8 C-10 C-1 1
Figure imgf000013_0002
Figure imgf000013_0002
C-16
Figure imgf000014_0001
C-16
Figure imgf000014_0001
Figure imgf000014_0002
Figure imgf000014_0002
Figure imgf000015_0001
Figure imgf000015_0001
\ // ■N N \ // ■ NN
N-N W /  N-N W /
N=N N-N  N = N N-N
R6 R  R6 R
C-41 C-42 C-43  C-41 C-42 C-43
Figure imgf000015_0002
Figure imgf000015_0002
C-45 C-46 C-47  C-45 C-46 C-47
Figure imgf000015_0003
Figure imgf000015_0003
C-48 C-49 C-50 C-51  C-48 C-49 C-50 C-51
R5 steht für einen Rest aus der Reihe Wasserstoff (nur in den Resten C-33, C-36 und C-42), Halogen, Cyano, Nitro, Amino, Hydroxy, Ci-C6-Alkyl, Ci-C6-Halogenalkyl, Cyano-Ci-C6-alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C3-C6-Cycloalkyl, C3-C6-Cycloalkyl-Ci-C6-alkyl, Ci-C6-Alkoxy, Ci-C6-Halogenalkoxy, C3-C6-Alkenyloxy, C3-C6-Alkinyloxy, C3-C6-Cycloalkyloxy, CI-CÖ-R 5 is a radical from the series hydrogen (only in the radicals C-33, C-36 and C-42), halogen, cyano, nitro, amino, hydroxy, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, cyano-Ci-C6-alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl-Ci-C 6 alkyl, C 6 alkoxy, Ci-C6-haloalkoxy, C3-C6-alkenyloxy, C 3 -C 6 alkynyloxy, C 3 -C 6 cycloalkyloxy, C Ö -
Alkylcarbonyloxy, C2-C6-Alkenylcarbonyloxy, C2-C6-Alkinylcarbonyloxy, C3-C6- Cycloalkylcarbonyloxy, Ci-C6-Alkoxycarbonyloxy, Ci-C6-Alkylsulfonyloxy, Ci-Ce- Alkylamino, C3-C6-Alkenylamino, C3-C6-Alkinylamino, C3-C6-Cycloalkylamino, CI-CÖ- Alkylthio, Ci-C6-Halogenalkylthio, C3-C6-Alkenylthio, C3-C6-Alkinylthio, C3-C6- Cycloalkylthio, Ci-Ce-Alkylsulfinyl, Ci-Ce-Alkylsulfonyl, Ci-C6-Alkylcarbonyl, Ci-C6-Alkylcarbonyloxy, C2-C6-alkenylcarbonyloxy, C2-C6-Alkinylcarbonyloxy, C3 -C6- cycloalkylcarbonyloxy, Ci-C6-alkoxycarbonyloxy, Ci-C6-alkylsulfonyloxy, Ci-Ce-alkylamino, C 3 -C 6 alkenylamino, C 3 -C 6 alkynylamino, C 3 -C 6 cycloalkylamino, C Ö - alkylthio, Ci-C 6 haloalkylthio, C 3 -C 6 -alkenylthio, C 3 -C 6 -alkinylthio, C 3 -C 6 - cycloalkylthio, Ci Ce-alkylsulfinyl, C 1 -C 6 -alkylsulfonyl, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -
Alkoxyimino-Ci-C6-alkyl, Ci-C6-Alkoxycarbonyl, Aminocarbonyl, Ci-C6-Alkylaminocarbonyl, Di-(Ci-C6)-alkylaminocarbonyl, Aminothiocarbonyl, Ci-C6-Alkylaminosulfonyl, CI-CÖ- Alkylsulfonylamino, Ci-C6-Alkylcarbonylamino, Ci-C6-Alkylthiocarbonylamino, Aryl, Aryloxy, Heteroaryl und Heteroaryloxy. R6 steht für einen Rest aus der Reihe Wasserstoff, Ci-C6-Alkyl, C3-C6-Cycloalkyl, CI-CÖ- Halogenalkyl, C3-C6-Alkenyl, C2-C6-Alkinyl, C3-C6-Cycloalkyl-Ci-C6-alkyl, Cyano-Ci-Ce-alkyl, Ci-C6-Alkylcarbonyl, C2-C6-Alkenylcarbonyl, Ci-C6-Halogenalkylcarbonyl, Alkoxyimino-Ci-C6-alkyl, Ci-C6-alkoxycarbonyl, aminocarbonyl, Ci-C6-alkylaminocarbonyl, di (Ci-C6) alkylaminocarbonyl, aminothiocarbonyl, Ci-C6-alkylaminosulfonyl, Cl-C Ö - alkylsulfonylamino, Ci-C6 Alkylcarbonylamino, C 1 -C 6 -alkylthiocarbonylamino, aryl, aryloxy, heteroaryl and heteroaryloxy. R 6 is a radical selected from hydrogen, Ci-C6-alkyl, C3-C6-cycloalkyl, CI-C Ö - haloalkyl, C 3 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 - C 6 -cycloalkyl-C 1 -C 6 -alkyl, cyano-C 1 -C 6 -alkyl, C 1 -C 6 -alkylcarbonyl, C 2 -C 6 -alkenylcarbonyl, C 1 -C 6 -haloalkylcarbonyl,
Halogenalkenylcarbonyl, Ci-C6-Alkoxy-Ci-C6-alkyl, Ci-C6-Alkoxycarbonyl,  Haloalkenylcarbonyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 1 -C 6 -alkoxycarbonyl,
Alkylsulfonyl und Ci-C6-Halogengenalkylsufonyl. steht auch für einen Rest aus der Reihe  Alkylsulfonyl and Ci-C6-Halogengenalkylsufonyl. is synonymous for a rest of the series
Figure imgf000016_0001
Figure imgf000016_0001
Figure imgf000016_0002
worin die gestrichelte Linie die Bindung zum Stickstoffatom in der Formel (I) bedeutet. V-Z steht für R18CH-CHR19 oder R18C=CR19. X steht für Sauerstoff oder Schwefel, n steht für 1 oder 2. R8 steht für einen Rest aus der Reihe Wasserstoff, Ci-C6-Alkyl, Ci-C6-Halogenalkyl, Cyano-Ci-C6- alkyl, Ci-C6-Alkoxy, Ci-C6-Halogenalkoxy, C2-C6-Alkenyl, Ci-C6-Alkoxy-Ci-C6-alkyl, jeweils gegebenenfalls durch Halogen substituiertes Ci-C6-Alkylcarbonyl und Ci-C6-Alkylsulfonyl, gegebenenfalls durch Halogen substituiertes Ci-C6-Alkoxycarbonyl, gegebenenfalls durch Halogen, Ci-C6-Alkyl, Ci-C6-Alkoxy, Ci-C6-Halogenalkyl und Cyano substituiertes C3-C6- Cycloalkylcarbonyl, oder für ein Kation, wie beispielsweise ein ein- oder zweiwertiges Metallion oder ein gegebenenfalls durch Ci-C6-Alkyl oder Aryl-Ci-C6-alkyl substituiertes Ammonium-Ion.
Figure imgf000016_0002
wherein the dashed line represents the bond to the nitrogen atom in the formula (I). VZ is R 18 CH-CHR 19 or R 18 C = CR 19 . X is oxygen or sulfur, n is 1 or 2. R 8 is a radical selected from hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, cyano-C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy , Ci-C6-haloalkoxy, C 2 -C 6 -alkenyl, Ci-C6-alkoxy-Ci-C6-alkyl, in each case optionally substituted by halogen Ci-C6-alkylcarbonyl and Ci-C6-alkylsulfonyl, optionally substituted by halogen Ci-C6 Alkoxycarbonyl, optionally substituted by halogen, Ci-C6-alkyl, Ci-C6-alkoxy, Ci-C6-haloalkyl and cyano-substituted C3-C6-cycloalkylcarbonyl, or a cation, such as a monovalent or divalent metal ion or an optionally substituted Ci-C6-alkyl or aryl-Ci-C6-alkyl substituted ammonium ion.
R9 steht für einen Rest aus der Reihe jeweils gegebenenfalls durch Halogen, Ci-C6-Alkoxy, Ci-Ce- Halogenalkoxy, Ci-C6-Alkylthio, Ci-C6-Halogenalkylthio, Ci-C6-Alkylsulfinyl, CI-CÖ- Halogenalkylsulfinyl, Ci-C6-Alkylsulfonyl und Ci-C6-Halogenalkylsulfonyl substituiertes CI-CÖ- Alkyl, C2-C6-Alkenyl und C2-C6-Alkinyl, jeweils gegebenenfalls durch Halogen, Ci-C6-Alkyl, Ci-R 9 is a radical from the series in each case optionally substituted by halogen, Ci-C6-alkoxy, Ci-Ce- haloalkoxy, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkylsulfinyl, CI-C Ö - haloalkylsulfinyl , Ci-C6-alkylsulfonyl, and Ci-C6-haloalkylsulfonyl-substituted CI-C Ö - alkyl, C 2 -C 6 alkenyl and C 2 -C 6 alkynyl, each optionally substituted by halogen, Ci-C6-alkyl, Ci-
C6-Halogenalkyl, Ci-C6-Alkoxy oder Ci-C6-Halogenalkoxy substituiertes C3-C6-Cycloalkyl, C3- C6-Cycloalkyl-Ci-C6-alkyl und C3-C6-Cycloalkenyl, in welchen ein oder zwei Ringglieder jeweils durch ein Heteroatom aus der Reihe Schwefel, Sauerstoff (wobei Sauers toffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff ersetzt sein kann (und dabei insbesondere für C 6 haloalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy, substituted C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl-C 1 -C 6 -alkyl and C 3 -C 6 cycloalkenyl in which one or two ring members each by a heteroatom selected from the group consisting of sulfur, oxygen (which may not be immediately adjacent to oxygen atoms) and nitrogen (and in particular for
Figure imgf000017_0001
wobei der Pfeil jeweils die Bindung zum S-Atom im Rest (D-1) markiert), jeweils gegebenenfalls durch Halogen, Cyano (auch im Alkylteil), Nitro, Ci-C6-Alkyl, Ci-C6-Halogenalkyl, C3-C6- Cycloalkyl, Ci-C6-Alkoxy, Ci-C6-Halogenalkoxy, Ci-C6-Alkylthio, Ci-C6-Halogenalkylthio, Ci- C6-Alkylsulfinyl, Ci-C6-Halogenalkylsulfinyl, Ci-C6-Alkylsulfonyl, Ci-C6-Halogenalkylsulfonyl, Amino, Ci-C6-Alkylamino, Di-(Ci-C6-alkyl)-amino, Ci-C6-Alkylcarbonylamino, CI-CÖ- Alkoxycarbonylamino, Ci-C6-Alkoxy-Ci-C6-alkyl, Ci-C6-Halogenalkoxy-Ci-C6-alkyl, C2-C6- Alkenyl, C2-C6-Alkinyl, C3-C6-Cycloalkyl-Ci-C6-alkyl, Ci-C6-Alkylcarbonyl, Ci-Ce- Alkoxycarbonyl oder Aminocarbonyl substituiertes Aryl, Heteroaryl, Aryl-Ci-C6-alkyl, Heteroaryl-Ci-C6-alkyl oder für NR'R", worin R' und R" unabhängig voneinander für einen Rest aus der Reihe Wasserstoff, Ci-C6-Alkyl, Ci-C6-Haloalkyl, C3-C6-Cycloalkyl, Ci-C6-Alkoxy, Ci- C6-Alkylcarbonyl und Ci-C6-Alkoxylcarbonyl stehen. steht für einen Rest aus der Reihe jeweils gegebenenfalls durch Halogen, Ci-C6-Alkoxy, Ci-Ce- Halogenalkoxy, Ci-Cö-Alkylthio, Ci-C6-Halogenalkylthio, Ci-C6-Alkylsulfinyl, CI-CÖ- Halogenalkylsulfinyl, Ci-C6-Alkylsulfonyl oder Ci-C6-Halogenalkylsulfonyl substituiertes CI-CÖ- Alkyl, Ci-C6-Alkoxy, C2-C6-Alkenyl und C2-C6-Alkinyl, jeweils gegebenenfalls durch Halogen, Ci-Cö-Alkyl, Ci-C6-Halogenalkyl, Ci-C6-Alkoxy oder Ci-C6-Halogenalkoxy substituiertes C3-C6- Cycloalkyl, C3-C6-Cycloalkyl-Ci-C6-alkyl und C3-C6-Cycloalkenyl, in welchen ein oder zwei Ringglieder jeweils durch ein Heteroatom aus der Reihe Schwefel, Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff ersetzt sein können, jeweils gegebenenfalls durch Halogen, Cyano (auch im Alkylteil), Nitro, Ci-Cö-Alkyl, Ci-Ce- Halogenalkyl, C3-C6-Cycloalkyl, Ci-C6-Alkoxy, Ci-C6-Halogenalkoxy, Ci-Cö-Alkylthio, Ci-Ce- Halogenalkylthio, Ci-C6-Alkylsulfinyl, Ci-C6-Halogenalkylsulfinyl, Ci-C6-Alkylsulfonyl, Ci-Ce- Halogenalkylsulfonyl, Amino, Ci-C6-Alkylamino, Di-(Ci-C6-alkyl)-amino, CI-CÖ- Alkylcarbonylamino, Ci-C6-Alkoxycarbonylamino, Ci-C6-Alkoxy-Ci-C6-alkyl, CI-CÖ- Halogenalkoxy-Ci-Ce-alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C3-C6-Cycloalkyl-Ci-C6-alkyl, Ci-Ce- Alkylcarbonyl, Ci-C6-Alkoxycarbonyl oder Aminocarbonyl substituiertes Aryl, Heteroaryl, Aryl- Ci-Cö-alkyl, Heteroaryl-Ci-C6-alkyl oder für NR'R", worin R' und R" unabhängig voneinander jeweils für einen Rest aus der Reihe Wasserstoff, Ci-Ce-Alkyl, Ci-Cö-Haloalkyl, C3-C6- Cycloalkyl, Ci-C6-Alkoxy, Ci-C6-Alkylcarbonyl und Ci-C6-Alkoxylcarbonyl stehen. R8 und R17 können auch zusammen mit der N-C(X) Gruppe, an die sie gebunden sind, einen gesättigten oder ungesättigten und gegebenenfalls durch Halogen, Ci-C6-Alkyl, Ci-C6-Halogenalkyl, CI-CÖ- Alkoxy, Ci-C6-Halogenalkoxy substituierten 5- bis 7-gliedrigen Ring bilden, der ein oder zwei weitere Heteroatome aus der Reihe Schwefel, Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff und/oder eine Carbonylgruppe enthalten kann, insbesondere können R8 und R17 zusammen mit der N-C(X) Gruppe, an die sie gebunden sind, für einen Rest aus der Reihe
Figure imgf000017_0001
wherein the arrow in each case marks the bond to the S atom in the radical (D-1)), in each case optionally by halogen, cyano (also in the alkyl part), nitro, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 6 -cycloalkyl Cycloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 1 -C 6 -alkylthio, C 1 -C 6 -haloalkylthio, C 1 -C 6 -alkylsulfinyl, C 1 -C 6 -haloalkylsulfinyl, C 1 -C 6 -alkylsulfonyl, C 1 -C 6 -haloalkylsulfonyl, amino, Ci-C6-alkylamino, di- (Ci-C6-alkyl) amino, Ci-C6-alkylcarbonylamino, CI-C Ö - alkoxycarbonylamino, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-halogenoalkoxy -C-C6-alkyl, C 2 -C6- alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl-Ci-C 6 alkyl, Ci-C6 alkylcarbonyl, Ci-Ce alkoxycarbonyl or Aminocarbonyl-substituted aryl, heteroaryl, aryl-C 1 -C 6 -alkyl, heteroaryl-C 1 -C 6 -alkyl or for NR'R ", in which R 'and R" independently of one another represent a radical from the series consisting of hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkylcarbonyl and C 1 -C 6 -alkoxylcarbonyl. is a radical from the series in each case optionally substituted by halogen, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 1 -C 6 -alkylthio, C 1 -C 6 -haloalkylthio, C 1 -C 6 -alkylsulfinyl, C 1 -C 8 -haloalkylsulfinyl, C6-alkylsulfonyl or Ci-C6-haloalkylsulfonyl-substituted CI-C Ö - alkyl, Ci-C6 alkoxy, C 2 -C 6 alkenyl and C 2 -C 6 alkynyl, each optionally substituted by halogen, Ci-COE-alkyl, Ci- C6-haloalkyl, Ci-C6-alkoxy or Ci-C6-haloalkoxy-substituted C3-C6-cycloalkyl, C3-C6-cycloalkyl-Ci-C6-alkyl and C3-C6-cycloalkenyl, in which one or two ring members in each case by a heteroatom from the series sulfur, oxygen (oxygen atoms may not be immediately adjacent) and nitrogen may be replaced, in each case optionally by halogen, cyano (also in the alkyl part), nitro, Ci-Cö-alkyl, Ci-Ce- haloalkyl, C 3 - C 6 -cycloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 1 -C 6 -alkylthio, C 1 -C 6 -haloalkylthio, C 1 -C 6 -alkylsulfinyl, C 1 -C 6 -haloalkylsulfinyl, C 1 -C 6 -alkyl lkylsulfonyl, Ci-Ce haloalkylsulfonyl, amino, Ci-C6-alkylamino, di- (Ci-C6-alkyl) amino, CI-C Ö - alkylcarbonylamino, Ci-C6-alkoxycarbonylamino, Ci-C6-alkoxy-Ci-C6 -alkyl, COE haloalkoxy-Ci-Ce-alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl-Ci-C 6 alkyl, Ci-Ce- Alkylcarbonyl, Ci-C6-alkoxycarbonyl or aminocarbonyl-substituted aryl, heteroaryl, aryl-Ci-Cö-alkyl, heteroaryl-Ci-C6-alkyl or NR'R ", wherein R 'and R" are each independently a radical from the Series hydrogen, Ci-Ce-alkyl, Ci-Cö-Haloalkyl, C3-C6-Cycloalkyl, Ci-C6-Alkoxy, Ci-C6-Alkylcarbonyl and Ci-C6-Alkoxylcarbonyl stand. R 8 and R 17 can also be used together with the NC (X) group to which they are attached, a saturated or unsaturated and optionally halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, CI-C Ö - alkoxy, Ci-C6-haloalkoxy-substituted 5- to 7-membered ring form, which may contain one or two further heteroatoms from the series sulfur, oxygen (oxygen atoms may not be immediately adjacent) and nitrogen and / or a carbonyl group, in particular R 8 and R 17, together with the NC (X) group to which they are attached, are out of line for a remainder
Figure imgf000018_0001
stehen (worin der Pfeil jeweils die Bindung zum S-Atom im Rest (D-8) markiert).
Figure imgf000018_0001
(in which the arrow in each case marks the bond to the S atom in the radical (D-8)).
R8 und R9 können im Rest (D-1) auch zusammen mit der N-S(0)n Gruppe, an die sie gebunden sind, einen gesättigten oder ungesättigten und gegebenenfalls durch Halogen, Ci-C6-Alkyl, Ci-Ce- Halogenalkyl, Ci-C6-Alkoxy, Ci-C6-Halogenalkoxy substituierten 5- bis 7-gliedrigen Ring bilden, der ein oder zwei Heteroatome aus der Reihe Schwefel, Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff und/oder mindestens eine und bevorzugt genau eine Carbonylgruppe enthalten kann, insbesondere können R8 und R9 zusammen mit der N-S(0)n Gruppe, an die sie gebunden sind, für einen Rest aus der Reihe R 8 and R 9 in the radical (D-1) together with the NS (0) n group to which they are attached, a saturated or unsaturated and optionally by halogen, Ci-C6-alkyl, Ci-Ce- haloalkyl , Ci-C6-alkoxy, Ci-C6-haloalkoxy-substituted 5- to 7-membered ring, the one or two heteroatoms selected from the group sulfur, oxygen (oxygen atoms may not be immediately adjacent) and nitrogen and / or at least one and may preferably contain exactly one carbonyl group, in particular R 8 and R 9 may together with the NS (0) n group to which they are attached, stand for a residue from the series
Figure imgf000018_0002
stehen (worin der Pfeil jeweils die Bindung zur C(X)-Gruppe markiert). und R stehen unabhängig voneinander für Wasserstoff oder einen jeweils gegebenenfalls substituierten Rest aus der Reihe Ci-C6-Alkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, Phenyl und Phenylalkyl. I i
Figure imgf000018_0002
(in which the arrow in each case marks the bond to the C (X) group). and R independently of one another represent hydrogen or an optionally substituted radical from the group consisting of C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, phenyl and phenylalkyl. I i
Besonders bevorzugte Substituenten bzw. Bereiche der in den Verbindungen der Formel aufgeführten Reste werden im Folgenden erläutert.  Particularly preferred substituents or ranges of the radicals listed in the compounds of the formula are explained below.
A steht für einen Rest aus der Reihe A stands out for the rest
Figure imgf000019_0001
Figure imgf000019_0001
A-a A-h worin die gestrichelte Linie die Bindung zu B bedeutet.  A-a A-h wherein the dotted line represents the bond to B.
B steht für B stands for
Figure imgf000019_0002
Figure imgf000019_0002
B-1 worin die gestrichelte Linie die Bindung zu A bedeutet und der Pfeil die Bindung zur Gruppe NR2R3 bedeutet. steht für einen Rest aus der Reihe Wasserstoff, Ci-C4-Alkyl, Ci-C4-Halogenalkyl, C2-C4- Alkenyl, C2-C4-Alkinyl, C3-C6-Cycloalkyl und C3-C6-Halogencycloalkyl. steht für einen Rest aus der Reihe Halogen, Cyano, Nitro, Ci-C4-Alkyl, Ci-C4-Halogenalkyl, C2- C4-Alkenyl, C2-C4-Halogenalkenyl, Ci-C4-Alkoxy, Ci-C4-Halogenalkoxy, C3-C6-Cycloalkyl, C3-C6-Halogencycloalkyl, Ci-C4-Alkylthio, Ci-C4-Halogenalkylthio, Ci-C4-Alkylsulfinyl, Ci- C4-Halogenalylsulfinyl, Ci-C4-Alkylsulfonyl, Ci-C4-Halogenalkylsulfonyl. steht für einen Rest aus der Reihe Wasserstoff, Ci-C4-Alkyl, C2-C4-Alkenyl, C2-C4-Alkinyl, C3- C6-Cycloalkyl, C3-C6-Cycloalkenyl, Ci-C4-Alkoxy, C2-C4-Alkenyloxy, C2-C4-Alkinyloxy, C3-C6-Cycloalkyloxy, Ci-C4-Alkylthio-Ci-C4-alkyl, C2-C4-Alkenylthio-Ci-C4-alkyl, Cyano-Ci- C4-alkyl, Ci-C4-Alkoxy-Ci-C4-alkyl. R3 steht für einen Rest der Formel
Figure imgf000020_0001
steht für einen Rest aus der Reihe Ci-C4-Alkyl, Ci-C4-Halogenalkyl, Ci-C4-Alkylthio-Ci-C4- alkyl, Ci-C4-Alkylsulfinyl-Ci-C4-alkyl, Ci-C4-Alkylsulfonyl-Ci-C4-alkyl, Ci-C4-Halogenalkyl- thio-Ci-C4-alkyl, Ci-C4-Halogenalkylsulfinyl-Ci-C4-alkyl, Ci-C4-Halogenalkylsulfonyl-Ci-C4- alkyl, Ci-C4-Alkylthio-C2-C4-alkenyl, Ci-C4-Alkylsulfinyl-C2-C4-alkenyl, Ci-C4-Alkylsulfonyl- C2-C4-alkenyl, C2-C4-Alkenylthio-Ci-C4-alkyl, C2-C4-Alkenylsulfinyl-Ci-C4-alkyl, C2-C4- Alkenylsulfonyl-Ci-C4-alkyl, Ci-C4-Alkylcarbonyl-Ci-C4-alkyl, Ci-C4-Halogenalkylcarbonyl- Ci-C4-alkyl, Ci-C4-Alkoxy-Ci-C4-alkyl, Ci-C4-Halogenalkoxy-Ci-C4-alkyl, Ci-C4- Alkoxycarbonyl-Ci-C4-alkyl, Ci-C4-Halogenalkoxycarbonyl-Ci-C4-alkyl. steht auch für gegebenenfalls durch Halogen, Cyano, Nitro, Amino, Hydroxy, Ci-C6-Alkyl, Ci- Ce-Halogenalkyl, C2-C6-Alkenyl, C2-C6-Alkinyl, C3-C6-Cycloalkyl, Ci-Ce-Alkoxy, Ci-C6- Halogenalkoxy, C3-C6-Alkenyloxy, C3-C6-Alkinyloxy, Ci-C6-Alkoxycarbonyloxy, Ci-Ce- Alkylamino, C3-C6-Alkenylamino, C3-C6-Alkinylamino, C3-C6-Cycloalkylamino, CI-CÖ- Alkylthio, Ci-C6-Halogenalkylthio, C3-C6-Alkenylthio, C3-C6-Alkinylthio, C3-C6- Cycloalkylthio, Ci-C6-Alkylsulfinyl, Ci-C6-Alkylsulfonyl, Ci-C6-Alkylcarbonyl, Aminocarbonyl, Ci-C6-Alkylaminocarbonyl, Di-(Ci-C6-alkyl)-aminocarbonyl, CI-CÖ- Alkylcarbonylamino substituiertes Phenyl oder einen Rest aus der Reihe B-1 wherein the dashed line represents the bond to A and the arrow represents the bond to the group NR 2 R 3 . represents a radical from the series consisting of hydrogen, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, C 3 -C 6 -cycloalkyl and C 3 -C 6 -halocycloalkyl. stands for a radical from the series halogen, cyano, nitro, Ci-C4-alkyl, Ci-C 4 haloalkyl, C 2 - C 4 alkenyl, C 2 -C 4 haloalkenyl, Ci-C 4 alkoxy, Ci-C 4 haloalkoxy, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, Ci-C 4 alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylsulfinyl, Ci- C 4 -Halogenalylsulfinyl, C -C 4 alkylsulfonyl, Ci-C4-haloalkylsulfonyl. is a radical from the series consisting of hydrogen, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkenyl, C 1 -C 4 - alkoxy, C 2 -C 4 alkenyloxy, C 2 -C 4 alkynyloxy, C 3 -C 6 cycloalkyloxy, Ci-C4-alkylthio-Ci-C 4 alkyl, C 2 -C 4 alkenylthio-Ci C 4 -alkyl, cyano-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl. R 3 is a radical of the formula
Figure imgf000020_0001
stands for a radical from the group Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkylthio-Ci-C4-alkyl, Ci-C4-alkylsulfinyl-Ci-C4-alkyl, Ci-C 4 - alkylsulfonyl-Ci-C4-alkyl, Ci-C 4 haloalkyl thio-Ci-C4-alkyl, Ci-C4-haloalkylsulfinyl-Ci-C4-alkyl, Ci-C4-haloalkylsulfonyl-Ci-C4-alkyl, Ci- C 4 -alkylthio-C 2 -C 4 alkenyl, C 4 alkylsulfinyl-C 2 -C 4 alkenyl, Ci-C 4 alkylsulfonyl C 2 -C 4 alkenyl, C 2 -C 4 -alkenylthio -C-C 4 alkyl, C 2 -C 4 alkenylsulfinyl-Ci-C 4 alkyl, C 2 -C 4 - alkenylsulfonyl-Ci-C4-alkyl, Ci-C4-alkylcarbonyl-Ci-C4-alkyl, Ci C4-haloalkylcarbonyl Ci-C4 alkyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-haloalkoxy-Ci-C4-alkyl, Ci-C4 - alkoxycarbonyl-Ci-C4 -alkyl, Ci-C4-haloalkoxycarbonyl-Ci-C4-alkyl. is also optionally substituted by halogen, cyano, nitro, amino, hydroxy, C 1 -C 6 -alkyl, ce-Ce-haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkyl , C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy, C 3 -C 6 -alkenyloxy, C 3 -C 6 -alkynyloxy, C 1 -C 6 -alkoxycarbonyloxy, C 1 -C 6 -alkylamino, C 3 -C 6 -alkenylamino, C 3 -C 6 -alkynylamino, C3-C6-cycloalkylamino, CI-C Ö - alkylthio, Ci-C 6 haloalkylthio, C 3 -C 6 -alkenylthio, C 3 -C 6 -alkinylthio, C 3 -C 6 - cycloalkylthio, Ci-C6-alkylsulfinyl, (Ci-C6-alkyl) aminocarbonyl, CI-C Ö Ci-C6-alkylsulfonyl, Ci-C6-alkylcarbonyl, aminocarbonyl, Ci-C6-alkylaminocarbonyl, di - alkylcarbonylamino substituted phenyl or a radical from the series
Figure imgf000020_0002
Figure imgf000020_0002
C-1 C-2 C-3 C-4  C-1 C-2 C-3 C-4
Figure imgf000020_0003
Figure imgf000020_0003
C-5 C-6 C-1 0 C-1 1  C-5 C-6 C-1 0 C-1 1
Figure imgf000020_0004
Figure imgf000020_0004
C-1 3 C-1 3
Figure imgf000021_0001
Figure imgf000021_0002
Figure imgf000021_0001
Figure imgf000021_0002
C-27 C-31 C-35 C-36 C-27 C-31 C-35 C-36
Figure imgf000021_0003
Figure imgf000021_0003
C-39 C-46 C-49 C-51  C-39 C-46 C-49 C-51
R3 steht auch für einen Rest aus der Reihe R 3 is also out of line for a rest
Figure imgf000021_0004
worin die gestrichelte Linie die Bindung zum Stickstoffatom in der Formel (I) bedeutet. X steht für Sauerstoff, n steht für 2.
Figure imgf000021_0004
wherein the dashed line represents the bond to the nitrogen atom in the formula (I). X is oxygen, n is 2.
R5 steht für einen Rest aus der Reihe Wasserstoff (nur im Rest B-36), Halogen, Cyano, Nitro, Hydroxy, Ci-C4-Alkyl, Ci-C4-Halogenalkyl, Cyano-Ci-C4-alkyl, C2-C4-Alkenyl, C2-C -Alkinyl, C3-C6-Cycloalkyl, C3-C6-Cycloalkyl-Ci-C4-alkyl, Ci-C4-Alkoxy, Ci-C4-Halogenalkoxy, C3-C4- Alkenyloxy, C3-C -Alkinyloxy, C3-C6-Cycloalkyloxy, Ci-C -Alkylsulfinyl, Ci-C -Alkylthio, Ci- C4-Halogenalkylthio, Ci-C4-Alkylsulfonyl, Ci-C4-Alkoxyimino-Ci-C4-alkyl, Aryl, Aryloxy, Heteroaryl und Heteroaryloxy. steht für einen Rest aus der Reihe Wasserstoff, Ci-C4-Alkyl, C3-C6-Cycloalkyl und C1-C4- Halogenalkyl. steht für einen Rest aus der Reihe Wasserstoff, Ci-C4-Alkyl und Ci-C4-Alkoxy-Ci-C4-alkyl, jeweils gegebenenfalls durch Halogen substituiertes Ci-C4-Alkylcarbonyl und C1-C4- Alkylsulfonyl, gegebenenfalls durch Halogen substituiertes Ci-C4-Alkoxycarbonyl, gegebenenfalls durch Halogen, Ci-C4-Alkyl, Ci-C4-Alkoxy, Ci-C4-Halogenalkyl und Cyano substituiertes C3-C6-Cycloalkylcarbonyl, oder für ein Kation, wie beispielsweise ein ein- oder zweiwertiges Metallion oder ein gegebenenfalls durch Ci-C4-Alkyl oder Aryl-Ci-C4-alkyl substituiertes Ammonium-Ion. steht für einen Rest aus der Reihe jeweils gegebenenfalls durch Halogen, Ci-C4-Alkoxy, C1-C4- Halogenalkoxy, Ci-C4-Alkylthio, Ci-C4-Halogenalkylthio, Ci-C4-Alkylsulfinyl, C1-C4- Halogenalkylsulfinyl, Ci-C4-Alkylsulfonyl und Ci-C4-Halogenalkylsulfonyl substituiertes C1-C4- Alkyl, C2-C4-Alkenyl und C2-C4-Alkinyl, jeweils gegebenenfalls durch Halogen, Ci-C4-Alkyl, Ci- C4-Halogenalkyl, Ci-C4-Alkoxy, Ci-C4-Halogenalkoxy substituiertes C3-C6-Cycloalkyl, C3-C6- Cycloalkyl-Ci-C4-alkyl und C3-C4-Cycloalkenyl, in welchen ein oder zwei Ringglieder jeweils durch ein Heteroatom aus der Reihe Schwefel, Sauerstoff (wobei Sauers toffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff ersetzt sein können (und dabei insbesondere für R 5 is (only in the radical B-36), halogen, cyano, nitro, hydroxy, Ci-C4-alkyl, Ci-C alkyl 4 haloalkyl, cyano-Ci-C 4 is a radical selected from hydrogen, C 2 -C 4 alkenyl, C 2 -C alkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 cycloalkyl-Ci-C4-alkyl, Ci-C 4 alkoxy, Ci-C 4 - haloalkoxy, C 3 -C 4 - alkenyloxy, C 3 -C alkynyloxy, C 3 -C 6 cycloalkyloxy, Ci-C alkylsulfinyl, Ci-C alkylthio, Ci- C4-haloalkylthio, Ci-C 4 alkylsulfonyl, C 1 -C 4 -alkoxyimino-C 1 -C 4 -alkyl, aryl, aryloxy, heteroaryl and heteroaryloxy. is a radical selected from the group consisting of hydrogen, C 1 -C 4 -alkyl, C 3 -C 6 -cycloalkyl and C 1 -C 4 -haloalkyl. is a radical from the series consisting of hydrogen, C 1 -C 4 -alkyl and C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, in each case optionally halogen-substituted C 1 -C 4 -alkylcarbonyl and C 1 -C 4 -alkylsulfonyl, optionally substituted by halogen C 1 -C 4 -alkoxycarbonyl, C 3 -C 6 -cycloalkylcarbonyl optionally substituted by halogen, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl and cyano, or a cation, such as, for example, a monovalent or divalent metal ion or an optionally substituted by Ci-C4-alkyl or aryl-Ci-C4-alkyl-substituted ammonium ion. is a radical from the series in each case optionally substituted by halogen, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -haloalkylthio, C 1 -C 4 -alkylsulfinyl, C 1 -C 4 - haloalkylsulfinyl, Ci-C4-alkylsulfonyl and Ci-C4-haloalkylsulfonyl-substituted C 1 -C 4 - alkyl, C 2 -C 4 alkenyl and C 2 -C 4 alkynyl each optionally substituted by halogen, Ci-C 4 alkyl, C - C4-haloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy-substituted C3-C6-cycloalkyl, C3-C6-cycloalkyl-Ci-C4-alkyl and C3-C4-cycloalkenyl, in which one or two ring members each by a Heteroatom from the series sulfur, oxygen (which Sauer may not be directly adjacent toffatome) and nitrogen may be replaced (and in particular for
Figure imgf000022_0001
wobei der Pfeil jeweils die Bindung zum S-Atom in dem Rest (D-l) markiert), jeweils gegebenenfalls durch Halogen, Cyano (auch im Alkylteil), Nitro, Ci-C4-Alkyl, C1-C4- Halogenalkyl, C3-C6-Cycloalkyl, Ci-C4-Alkoxy, Ci-C4-Halogenalkoxy, Ci-C4-Alkylthio, C1-C4- Halogenalkylthio, Ci-C4-Alkylsulfinyl, Ci-C4-Halogenalkylsulfinyl, Ci-C4-Alkylsulfonyl, C1-C4- Halogenalkylsulfonyl, Amino, Ci-C4-Alkylamino, Di-(Ci-C4-alkyl)-amino, C1-C4- Alkylcarbonylamino, Ci-C4-Alkoxycarbonylamino, Ci-C4-Alkoxy-Ci-C4-alkyl, C1-C4- Halogenalkoxy-Ci-C4-alkyl, C2-C4-Alkenyl, C2-C4-Alkinyl, C3-C6-Cycloalkyl-Ci-C4-alkyl, C1-C4- Alkylcarbonyl, Ci-C4-Alkoxycarbonyl oder Aniinocarbonyl substituiertes Aryl, Heteroaryl, Aryl- Ci-C4-alkyl und Heteroaryl-Ci-C4-alkyl oder für NR'R", worin R' und R" unabhängig voneinander für einen Rest aus der Reihe Wasserstoff und Ci-C4-Alkyl stehen. steht für einen Rest aus der Reihe jeweils gegebenenfalls durch Halogen, Ci-C4-Alkoxy, C1-C4- Halogenalkoxy, Ci-C4-Alkylthio, Ci-C4-Halogenalkylthio, Ci-C4-Alkylsulfinyl, C1-C4- Halogenalkylsulfinyl, Ci-C4-Alkylsulfonyl und Ci-C4-Halogenalkylsulfonyl substituiertes C1-C4- Alkyl, C2-C4-Alkenyl und C2-C4-Alkinyl, jeweils gegebenenfalls durch Halogen, Ci-C4-Alkyl, Ci- C4-Halogenalkyl, Ci-C4-Alkoxy, Ci-C4-Halogenalkoxy substituiertes C3-C6-Cycloalkyl, C3-C6- Cycloalkyl-Ci-C4-alkyl und C3-C4-Cycloalkenyl, in welchen ein oder zwei Ringglieder jeweils durch ein Heteroatom aus der Reihe Schwefel, Sauerstoff (wobei Sauers toffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff ersetzt sein können (und dabei insbesondere für
Figure imgf000022_0001
where the arrow in each case the bond to the S atom in the radical (Dl) labeled), in each case optionally halogen-, cyano- (also in the alkyl), nitro, Ci-C 4 alkyl, C 1 -C 4 - haloalkyl, C 3 C6-cycloalkyl, Ci-C 4 alkoxy, Ci-C4-haloalkoxy, Ci-C 4 alkylthio, C 1 -C 4 - haloalkylthio, Ci-C4-alkylsulfinyl, Ci-C4-haloalkylsulfinyl, Ci C 4 alkylsulfonyl, C 1 -C 4 - haloalkylsulfonyl, amino, Ci-C 4 alkylamino, di- (Ci-C 4 alkyl) amino, C 1 -C 4 - alkylcarbonylamino, Ci-C4-alkoxycarbonylamino, Ci -C 4 -alkoxy-C 1 -C 4 -alkyl, C 1 -C 4 -haloalkoxy-C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, C 3 -C 6 -cycloalkyl-C C 4 alkyl, C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl or aniinocarbonyl-substituted aryl, heteroaryl, aryl-C 1 -C 4 -alkyl and heteroaryl-C 1 -C 4 -alkyl or for NR'R ", in which R 'and R "independently of one another represent a radical from the series consisting of hydrogen and C 1 -C 4 -alkyl. 4 -alkoxy represents a radical from the series in each case optionally substituted by halogen, Ci-C, C 1 -C 4 - haloalkoxy, Ci-C4-alkylthio, Ci-C4-haloalkylthio, Ci-C4-alkylsulfinyl, C1-C4 haloalkylsulfinyl , Ci-C4-alkylsulfonyl and Ci-C4-haloalkylsulfonyl-substituted C 1 -C 4 - alkyl, C 2 -C 4 alkenyl and C 2 -C 4 alkynyl each optionally substituted by halogen, Ci-C 4 alkyl , C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, substituted C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkyl-C 1 -C 4 -alkyl and C 3 -C 4 -cycloalkenyl in which one or two ring members are each represented by a heteroatom from the series sulfur, oxygen (which may not be directly adjacent to oxygen atoms) and nitrogen may be replaced (and in particular for
Figure imgf000023_0001
wobei der Pfeil jeweils die Bindung zur C(X)-Gruppe in dem Rest (D-8) markiert), jeweils gegebenenfalls durch Halogen, Cyano (auch im Alkylteil), Nitro, Ci-C4-Alkyl, C1-C4- Halogenalkyl, C3-C6-Cycloalkyl, Ci-C4-Alkoxy, Ci-C4-Halogenalkoxy, Ci-C4-Alkylthio, C1-C4- Halogenalkylthio, Ci-C4-Alkylsulfinyl, Ci-C4-Halogenalkylsulfinyl, Ci-C4-Alkylsulfonyl, C1-C4- Halogenalkylsulfonyl, Amino, Ci-C4-Alkylamino, Di-(Ci-C4-alkyl)-amino, C1-C4- Alkylcarbonylamino, Ci-G Alkoxycarbonylamino, Ci-C4-Alkoxy-Ci-C4-alkyl, C1-C4- Halogenalkoxy-Ci-C4-alkyl, C2-C4-Alkenyl, C2-C4-Alkinyl, C3-C6-Cycloalkyl-Ci-C4-alkyl, C1-C4- Alkylcarbonyl, Ci-C4-Alkoxycarbonyl oder Aminocarbonyl substituiertes Aryl, Heteroaryl, Aryl- Ci-C4-alkyl und Heteroaryl-Ci-C4-alkyl oder für NR'R", worin R' und R" unabhängig voneinander für einen Rest aus der Reihe Wasserstoff und Ci-C4-Alkyl stehen.
Figure imgf000023_0001
wherein the arrow in each case marks the bond to the C (X) group in the radical (D-8)), in each case optionally by halogen, cyano (also in the alkyl part), nitro, C 1 -C 4 -alkyl, C 1 -C 4 - haloalkyl, C 3 -C 6 cycloalkyl, Ci-C 4 alkoxy, Ci-C4-haloalkoxy, Ci-C 4 alkylthio, C 1 -C 4 - haloalkylthio, Ci-C4-alkylsulfinyl, Ci-C4-haloalkylsulfinyl, C 1 -C 4 -alkylsulfonyl, C 1 -C 4 -haloalkylsulfonyl, amino, C 1 -C 4 -alkylamino, di- (C 1 -C 4 -alkyl) amino, C 1 -C 4 -alkylcarbonylamino, C 1 -C 4 -alkoxycarbonylamino, C 1 -C 4 -alkyl alkoxy-Ci-C4-alkyl, C1-C4-haloalkoxy-Ci-C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 6 cycloalkyl-Ci-C4- -alkyl, C 1 -C 4 -alkylcarbonyl, C 1 -C 4 -alkoxycarbonyl or aminocarbonyl-substituted aryl, heteroaryl, aryl-C 1 -C 4 -alkyl and heteroaryl-C 1 -C 4 -alkyl or for NR'R ", in which R 'and R "independently of one another represent a radical from the series of hydrogen and C 1 -C 4 -alkyl.
Ganz besonders bevorzugte Substituenten bzw. Bereiche der in den Verbindungen der Formel (I) aufgeführten Reste werden im Folgenden erläutert. Very particularly preferred substituents or ranges of the radicals listed in the compounds of the formula (I) are explained below.
A steht für A stands for
Figure imgf000023_0002
Figure imgf000023_0002
A-h Ah
B steht für B stands for
Figure imgf000023_0003
Figure imgf000023_0003
B-1 R1 steht für Chlor. B-1 R 1 is chlorine.
R2 steht für Wasserstoff. R 2 is hydrogen.
R3 steht für den Rest der Formel
Figure imgf000024_0001
R4 steht für Ci-C4-Alkylthio-Ci-C4-alkyl oder für gegebenenfalls durch einen oder zwei Reste aus der Reihe Halogen, Nitro und Ci-C4-Halogenalkyl substituiertes Phenyl. R 3 represents the remainder of the formula
Figure imgf000024_0001
R 4 stands for Ci-C4-alkylthio-Ci-C 4 -alkyl or optionally substituted by one or two radicals from the series halogen, nitro and Ci-C4-haloalkyl substituted phenyl.
Wenn in obigen Definitionen in Ringen Schwefel und/oder Stickstoff vorkommen, wie beispielsweise in Ausdrücken wie„in welchen die Ringe mindestens ein Heteroatom aus der Reihe Schwefel, Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff enthalten können" oder „in welchen ein oder zwei Ringglieder jeweils durch ein Heteroatom aus der Reihe Schwefel, Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff ersetzt sein können", dann kann, sofern nichts anderes angegeben ist, der Schwefel auch als SO oder SO2 vorliegen, der Stickstoff, sofern er nicht als -N= vorliegt, neben NH auch als N-Alkyl (insbesondere N-Ci-C6-Alkyl) vorliegen. In den breitesten und den bevorzugten Definitionen ist, sofern nichts anderes angegeben ist, When sulfur and / or nitrogen occur in the above definitions in rings, as for example in terms such as "in which the rings may contain at least one heteroatom selected from sulfur, oxygen (oxygen atoms may not be immediately adjacent) and nitrogen" or "in which one or two ring members each may be replaced by a heteroatom selected from the group consisting of sulfur, oxygen (where oxygen atoms are not immediately adjacent) and nitrogen ", then, unless otherwise indicated, the sulfur may also be present as SO or SO 2 , which Nitrogen, if it is not present as -N =, in addition to NH also as N-alkyl (especially N-Ci-C6-alkyl) are present. In the broadest and preferred definitions, unless otherwise stated,
Halogen ausgewählt aus der Reihe Fluor, Chlor, Brom und Iod, bevorzugt wiederum aus der Reihe Fluor, Chlor und Brom, Halogen selected from the group fluorine, chlorine, bromine and iodine, preferably again from the series fluorine, chlorine and bromine,
Aryl (auch als Teil einer größeren Einheit, wie beispielsweise Arylalkyl) ausgewählt aus der Reihe Phenyl, Naphthyl, Anthryl, Phenanthrenyl und steht wiederum bevorzugt für Phenyl, Hetaryl (gleichbedeutend mit Heteroaryl, auch als Teil einer größeren Einheit, wie beispielsweise Hetarylalkyl) ausgewählt aus der Reihe Furyl, Thienyl, Pyrrolyl, Pyrazolyl, Imidazolyl, 1,2,3-Triazolyl, 1 ,2,4-Triazolyl, Oxazolyl, Isoxazolyl, Thiazolyl, Isothiazolyl, 1,2,3-Oxadiazolyl, 1 ,2,4-Oxadiazolyl, 1,3,4-Oxadiazolyl, 1,2,5-Oxadiazolyl, 1,2,3-Thiadiazolyl, 1 ,2,4-Thiadiazolyl, 1,3,4-Thiadiazolyl, 1,2,5- Thiadiazolyl, Pyridyl, Pyrimidinyl, Pyridazinyl, Pyrazinyl, 1,2,3-Triazinyl, 1 ,2,4-Triazinyl, 1,3,5- Triazinyl, Benzofuryl, Benzisofuryl, Benzothienyl, Benzisothienyl, Indolyl, Isoindolyl, Indazolyl, Benzothiazolyl, Benzisothiazolyl, Benzoxazolyl, Benzisoxazolyl, Benzimidazolyl, 2,1,3- Benzoxadiazole, Chinolinyl, Isochinolinyl, Cinnolinyl, Phthalazinyl, Chinazolinyl, Chinoxalinyl, Naphthyridinyl, Benzotriazinyl, Purinyl, Pteridinyl und Indolizinyl. Aryl (also as part of a larger unit, such as arylalkyl) selected from the group phenyl, naphthyl, anthryl, phenanthrenyl and in turn preferably represents phenyl, hetaryl (equivalent to heteroaryl, also as part of a larger unit, such as hetarylalkyl) selected from the series furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1, 2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1, 2,4- Oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1, 2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, Pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1, 2,4-triazinyl, 1,3,5-triazinyl, benzofuryl, benzisofuryl, benzothienyl, benzisothienyl, indolyl, isoindolyl, indazolyl, benzothiazolyl, benzisothiazolyl, Benzoxazolyl, benzisoxazolyl, benzimidazolyl, 2,1,3-benzoxadiazoles, quinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl , Benzotriazinyl, purinyl, pteridinyl and indolizinyl.
In den besonders bevorzugten Definitionen ist, sofern nichts anderes angegeben ist, „„ In the particularly preferred definitions, unless stated otherwise, ""
- 24 - - 24 -
Halogen ausgewählt aus der Reihe Fluor, Chlor, Brom und lod, bevorzugt wiederum aus der Reihe Fluor, Chlor und Brom, Halogen selected from the group fluorine, chlorine, bromine and iodine, preferably in turn from the series fluorine, chlorine and bromine,
Aryl (auch als Teil einer größeren Einheit, wie beispielsweise Arylalkyl) ausgewählt aus der Reihe Phenyl, Naphthyl, Anthryl, Phenanthrenyl und steht wiederum bevorzugt für Phenyl, Hetaryl (auch als Teil einer größeren Einheit, wie beispielsweise Hetarylalkyl) ausgewählt aus der Reihe Furyl, Thienyl, Pyrrolyl, Pyrazolyl, Imidazolyl, 1,2,3-Triazolyl, 1 ,2,4-Triazolyl, Oxazolyl, Isoxazolyl, Thiazolyl, Isothiazolyl, 1,2,3-Oxadiazolyl, 1 ,2,4-Oxadiazolyl, 1,3,4-Oxadiazolyl, 1,2,5-Oxadiazolyl, 1,2,3-Thiadiazolyl, 1 ,2,4-Thiadiazolyl, 1,3,4-Thiadiazolyl, 1,2,5-Thiadiazolyl, Pyridyl, Pyrimidinyl, Pyridazinyl, Pyrazinyl, 1,2,3-Triazinyl, 1 ,2,4-Triazinyl, 1,3,5-Triazinyl. Durch Halogen substituierte Reste, z.B. Haloalkyl (= Halogenalkyl), sind einfach oder mehrfach bis zur maximal möglichen Substituentenzahl halogeniert. Bei mehrfacher Halogenierung können die Halogenatome gleich oder verschieden sein. Halogen steht dabei für Fluor, Chlor, Brom und lod, insbesondere für Fluor, Chlor und Brom. Aryl (also as part of a larger unit, such as, for example, arylalkyl) selected from among phenyl, naphthyl, anthryl, phenanthrenyl and in turn preferably represents phenyl, hetaryl (also as part of a larger unit, such as, for example, hetarylalkyl) selected from the series furyl, Thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1, 2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3-oxadiazolyl, 1, 2,4-oxadiazolyl, 1, 3,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1, 2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyrimidinyl, Pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1, 2,4-triazinyl, 1,3,5-triazinyl. Halogen substituted radicals, e.g. Haloalkyl (= haloalkyl) are halogenated once or several times up to the maximum possible number of substituents. For multiple halogenation, the halogen atoms may be the same or different. Halogen stands for fluorine, chlorine, bromine and iodine, in particular fluorine, chlorine and bromine.
Gesättigte oder ungesättigte Kohlenwasserstoffreste wie Alkyl oder Alkenyl können, auch in Verbin- dung mit Heteroatomen, wie z.B. in Alkoxy, soweit möglich, jeweils geradkettig oder verzweigt sein. Saturated or unsaturated hydrocarbon radicals, such as alkyl or alkenyl, may also be used in conjunction with heteroatoms, e.g. in alkoxy, as far as possible, in each case straight-chain or branched.
Gegebenenfalls substituierte Reste können einfach oder mehrfach substituiert sein, wobei bei Mehrfachsubstitutionen die Substituenten gleich oder verschieden sein können. Optionally substituted radicals may be monosubstituted or polysubstituted, with multiple substituents the substituents may be the same or different.
Als Metallionen im Rest R8 kommen beispielsweise Alkalimetallionen wie Li+, Na+, Cs+ und K+ und Erdalkalimetallionen wie Mg++ und Ca++ in Frage. Die oben aufgeführten allgemeinen oder in Vorzugsbereichen aufgeführten Restedefinitionen bzw. Erläuterungen gelten für die Endprodukte (auch für die Verbindungen der später aufgeführten Formeln (I-A) bis (I-M)) und für die Ausgangsprodukte und Zwischenprodukte entsprechend. Diese Restedefinitionen können untereinander, also auch zwischen den jeweiligen Vorzugsbereichen, beliebig kombiniert werden. Erfindungsgemäß bevorzugt werden Verbindungen der Formel (I), in welchen eine Kombination der vorstehend als bevorzugt aufgeführten Bedeutungen vorliegt. Suitable metal ions in the radical R 8 are, for example, alkali metal ions such as Li + , Na + , Cs + and K + and alkaline earth metal ions such as Mg ++ and Ca ++ . The abovementioned general or preferred radical definitions or explanations apply to the end products (also for the compounds of the formulas (IA) to (IM) listed below) and correspondingly to the starting materials and intermediates. These remainder definitions can be combined with one another as desired, ie also between the respective preferred ranges. Preference according to the invention is given to compounds of the formula (I) which contain a combination of the meanings listed above as being preferred.
Erfindungsgemäß besonders bevorzugt werden Verbindungen der Formel (I), in welchen eine Kombination der vorstehend als besonders bevorzugt aufgeführten Bedeutungen vorliegt. Particular preference according to the invention is given to compounds of the formula (I) in which a combination of the meanings listed above as being particularly preferred is present.
Erfindungsgemäß ganz besonders bevorzugt werden Verbindungen der Formel (I), in welchen eine Kombination der vorstehend als ganz besonders bevorzugt aufgeführten Bedeutungen vorliegt. In einer bevorzugten Ausführungsform betrifft die Erfindung Verbindungen der Formel (I-A)
Figure imgf000026_0001
Very particular preference according to the invention is given to compounds of the formula (I) which contain a combination of the meanings given above as being very particularly preferred. In a preferred embodiment, the invention relates to compounds of the formula (IA)
Figure imgf000026_0001
In einer weiteren bevorzugten Ausführungsform betrifft die Erfindung Verbindungen der Formel (I-B)
Figure imgf000026_0002
In a further preferred embodiment, the invention relates to compounds of the formula (IB)
Figure imgf000026_0002
einer weiteren bevorzugten Ausführungsform betrifft die Erfindung Verbindungen der Formel (I-C)
Figure imgf000026_0003
In a further preferred embodiment, the invention relates to compounds of the formula (IC)
Figure imgf000026_0003
In einer weiteren bevorzugten Ausführungsform betrifft die Erfindung Verbindungen der Formel (I-D)
Figure imgf000026_0004
In a further preferred embodiment, the invention relates to compounds of the formula (ID)
Figure imgf000026_0004
In einer weiteren bevorzugten Ausführungsform betrifft die Erfindung Verbindungen der Formel (I-E)
Figure imgf000027_0001
In a further preferred embodiment, the invention relates to compounds of the formula (IE)
Figure imgf000027_0001
In einer weiteren bevorzugten Ausführungsform betrifft die Erfindung Verbindungen der Formel (I-F)
Figure imgf000027_0002
In a further preferred embodiment, the invention relates to compounds of the formula (IF)
Figure imgf000027_0002
In einer weiteren bevorzugten Ausführungsform betrifft die Erfindung Verbindungen der Formel (I-G)
Figure imgf000027_0003
In a further preferred embodiment, the invention relates to compounds of the formula (IG)
Figure imgf000027_0003
In einer weiteren bevorzugten Ausführungsform betrifft die Erfindung Verbindungen der Formel (I-H)
Figure imgf000027_0004
In a further preferred embodiment, the invention relates to compounds of the formula (IH)
Figure imgf000027_0004
In einer weiteren bevorzugten Ausführungsform betrifft die Erfindung Verbindungen der Formel (I-J) In a further preferred embodiment, the invention relates to compounds of the formula (I-J)
Figure imgf000027_0005
^
Figure imgf000027_0005
^
In einer weiteren bevorzugten Ausführungsform betrifft die Erfindung Verbindungen der Formel (I-K) In a further preferred embodiment, the invention relates to compounds of the formula (I-K)
Figure imgf000028_0001
Figure imgf000028_0001
In einer weiteren bevorzugten Ausführungsform betrifft die Erfindung Verbindungen der Formel (I-L) In a further preferred embodiment, the invention relates to compounds of the formula (I-L)
Figure imgf000028_0002
einer weiteren bevorzugten Ausführungsform betrifft die Erfindung Verbindungen der Formel (I-M)
Figure imgf000028_0002
In a further preferred embodiment, the invention relates to compounds of the formula (III)
Figure imgf000028_0003
Figure imgf000028_0003
In den Formeln (I-A) bis (I-M) haben die Reste R, R1, R2 und R3 die weiter oben genannten Bedeutungen. In the formulas (IA) to (IM), the radicals R, R 1 , R 2 and R 3 have the meanings mentioned above.
Die erfindungsgemäßen Verbindungen der Formel (I) und deren Säureadditionssalze und Metallsalz- komplexe besitzen gute Wirksamkeit, insbesondere zur Bekämpfung von tierischen Schädlingen, zu denen Arthropoden und insbesondere Insekten zählen. The compounds of the formula (I) according to the invention and their acid addition salts and metal salt complexes have good activity, in particular for controlling animal pests, which include arthropods and in particular insects.
Die Verbindungen der Formel (I) können gegebenenfalls auch in Abhängigkeit von der Art der Substituenten als Stereoisomere, d.h. als geometrische und/oder als optische Isomere oder Isomerengemische vorliegen in unterschiedlichen Zusammensetzungen vorliegen. Sowohl die reinen Stereoisomeren als auch beliebige Gemische dieser Isomeren sind Gegenstand dieser Erfindung, auch wenn hier im Allgemeinen nur von Verbindungen der Formel (I) die Rede ist. The compounds of formula (I) may also be optionally substituted as stereoisomers, i.e., depending on the nature of the substituents. as geometric and / or as optical isomers or mixtures of isomers are present in different compositions. Both the pure stereoisomers and any mixtures of these isomers are the subject of this invention, although in general only compounds of the formula (I) are mentioned here.
Die erfindungsgemäßen Verbindungen der Formel (I) können in verschiedenen polymorphen Formen oder als Mischung verschiedener polymorpher Formen vorliegen. Sowohl die reinen Polymorphe als auch die Polymorphgemische sind Gegenstand der Erfindung und können erfindungsgemäß verwendet werden. The compounds of the formula (I) according to the invention can be present in different polymorphic forms or as a mixture of different polymorphic forms. Both the pure polymorphs and the polymorph mixtures are the subject of the invention and can be used according to the invention.
Vorzugsweise werden jedoch die optisch aktiven, stereoisomeren Formen der Verbindungen der Formel (I) und deren Salze erfindungsgemäß verwendet. Die Erfindung betrifft daher sowohl die reinen Enantiomeren und Diastereomeren, als auch deren Gemische zur Bekämpfung von tierischen Schädlingen, zu denen Arthropoden und insbesondere Insekten zählen. Preferably, however, the optically active stereoisomeric forms of the compounds of the formula (I) and salts thereof are used according to the invention. The invention therefore relates to both the pure enantiomers and diastereomers, as well as their mixtures for controlling animal pests, which include arthropods and in particular insects.
Als geeignete Salze der Verbindungen der allgemeinen Formel (I) können übliche nicht toxische Salze, d. h. Salze mit entsprechenden Basen und Salze mit zugesetzten Säuren genannt werden. Vorzugsweise sind Salze mit anorganischen Basen, wie Alkalimetallsalze, beispielsweise Natrium-, Kalium- oder Cäsiumsalze, Erdalkalimetallsalze, beispielsweise Calzium- oder Magnesiumsalze, Ammoniumsalze, Salze mit organischen Basen sowie mit anorganischen Aminen, beispielsweise Triethylammonium-, Dicyclohexylammonium-, Ν,Ν'-Dibenzylethylendiammonium-, Pyridinium-, Picolinium- oder Ethanolammoniumsalze, Salze mit anorganischen Säuren, beispielsweise Hydrochloride, Hydrobromide, Dihydrosulfate, Trihydrosulfate, oder Phosphate, Salze mit organischen Carbonsäuren oder organischen Sulfosäure, beispielsweise Formiate, Acetate, Trifluoracetate, Maleate, Tartrate, Methansulfonate, Benzolsulfonate oder para-Toluolsulfonate, Salze mit basischen Aminosäuren, beispielsweise Arginate, Aspartate oder Glutamate und Ähnliches zu nennen. Die erfindungsgemässen Verbindungen der Formel (I) können nach üblichen, dem Fachmann bekannten Methoden hergestellt werden. Verschiedene Herstellungsmethoden, die gleichfalls Gegenstand der Erfindung sind, sind in den folgenden Reaktionsschemata I-IV beschrieben,. Suitable salts of the compounds of general formula (I) may be conventional non-toxic salts, i. H. Salts with corresponding bases and salts with added acids. Preferably, salts with inorganic bases, such as alkali metal salts, for example sodium, potassium or cesium salts, alkaline earth metal salts, for example calcium or magnesium salts, ammonium salts, salts with organic bases and with inorganic amines, for example triethylammonium, dicyclohexylammonium, Ν, Ν'- Dibenzylethylenediammonium, pyridinium, picolinium or ethanolammonium salts, salts with inorganic acids, for example hydrochlorides, hydrobromides, dihydrosulfates, trihydrosulfates, or phosphates, salts with organic carboxylic acids or organic sulfonic acid, for example formates, acetates, trifluoroacetates, maleates, tartrates, methanesulfonates, benzenesulfonates or para-toluenesulfonates, salts with basic amino acids, for example arginates, aspartates or glutamates, and the like. The novel compounds of the formula (I) can be prepared by customary methods known to the person skilled in the art. Various preparation methods, which are also the subject of the invention, are described in the following Reaction Schemes I-IV.
Verbindungen der Formel (I), in denen der Heterocyclus A für gegegebenenfalls mit einem Rest R substituiertes Pyrazol-4-yl (A-a), Isothiazol-4-yl (A-b), Isoxazol-4-yl (A-c) oder Pyrazin-2-yl (A-h) steht, und der Heterocyclus B für N-Pyrazol-l-yl, das in 3-Position mit einem Rest R1 substituiert ist (B- 1), steht, können beispielsweise nach den Methoden A und B gemäss Reaktionsschema I dargestellt werden. Compounds of the formula (I) in which the heterocycle A is optionally substituted by an R radical substituted pyrazol-4-yl (Aa), isothiazol-4-yl (Ab), isoxazol-4-yl (Ac) or pyrazine-2 yl (Ah), and the heterocycle B is N-pyrazol-1-yl, which is substituted in the 3-position by a radical R 1 (B-1), can, for example, according to the methods A and B according to Reaction Scheme I. being represented.
Reaktionsschema I Reaction scheme I
Figure imgf000030_0001
Figure imgf000030_0001
Im Reaktionsschema I haben A, R1, R2 und R3 die oben genannten Bedeutungen. N-Pyrazol-l-yl steht für B, LG steht für eine gegebenenfalls in-situ erzeugte nucleofuge Abgangsgruppe ("Leaving Group") und PG bedeutet Schutzgruppe („Protection Group"). Beispielsweise können heterocyclische Verbindungen der Formel (A-l), die entweder Halogensubstituiert sind (LG = Cl, Br, I) oder eine andere geeignete Abgangsgruppe LG besitzen (z. B. LG = O- SO2CF3, O-SO2CH3), nach Methode A (vgl. Mini-Reviews in Organic Chemistry 2008, 5, 323-330; Molecules 2009, 14, 5169-5178; Pyrazol: Eur. J. Org. Chem. 2004, 4, 695-709) mit den entsprechenden 3-substituierten Pyrazolen der Formel (A-2) in Gegenwart geeigneter Katalysatoren aus der Reihe der Übergangsmetallsalze in einem ersten Reaktionsschritt zu Verbindungen der Formel (A-3) umgesetzt werden, die dann in einem zweiten Reaktionsschritt in 4-Position unter Bildung der Verbindungen (A-4) nitriert werden. In Reaction Scheme I, A, R 1 , R 2 and R 3 have the meanings given above. N-pyrazol-1-yl is B, LG is an in situ generated nucleofuge leaving group and PG is a protection group, for example heterocyclic compounds of the formula (A1), are either halogen-substituted (LG = Cl, Br, I) or have another suitable leaving group LG (eg LG = O-SO 2 CF 3, O-SO 2 CH 3), according to Method A (see Mini-Reviews in Organic Chemistry 2008, 5 , 323-330; Molecules 2009, 14, 5169-5178; pyrazole: Eur. J. Org. Chem. 2004, 4, 695-709) with the corresponding 3-substituted pyrazoles of the formula (A-2) in the presence of suitable catalysts from the series of transition metal salts in a first reaction step to compounds of formula (A-3) are reacted, which are then nitrated in a second reaction step in the 4-position to form the compounds (A-4).
Wird bei dem erfindungsgemäßen Verfahren zur Herstellung der neuen Verbindungen der Formel (I-D) nach Methode A als Verbindung der Formel (A-l) das 2-Iodpyrazin (A = Pyrazin-2-yl, LG = I) und als Verbindung der Formel (A-2) 3-Chlor-lH-pyrazol (R1 = Cl) eingesetzt, so entsteht zunächst 2-(3-Chlor- lH-pyrazol-l-yl)-pyrazin (A = Pyrazin-2-yl, R1 = Cl). Nachfolgende Nitrierung führt dann zu 2-(3- Chlor-4-nitro-lH-pyrazol-l-yl)-pyrazin (A-4, A = Pyrazin-2-yl, R1 = Cl), das in einem zweiten Reaktionsschritt zu 2-(3-Chlor-4-amino-lH-pyrazol-l-yl)-pyrazin (A-5, A = Pyrazin-2-yl, R1 = Cl) reduziert wird (vgl. auch I-A bis I-D sowie Her Stellungsbeispiele, Beispiel 1, Stufen 1 bis 3). 3Q If, in the process according to the invention for the preparation of the novel compounds of the formula (ID) according to Method A, the compound of the formula (A1) is 2-iodopyrazine (A = pyrazine-2-yl, LG = I) and as compound of the formula (A) 2) 3-chloro-lH-pyrazole (R 1 = Cl) is used, the result is first 2- (3-chloro-1H-pyrazol-1-yl) pyrazine (A = pyrazine-2-yl, R 1 = Cl ). Subsequent nitration then results in 2- (3-chloro-4-nitro-1H-pyrazol-1-yl) -pyrazine (A-4, A = pyrazine-2-yl, R 1 = Cl), which in a second reaction step to 2- (3-chloro-4-amino-1H-pyrazol-1-yl) -pyrazine (A-5, A = pyrazine-2-yl, R 1 = Cl) is reduced (see also IA to ID and Her Example Examples, Example 1, Steps 1 to 3). 3Q
Nitrierungen sind nach üblichen Verfahren, wie sie beispielsweise in Houben-Weyl, Methoden der Organischen Chemie, Band XI/2 (Georg Thieme Verlag Stuttgart 1958), S. 99-116 beschrieben sind, durchführbar. Als Nitrierungsreagenzien seien rauchende oder 100 ige Salpetersäure gegebenenfalls in Gegenwart von Schwefelsäure (M. J. Middleton et al., /. Heterocyclic Chem. 1970, 7, S. 1045-1049; L. W. Deady et al. Aust. J. Chem. 1982, 35 (10), S. 2025-2034; EP 0192060) oder die Verwendung von Salpetersäureestern, Acylnitrat oder Nitroniumtetrafluoroborat genannt. Nitrations can be carried out by customary processes, as described, for example, in Houben-Weyl, Methods of Organic Chemistry, Volume XI / 2 (Georg Thieme Verlag Stuttgart 1958), pages 99-116. Suitable nitrating reagents are fuming or 100% nitric acid, optionally in the presence of sulfuric acid (MJ Middleton et al., / Heterocyclic Chem. 1970, 7, pp. 1045-1049, LW Deady et al., Aust. J. Chem. 10), pp 2025-2034; EP 0192060) or the use of nitric acid esters, acyl nitrate or nitronium tetrafluoroborate.
Zur Durchführung der Nitrierung werden als Nitrierungsagenzien bevorzugt rauchende oder 98- 100 ige Salpetersäure in Gegenwart von Schwefelsäure eingesetzt (vgl. Herstellungsbeispiel 1, Stufe 2). Die Reduktion (Hydrogenolyse) der Verbindungen (A-4) führt zu den Verbindungen der Formel (A-5), die dann zu Verbindungen der Formel (I) umgesetzt werden können. To carry out the nitration, preference is given to using fuming or 98-100% nitric acid in the presence of sulfuric acid as nitrating agents (compare Preparation Example 1, Stage 2). The reduction (hydrogenolysis) of the compounds (A-4) leads to the compounds of the formula (A-5), which can then be converted to compounds of the formula (I).
Besonders bevorzugt ist die Hydrogenolyse von Verbindungen der Formel (A-4) in Gegenwart eines Hydrierkatalysators. Particularly preferred is the hydrogenolysis of compounds of formula (A-4) in the presence of a hydrogenation catalyst.
Als Katalysatoren zur Durchführung der katalytischen Hydrierung kommen alle üblichen Hydrierkatalysatoren in Frage, beispielsweise Platin-Katalysatoren (Platin-Platte, Platin-Schwamm, Platin-Schwarz, kolloidales Platin, Platinoxid, Platindraht usw.), Palladium-Katalysatoren (beispielsweise Palladium-Schwamm, Palladium-Schwarz, Palladiumoxid, Palladium-Kohle, kolloidales Palladium, Palladium-Bariumsulfat, Palladium-Bariumkarbonat, Palladium-Hydroxid usw.), Ruthenium- Katalysatoren, Cobalt-Katalysatoren (beispielsweise reduziertes Cobalt, Raney Cobalt usw.), Kupfer- Katalysatoren (beispielsweise reduziertes Kupfer, Raney-Kupfer, Ullman-Kupfer usw.). Vorzugsweise verwendet man jedoch Edelmetall-Katalysatoren, beispielsweise Platin- und Palladium- oder Ruthenium-Katalysatoren, gegebenenfalls auf einem geeigneten Träger wie Kohlenstoff oder Silizium. Suitable catalysts for carrying out the catalytic hydrogenation are all customary hydrogenation catalysts, for example platinum catalysts (platinum plate, platinum sponge, platinum black, colloidal platinum, platinum oxide, platinum wire, etc.), palladium catalysts (for example palladium sponge, Palladium black, palladium oxide, palladium-carbon, colloidal palladium, palladium-barium sulfate, palladium-barium carbonate, palladium hydroxide, etc.), ruthenium catalysts, cobalt catalysts (e.g., reduced cobalt, Raney cobalt, etc.), copper catalysts ( for example, reduced copper, Raney copper, Ullman copper, etc.). However, preference is given to using noble metal catalysts, for example platinum and palladium or ruthenium catalysts, if appropriate on a suitable support such as carbon or silicon.
Als Hydrierkatalysatoren finden vorzugsweise Palladium- oder Platin-Katalysatoren Verwendung, insbesondere Palladium-Hydroxyd-Kohle oder Platinoxid (vgl. Herstellungsbeispiel 1, Stufe 3). Alternativ können auch die heterocyclischen Verbindungen der Formel (A-l) mit 3-substituierten Pyrazolen der Formel (A-6) nach Methode B in einem ersten Reaktionsschritt zu Verbindungen der Formel (A-7) umgesetzt werden, die dann entweder in einem zweiten Reaktionsschritt unter Entfernung der Schutzgruppe PG zu Verbindungen der Formel (A-5) oder gleich zu Verbindungen der Formel (I-A bis I-D) umgesetzt werden können. Die Verbindungen der Formel (A-l) sind teilweise bekannt bzw. können nach im Prinzip bekannten Herstellungsverfahren erhalten werden, vgl. beispielsweise für A-LG = 2-(Tributylstannyl)-pyrazin (LG = Sn(«-Butyl)3 (WO 2000/024745 AI); Pyrazin-2-yl-boronsäure (LG = B(OH)2) oder 2-(4,4,5,5- Tetramethyl-l,3,2-dioxaborolan-2-yl)-pyrazin (LG = B[-OC(CH3)2 C(CH3)20-]) (beide kommerziell erhältlich); 2-Iodpyrazin (LG = I; WO 2009/114313 A2), 2-Brompyrazin (LG = Br; US-Pat. 2403710) oder 2-Chlorpyrazin (LG = Cl; US-Pat. 2391745); 4-(4,4,5,5-Tetramethyl-l ,3,2-dioxaborolan-2-yl)- isothiazol (LG = B[-OC(CH3)2C(CH3)20-] ; kommerziell erhältlich), 4-(5,5-Dimethyl-l ,3,2- dioxaborinan-2-yl)-isothiazol (LG = B[-OCH2 C(CH3)2CH20-], WO 2002/076983); 4-Iodisothiazol (LG = I; D. W. Brown, M. Sainsbury, Science of Synthesis 11 , 507-572, 2002), 4-Bromisothiazol (LG = Br) oder 4-Chlorisothiazol (LG = Cl; I. F. Huebenett et al., Angew. Chem. 75 (24), 1189-1193, 1963); Isoxazol-4-yl-boronsäure (LG = B(OH)2, WO 2009/087212) oder 4-(4,4,5,5-Tetramethyl-l ,3,2- dioxaborolan-2-yl)-isoxazol (LG = B [-OC(CH3)2C(CH3)20-], J. Velcicky et al., . Amer. Chem. Soc. 133 (18), 6948-6952, 2011); 4-Iodisoxazol (LG = I; WO 2005/019211 A2), 4-Bromisoxazol (LG = Br; B. J. Wakefield, Science of Synthesis 11 , 229-288, 2002); 4-(Tributylstannyl)-lH-pyrazol (LG = Sn(n- Butyl)3) und l-Ethyl-4-(tributylstannyl)-lH-pyrazol (LG = Sn(«-Butyl)3) (WO 95/22545 AI), (1H- Pyrazol-4-yl)-boronsäure (LG = B(OH)2, WO 2004/081008 AI) oder 4-(4,4,5,5-Tetramethyl-l ,3,2- dioxaborolan-2-yl)-lH-pyrazol (LG = B [-OC(CH3)2C(CH3)20-], WO 2000/027853 AI), ( 1 -Methyl- 1H- pyrazol-4-yl)-boronsäure (LG = B(OH)2,WO 2005/063755 AI) oder l-Methyl-4-(4,4,5,5-tetramethyl- l ,3,2-dioxaborolan-2-yl)-lH-pyrazol (LG = B[-OC(CH3)2C(CH3)20-], WO 2005/ 085227 AI), 1- Cyclopropyl-4-(4,4,5,5-tetramethyl-l ,3,2-dioxaborolan-2-yl)-lH-pyrazol (LG = B[-The hydrogenation catalysts used are preferably palladium or platinum catalysts, in particular palladium-hydroxide-carbon or platinum oxide (cf., Preparation Example 1, Step 3). Alternatively, the heterocyclic compounds of the formula (Al) with 3-substituted pyrazoles of the formula (A-6) according to method B in a first reaction step to compounds of formula (A-7) are reacted, which then either in a second reaction step Removal of the protective group PG to compounds of formula (A-5) or equal to compounds of formula (IA to ID) can be implemented. The compounds of the formula (A1) are known in some cases or can be obtained by production processes known in principle, cf. for example, for A-LG = 2- (tributylstannyl) pyrazine (LG = Sn (--butyl) 3 (WO 2000/024745 A1); pyrazine-2-ylboronic acid (LG = B (OH) 2 ) or 2- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) pyrazine (LG = B [-OC (CH 3) 2 C (CH 3) 20-]) (both commercially available available); 2-iodopyrazine (LG = I; WO 2009/114313 A2), 2-bromopyrazine (LG = Br; US Pat. No. 2403710) or 2-chloropyrazine (LG = Cl; US Pat. No. 2391745); 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -isothiazole (LG = B [-OC (CH 3 ) 2 C (CH 3 ) 2 O-]; commercial available), 4- (5,5-dimethyl-1,3,2-dioxaborinan-2-yl) isothiazole (LG = B [-OCH 2 C (CH 3 ) 2 CH 2 O-], WO 2002/076983 ); 4-iodoisothiazole (LG = I, DW Brown, M. Sainsbury, Science of Synthesis 11, 507-572, 2002), 4-bromoisothiazole (LG = Br) or 4-chloroisothiazole (LG = Cl, IF Huebenett et al. Angew. Chem. 75 (24), 1189-1193, 1963); Isoxazol-4-ylboronic acid (LG = B (OH) 2 , WO 2009/087212) or 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -isoxazole ( LG = B [-OC (CH 3 ) 2 C (CH 3 ) 2 O-], J. Velcicky et al., Amer. Chem. Soc., 133 (18), 6948-6952, 2011); 4-iodoisoxazole (LG = I, WO 2005/019211 A2), 4-bromoisoxazole (LG = Br; BJ Wakefield, Science of Synthesis 11, 229-288, 2002); 4- (tributylstannyl) -1H-pyrazole (LG = Sn (n-butyl) 3) and 1-ethyl-4- (tributylstannyl) -1H-pyrazole (LG = Sn (--butyl) 3 ) (WO 95/22545 Al), (1H-pyrazol-4-yl) -boronic acid (LG = B (OH) 2 , WO 2004/081008 Al) or 4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane -2-yl) -LH-pyrazole (LG = B [-OC (CH 3 ) 2 C (CH 3 ) 2 O-], WO 2000/027853 Al), (1-methyl-1H-pyrazol-4-yl ) -boronic acid (LG = B (OH) 2 , WO 2005/063755 Al) or 1-methyl-4- (4,4,5,5-tetramethyl-1, 3,2-dioxaborolan-2-yl) -H pyrazole (LG = B [-OC (CH 3 ) 2 C (CH 3 ) 2 O-], WO 2005/085227 Al), 1-cyclopropyl-4- (4,4,5,5-tetramethyl-1, 3,2-dioxaborolan-2-yl) -LH-pyrazole (LG = B [¢
OC(CH3)2C(CH3)20-] , WO 2009/091374 A2), 4-Iod-lH-pyrazol (LG = I; WO 2010/083283), 4-Brom- lH-pyrazol (LG = Br; WO 2010/018481); 4-Iod-l-methyl-lH-pyrazol (LG = I; WO2001/034137 A2), 4-Brom-l -methyl-lH-pyrazol (LG = Br; WO 93/21186 AI); l-Cyclopropyl-4-iod-lH-pyrazole (LG = I; WO 2010/090290 AI), l-(Difluoromethyl)-4-iod-lH-pyrazol oder 4-Iod-(l ,l ,2,2-tetrafluoroethal)-lH- pyrazol (LG = I; WO 2008/088692 A2); Pyridazin-4-yl-boronsäure (LG = B(OH)2, WO 2009/155527 A2) oder 2-(4,4,5,5-Tetramethyl-l ,3,2-dioxaborolan-4-yl)-pyridazin (LG = B[-OC(CH3)2C(CH3)20-]), M. Helm et al., Angew. Chem. Int. Ed. 44 (25), 3889-3892, 2005); 4-Iodpyridazin (LG = I; A. Seggio et al., . Org. Chem. 72 (17), 6602-6605, 2007), 4-Brompyridazin (LG = I; JP 63250385 A), 4- (Tributylstannyl)-pyridazin (LG = Sn(«-Butyl)3 (WO 2001/023383 AI); 4-Pyrid-4-yl-boronsäure (LG = B(OH)2) oder 4-(4,4,5,5-Tetramethyl-l ,3,2-dioxaborolan-4-yl)-pyridin (LG = B[-OC(CH3)2C(CH3)20-]) (beide kommerziell erhältlich); 4-(Tributylstannyl)-pyridin (LG = Sn(«-Butyl)3) (US-Pat. 4959363 A), 4-Iodpyridin oder 2-Iodpyridin (LG = I; WO 99/59587 AI); 2-(Tributylstannyl)-pyridin (LG = Sn(«- Butyl)3) (US-Pat. 5521173 A), 2-Pyrid-4-yl-boronsäure (LG = B(OH)2) oder 2-(4,4,5,5-Tetramethyl- l ,3,2-dioxaborolan-4-yl)-pyridin (LG = B [-OC(CH3)2C(CH3)20-]) (beide kommerziell erhältlich); 5- (Tributylstannyl)-l ,3-thiazol (LG = Sn(«-Butyl)3) (WO 2002/062423 AI), l ,3-Thiazol-5-yl-boronsäure (LG = B(OH)2) oder 5-(4,4,5,5-Tetramethyl-l ,3,2-dioxaborolan-4-yl)-l ,3-thiazol (LG = B[- OC(CH3)2C(CH3)20-]) (N. Primas et al., Tetrahedron 65 (29-30), 5739-5746, 2009); 5-Iodthiazol (LG = I; D. Kikelj , U. Urleb, Science of Synthesis 11, 627-833, 2002) oder 5-Bromthiazol (LG = Br; WO 2008/057336 A2). OC (CH 3 ) 2 C (CH 3 ) 2 O-], WO 2009/091374 A2), 4-iodo-1H-pyrazole (LG = I, WO 2010/083283), 4-bromo-1H-pyrazole (LG = Br; WO 2010/018481); 4-iodo-1-methyl-1H-pyrazole (LG = I; WO2001 / 034137A2), 4-bromo-1-methyl-1H-pyrazole (LG = Br; WO 93/21186 A1); 1-cyclopropyl-4-iodo-1H-pyrazoles (LG = I, WO 2010/090290 A1), 1- (difluoromethyl) -4-iodo-1H-pyrazole or 4-iodo (1, 1, 2, 2) tetrafluoroethal) -LH-pyrazole (LG = I, WO 2008/088692 A2); Pyridazin-4-ylboronic acid (LG = B (OH) 2 , WO 2009/155527 A2) or 2- (4,4,5,5-tetramethyl-1,2,2-dioxaborolan-4-yl) -pyridazine (LG = B [-OC (CH 3 ) 2 C (CH 3 ) 2 O-]), M. Helm et al., Angew. Chem. Int. Ed. 44 (25), 3889-3892, 2005); 4-iodopyridazine (LG = I, A. Seggio et al., Org. Chem. 72 (17), 6602-6605, 2007), 4-bromopyridazine (LG = I, JP 63250385 A), 4- (tributylstannyl) -pyridazine (LG = Sn (--butyl) 3 (WO 2001/023383 Al); 4-pyrid-4-ylboronic acid (LG = B (OH) 2 ) or 4- (4,4,5,5- Tetramethyl-l, 3,2-dioxaborolan-4-yl) -pyridine (LG = B [-OC (CH 3 ) 2 C (CH 3 ) 2 O-]) (both commercially available); 4- (tributylstannyl) - pyridine (LG = Sn (--butyl) 3 ) (U.S. Patent No. 4,959,363 A), 4-iodopyridine or 2-iodopyridine (LG = I, WO 99/59587 A1), 2- (tributylstannyl) -pyridine (LG = Sn (--butyl) 3 ) (US Pat. No. 5,521,173 A), 2-pyrid-4-ylboronic acid (LG = B (OH) 2 ) or 2- (4,4,5,5-tetramethyl-1-one , 3,2-dioxaborolan-4-yl) -pyridine (LG = B [-OC (CH 3 ) 2 C (CH 3 ) 2 O-]) (both commercially available); 5- (tributylstannyl) -1, 3 -thiazole (LG = Sn (--butyl) 3 ) (WO 2002/062423 Al), l, 3-thiazol-5-ylboronic acid (LG = B (OH) 2 ) or 5- (4,4,5 , 5-tetramethyl-1,3,2-dioxaborolan-4-yl) -1,3-thiazole (LG = B [-OC (CH 3 ) 2 C (CH 3 ) 2 O-]) (N. Primas et al., Tetrah edron 65 (29-30), 5739-5746, 2009); 5-iodothiazole (LG = I, D. Kikelj, U. Urleb, Science of Synthesis 11, 627-833, 2002) or 5-bromothiazole (LG = Br, WO 2008/057336 A2).
Die Verbindungen der Formel (A-2) sind teilweise bekannt bzw. können nach im Prinzip bekannten Herstellungsverfahren erhalten werden; beispielhaft seien genannt: R1 = Halogen, 3-Fluor-lH-pyrazol (F. Fabra et al., Tetrahedron Lett. 34, 3179-3180, 1979), 3-Chlor-lH-pyrazol (WO 2002/070483 AI), 3- Brom-lH-pyrazol (WO 2003/015519 AI), 3-Iod-lH-pyrazol (WO 2006/021881 A2) R1 = Cyan; 1H- Pyrazol-3-carbonitril (WO 94/29300 AI); R1 = Nitro, 3-Nitro-lH-pyrazol (WO 2002/064592 AI); R1 = Trifluoromethyl, 3-(Trifluormethyl)-lH-pyrazol (WO 2009/014730 AI); R1 = Cyclopropyl, 3- Cyclopropyl- lH-pyrazol (WO 2012/062783 AI); R1 = Methylthio, 3-(Methylthio)-lH-pyrazol (WO 2007/043677 AI) oder R1 = Methylsulfonyl, 3-(Methylsulfonyl)-lH-pyrazol (R. Helder et al., Tetrahedron 29 (10), 1375-1378, 1973). The compounds of the formula (A-2) are known in some cases or can be obtained by production processes known in principle; may be mentioned by way of example: R 1 = halogen, 3-fluoro-lH-pyrazole Fabra et al., Tetrahedron Lett. 34, 3179-3180, 1979), 3-chloro-1H-pyrazole (WO 2002/070483 A1), 3-bromo-1H-pyrazole (WO 2003/015519 A1), 3-iodo-1H-pyrazole (WO 2006/021881 A2) R 1 = cyano; 1H-pyrazole-3-carbonitrile (WO 94/29300 Al); R 1 = nitro, 3-nitro-1H-pyrazole (WO 2002/064592 Al); R 1 = trifluoromethyl, 3- (trifluoromethyl) -1H-pyrazole (WO 2009/014730 Al); R 1 = cyclopropyl, 3-cyclopropyl-1H-pyrazole (WO 2012/062783 Al); R 1 = methylthio, 3- (methylthio) -1H-pyrazole (WO 2007/043677 A1) or R 1 = methylsulfonyl, 3- (methylsulfonyl) -1H-pyrazole (R. Helder et al., Tetrahedron 29 (10), 1375-1378, 1973).
Verbindungen der Formel (A-3), in denen R1 für Wasserstoff steht, sind bereits bekannt geworden: 2- (lH-Pyrazol-l-yl)-pyrazin (X. Deng, et al. . Org. Chem. 76 (20), 8262-8269, 2011), l-Methyl-4-(lH- pyrazol-l-yl)-lH-pyrazol (US-Pat. 2003/0236413 AI); 4-(lH-Pyrazol-l-yl)-pyridine (F. Chevallier, et al. Organic & Biomolecular Chemistry 9 (12), 4671-4684, 2011) und 2-(lH-Pyrazol-l-yl)-pyridine (X. Deng, et al. . Org. Chem. 76 (20), 8262-8269, 2011). Darüber hinaus sind Verbindungen der Formel (A-3) bekannt geworden, in denen R1 für Ethoxycarbonyl steht: l-(4-Pyrazinyl)-lH-pyrazol-3- carbonsäureethylester (WO 2008/019357 A2). Für Verbindungen der Formel (A-3), in denen R1 für Wasserstoff steht, ist die Nitrierung unter Bildung von Verbindungen der Formel (A-4) bekannt geworden: 2-(4-Nitro-lH-pyrazol-l-yl)-pyridine (M. A. Khan, et al. . Het. Chem. 18, 9-14, 1981). Compounds of the formula (A-3) in which R 1 is hydrogen have already been disclosed: 2- (1H-pyrazol-1-yl) -pyrazine (X. Deng, et al., Org. Chem. 20), 8262-8269, 2011), 1-methyl-4- (1H-pyrazol-1-yl) -LH-pyrazole (U.S.Patent 2003/0236413Al); 4- (1H-pyrazol-1-yl) -pyridines (F. Chevallier, et al., Organic & Biomolecular Chemistry 9 (12), 4671-4684, 2011) and 2- (1H-pyrazol-1-yl) -pyridines (X. Deng, et al., Org. Chem. 76 (20), 8262-8269, 2011). In addition, compounds of the formula (A-3) have become known in which R 1 is ethoxycarbonyl: 1- (4-pyrazinyl) -1H-pyrazole-3-carboxylic acid ethyl ester (WO 2008/019357 A2). For compounds of formula (A-3) in which R 1 is hydrogen, nitration has become known to give compounds of formula (A-4): 2- (4-nitro-1H-pyrazol-1-yl) -pyridine (MA Khan, et al., Het. Chem. 18, 9-14, 1981).
Für Verbindungen der Formel (A-4), in denen R1 für Wasserstoff steht, ist die Reduktion der Nitrogruppe unter Bildung von Verbindungen der Formel (A-5) bekannt geworden: 2-(4-Amino-lH- pyrazol-l-yl)-pyridine (M. A. Khan, et al. . Het. Chem. 18, 9-14, 1981). For compounds of the formula (A-4) in which R 1 is hydrogen, the reduction of the nitro group to form compounds of the formula (A-5) has become known: 2- (4-amino-1H-pyrazole-1) yl) -pyridines (MA Khan, et al., Het. Chem. 18, 9-14, 1981).
Verbindungen der Formel (A-6) sind teilweise bekannt bzw. können nach im Prinzip bekannten Herstellungsverfahren erhalten werden; beispielhaft seien genannt: R1 = Halogen, PG = tert- butyloxacarbonyl (Boc), N-(3-Chlor-lH-pyrazol-4-yl)-carbaminsäure-l,l-dimethylethylester und N-(3- Brom-lH-pyrazol-4-yl)-carbaminsäure-l,l-dimethylethylesterter (US 2012/0110702 AI). Verbindungen der Formel (A-7), in denen R1 für Wasserstoff steht, sind bereits bekannt geworden: N-[l- (2-pyridinyl)-lH-pyrazol-4-yl)-carbaminsäure-l,l-dimethylethylester (WO 2011/089132 AI). Compounds of formula (A-6) are in part known or can be obtained by production processes known in principle; Examples include: R 1 = halogen, PG = tert-butyloxacarbonyl (Boc), N- (3-chloro-lH-pyrazol-4-yl) -carbaminsäure l, l-dimethylethyl ester and N- (3-bromo-lH pyrazol-4-yl) -carbamic acid 1,1-dimethylethyl ester (US 2012/0110702 Al). Compounds of the formula (A-7) in which R 1 is hydrogen have already been disclosed: N- [1- (2-pyridinyl) -1H-pyrazol-4-yl) -carbamic acid 1,1-dimethylethyl ester ( WO 2011/089132 AI).
Verbindungen der Formel (I), in denen der Heterocyclus A beispielsweise für gegegebenenfalls mit einem Rest R substituiertes Pyrazol-4-yl (A-a), Isothiazol-4-yl (A-b), Isoxazol-4-yl (A-c) oder Pyrazin- 2-yl (A-h) steht, und der Heterocyclus B für l,3-Thiazol-2-yl steht, das in 4-Position mit einem Rest R1 substituiert ist, können beispielsweise nach Methode C gemäss Reaktionsschema II dargestellt werden. Compounds of the formula (I) in which the heterocycle A is, for example, optionally substituted by an R radical substituted pyrazol-4-yl (Aa), isothiazol-4-yl (Ab), isoxazol-4-yl (Ac) or pyrazine -yl (Ah), and the heterocycle B is l, 3-thiazol-2-yl, which is substituted in the 4-position by a radical R 1 , for example, by Method C according to Reaction Scheme II are shown.
Reaktionsschema II
Figure imgf000034_0001
Reaction scheme II
Figure imgf000034_0001
PG = CO-O-fert-But (Boc)  PG = CO-O-fert-But (Boc)
Hai = Halogen, bevorzugt Brom oder lod  Hal = halogen, preferably bromine or iodine
Im Reaktionsschema II haben A, R1, R2 und R3 die oben genannten Bedeutungen. l,3-Thiazol-2-yl steht für B, LG steht für eine gegebenenfalls in-situ erzeugte nucleofuge Abgangsgruppe ("Leaving Group"), Hai steht für Halogen (bevorzugt Brom oder lod) und PG bedeutet Schutzgruppe („Protection Group"). Beispielsweise können heterocyclische Verbindungen der Formel (A-1) mit den entsprechenden 4,5- disubstituierten 1,3-Thiazolen der Formel (A-8), die eine geeignete Schutzgruppe PG besitzen (z. B. PG = teri-butyloxacarbonyl (Boc)), nach Methode C zu Verbindungen der Formel (A-9) umgesetzt werden, die weiter zu Verbindungen der Formel (I) umgesetzt werden können (vgl. auch I-E bis I-H). In Reaction Scheme II, A, R 1 , R 2 and R 3 have the meanings given above. l, 3-thiazol-2-yl is B, LG is an in situ generated nucleofuge leaving group, Hai is halogen (preferably bromine or iodine) and PG is protecting group ("Protection Group"). For example, heterocyclic compounds of formula (A-1) may be reacted with the corresponding 4,5-disubstituted 1,3-thiazoles of formula (A-8) having a suitable protective group PG (e.g., PG = tertiarybutyloxacarbonyl (Boc)), according to method C to give compounds of the formula (A-9) which can be further converted into compounds of the formula (I) (compare also IE to IH).
Beispielsweise können Heteroarylboronsäuren (LG = B(OH)3) oder (Hetero)arylboronsäureester (LG = B(OR)3) der Formel (A-1) mit den entsprechenden Halogen-substituierten Heteroarylverbindungen, beispielsweise Halogen-substituierten 1,3-Thiazolen der Formel (A-8), nach bekannten Methoden (vgl. Chem. Rev. 1995, 95, 2457-2483; Tetrahedron 2002, 58, 9633-9695; Metal-Catalyzed Cross-Coupling Reactions (Eds.: A. de Meijere, F. Diederich), 2nd ed., Wiley-VCH, Weinheim, 2004) in Gegenwart geeigneter Katalysatoren aus der Reihe der Übergangsmetallsalze zu Verbindungen der Formel (A-9) umgesetzt werden. For example, heteroarylboronic acids (LG = B (OH) 3 ) or (hetero) arylboronic acid esters (LG = B (OR) 3 ) of the formula (A-1) with the corresponding halogen-substituted heteroaryl compounds, for example halogen-substituted 1,3-thiazoles of the formula (A-8), according to known methods (compare Chem Rev. 1995, 95, 2457-2483, Tetrahedron 2002, 58, 9633-9695, Metal-Catalyzed Cross-Coupling Reactions (Eds .: A. de Meijere , F. Diederich), 2 nd ed., Wiley-VCH, Weinheim, 2004) in the presence of suitable catalysts from the series of transition metal salts to give compounds of formula (A-9).
Die Verbindungen der Formel (A-8) sind teilweise bekannt bzw. können nach bekannten Herstellungsverfahren erhalten werden; beispielhaft seien genannt: Halogen = Brom; R1 = Chlor, R2 = Ethyl, PG = teri-Butyloxycarbonyl (Boc); N-(2-Brom-4-chlor-5-thiazolyl)-N-ethyl-carbaminsäure-l,l- dimethylester (WO 2010/129497 AI); Halogen = Brom; R1 = Methyl, R2 = Wasserstoff, PG = tert- Butyloxycarbonyl (Boc); N-(2-Brom-4-methyl-5-thiazolyl)-carbaminsäure-l,l-dimethylester (WO 2010/129497 AI); Halogen = Brom; R1 und R2 = Methyl, PG = tert-Butyloxycarbonyl (Boc); N-(2- Brom-4-methyl-5-thiazolyl)-N-methyl-carbaminsäure-l,l-dimethylester (WO 2010/129497 AI); Halogen = Chlor; R1 = Trifluormethyl, R2 = Wasserstoff, PG = teri-Butyloxycarbonyl (Boc); N-[2- Chlor-4-(trifluormethyl)-5-thiazolyl]-carbaminsäure-l,l-dimethylester (S. M. South . Het. Chem. 28 (4), 1003-1011, 1991); Halogen = lod; R1 = Ethoxycarbonyl, R2 = Wasserstoff, PG = tert- Butyloxycarbonyl (Boc); 5-[[(l,l-dimethylethoxy)carbonyl]amino]-2-iodo-4-thiazolcarbonsäureethyl- ester (WO 2010/011375 A2). The compounds of formula (A-8) are in part known or can be obtained by known preparation processes; may be mentioned by way of example: halogen = bromine; R 1 = chloro, R 2 = ethyl, PG = teri-butyloxycarbonyl (Boc); N- (2-bromo-4-chloro-5-thiazolyl) -N-ethyl-carbamic acid 1,1-dimethyl ester (WO 2010/129497 A1); Halogen = bromine; R 1 = methyl, R 2 = hydrogen, PG = tert-butyloxycarbonyl (Boc); N- (2-bromo-4-methyl-5-thiazolyl) -carbamic acid 1,1-dimethyl ester (WO 2010/129497 A1); Halogen = bromine; R 1 and R 2 = methyl, PG = tert-butyloxycarbonyl (Boc); N- (2-bromo-4-methyl-5-thiazolyl) -N-methyl-carbamic acid 1,1-dimethyl ester (WO 2010/129497 A1); Halogen = chlorine; R 1 = trifluoromethyl, R 2 = hydrogen, PG = teri-butyloxycarbonyl (Boc); N- [2-chloro-4- (trifluoromethyl) -5-thiazolyl] -carbamic acid 1,1-dimethyl ester (SM South, Het. Chem., 28 (4), 1003-1011, 1991); Halogen = iodine; R 1 = ethoxycarbonyl, R 2 = hydrogen, PG = tert- Butyloxycarbonyl (Boc); 5 - [[(l, l-dimethylethoxy) carbonyl] amino] -2-iodo-4-thiazolecarboxylic acid ethyl ester (WO 2010/011375 A2).
Verbindungen der Formel (A-9), in denen R1 und R2 für Wasserstoff stehen, sind bereits bekannt geworden: N-[2-(2-Pyridinyl)-5-thiazolyl]-carbaminsäure-l,l-dimethylester (WO 2011/089132 AI). Compounds of the formula (A-9) in which R 1 and R 2 are hydrogen have already been disclosed: N- [2- (2-pyridinyl) -5-thiazolyl] -carbamic acid 1,1-dimethyl ester (WO 2011/089132 AI).
Verbindungen der Formel (I), in denen der Heterocyclus A beispielsweise für gegegebenenfalls mit einem Rest R substituiertes Pyrazol-4-yl (vgl. I-A), Isothiazol-4-yl (vgl. I-B), Isoxazol-4-yl (vgl. I-C) oder Pyrazin-2-yl (vgl. I-D) steht, und der Heterocyclus B für l,3,4-Thiadiazol-2-yl (B-3) steht, können beispielsweise nach der Methode C gemäss Reaktionsschema III dargestellt werden. Compounds of the formula (I) in which the heterocycle A is substituted, for example, by pyrazol-4-yl optionally substituted by one R (see IA), isothiazol-4-yl (see IB), isoxazol-4-yl (cf. IC) or pyrazine-2-yl (see ID), and the heterocycle B is l, 3,4-thiadiazol-2-yl (B-3), for example, by the method C according to Reaction Scheme III.
Reaktionsschema III Reaction scheme III
Figure imgf000035_0001
Figure imgf000035_0001
(l-l) bis (l-L) LG = -B(OH)2, , Sn(n-Bu)3 (II) to (III) LG = -B (OH) 2 ,, Sn (n-Bu) 3
Figure imgf000035_0002
Figure imgf000035_0002
PG = CO-O-fert-But (Boc), CO-0-CH2-CH=CH2 (Alloc) PG = CO-O-tert-But (Boc), CO-O-CH 2 -CH = CH 2 (Alloc)
Hai = Halogen, bevorzugt Chlor, Brom oder lod  Hal = halogen, preferably chlorine, bromine or iodine
Im Reaktionsschema III haben A, R2 und R3 die oben genannten Bedeutungen. LG steht für eine gegebenenfalls in-situ erzeugte nucleofuge Abgangsgruppe ("Leaving Group"), Hai steht für Halogen (bevorzugt Brom oder lod) und PG bedeutet Schutzgruppe („Protection Group"). In Reaction Scheme III, A, R 2 and R 3 have the meanings given above. LG stands for an in-situ generated nucleofuge leaving group, Hai stands for halogen (preferably bromine or iodine) and PG means protection group.
Beispielsweise können heterocyclische Verbindungen der Formel (A-1) mit den entsprechenden 5- substituierten 1,3,4-Thiadiazolen der Formel (A-10), die eine geeignete Schutzgruppe PG tragen (z. B. PG = teri-butyloxacarbonyl (Boc)), nach Methode C zu Verbindungen der Formel (A-11) umgesetzt werden, die weiter zu Verbindungen der Formel (I) umgesetzt werden können (vgl. auch I-I bis I-L). For example, heterocyclic compounds of formula (A-1) may be reacted with the corresponding 5-substituted-1,3,4-thiadiazoles of formula (A-10) bearing a suitable PG protecting group (e.g., PG = tertiarybutyloxacarbonyl (Boc )), are converted by method C to compounds of formula (A-11), which can be further reacted to compounds of formula (I) (see also II to IL).
Beispielsweise können Heteroarylboronsäuren (LG = B(OH)3) oder (Hetero)arylboronsäureester (LG = B(OR)3) der Formel (A-1) mit den entsprechenden Halogen-substituierten Heteroarylverbindungen, beispielsweise Halogen-substituierten 1,3-Thiadiazolen der Formel (A-10), nach der im Reaktionschema III genannten Methode C in Gegenwart geeigneter Katalysatoren aus der Reihe der Übergangsmetallsalze zu Verbindungen der Formel (A-11) umgesetzt werden. For example, heteroarylboronic acids (LG = B (OH) 3 ) or (hetero) arylboronic acid esters (LG = B (OR) 3 ) of the formula (A-1) with the corresponding halogen-substituted heteroaryl compounds, for example halogen-substituted 1,3-thiadiazoles of the formula (A-10), according to the method mentioned in Reaction Scheme III C in the presence of suitable catalysts from the series of transition metal salts to give compounds of formula (A-11).
Verbindungen der Formel (A-1) sind teilweise bekannt bzw. können nach den weiter oben genannten Herstellungsverfahren erhalten werden. Verbindungen der Formel (A-10) sind teilweise bekannt bzw. können nach im Prinzip bekannten Herstellungsverfahren erhalten werden; beispielhaft seien genannt: Halogen = Brom; R2 = Wasserstoff, PG = teri-Butyloxycarbonyl (Boc); N-(5-Brom-l,3,4-thiadiazol-2-yl)-carbaminsäure-l,l-dimethylester (kommerziell erhältlich); Halogen = Brom; R2 = Wasserstoff, PG = Allyloxycarbonyl (Alloc); N-(5- Brom-l,3,4-thiadiazol-2-yl)-carbaminsäure-2-propenylester (JP 51000611) oder Halogen = Chlor; R2 = Wasserstoff, PG = Allyloxycarbonyl (Alloc); N-(5-Chlor-l,3,4-thiadiazol-2-yl)-carbaminsäure-2- propenylester (JP 51000611). Compounds of the formula (A-1) are known in some cases or can be obtained by the production processes mentioned above. Compounds of the formula (A-10) are in part known or can be obtained by production processes known in principle; may be mentioned by way of example: halogen = bromine; R 2 = hydrogen, PG = teri-butyloxycarbonyl (Boc); N- (5-bromo-1,3,4-thiadiazol-2-yl) -carbamic acid 1,1-dimethyl ester (commercially available); Halogen = bromine; R 2 = hydrogen, PG = allyloxycarbonyl (Alloc); N- (5-bromo-1,3,4-thiadiazol-2-yl) -carbamic acid 2-propenyl ester (JP 51000611) or halogen = chlorine; R 2 = hydrogen, PG = allyloxycarbonyl (Alloc); N- (5-chloro-l, 3,4-thiadiazol-2-yl) -carbamic acid-2-propenyl ester (JP 51000611).
Einige Verbindungen der Formel (A-l l) sind bekannt: R1 = Wasserstoff, R2 = 2,2,2- Trichloroethoxycarbonyl; N-[5-(2-Pyridinyl)-l,3,5-thiadiazol-2-yl]-carbaminsäure-2,2,2-trichloroethyl- ester oder N-[5-(4-Pyridinyl)-l,3,5-thiadiazol-2-yl]-carbaminsäure-2,2,2-trichloroethyl-ester (WO 99/28309 AI ; ΚΥΝ-ΟΗ Inhibitoren); R1 = Wasserstoff, R2 = Ethoxycarbonyl; N-[5-(2-Pyrazinyl)-l,3,4- thiadiazol-2-yl]-carbaminsäureethylester (A. Siwek et al., Heteroatom Chemistry 21 (4), 256-264, 2010). Some compounds of the formula (Al 1) are known: R 1 = hydrogen, R 2 = 2,2,2-trichloroethoxycarbonyl; N- [5- (2-Pyridinyl) -l, 3,5-thiadiazol-2-yl] -carbamic acid 2,2,2-trichloroethyl ester or N- [5- (4-pyridinyl) -l, 3 , 5-thiadiazol-2-yl] -carbamic acid 2,2,2-trichloroethyl ester (WO 99/28309 Al; ΚΥΝ-ΟΗ inhibitors); R 1 = hydrogen, R 2 = ethoxycarbonyl; N- [5- (2-pyrazinyl) -1,3,4-thiadiazol-2-yl] -carbamic acid ethyl ester (A. Siwek et al., Heteroatom Chemistry 21 (4), 256-264, 2010).
Die Herstellung der Verbindungen der Formel (I) und Derivatisierungen der weiter oben genannten Verbindungen der Formeln (A-5), (A-7), (A-9) und (A-l l) können nach literaturbekannten Methoden gemäss Reaktionsschema IV erfolgen, The compounds of the formula (I) and derivatizations of the abovementioned compounds of the formulas (A-5), (A-7), (A-9) and (A-1) can be prepared by methods known from the literature according to Reaction Scheme IV,
Reaktionsschema IV Reaction scheme IV
N-Deblockierunq N-Deblockierunq
A-B-NH-PG ► A-B-NH,  A-B-NH-PG ►A-B-NH,
( 1-1 ) ( I-2 )  (1-1) (I-2)
N-Alkylierung j | N-Alkylierung / N-Acylierung / N-Sulfonierung  N-alkylation j | N-alkylation / N-acylation / N-sulfonation
N-Deblockierung A-B-NHR,  N-deblocking A-B-NHR,
A-B-NR,-PG  A-B-NR, -PG
( I-3 ) ( I-4 )  (I-3) (I-4)
N-Alkylierung / N-Acylierung / N-Sulfonierung N-alkylation / N-acylation / N-sulfonation
PG = ferf-Butyloxycarbonyl (Boc) A-B-NR2NR3 PG = ferf-butyloxycarbonyl (Boc) AB-NR 2 NR 3
Allyloxycarbonyl (Alloc) ^ | ^  Allyloxycarbonyl (Alloc) ^ | ^
Im Reaktionsschema IV haben A, B, R2 und R3 die oben genannten Bedeutungen, PG bedeutet Schutzgruppe („Protection Group"). Zur Herstellung von Verbindungen der Formel (I-l) können als geeignete Schutzgruppen (PG) für Aminogruppen beispielsweise substituierte Carbamate, Amide, N-Alkylamine, N-Arylamine, Iminderivate, Enaminderivate, N-Sulfenylderivate, N-Sulfonylderivate oder N-Diarylphosphinyl- derivate verwendet werden (vgl. Greene T. W., Wuts P. G. W. in Protective Croups in Organic Synthesis; John Wiley & Sons, Inc. 1999,„Protection for the Amino Group", S. 494). Bevorzugt werden Schutzgruppen des Carbamat-Typs verwendet. _ In Reaction Scheme IV, A, B, R 2 and R 3 are as defined above, PG means Protection Group. Amides, N-alkylamines, N-arylamines, imine derivatives, enamine derivatives, N-sulfenyl derivatives, N-sulfonyl derivatives or N-diarylphosphinyl derivatives can be used (see Greene TW, Wuts PGW in Protective Croups in Organic Synthesis, John Wiley & Sons, Inc 1999, "Protection for the Amino Group", p. 494). Preferably, carbamate-type protecting groups are used. _
- 36 - - 36 -
Verbindungen der Formeln (1-2) und (1-4) können aus den Verbindungen der Formel (1-1) bzw. (1-3) durch Entfernung der Schutzgruppe hergestellt werden. Compounds of formulas (1-2) and (1-4) can be prepared from the compounds of formula (1-1) and (1-3) by deprotection, respectively.
Im Allgemeinen können für die Entfernung der Schutzgruppe saure oder basische Reaktionshilfsmittel nach literaturbekannter Verfahrensweise verwendet werden. Bei Verwendung von Schutzgruppen des Carbamat-Typs werden bevorzugt saure Reaktionshilfsmittel verwendet. Bei Verwendung der tert- Butylcarbamat-Schutzgruppe (Boc-Gruppe) werden beispielsweise Mischungen von Mineralsäuren wie Salzsäure, Bromwasserstoffsäure, Salpetersäure, Schwefelsäure, Phosphorsäure oder von organischen Säuren wie Benzoesäure, Ameisensäure, Essigsäure, Trifluoressigsäure, Methansulfonsäure, Benzolsulionsäure oder Toluolsulionsäure in einem geeigneten Verdünnungsmittel wie Wasser und/oder einem organischen Lösungsmittel wie Tetrahydrofuran, Dioxan, Dichlormethan, Chloroform, Essigester, Ethanol oder Methanol verwendet. Bevorzugt sind Mischungen von Salzsäure oder Essigsäure mit Wasser und/oder einem organischen Lösungsmittel wie Essigester. In general, acidic or basic reaction auxiliaries can be used according to the literature procedure for the removal of the protective group. When using carbamate-type protecting groups, preference is given to using acidic reaction auxiliaries. When the tert-butylcarbamate protecting group (Boc group) is used, for example, mixtures of mineral acids such as hydrochloric, hydrobromic, nitric, sulfuric, phosphoric or organic acids such as benzoic, formic, acetic, trifluoroacetic, methanesulfonic, benzenesulfonic or toluenesulfonic acid in a suitable diluent such as water and / or an organic solvent such as tetrahydrofuran, dioxane, dichloromethane, chloroform, ethyl acetate, ethanol or methanol. Preference is given to mixtures of hydrochloric acid or acetic acid with water and / or an organic solvent such as ethyl acetate.
Die Verbindungen der Formeln (1-1), (1-2) und (1-4) können nach im Prinzip bekannten Methoden mit geeigneten Reaktionspartnern und in Gegenwart von Verdünnungsmitteln und basischen Reaktionshilfsmitteln unter Bildung von Verbindungen der Formeln (1-3), (1-4) und (I) N-alkyliert, N- acyliert oder N-sulfonyliert werden (vgl. Herstellungsbeispiele, Beispiele 1 und 2). The compounds of the formulas (1-1), (1-2) and (1-4) can be prepared by methods known in principle with suitable reactants and in the presence of diluents and basic reaction auxiliaries to give compounds of the formulas (1-3), (1-4) and (I) N-alkylated, N-acylated or N-sulfonylated (see Preparation Examples, Examples 1 and 2).
Verdünnungsmittel werden vorteilhaft in einer solchen Menge eingesetzt, dass das Reaktionsgemisch während des ganzen Verfahrens gut rührbar bleibt. Als Verdünnungsmittel zur Durchführung des erfindungsgemäßen Verfahrens kommen alle unter den Reaktionsbedingungen inerten organischen Lösungsmittel in Frage. Diluents are advantageously used in such an amount that the reaction mixture remains easy to stir throughout the process. Suitable diluents for carrying out the process according to the invention are all organic solvents which are inert under the reaction conditions.
Als Beispiele sind zu nennen: Halogenkohlenwasserstoffe, insbesondere Chlorkohlenwasserstoffe, wie Tetraethylen, Tetrachlorethan, Dichlorpropan, Methylenchlorid, Dichlorbutan, Chloroform, Tetrachlorkohlenstoff, Trichlorethan, Trichlorethylen, Pentachlorethan, Difluorbenzol, 1 ,2-Dichlorethan, Chlorbenzol, Brombenzol, Dichlorbenzol, Chlortoluol, Trichlorbenzol; Alkohole wie Methanol, Ethanol, Isopropanol, Butanol; Ether wie Ethylpropylether, Methyl-tert-butylether, «-Butylether, Anisol, Phenetol, Cyclohexylmethylether, Dimethylether, Diethylether, Diproplether, Diisopropylether, Oi-n- butylether, Diisobutylether, Diisoamylether, Ethylenglycoldimethylether, Tetrahydrofuran, Dioxan, Dichlordiethylether und Polyether des Ethylenoxids und/oder Propylenoxids; Amine wie Trimethyl-, Triethyl-, Tripropyl-, Tributylamin, N-Methylmorpholin, Pyridin und Tetramethylendiamin; Nitrokohlenwasserstoffe wie Nitromethan, Nitroethan, Nitropropan, Nitrobenzol, Chlornitrobenzol, o- Nitrotoluol; Nitrile wie Acetonitril, Propionitril, Butyronitril, Isobutyronitril, Benzonitril, m- Chlorbenzonitril sowie Verbindungen wie Tetrahydrothiophendioxid und Dimethylsulfoxid, Tetramethylensulfoxid, Dipropylsulfoxid, Benzylmethylsulfoxid, Diisobutylsulfoxid, Dibutylsulfoxid, Diisoamylsulfoxid; Sulfone wie Dimethyl-, Diethyl-, Dipropyl-, Dibutyl-, Diphenyl-, Dihexyl-, Methylethyl-, Ethylpropyl-, Ethylisobutyl- und Pentamethylensulfon; aliphatische, cycloaliphatische oder aromatische Kohlenwasserstoffe wie Pentan, Hexan, Heptan, Oktan, Nonan und technische Kohlenwasserstoffe; beispielsweise sogenannte White Spirits mit Komponenten mit Siedepunkten im Bereich beispielsweise von 40°C bis 250°C, Cymol, Benzinfraktionen innerhalb eines Siedeinterwalles von 70°C bis 190°C, Cyclohexan, Methylcyclohexan, Petrolether, Ligroin, Octan, Benzol, Toluol, Chlorbenzol, Brombenzol, Nitrobenzol, Xylol; Ester wie Methyl-, Ethyl-, Butyl-, Isobutylacetat, sowie Dimethyl-, Dibutyl-, Ethylencarbonat; Amide wie Hexamethylenphosphorsäuretriamid, Formamid, N- Methyl-formamid, N,N-Dimethyl-formamid, N,N-Dipropyl-formamid, N,N-Dibutyl-formamid, N- Methyl-pyrrolidin, N-Methyl-caprolactam, l,3-Dimethyl-3,4,5,6-tetrahydro-2(lH)-pyrimidin, Octylpyrrolidon, Octylcaprolactam, l,3-Dimethyl-2-imidazolindion, N-Formyl-piperidin, N,N'-1,4- Diformylpiperazin; Ketone wie Aceton, Acetophenon, Methylethylketon, Methylbutylketon. Examples include: halogenated hydrocarbons, especially chlorinated hydrocarbons such as tetraethylene, tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, carbon tetrachloride, trichloroethane, trichlorethylene, pentachloroethane, difluorobenzene, 1, 2-dichloroethane, chlorobenzene, bromobenzene, dichlorobenzene, chlorotoluene, trichlorobenzene; Alcohols such as methanol, ethanol, isopropanol, butanol; Ethers such as ethyl propyl ether, methyl tert-butyl ether, n-butyl ether, anisole, phenetole, cyclohexylmethyl ether, dimethyl ether, diethyl ether, dipropl ether, diisopropyl ether, ni-n-butyl ether, diisobutyl ether, diisoamyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, dichlorodiethyl ether and polyethers of ethylene oxide and or propylene oxide; Amines such as trimethyl, triethyl, tripropyl, tributylamine, N-methylmorpholine, pyridine and tetramethylenediamine; Nitrohydrocarbons such as nitromethane, nitroethane, nitropropane, nitrobenzene, chloronitrobenzene, o-nitrotoluene; Nitriles such as acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile, m-chlorobenzonitrile and compounds such as tetrahydrothiophene dioxide and dimethyl sulfoxide, tetramethylene sulfoxide, dipropyl sulfoxide, benzylmethylsulfoxide, diisobutylsulfoxide, dibutylsulfoxide, diisoamylsulfoxide; Sulfones such as dimethyl, diethyl, dipropyl, dibutyl, diphenyl, dihexyl, methylethyl, ethylpropyl, ethylisobutyl and pentamethylene sulfone; aliphatic, cycloaliphatic or aromatic hydrocarbons such as pentane, hexane, heptane, octane, nonane and technical hydrocarbons; For example, so-called white spirits with components with boiling points in the range, for example, from 40 ° C to 250 ° C, cymene, gasoline fractions within a Siedeinterwalles from 70 ° C to 190 ° C, cyclohexane, methylcyclohexane, petroleum ether, ligroin, octane, benzene, toluene, chlorobenzene , Bromobenzene, nitrobenzene, xylene; Esters such as methyl, ethyl, butyl, isobutyl acetate, as well as dimethyl, dibutyl, ethylene carbonate; Amides such as hexamethylenephosphoric triamide, formamide, N-methylformamide, N, N-dimethylformamide, N, N-dipropylformamide, N, N-dibutylformamide, N-methylpyrrolidine, N-methyl-caprolactam, I, 3-Dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidine, octylpyrrolidone, octyl-caprolactam, 1,3-dimethyl-2-imidazolinedione, N-formyl-piperidine, N, N'-1,4- diformyl piperazine; Ketones such as acetone, acetophenone, methyl ethyl ketone, methyl butyl ketone.
Es können auch Gemische der genannten Lösungs- und Verdünnungsmittel eingesetzt werden. It is also possible to use mixtures of the solvents and diluents mentioned.
Bevorzugte Verdünnungsmittel zur Durchführung des erfindungsgemäßen Verfahrens sind Halogenkohlenwasserstoffe, insbesondere Chlorkohlenwasserstoffe, wie Tetraethylen, Tetrachlorethan, Dichlorpropan, Methylenchlorid, Dichlorbutan, Chloroform, Tetrachlorkohlenstoff, Trichlorethan, Trichlorethylen, Pentachlorethan, Difluorbenzol, 1 ,2-Dichlorethan, Chlorbenzol, Brombenzol, Dichlorbenzol, Chlortoluol und Trichlorbenzol. Preferred diluents for carrying out the process according to the invention are halogenated hydrocarbons, in particular chlorohydrocarbons, such as tetraethylene, tetrachloroethane, dichloropropane, methylene chloride, dichlorobutane, chloroform, carbon tetrachloride, trichloroethane, trichlorethylene, pentachloroethane, difluorobenzene, 1, 2-dichloroethane, chlorobenzene, bromobenzene, dichlorobenzene, chlorotoluene and trichlorobenzene.
Zur Herstellung der Verbindungen der Formeln (1-4) und (I) können auch geeignete (Thio)Carbonsäuren oder Sulfonsäuren mittels bekannter Aktivierungsmethoden in-situ aktiviert werden. For the preparation of the compounds of formulas (1-4) and (I), it is also possible to activate suitable (thio) carboxylic acids or sulfonic acids in situ by means of known activation methods.
Als Aktivierungsreagenzien können alle Reagenzien verwendet werden, die zur Herstellung einer Amid- oder Hydrazidbindung geeignet sind (vgl. z. B. Houbel-Weyl, Methoden der organischen Chemie, Band 15/2; Bodansky et al., Peptide Synthesis 2nd ed. (Wiley & Sons, New York 1976) oder Gross, Meienhofer, The Peptides: Analysis, Synthesis, Biology (Academy Press, New York 1979). Bevorzugt ist die Kupplung mit Phosphoniumreagenzien wie Bis(2-oxo-3-oxazolidinyl)phosphoniumsäurechlorid (BOP-Cl), Benzotriazol- 1 -yl-oxy-tris(dimethylamino-phosphonium)-hexafluorophosphat (BOP), Benzotriazol-l-yl-tris-pyrrolidino-phosphonium-hexafluorophosphat (PyBOB®), Bromo-tris- pyrrolidino-phosphonium-hexafluorophospha (PyBroP®) oder mit Phosphonsäureesterreagenzien, wie Cyanphosphonsäurediethylester (DEPC) und Diphenylphosphorylazid (DPPA). Activation reagents which may be used are all reagents which are suitable for the preparation of an amide or hydrazide bond (cf., for example, Houbel-Weyl, Methods of Organic Chemistry, Volume 15/2, Bodansky et al., Peptide Synthesis 2 nd ed. (Wiley & Sons, New York 1976) or Gross, Meienhofer, The Peptides: Analysis, Synthesis, Biology (Academy Press, New York 1979). Preferably, the coupling with phosphonium reagents such as bis (2-oxo-3-oxazolidinyl) phosphonium chloride ( BOP-Cl), benzotriazole-1-yl-oxy-tris (dimethylamino-phosphonium) hexafluorophosphate (BOP), benzotriazol-l-yl-tris-pyrrolidino-phosphonium hexafluorophosphate (PyBOB ®), bromo-tris- pyrrolidino-phosphonium -hexafluorophospha (PyBroP ®) or Phosphonsäureesterreagenzien such as diethyl cyanophosphonate (DEPC) and diphenylphosphoryl azide (DPPA).
Bevorzugte Aktivierungsmittel für die (Thio)Carbonsäuren oder Sulfonsäuren sind beispielsweise Phosphoniumreagenzien wie Bis(2-oxo-3-oxazolidinyl)phosphoniumsäurechlorid (BOP-Cl) (vgl. auch Herstellungsbeispiele, Beispiel 1, Stufe 4 und Beispiel 2). Preferred activating agents for the (thio) carboxylic acids or sulfonic acids are, for example, phosphonium reagents such as bis (2-oxo-3-oxazolidinyl) phosphonium chloride (BOP-Cl) (compare also Preparation Examples, Example 1, Step 4 and Example 2).
Als basische Reaktionshilfsmittel zur Durchführung des erfindungsgemäßen Verfahrens gemäss Reaktionsschema IV können alle geeigneten Säurebindemittel eingesetzt werden, beispielsweise Amine, insbesondere tertiäre Amine, sowie Alkali- und Erdalkaliverbindungen. Beispielhaft seien erwähnt die Hydroxide, Hydride, Oxide und Carbonate des Lithiums, Natriums, Kaliums, Magnesiums, Calciums und Bariums, ferner weitere basische Verbindungen wie Amidinbasen oder Guanidinbasen wie 7-Methyl-l,5,7-triaza-bicyclo(4.4.0)dec-5-en (MTBD); Diazabicyclo(4.3.0)nonen (DBN), Diazabicyclo(2.2.2)octan (DABCO), 1,8-Diazabicyclo(5.4.0)undecen (DBU), Cyclohexyltetrabutyl-guanidin (CyTBG), Cyclohexyltetramethylguanidin (CyTMG), Ν,Ν,Ν,Ν- Tetramethyl-l,8-naphthalindiamin, Pentamethylpiperidin, tertiäre Amine wie Triethylamin, Trimethylamin, Tribenzylamin, Triisopropylamin, Tributylamin, Tricyclohexylamin, Triamylamin, Trihexylamin, N,N-Dimethylanilin, N,N-Dimethyl-toluidin, N,N-Dimethyl-p-aminopyridin, N-Methyl- pyrrolidin, N-Methyl-piperidin, N-Methyl-imidazol, N-Methyl-pyrazol, N-Methyl-morpholin, N-Methyl- hexamethylendiamin, Pyridin, 4-Pyrrolidinopyridin, 4-Dimethylamino-pyridin, Chinolin, α-Picolin, ß- Picolin, Isochinolin, Pyrimidin, Acridin, N,N,N',N'-Tetramethylendiamin, N,N',N'-Tetraethylendiamin, Chinoxalin, N-Propyl-diisopropylamin, N-Ethyl-diisopropylamin (Hünig' s Base), NN'-Dimethyl- cyclohexylamin, 2,6-Lutidin, 2,4-Lutidin oder Triethyldiamin. As basic reaction auxiliaries for carrying out the process according to the invention in Reaction Scheme IV, it is possible to use all suitable acid binders, for example amines, in particular tertiary amines, and also alkali metal and alkaline earth metal compounds. Examples include the hydroxides, hydrides, oxides and carbonates of lithium, sodium, potassium, magnesium, calcium and barium, further basic compounds such as amidine bases or guanidine bases such as 7-methyl-l, 5,7-triaza-bicyclo (4.4.0 ) dec-5-ene (MTBD); Diazabicyclo (4.3.0) nonene (DBN), diazabicyclo (2.2.2) octane (DABCO), 1,8-diazabicyclo (5.4.0) undecene (DBU), cyclohexyltetrabutyl-guanidine (CyTBG), cyclohexyltetramethylguanidine (CyTMG), Ν , Ν, Ν, Ν-tetramethyl-l, 8-naphthalenediamine, pentamethylpiperidine, tertiary amines such as triethylamine, trimethylamine, tribenzylamine, triisopropylamine, tributylamine, tricyclohexylamine, triamylamine, trihexylamine, N, N-dimethylaniline, N, N-dimethyl-toluidine, N, N-dimethyl-p-aminopyridine, N-methylpyrrolidine, N-methyl-piperidine, N-methyl-imidazole, N-methyl-pyrazole, N-methyl-morpholine, N-methyl-hexamethylenediamine, pyridine, 4- Pyrrolidinopyridine, 4-dimethylamino-pyridine, quinoline, α-picoline, β-picoline, isoquinoline, pyrimidine, acridine, N, N, N ', N'-tetramethylenediamine, N, N', N'-tetraethylenediamine, quinoxaline, N- Propyl-diisopropylamine, N-ethyl-diisopropylamine (Hünig's base), N, N'-dimethylcyclohexylamine, 2,6-lutidine, 2,4-lutidine or triethyldiamine.
Vorzugsweise finden zur Herstellung von Verbindungen der Formel (1-3) Hydroxide des Lithiums, Kaliums oder Natriums Verwendung. Zur Herstellung von Verbindungen der Formel (1-4) werden vorzugsweise tertiäre Amine wie N-Propyl-diisopropylamin oder N-Ethyl-diisopropylamin (Hünig' s Base) eingesetzt. Preferably, for the preparation of compounds of formula (1-3) hydroxides of lithium, potassium or sodium are used. For the preparation of compounds of formula (1-4) tertiary amines such as N-propyl-diisopropylamine or N-ethyl-diisopropylamine (Hünig's base) are preferably used.
Bei der Herstellung von Verbindungen der Formel (I) werden in Abhängigkeit von R2 bevorzugt Hydroxide des Lithiums, Kaluims oder Natriums (R2 steht für einen Acceptorrest wie Acyl, Sulfonyl, etc.) oder tertiäre Amine wie N-Propyl-diisopropylamin oder N-Ethyl-diisopropylamin (Hünig' s Base) verwendet (R2 steht für gegebenenfalls substituiertes Alkyl, Alkenyl, Alkinyl, etc.). In the preparation of compounds of the formula (I), preference is given to hydroxides of lithium, potassium or sodium (R 2 is an acceptor radical such as acyl, sulfonyl, etc.) or tertiary amines such as N-propyl-diisopropylamine or N, depending on R 2 Ethyl-diisopropylamine (Hünig's base) (R 2 is optionally substituted alkyl, alkenyl, alkynyl, etc.).
Die erfindungsgemäßen bzw. erfindungsgemäß zu verwendenden Wirkstoffe eignen sich bei guter Pflanzenverträglichkeit, günstiger Warmblütertoxizität und guter Umweltverträglichkeit zum Schutz von Pflanzen und Pflanzenorganen, zur Steigerung der Ernteerträge, Verbesserung der Qualität des Erntegutes und zur Bekämpfung von tierischen Schädlingen, insbesondere Insekten, Spinnentieren, Helminthen, Nematoden und Mollusken, die in der Landwirtschaft, im Gartenbau, bei der Tierzucht, in Forsten, in Gärten und Freizeiteinrichtungen, im Vorrats- und Materialschutz sowie auf dem Hygienesektor vorkommen. Sie können vorzugsweise als Pflanzenschutzmittel eingesetzt werden. Sie sind gegen normal sensible und resistente Arten sowie gegen alle oder einzelne Entwicklungsstadien wirksam. Zu den oben erwähnten Schädlingen gehören: The active compounds according to the invention or to be used in accordance with the invention are suitable for plant tolerance, favorable warm-blooded toxicity and good environmental compatibility for protecting plants and plant organs, for increasing crop yields, improving the quality of the crop and for controlling animal pests, in particular insects, arachnids, helminths, Nematodes and molluscs found in agriculture, horticulture, livestock, forestry, gardens and recreational facilities, in the protection of materials and materials and in the hygiene sector. They can preferably be used as crop protection agents. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The above mentioned pests include:
Schädlinge aus dem Stamm der Arthropoda, insbesondere aus der Klasse der Arachnida z.B. Acarus spp., Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Amphitetranychus viennensis, Argas spp., Boophilus spp., Brevipalpus spp., Bryobia graminum, Bryobia praetiosa, Centruroides spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermacentor spp., Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Glycyphagus domesticus, Halotydeus destructor, Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus spp., Loxosceles spp., Metatetranychus spp., Neutrombicula autumnalis, Nuphersa spp., Oligonychus spp., Ornithodorus spp., Ornithonyssus spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Steneotarsonemus spp., Steneotarsonemus spinki, Tarsonemus spp., Tetranychus spp., Trombicula alfreddugesi, Vaejovis spp., Vasates lycopersici. ; aus der Klasse der Chilopoda z.B. Geophilus spp., Scutigera spp.; aus der Ordnung oder der Klasse der Collembola z.B. Onychiurus armatus.; aus der Klasse der Diplopoda z.B. Blaniulus guttulatus; aus der Klasse der Insecta, z.B. aus der Ordnung der Blattodea z.B. Blattella asahinai, Blattella germanica, Blatta orientalis, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta spp., Supella longipalpa; aus der Ordnung der Coleoptera z.B. Acalymma vittatum, Acanthoscelides obtectus, Adoretus spp., Agelastica alni, Agriotes spp., Alphitobius diaperinus, Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp., Apion spp., Apogonia spp., Atomaria spp., Attagenus spp., Bruchidius obtectus, Bruchus spp., Cassida spp., Cerotoma trifurcata, Ceutorrhynchus spp., Chaetocnema spp., Cleonus mendicus, Conoderus spp., Cosmopolites spp., Costelytra zealandica, Ctenicera spp., Curculio spp., Cryptolestes ferrugineus, Cryptorhynchus lapathi, Cylindrocopturus spp., Dermestes spp., Diabrotica spp., Dichocrocis spp., Dicladispa armigera, Diloboderus spp., Epilachna spp., Epitrix spp., Faustinus spp., Gibbium psylloides, Gnathocerus cornutus, Hellula undalis, Heteronychus arator, Heteronyx spp., Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypomeces squamosus, Hypothenemus spp., Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lema spp., Leptinotarsa decemlineata, Leucoptera spp., Lissorhoptrus oryzophilus, Lixus spp., Luperodes spp., Lyctus spp., Megascelis spp., Melanotus spp., Meligethes aeneus, Melolontha spp., Migdolus spp., Monochamus spp., Naupactus xanthographus, Necrobia spp., Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorrhynchus spp., Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga spp., Phyllophaga helleri, Phyllotreta spp., Popillia japonica, Premnotrypes spp., Prostephanus truncatus, Psylliodes spp., Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp., Sitophilus oryzae, Sphenophorus spp., Stegobium paniceum, Sternechus spp., Symphyletes spp., Tanymecus spp., Tenebrio molitor, Tenebrioides mauretanicus, Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp.; aus der Ordnung der Diptera z.B. Aedes spp., Agromyza spp., Anastrepha spp., Anopheles spp., Asphondylia spp., Bactrocera spp., Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capitata, Chironomus spp., Chrysomyia spp., Chrysops spp., Chrysozona pluvialis, Cochliomyia spp., Contarinia spp., Cordylobia anthropophaga, Cricotopus sylvestris, Culex spp., Culicoides spp., Culiseta spp., Cuterebra spp., Dacus oleae, Dasyneura spp., Delia spp., Dermatobia hominis, Drosophila spp., Echinocnemus spp., Fannia spp., Gasterophilus spp., Glossina spp., Haematopota spp., Hydrellia spp., Hydrellia griseola, Hylemya spp., Hippobosca spp., Hypoderma spp., Liriomyza spp., Lucilla spp., Lutzomyia spp., Mansonia spp., Musca spp., Oestrus spp., Oscinella frit, Paratanytarsus spp., Paralauterborniella subcincta, Pegomyia spp., Phlebotomus spp., Phorbia spp., Phormia spp., Piophila casei, Prodiplosis spp., Psila rosae, Rhagoletis spp., Sarcophaga spp., Simulium spp., Stomoxys spp., Tabanus spp., Tetanops spp., Tipula spp.; aus der Ordnung der Heteroptera z.B. Anasa tristis, Antestiopsis spp., Boisea spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Collaria spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Euschistus spp., Eurygaster spp., Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptocorisa varicornis, Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae, Monaionion atratum, Nezara spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp., Psallus spp., Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp. ; aus der Ordnung der Homoptera z.B. Acizzia acaciaebaileyanae, Acizzia dodonaeae, Acizzia uncatoides, Acrida turrita, Acyrthosipon spp., Acrogonia spp., Aeneolamia spp., Agonoscena spp., Aleyrodes proletella, Aleurolobus barodensis, Aleurothrixus floccosus, Allocaridara malayensis, Amrasca spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphis spp., Arboridia apicalis, Arytainilla spp., Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia tabaci, Blastopsylla occidentalis, Boreioglycaspis melaleucae, Brachycaudus helichrysi, Brachycolus spp., Brevicoryne brassicae, Cacopsylla spp., Calligypona marginata, Carneocephala fulgida, Ceratovacuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chondracris rosea, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Cryptoneossa spp., Ctenarytaina spp., Dalbulus spp., Dialeurodes citri, Diaphorina citri, Diaspis spp., Drosicha spp., Dysaphis spp., Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Eucalyptolyma spp., Euphyllura spp., Euscelis bilobatus, Ferrisia spp., Geococcus coffeae, Glycaspis spp., Heteropsylla cubana, Heteropsylla spinulosa, Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Macrosteies facifrons, Mahanarva spp., Melanaphis sacchari, Metcalfiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettix spp., Nettigoniclla spectra, Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Oxya chinensis, Pachypsylla spp., Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., Peregrinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp., Prosopidopsylla flava, Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., Psyllopsis spp., Psylla spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus titanus, Schizaphis graminum, Selenaspidus articulatus, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Siphoninus phillyreae, Tenalaphara malayensis, Tetragonocephela spp., Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes vaporariorum, Trioza spp., Typhlocyba spp., Unaspis spp., Viteus vitifolii, Zygina spp.; aus der Ordnung der Hymenoptera z.B. Acromyrmex spp., Athalia spp., Atta spp., Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Sirex spp., Solenopsis invicta, Tapinoma spp., Urocerus spp., Vespa spp., Xeris spp.; aus der Ordnung der Isopoda z.B. Armadillidium vulgare, Oniscus asellus, Porcellio scaber; aus der Ordnung der Isoptera z.B. Coptotermes spp., Cornitermes cumulans, Cryptotermes spp., Incisitermes spp., Microtermes obesi, Odontotermes spp., Reticulitermes spp.; aus der Ordnung der Lepidoptera z.B. Achroia grisella, Acronicta major, Adoxophyes spp., Aedia leucomelas, Agrotis spp., Alabama spp., Amyelois transitella, Anarsia spp., Anticarsia spp., Argyroploce spp., Barathra brassicae, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp., Caloptilia theivora, Capua reticulana, Carpocapsa pomonella, Carposina niponensis, Cheimatobia brumata, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocerus spp., Cnaphalocrocis medinalis, Cnephasia spp., Conopomorpha spp., Conotrachelus spp., Copitarsia spp., Cydia spp., Dalaca noctuides, Diaphania spp., Diatraea saccharalis, Earias spp., Ecdytolopha aurantium, Elasmopalpus lignosellus, Eidana saccharina, Ephestia spp., Epinotia spp., Epiphyas postvittana, Etiella spp., Eulia spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Feltia spp., Galleria mellonella, Gracillaria spp., Grapholitha spp., Hedylepta spp., Helicoverpa spp., Heliothis spp., Hofmannophila pseudospretella, Homoeosoma spp., Homona spp., Hyponomeuta padella, Kakivoria flavofasciata, Laphygma spp., Laspeyresia molesta, Leucinodes orbonalis, Leucoptera spp., Lithocolletis spp., Lithophane antennata, Lobesia spp., Loxagrotis albicosta, Lymantria spp., Lyonetia spp., Malacosoma neustria, Maruca testulalis, Mamstra brassicae, Melanitis leda, Mocis spp., Monopis obviella, Mythimna separata, Nemapogon cloacellus, Nymphula spp., Oiketicus spp., Oria spp., Orthaga spp., Ostrinia spp., Oulema oryzae, Panolis flammea, Parnara spp., Pectinophora spp., Perileucoptera spp., Phthorimaea spp., Phyllocnistis citrella, Phyllonorycter spp., Pieris spp., Platynota stultana, Plodia interpunctella, Plusia spp., Plutella xylostella, Prays spp., Prodenia spp., Protoparce spp., Pseudaletia spp., Pseudaletia unipuncta, Pseudoplusia includens, Pyrausta nubilalis, Rachiplusia nu, Schoenobius spp., Scirpophaga spp., Scirpophaga innotata, Scotia segetum, Sesamia spp., Sesamia inferens, Sparganothis spp., Spodoptera spp., Spodoptera praefica, Stathmopoda spp., Stomopteryx subsecivella, „„ Pests of the genus Arthropoda, in particular of the class Arachnida eg Acarus spp., Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Amphitetranychus viennensis, Argas spp., Boophilus spp., Brevipalpus spp., Bryobia graminum , Bryobia praetiosa, Centruroides spp., Chorioptes spp., Dermanyssus gallinae, Dermatophagoides pteronyssinus, Dermatophagoides farinae, Dermacentor spp., Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Glycyphagus domesticus, Halotydeus destructor, Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus spp., Loxosceles spp., Metatetranychus spp., Neutrombicula autumnalis, Nuphersa spp., Oligonychus spp., Ornithodorus spp., Ornithonyssus spp., Panonychus Spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Steneotarsonemus spp., Steneotarsonemus spinki, Tarsonemus spp., Tetranychus spp., Trombicula alfreddugesi, Vaejovis spp. Vasates lycopersici. ; from the genus of Chilopoda, for example Geophilus spp., Scutigera spp .; from the order or class of Collembola eg Onychiurus armatus .; from the class Diplopoda eg Blaniulus guttulatus; from the class of the Insecta, eg from the order of the Blattodea eg Blattella asahinai, Blattella germanica, Blatta orientalis, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta spp., Supella longipalpa; from the order Coleoptera eg Acalymma vittatum, Acanthoscelides obtectus, Adoretus spp., Agelastica alni, Agriotes spp., Alphitobius diaperinus, Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp., Apion spp., Apogonia spp , Atomaria spp., Attagenus spp., Bruchidius obtectus, Bruchus spp., Cassida spp., Cerotoma trifurcata, Ceutorrhynchus spp., Chaetocnema spp., Cleonus mendicus, Conoderus spp., Cosmopolites spp., Costelytra zealandica, Ctenicera spp. Curculio spp., Cryptolestes ferruginus, Cryptorhynchus lapathi, Cylindrocopturus spp., Dermestes spp., Diabrotica spp., Dichocrocis spp., Dicladispa armigera, Diloboderus spp., Epilachna spp., Epitrix spp., Faustinus spp., Gibbium psylloides, Gnathocerus cornutus , Hellula and alis, Heteronychus arator, Heteronyx spp., Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypomeces squamosus, Hypothenemus spp., Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridius spp., Lema spp., Leptinotarsa decemlineata, Leucoptera spp., Lissorhoptrus oryzophilus, Lixus spp., Luperodes spp., Lyctus spp., Megascelis spp., Melanotus spp., Meligethes aeneus, Melolontha spp., Migdolus spp., Monochamus spp , Naupactus xanthographus, Necrobia spp., Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorrhynchus spp., Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga spp., Phyllophaga helleri, Phyllotreta spp., Popillia japonica, Premnotrypes spp., Prostephanus truncatus, Psylliodes spp., Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp., Sitophilus oryzae, Sphenophorus spp., Stegobium paniceum, Starchus spp., Symphyletes spp., Tanymecus spp., Tenebrio molitor, Tenebrioides mauretanicus, Tribolium spp ., Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp .; from the order of Diptera eg Aedes spp., Agromyza spp., Anastrepha spp., Anopheles spp., Asphondylia spp., Bactrocera spp., Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capitata, Chironomus spp., Chrysomyia spp., Chrysops spp., Chrysozona pluvialis, Cochliomyia spp., Contarinia spp., Cordylobia anthropophaga, Cricotopus sylvestris, Culex spp., Culicoides spp., Culiseta spp., Cuterebra spp., Dacus oleae , Dasyneura spp., Delia spp., Dermatobia hominis, Drosophila spp., Echinocnemus spp., Fannia spp., Gasterophilus spp., Glossina spp., Haematopota spp., Hydrellia spp., Hydrellia griseola, Hylemya spp., Hippobosca spp. , Hypoderma spp., Liriomyza spp., Lucilla spp., Lutzomyia spp., Mansonia spp., Musca spp., Oestrus spp., Oscinella frit, Paratanytarsus spp., Paralauterborniella subcincta, Pegomyia spp., Phlebotomus spp., Phorbia spp. , Phormia spp., Piophila casei, Prodiplosis spp., Psila rosae, Rhagoletis spp., Sarcophaga spp., Simulium spp., Stomoxys spp., Tabanus spp., Tetanops spp., Tipula spp .; from the order of the Heteroptera eg Anasa tristis, Antestiopsis spp., Boisea spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Collaria spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Eushtus spp., Eurygaster spp., Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptocoris varicornis, Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae, Monaionion atratum, Nezara spp., Oebalus spp. , Pentomidae, Piesma quadrata, Piezodorus spp., Psallus spp., Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scaptocoris castanea, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp. ; from the order of Homoptera eg Acizzia acaciaebaileyanae, Acizzia dodonaeae, Acizzia uncatoides, Acrida turrita, Acyrthosipon spp., Acrogonia spp., Aeneolamia spp., Agonoscena spp., Aleyrodes proletella, Aleurolobus barodensis, Aleurothrixus floccosus, Allocaridara malayensis, Amrasca spp. Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphis spp., Arboridia apicalis, Arytainilla spp., Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia tabaci, Blastopsylla occidentalis, Boreioglycaspis melaleucae, Brachycaudus helichrysi, Brachycolus spp , Brevicoryne brassicae, Cacopsylla spp., Calligypona marginata, Carneocephala fulgida, Ceratovacuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chondracris rosea, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp Cryptonezusa spp., Ctenarytaina spp., Dalbulus spp., Dialeurodes citri, Diaphorin a citri, Diaspis spp., Drosicha spp., Dysaphis spp., Dysmicoccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Eucalyptolyma spp., Euphyllura spp., Euscelis bilobatus, Ferrisia spp., Geococcus coffeae, Glycaspis spp., Heteropsylla cubana, Heteropsylla spinulosa, Homalodisca coagulata, Hyalopterus arundinis, Icerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Macrosteies facifrons, Mahanarva spp , Melanaphis sacchari, Metcalfiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettix spp., Nettigoniclla spectra, Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Oxya chinensis, Pachypsylla spp., Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., Peregrinus maidis, Phenacoccus Spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp., Prosopidopsylla flava, Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., Psyllopsis spp., Psylla spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus Spp., Quesada gigas, Rastrococcus spp., Rhopalosiphum spp., Saissetia spp., Scaphoideus titanus, Schizaphis graminum, Selenaspidus articulatus, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Siphoninus phillyreae, Tenalaphara malayensis, Tetragonocephela spp. , Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes vaporariorum, Trioza spp., Typhlocyba spp., Unaspis spp., Viteus vitifolii, Zygina spp .; from the order of Hymenoptera eg Acromyrmex spp., Athalia spp., Atta spp., Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Sirex spp., Solenopsis invicta, Tapinoma spp., Urocerus spp., Vespa spp ., Xeris spp .; from the order of Isopoda, for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber; from the order of Isoptera eg Coptotermes spp., Cornitermes cumulans, Cryptotermes spp., Incisitermes spp., Microtermes obesi, Odontotermes spp., Reticulitermes spp .; from the order of the Lepidoptera eg Achroia grisella, Acronica major, Adoxophyes spp., Aedia leucomelas, Agrotis spp., Alabama spp., Amyelois transitella, Anarsia spp., Anticarsia spp., Argyroploce spp., Barathra brassicae, Borbo cinnara, Bucculatrix thurberiella , Bupalus piniarius, Busseola spp., Cacoecia spp., Caloptilia theivora, Capua reticulana, Carpocapsa pomonella, Carposina niponensis, Cheimatobia brumata, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocerus spp., Cnaphalocrocis medinalis, Cnephasia spp., Conopomorpha Spp., Conotrachelus spp., Copitarsia spp., Cydia spp., Dalaca noctuides, Diaphania spp., Diatraea saccharalis, Earias spp., Ecdytolopha aurantium, Elasmopalpus lignosellus, Eidana saccharina, Ephestia spp., Epinotia spp., Epiphyas postvittana, Etiella spp., Eulia spp., Eupoecilia ambiguella, Euproctis spp., Euxoa spp., Feltia spp., Galleria mellonella, Gracillaria spp., Grapholitha spp., Hedylepta spp., Helicoverpa spp., Heliothis spp., Hofmannophila p seudospretella, Homoeosoma spp., Homona spp., Hyponomeuta padella, Kakivoria flavofasciata, Laphygma spp., Laspeyresia molesta, Leucinodes orbonalis, Leucoptera spp., Lithocolletis spp., Lithophane antennata, Lobesia spp., Loxagrotis albicosta, Lymantria spp., Lyonetia spp , Malacosoma neustria, Maruca testulalis, Mamstra brassicae, Melanitis leda, Mocis spp., Monopis obviella, Mythimna separata, Nemapogon cloacellus, Nymphula spp., Oiketicus spp., Oria spp., Orthaga spp., Ostrinia spp., Oulema oryzae, Panolis flammea, Parnara spp., Pectinophora spp., Perileucoptera spp., Phthorimaea spp., Phyllocnistis citrella, Phyllonorycter spp., Pieris spp., Platynota stultana, Plodia interpunctella, Plusia spp., Plutella xylostella, Prays spp., Prodenia spp. , Protoparce spp., Pseudaletia spp., Pseudaletia unipuncta, Pseudoplusia includens, Pyrausta nubilalis, Rachiplusia nu, Schoenobius spp., Scirpophaga spp., Scirpophaga innotata, Scotia segetum, Sesamia spp., Sesamia inferens, Sparganothis spp. , Spodoptera spp., Spodoptera praefica, Stathmopoda spp., Stomopteryx subsecivella, ""
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Synanthedon spp., Tecia solanivora, Thermesia gemmatalis, Tinea cloacella, Tinea pellionella, Tineola bisselliella, Tortrix spp., Trichophaga tapetzella, Trichoplusia spp., Tryporyza incertulas, Tuta absoluta, Virachola spp.; aus der Ordnung der Orthoptera oder Saltatoria z.B. Acheta domesticus, Dichroplus spp., Gryllotalpa spp., Hieroglyphus spp., Locusta spp., Melanoplus spp., Schistocerca gregaria; aus der Ordnung der Phthiraptera z.B. Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Phylloera vastatrix, Phtirus pubis, Trichodectes spp.; aus der Ordnung der Psocoptera z.B. Lepinotus spp., Liposcelis spp.; aus der Ordnung der Siphonaptera z.B. Ceratophyllus spp., Ctenocephalides spp., Pulex irritans, Tunga penetrans, Xenopsylla cheopsis; aus der Ordnung der Thysanoptera z.B. Anaphothrips obscurus, Baliothrips biformis, Drepanothrips reuteri, Enneothrips Hävens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamomi, Thrips spp.; aus der Ordnung der Zygentoma (= Thysanura), z. B. Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus, Thermobia domestica; aus der Klasse der Symphyla z.B. Scutigerella spp.; Synanthedon spp., Tecia solanivora, Thermesia gemmatalis, Tinea cloacella, Tinea pellionella, Tineola bisselliella, Tortrix spp., Trichophaga tapetzella, Trichoplusia spp., Tryporyza incertulas, Tuta absoluta, Virachola spp .; from the order of Orthoptera or Saltatoria e.g. Acheta domesticus, Dichroplus spp., Gryllotalpa spp., Hieroglyphus spp., Locusta spp., Melanoplus spp., Schistocerca gregaria; from the order of Phthiraptera e.g. Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Phylloera vastatrix, Phtirus pubis, Trichodectes spp .; from the order of Psocoptera e.g. Lepinotus spp., Liposcelis spp .; from the order of siphonaptera e.g. Ceratophyllus spp., Ctenocephalides spp., Pulex irritans, Tunga penetrans, Xenopsylla cheopsis; from the order of Thysanoptera e.g. Anaphothrips obscurus, Baliothrips biformis, Drepanothrips reuteri, Enneothrips hevens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamomi, Thrips spp .; from the order of Zygentoma (= Thysanura), z. Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus, Thermobia domestica; from the class of Symphyla e.g. Scutigerella spp .;
Schädlinge aus dem Stamm der Mollusca, insbesondere aus der Klasse der Bivalvia, z.B. Dreissena spp., sowie aus der Klasse der Gastropoda z.B. Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea spp., Succinea spp.; Tierparasiten aus den Stämmen der Plathelminthes und Nematoda, z.B. Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp., Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp., Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti; Pflanzenschädlinge aus dem Stamm der Nematoda, d.h. pflanzenparasitäre Nematoden, insbesondere Aphelenchoides spp., Bursaphelenchus spp., Ditylenchus spp., Globodera spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus spp., Trichodorus spp., Tylenchulus spp., Xiphinema spp., Helicotylenchus spp., Tylenchorhynchus spp., Scutellonema spp., Paratrichodorus spp., Meloinema spp., Paraphelenchus spp., Aglenchus spp., Belonolaimus spp., Nacobbus spp., Rotylenchulus spp., Rotylenchus spp., Neotylenchus spp., Paraphelenchus spp., Dolichodorus spp., Hoplolaimus spp., Punctodera spp., Criconemella spp., Quinisulcius spp., Hemicycliophora spp., Anguina spp., Subanguina spp., Hemicriconemoides spp., Psilenchus spp., Pseudohalenchus spp., Criconemoides spp., Cacopaurus spp. Pests from the strain of Mollusca, in particular from the class of bivalvia, eg Dreissena spp., And from the class of Gastropoda eg Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea spp., Succinea spp .; Animal parasites from the strains of Plathelminthes and Nematoda, eg Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp., Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp. , Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosome spp., Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis , Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti; Plant pests from the Nematoda strain, ie plant parasitic nematodes, in particular Aphelenchoides spp., Bursaphelenchus spp., Ditylenchus spp., Globodera spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus spp., Trichodorus spp., Tylenchulus spp., Xiphinema spp., Helicotylenchus spp., Tylenchorhynchus spp., Scutellonema spp., Paratrichodorus spp., Meloinema spp., Paraphelenchus spp , Aglenchus spp., Belonolaimus spp., Nacobbus spp., Rotylenchulus spp., Rotylenchus spp., Neotylenchus spp., Paraphelenchus spp., Dolichodorus spp., Hoplolaimus spp., Punctodera spp., Criconemella spp., Quinisulcius spp. Hemicycliophora spp., Anguina spp., Subanguina spp., Hemicriconemoides spp., Psilenchus spp., Pseudohalenchus spp., Criconemoides spp., Cacopaurus spp.
Weiterhin lässt sich aus dem Unterreich der Protozoa die Ordnung der Coccidia z.B. Eimeria spp. bekämpfen. Die vorliegende Erfindung betrifft weiterhin Formulierungen und daraus bereitete Anwendungsformen als Pflanzenschutzmittel und/oder Schädlingsbekämpfungsmittel wie z. B. Drench-, Drip- und Spritzbrühen, umfassend mindestens einen der erfindungsgemäßen Wirkstoffe. Gegebenenfalls enthalten die Anwendungsformen weitere Pflanzenschutzmittel und/oder Schädlingsbekämpfungsmittel und/oder die Wirkung verbessernde Adjuvantien wie Penetrationsförderer, z. B. vegetative Öle wie beispielsweise Rapsöl, Sonnenblumenöl, Mineralöle wie beispielsweise Paraffinöle, Alkylester vegetativer Fettsäuren wie beispielsweise Rapsöl- oder Sojaölmethylester oder Alkanol-alkoxylate und/oder Spreitmittel wie beispielsweise Alkylsiloxane und/oder Salze z.B. organische oder anorganische Ammonium- oder Phosphoniumsalze wie beispielsweise Ammoniumsulfat oder Diammonium-hydrogenphosphat und/oder die Retention fördernde Mittel wie z. B. Dioctylsulfosuccinat oder Hydroxypropyl-guar Polymere und/oder Humectants wie z.B. Glycerin und/oder Dünger wie beispielsweise Ammonium-, Kalium- oder Phosphor-enthaltende Dünger. Furthermore, from the sub-kingdom of protozoa, the order of coccidia can be determined, e.g. Eimeria spp. fight. The present invention further relates to formulations and application forms prepared therefrom as crop protection agents and / or pesticides such. B. drench, drip and spray, comprising at least one of the active compounds according to the invention. If appropriate, the use forms contain other crop protection agents and / or pesticides and / or the effect of improving adjuvants such as penetration enhancers, eg. For example, vegetative oils such as rapeseed oil, sunflower oil, mineral oils such as paraffin oils, alkyl esters of vegetal fatty acids such as rapeseed oil or soybean oil methyl ester or alkanol alkoxylates and / or spreading agents such as alkyl siloxanes and / or salts, e.g. organic or inorganic ammonium or phosphonium salts such as ammonium sulfate or diammonium hydrogen phosphate and / or retention-promoting agents such. Dioctylsulfosuccinate or hydroxypropyl-guar polymers and / or humectants, e.g. Glycerol and / or fertilizers such as ammonium, potassium or phosphorus-containing fertilizer.
Übliche Formulierungen sind beispielsweise wasserlösliche Flüssigkeiten (SL), Emulsionskonzentrate (EC), Emulsionen in Wasser (EW), Suspensionskonzentrate (SC, SE, FS, OD), in Wasser dispergierbare Granulate (WG), Granulate (GR) und Kapselkonzentrate (CS); diese und weitere mögliche Formuliertypen sind beispielsweise durch Crop Life International und in Pesticide Specifications, Manual on development and use of FAO and WHO specifications for pesticides, FAO Plant Production and Protection Papers - 173, prepared by the FAO/WHO Joint Meeting on Pesticide Specifications, 2004, ISBN: 9251048576 beschrieben. Gegebenenfalls enthalten die Formulierungen neben einem oder mehreren erfindungsgemäßen Wirkstoffen weitere agrochemische Wirkstoffe. Vorzugsweise handelt es sich um Formulierungen oder Anwendungsformen, welche Hilfsstoffe wie beispielsweise Streckmittel, Lösemittel, Spontanitätsförderer, Trägerstoffe, Emulgiermittel, Dispergiermittel, Frostschutzmittel, Biozide, Verdicker und/oder weitere Hilfsstoffe wie beispielsweise Adjuvantien enthalten. Ein Adjuvant in diesem Kontext ist eine Komponente, die die biologische Wirkung der Formulierung verbessert, ohne dass die Komponente selbst eine biologische Wirkung hat. Beispiele für Adjuvantien sind Mittel, die die Retention, das Spreitverhalten, das Anhaften an der Blattoberfläche oder die Penetration fördern. Typical formulations are, for example, water-soluble liquids (SL), emulsion concentrates (EC), emulsions in water (EW), suspension concentrates (SC, SE, FS, OD), water-dispersible granules (WG), granules (GR) and capsule concentrates (CS). ; These and other possible formulation types are described, for example, by Crop Life International and in Pesticide Specifications, Manual on Development and Use of FAO and WHO Specifications for Pesticides, FAO Plant Production and Protection Papers - 173, prepared by the FAO / WHO Joint Meeting on Pesticide Specifications, 2004, ISBN: 9251048576. If appropriate, the formulations contain, in addition to one or more active compounds according to the invention, further agrochemical active substances. They are preferably formulations or use forms which contain auxiliaries, such as extenders, solvents, spontaneity promoters, carriers, emulsifiers, dispersants, antifreeze agents, biocides, thickeners and / or further auxiliaries, for example adjuvants. An adjuvant in this context is a component that enhances the biological effect of the formulation without the component itself having a biological effect. Examples of adjuvants are agents which enhance retention, spreading behavior, adherence to the Promote leaf surface or penetration.
Diese Formulierungen werden in bekannter Weise hergestellt, z.B. durch Vermischen der Wirkstoffe mit Hilfsstoffen wie beispielsweise Streckmitteln, Lösemitteln und/oder festen Trägerstoffen und/oder weiteren Hilfsstoffen wie beispielsweise oberflächenaktive Stoffe. Die Herstellung der Formulierungen erfolgt entweder in geeigneten Anlagen oder auch vor oder während der Anwendung. These formulations are prepared in a known manner, e.g. by mixing the active ingredients with excipients such as extenders, solvents and / or solid carriers and / or other excipients such as surfactants. The preparation of the formulations is carried out either in suitable systems or before or during use.
Als Hilfsstoffe können solche Stoffe Verwendung finden, die geeignet sind, der Formulierung des Wirkstoffs oder den aus diesen Formulierungen bereiteten Anwendungsformen (wie z.B. gebrauchsfähigen Pflanzenschutzmitteln wie Spritzbrühen oder Saatgutbeizen) besondere Eigenschaften, wie bestimmte physikalische, technische und/oder biologische Eigenschaften zu verleihen. Als Streckmittel eignen sich z.B. Wasser, polare und unpolare organische chemische Flüssigkeiten z.B. aus den Klassen der aromatischen und nicht-aromatischen Kohlenwasserstoffe (wie Paraffine, Alkylbenzole, Alkylnaphthaline, Chlorbenzole), der Alkohole und Polyole (die ggf. auch substituiert, verethert und/oder verestert sein können), der Ketone (wie Aceton, Cyclohexanon), Ester (auch Fette und Öle) und (Poly-)Ether, der einfachen und substituierten Amine, Amide, Lactame (wie N- Alkylpyrrolidone) und Lactone, der Sulfone und Sulfoxide (wie Dirne thylsulfoxid). Excipients which can be used are those which are suitable for imparting special properties, such as physical, technical and / or biological properties, to the formulation of the active substance or to the forms of use prepared from these formulations (for example usable plant protection agents such as spray mixtures or seed dressing). As extender, e.g. Water, polar and non-polar organic chemical liquids e.g. from the classes of aromatic and non-aromatic hydrocarbons (such as paraffins, alkylbenzenes, alkylnaphthalenes, chlorobenzenes), alcohols and polyols (which may also be substituted, etherified and / or esterified), ketones (such as acetone, cyclohexanone), Esters (including fats and oils) and (poly) ethers, simple and substituted amines, amides, lactams (such as N-alkylpyrrolidones) and lactones, sulfones and sulfoxides (such as methyl sulfoxide).
Im Falle der Benutzung von Wasser als Streckmittel können z.B. auch organische Lösemittel als Hilfslösemittel verwendet werden. Als flüssige Lösemittel kommen im Wesentlichen infrage: Aromaten wie Xylol, Toluol oder Alkylnaphthaline, chlorierte Aromaten oder chlorierte aliphatische Kohlenwasserstoffe wie Chlorbenzole, Chlorethylene oder Methylenchlorid, aliphatische Kohlenwasserstoffe, wie Cyclohexan oder Paraffine, z.B. Erdölfraktionen, mineralische und pflanzliche Öle, Alkohole wie Butanol oder Glykol sowie deren Ether und Ester, Ketone wie Aceton, Methylethylketon, Meth- ylisobutylketon oder Cyclohexanon, stark polare Lösemittel wie Dimethylformamid und Dimethylsulfoxid sowie Wasser. In the case of using water as an extender, e.g. also organic solvents can be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide and water.
Grundsätzlich können alle geeigneten Lösemittel verwendet werden. Geeignete Lösemittel sind beispielsweise aromatische Kohlenwasserstoffe wie z.B. Xylol, Toluol oder Alkylnaphthaline, chlorierte aromatische oder aliphatische Kohlenwasserstoffe wie z.B. Chlorbenzol, Chlorethylen, oder Methylenchlorid, aliphatische Kohlenwasserstoffe wie z.B. Cyclohexan, Paraffine, Erdölfraktionen, mineralische und pflanzliche Öle, Alkohole wie z.B. Methanol, Ethanol, iso-Propanol, Butanol oder Glykol sowie deren Ether und Ester, Ketone wie z.B. Aceton, Methylethylketon, Methylisobutylketon oder Cyclo- hexanon, stark polare Lösemittel wie Dimethylsulfoxid sowie Wasser. In principle, all suitable solvents can be used. Suitable solvents are, for example, aromatic hydrocarbons, e.g. Xylene, toluene or alkylnaphthalenes, chlorinated aromatic or aliphatic hydrocarbons, e.g. Chlorobenzene, chloroethylene, or methylene chloride, aliphatic hydrocarbons, e.g. Cyclohexane, paraffins, petroleum fractions, mineral and vegetable oils, alcohols such as e.g. Methanol, ethanol, iso-propanol, butanol or glycol and their ethers and esters, ketones such as e.g. Acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strong polar solvents such as dimethyl sulfoxide and water.
Grundsätzlich können alle geeigneten Trägerstoffe eingesetzt werden. Als Trägerstoffe kommen insbesondere infrage: z.B. Ammoniumsalze und natürliche Gesteinsmehle wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehl, wie hochdisperse Kieselsäure, Aluminiumoxid und natürliche oder synthetische Silikate, Harze, Wachse und „„ In principle, all suitable carriers can be used. Suitable carriers are in particular: for example, ammonium salts and ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock flour, such as finely divided silica, alumina and natural or synthetic silicates, resins, waxes and ""
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/oder feste Düngemittel. Mischungen solcher Trägerstoffe können ebenfalls verwendet werden. Als Trägerstoffe für Granulate kommen infrage: z.B. gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Papier, Kokosnussschalen, Maiskolben und Tabakstängel. / or solid fertilizers. Mixtures of such carriers can also be used. Suitable carriers for granules are: e.g. Cracked and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, paper, coconut shells, corn cobs and tobacco stems.
Auch verflüssigte gasförmige Streckmittel oder Lösemittel können eingesetzt werden. Insbesondere eignen sich solche Streckmittel oder Trägerstoffe, welche bei normaler Temperatur und unter Normaldruck gasförmig sind, z.B. Aerosol-Treibgase wie Halogenkohlenwasserstoffe sowie Butan, Propan, Stickstoff und Kohlendioxid. Beispiele für Emulgier- und/oder Schaum erzeugende Mittel, Dispergiermittel oder Benetzungsmittel mit ionischen oder nicht-ionischen Eigenschaften oder Mischungen dieser oberflächenaktiven Stoffe sind Salze von Polyacrylsäure, Salze von Lignosulphonsäure, Salze von Phenolsulphonsäure oder Naphthalinsulphonsäure, Polykondensate von Ethylenoxid mit Fettalkoholen oder mit Fettsäuren oder mit Fettaminen, mit substituierten Phenolen (vorzugsweise Alkylphenole oder Arylphenole), Salze von Sulphobernsteinsäureestern, Taurinderivate (vorzugsweise Alkyltaurate), Phosphorsäureester von polyethoxylierten Alkoholen oder Phenole, Fettsäureester von Polyolen und Derivate der Verbindungen enthaltend Sulphate, Sulphonate und Phosphate, z.B. Alkylarylpolyglycolether, Alkylsulfonate, Alkyl- sulfate, Arylsulfonate, Eiweißhydrolysate, Lignin-Sulfitablaugen und Methylcellulose. Die Anwesenheit einer oberflächenaktiven Substanz ist vorteilhaft, wenn einer der Wirkstoff und/oder einer der inerten Trägerstoffe nicht in Wasser löslich ist und wenn die Anwendung in Wasser erfolgt. Also, liquefied gaseous diluents or solvents can be used. Particularly suitable are those diluents or carriers which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. Examples of emulsifying and / or foaming agents, dispersants or wetting agents having ionic or non-ionic properties or mixtures of these surfactants are salts of polyacrylic acid, salts of lignosulphonic acid, salts of phenolsulphonic acid or naphthalenesulphonic acid, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, with substituted phenols (preferably alkylphenols or arylphenols), salts of sulphosuccinic acid esters, taurine derivatives (preferably alkyl taurates), phosphoric acid esters of polyethoxylated alcohols or phenols, fatty acid esters of polyols and derivatives of the compounds containing sulphates, sulphonates and phosphates, eg Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, arylsulfonates, protein hydrolysates, lignin-sulphite liquors and methylcellulose. The presence of a surfactant is advantageous when one of the active ingredients and / or one of the inert carriers is not soluble in water and when applied in water.
Als weitere Hilfsstoffe können in den Formulierungen und den daraus abgeleiteten Anwendungsformen Farbstoffe wie anorganische Pigmente, z.B. Eisenoxid, Titanoxid, Ferrocy anblau und organische Farbstoffe wie Alizarin-, Azo- und Metallphthalocyaninfarbstoffe und Nähr- und Spurennährstoffe wie Salze von Eisen, Mangan, Bor, Kupfer, Kobalt, Molybdän und Zink vorhanden sein. Weiterhin enthalten sein können Stabilisatoren wie Kältestabilisatoren, Konservierungsmittel, Oxidationsschutzmittel, Lichtschutzmittel oder andere die chemische und / oder physikalische Stabilität verbessernde Mittel. Weiterhin enthalten sein können schaumerzeugende Mittel oder Entschäumer. As further adjuvants, in the formulations and the applications derived therefrom, dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes, and nutrient and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc. Stabilizers such as cold stabilizers, preservatives, antioxidants, light stabilizers or other chemical and / or physical stability-improving agents may also be present. It may also contain foam-forming agents or defoamers.
Ferner können die Formulierungen und daraus abgeleiteten Anwendungsformen als zusätzliche Hilfsstoffe auch Haftmittel wie Carboxymethylcellulose, natürliche und synthetische pulverige, körnige oder latexförmige Polymere enthalten wie Gummiarabikum, Polyvinylalkohol, Polyvinylacetat sowie natürliche Phospholipide wie Kephaline und Lecithine und synthetische Phospholipide. Weitere Hilfsstoffe können mineralische und vegetabile Öle sein. In addition, the formulations and the use forms derived therefrom may also contain, as additional auxiliaries, adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-containing polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate and natural phospholipids such as cephalins and lecithins and synthetic phospholipids. Other auxiliaries may be mineral and vegetable oils.
Gegebenenfalls können noch weitere Hilfsstoffe in den Formulierungen und den daraus abgeleiteten Anwendungsformen enthalten sein. Solche Zusatzstoffe sind beispielsweise Duftstoffe, schützende „ Optionally, further auxiliaries may be present in the formulations and in the use forms derived therefrom. Such additives are, for example, perfumes, protective "
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Kolloide, Bindemittel, Klebstoffe, Verdicker, thixotrope Stoffe, Penetrationsförderer, Retentionsförderer, Stabilisatoren, Sequestiermittel, Komplexbildner, Humectans, Spreitmittel. Im Allgemeinen können die Wirkstoffe mit jedem festen oder flüssigen Zusatzstoff, welches für Formulierungszwecke gewöhnlich verwendet wird, kombiniert werden. Als Retentionsförderer kommen alle diejenigen Substanzen in Betracht, die die dynamische Oberflächenspannung verringern wie beispielsweise Dioctylsulfosuccinat oder die die Visko-Elastizität erhöhen wie beispielsweise Hydroxypropyl-guar Polymere. Colloids, binders, adhesives, thickeners, thixotropic substances, penetrants, retention promoters, stabilizers, sequestrants, complexing agents, humectants, spreading agents. In general, the active ingredients can be combined with any solid or liquid additive commonly used for formulation purposes. As retention promoters are all those substances which reduce the dynamic surface tension such as dioctylsulfosuccinate or increase the visco-elasticity such as hydroxypropyl guar polymers.
Als Penetrationsförderer kommen im vorliegenden Zusammenhang alle diejenigen Substanzen in Betracht, die üblicherweise eingesetzt werden, um das Eindringen agrochemischer Wirkstoffen in Pflanzen zu verbessern. Penetrationsförderer werden in diesem Zusammenhang dadurch definiert, dass sie aus der (in der Regel wässerigen) Applikationsbrühe und/oder aus dem Spritzbelag in die Kutikula der Pflanze eindringen und dadurch die Stoffbeweglichkeit (Mobilität) der Wirkstoffe in der Kutikula erhöhen können. Die in der Literatur (Baur et al., 1997, Pesticide Science 51, 131-152) beschriebene Methode kann zur Bestimmung dieser Eigenschaft eingesetzt werden. Beispielhaft werden genannt Alkoholalkoxylate wie beispielsweise Kokosfettethoxylat (10) oder Isotridecylethoxylat (12), Fettsäureester wie beispielsweise Rapsöl- oder Sojaölmethylester, Fettamine Alkoxylate wie beispielsweise Tallowamine ethoxylat (15) oder Ammonium- und/oder Phosphonium-Salze wie beispielsweise Ammoniumsulfat oder Diammonium-hydrogenphosphat. Suitable penetration promoters in the present context are all those substances which are usually used to improve the penetration of agrochemical active substances into plants. Penetration promoters are in this context defined by the fact that they can penetrate from the (usually aqueous) application broth and / or from the spray coating into the cuticle of the plant and thereby increase the material mobility (mobility) of the active ingredients in the cuticle. The method described in the literature (Baur et al., 1997, Pesticide Science 51, 131-152) can be used to determine this property. Examples include alcohol alkoxylates such as coconut oil ethoxylate (10) or Isotridecylethoxylat (12), fatty acid esters such as rapeseed oil or soybean oil, fatty amine alkoxylates such as Tallowamine ethoxylate (15) or ammonium and / or phosphonium salts such as ammonium sulfate or diammonium hydrogen phosphate.
Die Formulierungen enthalten bevorzugt zwischen 0,00000001 und 98 Gew.- Wirkstoff oder, besonders bevorzugt zwischen 0,01 und 95 Gew.- Wirkstoff, besonders bevorzugt zwischen 0,5 und 90 Gew.- Wirkstoff, bezogen auf das Gewicht der Formulierung. The formulations preferably contain between 0.00000001 and 98% by weight of active ingredient or, more preferably, between 0.01 and 95% by weight of active compound, more preferably between 0.5 and 90% by weight of active ingredient, based on the weight of the formulation.
Der Wirkstoffgehalt der aus den Formulierungen bereiteten Anwendungsformen (Pflanzenschutzmittel) kann in weiten Bereichen variieren. Die Wirkstoffkonzentration der Anwendungsformen kann üblicherweise zwischen 0,00000001 und 95 Gew.- Wirkstoff, vorzugsweise zwischen 0,00001 und 1 Gew.- , bezogen auf das Gewicht der Anwendungsform, liegen. Die Anwendung geschieht in einer den Anwendungsformen angepaßten üblichen Weise. The active substance content of the application forms (pesticides) prepared from the formulations can vary within wide ranges. The active ingredient concentration of the use forms can usually be between 0.00000001 and 95% by weight of active ingredient, preferably between 0.00001 and 1% by weight, based on the weight of the application form. The application is done in a custom forms adapted to the application.
Die die erfindungsgemäßen bzw. erfindungsgemäß zu verwendenden Wirkstoffe können als solche oder in ihren Formulierungen auch in Mischung mit einem oder mehreren geeigneten Fungiziden, Bakteriziden, Akariziden, Molluskiziden, Nematiziden, Insektiziden, Mikrobiologika, Nützlingen, Düngemitteln, Vogelrepellentien, Phytotonics, Sterilantien, Synergisten, Safenern, Semiochemicals und/oder Pflanzenwachstumsregulatoren verwendet werden, um so z.B. das Wirkungsspektrum zu verbreitern, die Wirkdauer zu verlängern, die Wirkgeschwindigkeit zu steigern, Repellenz zu verhindern oder Resistenzentwicklungen vorzubeugen. Desweiteren können solche Wirkstoffkombinationen das Pflanzenwachstum und/oder die Toleranz gegenüber abiotischen Faktoren wie z. B. hohen oder t rn The active substances to be used according to the invention or according to the invention can also be used as such or in their formulations as a mixture with one or more suitable fungicides, bactericides, acaricides, molluscicides, nematicides, insecticides, microbiologicals, beneficials, fertilizers, bird repellents, phytotonics, sterilants, synergists, Safeners, semiochemicals and / or plant growth regulators can be used, for example, to broaden the spectrum of action, to extend the duration of action, to increase the rate of action, to prevent repellence or to prevent the development of resistance. Furthermore, such drug combinations plant growth and / or tolerance to abiotic factors such. B. high or t rn
- 47 - niedrigen Temperaturen, gegen Trockenheit oder gegen erhöhten Wasser- bzw. Bodensalzgehalt verbessern. Auch lässt sich das Blüh- und Fruchtverhalten verbessern, die Keimfähigkeit und Bewurzelung optimieren, die Ernte erleichtern und Ernteerträge steigern, die Reife beeinflussen, die Qualität und/oder den Ernährungswert der Ernteprodukte steigern, die Lagerfähigkeit verlängern und/oder die Bearbeitbarkeit der Ernteprodukte verbessern. Durch Kombination der erfindungsgemäßen bzw. erfindungsgemäß zu verwendenden Wirkstoffe mit Mischpartnern erhält man synergistische Effekte, d.h. die Wirksamkeit der jeweiligen Mischung ist größer als aufgrund der Wirksamkeiten der Einzelkomponenten zu erwarten war. Generell können die Kombinationen sowohl in Vor-, Tank- oder Fertigmischungen als auch in Saatgutanwendungen verwendet werden. Die hier mit ihrem „common name" genannten Wirkstoffe sind bekannt und beispielsweise im Pestizidhandbuch („The Pesticide Manual" 14th Ed., British Crop Protection Council 2006) beschrieben oder im Internet recherchierbar (z.B. http://www.alanwood.net/pesticides).  - 47 - low temperatures, against dryness or against increased water or Bodensalzgehalt improve. Also, flowering and fruiting behavior can be improved, germination and rooting can be optimized, harvesting and crop yields increased, maturity can be enhanced, crop quality and / or nutritional value increased, shelf life extended and / or crop productivity improved. By combining the active ingredients according to the invention or to be used according to the invention with mixing partners, synergistic effects are obtained, ie. the effectiveness of the respective mixture is greater than was to be expected due to the efficiencies of the individual components. In general, the combinations can be used both in pre-mix, tank or finished mixes and in seed applications. The active substances mentioned here with their "common name" are known and described, for example, in the Pesticide Handbook ("The Pesticide Manual" 14th Ed., British Crop Protection Council 2006) or searchable on the Internet (eg http://www.alanwood.net/pesticides ).
Als Mischpartner geeignete Insektizide / Akarizide / Nematizide sind As mixing partners suitable insecticides / acaricides / nematicides are
(1) Acetylcholinesterase (AChE) Inhibitoren, wie beispielsweise Carbamate, z.B. Alanycarb, Aldicarb, Bendiocarb, Benfuracarb, Butocarboxim, Butoxycarboxim, Carbaryl, Carbofuran, Carbosulfan, Ethiofencarb, Fenobucarb, Formetanate, Furathiocarb, Isoprocarb, Methiocarb, Methomyl, Metolcarb, Oxamyl, Pirimicarb, Propoxur, Thiodicarb, Thiofanox, Triazamate, Trimethacarb, XMC und Xylylcarb; oder (1) Acetylcholinesterase (AChE) inhibitors such as carbamates, e.g. Alanycarb, Aldicarb, Bendiocarb, Benfuracarb, Butocarboxime, Butoxycarboxime, Carbaryl, Carbofuran, Carbosulfan, Ethiofencarb, Fenobucarb, Formetanate, Furathiocarb, Isoprocarb, Methiocarb, Methomyl, Metolcarb, Oxamyl, Pirimicarb, Propoxur, Thiodicarb, Thiofanox, Triazamate, Trimethacarb, XMC and xylylcarb; or
Organophosphate, z.B. Acephate, Azamethiphos, Azinphos-ethyl, Azinphos-methyl, Cadusafos, Chlorethoxyfos, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos-methyl, Coumaphos, Cyanophos, Demeton-S-methyl, Diazinon, Dichlorvos/DDVP, Dicrotophos, Dimethoate, Dimethylvinphos, Disulfoton, EPN, Ethion, Ethoprophos, Famphur, Fenamiphos, Fenitrothion, Fenthion, Fosthiazate, Heptenophos, Imicyafos, Isofenphos, Isopropyl O-(methoxyaminothio-phosphoryl) salicylat, Isoxathion, Malathion, Mecarbam, Methamidophos, Methidathion, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion, Parathion-methyl, Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimiphos-methyl, Profenofos, Propetamphos, Prothiofos, Pyraclofos, Pyridaphenthion, Quinalphos, Sulfotep, Tebupirimfos, Temephos, Terbufos, Tetrachlorvinphos, Thiometon, Triazophos, Trichlorfon und Vamidothion. Organophosphates, e.g. Acephate, Azamethiphos, Azinophos-ethyl, Azinophos-methyl, Cadusafos, Chloroethoxyfos, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos-methyl, Coumaphos, Cyanophos, Demeton-S-methyl, Diazinone, Dichlorvos / DDVP, Dicrotophos, Dimethoates, Dimethylvinphos, Disulfone, EPN, Ethion, Ethoprophos, Famphur, Fenamiphos, Fenitrothion, Fenthion, Fosthiazate, Heptenophos, Imicyafos, Isofenphos, Isopropyl O- (methoxyaminothio-phosphoryl) salicylate, Isoxathione, Malathion, Mecarbam, Methamidophos, Methidathione, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion, Parathion-methyl, Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimiphos-methyl, Profenofos, Propetamphos, Prothiofos, Pyraclofos, Pyridaphenthion, Quinalphos, Sulfotep, Tebupirimfos, Temephos, Terbufos, Tetrachlorvinphos, Thiometon, Triazophos, trichlorophone and vamidothion.
(2) GABA-gesteuerte Chlorid-Kanal-Antagonisten, wie beispielsweise Cyclodien-organochlorine, z.B. Chlordane und Endosulfan; oder (2) GABA-controlled chloride channel antagonists, such as cyclodiene organochlorines, e.g. Chlordane and endosulfan; or
Phenylpyrazole (Fiprole), z.B. Ethiprole und Fipronil. Phenylpyrazoles (fiproles), e.g. Ethiprole and fipronil.
(3) Natrium-Kanal-Modulatoren / Spannungsabhängige Natrium-Kanal-Blocker, wie beispielsweise Pyrethroide, z.B. Acrinathrin, Allethrin, d-cis-trans Allethrin, d-trans Allethrin, Bifenthrin, Bioallethrin, Bioallethrin S-cyclopentenyl Isomer, Bioresmethrin, Cycloprothrin, Cyfluthrin, beta-Cyfluthrin, Cyhalothrin, lambda-Cyhalothrin, gamma-Cyhalothrin, Cypermethrin, alpha-Cypermethrin, beta- Cypermethrin, theta-Cypermethrin, zeta-Cypermethrin, Cyphenothrin [(lR)-trans-Isomere], Deltamethrin, Empenthrin [(EZ)-(lR)-Isomere), Esfenvalerate, Etofenprox, Fenpropathrin, Fenvalerate, Flucythrinate, Flumethrin, tau-Fluvalinate, Halfenprox, Imiprothrin, Kadethrin, Permethrin, Phenothrin [(lR)-trans- Isomer), Prallethrin, Pyrethrine (pyrethrum), Resmethrin, Silafluofen, Tefluthrin, Tetramethrin, Tetramethrin [(1R)- Isomere)], Tralomethrin und Transfluthrin; oder (3) Sodium channel modulators / voltage dependent sodium channel blockers, such as Pyrethroids, eg acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin [(lR) trans isomers], deltamethrin, empenthrin [(EZ) (lR) isomers], esfenvalerates, etofenprox, fenpropathrin, fenvalerates , Flucythrinates, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, kadethrin, permethrin, phenothrin [(lR) -trans- isomer), prallethrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R) isomers )], Tralomethrin and transfluthrin; or
DDT; oder Methoxychlor. (4) Nikotinerge Acetylcholin-Rezeptor (nAChR) Agonisten, wie beispielsweise DDT; or methoxychlor. (4) nicotinergic acetylcholine receptor (nAChR) agonists, such as
Neonikotinoide, z.B. Acetamiprid, Clothianidin, Dinotefuran, Imidacloprid, Nitenpyram, Thiacloprid und Thiamethoxam; oder Neonicotinoids, e.g. Acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or
Nikotin; oder Nicotine; or
Sulfoxaflor. (5) Nikotinerge Acetylcholin-Rezeptor (nAChR) allosterische Aktivatoren, wie beispielsweise Spinosine, z.B. Spinetoram und Spinosad. Sulfoxaflor. (5) nicotinergic acetylcholine receptor (nAChR) allosteric activators such as spinosines, e.g. Spinetoram and spinosad.
(6) Chlorid-Kanal-Aktivatoren, wie beispielsweise (6) chloride channel activators, such as
Avermectine/Milbemycine, z.B. Abamectin, Emamectin-benzoat, Lepimectin und Milbemectin. Avermectins / milbemycins, e.g. Abamectin, Emamectin benzoate, Lepimectin and Milbemectin.
(7) Juvenilhormon-Imitatoren, wie beispielsweise Juvenilhormon-Analoge, z.B. Hydroprene, Kinoprene und Methoprene; oder Fenoxycarb; oder Pyriproxyfen. (7) Juvenile hormone mimics, such as juvenile hormone analogs, e.g. Hydroprene, kinoprene and methoprene; or fenoxycarb; or pyriproxyfen.
(8) Wirkstoffe mit unbekannten oder nicht spezifischen Wirkmechanismen, wie beispielsweise Alkylhalide, z.B. Methylbromid und andere Alkylhalide; oder (8) agents with unknown or nonspecific modes of action, such as alkyl halides, e.g. Methyl bromide and other alkyl halides; or
Chloropicrin; oder Sulfurylfluorid; oder Borax; oder Brechweinstein. (9) Selektive Fraßhemmer, z.B. Pymetrozine; oder Flonicamid. chloropicrin; or sulfuryl fluoride; or borax; or tartar emetic. (9) Selective feeding inhibitors, e.g. pymetrozine; or flonicamide.
(10) Milbenwachstumsinhibitoren, z.B. Clofentezine, Hexythiazox und Diflovidazin; oder Etoxazole. (10) mite growth inhibitors, eg clofentezine, hexythiazox and diflovidazine; or Etoxazole.
(11) Mikrobielle Disruptoren der Insektendarmmembran, z.B. Bacillus thuringiensis Subspezies israelensis, Bacillus thuringiensis Subspezies aizawai, Bacillus thuringiensis Subspezies kurstaki, Bacillus thuringiensis Subspezies tenebrionis und B.t. Pllanzenproteine: CrylAb, CrylAc, CrylFa, CrylA.105, Cry2Ab, Vip3A, mCry3A, Cry3 Ab, Cry3Bb, Cry34 Ab 1/35 Ab 1 ; oder (11) Insect intestinal membrane microbial disruptors, e.g. Bacillus thuringiensis subspecies israelensis, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis and B.t. Plural proteins: CrylAb, CrylAc, CrylFa, CrylA.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, Cry34 From 1/35 From 1; or
Bacillus sphaericus. Bacillus sphaericus.
(12) Inhibitoren der oxidativen Phosphorylierung, ATP-Disruptoren, wie beispielsweise Diafenthiuron; oder (12) inhibitors of oxidative phosphorylation, ATP disruptors such as diafenthiuron; or
Organozinn Verbindungen, z.B. Azocyclotin, Cyhexatin und Fenbutatin-oxid; oder Propargite; oder Tetradifon. Organotin Compounds, e.g. Azocyclotine, cyhexatin and fenbutatin oxide; or propargite; or tetradifon.
(13) Entkoppler der oxidativen Phoshorylierung durch Unterbrechung des H-Protongradienten, wie beispielsweise Chlorfenapyr, DNOC und Sullluramid. (13) Decoupling of oxidative phosphorylation by interruption of the H proton gradient, such as chlorfenapyr, DNOC, and sullluramide.
(14) Nikotinerge Acetylcholin-Rezeptor-Antagonisten, wie beispielsweise Bensultap, Cartap-hydrochlorid, Thiocyclam und Thiosultap-Natrium. (15) Inhibitoren der Chitinbiosynthese, Typ 0, wie beispielsweise Bistrilluron, Chlorlluazuron, Dillubenzuron, Flucycloxuron, Flufenoxuron, Hexallumuron, Lufenuron, Novaluron, Novillumuron, Tellubenzuron und Triilumuron. (14) Nicotinergic acetylcholine receptor antagonists such as Bensultap, Cartap hydrochloride, thiocyclam and thiosultap sodium. (15) Type 0 inhibitors of chitin biosynthesis, such as bistrilluron, chloraluazuron, dillubenzuron, flucycloxuron, flufenoxuron, hexallumuron, lufenuron, novaluron, novillumuron, tellubenzuron, and triilumuron.
(16) Inhibitoren der Chitinbiosynthese, Typ 1, wie beispielsweise Buprofezin. (16) inhibitors of chitin biosynthesis, type 1, such as buprofezin.
(17) Häutungsstörende Wirkstoffe, Dipteran, wie beispielsweise Cyromazine. (18) Ecdyson-Rezeptor Agonisten, wie beispielsweise Chromafenozide, Halofenozide, Methoxyfenozide und Tebufenozide. (17) Moulting agents, dipteran, such as cyromazine. (18) ecdysone receptor agonists, such as chromafenozides, halofenozides, methoxyfenozides, and tebufenozides.
(19) Oktopaminerge Agonisten, wie beispielsweise Amitraz. (19) Octopaminergic agonists, such as amitraz.
(20) Komplex-III-Elektronentransportinhibitoren, wie beispielsweise Hydramethylnon; oder Acequinocyl; oder Fluacrypyrim. (21) Komplex-I-Elektronentransportinhibitoren, beispielsweise (20) complex III electron transport inhibitors such as hydramethylnone; or acequinocyl; or fluacrypyrim. (21) Complex I electron transport inhibitors, for example
METI-Akarizide, z.B. Fenazaquin, Fenpyroximate, Pyrimidifen, Pyridaben, Tebufenpyrad und Tolfenpyrad; oder Rotenone (Derris). METI acaricides, eg fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad; or Rotenone (Derris).
(22) Spannungsabhängige Natriumkanal-Blocker, z.B. Indoxacarb; oder Metaflumizone. (22) voltage dependent sodium channel blockers, e.g. indoxacarb; or metaflumizone.
(23) Inhibitoren der Acetyl-CoA-Carboxylase, wie beispielsweise (23) inhibitors of acetyl-CoA carboxylase, such as
Tetron- und Tetramsäurederivate, z.B. Spirodiclofen, Spiromesifen und Spirotetramat. (24) Komplex-IV-Elektronentransportinhibitoren, wie beispielsweise Tetronic and tetramic acid derivatives, e.g. Spirodiclofen, spiromesifen and spirotetramat. (24) complex IV electron transport inhibitors such as
Phosphine, z.B. Aluminiumphosphid, Calciumphosphid, Phosphin und Zinkphosphid; oder Cyanid. Phosphines, e.g. Aluminum phosphide, calcium phosphide, phosphine and zinc phosphide; or cyanide.
(25) Komplex-II-Elektronentransportinhibitoren, wie beispielsweise Cyenopyrafen und Cyflumetofen. (25) Complex II electron transport inhibitors such as cyenopyrafen and cyflumetofen.
(28) Ryanodinrezeptor-Effektoren, wie beispielsweise Diamide, z.B. Chlorantraniliprole, Cyantraniliprole und Flubendiamide. (28) ryanodine receptor effectors such as diamides, e.g. Chlorantraniliprole, Cyantraniliprole and Flubendiamide.
Weitere Wirkstoffe, wie beispielsweise Amidoflumet, Azadirachtin, Benclothiaz, Benzoximate, Bifenazate, Bromopropylate, Chinomethionat, Cryolite, Dicofol, Diflovidazin, Fluensulfone, Flufenerim, Flufiprole, Fluopyram, Fufenozide, Imidaclothiz, Iprodione, Meperfluthrin, Pyridalyl, Pyrifluquinazon, Tetramethylfluthrin und lodmethan; desweiteren Präparate auf Basis von Bacillus firmus (insbesondere Stamm CNCM 1-1582, beispielsweise VOTiVO™, BioNem) sowie folgende Verbindungen: Other agents such as amidoflumet, azadirachtin, benclothiaz, benzoximate, bifenazate, bromopropylate, quinomethionate, cryolite, dicofol, diflovidazine, fluensulfone, flufenerim, flufiprole, fluopyram, fufenocide, imidaclothiz, iprodione, meperfluthrin, pyralidyl, pyrifluquinazone, tetramethylfluthrin and iodomethane; furthermore preparations based on Bacillus firmus (in particular strain CNCM 1-1582, for example VOTiVO ™, BioNem) and the following compounds:
3 -Brom-N- { 2-brom-4-chlor-6- [( 1 -cyclopropylethyl)carbamoyl]phenyl } - 1 -(3 -chlorpyridin-2-yl) - 1 H- pyrazol-5-carboxamid (bekannt aus WO2005/077934), 4-{ [(6-Brompyrid-3-yl)methyl](2- fluorethyl)amino}furan-2(5H)-on (bekannt aus WO2007/115644), 4-{ [(6-Fluorpyrid-3-yl)methyl](2,2- difluorethyl)amino}furan-2(5H)-on (bekannt aus WO2007/115644), 4-{ [(2-Chlor-l,3-thiazol-5- yl)methyl](2-fluorethyl)amino}furan-2(5H)-on (bekannt aus WO2007/115644), 4-{ [(6-Chlorpyrid-3- yl)methyl](2-fluorethyl)amino}furan-2(5H)-on (bekannt aus WO2007/115644), Flupyradifurone, 4-{ [(6- Chlor-5-fluorpyrid-3-yl)methyl](methyl)amino}furan-2(5H)-on (bekannt aus WO2007/115643), 4-{ [(5,6- Dichlorpyrid-3-yl)methyl](2-fluorethyl)amino}furan-2(5H)-on (bekannt aus WO2007/115646), 4-{ [(6- Chlor-5-fluorpyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-on (bekannt aus WO2007/115643), 4- { [(6-Chlorpyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-on (bekannt aus EP-A-0 539 588), 4-{ [(6- Chlorpyrid-3-yl)methyl](methyl)amino}furan-2(5H)-on (bekannt aus EP-A-0 539 588), { [l-(6- Chlorpyridin-3-yl)ethyl](methyl)oxido-λ4-sulfanyliden}cyanamid (bekannt aus WO2007/149134) und seine Diastereomere { [(lR)-l-(6-Chlorpyridin-3-yl)ethyl](methyl)oxido-λ4-sulfanyliden}cyanamid (A) und { [(lS)-l-(6-Chlorpyridin-3-yl)ethyl](methyl)oxido-λ4-sulfanyliden}cyanamid (B) (ebenfalls bekannt aus WO2007/149134) sowie Diastereomere [(R)-Methyl(oxido){(lR)-l-[6-(trifluormethyl)pyridin-3- yl] ethyl } ^4-sulf anyliden] cyanamid (AI) und [(S)-Methyl(oxido) {(1S)-1- [6-(trifluormethyl)pyridin-3 - yl]ethyl}-λ4-sulfanyliden]cyananlid (A2), bezeichnet als Diastereomerengruppe A (bekannt aus WO 2010/074747, WO 2010/074751), [(R)-Methyl(oxido){(lS)-l-[6-(trifluormethyl)pyridin-3-yl]ethyl}^4- sulf anyliden] cyanamid (B 1) und [(S)-Methyl(oxido) { ( 1R)-1 -[6-(trilluormethyl)pyridin-3-yl]ethyl } -λ4- sulf anyliden] cyanamid (B2), bezeichnet als Diastereomerengruppe B (ebenfalls bekannt aus WO 2010/074747, WO 2010/074751) und l l-(4-Chlor-2,6-dimethylphenyl)-12-hydroxy-l,4-dioxa-9- azadispiro[4.2.4.2]tetradec-l l-en-10-on (bekannt aus WO2006/089633), 3-(4'-Fluor-2,4-dimethyl- biphenyl-3-yl)-4-hydroxy-8-oxa-l-azaspiro[4.5]dec-3-en-2-on (bekannt aus WO2008/067911), l-{2- Fluor-4-methyl-5-[(2,2,2-trifluorethyl)sulfinyl]phenyl}-3-(trifluormethyl)-lH-l,2,4-triazol-5-amin (bekannt aus WO2006/043635), Afidopyropen (bekannt aus WO2008/066153), 2-Cyan-3- (difluormethoxy)-N,N-dimethylbenzolsulfonamid (bekannt ausWO2006/056433), 2-Cyan-3- (difluormethoxy)-N-methylbenzolsulfonamid (bekannt aus WO2006/100288), 2-Cyan-3- (difluormethoxy)-N-ethylbenzolsulfonamid (bekannt aus WO2005/035486), 4-(Difluormethoxy)-N-ethyl- N-methyl-l,2-benzothiazol-3-amin-l,l-dioxid (bekannt aus WO2007/057407), N-[l-(2,3- Dimethylphenyl)-2-(3,5-dimethylphenyl)ethyl]-4,5-dihydro-l,3-thiazol-2-amin (bekannt aus3-Bromo-N- {2-bromo-4-chloro-6- [(1-cyclopropylethyl) carbamoyl] phenyl} -1- (3-chloropyridin-2-yl) -1 H -pyrazole-5-carboxamide (known from WO2005 / 077934), 4- {[(6-bromopyrid-3-yl) methyl] (2-fluoroethyl) amino} furan-2 (5H) -one (known from WO2007 / 115644), 4- {[(6 -Fluoropyrid-3-yl) methyl] (2,2-difluoroethyl) amino} furan-2 (5H) -one (known from WO2007 / 115644), 4- {[(2-chloro-1,3-thiazole-5 - yl) methyl] (2-fluoroethyl) amino} furan-2 (5H) -one (known from WO2007 / 115644), 4- {[(6-chloropyrid-3-yl) methyl] (2-fluoroethyl) amino} furan-2 (5H) -one (known from WO2007 / 115644), flupyradifurone, 4- {[(6-chloro-5-fluoropyrid-3-yl) methyl] (methyl) amino} furan-2 (5H) -one (known from WO2007 / 115643), 4- {[(5,6-dichloropyrid-3-yl) methyl] (2-fluoroethyl) amino} furan-2 (5H) -one (known from WO2007 / 115646), 4- {[(6-chloro-5-fluoropyrid-3-yl) methyl] (cyclopropyl) amino} furan-2 (5H) -one (known from WO2007 / 115643), 4- {[(6-chloropyrid-3-yl ) methyl] (cyclopropyl) amino} furan-2 (5H) -one (known from EP-A-0 539 588), 4- {[(6-chloropyrid-3-yl) methyl] (m ethyl) amino} furan-2 (5H) -one (known from EP-A-0 539 588), {[1- (6-chloropyridin-3-yl) ethyl] (methyl) oxido- 4- sulfanylidene} cyanamide (known from WO2007 / 149134) and its diastereomers {[(lR) -l- (6-chloropyridin-3-yl) ethyl] (methyl) oxido-λ 4 -sulfanyliden} cyanamide (A) and {[(lS) - 1- (6-chloropyridin-3-yl) ethyl] (methyl) oxido-λ 4 -sulfanylidene} cyanamide (B) (also known from WO2007 / 149134) and diastereomers [(R) -methyl (oxido) {(IR) -l- [6- (trifluoromethyl) pyridin-3- yl] ethyl} ^ 4 -sulf anyliden] cyanamide (AI) and [(S) -methyl (oxido) {(1S) -1- [6- (trifluoromethyl) pyridin-3 - yl] ethyl} -λ 4 -sulfanyliden ] cyananlide (A2), referred to as diastereomeric group A (known from WO 2010/074747, WO 2010/074751), [(R) -methyl (oxido) {(1S) -l- [6- (trifluoromethyl) pyridine-3] yl] ethyl} ^ 4 -sulfanylidene] cyanamide (B 1) and [(S) -methyl (oxido) {(1R) -1 - [6- (trifluoromethyl) pyridin-3-yl] ethyl} -λ 4 - sulfanylidene] cyanamide (B2), referred to as diastereomeric group B (also known from WO 2010/074747, WO 2010/074751) and 1- (4-chloro-2,6-dimethylphenyl) -12-hydroxy-1, 4 dioxa-9-azadispiro [4.2.4.2] tetradec-1-en-10-one (known from WO2006 / 089633), 3- (4'-fluoro-2,4-dimethyl-biphenyl-3-yl) -4 -hydroxy-8-oxa-1-azaspiro [4.5] dec-3-en-2-one (known from WO2008 / 067911), 1- {2-fluoro-4-methyl-5 - [(2,2,2 trifluoroethyl) sulfinyl] phenyl} -3- (trifluoromethyl) -1H-l, 2,4-triazol-5-amine (known from WO2006 / 043635), afidopyropes (known from WO2008 / 066153), 2-cyano-3 (difluoromethoxy) -N, N-dime ethylbenzenesulfonamide (known from WO2006 / 056433), 2-cyano-3- (difluoromethoxy) -N-methylbenzenesulfonamide (known from WO2006 / 100288), 2-cyano-3- (difluoromethoxy) -N-ethylbenzenesulfonamide (known from WO2005 / 035486), 4- (difluoromethoxy) -N-ethyl-N-methyl-1,2-benzothiazol-3-amine-1,1-dioxide (known from WO2007 / 057407), N- [1- (2,3-dimethylphenyl) - 2- (3,5-dimethylphenyl) ethyl] -4,5-dihydro-1,3-thiazol-2-amine (known from
WO2008/104503), { r (2E)-3-(4-Ch^henyl)prop-2-en -yl]-5-fluorspiro[indol-3,4'-piperidin]-l(2H)- yl}(2-chlorpyridin-4-yl)methanon (bekannt aus WO2003/106457), 3-(2,5-Dimethylphenyl)-4-hydroxy-8- methoxy-l,8-diazaspiro[4.5]dec-3-en-2-on (bekannt aus WO2009/049851), 3-(2,5-Dimethylphenyl)-8- methoxy-2-oxo-l,8-diazaspiro[4.5]dec-3-en-4-yl-ethylcarbonat (bekannt aus WO2009/049851), 4-(But-2- in-l-yloxy)-6-(3,5-dimethylpiperidin-l-yl)-5-fluorpyrimidin (bekannt aus WO2004/099160), (2,2,3,3,4,4,5,5-Octafluorpentyl)(3,3,3-trifluorpropyl)malononitril (bekannt aus WO2005/063094), (2,2,3,3,4,4,5,5-Octafluorpentyl)(3,3,4,4,4-pentafluorbutyl)malononitril (bekannt aus WO2005/063094), 8- [2-(Cyclopropylmethoxy) -4-(trifluormethyl)phenoxy] -3 - [6-(trifluormethyl)pyridazin-3 -yl] -3 - azabicyclo[3.2.1]octan (bekannt aus WO2007/040280), Flometoquin, PF1364 (CAS-Reg.Nr. 1204776-60- 2) (bekannt aus JP2010/018586), 5-[5-(3,5-Dichlorphenyl)-5-(trifluormethyl)-4,5-dihydro-l,2-oxazol-3- yl]-2-(lH-l,2,4-triazol-l-yl)benzonitril (bekannt aus WO2007/075459), 5-[5-(2-Chlorpyridin-4-yl)-5- (trifluormethyl)-4,5-dihydro- 1 ,2-oxazol-3-yl] -2-( 1 H- 1 ,2,4-triazol- 1 -yl)benzonitril (bekannt aus WO2007/075459), 4-[5-(3,5-Dichlorphenyl)-5-(trifluormethyl)-4,5-dihydro-l,2-oxazol-3-yl]-2-methyl-N- {2-oxo-2-[(2,2,2-trifluorethyl)amino]ethyl}benzamid (bekannt aus WO2005/085216), 4-{ [(6- Chlorpyridin-3-yl)methyl](cyclopropyl)amino}-l,3-oxazol-2(5H)-on, 4-{ [(6-Chlorpyridin-3- yl)methyl] (2,2-difluorethyl)amino } - 1 ,3-oxazol-2(5H)-on, 4- { [(6-Chlorpyridin-3-yl)methyl] (ethyl)amino } - l,3-oxazol-2(5H)-on, 4-{ [(6-Chlorpyridin-3-yl)methyl](methyl)amino}-l,3-oxazol-2(5H)-on (alle bekannt aus WO2010/005692), Pyflubumide (bekannt aus WO2002/096882), Methyl-2-[2-({ [3-brom-l-(3- chlorpyridin-2-yl)- 1 H-pyrazol-5 -yl] carbonyl } amino) -5 -chlor-3 -methylbenzoyl] -2-methylhydrazincarboxy- lat (bekannt aus WO2005/085216), Methyl-2-[2-({ [3-brom-l-(3-chlorpyridin-2-yl)-lH-pyrazol-5- yl]carbonyl}amino)-5-cyan-3-methylbenzoyl]-2-ethylhydrazincarboxylat (bekannt aus WO2005/085216), Methyl-2- [2-( { [3 -brom- 1 -(3 -chlorpyridin-2-yl) - 1 H-pyrazol-5 -yl] carbonyl } amino)-5 -cyan-3 -methyl- benzoyl]-2-methylhydrazincarboxylat (bekannt aus WO2005/085216), Methyl-2-[3,5-dibrom-2-({ [3- brom- 1 -(3 -chlorpyridin-2-yl)- 1 H-pyrazol-5 -yl] carbonyl } amino)benzoyl] - 1 ,2-diethylhydrazincarboxylat (bekannt aus WO2005/085216), Methyl-2-[3,5-dibrom-2-({ [3-brom-l-(3-chlorpyridin-2-yl)-lH-pyrazol-5- yl] carbonyl }amino)benzoyl]-2-ethylhydrazincarboxylat (bekannt aus WO2005/085216), (5RS,7RS;5RS,7SR)-l-(6-Chlor-3-pyridylmethyl)-l,2,3,5,6,7-hexahydro-7-methyl-8-nitro-5-propoxy- imidazol[l,2-a]pyridin (bekannt aus WO2007/101369), 2-{6-[2-(5-Huorpyridin-3-yl)-l,3-thiazol-5- yl]pyridin-2-yl}pyrimidin (bekannt aus WO2010/006713), 2-{6-[2-(Pyridin-3-yl)-l,3-thiazol-5-yl]pyridin-WO2008 / 104503), {r (2E) -3- (4-chloro) prop-2-enyl] -5-fluorospiro [indole-3,4'-piperidine] -1 (2H) -yl} (2-chloropyridin-4-yl) methanone (known from WO2003 / 106457), 3- (2,5-dimethylphenyl) -4-hydroxy-8-methoxy-1,8-diazaspiro [4.5] dec-3-ene 2-one (known from WO2009 / 049851), 3- (2,5-dimethylphenyl) -8-methoxy-2-oxo-1,8-diazaspiro [4.5] dec-3-en-4-yl-ethyl carbonate (known from WO2009 / 049851), 4- (but-2-in-1-yloxy) -6- (3,5-dimethylpiperidin-1-yl) -5-fluoropyrimidine (known from WO2004 / 099160), (2,2, 3,3,4,4,5,5-octafluoropentyl) (3,3,3-trifluoropropyl) malononitrile (known from WO2005 / 063094), (2,2,3,3,4,4,5,5-octafluoropentyl ) (3,3,4,4,4-pentafluorobutyl) malononitrile (known from WO2005 / 063094), 8- [2- (cyclopropylmethoxy) -4- (trifluoromethyl) phenoxy] -3- [6- (trifluoromethyl) pyridazine] 3 -yl] -3-azabicyclo [3.2.1] octane (known from WO2007 / 040280), flometoquine, PF1364 (CAS reference No. 1204776-60-2) (known from JP2010 / 018586), 5- [5 - (3,5-dichlorophenyl) -5- (trifluoromethyl) -4,5-dihydro-1,2-oxazol-3-yl] -2- (1H-l, 2,4-triazo II-yl) benzonitrile (known from WO2007 / 075459), 5- [5- (2-chloropyridin-4-yl) -5- (trifluoromethyl) -4,5-dihydro-1,2-oxazol-3-yl] -2- (1H-1,2,4-triazol-1-yl) benzonitrile (known from WO2007 / 075459), 4- [5- (3,5-dichlorophenyl) -5- (trifluoromethyl) -4.5 dihydro-l, 2-oxazol-3-yl] -2-methyl-N- {2-oxo-2 - [(2,2,2-trifluoroethyl) amino] ethyl} benzamide (known from WO2005 / 085216), 4- {[(6-chloropyridin-3-yl) methyl] (cyclopropyl) amino} -1,3-oxazol-2 (5H) -one, 4- {[(6-chloropyridin-3-yl) methyl] ( 2,2-difluoroethyl) amino} -1,3-oxazol-2 (5H) -one, 4- {[(6-chloropyridin-3-yl) methyl] (ethyl) amino} -1,3-oxazole-2 (5H) -one, 4- {[(6-chloropyridin-3-yl) methyl] (methyl) amino} -1,3-oxazol-2 (5H) -one (all known from WO2010 / 005692), pyflubumides ( known from WO2002 / 096882), methyl 2- [2 - ({[3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazol-5-yl] carbonyl} amino) -5-chloro 3-methylbenzoyl] -2-methylhydrazinecarboxylate (known from WO2005 / 085216), methyl 2- [2 - ({[3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5 - yl] carbonyl} amino) -5-cyano 3-methylbenzoyl] -2-ethylhydrazinecarboxylate (known from WO2005 / 085216), methyl 2- [2- ({[3-bromo-1 - (3-chloropyridin-2-yl) -1H-pyrazole-5-one yl] carbonyl} amino) -5-cyan-3-methyl benzoyl] -2-methylhydrazinecarboxylate (known from WO2005 / 085216), methyl 2- [3,5-dibromo-2 - ({[3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole -5-yl] carbonyl} amino) benzoyl] -1,2-diethylhydrazinecarboxylate (known from WO2005 / 085216), methyl 2- [3,5-dibromo-2 - ({[3-bromo-1- (3- chloropyridin-2-yl) -1H-pyrazol-5-yl] carbonyl} amino) benzoyl] -2-ethylhydrazinecarboxylate (known from WO2005 / 085216), (5RS, 7RS; 5RS, 7SR) -l- (6-chloro) 3-pyridylmethyl) -1,2,3,5,6,7-hexahydro-7-methyl-8-nitro-5-propoxy-imidazol [1,2-a] pyridine (known from WO2007 / 101369), 2- {6- [2- (5-Huoropyridin-3-yl) -l, 3-thiazol-5-yl] pyridin-2-yl} pyrimidine (known from WO2010 / 006713), 2- {6- [2- ( pyridin-3-yl) -l, 3-thiazol-5-yl] pyridine
2- yl}pyrimidin (bekannt aus WO2010/006713), l-(3-Chlorpyridin-2-yl)-N-[4-cyan-2-methyl-6- (methylcarbamoyl)phenyl] -3 - { [5 -(trifluormethyl)- 1 H-tetrazol- 1 -yl] methyl } - 1 H-pyrazol-5 -carboxamid (bekannt aus WO2010/069502), l-(3-Chlorpyridin-2-yl)-N-[4-cyan-2-methyl-6-(methylcarba- moyl)phenyl] -3 - { [5 -(trifluormethyl) -2H-tetrazol-2-yl] methyl } - 1 H-pyrazol-5 -carboxamid (bekannt aus WO2010/069502), N-[2-(tert-Butylcarbamoyl)-4-cyan-6-methylphenyl]-l-(3-chlorpyridin-2-yl)-3-{ [5- (trifluormethyl)-lH-tetrazol-l-yl]methyl}-lH-pyrazol-5-carboxamid (bekannt aus WO2010/069502), N- [2-(tert-Butylcarbamoyl) -4-cyan-6-methylphenyl] - 1 -(3 -chlorpyridin-2-yl) -3 - { [5 -(trifluormethyl) -2H- tetrazol-2-yl]methyl}-lH-pyrazol-5-carboxamid (bekannt aus WO2010/069502), (lE)-N-[(6-Chlorpyridin-2-yl} pyrimidine (known from WO2010 / 006713), 1- (3-chloropyridin-2-yl) -N- [4-cyano-2-methyl-6- (methylcarbamoyl) phenyl] -3 - {[5-10] (trifluoromethyl) -1 H -tetrazol-1-yl] methyl} -1 H -pyrazole-5-carboxamide (known from WO2010 / 069502), 1- (3-chloropyridin-2-yl) -N- [4-cyano 2-methyl-6- (methylcarbamoyl) phenyl] -3 - {[5- (trifluoromethyl) -2H-tetrazol-2-yl] methyl} -1H-pyrazole-5-carboxamide (known from WO2010 / 069502 ), N- [2- (tert -butylcarbamoyl) -4-cyano-6-methylphenyl] -1- (3-chloropyridin-2-yl) -3- {[5- (trifluoromethyl) -1H-tetrazole] yl] methyl} -1H-pyrazole-5-carboxamide (known from WO2010 / 069502), N- [2- (tert-butylcarbamoyl) -4-cyano-6-methylphenyl] -1- (3-chloropyridin-2-yl ) -3 - {[5 - (trifluoromethyl) -2H-tetrazol-2-yl] methyl} -1H-pyrazole-5-carboxamide (known from WO2010 / 069502), (IE) -N - [(6-chloropyridine)
3- yl)methyl]-N'-cyan-N-(2,2-difluorethyl)ethanimidamid (bekannt aus WO2008/009360), N-[2-(5-Amino- l,3,4-thiadiazol-2-yl)-4-chlor-6-methylphenyl]-3-brom-l-(3-chlo yridin-2-yl)-lH-pyrazol-5-carboxamid (bekannt aus CN102057925), Methyl-2-[3,5-dibrom-2-({ [3 -brom-1 -(3 -chlorpyridin-2-yl)-l H-pyrazol-5 - yl] carbonyl }amino)benzoyl]-2-ethyl-l-methylhydrazincarboxylat (bekannt aus WO2011/049233), Heptafluthrin, Pyriminostrobin, Flufenoxystrobin und 3-Chlor-N2-(2-cyanpropan-2-yl)-N1-[4- (l,l,l,2,3,3,3-heptafluorpropan-2-yl)-2-methylphenyl]phthalamid (bekannt aus WO2012/034472). 3-yl) methyl] -N'-cyano-N- (2,2-difluoroethyl) ethanimidamide (known from WO2008 / 009360), N- [2- (5-amino-1, 3,4-thiadiazole-2-one] yl) -4-chloro-6-methylphenyl] -3-bromo-1- (3-chloro-2-yl) -1H-pyrazole-5-carboxamide (known from CN102057925), methyl 2- [3,5 dibromo-2 - ({[3-bromo-1 - (3-chloropyridin-2-yl) -1H-pyrazol-5-yl] carbonyl} amino) benzoyl] -2-ethyl-1-methylhydrazinecarboxylate (known from WO2011 / 049233), heptafluthrin, pyriminostrobin, flufenoxystrobin and 3-chloro-N 2 - (2-cyanopropan-2-yl) -N 1 - [4- (1,1,2,3,3,3,3-heptafluoropropane -2-yl) -2-methylphenyl] phthalamide (known from WO2012 / 034472).
Als Mischpartner geeignete Fungizide sind: Fungicides suitable as mixing partners are:
(1) Inhibitoren der Ergosterol-Biosynthese, wie beispielsweise Aldimorph, Azaconazol, Bitertanol, Bromuconazol, Cyproconazol, Diclobutrazol, Difenoconazol, Diniconazol, Diniconazol-M, Dodemorph, Dodemorph Acetat, Epoxiconazol, Etaconazol, Fenarimol, Fenbuconazol, Fenhexamid, Fenpropidin, Fenpropimorph, Fluquinconazol, Flurprimidol, Flusilazol, Flutriafol, Furconazol, Furconazol-Cis, Hexaconazol, Imazalil, Imazalil Sulfat, Imibenconazol, Ipconazol, Metconazol, Myclobutanil, Naftifin, Nuarimol, Oxpoconazol, Paclobutrazol, Pefurazoat, Penconazol, Piperalin, Prochloraz, Propiconazol, Prothioconazol, Pyributicarb, Pyrifenox, Quinconazol, Simeconazol, Spiroxamin, Tebuconazol, Terbinafin, Tetraconazol, Triadimefon, Triadimenol, Tridemorph, Triflumizol, Triforin, Triticonazol, Uniconazol, Uniconazol-p, Viniconazol, Voriconazol, l-(4-Chlorphenyl)-2-(lH-l,2,4-triazol-l- yl)cycloheptanol, Methyl- 1 -(2,2-dimethyl-2,3-dihydro- 1 H-inden- 1 -yl)- 1 H-imidazol-5-carboxylat, N'- { 5- (Difluormethyl)-2-methyl-4-[3-(trimethylsilyl)propoxy]phenyl}-N-ethyl-N-methylimidoformamid, N- Ethyl-N-methyl-N'- { 2-methyl-5 -(trifluormethyl) -4- [3 -(trimethylsilyl)propoxy]phenyl } imidoformamid und 0-[ 1 -(4-Methoxyphenoxy)-3,3-dimethylbutan-2-yl] - 1 H-imidazol- 1 -carbothioat. (2) Inhibitoren der Respiration (Atmungsketten-Inhibitoren), wie beispielsweise Bixafen, Boscalid, Carboxin, Diflumetorim, Fenfuram, Fluopyram, Flutolanil, Fluxapyroxad, Furametpyr, Furmecyclox, Isopyrazam Mischung des syn-epimeren Razemates 1RS,4SR,9RS und des anti-empimeren Razemates 1RS,4SR,9SR, Isopyrazam (anti-epimeres Razemat ), Isopyrazam (anti-epimeres Enantiomer 1R,4S,9S), Isopyrazam (anti-epimeres Enantiomer 1S,4R,9R), Isopyrazam (syn-epimeres Razemat 1RS,4SR,9RS), Isopyrazam (syn-epimeres Enantiomer 1R,4S,9R), Isopyrazam (syn-epimeres Enantiomer 1S,4R,9S), Mepronil, Oxycarboxin, Penflufen, Penthiopyrad, Sedaxane, Thifluzamid, l-Methyl-N-[2-(l, 1,2,2- tetrailuorethoxy)phenyl] -3 -(triiluormethyl) - 1 H-pyrazol-4-carboxamid, 3 -(Dilluormethyl) - 1 -methyl-N- [2- (l,l,2,2-tetrailuorethoxy)phenyl]-lH-pyrazol-4-carboxamid, 3-(Diiluormethyl)-N-[4-iluor-2-(l, 1,2,3,3,3- hexalluorpropoxy)phenyl] - 1 -methyl- 1 H-pyrazol-4-carboxamid, N- [ 1 -(2,4-Dichlorphenyl)- 1 -methoxy- propan-2-yl] -3 -(dilluormethyl)- 1 -methyl- 1 H-pyrazol-4-carboxamid, 5 , 8 -Diiluor-N- [2-(2-lluor-4- { [4-(tri- lluormethyl)pyridin-2-yl]oxy}phenyl)ethyl]quinazolin-4-amin, N-[9-(Dichlormethylen)-l,2,3,4-tetra- hydro- 1 ,4-methanonaphthalen-5 -yl] -3 -(dilluormethyl) - 1 -methyl- 1 H-pyrazol-4-carboxamid, N- [( 1 S ,4R) -9- (Dichlormethylen)- 1 ,2,3 ,4-tetrahydro- 1 ,4-methanonaphthalen-5 -yl] -3 -(dilluormethyl) - 1 -methyl- 1 H- pyrazol-4-carboxamid und N-[(lR,4S)-9-(Dichlormethylen)-l,2,3,4-tetrahydro-l,4-methanonaphthalen-5- yl] -3 -(dilluormethyl)- 1 -methyl- 1 H-pyrazol-4-carboxamid. (1) inhibitors of ergosterol biosynthesis, such as aldimorph, azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-M, dodemorph, dodemorph acetate, epoxiconazole, etaconazole, fenarimol, fenbuconazole, fenhexamide, fenpropidin, fenpropimorph, Fluquinconazole, flurprimidol, flusilazole, flutriafol, furconazole, furconazole cis, hexaconazole, imazalil, imazalil sulfate, imibenconazole, ipconazole, metconazole, myclobutanil, naftifine, nuarimol, oxpoconazole, paclobutrazole, pefurazoate, penconazole, piperaline, prochloraz, propiconazole, prothioconazole, pyributicarb , Pyrifenox, Quinconazole, Simeconazole, Spiroxamine, Tebuconazole, Terbinafine, Tetraconazole, Triadimefon, Triadimenol, Tridemorph, Triflumizol, Triforin, Triticonazole, Uniconazole, Uniconazole-p, Viniconazole, Voriconazole, 1- (4-Chlorophenyl) -2- (lH- l, 2,4-triazol-1-yl) cycloheptanol, methyl 1 - (2,2-dimethyl-2,3-dihydro-1H-inden-1-yl) -1H-imidazole-5-carboxylate, N '- {5- (difluoromethyl) - 2-methyl-4- [3- (trimethylsilyl) propoxy] phenyl} -N-ethyl-N-methylimidoformamide, N-ethyl-N-methyl-N '- {2-methyl-5 - (trifluoromethyl) -4- 3 - (trimethylsilyl) propoxy] phenyl} imidoformamide and 0- [1- (4-methoxyphenoxy) -3,3-dimethylbutan-2-yl] -1H-imidazole-1-carbothioate. (2) inhibitors of respiration (respiratory chain inhibitors), such as bixafen, boscalid, carboxin, diflumetorim, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, furmecyclox, isopyrazam mixture of the syn-epimeric racemate 1RS, 4SR, 9RS and the anti- more reactive racemate 1RS, 4SR, 9SR, isopyrazam (anti-epimeric racemate), isopyrazam (anti-epimeric enantiomer 1R, 4S, 9S), isopyrazam (anti-epimeric enantiomer 1S, 4R, 9R), isopyrazam (syn-epimeric racemate 1RS, 4SR, 9RS), isopyrazam (syn-epimeric enantiomer 1R, 4S, 9R), isopyrazam (syn-epimeric enantiomer 1S, 4R, 9S), mepronil, oxycarboxine, penflufen, penthiopyrad, sedaxanes, thifluzamide, l-methyl-N- [ 2- (l, 1,2,2-tetrailorethoxy) phenyl] -3- (trifluoromethyl) -1 H -pyrazole-4-carboxamide, 3- (dilluoromethyl) -1-methyl-N- [2- (1, l , 2,2-tetrailorethoxy) phenyl] -1H-pyrazole-4-carboxamide, 3- (diisulforomethyl) -N- [4-iluor-2- (1,2,2,3,3,3-hexalloropropoxy) phenyl] 1-methyl-1H-pyrazole-4-carboxamide, N- [1- (2,4-dichlorophenyl) -1-methoxy-propane-2 -yl] -3- (dillomethyl) -1-methyl-1H-pyrazole-4-carboxamide, 5, 8-diluoro-N- [2- (2-fluoro-4- {[4- (trifluoromethyl) pyridin-2-yl] oxy} phenyl) ethyl] quinazolin-4-amine, N- [9- (dichloromethylene) -l, 2,3,4-tetrahydro-1, 4-methanonaphthalene-5-yl] - 3 - (dillomethyl) -1-methyl-1H-pyrazole-4-carboxamide, N- [(1S, 4R) -9- (dichloromethylene) -1,2,3,4-tetrahydro-1,4-methanonaphthalene -5-yl] -3- (dillomethyl) -1-methyl-1H-pyrazole-4-carboxamide and N - [(lR, 4S) -9- (dichloromethylene) -l, 2,3,4-tetrahydro- 1, 4-methanonaphthalene-5-yl] -3- (dillomethyl) -1-methyl-1H-pyrazole-4-carboxamide.
(3) Inhibitoren der Respiration (Atmungsketten-Inhibitoren) am Komplex III der Atumungskette, wie beispielsweise Ametoctradin, Amisulbrom, Azoxystrobin, Cyazofamid, Coumethoxystrobin, Coumoxystrobin, Dimoxystrobin, Enestroburin, Famoxadon, Fenamidon, Fenoxystrobin, Fluoxastrobin, Kresoxim-Methyl, Metominostrobin, Orysastrobin, Picoxystrobin, Pyraclostrobin, Pyrametostrobin, Pyraoxystrobin, Pyribencarb, Triclopyricarb, Trilloxystrobin, (2E)-2-(2-{ [6-(3-Chlor-2-methylphenoxy)-5- fluo yrimidin-4-yl]oxy}phenyl)-2-(methoxyimino)-N-methylethanamid, (2E)-2-(Methoxyimino)-N- methyl-2-(2- { [({(1Ε)-1-[3 -(trifluormethyl)phenyl] ethyliden } amino)oxy] methyl } phenyl)ethanamid, (2E)- 2-(Methoxyimino)-N-methyl-2-{2-[(E)-({ l-[3- (trifluormethyl)phenyl]ethoxy}imino)methyl]phenyl}ethanamid, (2E)-2-{2-[({ [(1Ε)-1-(3-{ [(E)-l-Fluor-2- phenylethenyl]oxy }phenyl)ethyliden] amino } oxy)methyl]phenyl } -2-(methoxyimino)-N-methylethanamid, (2E)-2-{2-[({ [(2E,3E)-4-(2,6-Dichlorphenyl)but-3-en-2-yliden]amino}oxy)methyl]phenyl}-2-(methoxy- imino) -N-methylethanamid, 2-Chlor-N-( 1 , 1 ,3 -trimethyl-2,3 -dihydro- 1 H-inden-4-yl)pyridin-3 -carboxamid, 5 -Methoxy-2-methyl-4-(2- { [({(1E)-1- [3 -(triiluormethyl)phenyl] ethyliden } amino)oxy] methyl Jphenyl) -2,4- dihydro-3H- 1 ,2,4-triazol-3-on, Methyl-(2E)-2-{ 2-[({ cyclopropyl[(4-methoxy- phenyl)imino]methyl}sulfanyl)methyl]phenyl}-3-methoxyprop-2-enoat, N-(3-Ethyl-3,5,5-trimethyl- cyclohexyl)-3-(formylamino)-2-hydroxybenzamid, 2-{2-[(2,5-Dimethylphenoxy)methyl]phenyl}-2- methoxy-N-methylacetamid und (2R)-2-{2-[(2,5-Dimethylphenoxy)methyl]phenyl}-2-methoxy-N- methylacetamid. (4) Inhibitoren der Mitose und Zellteilung, wie beispielsweise Benomyl, Carbendazim, Chlorfenazol, Diethofencarb, Ethaboxam, Fluopicolid, Fuberidazol, Pencycuron, Thiabendazol, Thiophanat-Methyl, „ Λ (3) inhibitors of respiration (respiratory chain inhibitors) at the complex III of the respiratory chain, such as ametoctradine, amisulbrom, azoxystrobin, cyazofamide, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, famoxadone, fenamidone, fenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin , Picoxystrobin, Pyraclostrobin, Pyrametostrobin, Pyraoxystrobin, Pyribencarb, Triclopyricarb, Trilloxystrobin, (2E) -2- (2- {[6- (3-chloro-2-methylphenoxy) -5-fluoro-imidin-4-yl] oxy} phenyl ) -2- (methoxyimino) -N-methylethaneamide, (2E) -2- (methoxyimino) -N-methyl-2- (2- {[({(1 (1)} -1- [3- (trifluoromethyl) phenyl] ethylidene } amino) oxy] methyl} phenyl) ethanamide, (2E) - 2- (methoxyimino) -N-methyl-2- {2 - [(E) - ({1- [3- (trifluoromethyl) phenyl] ethoxy} imino ) methyl] phenyl} ethanamide, (2E) -2- {2 - [({[(1Ε) -1- (3 - {[(E) -1-fluoro-2-phenylethenyl] oxy} phenyl) ethylidene] amino } oxy) methyl] phenyl} -2- (methoxyimino) -N-methylethaneamide, (2E) -2- {2 - [({[(2E, 3E) -4- (2,6-dichlorophenyl) but-3-] en-2-ylidene] a mino} oxy) methyl] phenyl} -2- (methoxyimino) -N-methylethanamide, 2-chloro-N- (1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl ) pyridine-3-carboxamide, 5-methoxy-2-methyl-4- (2- {[({(1E) -1- [3 - (trifluoromethyl) phenyl] ethylidene} amino) oxy] methyl Jphenyl) -2, 4-dihydro-3H-1, 2,4-triazol-3-one, methyl (2E) -2- {2 - [({cyclopropyl [(4-methoxyphenyl) imino] methyl} sulfanyl) methyl] phenyl } -3-methoxyprop-2-enoate, N- (3-ethyl-3,5,5-trimethylcyclohexyl) -3- (formylamino) -2-hydroxybenzamide, 2- {2 - [(2,5-dimethylphenoxy ) methyl] phenyl} -2-methoxy-N-methylacetamide and (2R) -2- {2 - [(2,5-dimethylphenoxy) methyl] phenyl} -2-methoxy-N-methylacetamide. (4) Mitosis and cell division inhibitors, such as benomyl, carbendazim, chlorfenazole, diethofencarb, ethaboxam, fluopicolide, fuberidazole, pencycuron, thiabendazole, thiophanate-methyl, " Λ
- 54 - - 54 -
Thiophanat, Zoxamid, 5-Chlor-7-(4-methylpiperidin-l-yl)-6-(2,4,6-triiluorphenyl)[l,2,4]triazolo[l,5- ajpyrimidin und 3-Chlor-5-(6-chlo yridin-3-yl)-6-methyl-4-(2,4,6-triίluorphenyl)pyridazin. Thiophanate, zoxamide, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl) [l, 2,4] triazolo [l, 5-ajpyrimidine and 3-chloro 5- (6-chloro-3-yl) -6-methyl-4- (2,4,6-trifluorophenyl) pyridazine.
(5) Verbindungen mit Multisite-Aktivität, wie beispielsweise Bordeauxmischung, Captafol, Captan, Chlorothalonil, Kupferzubereitungen wie Kupferhydroxid, Kupfernaphthenat, Kupferoxid, Kupferoxychlorid, Kupfersulfat, Dichlofiuanid, Dithianon, Dodine, Dodine freie Base, Ferbam, Fluorofolpet, Folpet, Guazatin, Guazatinacetat, Iniinoctadin, Iniinoctadinalbesilat, Iminoctadintriacetat, Mankupfer, Mancozeb, Maneb, Metiram, Zinkmetiram, Kupfer-Oxin, Propamidin, Propineb, Schwefel und Schwefelzubereitungen wie beispielsweise Calciumpolysuliid, Thiram, Tolylfluanid, Zineb und Ziram. (6) Resistenzinduktoren, wie beispielsweise Acibenzolar-S-Methyl, Isotianil, Probenazol und Tiadinil. (5) Compounds with multisite activity, such as Bordeaux mixture, captafol, captan, chlorothalonil, copper preparations such as copper hydroxide, copper naphthenate, copper oxide, copper oxychloride, copper sulfate, dichlofiuanide, dithianone, dodine, dodine free base, Ferbam, Fluorofolpet, Folpet, guazatine, guazatin acetate , Ininoctadine, ininoctadinalesilate, iminoctadine triacetate, mancopper, mancozeb, maneb, metiram, zinc metiram, copper oxine, propamidine, propineb, sulfur and sulfur preparations such as calcium polysulide, thiram, tolylfluanid, zineb and ziram. (6) resistance inducers such as acibenzolar-S-methyl, isotianil, probenazole and tiadinil.
(7) Inhibitoren der Aminosäure- und Protein-Biosynthese, wie beispielsweise Andoprim, Blasticidin-S, Cyprodinil, Kasugamycin, Kasugamycin Hydrochlorid Hydrat, Mepanipyrim, Pyrimethanil und 3-(5- Fluor-3 ,3,4,4-tetramethyl-3 ,4-dihydroisoquinolin- 1 -yl)quinolin. (7) Inhibitors of amino acid and protein biosynthesis, such as andoprim, blasticidin-S, cyprodinil, kasugamycin, kasugamycin hydrochloride hydrate, mepanipyrim, pyrimethanil, and 3- (5-fluoro-3, 3,4,4-tetramethyl-3 , 4-dihydroisoquinolin-1-yl) quinoline.
(8) Inhibitoren der ATP Produktion, wie beispielsweise Fentin Acetat, Fentin Chlorid, Fentin Hydroxid und Silthiofam. (8) inhibitors of ATP production, such as fentin acetate, fentin chloride, fentin hydroxide and silthiofam.
(9) Inhibitoren der Zellwandsynthese, wie beispielsweise Benthiavalicarb, Dimethomorph, Flumorph, Iprovalicarb, Mandipropamid, Polyoxins, Polyoxorim, Validamycin A und Valifenalat. (9) inhibitors of cell wall synthesis, such as benthiavalicarb, dimethomorph, flumorph, iprovalicarb, mandipropamide, polyoxins, polyoxorim, validamycin A, and valifenalate.
(10) Inhibitoren der Lipid- und Membran-Synthese, wie beispielsweise Biphenyl, Chloroneb, Dicloran, Edifenphos, Etridiazol, Iodocarb, Iprobenfos, Isoprothiolan, Propamocarb, Propamocarb Hydrochlorid, Prothiocarb, Pyrazophos, Quintozen, Tecnazene und Tolclofos-Methyl. (10) inhibitors of lipid and membrane synthesis such as biphenyl, chloroneb, dicloran, edifenphos, etridiazole, iodocarb, Iprobenfos, isoprothiolane, propamocarb, propamocarb hydrochloride, prothiocarb, pyrazophos, quintozene, tecnazene and tolclofos-methyl.
(11) Inhibitoren der Melanin-Biosynthese, wie beispielsweise Carpropamid, Diclocymet, Fenoxanil, Fthalid, Pyroquilon, Tricyclazol und 2,2,2-Trifluorethyl {3-methyl-l-[(4-methylbenzoyl)amino]butan-2- yljcarbamat. (11) Inhibitors of melanin biosynthesis, such as carpropamide, diclocymet, fenoxanil, fthalide, pyroquilone, tricyclazole and 2,2,2-trifluoroethyl {3-methyl-1 - [(4-methylbenzoyl) amino] butan-2-yl carbamate ,
(12) Inhibitoren der Nukleinsäuresynthese, wie beispielsweise Benalaxyl, Benalaxyl-M (Kiralaxyl), Bupirimat, Clozylacon, Dimethirimol, Ethirimol, Furalaxyl, Hymexazol, Metalaxyl, Metalaxyl-M(12) Inhibitors of nucleic acid synthesis such as benalaxyl, benalaxyl-M (kiralaxyl), bupirimate, clozylacon, dimethirimol, ethirimol, furalaxyl, hymexazole, metalaxyl, metalaxyl-M
(Mefenoxam), Ofurace, Oxadixyl und Oxolinsäure. (Mefenoxam), Ofurace, Oxadixyl and Oxolic Acid.
(13) Inhibitoren der Signaltransduktion, wie beispielsweise Chlozolinat, Fenpiclonil, Fludioxonil, Iprodion, Procymidon, Quinoxyfen und Vinclozolin. (13) signal transduction inhibitors such as chlozolinate, fenpiclonil, fludioxonil, iprodione, procymidone, quinoxyfen and vinclozolin.
(14) Entkoppler, wie beispielsweise Binapacryl, Dinocap, Ferimzon, Fluazinam und Meptyldinocap. (15) Weitere Verbindungen, wie beispielsweise Benthiazol, Bethoxazin, Capsimycin, Carvon, Chinomethionat, Pyriofenon (Chlazafenon), Cufraneb, Cyilufenamid, Cymoxanil, Cyprosulfamide, Dazomet, Debacarb, Dichlorophen, Diclomezin, Difenzoquat, Difenzoquat Methylsulphat, Diphenylamin, Ecomat, Fenpyrazamin, Flumetover, Fluoromid, Flusulfamid, Flutianil, Fosetyl-Aluminium, Fosetyl- Calcium, Fosetyl-Natrium, Hexachlorbenzol, Irumamycin, Methasulfocarb, Methylisothiocyanat, Metrafenon, Mildiomycin, Natamycin, Nickel Dimethyldithiocarbamat, Nitrothal-Isopropyl, Octhilinone, Oxamocarb, Oxyfenthiin, Pentachlorphenol und dessen Salze, Phenothrin, Phosphorsäure und deren Salze, Propamocarb-Fosetylat, Propanosin-Natrium, Proquinazid, Pyrimorph, (2E)-3-(4-Tert-butylphenyl)-3-(2- chlorpyridin-4-yl)- 1 -(morpholin-4-yl)prop-2-en- 1 -on, (2Z)-3-(4-Tert-butylphenyl)-3-(2-chlorpyridin-4-yl)- l-(morpholin-4-yl)prop-2-en-l-on, Pyrrolnitrin, Tebuiloquin, Tecloftalam, Tolnifanid, Triazoxid, Trichlamid, Zarilamid, (3S,6S,7R,8R)-8-Benzyl-3-[({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2- yl}carbonyl)amino]-6-methyl-4,9-dioxo-l,5-dioxonan-7-yl 2-methylpropanoat, l-(4-{4-[(5R)-5-(2,6- Diiluorphenyl)-4,5 -dihydro- 1 ,2-oxazol-3 -yl] - 1 ,3 -thiazol-2-yl Jpiperidin- 1 -yl) -2- [5 -methyl-3 -(triiluor- methyl)-lH-pyrazol-l-yl]ethanon, l-(4-{4-[(5S)-5-(2,6-Diiluorphenyl)-4,5-dihydro-l,2-oxazol-3-yl]-l,3- thiazol-2-yl } piperidin- 1 -yl) -2- [5 -methyl-3 -(triiluormethyl) - 1 H-pyrazol- 1 -yl] ethanon, 1 -(4- { 4- [5 -(2,6- Diiluorphenyl)-4,5 -dihydro- 1 ,2-oxazol-3 -yl] - 1 ,3 -thiazol-2-yl Jpiperidin- 1 -yl) -2- [5 -methyl-3 -(triiluormethyl) - 1 H-pyrazol- 1 -yl] ethanon, 1 -(4-Methoxyphenoxy)-3 ,3 -dimethylbutan-2-yl- 1 H-imidazol- 1 - carboxylat, 2,3,5,6-Tetrachlor-4-(methylsulfonyl)pyridin, 2,3-Dibutyl-6-chlorthieno[2,3-d]pyrimidin- 4(3H)-on, 2,6-Dimethyl-lH,5H-[l,4]dithiino[2,3-c:5,6-c']dipyrrol-l,3,5,7(2H,6H)-tetron, 2- [5 -Methyl-3 - (triiluormethyl)-lH-pyrazol-l-yl]-l-(4-{4-[(5R)-5-phenyl-4,5-dihydro-l,2-oxazol-3-yl]-l,3-thiazol-2- yl Jpiperidin- 1 -yl)ethanon, 2- [5 -Methyl-3 -(triiluormethyl) - 1 H-pyrazol- 1 -yl] - l-(4-{4-[(5S)-5 -phenyl-4,5 - dihydro- 1 ,2-oxazol-3 -yl] - 1 ,3 -thiazol-2-yl } piperidin- 1 -yl)ethanon, 2- [5 -Methyl-3 -(triiluormethyl) - 1 H- pyrazol- 1 -yl] - 1 - { 4- [4-(5-phenyl-4,5-dihydro- 1 ,2-oxazol-3-yl)- 1 ,3-thiazol-2-yl]piperidin- 1 -yl } ethanon, 2- Butoxy-6-iod-3-propyl-4H-chromen-4-on, 2-Chlor-5-[2-chlor-l-(2,6-diiluor-4-methoxyphenyl)-4-methyl- lH-imidazol-5-yl]pyridin, 2-Phenylphenol und dessen Salze, 3-(4,4,5-Triiluor-3,3-dimethyl-3,4- dihydroisoquinolin-l-yl)quinolin, 3,4,5-Trichlorpyridin-2,6-dicarbonitril, 3-[5-(4-Chlorphenyl)-2,3- dimethyl-l,2-oxazolidin-3-yl]pyridin, 3-Chlor-5-(4-chlorphenyl)-4-(2,6-diiluorphenyl)-6-methylpyridazin, 4-(4-Chlorphenyl)-5-(2,6-diiluorphenyl)-3,6-dimethylpyridazin, 5-Amino-l,3,4-thiadiazol-2-thiol, 5- Chlor-N'-phenyl-N'-(prop-2-in-l-yl)thiophen-2-sulfonohydrazid, 5-Fluor-2-[(4-iluorbenzyl)oxy]pyrimidin- 4-amin, 5-Fluor-2-[(4-methylbenzyl)oxy]pyrimidin-4-amin, 5-Methyl-6-octyl[l,2,4]triazolo[l,5- a]pyrimidin-7-amin, Ethyl-(2Z)-3-amino-2-cyan-3-phenylprop-2-enoat, N'-(4-{ [3-(4-Chlorbenzyl)-l ,2,4- thiadiazol-5 -yl] oxy } -2,5 -dimethylphenyl) -N-ethyl-N-methylimidoformamid, N-(4-Chlorbenzyl)-3 - [3 - methoxy-4-(prop-2-in-l-yloxy)phenyl]propanamid, N-[(4-Chlorphenyl)(cyan)methyl]-3-[3-methoxy-4- (prop-2-in-l-yloxy)phenyl]propanamid, N-[(5-Brom-3-chlorpyridin-2-yl)methyl]-2,4-dichlorpyridin-3- carboxamid, N- [ 1 -(5 -Brom-3 -chlorpyridin-2-yl)ethyl] -2,4-dichlorpyridin-3 -carboxamid, N- [ 1 -(5 -Brom-3 - chlorpyridin-2-yl)ethyl] -2-iluor-4-iodpyridin-3 -carboxamid, N- { (E) - [(Cyclopropylmethoxy)imino] [6- (diiluormethoxy)-2,3-diiluorphenyl]methyl}-2-phenylacetamid, N-{(Z)-[(Cyclopropylmethoxy)imino][6- (difluormethoxy) -2,3 -difluorphenyl] methyl } -2-phenylacetamid, N'- { 4- [(3 -Tert-butyl-4-cyano- 1 ,2-thiazol- 5 -yl)oxy] -2-chlor-5 -methylphenyl } -N-ethyl-N-methylimidoformamid, N-Methyl-2-( 1 - { [5 -methyl-3 - (trifluormethyl)- 1 H-pyrazol- 1 -yl] acetyl }piperidin-4-yl)-N-( 1 ,2,3 ,4-tetrahydronaphthalen- 1 -yl)-l ,3-thiazol- 4-carboxamid, N-Methyl-2-(l-{ [5-methyl-3-(trifluormethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-N- [( 1 R) - 1 ,2,3 ,4-tetrahydronaphthalen- 1 -yl] - 1 ,3 -thiazol-4-carboxamid, N-Methyl-2-( 1 - { [5 -methyl-3 -(trifluor- methyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-N-[(lS)-l,2,3,4-tetrahydronaphthalen-l-yl]-l,3-thiazol-4- carboxamid, Pentyl- { 6-[( { [( 1 -methyl- 1 H-tetrazol-5-yl)(phenyl)methyliden] amino }oxy)methyl]pyridin-2- yljcarbamat, Phenazin-1 -carbonsäure, Chinolin-8-ol, Chinolin-8-olsulfat(2:l) und Tert-butyl {6-[({ [(l- methyl- 1 H-tetrazol-5-yl)(phenyl)methylen] amino }oxy)methyl]pyridin-2-yl } carbamat. (16) Weitere Verbindungen, wie beispielsweise l-Methyl-3-(trifluormethyl)-N-[2'-(trifluor- methyl)biphenyl-2-yl] - 1 H-pyrazol-4-carboxamid, N-(4'-Chlorbiphenyl-2-yl) -3 -(difluormethyl) - 1 -methyl- 1 H-pyrazol-4-carboxamid, N-(2' ,4'-Dichlorbiphenyl-2-yl) -3 -(difluormethyl)- 1 -methyl- 1 H-pyrazol-4-car- boxamid, 3-(Difluormethyl)-l-methyl-N-[4'-(trifluormethyl)biphenyl-2-yl]-lH-pyrazol-4-carboxamid, N- (2',5'-Difluorbiphenyl-2-yl)- 1 -methyl-3-(trifluormethyl)- lH-pyrazol-4-carboxamid, 3 -(Difluormethyl) -1 - methyl-N-[4'-(prop- 1 -in- 1 -yl)biphenyl-2-yl] -lH-pyrazol-4-carboxamid, 5 -Fluor- 1 ,3-dimethyl-N-[4'-(prop- 1 -in- 1 -yl)biphenyl-2-yl] - 1 H-pyrazol-4-carboxamid, 2-Chlor-N-[4'-(prop- 1 -in- 1 -yl)biphenyl-2-yl]pyridin- 3 -carboxamid, 3 -(Difluormethyl)-N- [4'-(3 ,3 -dimethylbut- 1 -in- 1 -yl)biphenyl-2-yl] - 1 -methyl- 1 H-pyrazol-4- carboxamid, N- [4'-(3 ,3 -Dimethylbut- 1 -in- 1 -yl)biphenyl-2-yl] -5 -fluor- 1 ,3 -dimethyl- 1 H-pyrazol-4-carboxa- mid, 3-(Difluormethyl)-N-(4'-ethinylbiphenyl-2-yl)-l-methyl-lH-pyrazol-4-carboxamid, N-(4'-Ethinyl- biphenyl-2-yl)-5-fluor-l,3-dimethyl-lH-pyrazol-4-carboxamid, 2-Chlor-N-(4'-ethinylbiphenyl-2-yl)pyri- din-3 -carboxamid, 2-Chlor-N-[4'-(3,3-dimethylbut-l -in- 1 -yl)biphenyl-2-yl]pyridin-3-carboxamid, 4- (Difluormethyl) -2-methyl-N- [4'-(trifluormethyl)biphenyl-2-yl] - 1 ,3 -thiazol-5 -carboxamid, 5 -Fluor-N- [4'- (3 -hydroxy-3 -methylbut- 1 -in- 1 -yl)biphenyl-2-yl] - 1 ,3 -dimethyl- 1 H-pyrazol-4-carboxamid, 2-Chlor-N- [4'- (3-hydroxy-3-methylbut-l-in-l-yl)biphenyl-2-yl]pyridin-3-carboxamid, 3-(Difluormethyl)-N-[4'-(3- methoxy-3 -methylbut- 1 -in- 1 -yl)biphenyl-2-yl] - 1 -methyl- 1 H-pyrazol-4-carboxamid, 5 -Fluor-N- [4'-(3 - methoxy-3 -methylbut- 1 -in- 1 -yl)biphenyl-2-yl] - 1 ,3 -dimethyl- 1 H-pyrazol-4-carboxamid, 2-Chlor-N- [4'-(3 - methoxy-3-methylbut-l-in-l-yl)biphenyl-2-yl]pyridin-3-carboxamid, (5-Brom-2-methoxy-4-methyl-pyri- din-3-yl)(2,3,4-trimethoxy-6-methylphenyl)methanon, N-[2-(4-{ [3-(4-Chlorphenyl)prop-2-in-l-yl]oxy}-3- methoxyphenyl)ethyl]-N2-(methylsulfonyl)valinamid, 4-Oxo-4-[(2-phenylethyl)amino]butansäure und But-3-yn- 1 -yl { 6- [( { [(Z)-( 1 -methyl- 1 H-tetrazol-5-yl)(phenyl)methylen] amino }oxy)methyl]pyridin-2- yl} carbamat. (14) Decouplers such as binapacryl, dinocap, ferimzone, fluazinam and meptyldinocap. (15) Other compounds such as benthiazole, bethoxazine, capsimycin, carvone, quinomethionate, pyriofenone (Chlazafenone), Cufraneb, cyilufenamide, cymoxanil, cyprosulfamide, dazomet, debacarb, dichlorophen, diclomethine, difenzoquat, difenzoquat methylsulphate, diphenylamine, ecomat, fenpyrazamine, Flumetover, fluoromide, flusulfamide, flutianil, fosetyl-aluminum, fosetyl-calcium, fosetyl-sodium, hexachlorobenzene, irumamycin, methasulfocarb, methylisothiocyanate, metrafenone, mildiomycin, natamycin, nickel dimethyldithiocarbamate, nitrothal-isopropyl, octhilinone, oxamocarb, oxyfenthiine, pentachlorophenol and the like Salts, Phenothrin, Phosphoric Acid and Salts, Propamocarb Fosetylate, Propanosine Sodium, Proquinazide, Pyrimorph, (2E) -3- (4-tert-butylphenyl) -3- (2-chloropyridin-4-yl) -1 - ( morpholin-4-yl) prop-2-en-1-one, (2Z) -3- (4-tert-butylphenyl) -3- (2-chloropyridin-4-yl) -1- (morpholin-4-yl ) prop-2-en-1-one, pyrroline nitrine, tebuiloquine, tecloftalam, tolnifanide, triazoxide, trichlamide, zaril amide, (3S, 6S, 7R, 8R) -8-Benzyl-3 - [({3 - [(isobutyryloxy) methoxy] -4-methoxypyridin-2-yl} carbonyl) amino] -6-methyl-4,9 dioxo-l, 5-dioxonan-7-yl 2-methylpropanoate, 1- (4- {4 - [(5R) -5- (2,6-di-fluorophenyl) -4,5-dihydro-1,2-oxazole 3 -yl] -1,3-thiazol-2-yl] piperidine-1-yl) -2- [5-methyl-3 - (trifluoromethyl) -1H-pyrazol-1-yl] ethanone, 1 ( 4- {4 - [(5 S) -5- (2,6-Di-fluorophenyl) -4,5-dihydro-1,2-oxazol-3-yl] -1,3-thiazol-2-yl} piperidine-1 -yl) -2- [5-methyl-3 - (trifluoromethyl) -1-H-pyrazol-1-yl] ethanone, 1- (4- {4- [5- (2,6-di-fluorophenyl) -4.5 -dihydro-1,2-oxazol-3-yl] -1,3-thiazol-2-yl] piperidine-1-yl) -2- [5-methyl-3 - (tri-methyl) -1H-pyrazole-1 - yl] ethanone, 1- (4-methoxyphenoxy) -3,3-dimethylbutan-2-yl-1H-imidazole-1-carboxylate, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2, 3-dibutyl-6-chlorothieno [2,3-d] pyrimidine-4 (3H) -one, 2,6-dimethyl-1H, 5H- [1,4] dithiino [2,3-c: 5,6- c '] dipyrrole-l, 3,5,7 (2H, 6H) -tetrone, 2- [5-methyl-3 - (trifluoromethyl) -1H-pyrazol-1-yl] -l- (4- {4- [(5R) -5-phen yl-4,5-dihydro-l, 2-oxazol-3-yl] -l, 3-thiazol-2-yl, piperidine-1-yl) ethanone, 2- [5-methyl-3 - (trifluoromethyl) -1 H -pyrazol-1-yl] -1- (4- {4 - [(5S) -5-phenyl-4,5-dihydro-1,2-oxazol-3-yl] -1,3-thiazole-2 -yl} piperidin-1-yl) ethanone, 2- [5-methyl-3 - (trifluoromethyl) -1 H -pyrazol-1-yl] -1- {4- [4- (5-phenyl-4,5 dihydro-1,2-oxazol-3-yl) -1,3-thiazol-2-yl] piperidine-1-yl} ethanone, 2-butoxy-6-iodo-3-propyl-4H-chromen-4- on, 2-chloro-5- [2-chloro-l- (2,6-di-chloro-4-methoxyphenyl) -4-methyl-1H-imidazol-5-yl] pyridine, 2-phenylphenol and its salts, (4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl) quinoline, 3,4,5-trichloropyridine-2,6-dicarbonitrile, 3- [5- (4-chlorophenyl ) -2,3-dimethyl-1,2-oxazolidin-3-yl] pyridine, 3-chloro-5- (4-chlorophenyl) -4- (2,6-dichlorophenyl) -6-methylpyridazine, 4- (4 -Chlorophenyl) -5- (2,6-di-fluorophenyl) -3,6-dimethyl-pyridazine, 5-amino-1, 3,4-thiadiazole-2-thiol, 5-chloro-N'-phenyl-N '- (prop 2-yn-1-yl) thiophene-2-sulfonohydrazide, 5-fluoro-2 - [(4-iluorobenzyl) oxy] py Rimidine-4-amine, 5-fluoro-2 - [(4-methylbenzyl) oxy] pyrimidin-4-amine, 5-methyl-6-octyl [l, 2,4] triazolo [l, 5-a] pyrimidine 7-amine, ethyl (2Z) -3-amino-2-cyano-3-phenylprop-2-enoate, N '- (4- {[3- (4-chlorobenzyl) -l, 2,4-thiadiazole] 5 -yl] oxy} -2,5-dimethylphenyl) -N-ethyl-N-methylimidoformamide, N- (4-chlorobenzyl) -3 - [3-methoxy-4- (prop-2-yn-1-yloxy) phenyl] propanamide, N - [(4-chlorophenyl) (cyano) methyl] -3- [3-methoxy-4- (prop-2-yn-1-yloxy) phenyl] propanamide, N - [(5-bromo- 3-chloropyridin-2-yl) methyl] -2,4-dichloropyridine-3-carboxamide, N- [1- (5-bromo-3-chloropyridin-2-yl) ethyl] -2,4-dichloropyridine-3 - carboxamide, N- [1- (5-Bromo-3-chloropyridin-2-yl) ethyl] -2-iluor-4-iodopyridine-3-carboxamide, N- {(E) - [(cyclopropylmethoxy) imino] [6 - (di-uromethoxy) -2,3-dichlorophenyl] methyl} -2-phenylacetamide, N - {(Z) - [(cyclopropylmethoxy) imino] [6- (difluoromethoxy) -2,3 -difluorophenyl] methyl} -2-phenylacetamide, N '- {4- [(3-tert-butyl-4-cyano-1,2-thiazol-5-yl) oxy] -2- chloro-5-methylphenyl} -N-ethyl-N-methylimidoformamide, N -methyl-2- (1 - {[5-methyl-3 - (trifluoromethyl) -1 H -pyrazol-1-yl] -acetyl} -piperidine-4 -yl) -N- (1,3,3,4-tetrahydronaphthalen-1-yl) -1,3-thiazole-4-carboxamide, N -methyl-2- (1 - {[5-methyl-3 - trifluoromethyl) -1H-pyrazol-1-yl] acetyl} piperidin-4-yl) -N- [(1 R) -1,2,3,4-tetrahydronaphthalene-1-yl] -1,3-thiazole-4 carboxamide, N-methyl-2- (1 - {[5-methyl-3 - (trifluoromethyl) -1H-pyrazol-1-yl] acetyl} piperidin-4-yl) -N - [(IS) - l, 2,3,4-tetrahydronaphthalene-1-yl] -1,3-thiazole-4-carboxamide, pentyl {6 - [({[(1-methyl-1H-tetrazol-5-yl) (phenyl ) methylidene] amino} oxy) methyl] pyridin-2-yl carbamate, phenazine-1-carboxylic acid, quinolin-8-ol, quinoline-8-olsulfate (2: 1) and tert-butyl {6 - [({[(i - methyl-1H-tetrazol-5-yl) (phenyl) methylene] amino} oxy) methyl] pyridin-2-yl} carbamate. (16) Other compounds such as, for example, 1-methyl-3- (trifluoromethyl) -N- [2 '- (trifluoromethyl) biphenyl-2-yl] -1-H-pyrazole-4-carboxamide, N- (4' -Chlorobiphenyl-2-yl) -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide, N- (2 ', 4'-dichlorobiphenyl-2-yl) -3- (difluoromethyl) -1 -methyl-1H-pyrazole-4-carboxamide, 3- (difluoromethyl) -1-methyl-N- [4 '- (trifluoromethyl) biphenyl-2-yl] -1H-pyrazole-4-carboxamide, N- (2 ', 5'-Difluorobiphenyl-2-yl) -1-methyl-3- (trifluoromethyl) -1H-pyrazole-4-carboxamide, 3- (difluoromethyl) -1-methyl-N- [4' - (prop - 1-in-1-yl) biphenyl-2-yl] -1H-pyrazole-4-carboxamide, 5-fluoro-1,3-dimethyl-N- [4 '- (prop-1-yn-1-yl ) biphenyl-2-yl] -1-H-pyrazole-4-carboxamide, 2-chloro-N- [4 '- (prop-1-yn-1-yl) biphenyl-2-yl] -pyridine-3-carboxamide, 3 - (Difluoromethyl) -N- [4 '- (3,3-dimethylbut-1-yn-1-yl) biphenyl-2-yl] -1-methyl-1H-pyrazole-4-carboxamide, N- [ 4 '- (3,3-dimethylbut-1-yn-1-yl) biphenyl-2-yl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide, 3- (difluoromethyl ) - N- (4'-ethynyl-biphenyl-2-yl) -l-methyl-1H-pyrazole-4-carboxamide, N- (4'-ethynylbiphenyl-2-yl) -5-fluoro-1,3-dimethyl 1H-pyrazole-4-carboxamide, 2-chloro-N- (4'-ethynyl-biphenyl-2-yl) -pyridine-3-carboxamide, 2-chloro-N- [4 '- (3,3-dimethylbut-1 -in 1 -yl) biphenyl-2-yl] pyridine-3-carboxamide, 4- (difluoromethyl) -2-methyl-N- [4 '- (trifluoromethyl) biphenyl-2-yl] -1,3-thiazole 5-carboxamide, 5-fluoro-N- [4'- (3-hydroxy-3-methylbut-1-yn-1-yl) biphenyl-2-yl] -1,3-dimethyl-1H-pyrazole 4-carboxamide, 2-chloro-N- [4'- (3-hydroxy-3-methylbut-1-yn-1-yl) biphenyl-2-yl] pyridine-3-carboxamide, 3- (difluoromethyl) -N - [4 '- (3-methoxy-3-methylbut-1-yn-1-yl) biphenyl-2-yl] -1-methyl-1H-pyrazole-4-carboxamide, 5-fluoro-N- [4 '- (3-methoxy-3-methylbut-1-yn-1-yl) biphenyl-2-yl] -1,3-dimethyl-1H-pyrazole-4-carboxamide, 2-chloro-N- [4' - (3-methoxy-3-methylbut-1-yn-1-yl) biphenyl-2-yl] pyridine-3-carboxamide, (5-bromo-2-methoxy-4-methyl-pyridin-3-yl ) (2,3,4-trimethoxy-6-methylphenyl) -methanone, N- [2- (4- {[3- (4-chloro phenyl) prop-2-ynyl] -3-methoxyphenyl) ethyl] -N2- (methylsulfonyl) valinamide, 4-oxo-4 - [(2-phenylethyl) amino] butanoic acid and but-3-yn - 1 -yl {6- [({[(Z) - (1-methyl-1 H -tetrazol-5-yl) (phenyl) methylen] amino} oxy) methyl] pyridin-2-yl} carbamate.
Alle genannten Mischpartner der Klassen (1) bis (16) können, wenn sie auf Grund ihrer funktionellen Gruppen dazu imstande sind, gegebenenfalls mit geeigneten Basen oder Säuren Salze bilden. All of the above-mentioned mixing partners of classes (1) to (16), if they are capable of doing so on the basis of their functional groups, may optionally form salts with suitable bases or acids.
Erfindungsgemäß können alle Pflanzen und Pflanzenteile behandelt werden. Unter Pflanzen werden hierbei alle Pflanzen und Pflanzenpopulationen verstanden wie erwünschte und unerwünschte Wildpflanzen oder Kulturpflanzen (einschließlich natürlich vorkommender Kulturpflanzen). Kulturpflanzen können Pflanzen sein, die durch konventionelle Züchtungs- und Optimierungsmethoden oder durch biotechnologische und gentechnologische Methoden oder Kombinationen dieser Methoden erhalten werden können, einschließlich der transgenen Pflanzen und einschließlich der durch Sortenschutzrechte schützbaren oder nicht schützbaren Pflanzensorten. Unter Pflanzenteilen sollen alle oberirdischen und unterirdischen Teile und Organe der Pflanzen wie Spross, Blatt, Blüte und Wurzel verstanden werden, wobei beispielhaft Blätter, Nadeln, Stängel, Stämme, Blüten, Fruchtkörper, Früchte und Samen sowie Wurzeln, Knollen und Rhizome aufgeführt werden. Zu den Pflanzenteilen gehört auch Erntegut sowie vegetatives und generatives Vermehrungsmaterial, beispielsweise Stecklinge, Knollen, Rhizome, Ableger und Samen. Wie bereits oben erwähnt, können erfindungsgemäß alle Pflanzen und deren Teile behandelt werden. In einer bevorzugten Ausführungsform werden wild vorkommende oder durch konventionelle biologische Zuchtmethoden wie Kreuzung oder Protoplastenfusion erhaltene Pflanzenarten und Pfianzensorten sowie deren Teile behandelt. In einer weiteren bevorzugten Ausführungsform werden transgene Pflanzen und Pfianzensorten, die durch gentechnologische Methoden gegebenenfalls in Kombination mit konventionellen Methoden erhalten wurden (Genetically Modified Organisms) und deren Teile behandelt. Der Begriff„Teile" bzw. „Teile von Pflanzen" oder „Pfianzenteile" wurde oben erläutert. Besonders bevorzugt werden erfindungsgemäß Pflanzen der jeweils handelsüblichen oder in Gebrauch befindlichen Pflanzensorten behandelt. Unter Pfianzensorten versteht man Pflanzen mit neuen Eigenschaften („Traits"), die sowohl durch konventionelle Züchtung, durch Mutagenese oder durch rekombinante DNA-Techniken gezüchtet worden sind. Dies können Sorten, Rassen, Bio- und Genotypen sein. According to the invention, all plants and parts of plants can be treated. In this context, plants are understood as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). crops may be plants which may be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering techniques or combinations of these methods, including transgenic plants and including plant varieties that are protectable or unprotectable by plant variety rights. Plant parts are understood to mean all aboveground and subterranean parts and organs of plants such as shoot, leaf, flower and root, examples of which include leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, and roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds. As already mentioned above, according to the invention all plants and their parts can be treated. In a preferred embodiment, wild plant species or varieties of plants obtained by conventional biological breeding methods such as crossing or protoplast fusion and their parts are treated. In a further preferred embodiment, transgenic plants and varieties of plants which have been obtained by genetic engineering methods, if appropriate in combination with conventional methods (Genetically Modified Organisms), and parts thereof are treated. The term "parts" or "parts of plants" or "Pfianzenteile" has been explained above.Particular plants according to the invention are treated according to the invention of the respective commercially available or in use plant varieties.Piezian cultivars are understood as meaning plants with new properties ("traits") have been bred either by conventional breeding, by mutagenesis or by recombinant DNA techniques. These may be varieties, breeds, biotypes and genotypes.
Die Behandlung der Pflanzen und Pflanzenteile mit den erfindungsgemäßen bzw. erfindungsgemäß zu verwendenden Wirkstoffen, Wirkstoffkombinationen bzw. Mitteln erfolgt direkt oder durch Einwirkung auf deren Umgebung, Lebensraum oder Lagerraum nach den üblichen Behandlungsmethoden, z.B. durch Tauchen, (Ver-) Spritzen, (Ver-)Sprühen, Berieseln, Verdampfen, Zerstäuben, Vernebeln, (Ver- )Streuen, Verschäumen, Bestreichen, Verstreichen, Injizieren, Gießen (drenchen), Tröpfchenbewässerung und bei Vermehrungsmaterial, insbesondere bei Saatgut, weiterhin durch Trockenbeizen, Nassbeizen, Schlämmbeizen, Inkrustieren, ein- oder mehrschichtiges Umhüllen usw. Es ist ferner möglich, die Wirkstoffe nach dem Ultra-Low- Volume -Verfahren auszubringen oder die Wirkstoffzubereitung oder den Wirkstoff selbst in den Boden zu injizieren. Eine bevorzugte direkte Behandlung der Pflanzen ist die Blattapplikation, d.h. die Wirkstoffe, Wirkstoffkombinationen bzw. Mittel werden auf das Blattwerk aufgebracht, wobei die Behandlungsfrequenz und die Aufwandmenge auf den Befallsdruck des jeweiligen Pathogens, Schädlings bzw. Unkrauts abgestimmt sein kann. The treatment of the plants and plant parts with the active substances or active compound combinations or agents to be used according to the invention or according to the invention is carried out directly or by acting on their environment, habitat or storage space according to the usual treatment methods, e.g. by dipping, spraying, spraying, sprinkling, evaporating, atomising, atomizing, sprinkling, foaming, brushing, spreading, injecting, pouring, drip irrigation and propagating material, in particular in the case of seeds Furthermore, by dry pickling, wet pickling, slurry pickling, encrusting, single or multi-layer wrapping, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient itself into the soil. A preferred direct treatment of the plants is foliar application, i. the active compounds, active ingredient combinations or agents are applied to the foliage, wherein the treatment frequency and the application rate can be adapted to the infestation pressure of the respective pathogen, pest or weed.
Bei systemisch wirksamen Verbindungen gelangen die Wirkstoffe, Wirkstoffkombinationen bzw. Mittel über das Wurzelwerk in die Pflanzen. Die Behandlung der Pflanzen erfolgt dann durch Einwirkung der Wirkstoffe, Wirkstoffkombinationen bzw. Mittel auf den Lebensraum der Pflanze. Das kann beispielsweise durch Drenchen, Einmischen in den Boden oder die Nährlösung sein, d.h. der Standort der Pflanze (z.B. Boden oder hydroponische Systeme) wird mit einer flüssigen Form der Wirkstoffe, Wirkstoffkombinationen bzw. Mittel getränkt, oder durch die Bodenapplikation, d.h. die erfindungsgemäßen Wirkstoffe, Wirkstoffkombinationen bzw. Mittel werden in fester Form, (z.B. in Form eines Granulats) in den Standort der Pflanzen eingebracht. Bei Wasserreiskulturen kann das auch durch Zudosieren der Erfindung in einer festen Anwendungsform (z.B. als Granulat) in ein überflutetes Reisfeld sein. In the case of systemically active compounds, the active ingredients, active ingredient combinations or agents reach the plants via the root system. The treatment of the plants is then carried out by the action of Active ingredients, active ingredient combinations or agents on the habitat of the plant. This can be, for example, by drenching, mixing into the soil or the nutrient solution, ie the location of the plant (eg soil or hydroponic systems) is impregnated with a liquid form of the active ingredients, active ingredient combinations or compositions, or by the soil application, ie the active compounds according to the invention , Active ingredient combinations or agents are introduced in solid form, (eg in the form of granules) in the location of the plants. In water rice crops, this may also be by metered addition of the invention in a solid form (eg as granules) into a flooded paddy field.
Die Bekämpfung von Tierischen Schädlingen durch die Behandlung des Saatguts von Pflanzen ist seit langem bekannt und ist Gegenstand ständiger Verbesserungen. Dennoch ergeben sich bei der Behandlung von Saatgut eine Reihe von Problemen, die nicht immer zufrieden stellend gelöst werden können. So ist es erstrebenswert, Verfahren zum Schutz des Saatguts und der keimenden Pflanze zu entwickeln, die das zusätzliche Ausbringen von Pflanzenschutzmitteln bei der Lagerung, nach der Saat oder nach dem Auflaufen der Pflanzen überflüssig machen oder zumindest deutlich verringern. Es ist weiterhin erstrebenswert, die Menge des eingesetzten Wirkstoffs dahingehend zu optimieren, dass das Saatgut und die keimende Pflanze vor dem Befall durch Tierische Schädlinge bestmöglich geschützt werden, ohne jedoch die Pflanze selbst durch den eingesetzten Wirkstoff zu schädigen. Insbesondere sollten Verfahren zur Behandlung von Saatgut auch die intrinsischen Insektiziden bzw. nematiziden Eigenschaften schädlingsresistenter bzw. - toleranter transgener Pflanzen einbeziehen, um einen optimalen Schutz des Saatguts und der keimenden Pflanze bei einem minimalen Aufwand an Pflanzenschutzmitteln zu erreichen. The control of animal pests by the treatment of the seed of plants has long been known and is the subject of constant improvement. Nevertheless, there are a number of problems in the treatment of seeds that can not always be satisfactorily resolved. Thus, it is desirable to develop methods for the protection of the seed and the germinating plant, which make unnecessary or at least significantly reduce the additional application of pesticides during storage, after sowing or after emergence of the plants. It is also desirable to optimize the amount of the active ingredient used so that the seed and the germinating plant are best protected against attack by animal pests, but without damaging the plant itself by the active ingredient used. In particular, seed treatment methods should also include the intrinsic insecticidal or nematicidal properties of pest-resistant transgenic plants in order to achieve optimum protection of the seed and of the germinating plant with a minimum of pesticide use.
Die vorliegende Erfindung bezieht sich daher insbesondere auch auf ein Verfahren zum Schutz von Saatgut und keimenden Pflanzen vor dem Befall von Schädlingen, indem das Saatgut mit einem erfindungsgemäßen bzw. erfindungsgemäß zu verwendenden Wirkstoff behandelt wird. Das erfindungsgemäße Verfahren zum Schutz von Saatgut und keimenden Pflanzen vor dem Befall von Schädlingen umfasst ein Verfahren, in dem das Saatgut gleichzeitig in einem Vorgang mit einem Wirkstoff der Formel (I) und Mischungspartner behandelt wird. Es umfasst auch ein Verfahren, in dem das Saatgut zu unterschiedlichen Zeiten mit einem Wirkstoff der Formel (I) und Mischungspartner behandelt wird. Die Erfindung bezieht sich ebenfalls auf die Verwendung der erfindungsgemäßen Wirkstoffe zur Behandlung von Saatgut zum Schutz des Saatguts und der daraus entstehenden Pflanze vor Tierischen Schädlingen. The present invention therefore also relates in particular to a method for protecting seed and germinating plants from attack by pests by treating the seed with an active substance according to the invention or to be used according to the invention. The method according to the invention for the protection of seeds and germinating plants from infestation by pests comprises a method in which the seed is treated simultaneously in one operation with an active compound of the formula (I) and mixing partner. It also includes a method in which the seed is treated at different times with an active ingredient of formula (I) and mixing partner. The invention also relates to the use of the active ingredients according to the invention for the treatment of seed for the protection of the seed and the resulting plant from animal pests.
Weiterhin bezieht sich die Erfindung auf Saatgut, welches zum Schutz vor tierischen Schädlingen mit einem erfindungsgemäßen Wirkstoff behandelt wurde. Die Erfindung bezieht sich auch auf Saatgut, welches zur gleichen Zeit mit einem Wirkstoff der Formel (I) und Mischungspartner behandelt wurde. Die Erfindung bezieht sich weiterhin auf Saatgut, welches zu unterschiedlichen Zeiten mit einem Wirkstoff der Formel (I) und Mischungspartner behandelt wurde. Bei Saatgut, welches zu unterschiedlichen Zeiten mit einem Wirkstoff der Formel (I) und Mischungspartner behandelt wurde, können die einzelnen Wirkstoffe des erfindungsgemäßen Mittels in unterschiedlichen Schichten auf dem Saatgut enthalten sein. Dabei können die Schichten, die einen Wirkstoff der Formel (I) und Mischungspartner enthalten, gegebenenfalls durch eine Zwischenschicht getrennt sein. Die Erfindung bezieht sich auch auf Saatgut, bei dem ein Wirkstoff der Formel (I) und Mischungspartner als Bestandteil einer Umhüllung oder als weitere Schicht oder weitere Schichten zusätzlich zu einer Umhüllung aufgebracht sind. Des Weiteren bezieht sich die Erfindung auf Saatgut, welches nach der Behandlung mit dem Wirkstoff der Formel (I) bzw. einer ihn enthaltenden Wirkstoffkombination einem Filmcoating - Verfahren unterzogen wurde, um Staubabrieb am Saatgut zu vermeiden. Furthermore, the invention relates to seed which has been treated with an active ingredient according to the invention for protection against animal pests. The invention also relates to seed treated at the same time with an active ingredient of formula (I) and mixing partner. The invention further relates to seed which has been treated at different times with an active compound of the formula (I) and mixing partner. In the case of seed which has been treated at different times with an active compound of the formula (I) and with a mixing partner, the individual active substances of the agent according to the invention may be present in different layers on the seed. In this case, the layers which contain an active ingredient of the formula (I) and mixing partners may optionally be separated by an intermediate layer. The invention also relates to seed in which an active compound of the formula (I) and mixing partner are applied as a constituent of a coating or as a further layer or further layers in addition to a coating. Furthermore, the invention relates to seed, which after the treatment with the active ingredient of the formula (I) or an active ingredient combination containing it has been subjected to a film coating process in order to avoid dust abrasion on the seed.
Einer der Vorteile der vorliegenden Erfindung ist es, dass aufgrund der besonderen systemischen Eigenschaften der erfindungsgemäßen Mittel die Behandlung des Saatguts mit diesen Mitteln nicht nur das Saatgut selbst, sondern auch die daraus hervorgehenden Pflanzen nach dem Auflaufen vor Tierischen Schädlingen schützt. Auf diese Weise kann die unmittelbare Behandlung der Kultur zum Zeitpunkt der Aussaat oder kurz danach entfallen. One of the advantages of the present invention is that because of the particular systemic properties of the agents of the invention, the treatment of the seed with these agents not only protects the seed itself, but also the resulting plants after emergence from animal pests. In this way, the immediate treatment of the culture at the time of sowing or shortly afterwards can be omitted.
Ein weiterer Vorteil ist darin zu sehen, dass durch die Behandlung des Saatguts mit Wirkstoff der Formel (I) bzw. ihn enthaltenden Wirkstoffkombination Keimung und Auflauf des behandelten Saatguts gefördert werden können. Another advantage is the fact that by the treatment of the seed with active ingredient of the formula (I) or combination of active substances containing germination and emergence of the treated seed can be promoted.
Ebenso ist es als vorteilhaft anzusehen, dass Wirkstoffe der Formel (I) und die genannten Wirkstoffkombinationen insbesondere auch bei transgenem Saatgut eingesetzt werden können. Likewise, it is to be regarded as advantageous that active compounds of the formula (I) and the named active substance combinations can be used in particular also in the case of transgenic seed.
Zu nennen ist auch, dass Wirkstoffe der Formel (I) in Kombination mit Mitteln der Signaltechnologie eingesetzt werden können, wodurch beispielhaft eine bessere Besiedlung mit Symbionten, wie zum Beispiel Rhizobien, Mycorrhiza und/oder endophytischen Bakterien, stattfindet und/oder es zu einer optimierten Stickstofffixierung kommt. It should also be mentioned that active compounds of the formula (I) can be used in combination with signal technology agents, by way of example a better colonization with symbionts, such as rhizobia, mycorrhiza and / or endophytic bacteria, taking place and / or optimizing them Nitrogen fixation is coming.
Die erfindungsgemäßen Mittel eignen sich zum Schutz von Saatgut jeglicher Pflanzensorte, die in der Landwirtschaft, im Gewächshaus, in Forsten oder im Gartenbau eingesetzt wird. Insbesondere handelt es sich dabei um Saatgut von Getreide (z. B. Weizen, Gerste, Roggen, Hirse und Hafer), Mais, Baum- wolle, Soja, Reis, Kartoffeln, Sonnenblume, Kaffee, Tabak, Canola, Raps, Rübe (z.B. Zuckerrübe und Futterrübe), Erdnuss, Gemüse (z. B. Tomate, Gurke, Bohne, Kohlgewächse, Zwiebeln und Salat), Obstpflanzen, Rasen und Zierpflanzen. Besondere Bedeutung kommt der Behandlung des Saatguts von Getreide (wie Weizen, Gerste, Roggen und Hafer), Mais, Soja, Baumwolle, Canola, Raps und Reis zu. ^ The compositions according to the invention are suitable for the protection of seeds of any plant variety used in agriculture, in the greenhouse, in forests or in horticulture. In particular, these are seeds of cereals (eg wheat, barley, rye, millet and oats), maize, cotton, soy, rice, potatoes, sunflower, coffee, tobacco, canola, rapeseed, turnip (eg Sugar beet and fodder beet), peanut, vegetables (eg tomato, cucumber, bean, cabbage, onions and lettuce), fruit plants, turf and ornamental plants. Of particular importance is the treatment of seeds of cereals (such as wheat, barley, rye and oats), corn, soya, cotton, canola, oilseed rape and rice. ^
- 60 - - 60 -
Wie vorstehend bereits erwähnt, kommt auch der Behandlung von transgenem Saatgut mit Wirkstoffen der Formel (I) bzw. einer Wirkstoffkombination eine besondere Bedeutung zu. Dabei handelt es sich um das Saatgut von Pflanzen, die in der Regel zumindest ein heterologes Gen enthalten, das die Expression eines Polypeptids mit insbesondere Insektiziden bzw. nematiziden Eigenschaften steuert. Die heterologen Gene in transgenem Saatgut können dabei aus Mikroorganismen wie Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus oder Gliocladium stammen. Die vorliegende Erfindung eignet sich besonders für die Behandlung von transgenem Saatgut, das zumindest ein heterologes Gen enthält, das aus Bacillus sp. stammt. Besonders bevorzugt handelt es sich dabei um ein heterologes Gen, das aus Bacillus thuringiensis stammt. Im Rahmen der vorliegenden Erfindung wird der Wirkstoff der Formel (I) allein (bzw. als Wirkstoffkombination) oder in einer geeigneten Formulierung auf das Saatgut aufgebracht. Vorzugsweise wird das Saatgut in einem Zustand behandelt, in dem es so stabil ist, dass keine Schäden bei der Behandlung auftreten. Im Allgemeinen kann die Behandlung des Saatguts zu jedem Zeitpunkt zwischen der Ernte und der Aussaat erfolgen. Üblicherweise wird Saatgut verwendet, das von der Pflanze getrennt und von Kolben, Schalen, Stängeln, Hülle, Wolle oder Fruchtfleisch befreit wurde. So kann zum Beispiel Saatgut verwendet werden, das geerntet, gereinigt und bis zu einem Feuchtigkeitsgehalt von unter 15 Gew.- getrocknet wurde. Alternativ kann auch Saatgut verwendet werden, das nach dem Trocknen z.B. mit Wasser behandelt und dann erneut getrocknet wurde. As already mentioned above, the treatment of transgenic seed with active ingredients of the formula (I) or a combination of active substances is of particular importance. These are the seeds of plants, which as a rule contain at least one heterologous gene which controls the expression of a polypeptide with in particular insecticidal or nematicidal properties. The heterologous genes in transgenic seed can come from microorganisms such as Bacillus, Rhizobium, Pseudomonas, Serratia, Trichoderma, Clavibacter, Glomus or Gliocladium. The present invention is particularly useful for the treatment of transgenic seed containing at least one heterologous gene derived from Bacillus sp. comes. Most preferably, this is a heterologous gene derived from Bacillus thuringiensis. In the context of the present invention, the active ingredient of the formula (I) is applied to the seed alone (or as active ingredient combination) or in a suitable formulation. Preferably, the seed is treated in a state where it is so stable that no damage occurs during the treatment. In general, the treatment of the seed can be done at any time between harvesting and sowing. Usually, seed is used which has been separated from the plant and freed from flasks, shells, stems, hull, wool or pulp. For example, seeds may be used which have been harvested, cleaned and dried to a moisture content of less than 15% by weight. Alternatively, seed may also be used which, after drying, e.g. treated with water and then dried again.
Im Allgemeinen muss bei der Behandlung des Saatguts darauf geachtet werden, dass die Menge des auf das Saatgut aufgebrachten erfindungsgemäßen Mittels und/oder weiterer Zusatzstoffe so gewählt wird, dass die Keimung des Saatguts nicht beeinträchtigt bzw. die daraus hervorgehende Pflanze nicht geschädigt wird. Dies ist vor allem bei Wirkstoffen zu beachten, die in bestimmten Aufwandmengen phytotoxische Effekte zeigen können. In general, care must be taken in the treatment of the seed that the amount of the agent and / or other additives applied to the seed is chosen so that germination of the seed is not impaired or the resulting plant is not damaged. This is especially important for active ingredients, which can show phytotoxic effects in certain application rates.
Die erfindungsgemäßen Mittel können unmittelbar aufgebracht werden, also ohne weitere Komponenten zu enthalten und ohne verdünnt worden zu sein. In der Regel ist es vorzuziehen, die Mittel in Form einer geeigneten Formulierung auf das Saatgut aufzubringen. Geeignete Formulierungen und Verfahren für die Saatgutbehandlung sind dem Fachmann bekannt und werden z.B. in den folgenden Dokumenten beschrieben: US 4,272,417 A, US 4,245,432 A, US 4,808,430 A, US 5,876,739 A, US 2003/0176428 AI, WO 2002/080675 AI, WO 2002/028186 A2. Die erfindungsgemäß verwendbaren Wirkstoffe/Wirkstoffkombinationen können in die üblichen Beizmittel-Formulierungen überführt werden, wie Lösungen, Emulsionen, Suspensionen, Pulver, Schäume, Slurries oder andere Hüllmassen für Saatgut, sowie ULV-Formulierungen. The agents according to the invention can be applied directly, ie without containing further components and without being diluted. In general, it is preferable to apply the agents to the seed in the form of a suitable formulation. Suitable formulations and methods for seed treatment are known to those skilled in the art and are described e.g. in the following documents: US 4,272,417 A, US 4,245,432 A, US 4,808,430 A, US 5,876,739 A, US 2003/0176428 AI, WO 2002/080675 AI, WO 2002/028186 A2. The active compounds / active substance combinations that can be used according to the invention can be converted into the customary seed dressing formulations, such as solutions, emulsions, suspensions, powders, foams, slurries or other seed coating compositions, as well as ULV formulations.
Diese Formulierungen werden in bekannter Weise hergestellt, indem man die Wirkstoffe/ Wirkstoffkombinationen mit üblichen Zusatzstoffen vermischt, wie zum Beispiel übliche Streckmittel sowie - 61 -These formulations are prepared in a known manner by mixing the active ingredients / drug combinations with conventional additives, such as conventional extenders and - 61 -
Lösungs- oder Verdünnungsmittel, Farbstoffe, Netzmittel, Dispergiermittel, Emulgatoren, Entschäumer, Konservierungsmittel, sekundäre Verdickungsmittel, Kleber, Gibberelline und auch Wasser. Solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and also water.
Als Farbstoffe, die in den erfindungsgemäß verwendbaren Beizmittel-Formulierungen enthalten sein können, kommen alle für derartige Zwecke üblichen Farbstoffe in Betracht. Dabei sind sowohl in Wasser wenig lösliche Pigmente als auch in Wasser lösliche Farbstoffe verwendbar. Als Beispiele genannt seien die unter den Bezeichnungen Rhodamin B, C.I. Pigment Red 112 und C.I. Solvent Red 1 bekannten Farbstoffe. Dyes which may be present in the seed dressing formulations which can be used according to the invention are all dyes customary for such purposes. Both water-insoluble pigments and water-soluble dyes are useful in this case. Examples which may be mentioned under the names rhodamine B, C.I. Pigment Red 112 and C.I. Solvent Red 1 known dyes.
Als Netzmittel, die in den erfindungsgemäß verwendbaren Beizmittel-Formulierungen enthalten sein können, kommen alle zur Formulierung von agrochemischen Wirkstoffen üblichen, die Benetzung fördernden Stoffe in Frage. Vorzugsweise verwendbar sind Alkylnaphthalin-Sulfonate, wie Diisopropyl- oder Diisobutyl-naphthalin-Sulfonate. Suitable wetting agents which may be present in the seed dressing formulations which can be used according to the invention are all wetting-promoting substances customary for the formulation of agrochemical active compounds. Preferably used are alkylnaphthalene sulfonates, such as diisopropyl or diisobutyl naphthalene sulfonates.
Als Dispergiermittel und/oder Emulgatoren, die in den erfindungsgemäß verwendbaren Beizmittel- Formulierungen enthalten sein können, kommen alle zur Formulierung von agrochemischen Wirkstoffen üblichen nichtionischen, anionischen und kationischen Dispergiermittel in Betracht. Vorzugsweise verwendbar sind nichtionische oder anionische Dispergiermittel oder Gemische von nichtionischen oder anionischen Dispergiermitteln. Als geeignete nichtionische Dispergiermittel sind insbesondere Ethylen- oxid-Propylenoxid Blockpolymere, Alkylphenolpolyglykolether sowie Tristryrylphenolpolyglykolether und deren phosphatierte oder sulfatierte Derivate zu nennen. Geeignete anionische Dispergiermittel sind insbesondere Ligninsulfonate, Polyacrylsäuresalze und Arylsulfonat-Formaldehydkondensate. Als Entschäumer können in den erfindungsgemäß verwendbaren Beizmittel-Formulierungen alle zur Formulierung von agrochemischen Wirkstoffen üblichen schaumhemmenden Stoffe enthalten sein. Vorzugsweise verwendbar sind Silikonentschäumer und Magnesiumstearat. Suitable dispersants and / or emulsifiers which may be present in the seed dressing formulations which can be used according to the invention are all nonionic, anionic and cationic dispersants customary for the formulation of agrochemical active compounds. Preferably usable are nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants. Particularly suitable nonionic dispersants are, in particular, ethylene oxide-propylene oxide block polymers, alkylphenol polyglycol ethers and tristryrylphenol polyglycol ethers and their phosphated or sulfated derivatives. Suitable anionic dispersants are in particular lignosulfonates, polyacrylic acid salts and arylsulfonate-formaldehyde condensates. Defoamers which may be present in the seed dressing formulations which can be used according to the invention are all foam-inhibiting substances customary for the formulation of agrochemical active compounds. Preferably usable are silicone defoamers and magnesium stearate.
Als Konservierungsmittel können in den erfindungsgemäß verwendbaren Beizmittel-Formulierungen alle für derartige Zwecke in agrochemischen Mitteln einsetzbaren Stoffe vorhanden sein. Beispielhaft genannt seien Dichlorophen und Benzylalkoholhemiformal. Preservatives which may be present in the seed dressing formulations which can be used according to the invention are all substances which can be used for such purposes in agrochemical compositions. Examples include dichlorophen and Benzylalkoholhemiformal.
Als sekundäre Verdickungsmittel, die in den erfindungsgemäß verwendbaren Beizmittel-Formulierungen enthalten sein können, kommen alle für derartige Zwecke in agrochemischen Mitteln einsetzbaren Stoffe in Frage. Vorzugsweise in Betracht kommen Cellulosederivate, Acrylsäurederivate, Xanthan, modifizierte Tone und hochdisperse Kieselsäure. Als Kleber, die in den erfindungsgemäß verwendbaren Beizmittel-Formulierungen enthalten sein können, kommen alle üblichen in Beizmitteln einsetzbaren Bindemittel in Frage. Vorzugsweise genannt seien Polyvinylpyrrolidon, Polyvinylacetat, Polyvinylalkohol und Tylose. n Suitable secondary thickeners which may be present in the seed dressing formulations which can be used according to the invention are all substances which can be used for such purposes in agrochemical compositions. Preference is given to cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and finely divided silica. Suitable adhesives which may be present in the seed dressing formulations which can be used according to the invention are all customary binders which can be used in pickling agents. Preferably mentioned are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and Tylose. n
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Als Gibberelline, die in den erfindungsgemäß verwendbaren Beizmittel-Formulierungen enthalten sein können, kommen vorzugsweise die Gibberelline AI, A3 (= Gibberellinsäure), A4 und A7 infrage, besonders bevorzugt verwendet man die Gibberellinsäure. Die Gibberelline sind bekannt (vgl. R. Wegler „Chemie der Pflanzenschutz- und Schädlingsbekämpfungsmittel", Bd. 2, Springer Verlag, 1970, S. 401- 412). Gibberellins which may be present in the seed dressing formulations which can be used in accordance with the invention are preferably the gibberellins AI, A3 (= gibberellic acid), A4 and A7, particularly preferably gibberellic acid. The gibberellins are known (see R. Wegler "Chemie der Pflanzenschutz- und Schädlingsbekungsmittel", Vol. 2, Springer Verlag, 1970, pp. 401-412).
Die erfindungsgemäß verwendbaren Beizmittel-Formulierungen können entweder direkt oder nach vorherigem Verdünnen mit Wasser zur Behandlung von Saatgut der verschiedensten Art eingesetzt werden. So lassen sich die Konzentrate oder die daraus durch Verdünnen mit Wasser erhältlichen Zubereitungen einsetzen zur Beizung des Saatgutes von Getreide, wie Weizen, Gerste, Roggen, Hafer und Triticale, sowie des Saatgutes von Mais, Reis, Raps, Erbsen, Bohnen, Baumwolle, Sonnenblumen und Rüben oder auch von Gemüsesaatgut der verschiedensten Natur. Die erfindungsgemäß verwendbaren Beizmittel- Formulierungen oder deren verdünnte Zubereitungen können auch zum Beizen von Saatgut transgener Pflanzen eingesetzt werden. Dabei können im Zusammenwirken mit den durch Expression gebildeten Substanzen auch zusätzliche synergistische Effekte auftreten. Zur Behandlung von Saatgut mit den erfindungsgemäß verwendbaren Beizmittel-Formulierungen oder den daraus durch Zugabe von Wasser hergestellten Zubereitungen kommen alle üblicherweise für die Beizung einsetzbaren Mischgeräte in Betracht. Im einzelnen geht man bei der Beizung so vor, dass man das Saatgut in einen Mischer gibt, die jeweils gewünschte Menge an Beizmittel-Formulierungen entweder als solche oder nach vorherigem Verdünnen mit Wasser hinzufügt und bis zur gleichmäßigen Verteilung der Formulierung auf dem Saatgut mischt. Gegebenenfalls schließt sich ein Trocknungsvorgang an. The seed dressing formulations which can be used according to the invention can be used either directly or after prior dilution with water for the treatment of seed of various kinds. Thus, the concentrates or the preparations obtainable therefrom by dilution with water can be used for dressing the seeds of cereals such as wheat, barley, rye, oats and triticale, as well as the seeds of corn, rice, rape, peas, beans, cotton, sunflowers and beets or even vegetable seeds of various nature. The seed dressing formulations which can be used according to the invention or their diluted preparations can also be used for pickling seeds of transgenic plants. In this case, additional synergistic effects may occur in interaction with the substances formed by expression. For the treatment of seed with the seed dressing formulations which can be used according to the invention or the preparations prepared therefrom by the addition of water, all mixing devices customarily usable for the dressing can be considered. Specifically, in the pickling procedure, the seed is placed in a mixer which adds either desired amount of seed dressing formulations either as such or after prior dilution with water and mixes until evenly distributed the formulation on the seed. Optionally, a drying process follows.
Die Aufwandmenge an den erfindungsgemäß verwendbaren Beizmittel-Formulierungen kann innerhalb eines größeren Bereiches variiert werden. Sie richtet sich nach dem jeweiligen Gehalt $ des/der Wirkstoffs/Wirkstoffe in den Formulierungen und nach dem Saatgut. Die Aufwandmengen bei $ Wirkstoffen/Wirkstoffkombinationen liegen im Allgemeinen zwischen 0,001 und 50 g pro Kilogramm Saatgut, vorzugsweise zwischen 0,01 und 15 g pro Kilogramm Saatgut. The application rate of the seed dressing formulations which can be used according to the invention can be varied within a relatively wide range. It depends on the respective content $ of the active substance (s) in the formulations and on the seed. The application rates for active compounds / active substance combinations are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 15 g per kilogram of seed.
Aus dem Stand der Technik ist nicht bekannt, dass die Wirkstoffe der Formel (I) gegen biotische Stressfaktoren und/oder abiotischen Stress von Pflanzen oder im Hinblick auf das Pflanzenwachstum eine Wirkung zeigen. Es wurde nun gefunden, dass die erfindungsgemäßen Wirkstoffe der Formel (I) zur Steigerung der pflanzeneigenen Abwehrkräfte (Pathogenabwehr in Pflanzen) geeignet sind. It is not known from the prior art that the active compounds of the formula (I) have an effect against biotic stress factors and / or abiotic stress of plants or with regard to plant growth. It has now been found that the active compounds of the formula (I) according to the invention are suitable for increasing the plant's own defenses (pathogen defense in plants).
Es ist bekannt, dass Pflanzen auf natürliche Stressbedingungen, wie beispielsweise Kälte, Hitze, Trockenheit, Verwundung, Pathogenbefall (Viren, Bakterien, Pilze), Insekten etc. aber auch auf Herbizide mit spezifischen oder unspezifischen Abwehrmechanismen reagieren (Pflanzenbiochemie, - 63 -It is known that plants react to natural stress conditions, such as, for example, cold, heat, dryness, wounding, pathogen infestation (viruses, bacteria, fungi), insects, etc., but also to herbicides with specific or nonspecific defense mechanisms (plant biochemistry, - 63 -
S. 393-462, Spektrum Akademischer Verlag, Heidelberg, Berlin, Oxford, Hans W. Heidt, 1996.; Biochemistry and Molecular Biology of Plants, S. 1102-1203, American Society of Plant Physiologists, Rockville, Maryland, eds. Buchanan, Gruissem, Jones, 2000). Dabei dienen z. B. durch Verwundung entstandene Zellwandbestandteile oder spezifische vom Pathogen stammende Signalsubstanzen als Induktoren pflanzlicher Signaltransduktionsketten, die am Ende zur Bildung von gegen den Stressfaktor gerichteten Abwehrmolekülen führen. Hierbei kann es sich beispielsweise um (a) niedermolekulare Substanzen, wie z.B. Phytoalexine, (b) nicht-enzymatische Proteine, wie z. B.„Pathogenesis-related proteins" (PR-Proteine), (c) enzymatische Proteine, wie beispielsweise Chitinasen, Glucanasen, oder (d) um spezifische Inhibitoren essentieller Proteine, wie beispielsweise um Protease-Inhibitoren, Xylanase- Inhibitoren, handeln, welche das Pathogen direkt angreifen oder seine Proliferation behindern (Dangl and Jones, Nature 411, 826-833, 2001 ; Kessler and Baldwin, Annual Review of Plant Biology, 53, 299- 328, 2003). Pp. 393-462, Spektrum Akademischer Verlag, Heidelberg, Berlin, Oxford, Hans W. Heidt, 1996; Biochemistry and Molecular Biology of Plants, pp. 1102-1203, American Society of Plant Physiologists, Rockville, Maryland, eds. Buchanan, Gruissem, Jones, 2000). It serve z. B. caused by wounding cell wall components or specific pathogen-derived signal substances as inducers of plant signal transduction chains, which ultimately lead to the formation of anti-stress factor defense molecules. These may be, for example, (a) low molecular weight substances, e.g. Phytoalexins, (b) non-enzymatic proteins, such as. (C) enzymatic proteins such as chitinases, glucanases, or (d) specific inhibitors of essential proteins, such as protease inhibitors, xylanase inhibitors attack the pathogen directly or impede its proliferation (Dangl and Jones, Nature 411, 826-833, 2001; Kessler and Baldwin, Annual Review of Plant Biology, 53, 299-328, 2003).
Ein zusätzlicher Abwehrmechanismus ist die sogenannte hypersensitive Reaktion (HR), die über oxidativen Stress vermittelt wird und zum Absterben von Pflanzengewebe im Bereich eines Infektionsherdes führt, wodurch eine Ausbreitung von Pflanzenpathogenen, die auf lebende Zellen angewiesen sind, verhindert wird (Pennazio, New Microbiol. 18, 229-240, 1995). An additional defense mechanism is the so-called hypersensitive reaction (HR), which is mediated by oxidative stress and leads to the death of plant tissue in the area of an infection, thereby preventing the spread of plant pathogens that rely on living cells (Pennazio, New Microbiol. 18, 229-240, 1995).
Im weiteren Verlauf einer Infektion werden durch pflanzeneigene Botenstoffe Signale in nicht befallene Gewebe weitergegeben, die auch dort zur Auslösung von Abwehrreaktionen führen und die Entstehung von Sekundärinfektionen behindern (Systemic acquired resistance, SAR) (Ryals et al., The Plant Cell 8, 1809-1819, 1996). In the further course of an infection signals are transmitted by non-infested tissues by plant-derived messenger substances, which also lead there to the triggering of defense reactions and hinder the development of secondary infections (systemic acquired resistance, SAR) (Ryals et al., The Plant Cell 8, 1809- 1819, 1996).
Eine Reihe von pflanzenendogenen Signalstoffen, die in die Stresstoleranz bzw. die Pathogenabwehr involviert sind, sind bereits bekannt. Zu nennen sind hier beispielsweise Salicylsäure, Benzoesäure, Jasmonsäure oder Ethylen (Biochemistry and Molecular Biology of Plants, S. 850-929, American Society of Plant Physiologists, Rockville, Maryland, eds. Buchanan, Gruissem, Jones, 2000). Einige dieser Substanzen oder deren stabile synthetische Derivate und abgeleitete Strukturen sind auch bei externer Applikation auf Pflanzen oder Saatgutbeizung wirksam und aktivieren Abwehrreaktionen, die eine erhöhte Stress- bzw. Pathogentoleranz der Pflanze zur Folge haben (Sembdner, Parthier, Ann. Rev. Plant Physiol. Plant Mol. Biol. 44, 569-589, 1993). Die Salicylat-vermittelte Abwehr richtet sich besonders gegen phytopathogene Pilze, Bakterien und Viren (Ryals et al., The Plant Cell 8, 1809-1819, 1996). A number of plant endogenous signaling substances involved in stress tolerance and pathogen defense are already known. These include, for example, salicylic acid, benzoic acid, jasmonic acid or ethylene (Biochemistry and Molecular Biology of Plants, pp. 850-929, American Society of Plant Physiologists, Rockville, Maryland, eds. Buchanan, Gruissem, Jones, 2000). Some of these substances or their stable synthetic derivatives and derived structures are also effective in external application to plants or seed dressing and activate defense reactions that result in an increased stress or pathogen tolerance of the plant (Sembdner, Parthier, Ann. Rev. Plant Physiol. Plant Mol. Biol. 44, 569-589, 1993). The salicylate-mediated defense is particularly directed against phytopathogenic fungi, bacteria and viruses (Ryals et al., The Plant Cell 8, 1809-1819, 1996).
Ein bekanntes synthetisches Produkt, das eine der Salicylsäure vergleichbare Funktion übernimmt und eine Schutzwirkung gegen phytopathogene Pilze, Bakterien und Viren vermitteln kann, ist Benzothiadiazol (CGA 245704; Common name: Acibenzolar-5-methyl; Handelsname: Bion®) (Achuo et al., Plant Pathology 53 (1), 65-72, 2004; Tamblyn et al., Pesticide Science 55 (6), 676-677, 1999; EP-OS 0 313 512). Λ A known synthetic product, which one of the salicylic acid similar function is performed and can provide a protective effect against phytopathogenic fungi, bacteria and viruses, is benzothiadiazole (CGA 245704; Common name: acibenzolar-5-methyl; trade name: Bion ®) (Achuo et al. , Plant Pathology 53 (1), 65-72, 2004, Tamblyn et al., Pesticide Science 55 (6), 676-677, 1999, EP-OS 0 313 512). Λ
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Andere Verbindungen, die in die Gruppe der Oxylipine gehören, wie z.B. Jasmonsäure, und die durch sie ausgelösten Schutzmechanismen sind besonders gegen Schadinsekten wirksam (Walling, J. Plant Growth Regul. 19, 195-216, 2000) . Other compounds belonging to the group of oxylipins, e.g. Jasmonic acid, and the protective mechanisms triggered by them are particularly effective against noxious insects (Walling, J. Plant Growth Regul. 19, 195-216, 2000).
Desweiteren ist bekannt, dass die Behandlung von Pflanzen mit Insektiziden aus der Reihe der Neonikotinoide (Chlornikotinyle) zu einer erhöhten Resistenz der Pflanze gegenüber abiotischem Stress führt. Insbesondere gilt dies für das Imidacloprid (Brown et al., Beltwide Cotton Conference Proceedings 2231-2237, 2004). Dieser Schutz erfolgt durch Beeinflussung physiologischer und biochemischer Eigenschaften der Pflanzenzellen wie z.B. durch Verbesserung der Membranstabilität, Erhöhung der Kohlenhydratkonzentration, Steigerung der Polyolkonzentration und Antioxidantienaktivität (Gonias et al., Beltwide Cotton Conference Proceedings 2225-2229, 2004). Furthermore, it is known that the treatment of plants with insecticides from the series of neonicotinoids (Chlornikotinyle) leads to an increased resistance of the plant to abiotic stress. This is especially true of the imidacloprid (Brown et al., Beltwide Cotton Conference Proceedings 2231-2237, 2004). This protection is achieved by influencing the physiological and biochemical properties of the plant cells, e.g. by improving membrane stability, increasing carbohydrate concentration, increasing polyol concentration and antioxidant activity (Gonias et al., Beltwide Cotton Conference Proceedings 2225-2229, 2004).
Darüber hinaus ist der Effekt von Chlornikotinylen gegen biotische Stressfaktoren bekannt (Crop Protection 19 (5), 349-354, 2000; Journal of Entomological Science 37(1), 101-112, 2002; Annais of Biology (Hisar, India) 19 (2), 179-181, 2003). Beispielsweise führen Insektizide aus der Reihe der Neonikotinoide (Chlornikotinyle) zu einer erhöhten Expression von Genen aus der Reihe der „Pathogenesis-related Proteins" (PR-Proteine). PR-Proteine unterstützen die Pflanzen primär in der Abwehr von biotischen Stressoren, wie z.B. phytopathogene Pilze, Bakterien und Viren (DE 10 2005 045 174 A; DE 10 2005 022 994 A und WO 2006/122662 A; Thielert Pflanzenschutz-Nachrichten Bayer, 59 (1), 73-86, 2006; Francis et al., European Journal of Plant Pathology, publ. online 23.1.2009). In addition, the effect of chloronicotinylene against biotic stress factors is known (Crop Protection 19 (5), 349-354, 2000; Journal of Entomological Science 37 (1), 101-112, 2002; Annais of Biology (Hisar, India) 19 (5). 2), 179-181, 2003). For example, neonicotinoid insecticides (chlornicotinyls) lead to increased expression of pathogenesis-related proteins (PR proteins), which primarily support plants in the defense against biotic stressors, such as phytopathogens Fungi, Bacteria and Viruses (DE 10 2005 045 174 A; DE 10 2005 022 994 A and WO 2006/122662 A; Thielert Pflanzenschutz-Nachrichten Bayer, 59 (1), 73-86, 2006; Francis et al., European Journal of Plant Pathology, publ. online 23.1.2009).
Des Weiteren ist bekannt, dass die Behandlung von genetisch modifizierten Pflanzen mit Insektiziden aus der Reihe der Neonikotinoide (Chlornikotinyle) zu einer verbesserten Stresstoleranz der Pflanze führt (EP 1 731 037 A), beispielsweise auch gegenüber dem Herbizid Glyphosat (WO 2006/015697 A). Furthermore, it is known that the treatment of genetically modified plants with insecticides from the series of neonicotinoids (chloronicotinyls) leads to an improved stress tolerance of the plant (EP 1 731 037 A), for example also to the herbicide glyphosate (WO 2006/015697 A). ,
Somit ist bekannt, dass Pflanzen über mehrere endogene Reaktionsmechanismen verfügen, die eine wirksame Abwehr gegenüber verschiedensten Schadorganismen (biotischer Stress) und/oder abiotischem Stress bewirken können. Die Anzucht von gesunden und gleichmäßig gewachsenen Jungpflanzen bildet eine wesentliche Voraussetzung für den großflächigen Anbau und die ökonomische Bestandesführung landwirtschaftlicher, gartenbaulicher und forstwirtschaftlicher Kulturpflanzen. Thus, it is known that plants have a number of endogenous reaction mechanisms that can effect effective defense against various harmful organisms (biotic stress) and / or abiotic stress. The cultivation of healthy and uniformly grown seedlings is an essential prerequisite for the large-scale cultivation and economic management of agricultural, horticultural and forestry crops.
Zahlreiche Jungpflanzen-Anzuchtverfahren sind in der Land- und Forstwirtschaft sowie im Gartenbau etabliert. Hierbei werden als Anzuchtsubstrate neben gedämpfter Erde auch spezielle Substrate u.a. auf Basis von Torfmoosen, Kokosfasern, Steinwolle, wie z.B. Grodan®, Bims, Blähton, wie z.B. Lecaton® oder Lecadan®, Tongranulate, wie z.B. Seramis®, Schaumstoffe, wie z.B. Baystrat®, Vermiculite, Perlite, künstliche Erden, wie z.B. Hygromull®, oder Kombinationen dieser Substrate eingesetzt, in das entweder mit Fungiziden und/oder Insektiziden gebeiztes oder ungeheiztes Saatgut ausgesät wird. e Numerous seedling cultivation methods are established in agriculture, forestry and horticulture. Here, as growing substrates in addition to subdued earth also special substrates, among others based on peat moss, coir, rockwool, such as Grodan ®, pumice, expanded clay such as Lecaton ® or Lecadan ®, clay granules, such as Seramis ®, foam materials, such as Baystrat ® used, vermiculite, perlite, synthetic soils such as Hygro ®, or combinations of these substrates, in which either with fungicides and / or insecticides stained or unheated seed is sown. e
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In speziellen Kulturen, wie z.B. Tabak, werden Jungpflanzen zunehmend im sogenannten „Float- Verfahren" oder„Floating- Verfahren" angezogen (Leal, R. S., The use of Confidor S in the float , a new tobacco seedlings production System in the South of Brazil. Pflanzenschutz-Nachrichten Bayer (Deutsche Ausgabe) (2001), 54(3), Seiten 337 bis 352; Rudolph, R. D.; Rogers, W. D.; The efficacy of imidacloprid treatment for reduction in the severity of insect vectored virus diseases of tobacco. Pflanzenschutz-Nachrichten Bayer (Deutsche Ausgabe) (2001), 54(3), Seiten 311 bis 336). Bei diesem Verfahren wird das Saatgut in speziellen Behältern, z.B. Styropor-Lochtabletts, in spezieller Anzuchterde auf Basis Torf-Kultur-Substrat ausgesät und anschließend in Containern mit geeigneter Nährlösung bis zum Erreichen der gewünschten Verpflanzungsgröße kultiviert (Abbildung 1). Dabei gestattet man den Behältern auf der Nährlösung zu treiben, wovon sich der Name der Anzuchtmethode ableitet (Leal, 2001, s.o.). In Floating- Verfahren werden seit einigen Jahren zur Bekämpfung von saugenden Schädlingen Insektizide aus der Klasse der Neonicotiniode (Chlornikotinyle) eingesetzt. Üblicherweise werden die Pflanzen im Float- Verfahren kurz vor dem Verpflanzen mit Neonikotinoid (Chlornikotinyle) Insektiziden besprüht oder unmittelbar vor oder beim Verpflanzen ins Feld mit Neonikotinoid (Chlornikotinyle) Insektiziden angegossen, was als„Drenching" bezeichnet wird (Leal, 2001, s.o.; Rudolph and Rogers, 2001, s.o.). Beide Applikationsverfahren sind technisch relativ aufwendig. In special cultures, e.g. Tobacco, seedlings are increasingly being grown in the so-called "float" or "floating" process (Leal, RS, The use of Confidor S in the float, a new tobacco seedling production system in the South of Brazil.) Crop Protection News Bayer ( German Edition) (2001), 54 (3), pages 337 to 352; Rudolph, RD; Rogers, WD; Crop Protection News Bayer (German Edition ) (2001), 54 (3), pages 311 to 336). In this method, the seed is kept in special containers, e.g. Styrofoam perforated trays, seeded in a special potting soil based on peat culture substrate and then cultivated in containers with suitable nutrient solution until the desired transplant size is reached (Figure 1). The containers are allowed to run on the nutrient solution, from which the name of the growing method is derived (Leal, 2001, supra). Floating processes have been using insecticides from the class of neonicotiniodes (chlornicotinyls) for the control of sucking pests for several years. Usually, the plants are sprayed with neonicotinoid (chloronicotinyl) insecticides in the float process shortly before transplanting or are infused with neonicotinoid (chloronicotinyl) insecticides immediately before or during transplantation, which is termed "drenching" (Leal, 2001, supra; and Rogers, 2001, supra) Both methods of application are technically relatively complex.
Zum Schutz des auflaufenden Saat- oder Pflanzgutes vor pilzlichen Krankheitserregern und Schädlingen werden hierbei bis zur Verpflanzung Fungizide und Insektizide verwendet. Die Wahl der Pflanzenschutzmittel, der Ort und Zeitpunkt der Anwendung sowie die Aufwandmenge der Mittel richten sich hierbei vor allem nach der Art der auftretenden Pilzkrankheiten und Schädlinge, der spezifischen Wirkungsweise und Wirkungsdauer der Mittel sowie deren Pflanzenverträglichkeit, und kann somit unmittelbar an die spezifischen Erfordernisse unterschiedlicher Kulturen und Regionen angepasst werden. Die Wirkstoffe der Formel (I) führen dabei unabhängig von einer Insektenbekämpfung zu einem guten Schutz der Pflanze vor Schäden durch pilzliche, bakterielle oder virale Pathogene. Fungicides and insecticides are used to protect the crops of seed or plant material from fungal pathogens and pests until they are transplanted. The choice of pesticides, the place and time of application and the application rate of the funds depend here mainly on the type of fungal diseases and pests occurring, the specific mode of action and duration of action of the agents and their plant compatibility, and thus directly to the specific requirements of different Adapted to crops and regions. The active compounds of the formula (I) lead, regardless of insect control, to good protection of the plant from damage by fungal, bacterial or viral pathogens.
Ohne an eine Theorie gebunden sein zu wollen wird zurzeit davon ausgegangen, dass die Abwehr der Pathogene durch die Induktion von PR Proteinen als Folge einer Behandlung mit mindestens einem Wirkstoff der Formel (I) erfolgt. Insbesondere zeigt die erfindungsgemäße Verwendung in der Saatgutbehandlung, in der Bodenbehandlung, in speziellen Anzucht- und Kultivierungsverfahren (z.B. Floating Box, Rockwool, Hydroponic), aber auch Stamm- und Blattbehandlung die beschriebenen Vorteile. Kombinationen eines Wirkstoffs der Formel (I) unter anderem mit Insektiziden, Fungiziden und Bakteriziden zeigen synergistische Wirkung bei der Bekämpfung von Pflanzenkrankheiten. Die kombinierte Verwendung - 66 - der Wirkstoffe der Formel (I) mit gentechnisch veränderten Sorten in Bezug auf erhöhte abiotische Stresstoleranz führt darüberhinaus zu einer synergistischen Verbesserung des Wachstums. Without wishing to be bound by theory, it is currently believed that defense of the pathogens by induction of PR proteins occurs as a result of treatment with at least one drug of formula (I). In particular, the use according to the invention in seed treatment, in soil treatment, in special cultivation and cultivation processes (eg floating box, Rockwool, Hydroponic), but also in stem and leaf treatment, has the advantages described. Combinations of an active compound of the formula (I), inter alia, with insecticides, fungicides and bactericides have a synergistic effect in the control of plant diseases. The combined use In addition, the active substances of the formula (I) with genetically modified varieties with regard to increased abiotic stress tolerance lead to a synergistic improvement in growth.
Schließlich wurde erfindungsgemäß auch gefunden, dass die Wirkstoffe der Formel (I) nicht nur zur Steigerung der Pathogenabwehr in Pflanzen, sondern auch zur Verbesserung des Pflanzenwachstums und/oder zur Steigerung der Widerstandfähigkeit von Pflanzen gegenüber Pflanzenkrankheiten, welche durch Pilze, Bakterien, Viren, MLO (Mycoplasma-like organisms) und/oder RLO (Rickettsia-like organisms) verursacht werden, insbesondere gegenüber bodenbürtigen Pilzkrankheiten, und/oder zur Erhöhung der Widerstandsfähigkeit von Pflanzen gegenüber abiotischen Stressfaktoren geeignet sind. Finally, it has also been found according to the invention that the active compounds of the formula (I) not only increase the pathogen defense in plants, but also improve plant growth and / or increase the resistance of plants to plant diseases caused by fungi, bacteria, viruses, MLO (Mycoplasma -like organisms) and / or RLO (Rickettsia-like organisms) are caused, especially against soil-borne fungal diseases, and / or are suitable for increasing the resistance of plants to abiotic stress factors.
Zu den abiotischen Stressbedingungen können zum Beispiel Dürre, Kälte- und Hitzebedingungen, osmotischer Stress, Staunässe, erhöhter Bodensalzgehalt, erhöhtes Ausgesetztsein an Mineralien, Ozonbedingungen, Starklichtbedingungen, beschränkte Verfügbarkeit von Stickstoffnährstoffen, beschränkte Verfügbarkeit von Phosphornährstoffen oder Vermeidung von Schatten zählen. Abiotic stress conditions may include, for example, drought, cold and heat conditions, osmotic stress, waterlogging, increased soil salinity, increased exposure to minerals, ozone conditions, high light conditions, limited availability of nitrogen nutrients, limited availability of phosphorous nutrients, or avoidance of shade.
Gegenstand der vorliegenden Erfindung ist somit zunächst die Verwendung von mindestens einem Wirkstoff der Formel (I) zur Steigerung von pflanzeneigenen Abwehrkräften und/oder zur Verbesserung des Pflanzenwachstums und/oder zur Steigerung der Widerstandfähigkeit von Pflanzen gegenüber Pflanzenkrankheiten, welche durch Pilze, Bakterien, Viren, MLO (Mycoplasma-like organisms) und/oder RLO (Rickettsia-like organisms) verursacht werden, insbesondere gegenüber bodenbürtige Pilzkrankheiten, und/oder zur Steigerung der Widerstandsfähigkeit von Pflanzen gegenüber abiotischen Stressfaktoren. Unter der Bezeichnung Pflanzenwachstum werden im Rahmen der vorliegenden Erfindung verschiedenartige Vorteile für Pflanzen verstanden, die nicht unmittelbar mit der bekannten Pestiziden Wirksamkeit, bevorzugt der Insektiziden Wirksamkeit der Wirkstoffe der Formel (I) verbunden sind. Solche vorteilhaften Eigenschaften sind beispielsweise die nachfolgend genannten verbesserten Pflanzencharakteristika: beschleunigte Keimung und Auflaufen des Saat- und Pflanzgutes, verbessertes Wurzelwachstum hinsichtlich Oberfläche und Tiefe, vermehrte Ausläuferbildung oder BeStockung, stärkere und produktivere Ausläufer und Bestockungstriebe, Verbesserung des Sprosswachstums, erhöhte Standfestigkeit, vergrößerter Sprossbasisdurchmesser, vergrößerte Blattfläche, grünere Blattfarbe, höhere Erträge an Nähr- und Inhaltsstoffen, wie z.B. Kohlenhydrate, Fette, Öle, Proteine, Vitamine, Mineralstoffe, ätherische Öle, Farbstoffe, Fasern, bessere Faserqualität, früheres Blühen, gesteigerte Blütenanzahl, reduzierter Gehalt an toxischen Produkten wie Mycotoxine, reduzierter Gehalt an Rückständen oder unvorteilhaften Bestandteilen jeglicher Art oder bessere Verdaulichkeit, verbesserte Lagerstabilität des Erntegutes, verbesserte Toleranz gegenüber unvorteilhaften Temperaturen, verbesserte Toleranz gegenüber Dürre und Trockenheit wie auch Sauerstoffmangel durch Wasserüberschuss, verbesserte Toleranz gegenüber erhöhten Salzgehalten in Böden und Wasser, gesteigerte Toleranz gegenüber UV-Strahlung, gesteigerte Toleranz gegenüber Ozonstress, verbesserte ^ The present invention therefore relates firstly to the use of at least one active substance of the formula (I) for increasing plant-specific defense forces and / or for improving plant growth and / or for increasing the resistance of plants to plant diseases caused by fungi, bacteria, viruses, MLO (mycoplasma-like organisms) and / or RLO (Rickettsia-like organisms) are caused, in particular against soil-borne fungal diseases, and / or to increase the resistance of plants to abiotic stress factors. In the context of the present invention, the term plant growth is understood to mean various advantages for plants which are not directly related to the known pesticidal activity, preferably to the insecticidal activity of the active compounds of the formula (I). Such advantageous properties are, for example, the following improved plant characteristics: accelerated germination and emergence of the seed and planting material, improved surface and depth root growth, increased runners or stocking, stronger and more productive shoots and tillers, improvement in shoot growth, increased stability, increased shoot base diameter, increased leaf area, greener leaf color, higher yields of nutrients and ingredients, such as carbohydrates, fats, oils, proteins, vitamins, minerals, essential oils, dyes, fibers, better fiber quality, earlier flowering, increased number of flowers, reduced content of toxic products such as Mycotoxins, reduced content of residues or unfavorable components of any kind or better digestibility, improved storage stability of the crop, improved tolerance to unfavorable temperature improved tolerance to drought and dryness as well as oxygen deficiency due to excess water, improved tolerance to increased salt levels in soils and water, increased tolerance to UV radiation, increased tolerance to ozone stress, improved ^
Verträglichkeit gegenüber Herbiziden und anderen Pflanzenbehandlungsmitteln, verbesserte Wasseraufnahme und Photosyntheseleistung, vorteilhafte Pflanzeneigenschaften, wie beispielsweise Beschleunigung der Reifung, gleichmäßigere Abreife, größere Anziehungskraft für Nützlinge, verbesserte Bestäubung oder andere Vorteile, die einem Fachmann durchaus bekannt sind. Die weiter oben genannten verschiedenartigen Vorteile für Pflanzen lassen sich bekannterweise partiell zusammenfassen und mit allgemein gültigen Begriffen belegen. Soche Begriffe sind beispielsweise die nachfolgend aufgeführten Bezeichnungen: phytotonischer Effekt, Widerstandsfähigkeit gegenüber Stressfaktoren, weniger Pflanzenstress, Pflanzengesundheit, gesunde Pflanzen, Pflanzenfitness („Plant Fitness"), „Plant Wellness", „Plant Concept", „Vigor Effect", „Stress Shield", Schutzschild, „Crop Health",„Crop Health Properties",„Crop Health Products",„Crop Health Management",„Crop Health Therapy", „Plant Health", „Plant Health Properties", „Plant Health Products", „Plant Health Management",„Plant Health Therapy", Grünungseffekt („Greening Effect" oder„Re-greening Effect"), „Freshness" oder andere Begriffe, die einem Fachmann durchaus bekannt sind. Compatibility with herbicides and other plant treatment agents, improved water absorption and photosynthetic performance, beneficial plant properties such as acceleration of maturation, more uniform maturity, greater attractiveness for beneficials, improved pollination or other benefits well known to those skilled in the art. The various advantages for plants mentioned above can, as is known, be partially summarized and substantiated by generally valid terms. Soche terms are, for example, the following: phytotonic effect, resistance to stressors, less plant stress, plant health, healthy plants, Plant Fitness, Plant Wellness, Plant Concept, Vigor Effect, Stress Shield "Crop Health Properties", "Crop Health Products", "Crop Health Management", "Crop Health Therapy", "Plant Health", "Plant Health Properties", "Plant Health Products", "Plant Health Management", "Plant Health Therapy", "Greening Effect" or "Re-greening Effect"), "Freshness" or other terms that are well known to a person skilled in the art.
Es wurde ferner gefunden, dass Wirkstoffe der Formel (I) zu einer erhöhten Expression von Genen aus der Reihe der „Pathogenesis-related proteins" (PR-Proteine) führen. PR-Proteine unterstützen die Pflanzen primär in der Abwehr von biotischen Stressoren, wie z.B. phytopathogene Pilze, Bakterien und Viren. Dies hat zur Folge, dass Pflanzen nach Anwendung von Wirkstoffen der Formel (I) besser geschützt sind vor Infektionen phytopathogener Pilze, Bakterien und Viren. Bei notwendigem Einsatz von Insektiziden, Fungiziden und Bakteriziden in Mischung wie auch bei sequentieller Anwendung mit Wirkstoffen der Formel (I) wird deren Wirkung unterstützt. It has furthermore been found that active compounds of the formula (I) lead to an increased expression of genes from the series of "pathogenesis-related proteins" (PR proteins) .PRO proteins primarily support the plants in the defense against biotic stressors, such as phytopathogenic fungi, bacteria and viruses, which means that plants are better protected against infections of phytopathogenic fungi, bacteria and viruses by the use of active ingredients of formula (I) sequential application with active ingredients of the formula (I) whose action is supported.
Erfindunsgemäß wurde darüber hinaus gefunden, dass die Anwendung der Wirkstoffe der Formel (I) in Kombination mit einem Düngemittel wie weiter unten stehend definiert auf Pflanzen oder in deren Umgebung einen synergistischen wachstumssteigernden Effekt bewirkt. It has also been found according to the invention that the use of the active compounds of the formula (I) in combination with a fertilizer as defined below has a synergistic growth-increasing effect on or in the environment of plants.
Düngemittel die erfindungsgemäß zusammen mit den oben näher erläuterten Wirkstoffen oder Mitteln verwendet werden können sind im Allgemeinen organische und anorganische Stickstoff-haltige Verbindungen wie beispielsweise Harnstoffe, Harnstoff-Formaldehyd-Kondensationsprodukte, Aminosäuren, Ammoniumsalze und -nitrate, Kaliumsalze (bevorzugt Chloride, Sulfate, Nitrate), Phosphorsäuresalze und/oder Salze von Phosphoriger Säure (bevorzugt Kaliumsalze und Ammoniumsalze). Insbesondere zu nennen sind in diesem Zusammenhang die NPK-Dünger, d.h. Düngemittel, die Stickstoff, Phosphor und Kalium enthalten, Kalkammonsalpeter, d.h. Düngemittel, die noch Calcium enthalten, Ammonsulfatsalpeter (Allgemeine Formel
Figure imgf000068_0001
NH4NO3), Ammonphosphat und Ammonsulfat. Diese Düngemittel sind dem Fachmann allgemein bekannt, siehe auch beispielsweise Ullmann's Encyclopedia of Industrial Chemistry, 5. Edition, Vol. A 10, Seiten 323 bis 431, Verlagsgesellschaft, Weinheim, 1987. Die Düngemittel können auch Salze aus Mikronährstoffen (bevorzugt Calcium, Schwefel, Bor, Mangan, Magnesium, Eisen, Bor, Kupfer, Zink, Molybdän und Kobalt) und Phytohormonen (z. B. Vitamin Bl und Indol-3-ylessigsäure (IAA)) oder Gemische davon enthalten. Erfindungsgemäß eingesetzte Düngemittel können auch weitere Salze wie Monoammoniumphosphat (MAP), Diammoniumphosphat (DAP), Kaliumsulfat, Kaliumchlorid oder Magnesiumsulfat enthalten. Geeignete Mengen für die sekundären Nährstoffe oder Spurenelemente sind Mengen von 0,5 bis 5 Gew.- , bezogen auf das gesamte Düngemittel. Weitere mögliche Inhaltsstoffe sind Pflanzenschutzmittel, Insektizide oder Fungizide, Wachstumsregulatoren oder Gemische davon. Hierzu folgen weiter unten weitergehende Ausführungen. Die Düngemittel können beispielsweise in Form von Pulvern, Granulaten, Prills oder Kompaktaten eingesetzt werden. Die Düngemittel können jedoch auch in flüssiger Form, gelöst in einem wässrigen Medium, eingesetzt werden. In diesem Fall kann auch verdünnter wässriger Ammoniak als Stickstoffdüngemittel eingesetzt werden. Weitere mögliche Inhaltsstoffe für Düngemittel sind beispielsweise in Ullmann's Encyclopedia of Industrial Chemistry, 5. Auflage, 1987, Band A 10, Seiten 363 bis 401, DE-A 41 28 828, DE-A 19 05 834 und DE-A 196 31 764 beschrieben. Fertilizers which can be used according to the invention together with the above-described active agents or agents are generally organic and inorganic nitrogen-containing compounds such as ureas, urea-formaldehyde condensation products, amino acids, ammonium salts and nitrates, potassium salts (preferably chlorides, sulfates, nitrates ), Phosphoric acid salts and / or salts of phosphorous acid (preferably potassium salts and ammonium salts). Particularly noteworthy in this context are the NPK fertilizers, ie fertilizers containing nitrogen, phosphorus and potassium, calcium ammonium nitrate, ie fertilizers that still contain calcium, ammonium sulfate nitrate (General formula
Figure imgf000068_0001
NH4NO3), ammonium phosphate and ammonium sulfate. These fertilizers are well known to those skilled in the art, see also, for example, Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A 10, pages 323 to 431, Verlagsgesellschaft, Weinheim, 1987. The fertilizers may also contain salts of micronutrients (preferably calcium, sulfur, boron, manganese, magnesium, iron, boron, copper, zinc, molybdenum and cobalt) and phytohormones (eg, vitamin B1 and indol-3-ylacetic acid (IAA)). or mixtures thereof. Fertilizers used according to the invention may also contain other salts such as monoammonium phosphate (MAP), diammonium phosphate (DAP), potassium sulfate, potassium chloride or magnesium sulfate. Suitable amounts for the secondary nutrients or trace elements are amounts of from 0.5 to 5% by weight, based on the total fertilizer. Further possible ingredients are crop protection agents, insecticides or fungicides, growth regulators or mixtures thereof. Further explanations follow below. The fertilizers can be used, for example, in the form of powders, granules, prills or compactates. However, the fertilizers can also be used in liquid form dissolved in an aqueous medium. In this case, dilute aqueous ammonia can be used as nitrogen fertilizer. Further possible ingredients for fertilizers are described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, 1987, Volume A 10, pages 363 to 401, DE-A 41 28 828, DE-A 19 05 834 and DE-A 196 31 764 ,
Die allgemeine Zusammensetzung der Düngemittel, bei welchen es sich im Rahmen der vorliegenden Erfindung um Einzelnährstoff- und/oder Mehrnährstoffdünger handeln kann, beispielsweise aus Stickstoff, Kalium oder Phosphor, kann innerhalb eines breiten Bereichs variieren. Im Allgemeinen ist ein Gehalt von 1 bis 30 Gew.- Stickstoff (bevorzugt 5 bis 20 Gew.- ), von 1 bis 20 Gew.- Kalium (bevorzugt 3 bis 15 Gew.- ) und ein Gehalt von 1 bis 20 Gew.- Phosphor (bevorzugt 3 bis 10 Gew.- ) vorteilhaft. Der Gehalt von Mikroelementen ist üblicherweise im ppm Bereich, bevorzugt im Bereich von 1 bis 1000 ppm. The general composition of the fertilizers, which in the context of the present invention may be single nutrient and / or multi-nutrient fertilizers, for example nitrogen, potassium or phosphorus, may vary within a wide range. In general, a content of 1 to 30% by weight of nitrogen (preferably 5 to 20% by weight), of 1 to 20% by weight of potassium (preferably 3 to 15% by weight) and a content of 1 to 20% by weight. Phosphorus (preferably 3 to 10 parts by weight) advantageous. The content of microelements is usually in the ppm range, preferably in the range of 1 to 1000 ppm.
Im Rahmen der vorliegenden Erfindung kann das Düngemittel sowie der Wirkstoff der Formel (I) zeitgleich, d.h. synchron, verabreicht werden. Es ist jedoch auch möglich, zunächst das Düngemittel und dann den Wirkstoff der Formel (I) oder zunächst den Wirkstoff der Formel (I) und dann das Düngemittel anzuwenden. Bei nicht zeitgleicher Anwendung des Wirkstoffs der Formel (I) und des Düngemittels erfolgt im Rahmen der vorliegenden Erfindung jedoch die Anwendung in funktionellem Zusammenhang, insbesondere innerhalb eines Zeitraums von im Allgemeinen 24 Stunden, bevorzugt 18 Stunden, besonders bevorzugt 12 Stunden, speziell 6 Stunden, noch spezieller 4 Stunden, noch weiter spezieller innerhalb 2 Stunden. In ganz besonderen Ausführungsformen der vorliegenden Erfindung erfolgt die Anwendung der erfindungsgemäßen Wirkstoffe der allgemeinen Formel (I) und des Düngemittels in einem zeitlichen Rahmen von weniger als 1 Stunde, vorzugsweise weniger als 30 Minuten, besonders bevorzugt weniger als 15 Minuten. In the present invention, the fertilizer and the active ingredient of the formula (I) at the same time, i. synchronously, administered. However, it is also possible first to apply the fertilizer and then the active ingredient of the formula (I) or first the active ingredient of the formula (I) and then the fertilizer. In the case of non-simultaneous application of the active ingredient of the formula (I) and of the fertilizer, however, the application takes place in a functional context, in particular within a period of generally 24 hours, preferably 18 hours, more preferably 12 hours, especially 6 hours, even more specifically 4 hours, more specifically within 2 hours. In very particular embodiments of the present invention, the active compounds of the general formula (I) and of the fertilizer according to the invention are used in a time frame of less than 1 hour, preferably less than 30 minutes, more preferably less than 15 minutes.
Darüber hinaus ist es möglich, formstabile Mischungen, beispielsweise in der Form von Stäbchen, Granulaten, Tabletten etc., ausgehend von mindestens einem erfindungsgemäß zu verwendenden ^ In addition, it is possible to form stable mixtures, for example in the form of rods, granules, tablets, etc., starting from at least one invention to be used ^
- 69 - - 69 -
Wirkstoff und mindestens einem Düngemittel herzustellen. Um eine entsprechende formstabile Mischung herzustellen, können die entsprechenden Bestandteile miteinander gemischt und gegebenenfalls extrudiert werden bzw. kann der mindestens eine erfindungsgemäß zu verwendende Wirkstoff der Formel (I) auf das Düngemittel aufgezogen werden. Gegebenenfalls können auch Formulierungshilfsmittel in den formstabilen Mischungen, wie beispielsweise Streckmittel oder Haftkleber, verwendet werden, um eine Formstabilität der resultierenden Mischung zu erreichen. Durch die entsprechende Formstabilität eignen sich entsprechende Mischungen insbesondere für die Anwendung im Bereich„Home & Garden", d.h. bei einem Privatanwender oder Hobbygärtner, welche die formstabile Mischung bzw. die darin enthaltenden Bestandteile mit einer vorgegebenen, klar definierten Menge und ohne besondere Hilfsmittel verwenden können. To produce active ingredient and at least one fertilizer. In order to produce a corresponding dimensionally stable mixture, the corresponding constituents can be mixed with one another and optionally extruded or the at least one active compound of the formula (I) to be used according to the invention can be applied to the fertilizer. Optionally, formulation aids may also be used in the dimensionally stable mixtures, such as extenders or pressure-sensitive adhesives, to achieve dimensional stability of the resulting mixture. Due to the corresponding dimensional stability, corresponding mixtures are suitable, in particular for use in the "Home & Garden" sector, ie for a private user or home gardener, who can use the dimensionally stable mixture or the constituents contained therein with a predetermined, clearly defined amount and without special aids ,
Unabhängig hiervon können die Mischungen aus mindestens einem der erfindungsgemäß zu verwendenden Wirkstoffe und dem mindestens einen Düngemittel auch flüssig vorliegen, so dass - beispielsweise bei einem professionellen Anwender im Bereich der Landwirtschaft - die resultierende Mischung als so genannte Tanklösung ausgebracht werden kann. Durch die Verwendung mindestens eines der erfindungsgemäß zu verwendenen Wirkstoffe und mindestens einem Düngemittel wird ein vergrössertes Wurzelwachstum ermöglicht, welches wiederum eine höhere Nährstoffaufnahme ermöglicht und damit das Planzenwachstum fördert. Regardless of this, the mixtures of at least one of the active ingredients to be used according to the invention and the at least one fertilizer may also be liquid, so that-for example, in the case of a professional user in the field of agriculture-the resulting mixture can be applied as a so-called tank solution. By using at least one of the active ingredients to be used according to the invention and at least one fertilizer, an increased root growth is made possible, which in turn allows a higher nutrient uptake and thus promotes plant growth.
Die erfindungsgemäß zu verwendenden Wirkstoffe können, gegebenenfalls in Kombination mit Düngemitteln, bevorzugt an folgenden Pflanzen angewendet werden, wobei die folgende Aufzählung nicht beschränkend ist. The active compounds to be used according to the invention can, if appropriate in combination with fertilizers, preferably be applied to the following plants, the following listing not being restrictive.
Bevorzugt sind Pflanzen aus der Gruppe der Nutzpflanzen, Zierpflanzen, Rasenarten, allgemein genutzte Bäume, die in öffentlichen und privaten Bereichen als Zierpflanzen Verwendungen finden, und Forstbestand. Der Forstbestand umfasst Bäume für die Herstellung von Holz, Zellstoff, Papier und Produkten, die aus Teilen der Bäume hergestellt werden. Der Begriff Nutzpflanzen, wie hier verwendet, bezeichnet Kulturpflanzen, die als Pflanzen für die Gewinnung von Nahrungsmitteln, Futtermitteln, Treibstoffen oder für technische Zwecke eingesetzt werden. Preference is given to plants from the group of crops, ornamental plants, lawn species, generally used trees, which are used as ornamental plants in public and private areas, and forest stands. The forest stock includes trees for the production of wood, pulp, paper and products made from parts of the trees. The term crops as used herein refers to crops used as plants for the production of food, feed, fuel or for technical purposes.
Zu den Nutzpflanzen zählen z.B. folgende Pflanzenarten: Turf, Reben, Getreide, beispielsweise Weizen, Gerste, Roggen, Hafer, Triticale, Reis, Mais und Hirse; Rüben, beispielsweise Zuckerrüben und Futterrüben; Früchte, beispielsweise Kernobst, Steinobst und Beerenobst, beispielsweise Äpfel, Birnen, Pflaumen, Pfirsiche, Mandeln, Kirschen und Beeren, z. B. Erdbeeren, Himbeeren, Brombeeren; Hülsenfrüchte, beispielsweise Bohnen, Linsen, Erbsen und Sojabohnen; Ölkulturen, beispielsweise Raps, Senf, Mohn, Oliven, Sonnenblumen, Kokos, Castorölpflanzen, Kakaobohnen und Erdnüsse; Gurkengewächse, beispielsweise Kürbis, Gurken und Melonen; Fasergewächse, beispielsweise 7Q The crops include, for example, the following plant species: turf, vines, cereals, for example wheat, barley, rye, oats, triticale, rice, corn and millet; Beets, for example sugar beets and fodder beets; Fruits, such as pome fruit, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries and berries, eg. Strawberries, raspberries, blackberries; Legumes, such as beans, lentils, peas and soybeans; Oil crops such as rapeseed, mustard, poppy, olive, sunflower, coconut, castor oil, cocoa beans and peanuts; Cucurbits, for example squash, cucumbers and melons; Fiber plants, for example 7Q
Baumwolle, Flachs, Hanf und Jute; Citrusfrüchte, beispielsweise Orangen, Zitronen, Pampelmusen und Mandarinen; Gemüsesorten, beispielsweise Spinat, (Kopfj-Salat, Spargel, Kohlarten, Möhren, Zwiebeln, Tomaten, Kartoffeln und Paprika; Lorbeergewächse, beispielsweise Avocado, Cinnamomum, Kampfer, oder ebenso Pflanzen wie Tabak, Nüsse, Kaffee, Aubergine, Zuckerrohr, Tee, Pfeffer, Weinreben, Hopfen, Bananen, Naturkautschukgewächse sowie Zierpflanzen, beispielsweise Blumen, Sträucher, Laubbäume und Nadelbäume wie Koniferen. Diese Aufzählung stellt keine Limitierung dar. Cotton, flax, hemp and jute; Citrus fruits, such as oranges, lemons, grapefruit and mandarins; Vegetables such as spinach, (headj salad, asparagus, cabbage, carrots, onions, tomatoes, potatoes and peppers, laurel family, such as avocado, cinnamomum, camphor, or even plants such as tobacco, nuts, coffee, eggplant, sugarcane, tea, pepper , Vines, hops, bananas, natural rubber plants and ornamental plants, such as flowers, shrubs, deciduous trees and conifers, this list is not limiting.
Als besonders geeignete Zielkulturen sind folgende Pflanzen anzusehen: Bamwolle, Aubergine, Turf, Kernobst, Steinobst, Beerenobst, Mais, Weizen, Gerste, Gurke, Tabak, Reben, Reis, Getreide, Birne, Bohnen, Sojabohnen, Raps, Tomate, Paprika, Melonen, Kohl, Kartoffel und Apfel. Als Bäume seien beispielhaft genannt: Abies sp., Eucalyptus sp., Picea sp., Pinus sp., Aesculus sp., Platanus sp., Tilia sp., Acer sp., Tsuga sp., Fraxinus sp., Sorbus sp., Betula sp., Crataegus sp., Ulmus sp., Quercus sp., Fagus sp., Salix sp., Populus sp.. Particularly suitable target crops are the following plants: bamboo wool, eggplant, turf, pome fruit, stone fruit, berry fruit, corn, wheat, barley, cucumber, tobacco, vines, rice, cereals, pear, beans, soybeans, oilseed rape, tomatoes, peppers, melons , Cabbage, potato and apple. Examples of trees are: Abies sp., Eucalyptus sp., Picea sp., Pinus sp., Aesculus sp., Platanus sp., Tilia sp., Acer sp., Tsuga sp., Fraxinus sp., Sorbus sp., Betula sp., Crataegus sp., Ulmus sp., Quercus sp., Fagus sp., Salix sp., Populus sp.
Als bevorzugte Bäume können genannt werden: Aus der Baumart Aesculus: A. hippocastanum, A. pariflora, A. carnea; aus der Baumart Platanus: P. aceriflora, P. occidentalis, P. racemosa; aus der Baumart Picea: P. abies; aus der Baumart Pinus: P. radiate, P. ponderosa, P. contorta, P. sylvestre, P. elliottii, P. montecola, P. albicaulis, P. resinosa, P. palustris, P. taeda, P. flexilis, P. jeffregi, P. baksiana, P. strobes; aus der Baumart Eucalyptus: E. grandis, E. globulus, E. camadentis, E. nitens, E. obliqua, E. regnans, E. pilularus. The following can be mentioned as preferred trees: From the tree species Aesculus: A. hippocastanum, A. pariflora, A. carnea; from the tree species Platanus: P. aceriflora, P. occidentalis, P. racemosa; from the tree species Picea: P. abies; from the species Pinus: P. radiate, P. ponderosa, P. contorta, P. sylvestre, P. elliottii, P. montecola, P. albicaulis, P. resinosa, P. palustris, P. taeda, P. flexilis, P jeffregi, P. baksiana, P. strobes; from the tree species Eucalyptus: E. grandis, E. globulus, E. camadentis, E. nitens, E. obliqua, E. regnans, E. pilularus.
Als besonders bevorzugte Bäume können genannt werden: Aus der Baumart Pinus: P. radiate, P. ponderosa, P. contorta, P. sylvestre, P. strobes; aus der Baumart Eucalyptus: E. grandis, E. globulus, E. camadentis. As particularly preferred trees may be mentioned: From the tree species Pinus: P. radiate, P. ponderosa, P. contorta, P. sylvestre, P. strobes; from the tree species Eucalyptus: E. grandis, E. globulus, E. camadentis.
Als ganz besonders bevorzugte Bäume können genannt werden: Rosskastanie, Platanengewächse, Linde, Ahornbaum. Particularly preferred trees can be called: horse chestnut, sycamore, linden, maple tree.
Die vorliegende Erfindung kann auch an beliebigen Rasenarten („turigrasses") durchgeführt werden, einschließlich„cool season turigrasses" und„warm season turigrasses". Beispiele für Rasenarten für die kalte Jahreszeit sind Blaugräser („blue grasses"; Poa spp.), wie„Kentucky bluegrass" (Poa pratensis L.),„rough bluegrass" (Poa trivialis L.),„Canada bluegrass" (Poa compressa L.),„annual bluegrass" (Poa annua L.),„upland bluegrass" (Poa glaucantha Gaudin), „wood bluegrass" (Poa nemoralis L.) und„bulbous bluegrass" (Poa bulbosa L.); Straussgräser („Bentgrass", Agrostis spp.), wie„creeping bentgrass" (Agrostis palustris Huds.),„colonial bentgrass" (Agrostis tenuis Sibth.),„velvet bentgrass" (Agrostis canina L.),„South German Mixed Bentgrass" (Agrostis spp. einschließlich Agrostis tenius Sibth., Agrostis canina L., und Agrostis palustris Huds.), und„redtop" (Agrostis alba L.); Schwingel („Fescues", Festucu spp.), wie„red fescue" (Festuca rubra L. spp. rubra),„creeping fescue" (Festuca rubra L.), „chewings fescue" (Festuca rubra commutata Gaud.), „sheep fescue" (Festuca ovina L.), „hard fescue" (Festuca longifolia ThuilL), „hair fescue" (Festucu capillata Lam.), „tall fescue" (Festuca arundinacea Schreb.) und„meadow fescue" (Festuca elanor L.); Lolch („ryegrasses", Lolium spp.), wie „annual ryegrass" (Lolium multiflorum Lam.), „perennial ryegrass" (Lolium perenne L.) und„italian ryegrass" (Lolium multiflorum Lam.); und Weizengräser ("wheatgrasses", Agropyron spp..), wie "fairway wheatgrass" (Agropyron cristatum (L.) Gaertn.),„crested wheatgrass" (Agropyron desertorum (Fisch.) Schult.) und "western wheatgrass" (Agropyron smithii Rydb.). Beispiele für weitere "cool season turfgrasses" sind "beachgrass" (Ammophila breviligulata Fern.), "smooth bromegrass" (Bromus inermis Leyss.), Schilf ("cattails") wie "Timothy" (Phleum pratense L.), "sand cattail" (Phleum subulatum L.), "orchardgrass" (Dactylis glomerata L.), "weeping alkaligrass" (Puccinellia distans (L.) Pari.) und "crested dog's-tail" (Cynosurus cristatus L.). The present invention may also be practiced on any type of "turigrass", including "cool season turigrasses" and "warm season turigrasses." Examples of cold season lawn species are blue grasses (Poa spp "Kentucky bluegrass" (Poa pratensis L.), "rough bluegrass" (Poa trivialis L.), "Canada bluegrass" (Poa compressa L.), "annual bluegrass" (Poa annua L.), "upland bluegrass" (Poa glaucantha Gaudin), "wood bluegrass" (Poa nemoralis L.) and "bulbous bluegrass" (Poa bulbosa L.); ostrich grasses ("Bentgrass", Agrostis spp.), such as "creeping bentgrass" (Agrostis palustris Huds.), " colonial bentgrass "(Agrostis tenuis sib.)," velvet bentgrass "(Agrostis canina L.)," South German Mixed Bentgrass "(Agrostis spp including Agrostis tenius Sibth., Agrostis canina L., and Agrostis palustris Huds.), and "Redtop" (Agrostis alba L.); Fescue ("Fescues", Festucu spp.), Such as "red fescue" (Festuca rubra L. spp. Rubra), "creeping fescue" (Festuca rubra L.), "chewings fescue" (Festuca rubra commutata Gaud.), " sheep fescue "(Festuca ovina L.)," hard fescue "(Festuca longifolia ThuilL)," hair fescue "(Festucu capillata Lam.)," tall fescue "(Festuca arundinacea Schreb.) and" meadow fescue "(Festuca elanor L .), Lolium ("ryegrass", Lolium spp.), Such as "annual ryegrass" (Lolium multiflorum Lam.), "Perennial ryegrass" (Lolium perenne L.) and "Italian ryegrass" (Lolium multiflorum Lam.); And wheat grasses ("wheatgrasses", Agropyron spp.), such as "fairway wheatgrass" (Agropyron cristatum (L.) Gaertn.), "crested wheatgrass" (Agropyron desertorum (fish.) Schult.) and "western wheatgrass" (Agropyron smithii Rydb .). Examples of other "cool season turfgrasses" are "beachgrass" (Ammophila breviligulata Fern.), "Smooth bromegrass" (Bromus inermis leyss.), Reeds ("cattails") such as "Timothy" (Phleum pratense L.), "sand cattail "(Phleum subulatum L.)," orchardgrass "(Dactylis glomerata L.)," weeping alkaligrass "(Puccinellia distans (L.) Pari.) And" crested dog's-tail "(Cynosurus cristatus L.).
Beispiele für "warm season turfgrasses" sind„Bermudagrass" (Cynodon spp. L. C. Rieh), "zoysiagrass" (Zoysia spp. Willd.),„St. Augustine grass" (Stenotaphrum secundatum Walt Kuntze),„centipedegrass" (Eremochloa ophiuroides Munro Hack.), „carpetgrass" (Axonopus afflnis Chase), „Bahia grass" (Paspalum notatum Flügge),„Kikuyugrass" (Pennisetum clandestinum Höchst, ex Chiov.),„buffalo grass" (Buchloe daetyloids (Nutt.) Engelm.), "Blue gramma" (Bouteloua gracilis (H.B.K.) Lag. ex Griffiths), „seashore paspalum" (Paspalum vaginatum Swartz) und „sideoats grama" (Bouteloua curtipendula (Michx. Torr.). "Cool season turfgrasses" sind für die erfindungsgemäße Verwendung im Allgemeinen bevorzugt. Besonders bevorzugt sind Blaugras, Straussgras und„redtop", Schwingel und Lolch. Straussgras ist insbesondere bevorzugt. Examples of "warm season turfgrasses" are "Bermudagrass" (Cynodon spp., LC Rieh), "zoysiagrass" (Zoysia spp. Willd.), "St. Augustine grass" (Stenotaphrum secundatum Walt Kuntze), "centipedegrass" (Eremochloa ophiuroides Munro Hack.), "Carpetgrass" (Axonopus afflnis Chase), "Bahia grass" (Paspalum notatum flügge), "Kikuyugrass" (Pennisetum clandestinum Höchst, ex Chiov.), "Buffalo grass" (Buchloe daetyloids (Nutt.) Engelm.) , "Blue gramma" (Bouteloua gracilis (HBK) lag. Ex Griffiths), "seashore paspalum" (Paspalum vaginatum Swartz) and "sideoats grama" (Bouteloua curtipendula (Michx. Torr.). "Cool season turfgrasses" are for the present invention Use is generally preferred Bleach grass, ostrich grass and "redtop", fescue and lolly are particularly preferred. Ostrich grass is particularly preferred.
Die Wirkstoffe der Formel (I) und ihre Zusammensetzungen eignen sich zur Bekämpfung von tierischen Schädlingen auf dem Hygienesektor. Insbesondere kann die Erfindung im Haushalts-, Hygiene- und Vorratsschutz verwendet werden, vor allem zur Bekämpfung von Insekten, Spinnentieren und Milben, die in geschlossenen Räumen, wie beispielsweise Wohnungen, Fabrikhallen, Büros, Fahrzeugkabinen vorkommen. Zur Bekämpfung der tierischen Schädlinge werden die Wirkstoffe oder Zusammensetzungen allein oder in Kombination mit anderen Wirk- und/oder Hilfsstoffen verwendet. Bevorzugt werden sie in Haushaltsinsektizid-Produkten verwendet. Die erfindungsgemäßen Wirkstoffe sind gegen sensible und resistente Arten sowie gegen alle Entwicklungsstadien wirksam. The active compounds of the formula (I) and their compositions are suitable for controlling animal pests in the hygiene sector. In particular, the invention can be used in household, hygiene and storage protection, especially for controlling insects, arachnids and mites, which occur in enclosed spaces, such as apartments, factories, offices, vehicle cabins. To combat animal pests, the active compounds or compositions are used alone or in combination with other active ingredients and / or adjuvants. Preferably, they are used in household insecticide products. The active compounds according to the invention are active against sensitive and resistant species as well as against all stages of development.
Zu diesen Schädlingen gehören beispielsweise Schädlinge aus der Klasse Arachnida, aus den Ordnungen Scorpiones, Araneae und Opiliones, aus den Klassen Chilopoda und Diplopoda, aus der Klasse Insecta die Ordnung Blattodea, aus den Ordnungen Coleoptera, Dermaptera, Diptera, Heteroptera, Hymenoptera, Isoptera, Lepidoptera, Phthiraptera, Psocoptera, Saltatoria oder Orthoptera, Siphonaptera und Zygentoma und aus der Klasse Malacostraca die Ordnung Isopoda. These pests include, for example, pests of the class Arachnida, from the orders Scorpiones, Araneae and Opiliones, from the classes Chilopoda and Diplopoda, from the class Insecta the order Blattodea, from the orders Coleoptera, Dermaptera, Diptera, Heteroptera, Hymenoptera, Isoptera, Lepidoptera, Phthiraptera, Psocoptera, Saltatoria or Orthoptera, Siphonaptera and Zygentoma and from the class Malacostraca the order Isopoda.
Die Anwendung erfolgt beispielsweise in Aerosolen, drucklosen Sprühmitteln, z.B. Pump- und Zerstäubersprays, Nebelautomaten, Foggern, Schäumen, Gelen, Verdampferprodukten mit Verdampferplättchen aus Cellulose oder Kunststoff, Flüssigverdampfern, Gel- und Membranverdampfern, propellergetriebenen Verdampfern, energielosen bzw. passiven Verdampfungssystemen, Mottenpapieren, Mottensäckchen und Mottengelen, als Granulate oder Stäube, in Streuködern oder Köderstationen. Application is for example in aerosols, non-pressurized sprays, e.g. Pump and atomizer sprays, fog machines, foggers, foams, gels, evaporator products with cellulose or plastic evaporator plates, liquid evaporators, gel and membrane evaporators, propeller-driven evaporators, energy-less or passive evaporation systems, moth papers, moth cushions and moth gels, as granules or dusts, in litter or bait stations.
Darüber hinaus können die Wirkstoffe der Formel (I) zur Bekämpfung einer Vielzahl verschiedener Schädlinge einschließlich beispielsweise schädlicher saugender Insekten, beißender Insekten und anderen an Pflanzen parasitierenden Schädlingen, Vorratsschädlingen, Schädlingen, die industrielle Materialien zerstören und Hygieneschädlingen einschließlich Parasiten im Bereich Tiergesundheit verwendet und zu ihrer Bekämpfung wie zum Beispiel ihrer Auslöschung und Ausmerzung eingesetzt werden. Die vorliegende Erfindung schließt somit auch ein Verfahren zur Bekämpfung von Schädlingen ein. In addition, the active ingredients of formula (I) may be used to combat a variety of pests including, for example, noxious sucking insects, biting insects and other plant parasitic pests, storage pests, pests that destroy industrial materials, and use and include sanitary pests including animal health parasites Combat such as their extinction and eradication. The present invention thus also includes a method of controlling pests.
Auf dem Gebiet der Tiergesundheit, d.h. dem Gebiet der Tiermedizin, sind die erfindungsgemäßen Wirkstoffe gegen Tierparasiten, insbesondere Ektoparasiten oder Endoparasiten, wirksam. Der Begriff Endoparasiten umfasst insbesondere Helminthen und Protozoa wie Kokzidien. Ektoparasiten sind typischerweise und bevorzugt Arthropoden, insbesondere Insekten und Akariden. Auf dem Gebiet der Tiermedizin eignen sich die erfindungsgemäßen Verbindungen, die eine günstige Toxizität gegenüber Warmblütern aufweisen, für die Bekämpfung von Parasiten, die in der Tierzucht und Tierhaltung bei Nutztieren, Zuchttieren, Zootieren, Laboratoriumstieren, Versuchstieren und Haustieren auftreten. Sie sind gegen alle oder einzelne Entwicklungsstadien der Parasiten wirksam. In the field of animal health, i. In the field of veterinary medicine, the active compounds according to the invention are active against animal parasites, in particular ectoparasites or endoparasites. The term endoparasite includes in particular helminths and protozoa such as coccidia. Ectoparasites are typically and preferably arthropods, especially insects and acarids. In the field of veterinary medicine, the compounds of the present invention having favorable toxicity to warm-blooded animals are useful in the control of parasites found in livestock and livestock in livestock, breeding animals, zoo animals, laboratory animals, experimental animals and domestic animals. They are effective against all or individual stages of parasite development.
Zu den landwirtschaftlichen Nutztieren zählen zum Beispiel Säugetiere wie Schafe, Ziegen, Pferde, Esel, Kamele, Büffel, Kaninchen, Rentiere, Damhirsche und insbesondere Rinder und Schweine; oder Geflügel wie Truthähne, Enten, Gänse und insbesondere Hühner; oder Fische oder Krustentiere, z.B. in der Aquakultur; oder gegebenenfalls auch Insekten wie Bienen. Farm animals include, for example, mammals such as sheep, goats, horses, donkeys, camels, buffaloes, rabbits, reindeer, fallow deer, and especially cattle and pigs; or poultry such as turkeys, ducks, geese and, in particular, chickens; or fish or crustaceans, e.g. in aquaculture; or possibly insects such as bees.
Zu den Haustieren zählen zum Beispiel Säugetiere wie Hamster, Meerschweinchen, Ratten, Mäuse, Chinchillas, Frettchen oder insbesondere Hunde, Katzen; Stubenvögel; Reptilien; Amphibien oder Aquariumfische. The domestic animals include, for example, mammals such as hamsters, guinea pigs, rats, mice, chinchillas, ferrets or, in particular, dogs, cats; Caged birds; reptiles; Amphibians or aquarium fish.
Gemäß einer bevorzugten Ausführungsform werden die erfindungsgemäßen Verbindungen an Säugetiere verabreicht. Gemäß einer weiteren bevorzugten Ausführungsform werden die erfindungsgemäßen Verbindungen an Vögel, nämlich Stubenvögel oder insbesondere Geflügel, verabreicht. In a preferred embodiment, the compounds of the invention are administered to mammals. According to a further preferred embodiment, the compounds according to the invention are administered to birds, namely caged birds or, in particular, poultry.
Durch Verwendung der erfindungsgemäßen Wirkstoffe für die Bekämpfung von Tierparasiten sollen Krankheit, Todesfälle und Leistungsminderungen (bei Fleisch, Milch, Wolle, Häuten, Eiern, Honig und dergleichen) verringert bzw. vorgebeugt werden, so dass eine wirtschaftlichere und einfachere Tierhaltung ermöglicht wird und ein besseres Wohlbefinden der Tiere erzielbar ist. By using the active substances for combating animal parasites according to the invention, disease, deaths and reductions in performance (in the case of meat, milk, wool, hides, eggs, honey and the like) should be reduced or prevented so that a more economical and simpler animal husbandry is possible and a better Well-being of the animals is achievable.
In Bezug auf das Gebiet der Tiergesundheit bedeutet der Begriff "Bekämpfung" oder "bekämpfen", dass durch die Wirkstoffe wirksam das Auftreten des jeweiligen Parasiten in einem Tier, das mit solchen Parasiten in einem harmlosen Ausmaß infiziert ist, reduziert werden kann. Genauer gesagt bedeutet "bekämpfen" im vorliegenden Zusammenhang, dass der Wirkstoff den jeweiligen Parasiten abtöten, sein Wachstum verhindern oder seine Vermehrung verhindern kann. With regard to the field of animal health, the term "control" or "combat" means that the agents can effectively reduce the incidence of the particular parasite in an animal infected with such parasites to a harmless extent. More specifically, "combat" in the present context means that the active ingredient can kill the respective parasite, prevent its growth or prevent its replication.
Zu Beispielen für Arthropoden zählen, jedoch ohne Einschränkung: aus der Ordnung Anoplurida, zum Beispiel Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.; aus der Ordnung Mallophagida und den Unterordnungen Amblycerina and Ischnocerina, zum Beispiel Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.; aus der Ordnung Diptera und den Unterordnungen Nematocerina und Brachycerina, zum Beispiel Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Odagmia spp., Wilhelmia spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilla spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp., Rhinoestrus spp., Tipula spp.; aus der Ordnung Siphonapterida, zum Beispiel Pulex spp., Ctenocephalides spp., Tunga spp., Xenopsylla spp., Ceratophyllus spp.; aus der Ordnung Heteropterida, zum Beispiel Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.; sowie Lästlinge und Hygieneschädlinge aus der Ordnung Blattarida. Examples of arthropods include, but are not limited to, the order Anoplurida, for example Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp .; from the order Mallophagida and the suborders Amblycerina and Ischnocerina, for example Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp .; from the order Diptera and the suborders Nematocerina and Brachycerina, for example Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Odagmia Spp., Wilhelmia spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp. , Fannia spp., Glossina spp., Calliphora spp., Lucilla spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp., Rhinoestrus spp., Tipula spp .; from the order Siphonapterida, for example Pulex spp., Ctenocephalides spp., Tunga spp., Xenopsylla spp., Ceratophyllus spp .; from the order Heteropterida, for example Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp .; as well as pests and hygiene pests from the order Blattarida.
Weiterhin sind unter den Arthropoden die folgenden Akari beispielhaft, jedoch ohne Einschränkung, zu nennen: aus der Unterklasse Akari (Acarina) und der Ordnung Metastigmata, zum Beispiel aus der Familie Argasidae, wie Argas spp., Ornithodorus spp., Otobius spp., aus der Familie Ixodidae, wie Ixodes spp., Amblyomma spp., Rhipicephalus (Boophilus) spp. Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp. (die ursprüngliche Gattung der mehrwirtigen Zecken); aus der Ordnung Mesostigmata, wie Dermanyssus spp., Ornithonyssus spp., Pneumonyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp., Acarapis spp.; aus der Ordnung Actinedida (Prostigmata), zum Beispiel Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Neotrombiculla spp., Listrophorus spp.; und aus der Ordnung Acaridida (Astigmata), zum Beispiel Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp. Furthermore, among the arthropods, the following Akari are exemplary, but without limitation, from the subclass Akari (Acarina) and the order Metastigmata, for example, from the family Argasidae, such as Argas spp., Ornithodorus spp., Otobius spp., From the family Ixodidae, such as Ixodes spp., Amblyomma spp., Rhipicephalus (Boophilus) spp. Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp. (the original genus of multi-pronged ticks); from the order Mesostigmata, such as Dermanyssus spp., Ornithonyssus spp., Pneumonyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp., Acarapis spp .; from the order Actinedida (Prostigmata), for example, Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Neotrombiculla spp., Listrophorus spp .; and from the order Acaridida (Astigmata), for example Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp. , Knemidocoptes spp., Cytodites spp., Laminosioptes spp.
Zu Beispielen für parasitäre Protozoen zählen, jedoch ohne Einschränkung: Examples of parasitic protozoa include, but are not limited to:
Mastigophora (Flagellata), wie zum Beispiel Trypanosomatidae, zum Beispiel Trypanosoma b. brucei, T.b. gambiense, T.b. rhodesiense, T. congolense, T. cruzi, T. evansi, T. equinum, T. lewisi, T. percae, T. simiae, T. vivax, Leishmania brasiliensis, L. donovani, L. tropica, wie zum Beispiel Trichomonadidae, zum Beispiel Giardia lamblia, G. canis. Mastigophora (Flagellata), such as Trypanosomatidae, for example Trypanosoma b. brucei, T.b. gambiense, T.b. rhodesiense, T. congolense, T. cruzi, T. evansi, T. equinum, T. lewisi, T. percae, T. simiae, T. vivax, Leishmania brasiliensis, L. donovani, L. tropica, such as Trichomonadidae, for example Giardia lamblia, G. canis.
Sarcomastigophora (Rhizopoda), wie Entamoebidae, zum Beispiel Entamoeba histolytica, Hartmanellidae, zum Beispiel Acanthamoeba sp., Harmanella sp. Sarcomastigophora (Rhizopoda), such as Entamoebidae, for example Entamoeba histolytica, Hartmanellidae, for example Acanthamoeba sp., Harmanella sp.
Apicomplexa (Sporozoa), wie Eimeridae, zum Beispiel Eimeria acervulina, E. adenoides, E. alabamensis, E. anatis, E. anserina, E. arloingi, E. ashata, E. auburnensis, E. bovis, E. brunetti, E. canis, E. chinchillae, E. clupearum, E. columbae, E. contorta, E. crandalis, E. debliecki, E. dispersa, E. ellipsoidales, E. falciformis, E. faurei, E. flavescens, E. gallopavonis, E. hagani, E. intestinalis, E. iroquoina, E. irresidua, E. labbeana, E. leucarti, E. magna, E. maxima, E. media, E. meleagridis, E. meleagrimitis, E. mitis, E. necatrix, E. ninakohlyakimovae, E. ovis, E. parva, E. pavonis, E. perforans, E. phasani, E. piriformis, E. praecox, E. residua, E. scabra, E. spec, E. stiedai, E. suis, E. tenella, E. truncata, E. truttae, E. zuernii, Globidium spec, Isospora belli, I. canis, I. felis, I. ohioensis, I. rivolta, I. spec, I. suis, Cystisospora spec, Cryptosporidium spec, insbesondere C. parvum; wie Toxoplasmadidae, zum Beispiel Toxoplasma gondii, Hammondia heydornii, Neospora caninum, Besnoitia besnoitii; wie Sarcocystidae, zum Beispiel Sarcocystis bovicanis, S. bovihominis, S. ovicanis, S. ovifelis, S. neurona, S. spec, S. suihominis, wie Leucozoidae, zum Beispiel Leucozytozoon simondi, wie Plasmodiidae, zum Beispiel Plasmodium berghei, P. falciparum, P. malariae, P. ovale, P. vivax, P. spec, wie Piroplasmea, zum Beispiel Babesia argentina, B. bovis, B. canis, B. spec, Theileria parva, Theileria spec, wie Adeleina, zum Beispiel Hepatozoon canis, H. spec. Apicomplexa (Sporozoa), such as Eimeridae, for example Eimeria acervulina, E. adenoides, E. alabamensis, E. anatis, E. anserina, E. arloingi, E. ashata, E. auburnensis, E. bovis, E. brunetti, E canis, E. chinchillae, E. clupearum, E. columbae, E. contorta, E. crandalis, E. debliecki, E. dispersa, E. ellipsoidales, E. falciformis, E. faurei, E. flavescens, E. gallopavonis , E. hagani, E. intestinalis, E. iroquoina, E. irresidua, E. labbeana, E. leucarti, E. magna, E. maxima, E.media, E. meleagridis, E. meleagrimitis, E. mitis, E necatrix, E. ninakohlyakimovae, E.ovis, E.parva, E.pavonis, E. perforans, E. phasani, E. piriformis, E. praecox, E. residua, E. scabra, E.spec, E. stiedai E. suis, E. tenella, E. truncata, E. truttae, E. zuernii, Globidium spec., Isospora belli, I. canis, I. felis, I. ohioensis, I. rivolta, I. spec., I. suis , Cystisospora spec., Cryptosporidium spec., Especially C. parvum; such as Toxoplasmadidae, for example Toxoplasma gondii, Hammondia heydornii, Neospora caninum, Besnoitia besnoitii; such as Sarcocystidae, for example Sarcocystis bovicanis, S. bovihominis, S. ovicanis, S. ovifelis, S. neurona, S. spec., S. suihominis, such as Leucozoidae, for example Leucocytozoon simondi, such as Plasmodiidae, for example Plasmodium berghei, P. falciparum, P. malariae, P. ovale, P.vivax, P.spec, such as piroplasmea, for example Babesia argentina, B.bovis, B.canis, B.spec, Theileriaparva, Theileria spec, such as Adeleina, for example Hepatozoon canis, H. spec.
Zu Beispielen für pathogene Endoparasiten, bei denen es sich um Helminthen handelt, zählen Plattwürmer (z.B. Monogenea, Cestodes und Trematodes), Rundwürmer, Acanthocephala und Pentastoma. Zu weiteren Helminthen zählen, jedoch ohne Einschränkung: Examples of pathogenic endoparasites that are helminths include flatworms (e.g., Monogenea, Cestodes, and Trematodes), roundworms, Acanthocephala, and Pentastoma. Other helminths include, but are not limited to:
Monogenea: z.B.: Gyrodactylus spp., Dactylogyrus spp., Polystoma spp. Monogenea: e.g., Gyrodactylus spp., Dactylogyrus spp., Polystoma spp.
Cestodes: aus der Ordnung Pseudophyllidea zum Beispiel: Diphyllobothrium spp., Spirometra spp., Schistocephalus spp., Ligula spp., Bothridium spp., Diplogonoporus spp. Aus der Ordnung Cyclophyllida zum Beispiel: Mesocestoides spp., Anoplocephala spp., Paranoplocephala spp., Moniezia spp., Thysanosoma spp., Thysaniezia spp., Avitellina spp., Stilesia spp., Cittotaenia spp., Andyra spp., Bertiella spp., Taenia spp., Echinococcus spp., Hydatigera spp., Davainea spp., Raillietina spp., Hymenolepis spp., Echinolepis spp., Echinocotyle spp., Diorchis spp., Dipylidium spp., Joyeuxiella spp., Diplopylidium spp. Cestodes: from the order Pseudophyllidea for example: Diphyllobothrium spp., Spirometra spp., Schistocephalus spp., Ligula spp., Bothridium spp., Diplogonoporus spp. For example, from the order Cyclophyllida: Mesocestoides spp., Anoplocephala spp., Paranoplocephala spp., Moniezia spp., Thysanosoma spp., Thysaniezia spp., Avitellina spp., Stilesia spp., Cittotaenia spp., Andyra spp., Bertiella spp. , Taenia spp., Echinococcus spp., Hydatigera spp., Davainea spp., Raillietina spp., Hymenolepis spp., Echinolepis spp., Echinocotyle spp., Diorchis spp., Dipylidium spp., Joyeuxiella spp., Diplopylidium spp.
Trematodes: aus der Klasse Digenea zum Beispiel: Diplostomum spp., Posthodiplostomum spp., Schistosoma spp., Trichobilharzia spp., Ornithobilharzia spp., Austrobilharzia spp., Gigantobilharzia spp., Leucochloridium spp., Brachylaima spp., Echinostoma spp., Echinoparyphium spp., Echinochasmus spp., Hypoderaeum spp., Fasciola spp., Fasciolides spp., Fasciolopsis spp., Cyclocoelum spp., Typhlocoelum spp., Paramphistomum spp., Calicophoron spp., Cotylophoron spp., Gigantocotyle spp., Fischoederius spp., Gastrothylacus spp., Notocotylus spp., Catatropis spp., Plagiorchis spp., Prosthogonimus spp., Dicrocoelium spp., Eurytrema spp., Troglotrema spp., Paragonimus spp., Collyriclum spp., Nanophyetus spp., Opisthorchis spp., Clonorchis spp. Metorchis spp., Heterophyes spp., Metagonimus spp. Ründwürmer: Trichinellida zum Beispiel: Trichuris spp., Capillaria spp., Trichomosoides spp., Trichinella spp. Trematodes: from the genus Digenea, for example: Diplostomum spp., Posthodiplostomum spp., Schistosoma spp., Trichobilharzia spp., Ornithobilharzia spp., Austrobilharzia spp., Gigantobilharzia spp., Leucochloridium spp., Brachylaima spp., Echinostoma spp., Echinoparyphium spp., Echinochasmus spp., Hypoderaeum spp., Fasciola spp., Fasciolides spp., Fasciolopsis spp., Cyclocoelum spp., Typhlocoelum spp., Paramphistomum spp., Calicophoron spp., Cotylophoron spp., Gigantocotyle spp., Fischoederius spp. , Gastrothylacus spp., Notocotylus spp., Catatropis spp., Plagiorchis spp., Prosthogonimus spp., Dicrocoelium spp., Eurytrema spp., Troglotrema spp., Paragonimus spp., Collyriclum spp., Nanophyetus spp., Opisthorchis spp., Clonorchis spp. Metorchis spp., Heterophyes spp., Metagonimus spp. Roundworms: Trichinellida for example: Trichuris spp., Capillaria spp., Trichomosoides spp., Trichinella spp.
Aus der Ordnung Tylenchida zum Beispiel: Micronema spp., Strongyloides spp. For example, from the order Tylenchida: Micronema spp., Strongyloides spp.
Aus der Ordnung Rhabditina zum Beispiel: Strongylus spp., Triodontophorus spp., Oesophagodontus spp., Trichonema spp., Gyalocephalus spp., Cylindropharynx spp., Poteriostomum spp., Cyclococercus spp., Cylicostephanus spp., Oesophagostomum spp., Chabertia spp., Stephanurus spp., Ancylostoma spp., Uncinaria spp., Bunostomum spp., Globocephalus spp., Syngamus spp., Cyathostoma spp., Metastrongylus spp., Dictyocaulus spp., Muellerius spp., Protostrongylus spp., Neostrongylus spp., Cystocaulus spp., Pneumostrongylus spp., Spicocaulus spp., Elaphostrongylus spp. Parelaphostrongylus spp., Crenosoma spp., Paracrenosoma spp., Angiostrongylus spp., Aelurostrongylus spp., Filaroides spp., Parafilaroides spp., Trichostrongylus spp., Haemonchus spp., Ostertagia spp., Marshallagia spp., Cooperia spp., Nematodirus spp., Hyostrongylus spp., Obeliscoides spp., Amidostomum spp., Ollulanus spp. For example, from the order Rhabditina: Strongylus spp., Triodontophorus spp., Oesophagodontus spp., Trichonema spp., Gyalocephalus spp., Cylindropharynx spp., Poteriostomum spp., Cyclococercus spp., Cylicostephanus spp., Oesophagostomum spp., Chabertia spp. , Stephanurus spp., Ancylostoma spp., Uncinaria spp., Bunostomum spp., Globocephalus spp., Syngamus spp., Cyathostoma spp., Metastrongylus spp., Dictyocaulus spp., Muellerius spp., Protostrongylus spp., Neostrongylus spp., Cystocaulus spp., Pneumostrongylus spp., Spicocaulus spp., Elaphostrongylus spp. Parelaphostrongylus spp., Crenosoma spp., Paracrenosoma spp., Angiostrongylus spp., Aelurostrongylus spp., Filaroides spp., Parafilaroides spp., Trichostrongylus spp., Haemonchus spp., Ostertagia spp., Marshallagia spp., Cooperia spp., Nematodirus spp , Hyostrongylus spp., Obeliscoides spp., Amidostomum spp., Ollulanus spp.
Aus der Ordnung Spirurida zum Beispiel: Oxyuris spp., Enterobius spp., Passalurus spp., Syphacia spp., Aspiculuris spp., Heterakis spp.; Ascaris spp., Toxascaris spp., Toxocara spp., Baylisascaris spp., Parascaris spp., Anisakis spp., Ascaridia spp.; Gnathostoma spp., Physaloptera spp., Thelazia spp., Gongylonema spp., Habronema spp., Parabronema spp., Draschia spp., Dracunculus spp.; Stephanofilaria spp., Parafilaria spp., Setaria spp., Loa spp., Dirofilaria spp., Litomosoides spp., Brugia spp., Wuchereria spp., Onchocerca spp. For example, from the order Spirurida: Oxyuris spp., Enterobius spp., Passalurus spp., Syphacia spp., Aspiculuris spp., Heterakis spp .; Ascaris spp., Toxascaris spp., Toxocara spp., Baylisascaris spp., Parascaris spp., Anisakis spp., Ascaridia spp .; Gnathostoma spp., Physaloptera spp., Thelazia spp., Gongylonema spp., Habronema spp., Parabronema spp., Draschia spp., Dracunculus spp .; Stephanofilaria spp., Parafilaria spp., Setaria spp., Loa spp., Dirofilaria spp., Litomosoides spp., Brugia spp., Wuchereria spp., Onchocerca spp.
Acanthocephala: aus der Ordnung Oligacanthorhynchida z.B: Macracanthorhynchus spp., Prosthenorchis spp.; aus der Ordnung Polymorphida zum Beispiel: Filicollis spp.; aus der Ordnung Moniliformida zum Beispiel: Moniliformis spp., Acanthocephala: from the order Oligacanthorhynchida eg: Macracanthorhynchus spp., Prosthenorchis spp .; from the order Polymorphida for example: Filicollis spp .; from the order Moniliformida for example: Moniliformis spp.,
Aus der Ordnung Echinorhynchida zum Beispiel Acanthocephalus spp., Echinorhynchus spp., Leptorhynchoides spp. Pentastoma: aus der Ordnung Porocephalida zum Beispiel Linguatula spp. From the order Echinorhynchida for example Acanthocephalus spp., Echinorhynchus spp., Leptorhynchoides spp. Pentastoma: from the order Porocephalida for example Linguatula spp.
Auf dem Gebiet der Tiermedizin und der Tierhaltung erfolgt die Verabreichung der erfindungsgemäßen Wirkstoffe nach allgemein fachbekannten Verfahren, wie enteral, parenteral, dermal oder nasal in Form von geeigneten Präparaten. Die Verabreichung kann prophylaktisch oder therapeutisch erfolgen. In the field of veterinary medicine and animal husbandry, the administration of the active compounds according to the invention is carried out by methods well known in the art, such as enteral, parenteral, dermal or nasal in the form of suitable preparations. The administration can be prophylactic or therapeutic.
So bezieht sich eine Ausführungsform der vorliegenden Erfindung auf erfindungsgemäße Verbindungen für die Verwendung als Arzneimittel. Thus, one embodiment of the present invention relates to compounds of the invention for use as a medicament.
Ein weiterer Aspekt bezieht sich auf erfindungsgemäße Verbindungen für die Verwendung als Antiendoparasitikum, insbesondere ein Helminthizid oder ein Mittel gegen Protozoen. Zum Beispiel erfindungsgemäße Verbindungen für die Verwendung als Antiendoparasitikum, insbesondere ein Helminthizid oder Mittel gegen Protozoen, z.B. in der Tierzucht, in der Tierhaltung, in Ställen und auf dem Hygienesektor. Another aspect relates to compounds of the invention for use as antiendoparasitic agents, in particular a helminthicide or antiprotozoal agent. For example, compounds of the invention for use as antiendoparasitic agents, in particular a helminthicide or antiprotozoal agents, e.g. in animal husbandry, animal husbandry, stables and in the hygiene sector.
Ein weiterer Aspekt wiederum betrifft erfindungsgemäße Verbindungen für die Verwendung als Antiektoparasitikum, insbesondere ein Arthropodizid wie ein Insektizid oder ein Akarizid. Zum Beispiel erfindungsgemäße Verbindungen für die Verwendung als Antiektoparasitikum, insbesondere ein Arthropodizid wie ein Insektizid oder Akarizid, zum Beispiel in der Tierhaltung, in der Tierzucht, in Ställen, auf dem Hygienesektor. Another aspect, in turn, relates to compounds of the invention for use as an antiectica, in particular an arthropodicide such as an insecticide or an acaricide. For example, compounds according to the invention for use as anti-topazarasitic, in particular an arthropodicide such as an insecticide or acaricide, for example in animal husbandry, in animal husbandry, in stables, in the hygiene sector.
Die Wirkstoffe der Formel (I) und sie enthaltende Zusammensetzungen eignen sich zum Schutz von technischen Materialien gegen Befall oder Zerstörung durch Insekten, z.B. aus der Ordnung Coleoptera, Hymenoptera, Isoptera, Lepidoptera, Psocoptera und Zygentoma. The active compounds of the formula (I) and compositions containing them are suitable for the protection of industrial materials against attack or destruction by insects, e.g. from the order Coleoptera, Hymenoptera, Isoptera, Lepidoptera, Psocoptera and Zygentoma.
Unter technischen Materialien sind im vorliegenden Zusammenhang nicht lebende Materialien zu verstehen, wie vorzugsweise Kunststoffe, Klebstoffe, Leime, Papiere und Kartone, Leder, Holz, Holzverarbeitungsprodukte und Anstrichmittel. Die Anwendung der Erfindung zum Schutz von Holz ist besonders bevorzugt. Technical materials in the present context are non-living materials, such as preferably plastics, adhesives, glues, papers and cardboard, leather, wood, wood processing products and paints. The application of the invention for the protection of wood is particularly preferred.
In einer erfindungsgemäßen Ausführungsform enthalten die erfindungsgemäßen Zusammensetzungen oder Mittel noch mindestens ein weiteres Insektizid und/oder mindestens ein Fungizid. In einer weiteren Ausführungsform ist diese erfindungsgemäße Zusammensetzung eine anwendungsfertige (ready-to-use) Zusammensetzung, d.h., sie kann ohne weitere Änderungen auf das _ In one embodiment of the invention, the compositions or compositions according to the invention contain at least one further insecticide and / or at least one fungicide. In a further embodiment, this composition according to the invention is a ready-to-use composition, that is, it can be applied without further changes to the _
- 77 - entsprechende Material aufgebracht werden. Als weitere Insektizide oder als Fungizide kommen die oben genannten in Frage.  - 77 - appropriate material can be applied. As further insecticides or as fungicides, the above-mentioned in question.
Überraschenderweise wurde auch gefunden, dass die erfindungsgemäßen Wirkstoffe und Zusammensetzungen zum Schutz vor Bewuchs von Gegenständen, insbesondere von Schiffskörpern, Sieben, Netzen, Bauwerken, Kaianlagen und Signalanlagen, welche mit See- oder Brackwasser in Verbindung kommen, verwendet werden können. Gleichfalls können die erfindungsgemäßen Wirkstoffe und Zusammensetzungen allein oder in Kombinationen mit anderen Wirkstoffen als Antifouling-Mittel eingesetzt werden. Surprisingly, it has also been found that the active compounds and compositions according to the invention can be used to protect against fouling of objects, in particular hulls, sieves, nets, structures, quays and signal systems, which come into contact with seawater or brackish water. Likewise, the active compounds and compositions according to the invention can be used alone or in combinations with other active substances as antifouling agents.
Herstellungsbeispiele Preparation Examples
Beispiel 1: (/?,S -N-[3-Chlor-l-(2-pyrazinyl)-lH-pyrazol-l-yl]-2-methyl-3-(methylthio)- propanamid Example 1: (/?, S -N- [3-Chloro-1- (2-pyrazinyl) -1H-pyrazol-1-yl] -2-methyl-3- (methylthio) propanamide
Stufe 1: 2-(3-Chlor-lH-pyrazol-l-yl)-pyrazin Step 1: 2- (3-chloro-1H-pyrazol-1-yl) -pyrazine
Figure imgf000079_0001
Figure imgf000079_0001
1,54 g (7,48 mmol) 2-Iodpyrazin (bekannt aus WO 2009/114313 A2) und 0,51 g (4,98 mmol) 3-Chlor- lH-pyrazol (bekannt aus WO 2002/070483 AI) wurden in 10 ml Acetonitril verrührt und mit 35,68 mg (0,24 mmol) Kupfer(I)-oxid, 3,24 g (9,97 mmol) Cäsiumcarbonat und 0,13 g (0,99 mmol) Salicylaldoxim versetzt. Danach wurde der Reaktionsansatz ca. 18 Stunden bei Raumtemperatur gerührt. Zur Aufarbeitung wurde der gesamte Reaktionsansatz filtriert und die Lösung im Vakuum eingeengt. Der verbleibende Rückstand wurde mittels Reverse-Phase Chromatographie (Wasser-Acetonitril Gradient) gereinigt. 1.54 g (7.48 mmol) of 2-iodopyrazine (known from WO 2009/114313 A2) and 0.51 g (4.98 mmol) of 3-chloro-1H-pyrazole (known from WO 2002/070483 A1) in 10 ml of acetonitrile and with 35.68 mg (0.24 mmol) of copper (I) oxide, 3.24 g (9.97 mmol) of cesium carbonate and 0.13 g (0.99 mmol) of salicylaldoxime. Thereafter, the reaction mixture was stirred for about 18 hours at room temperature. For workup, the entire reaction mixture was filtered and the solution was concentrated in vacuo. The remaining residue was purified by reverse-phase chromatography (water-acetonitrile gradient).
Ausbeute: 251 mg (27 % d. Th.); HPLC-MS: logP (HCOOH) = 1,84 Stufe 2: 2-(3-Chlor-4-nitro-lH-pyrazol-l-yl)-pyrazin Yield: 251 mg (27% of theory); HPLC-MS: logP (HCOOH) = 1.84 Step 2: 2- (3-chloro-4-nitro-1H-pyrazol-1-yl) -pyrazine
Figure imgf000079_0002
Figure imgf000079_0002
Zur Nitrierung wurden 592 mg (3,27 mmol) 2-(3-Chlor-4-nitro-lH-pyrazol-l-yl)-pyrazin bei 0° C in 1,72 mL konz. Schwefelsäure verrührt und tropfenweise mit 1,48 mL konz. Salpetersäure versetzt. Danach wurde der Reaktionsansatz ca. 2 Stunden bei Raumtemperatur gerührt. Zur Aufarbeitung wurde der Reaktionsansatz vorsichtig auf Eis / Wasser gegeben und ca. 20 Minuten gerührt. Die ausgefallenen Kristalle wurden abgetrennt, auf Ton getrocknet und in dieser Form für die Folgereaktion verwendet. For nitration, 592 mg (3.27 mmol) of 2- (3-chloro-4-nitro-1H-pyrazol-1-yl) -pyrazine at 0 ° C in 1.72 mL conc. Stirred sulfuric acid and dropwise with 1.48 mL of conc. Nitric acid added. Thereafter, the reaction mixture was stirred for about 2 hours at room temperature. For workup, the reaction mixture was carefully added to ice / water and stirred for about 20 minutes. The precipitated crystals were separated, dried on clay and used in this form for the subsequent reaction.
Ausbeute: 654,3 mg (88 % d. Th.); HPLC-MS: logP (HCOOH) = 1,97 Masse (m z): 225,9 (M+H)+ Yield: 654.3 mg (88% of theory); HPLC-MS: logP (HCOOH) = 1.97 mass (mz): 225.9 (M + H) +
Ή-NMR (de-DMSO): 8,69, 8,83, 9,26, 9,66 (4H, hetaryl-H) ppm. W^-Korrelation (HSQC, CD3CN): 130,8, 132,9, 137,0 (pyrazol-Q, 136,6, 143,1, 145,4, 146,2 (pyrazin-C) ppm. Ή-NMR (de-DMSO): 8.69, 8.83, 9.26, 9.66 (4H, hetaryl-H) ppm. W ^ correlation (HSQC, CD 3 CN): 130.8, 132.9, 137.0 (pyrazole-Q, 136.6, 143.1, 145.4, 146.2 (pyrazine-C) ppm.
Stufe 3: 2-(3-Chlor-4-amino-lH-pyrazol-l-yl)-pyrazin Step 3: 2- (3-Chloro-4-amino-1H-pyrazol-1-yl) -pyrazine
Figure imgf000080_0001
Zur Reduktion wurden 205 mg (0,9 mmol) 2-(3-Chlor-4-nitro-lH-pyrazol-l-yl)-pyrazin in 3,8 mL Ethanol und 1,9 mL Essigsäureethylester verrührt. Nach Zugabe von 12,55 mg (0,05 mmol) Platin(IV)- oxid wurde der Reaktionsansatz 4 Stunden unter Verwendung von Wasserstoffgas hydriert. Zur Aufarbeitung wurde der Reaktionsansatz filtriert und die Lösung im Vakuum eingeengt.
Figure imgf000080_0001
For reduction, 205 mg (0.9 mmol) of 2- (3-chloro-4-nitro-1H-pyrazol-1-yl) -pyrazine were stirred in 3.8 ml of ethanol and 1.9 ml of ethyl acetate. After adding 12.55 mg (0.05 mmol) of platinum (IV) oxide, the reaction was hydrogenated for 4 hours using hydrogen gas. For workup, the reaction mixture was filtered and the solution was concentrated in vacuo.
Ausbeute: 168,8 mg (95 % d. Th.); HPLC-MS: logP (HCOOH) = 0.91 ; Masse (m/z): 196,0 (M+H)+ Stufe 4: (R,S)-N-[3-Chlor-l-(2-pyrazinyl)-lH-pyrazol]-2-methyl-3-(methylthio)-propanamid Yield: 168.8 mg (95% of theory); HPLC-MS: logP (HCOOH) = 0.91; Mass (m / z): 196.0 (M + H) + Stage 4: (R, S) -N- [3-chloro-1- (2-pyrazinyl) -1H-pyrazole] -2-methyl-3 - (methylthio) propanamide
Figure imgf000080_0002
Figure imgf000080_0002
84 mg (0,42 mmol) 2-(3-Chlor-4-amino-lH-pyrazol-l-yl)-pyrazin und 86,4 mg (0,64 mmol) (R,S)-2- Methyl-3-methylthio-propionsäure wurden in 4,2 ml Dichlormethan bei 0 °C verrührt und nacheinander bei dieser Temperatur mit 163,9 mg (0,64 mmol) Bis-(2-oxo-3-xazolidinyl)-phosphinsäurechlorid (BOP-Cl) und 172,05 mg (1,33 mmol) N,N-Diisopropyl-ethylamin (Hünig's Base) versetzt. Anschliessend wurde der Reaktionsansatz ca. 18 Stunden bei Raumtemperatur gerührt. Zur Aufarbeitung wurde der Reaktionsansatz im Vakuum eingeengt und der verbleibende Rückstand mittels Kieselgelchromatographie (Cyclohexan-Aceton Gradient) gereinigt. 84 mg (0.42 mmol) of 2- (3-chloro-4-amino-1H-pyrazol-1-yl) -pyrazine and 86.4 mg (0.64 mmol) of (R, S) -2-methyl- 3-methylthio-propionic acid was stirred in 4.2 ml of dichloromethane at 0 ° C and successively at this temperature with 163.9 mg (0.64 mmol) of bis (2-oxo-3-xazolidinyl) -phosphinic chloride (BOP-Cl ) and 172.05 mg (1.33 mmol) of N, N-diisopropyl-ethylamine (Hünig's base). Subsequently, the reaction mixture was stirred for about 18 hours at room temperature. For workup, the reaction mixture was concentrated in vacuo and the remaining residue purified by silica gel chromatography (cyclohexane-acetone gradient).
Ausbeute: 94,2 mg (60 % d. Th.); HPLC-MS: logP (HCOOH) = 2,11 ; Masse (m/z): 312,0 (M+H)+ Yield: 94.2 mg (60% of theory); HPLC-MS: logP (HCOOH) = 2.11; Mass (m / z): 312.0 (M + H) +
'H-NMR (CD3CN): 1,93-1,95 (3H, CH3), 1,21-1,25 (3H, CH3), 2,54-2,59 (m, 1H, CH2), 2,80-2,86 (: 2H, CH), 8,27 (br. 1H, NH), 8,40, 8,50, 8,90, 9,14 (4H, hetaryl-H) ppm. 1 H NMR (CD 3 CN): 1.93-1.95 (3H, CH 3 ), 1.21-1.25 (3H, CH 3 ), 2.54-2.59 (m, 1H, CH 2 ), 2.80-2.86 (: 2H, CH), 8.27 (br. 1H, NH), 8.40, 8.50, 8.90, 9.14 (4H, hetaryl-H ) ppm.
'H/^C-Korrelation (HSQC, CD3CN): 16,0 (SCH3), 17,9 (CH3), 38,4 (CH2S), 41,4 (CH), 120,9, 121,8, 135,4 (pyrazol-C), 135,6, 143,2, 143,3, 147,8 (pyrazin-C), 174,4 (C=0) ppm. Beispiel 2: N-[3-Chlor-l-(2-pyrazinyl)-lH-pyrazol-4-yl]-3-(methylthio)-propanamid 'H / C correlation (HSQC, CD 3 CN): 16.0 (SCH 3 ), 17.9 (CH 3 ), 38.4 (CH 2 S), 41.4 (CH), 120.9 , 121.8, 135.4 (pyrazole-C), 135.6, 143.2, 143.3, 147.8 (pyrazine-C), 174.4 (C = 0) ppm. Example 2: N- [3-Chloro-1- (2-pyrazinyl) -1H-pyrazol-4-yl] -3- (methylthio) -propanamide
Figure imgf000081_0001
Figure imgf000081_0001
Die N-Acylierungsreaktion erfolgte analog der Vorschrift des Beispiels 1 unter Verwendung von: 84,0 mg (0,42 mmol) 2-(3-Chlor-4-amino-lH-pyrazol-l-yl)-pyrazin 77,4 mg (0,64 mmol) 3-methylthio-propionsäure 4,2 ml Dichlormethan The N-acylation reaction was carried out analogously to the procedure of Example 1 using: 84.0 mg (0.42 mmol) of 2- (3-chloro-4-amino-1H-pyrazol-1-yl) -pyrazine 77.4 mg (0.64 mmol) of 3-methylthio-propionic acid 4.2 ml of dichloromethane
163,9 mg (0,64 mmol) Bis-(2-oxo-3-xazolidinyl)-phosphinsäurechlorid (BOP-Cl) 172,05 mg (1 ,33 mmol) N,N-Diisopropyl-ethylamin (Hünig' s Base) 163.9 mg (0.64 mmol) of bis (2-oxo-3-xazolidinyl) -phosphinic acid chloride (BOP-Cl) 172.05 mg (1.33 mmol) of N, N-diisopropyl-ethylamine (Hünig's Base )
Anschliessend wurde der Reaktionsansatz ca. 18 Stunden bei Raumtemperatur gerührt. Zur Aufarbeitung wurde der Reaktionsansatz im Vakuum eingeengt und der verbleibende Rückstand mittels Kieselgelchromatographie (Cyclohexan-Aceton Gradient) gereinigt. Subsequently, the reaction mixture was stirred for about 18 hours at room temperature. For workup, the reaction mixture was concentrated in vacuo and the remaining residue purified by silica gel chromatography (cyclohexane-acetone gradient).
Ausbeute: 58,8 mg (38 % d. Th.); HPLC-MS: logP (HCOOH) = 1 ,83 Masse (m/z): 298,0 (M+H)+; Yield: 58.8 mg (38% of theory); HPLC-MS: logP (HCOOH) = 1.83 Mass (m / z): 298.0 (M + H) + ;
'H-NMR (CD3CN): 1 ,92-1 ,96 (3H, CH3), 2,70-2,72 (m, 2H, CH2), 2,79-2,82 (m, 2H, CH2), 8,27 (br. 1H, NH), 8,40, 8,50, 8,89, 9,13 (4H, hetaryl-H) ppm. WC-Korrelation (HSQC, CD3CN): 15,5 (SCH3), 30, 1 (CH2S), 36,6 (CH2CO), 120,7, 121 ,8, 135,2 (pyrazol-C), 135,6, 143,2, 143,3, 147,8 (pyrazin-C), 170,5 (C=0) ppm. 1 H-NMR (CD 3 CN): 1, 92-1, 96 (3H, CH 3 ), 2.70-2.72 (m, 2H, CH 2 ), 2.79-2.82 (m, 2H, CH 2 ), 8.27 (br. 1H, NH), 8.40, 8.50, 8.89, 9.13 (4H, hetaryl-H) ppm. WC correlation (HSQC, CD 3 CN): 15.5 (SCH 3 ), 30, 1 (CH 2 S), 36.6 (CH 2 CO), 120.7, 121, 8, 135.2 (pyrazole -C), 135.6, 143.2, 143.3, 147.8 (pyrazine C), 170.5 (C = 0) ppm.
Beispiel 3: N-[3-Chlor-l-(2-pyrazinyl)-lH-pyrazol-4-yl]-3-chlorbenzoesäureamid Example 3: N- [3-Chloro-1- (2-pyrazinyl) -1H-pyrazol-4-yl] -3-chlorobenzoic acid amide
Figure imgf000081_0002
Figure imgf000081_0002
40 mg (0,20 mmol) 2-(3-Chlor-4-amino-lH-pyrazol-l-yl)-pyrazin und 46,5 mg (0,26 mmol) 3- Chlorbenzoylchlorid wurden in 5,0 ml Dichlormethan bei Raumtemperatur verrührt und mit 0,053 mL 51 40 mg (0.20 mmol) of 2- (3-chloro-4-amino-1H-pyrazol-1-yl) -pyrazine and 46.5 mg (0.26 mmol) of 3-chlorobenzoyl chloride were dissolved in 5.0 ml of dichloromethane stirred at room temperature and with 0.053 mL 51
(0,30 mmol) N,N-Diisopropyl-ethylamin (Hünig' s Base) versetzt. Anschliessend wurde der Reaktionsansatz ca. 18 Stunden bei Raumtemperatur gerührt. Zur Aufarbeitung wurde der Reaktionsansatz im Vakuum eingeengt und der verbleibende Rückstand mittels Kieselgelchromatographie (Cyclohexan-Aceton Gradient) gereinigt. Ausbeute: 56,9 mg (82 % d. Th.); HPLC-MS: logP (HCOOH) = 2,86; Masse (m/z): 334,0 (M)+ (0.30 mmol) of N, N-diisopropyl-ethylamine (Hünig's base). Subsequently, the reaction mixture was stirred for about 18 hours at room temperature. For workup, the reaction mixture was concentrated in vacuo and the remaining residue purified by silica gel chromatography (cyclohexane-acetone gradient). Yield: 56.9 mg (82% of theory); HPLC-MS: logP (HCOOH) = 2.86; Mass (m / z): 334.0 (M) +
In der nachstehenden Tabelle 1 sind weitere Verbindungen der Formel (I) aufgeführt. Die gestrichelte Linie im Rest R3 markiert die Bindung zum Ν-Atom in der Formel (I). Table 1 below lists further compounds of the formula (I). The dashed line in the radical R 3 marks the bond to the Ν-atom in the formula (I).
Tabelle 1 Table 1
Verbindungen der Formel (I) Compounds of the formula (I)
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000082_0001
Figure imgf000083_0001
a: HPLC-MS (logP, HCOOH); b: Masse (m/z)  a: HPLC-MS (logP, HCOOH); b: mass (m / z)
Biologische Beispiele Biological examples
Myzus persicae - Sprühtest  Myzus persicae - spray test
Lösungsmittel: 78 Gewichtsteile Aceton Solvent: 78 parts by weight of acetone
1 ,5 Gewichtsteile Dimethylformamid  1.5 parts by weight of dimethylformamide
Emulgator: 0,5 Gewichtsteile Alkylarylpolyglykolether Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether
Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat mit emulgatorhaltigem Wasser auf die gewünschte Konzentration. To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
Chinakohlblattscheiben (Brassica pekinensis), die von allen Stadien der Grünen Pfirsichblattlaus (Myzus persicae) befallen sind, werden mit einer Wirkstoffzubereitung der gewünschten Konzentration gespritzt. Nach 6 Tagen wird die Wirkung in % bestimmt. Dabei bedeutet 100 %, dass alle Blattläuse abgetötet wurden; 0 % bedeutet, dass keine Blattläuse abgetötet wurden. Chinese cabbage leaf discs (Brassica pekinensis) infested with all stages of the green peach aphid (Myzus persicae) are sprayed with an active compound preparation of the desired concentration. After 6 days, the effect is determined in%. 100% means that all aphids have been killed; 0% means that no aphids have been killed.
Bei diesem Test zeigte z. B. die folgende Verbindung eine Wirkung von 100% bei einer Aufwandmenge von 500g/ha: 1 In this test, z. For example, the following compound has an effect of 100% at a rate of 500g / ha: 1
Tetranvchus urticae - Sprühtest, OP-resistent Tetranvchus urticae - spray test, surgical-resistant
Lösungsmittel: 78 Gewichtsteile Aceton Solvent: 78 parts by weight of acetone
1 ,5 Gewichtsteile Dimethylformamid  1.5 parts by weight of dimethylformamide
Emulgator: 0,5 Gewichtsteile Alkylarylpolyglykolether Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat mit emulgatorhaltigem Wasser auf die gewünschte Konzentration. Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the indicated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
Bohnenblattscheiben (Phaseolus vulgaris), die von allen Stadien der Gemeinen Spinnmilbe (Tetranychus urticae) befallen sind, werden mit einer Wirkstoffzubereitung der gewünschten Konzentration gespritzt. Bean leaf discs (Phaseolus vulgaris) infected by all stages of the common spider mite (Tetranychus urticae) are sprayed with an active compound preparation of the desired concentration.
Nach 6 Tagen wird die Wirkung in % bestimmt. Dabei bedeutet 100 %, dass alle Spinnmilben abgetötet wurden; 0 % bedeutet, dass keine Spinnmilben abgetötet wurden. After 6 days, the effect is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites have been killed.
Bei diesem Test zeigte z. B. die folgende Verbindung eine Wirkung von 90% bei einer Aufwandmenge von 500g/ha: 10 In this test, z. For example, the following compound has an effect of 90% at a rate of 500g / ha: 10
Phaedon cochleariae - Sprühtest Phaedon cochleariae - spray test
Lösungsmittel: 78 Gewichtsteile Aceton Solvent: 78 parts by weight of acetone
1 ,5 Gewichtsteile Dimethylformamid  1.5 parts by weight of dimethylformamide
Emulgator: 0,5 Gewichtsteile Alkylarylpolyglykolether Zur Herstellung einer zweckmäßigen Wirkstoffzubereitung vermischt man 1 Gewichtsteil Wirkstoff mit den angegebenen Mengen Lösungsmittel und Emulgator und verdünnt das Konzentrat mit emulgatorhaltigem Wasser auf die gewünschte Konzentration. 0„ Emulsifier: 0.5 part by weight of alkylaryl polyglycol ether To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration. 0 "
- 84 - - 84 -
Chinakohlblattscheiben (Brassica pekinensis) werden mit einer Wirkstoffzubereitung der gewünschten Konzentration gespritzt und nach dem Abtrocknen mit Larven des Meerrettichblattkäfers (Phaedon cochleariae ) besetzt. Chinese cabbage leaf discs (Brassica pekinensis) are sprayed with a preparation of active compound of the desired concentration and, after drying, are populated with larvae of the horseradish leaf beetle (Phaedon cochleariae).
Nach 7 Tagen wird die Wirkung in % bestimmt. Dabei bedeutet 100 , dass alle Käferlarven abgetötet wurden; 0 % bedeutet, dass keine der Käferlarven abgetötet wurde. After 7 days, the effect is determined in%. 100 means that all beetle larvae have been killed; 0% means that none of the beetle larvae was killed.
Bei diesem Test zeigte z. B. die folgende Verbindung eine Wirkung von 100% bei einer Aufwandmenge von 500g/ha: 10 In this test, z. Example, the following compound has an effect of 100% at a rate of 500g / ha: 10

Claims

Patentansprüche claims
1. Verbindungen der Formel (I) 1. Compounds of the formula (I)
U FT U FT
(i), worin  (i), in which
A für einen Rest aus der Reihe A for a rest of the series
A-a A-b A-c A-d
Figure imgf000086_0002
Aa From Ac Ad
Figure imgf000086_0002
A-e A-f A-g A-h steht, worin die gestrichelte Linie die Bindung zu B bedeutet, A-e A-f A-g A-h, wherein the dotted line denotes the bond to B,
B für einen Rest aus der Reihe B for a rest of the series
Figure imgf000086_0003
steht, worin die gestrichelte Linie die Bindung zu A bedeutet und der Pfeil die Bindung zur Gruppe NR2R3 bedeutet, mit der Maßgabe, dass die Reste A-f und A-g nicht mit dem Rest B-3 kombiniert werden,
Figure imgf000086_0003
in which the dashed line denotes the bond to A and the arrow denotes the bond to the group NR 2 R 3 , with the proviso that the radicals Af and Ag are not combined with the radical B-3,
R für einen Rest aus der Reihe Wasserstoff, Alkyl, Halogenalkyl, Alkenyl, Alkinyl, R is a radical selected from the group consisting of hydrogen, alkyl, haloalkyl, alkenyl, alkynyl,
Cycloalkyl und Halogencycloalkyl steht, für einen Rest aus der Reihe Halogen, Cyano, Nitro, Alkyl, Halogenalkyl, Alkenyl, Halogenalkenyl, Alkoxy, Halogenalkoxy, Cycloalkyl, Halogencycloalkyl, Alkylthio, Halogenalkylthio, Alkylsulfinyl, Halogenalylsulfinyl, Alkylsulfonyl,Cycloalkyl and halocycloalkyl, a radical selected from the group halo, cyano, nitro, alkyl, haloalkyl, alkenyl, haloalkenyl, alkoxy, haloalkoxy, cycloalkyl, halocycloalkyl, alkylthio, haloalkylthio, alkylsulfinyl, haloalylsulfinyl, alkylsulfonyl,
Halogenalkylsulfonyl steht, für einen Rest aus der Reihe Wasserstoff, Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkenyl, Alkoxy, Alkenyloxy, Alkinyloxy, Cycloalkyloxy, Alkylthioalkyl, Alkenylthioalkyl, Cyanoalkyl, Alkoxyalkyl steht, für einen Rest der Formel Haloalkylsulfonyl is a radical from the series consisting of hydrogen, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, alkylthioalkyl, alkenylthioalkyl, cyanoalkyl, alkoxyalkyl, a radical of the formula
steht,
Figure imgf000087_0001
stands,
Figure imgf000087_0001
R4 für einen Rest aus der Reihe Alkyl, Halogenalkyl, Alkoxy, Halogenalkoxy, R 4 is a radical from the series alkyl, haloalkyl, alkoxy, haloalkoxy,
Alkoxyalkyloxy, Alkylthio, Alkylsulfinyl, Alkylsulfonyl, Halogenalkylthio, Halogenalkylsulfinyl, Halogenalkylsulfonyl, Alkylthioalkyl, Alkylsulfinylalkyl, Alkylsulfonylalkyl, Alkylthioalkyloxy, Alkylsulfinylalkyloxy, Alkylsulfonylalkyloxy, Halogenalkylthioalkyl, Halogenalkylsulfinylalkyl, Halogenalkylsulfonylalkyl, Alkylthioalkenyl, Alkylsulfinylalkenyl, Alkylsulfonylalkenyl, Alkenylthioalkyl, Alkenylsulfinylalkyl, Alkenylsulfonylalkyl, Alkylcarbonylalkyl, Alkoxyalkyloxy, alkylthio, alkylsulfinyl, alkylsulfonyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, Alkylthioalkyloxy, Alkylsulfinylalkyloxy, Alkylsulfonylalkyloxy, haloalkylthioalkyl, Halogenalkylsulfinylalkyl, Halogenalkylsulfonylalkyl, alkylthioalkenyl, Alkylsulfinylalkenyl, alkylsulfonylalkenyl, Alkenylthioalkyl, Alkenylsulfinylalkyl, Alkenylsulfonylalkyl, alkylcarbonylalkyl,
Halogenalkylcarbonylalkyl, Alkoxyalkyl, Halogenalkoxyalkyl, Alkoxycarbonylalkyl, Halogenalkoxycarbonylalkyl steht, oder für gegebenenfalls substituiertes Aryl oder für einen Rest aus der Reihe C-l bis C-51 Haloalkylcarbonylalkyl, alkoxyalkyl, haloalkoxyalkyl, alkoxycarbonylalkyl, haloalkoxycarbonylalkyl, or represents optionally substituted aryl or a radical from the series Cl to C-51
Figure imgf000088_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000089_0001
Figure imgf000089_0002
Figure imgf000089_0002
C-35 C-36
Figure imgf000090_0001
C-35 C-36
Figure imgf000090_0001
C-37 C-38 C-39  C-37 C-38 C-39
Figure imgf000090_0002
Figure imgf000090_0002
Figure imgf000090_0003
Figure imgf000090_0003
C-44 C-45 C-46 C-47
Figure imgf000090_0004
C-44 C-45 C-46 C-47
Figure imgf000090_0004
C-48 C-49 C-50 C-51 steht, worin  C-48 C-49 C-50 C-51 wherein
R5 für einen Rest aus der Reihe Wasserstoff (nur in den Resten C-33, C-36 und C-42), R 5 is a radical from the series hydrogen (only in the radicals C-33, C-36 and C-42),
Halogen, Cyano, Nitro, Amino, Hydroxy und jeweils gegebenenfalls substituiertes Alkyl, Alkenyl, Alkinyl, Cycloalkyl, Cycloalkylalkyl, Alkoxy, Alkenyloxy, Alkinyloxy, Cycloalkyloxy, Alkylcarbonyloxy, Alkenylcarbonyloxy, Alkinylcarbonyloxy, Cycloalkylcarbonyloxy, Alkoxycarbonyloxy, Alkylsulfonyloxy, Alkylamino, Alkenylamino, Alkinylamino, Cycloalkylamino, Alkylthio, Halogenalkylthio, Alkenylthio, Alkinylthio, Cycloalkylthio, Alkylsulfinyl, Alkylsulfonyl, Alkylcarbonyl, Alkoxyiminoalkyl, Alkoxycarbonyl, Aminocarbonyl, Alkylaminocarbonyl, Dialkylaminocarbonyl, Aniinothiocarbonyl, Alkylaniinosulfonyl, Alkylsulfonylamino, Alkylcarbonylamino, Alkenylcarbonylamino, Alkinylcarbonylamino, Halogen, cyano, nitro, amino, hydroxy and in each case optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyloxy, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, cycloalkylcarbonyloxy, alkoxycarbonyloxy, alkylsulfonyloxy, alkylamino, alkenylamino, alkynylamino, cycloalkylamino , Alkylthio, haloalkylthio, alkenylthio, alkynylthio, cycloalkylthio, alkylsulfinyl, alkylsulfonyl, alkylcarbonyl, alkoxyiminoalkyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, aniinothiocarbonyl, alkylaniinosulfonyl, alkylsulfonylamino, alkylcarbonylamino, alkenylcarbonylamino, alkynylcarbonylamino,
Cycloalkylcarbonylamino, Alkoxycarbonylamino, Alkylthiocarbonylamino, Bicycloalkyl, Aryl, Aryloxy, Heteroaryl und Heteroaryloxy steht, wobei die Substituenten unabhängig voneinander ausgewählt sind aus Halogen, Cyano, Nitro, Hydroxy und Amino, R6 für einen Rest aus der Reihe Wasserstoff, Alkyl, Cycloalkyl, Halogenalkyl, Alkenyl,Cycloalkylcarbonylamino, alkoxycarbonylamino, alkylthiocarbonylamino, bicycloalkyl, aryl, aryloxy, heteroaryl and heteroaryloxy, where the substituents are independently selected from halogen, cyano, nitro, hydroxy and amino, R 6 is a radical selected from the group consisting of hydrogen, alkyl, cycloalkyl, haloalkyl, alkenyl,
Alkinyl, Cycloalkylalkyl, Cyanoalkyl, Alkylcarbonyl, Alkenylcarbonyl, Halogenalkylcarbonyl, Halogenalkenylcarbonyl, Alkoxyalkyl, Alkoxycarbonyl, Alkylsulfonyl und Halogengenalkylsufonyl steht, oder Alkynyl, cycloalkylalkyl, cyanoalkyl, alkylcarbonyl, alkenylcarbonyl, haloalkylcarbonyl, haloalkenylcarbonyl, alkoxyalkyl, alkoxycarbonyl, alkylsulfonyl and haloalkylsulfonyl, or
R für einen Rest aus der Reihe R for a rest of the series
Figure imgf000091_0001
Figure imgf000091_0001
(0)„ (°-9)
Figure imgf000091_0002
(0) "(° - 9 )
Figure imgf000091_0002
Figure imgf000091_0003
steht, worin die gestrichelte Linie die Bindung zum Stickstoffatom in der Formel (I) bedeutet,
Figure imgf000091_0003
wherein the dashed line represents the bond to the nitrogen atom in the formula (I),
V-Z für eine Gruppe R18CH-CHR19 oder R18C=CR19 steht, VZ is a group R 18 CH-CHR 19 or R 18 C = CR 19 ,
X für Sauerstoff oder Schwefel steht, n für 1 oder 2 steht, X is oxygen or sulfur, n is 1 or 2,
R8 für einen Rest aus der Reihe Wasserstoff, Alkyl, Halogenalkyl, Cyanoalkyl, Alkoxy, R 8 is a radical selected from the group consisting of hydrogen, alkyl, haloalkyl, cyanoalkyl, alkoxy,
Halogenalkoxy, Alkenyl, Alkoxy alkyl, jeweils gegebenenfalls durch Halogen substituiertes Alkylcarbonyl und Alkylsulfonyl, gegebenenfalls durch Halogen substituiertes Alkoxycarbonyl, gegebenenfalls durch Halogen, Alkyl, Alkoxy, Haloalkoxy, alkenyl, alkoxyalkyl, in each case optionally halogen-substituted alkylcarbonyl and alkylsulfonyl, optionally halogen-substituted alkoxycarbonyl, if appropriate by halogen, alkyl, alkoxy,
Halogenalkyl und Cyano substituiertes Cycloalkylcarbonyl steht, oder für ein Kation, wie beispielsweise ein ein- oder zweiwertiges Metallion oder ein gegebenenfalls durch Alkyl oder Arylalkyl substituiertes Ammonium-Ion steht, Haloalkyl and cyano-substituted cycloalkylcarbonyl, or represents a cation, such as a monovalent or divalent metal ion or an optionally substituted by alkyl or arylalkyl ammonium ion,
R15 und R9 unabhängig voneinander für einen Rest aus der Reihe jeweils gegebenenfalls substituiertes Amino, Alkyl, Alkenyl und Alkinyl, jeweils gegebenenfalls substituiertesR 15 and R 9 independently of one another from the series each optionally substituted amino, alkyl, alkenyl and alkynyl, each optionally substituted
Cycloalkyl, Cycloalkylalkyl und Cycloalkenyl, in welchen die Ringe mindestens ein Heteroatom aus der Reihe Schwefel, Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff enthalten können, jeweils gegebenenfalls substituiertes Aryl, Heteroaryl, Arylalkyl und Heteroarylalkyl und eine gegebenenfalls substituierte Aminogruppe stehen, Cycloalkyl, cycloalkylalkyl and cycloalkenyl in which the rings may contain at least one heteroatom selected from the group consisting of sulfur, oxygen (where oxygen atoms are not immediately adjacent) and nitrogen, each optionally substituted aryl, heteroaryl, arylalkyl and heteroarylalkyl and an optionally substituted amino group,
R8 und R15 auch zusammen mit der N-S(0)n Gruppe, an die sie gebunden sind, einen gesättigten oder ungesättigten und gegebenenfalls substituierten 4- bis 8-gliedrigen Ring bilden können, der ein oder mehrere weitere Heteroatome aus der Reihe Schwefel, Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff und/oder mindestens eine Carbonylgruppe enthalten kann, R 8 and R 15 , together with the NS (0) n group to which they are attached, may also form a saturated or unsaturated and optionally substituted 4- to 8-membered ring containing one or more further heteroatoms selected from the group consisting of sulfur, Oxygen (where oxygen atoms are not allowed to be immediately adjacent) and nitrogen and / or at least one carbonyl group,
R17 für einen Rest aus der Reihe jeweils gegebenenfalls substituiertes Alkyl, Alkoxy, R 17 is a radical from the series in each case optionally substituted alkyl, alkoxy,
Alkenyl und Alkinyl, jeweils gegebenenfalls substituiertes Cycloalkyl, Cycloalkylalkyl und Cycloalkenyl, in welchen die Ringe mindestens ein Heteroatom aus der Reihe Schwefel, Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff enthalten können, jeweils gegebenenfalls substituiertes Aryl, Heteroaryl, Alkenyl and alkynyl, in each case optionally substituted cycloalkyl, cycloalkylalkyl and cycloalkenyl, in which the rings may contain at least one heteroatom from the group consisting of sulfur, oxygen (where oxygen atoms may not be immediately adjacent) and nitrogen, in each case optionally substituted aryl, heteroaryl,
Arylalkyl und Heteroarylalkyl und eine gegebenenfalls substituierte Aminogruppe steht, Arylalkyl and heteroarylalkyl and an optionally substituted amino group,
R16 für einen Rest aus der Reihe Wasserstoff, jeweils gegebenenfalls substituiertes Alkyl, R 16 is a radical from the series hydrogen, in each case optionally substituted alkyl,
Alkoxy, Alkenyl und Alkinyl, jeweils gegebenenfalls substituiertes Cycloalkyl, Cycloalkylalkyl und Cycloalkenyl, in welchen die Ringe mindestens ein Heteroatom aus der Reihe Schwefel, Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff enthalten können, jeweils gegebenenfalls substituiertes Aryl, Heteroaryl, Arylalkyl und Heteroarylalkyl und eine gegebenenfalls substituierte Aminogruppe steht, R8 und R17 auch zusammen mit der N-C(X) Gruppe, an die sie gebunden sind, einen gesättigten oder ungesättigten und gegebenenfalls substituierten 4- bis 8-gliedrigen Ring bilden können, der ein oder mehrere weitere Heteroatome aus der Reihe Schwefel, Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff und/oder mindestens eine Carbonylgruppe enthalten kann, Alkoxy, alkenyl and alkynyl, each optionally substituted cycloalkyl, cycloalkylalkyl and cycloalkenyl, in which the rings may contain at least one heteroatom selected from sulfur, oxygen (where oxygen atoms are not immediately adjacent) and nitrogen, each optionally substituted aryl, heteroaryl, arylalkyl and heteroarylalkyl and an optionally substituted amino group, R 8 and R 17 may also together with the NC (X) group to which they are attached form a saturated or unsaturated and optionally substituted 4- to 8-membered ring containing one or more further heteroatoms selected from sulfur, oxygen (where oxygen atoms are not allowed to be immediately adjacent) and may contain nitrogen and / or at least one carbonyl group,
R10 für Wasserstoff oder Alkyl steht, R 10 is hydrogen or alkyl,
R8 und R10 auch gemeinsam mit den N-Atomen an die sie gebunden sind, für einen gesättigten oder ungesättigten und gegebenenfalls substituierten 4- bis 8-gliedrigen Ring stehen können, der mindestens ein weiteres Heteroatom aus der Reihe Schwefel, Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff und/oder mindestens eine Carbonylgruppe enthalten kann, R 8 and R 10 may also together with the N atoms to which they are bonded, be a saturated or unsaturated and optionally substituted 4- to 8-membered ring, the at least one further heteroatom selected from the group sulfur, oxygen (wherein oxygen atoms not immediately adjacent) and may contain nitrogen and / or at least one carbonyl group,
8 9 8 9
R und R im Rest (D-l) auch zusammen mit der N-S(0)n-Gruppe, an die sie gebunden sind, einen gesättigten oder ungesättigten und gegebenenfalls substituierten 4- bis 8- gliedrigen Ring bilden können, der ein oder mehrere weitere Heteroatome aus der Reihe Schwefel, Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff und/oder mindestens eine Carbonylgruppe enthalten kann, R and R in the radical (Dl) together with the NS (0) n group to which they are attached, can form a saturated or unsaturated and optionally substituted 4- to 8-membered ring which comprises one or more further heteroatoms the series sulfur, oxygen (oxygen atoms may not be immediately adjacent) and nitrogen and / or at least one carbonyl group,
9 10 9 10
R und R auch zusammen mit der N-S(0)n Gruppe, an die sie gebunden sind, einen gesättigten oder ungesättigten und gegebenenfalls substituierten 4- bis 8-gliedrigen Ring bilden können, der ein oder mehrere weitere Heteroatome aus der Reihe Schwefel, Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff und/oder mindestens eine Carbonylgruppe enthalten kann, R and R may also together with the NS (0) n group to which they are attached form a saturated or unsaturated and optionally substituted 4- to 8-membered ring containing one or more further heteroatoms selected from the group consisting of sulfur, oxygen ( where oxygen atoms are not allowed to be immediately adjacent) and may contain nitrogen and / or at least one carbonyl group,
R8 und R16 auch zusammen mit dem N-Atom, an das sie gebunden sind, einen gesättigten oder ungesättigten und gegebenenfalls substituierten 4- bis 8-gliedrigen Ring bilden können, der ein oder mehrere weitere Heteroatome aus der Reihe Schwefel, Sauerstoff (wobei Sauers toffatome nicht unmittelbar benachbart sein dürfen) und Stickstoff und/oder mindestens eine Carbonylgruppe enthalten kann, R 8 and R 16 may also together with the N-atom to which they are attached form a saturated or unsaturated and optionally substituted 4- to 8-membered ring containing one or more further heteroatoms selected from the group consisting of sulfur and oxygen (where Sauer's toffatome may not be immediately adjacent) and may contain nitrogen and / or at least one carbonyl group,
L für Sauerstoff oder Schwefel steht, L is oxygen or sulfur,
11 12 11 12
R und R unabhängig voneinander für einen jeweils gegebenenfalls substituierten Rest aus der  R and R independently of one another are each an optionally substituted radical from
Reihe Alkyl, Alkenyl, Alkinyl, Alkoxy, Alkenyloxy, Alkinyloxy, Cycloalkyl, Cycloalkyloxy, Cycloalkenyloxy, Cycloalkylalkoxy, Alkylthio, Alkenylthio, Phenoxy, Series alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkyloxy, cycloalkenyloxy, cycloalkylalkoxy, alkylthio, alkenylthio, phenoxy,
Phenylthio, Benzyloxy, Benzylthio, Heteroaryloxy, Heteroarylthio, Heteroarylalkoxy und Heteroarylalkylthio stehen, 11 12 Phenylthio, benzyloxy, benzylthio, heteroaryloxy, heteroarylthio, heteroarylalkoxy and heteroarylalkylthio, 11 12
R und R auch gemeinsam mit dem Phosphoratom, an das sie gebunden sind, einen gesättigten oder ungesättigten und gegebenenfalls substituierten 5- bis 7-gliedrigen Ring bilden können, der ein oder zwei Heteroatome aus der Reihe Sauerstoff (wobei Sauerstoffatome nicht unmittelbar benachbart sein dürfen) und Schwefel enthalten kann und  R and R may also together with the phosphorus atom to which they are attached form a saturated or unsaturated and optionally substituted 5- to 7-membered ring containing one or two heteroatoms selected from oxygen (oxygen atoms may not be immediately adjacent) and may contain sulfur and
13 14 13 14
R und R unabhängig voneinander für einen jeweils gegebenenfalls substituierten Rest aus der  R and R independently of one another are each an optionally substituted radical from
Reihe Alkyl, Alkenyl, Alkinyl, Phenyl und Phenylalkyl stehen,  Series alkyl, alkenyl, alkynyl, phenyl and phenylalkyl,
R18 und R19 unabhängig voneinander für Wasserstoff oder einen jeweils gegebenenfalls substituierten Rest aus der Reihe Alkyl, Alkenyl, Alkinyl, Phenyl und Phenylalkyl stehen, R 18 and R 19 independently of one another represent hydrogen or a respectively optionally substituted radical from the series alkyl, alkenyl, alkynyl, phenyl and phenylalkyl,
Y1 und Y2 unabhängig voneinander für C=0 oder S(0)2 stehen und m für 1 , 2, 3 oder 4 steht. Y 1 and Y 2 are independently C = 0 or S (0) 2 and m is 1, 2, 3 or 4.
2. Mittel, gekennzeichnet durch einen Gehalt von mindestens einer Verbindung der Formel (I) gemäß Anspruch 1 und üblichen Streckmitteln und/oder oberflächenaktiven Substanzen. 2. agent, characterized by a content of at least one compound of formula (I) according to claim 1 and conventional extenders and / or surface-active substances.
3. Verfahren zum Bekämpfen von Schädlingen dadurch gekennzeichnet, dass man eine Verbindung der Formel (I) gemäß Anspruch 1 oder ein Mittel gemäß Anspruch 2 auf die Schädlinge und/oder ihren Lebensraum einwirken lässt. 3. A method for controlling pests, characterized in that a compound of formula (I) according to claim 1 or an agent according to claim 2 is allowed to act on the pests and / or their habitat.
4. Verwendung von Verbindungen der Formel (I) gemäß Anspruch 1 oder von Mitteln gemäß Anspruch 2 zum Bekämpfen von Schädlingen. 4. Use of compounds of formula (I) according to claim 1 or of agents according to claim 2 for controlling pests.
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