WO2018162312A1 - Spirocyclic derivatives - Google Patents

Spirocyclic derivatives Download PDF

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WO2018162312A1
WO2018162312A1 PCT/EP2018/055028 EP2018055028W WO2018162312A1 WO 2018162312 A1 WO2018162312 A1 WO 2018162312A1 EP 2018055028 W EP2018055028 W EP 2018055028W WO 2018162312 A1 WO2018162312 A1 WO 2018162312A1
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spp
alkyl
compounds
formula
methyl
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PCT/EP2018/055028
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French (fr)
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Karsten Koerber
Arun Narine
Martin John MCLAUGHLIN
Birgit GOCKEL
Nikolas HUWYLER
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/12—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains three hetero rings
    • C07D491/20—Spiro-condensed systems
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P33/00—Antiparasitic agents

Definitions

  • the present invention relates to spirocyclic compounds of formula I
  • R 11 is hydrogen, Ci-C6-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C6-halogenalkyl, C3-C6-cycloal- kyl, or C3-C6-halogencycycloalkyl;
  • R 12 , R 13 independently from each other are halogen, cyano, NO2, Ci-C6-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C6-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycycloalkyl, Ci-C6-alk- oxy, Ci-C6-halogenalkoxy, S(0) n -Ci-C6-alkyl, S(0) n -Ci-C6-halogenalkyl;
  • n 0, 1 , or 2;
  • W a is a group W a , or W b ;
  • G 1 , G 2 , G 3 are independently from each other CR a , or N;
  • R a is halogen, OH, SH, NO2, cyano, isocyano, isothiocyanato, Ci-C6-alkyl, C3-C6-cyclo- alkyl, C2-C4-alkenyl, C3-C6-cycloalkenyl, C2-C4-alkynyl, Ci-C6-alkoxy, C2-C4-alkenyl- oxy, C2-C4-alkynyloxy, C3-C6-cycloalkoxy, C3-C6-cycloalkenyloxy, S(0) n -Ci-C6-alkyl, cycloalkylthio, C2-C4-alkenylthio, C3-C6-cycloalkenylthio, C2-C4-alkinylthio, C(0)NH2, SF 5 , S0 2 -N(R 33 )R 35 , N(R 33 )R 35 , C(0)R 35 , C(0)
  • T O or S
  • R 2 is H, Ci-C6-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C3-C7-cycloalkyl, or Ci-C6-alkylcar- bonyl, phenyl-Ci-C4-alkyl, hetaryl-Ci-C4-alkyl; and
  • ⁇ is the bond to phenyl
  • Z is O, or S(0) n ;
  • R 311 is OH, cyano, Ci-C 2 -alkyl, or Ci-C 2 -haloalkyl
  • R 32 Ci-C6-alkyl, Ci-C6-haloalkyl, or a group as defined for R 31 ;
  • R 33 is H, or d-Ce-alkyl
  • R 34 is H, Ci-C 6 -alkyl, Ci-C 6 -haloalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -alkynyl, C 2 -C6-haloalkynyl, or C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C3-C6-cycloalkylmethyl, or C3-C6-halocycloalkylmethyl which rings are unsubstituted or substituted with a cyano;
  • R 35 H Ci-C 6 -alkyl, Ci-C 6 -haloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, CH 2 -CN, C 3 -C 6 -cycloal- kyl, C3-C6-halocycloalkyl, C3-C6-cycloalkylmethyl, C3-C6-halocycloalkylmethyl, phenyl and hetaryl which aromatic rings are unsubstituted or partially or fully substituted with R A ;
  • R 36 is H, Ci-C 6 -alkyl, or Ci-C 6 -haloalkyl
  • the invention relates to processes and intermediates for preparing the compounds of formula I, and also to active compound combinations, and compositions comprising them, and to their use for protecting growing plants from attack or infestation by invertebrate pests. Furthermore, the invention relates to methods of applying such compounds. The present inven- tion also relates to seed comprising such compounds.
  • Invertebrate pests and in particular arthropods and nematodes destroy growing and harvested crops and attack wooden dwelling and commercial structures, thereby causing large economic loss to the food supply and to property.
  • There is an ongoing need for new agents for combating invertebrate pests such as insects, arachnids and nematodes.
  • 2017/025590 describe pyrazoles or spirocyclic derivatives. These compounds are mentioned to be useful for combating invertebrate pests. Nevertheless, there remains a need for highly effective and versatile agents for combating invertebrate pests. It is therefore an object of the present invention to provide compounds having a good pesticidal activity and showing a broad activity spectrum against a large number of different invertebrate pests, especially against difficult to control pests, such as insects.
  • X' is halogen such as bromine or iodine
  • X" is a leaving group selected from halogen, mesylate, tosylate, or triflate) and II .2. a (Z is selected from oxygen or sulfur).
  • Compounds of formula I I .2. a are known and are commercially available.
  • This transformation is usually carried out at temperatures of from -78°C to 60°C, preferably from -50°C to 20 °C, in an inert solvent, in the presence of a base [cf. WO 2014/039422].
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and petrol ether, aromatic hydrocarbons such as toluene, o-, m-, and p-xylene, ethers such as diethyl- ether, Diisopropylether, tert.-butylmethylether, dioxane, anisole, 2-methyl-tetrahydrofuran and tetrahydrofurane, preferably ethers such as diethyl ether, tetrahydrofuran, tert.-butylmethylether, or 2-methyl-tetrahydrofuran. It is also possible to use mixtures of the solvents mentioned.
  • Suitable bases are, in general, organometallic compounds, such as alkali metal alkyls such as methyllithium, n-butyllithium, sec-butyllithium, tert.-butyllithium, phenyllithium, and alkaline earth metal alkyls, such as mehtylmagnesiumhalogenide, ethylmagnesiumhalide, isopropylmagnesi- umhalide, butylmagnesiumhalide, wherein the halide in the aforementioned terms can be selected from chlorine, bromine and iodine.
  • alkali metal and alkaline earth metals such as lithium, sodium, potassium or magnesium can be used.
  • alkali metal alkyls such as n-butyllithium or alkaline earth metal alkyls, such as isopropyl mag- nesium chloride or isopropyl magnesium bromide.
  • the bases are generally employed in equimolar amounts, or in excess.
  • the starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of I I.2. a, based on 11.1 . a.
  • Compounds of formula 11.1. a can be prepared from compounds of formula II.3. a by transformation of the hydroxy group into X". Compounds of formula II.3. a are known and are commercially available.
  • This transformation is usually carried out at temperatures of from -10°C to 120°C, preferably from 0°C to 80°C, in an inert solvent, in the presence or absence of a base depending on the nature of X".
  • X represents mesylate, tosylate or triflate
  • a sulfonyla- tion reagent and a base is required [cf. Freitas, Luiza B. de O. et al, European Journal of Medicinal Chemistry, 84, 595-604; 2014]
  • X represents a halogen
  • the re- actions do not require the addition of base but a halogenation reagent [cf. Lee, Choi Chuck et al, Journal of Organic Chemistry, 50(5), 705-7; 1985].
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and petrol ether, aromatic hydrocarbons such as toluene, o-, m-, and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, and chlorobenzene, ethers such as diethylether, Diisopropylether, tert.-butylmethylether, dioxane, anisole, and tetrahydrofurane, esters, such as ethyl acetate and butyl acetate, nitrils such as acetonitrile, and propionitrile, moreover dimethyl sulphoxide, dimethyl formamide, and dimethylacetamide, preferably aromatic hydrocarbons such as toluene, or methylene chloride, dimethyl formamide, dimethylacetamide, ethyl acetate and butyl acetate. It
  • Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide, and magnesium oxide, alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal and al- kaline earth metal carbonates, such as lithium carbonate, sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, moreover, organic bases, for example tertiary amines, such as trimethylamine, triethylamine, triisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines.
  • alkali metal and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate
  • alkali metal bicarbonates such as sodium bicarbonate or tertiary amines such as triethylamine.
  • the bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
  • Suitable sulfonylation reagents are methane sulfonyl chloride, toluenesulfonyl chloride or triflic anhydride.
  • Suitable halogenation reagents are for example chlorine, thionyl chloride, oxalyl chloride, phosphoryl chloride, phosphoryl bromide, phosphorus pentachloride and boron tribromide.
  • the starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of the sulfonylation reagent or the halo- genatin reagent based on II.3. a.
  • Halogenide Ila is then transformed to boronic acid of formula I lia.
  • This transformation is usually carried out at temperatures of from -78°C to 80 °C, preferably from -10°C to 50 °C, in an inert solvent, in the presence of a base [cf. Hattori, Yoshihide et al, Bioorganic & Medicinal Chemistry, 14(10), 3258-3262; 2006 ].
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and petrol ether, aromatic hydrocarbons such as toluene, o-, m-, and p-xylene, ethers such as diethyl- ether, Diisopropylether, tert.-butylmethylether, dioxane, anisole, 2-methyl-tetrahydrofuran and tetrahydrofurane, preferably ethers such as diethyl ether, tetrahydrofuran, tert.-butylmethylether, or 2-methyl-tetrahydrofuran. It is also possible to use mixtures of the solvents mentioned.
  • Suitable bases are, in general, organometallic compounds, such as alkali metal alkyls such as methyllithium, n-butyllithium, sec-butyllithium, tert.-butyllithium, phenyllithium, and alkaline earth metal alkyls, such as mehtylmagnesiumhalogenide, ethylmagnesiumhalide, isopropylmagnesi- umhalide, butylmagnesiumhalide, wherein the halide in the aforementioned terms can be se- lected from chlorine, bromine and iodine.
  • alkali metal and alkaline earth metals such as lithium, sodium, potassium or magnesium can be used.
  • alkali metal alkyls such as n-butyllithium or alkaline earth metal alkyls, such as isopropyl magnesium chloride or isopropyl magnesium bromide.
  • the bases are generally employed in equimolar amounts, or in excess.
  • the starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of Ila, based on Ilia.
  • boronic acid of formula Ilia to boronic acid esters of formula Illb, wherein A is Ci-C4-alkoxy, or both A groups form together a pinakolyl group ⁇ -0-C(RP) 2 -C(RP) 2 -0- ⁇ , wherein RP is Ci-C 6 -alkyl, and ⁇ denotes the bond to the boron atom.
  • a pyrazole derivative of formula IVa in which X is halogen, preferably bromine or iodine, and the other variables have the meaning as given for formula I.
  • Pyrazole derivatives IVa are known from WO 2016/174049. This transformation is usually carried out at temperatures of from 20°C to 180 °C, preferably from 25°C to 120 °C, in an inert solvent, in the presence of a base and a catalyst [cf. Kristensen, Jesper L. et al, Journal of Medicinal Chemistry, 53(19), 7021-7034; 2010 ].
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and pet- rol ether, aromatic hydrocarbons such as toluene, o-, m-, and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, and chlorobenzene, ethers such as diethylether, Diisopropylether, tert.-butylmethylether, dioxane, anisole, and tetrahydrofurane, nitrils such as acetonitrile, and propionitrile, ketons such as acetone, methyl ethyl ketone, diethyl ketone, and tert.
  • aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and pet- rol ether
  • aromatic hydrocarbons such as toluene, o-,
  • alcohols such as methanol, ethanol, n-propanol, isopropanol, n-buta- nol, and tert.-butanol, moreover dimethyl sulphoxide, dimethyl formamide, and dimethylacetam- ide, and water; preferably aromatic hydrocarbons such as toluene, ethers such as tetrahydrofu- ran, nitriles such as acetonitrile, dimethyl formamide, and dimethylacetamide, and water. It is also possible to use mixtures of the solvents mentioned.
  • Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide, and magnesium oxide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, alkali metal phosphates, such as sodium phosphate or potassium phosphate, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, triisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines.
  • alkali metal and alkaline earth metal hydroxides such as lithium hydro
  • alkali metal carbonates such as sodium carbonate and potassium carbonate
  • alkali metal phosphates such as sodium phosphate or potas- sium phosphate or tertiary amines, such as triethylamine.
  • the bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
  • the amine 111 is obtained from a halogenide of formula Ila by Buchwald-Hartwig Cross Coupling Reaction, e.g. with an imine lib under conditions known from WO 2015/049535.
  • This transformation is usually carried out at temperatures of from 10°C to 180 °C, preferably from 25°C to 120 °C, in an inert solvent, in the presence of a base and a catalyst.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and petrol ether, aromatic hydrocarbons such as toluene, o-, m-, and p-xylene, ethers such as diethylether, Diisopropylether, tert.-butylmethylether, dioxane, anisole, and tetrahydrofurane, nitrils such as acetonitrile, and propionitrile, moreover dimethyl sulphoxide, dimethyl formamide, and dimethylacetamide, preferably aromatic hydrocarbons such as toluene or ethers such as diethylether, Diisopropylether, tert.-butylmethylether and dioxane.
  • aromatic hydrocarbons such as toluene or ethers such as diethylether, Diisopropylether, tert.-butylmethylether and dio
  • Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide, and magnesium oxide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate, cesium carbonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, triisopropylethylamine and N-methyl- piperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylamino- pyridine, and also bicyclic amines.
  • organic bases for example tertiary amines, such as trimethylamine, triethylamine, triisopropylethy
  • alkali metal carbonates such as potassium carbonate, cesium carbonate and amines, such as triethylamine, triisopropylethylamine and N-methylpiperidine, pyridine.
  • the bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
  • Suitable catalysts are preferably Pd catalysts.
  • the Pd catalysts used are generally produced in situ from at least one palladium(ll) salt or a palladium(O) compound and the corresponding phosphine ligands. However, they may also be used directly as palladium(O) compound without reducing the initial catalytic activity.
  • Particularly preferred catalysts are selected from the following: Pd tetrakis, PdCI 2 (PPh3) 2 , CI 2 Pd(dppf), Pd 2 (dba)3, Pd(OAc) 2 , and PdCI 2 .
  • Particularly preferred ligands are the following: PP i3, dppf, 2,2'-bis-(diphenylphosphino)-1 ,1 '- binaphthyl (BINAP), AsPh 3 , (tBu) 3 P, and tri(o-tolyl)phos- phine(tri(o-tol)P).
  • the starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of lib, based on lla.
  • the amine of formula I lie is alkylated or acyl- ated with an agent of formula R 2 -X, wherein X is a nucleophilic leaving group, such as a halo- gen, preferably CI or Br, or acetate, under reaction conditions generally known in the art [cf. Selva, Maurizio et al, Journal of Organic Chemistry, 68(19), 7374-7378; 2003].
  • X is a nucleophilic leaving group, such as a halo- gen, preferably CI or Br, or acetate
  • the reaction is generally at temperatures of from 0°C to 120 °C, preferably from 20°C to 1 10°C.
  • R 2 H compounds of formula Vb.
  • the amine 111 is reacted with a pyrazole carbonic acid of formula IVb, which is known from WO 2016/026789.
  • This transformation is usually carried out at temperatures of from -10°C to 120°C, preferably from 0°C to 1 10°C, in an inert solvent, in the presence of a base and a catalyst [cf. WO
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and petrol ether, aromatic hydrocarbons such as toluene, o-, m-, and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, and chlorobenzene, ethers such as diethylether, Diisopropylether, tert.-butylmethylether, dioxane, anisole, and tetrahydrofurane, nitrils such as acetonitrile, and propionitrile, ketons such as acetone, methyl ethyl ketone, diethyl ketone, and tert.
  • esters such as ethyl acetate and butyl acetate, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert.-butanol, moreover dimethyl sulphoxide, dimethyl formamide, and dimethylacetamide, preferably aromatic hydrocarbons such as toluene, dimethyl formamide, dimethylacetamide, ethyl acetate and butyl acetate. It is also possible to use mixtures of the solvents mentioned.
  • Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide, and magnesium oxide, alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal and al- kaline earth metal carbonates, such as lithium carbonate, sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, triisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines.
  • alkali metal and alkaline earth metal carbonates such as sodium carbonate, potassium carbonate and calcium carbonate
  • alkali metal bicarbonates such as sodium bicarbonate or tertiary amines such as triethylamine
  • the bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
  • Suitable catalysts are acid activating reagents which form with the acid IVb an active ester species. They can be selected from dicyclohexyl carbodiimide, diisopropyl carbodiimide, car- bonyl diimidazole, 1-hydroxy-7-azabenzotriazole [HOAt], 1-hydroxy-7-benzotriazole [HOBt], 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, bromotripyrrolidinophosphonium hexafluorophosphate [PyBroP], 1 -[Bis(dimethylamino)methylene]-1 H-1 ,2,3-triazolo[4,5-b]pyri- dinium 3-oxid hexafluorophosphate [HATU].
  • the catalyst has to be added in equimolar amounts or in excess.
  • the protective group is then split off from compounds V (collectively for formulae Va and Vb) to yield the free azetidine of formula VI.
  • Compounds of formula VI can be obtained from compounds V by hydrolysis of the protective group. This transformation is usually carried out at temperatures of from -20°C to 100°C, preferably from 0°C to 40°C, using trifluoroacetic acid as a co-solvent in a solvent such as dichloro- methane or hydrochloric acid in ethers such as diethylether, Diisopropylether, tert.-butylmethylether, dioxane, and tetrahydrofurane (c.f. WO 2015/104422).
  • a solvent such as dichloro- methane or hydrochloric acid in ethers
  • ethers such as diethylether, Diisopropylether, tert.-butylmethylether, dioxane, and tetrahydrofurane (c.f. WO 2015/104422).
  • the starting materials required for preparing the compounds I are commercially available or known from the literature, or can be prepared in accordance with the literature cited.
  • reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, chromatographic purification of the crude products.
  • Some of the intermediates and end products are obtained in the form of colorless or slightly brownish viscous oils which are purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion.
  • the radicals attached to the backbone of formula I may contain one or more centers of chirali- ty.
  • the compounds of formula I are present in the form of different enantiomers or diastereomers, depending on the substituents.
  • the present invention relates to every possible stereoisomer of the formula I , i.e. to single enantiomers or diastereomers, as well as to mixtures thereof.
  • the compounds of formula I may be amorphous or may exist in one or more different crystal- line states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities.
  • the present invention relates to amorphous and crystalline compounds of formula I , mixtures of different crystalline states of the respective compound I , as well as amorphous or crystalline salts thereof.
  • Salts of the compounds of the formula I are preferably veterinary and/or agriculturally accepta- ble salts, preferably agriculturally acceptable salts. They can be formed in a customary manner, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality.
  • Veterinary and/or agriculturally useful salts of the compounds of formula I encompass especially the acid addition salts of those acids whose cations and anions, respectively, have no ad- verse effect on the pesticidal action of the compounds of formula I.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting compounds of formula I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobro- mic acid, sulfuric acid, phosphoric acid or nitric acid.
  • N-oxide includes any compound of formula I which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety.
  • the organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members.
  • the prefix C n -C m indicates in each case the possible number of carbon atoms in the group.
  • halogen denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine.
  • alkyl as used herein and in the alkyl moieties of alkylamino, alkylcarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl and alkoxyalkyl denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably from 1 to 3 carbon atoms.
  • Examples of an alkyl group are methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 1 -methyl- butyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, n-hexyl, 1 , 1 -dimethylpro- pyl, 1 ,2-dimethylpropyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 , 1 -dimethyl butyl , 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dime- thylbutyl, 1 -ethylbutyl, 2-
  • haloalkyl as used herein and in the haloalkyl moieties of haloalkylcarbonyl, haloalk- oxycarbonyl, haloalkylthio, haloalkylsulfonyl, haloalkylsulfinyl, haloalkoxy and haloalkoxyalkyl, denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms.
  • Preferred haloalkyl moieties are selected from Ci-C4- aloalkyl, more preferably from Ci-C3-haloalkyl or Ci-C2-haloalkyl, in particular from Ci-C2-fluoroalkyl such as fluoromethyl, difluoromethyl, trifluo- romethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and the like.
  • alkoxy denotes in each case a straight-chain or branched alkyl group which is bonded via an oxygen atom and has usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
  • alkoxy group examples are methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, 2-butyloxy, iso-butyloxy, tert.-butyloxy, and the like.
  • alkoxyalkyl refers to alkyl usually comprising 1 to 10, frequently 1 to 4, preferably 1 to 2 carbon atoms, wherein 1 carbon atom carries an alkoxy radical usually comprising 1 to 4, preferably 1 or 2 carbon atoms as defined above. Examples are CH2OCH3, CH2- OC2H5, 2-(methoxy)ethyl, and 2-(ethoxy)ethyl.
  • haloalkoxy denotes in each case a straight-chain or branched alk- oxy group having from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms, in particular fluorine atoms.
  • Preferred haloalkoxy moieties include C1-C4- haloalkoxy, in particular Ci-C2-fluoroalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoro- methoxy, 1 -fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-flu- oroethoxy, 2-chloro-2,2-difluoro-ethoxy, 2,2dichloro-2-fluorethoxy, 2,2,2-trichloroethoxy, penta- fluoroethoxy and the like.
  • Ci-C2-fluoroalkoxy such as fluoromethoxy, difluoromethoxy, trifluoro- methoxy, 1 -fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-
  • alkylthio (alkylsulfanyl: S-alkyl)
  • haloalkylthio refers to an alkylthio group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • haloalkylsulfinyl refers to an alkylsulfinyl group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • haloalkylsulfonyl refers to an alkylsulfonyl group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • haloalkylcarbonyl refers to an alkylcarbonyl group as mentioned above, wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • alkoxycarbonyl refers to an alkylcarbonyl group as defined above, which is bonded via an oxygen atom to the remainder of the molecule.
  • haloalkoxycarbonyl refers to an alkoxycarbonyl group as mentioned above, wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • alkenyl denotes in each case a singly unsaturated hydrocarbon radical having usually 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms, e.g. vinyl, allyl (2- propen-1 -yl), 1-propen-1-yl, 2-propen-2-yl, methallyl (2-methylprop-2-en-1 -yl), 2-buten-1-yl, 3- buten-1 -yl, 2-penten-1-yl, 3-penten-1 -yl, 4-penten-1-yl, 1-methylbut-2-en-1-yl, 2-ethylprop-2-en- 1-yl and the like.
  • haloalkenyl refers to an alkenyl group as defined above, wherein the hydrogen atoms are partially or totally replaced with halogen atoms.
  • alkynyl denotes in each case a singly unsaturated hydrocarbon radical having usually 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms, e.g. ethynyl, pro- pargyl (2-propyn-1 -yl), 1-propyn-1-yl, 1-methylprop-2-yn-1 -yl), 2-butyn-1 -yl, 3-butyn-1-yl, 1-pen- tyn-1-yl, 3-pentyn-1-yl, 4-pentyn-1-yl, 1-methylbut-2-yn-1 -yl, 1-ethylprop-2-yn-1-yl and the like.
  • haloalkynyl refers to an alkynyl group as defined above, wherein the hydrogen atoms are partially or totally replaced with halogen atoms.
  • cycloalkyl as used herein and in the cycloalkyl moieties of cycloalkoxy and cycloal- kylthio denotes in each case a monocyclic cycloaliphatic radical having usually from 3 to 10 or from 3 to 6 carbon atoms, such as cyclopropyl (C-C3H5), cyclobutyl (C-C4H7), cyclopentyl (c- C5H9), cyclohexyl (c-CeHu), cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl or cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • halocycloalkyl as used herein and in the halocycloalkyl moieties of halocycloalkoxy and halocycloalkylthio denotes in each case a monocyclic cycloaliphatic radical having usually from 3 to 10 C atoms or 3 to 6 C atoms, wherein at least one, e.g. 1 , 2, 3, 4 or 5 of the hydrogen atoms, are replaced by halogen, in particular by fluorine or chlorine.
  • Examples are 1 - and 2-fluo- rocyclopropyl, 1 ,2-, 2,2- and 2,3-difluorocyclopropyl, 1 ,2,2-trifluorocyclopropyl, 2,2,3,3-tetrafluo- rocyclpropyl, 1 - and 2-chlorocyclopropyl, 1 ,2-, 2,2- and 2,3-dichlorocyclopropyl, 1 ,2,2-trichloro- cyclopropyl, 2,2,3,3-tetrachlorocyclpropyl, 1 -,2- and 3-fluorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-difluorocyclopentyl, 1 -,2- and 3-chlorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-difluorocyclopentyl, 1 -,2- and 3-chlorocyclopen
  • cycloalkenyl as used herein and in the cycloalkenyl moieties of cycloalkenyloxy and cycloalkenylthio denotes in each case a monocyclic singly unsaturated non-aromatic radical having usually from 3 to 10, e.g. 3 or 4 or from 5 to 10 carbon atoms, preferably from 3- to 8 carbon atoms.
  • exemplary cycloalkenyl groups include cyclopropenyl, cycloheptenyl or cycloocte- nyl.
  • halocycloalkenyl as used herein and in the halocycloalkenyl moieties of halocyclo- alkenyloxy and halocycloalkenylthio denotes in each case a monocyclic singly unsaturated non- aromatic radical having usually from 3 to 10, e.g. 3 or 4 or from 5 to 10 carbon atoms, preferably from 3- to 8 carbon atoms, wherein at least one, e.g. 1 , 2, 3, 4 or 5 of the hydrogen atoms, are replaced by halogen, in particular by fluorine or chlorine. Examples are 3,3-difluorocyclopropen- 1-yl and 3,3-dichlorocyclopropen-1-yl.
  • carrier or “carbocyclyl” includes in general a 3- to 12-membered, preferably a 3- to 8-membered or a 5- to 8-membered, more preferably a 5- or 6-membered mono-cyclic, non-aromatic ring comprising 3 to 12, preferably 3 to 8 or 5 to 8, more preferably 5 or 6 carbon atoms.
  • the term “carbocycle” covers cycloalkyl and cycloalkenyl groups as defined above.
  • heterocycle or “heterocyclyl” includes in general 3- to 12-membered, preferably 5- or 6-membered, in particular 6-membered monocyclic heterocyclic non-aromatic radicals.
  • the heterocyclic non-aromatic radicals usually comprise 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, wherein S-atoms as ring members may be present as S, SO or SO2.
  • Examples of 5- or 6-membered heterocyclic radicals comprise saturated or unsaturated, non- aromatic heterocyclic rings, such as 2- and 3-azetidinyl, 2- and 3-oxetanyl, 2- and 3-thietanyl, 2- and 3-thietanyl-S-oxid (S-oxothietanyl), 2- and 3-thietanyl-S-dioxid (S-dioxothietanyl), 2- and 3- pyrrolidinyl, 2- and 3-tetrahydrofuranyl, 1 ,3-dioxolan-2-yl, thiolan-2-yl, S-oxothiolan-2-yl, S-diox- othiolan-2-yl, 4- and 5-oxazolidinyl, 1 ,3-dioxan-2-yl, 1 - and 3-thiopyran-2-yl, S-oxothiopyranyl, and S-dioxothiopyranyl
  • heteroaryl includes monocyclic 5- or 6-membered heteroaromatic radicals comprising as ring members 1 , 2, or 3 heteroatoms selected from N, O and S.
  • 5- or 6-membered heteroaromatic radicals include pyridyl, i.e. 2-, 3-, and 4-pyridyl, pyrimidinyl, i.e. 2-, 4- and 5-pyrimidinyl, pyrazinyl, pyridazinyl, i.e. 3- and 4-pyridazinyl, thienyl, i.e. 2- and 3-thienyl, furyl, i.e. 2- and 3-furyl, pyrrolyl, i.e.
  • the particularly preferred embodiments of the intermediates cor- respond to those of the compounds of the formula I.
  • R 11 is preferably Ci-C4-alkyl, C2-C3-alkenyl, C2-C3-alkynyl, or Ci-C2-halogenalkyl, in particular Ci-C4-alkyl, such as CH 3 , and C2H5.
  • R 12 is preferably N0 2 , Ci-C 6 -alkyl, C 2 -C 3 -alkenyl, C 2 -C 3 -alkynyl, Ci-C 4 -halogenalkyl, or S(0) n - Ci-C4-alkyl, in particular NO2, Ci-C4-halogenalkyl, or S(0) n -Ci-C4-alkyl, more preferably C1-C4- fluoroalkyl, such as CF3, and C2F5.
  • R 13 is preferably Ci-C4-alkyl, C2-C3-alkenyl, C2-C3-alkynyl, or Ci-C2-halogenalkyl, in particular Ci-C4-halogenalkyl, more preferably Ci-C4-fluoroalkyl, such as CF3, and C2F5.
  • a preferred embodiment relates to compounds wherein R 11 is CH3, R 12 is C2F5, and R 13 is CF3.
  • W is a group W a ; such compounds correspond to formula I.A.
  • Group W a is preferably selected from W1 to W7, particularly W a is a pyrazole:
  • One embodiment relates to compounds of formula IA wherein W a is W1 ; such compounds correspond to formula I.A1 .
  • Another embodiment relates to compounds of formula IA wherein W a is W2; such compounds correspond to formula I.A2.
  • Another embodiment relates to compounds of formula IA wherein W a is W3; such compounds correspond to formula I. A3.
  • Another embodiment relates to compounds of formula IA wherein W a is W4; such compounds correspond to formula I.A4.
  • Another embodiment relates to compounds of formula IA wherein W a is W5; such compounds correspond to formula I.A5.
  • Another embodiment relates to compounds of formula IA wherein W a is W6; such compounds correspond to formula I.A6.
  • Another embodiment relates to compounds of formula IA wherein W a is W7; such compounds correspond to formula I.A7.
  • R a as substituent of any of W1 to W7 is preferably H.
  • Another embodiment relates to compounds of formula I wherein W is a group W b ; such compounds correspond to formula I.B.
  • W b T is preferably O.
  • group W b R 2 is preferably H.
  • Z is preferably O.
  • R 3 is preferably selected from H, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl which aliphatic groups are unsubstituted or substituted by one radical R 31 , C3-C6-cycloalkyl, C3-C6-halocycloalkyl which cyclic groups are unsubstituted or sub- stituted by one radical R 32 ; heterocycle, or hetaryl which rings are unsubstituted or partially or fully substituted by R A ; R 31 is independently OH, cyano, Ci-C4-alkoxy, Ci-C4-haloalkoxy, S(0) n -Ci-C4-alkyl, S(0) n -Ci- C4-haloalkyl, Cs-Cs-cycloalkyl
  • R 311 is independently OH, cyano, Ci-C2-alkyl, or Ci-C2-haloalkyl;
  • n 0, 1 , or 2;
  • R 3 is selected from Ci-C4-alkyl, and Ci-C4-haloalkyl, which aliphatic groups are unsubstituted or substituted by one radical R 31 ; and Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl which cyclic groups are unsubstituted or substituted by one radical R 32 ;
  • R 31 is independently OH, cyano, Ci-C4-alkoxy, Ci-C4-haloalkoxy, S(0) n -Ci-C4-alkyl,
  • R 311 is independently OH, cyano, Ci-C2-alkyl, or Ci-C2-haloalkyl;
  • n O, 1 , or 2;
  • R 3 is selected from Ci-Cs-alkyl, CH2CF3, CH2CH2CF3, CH 2 OH,
  • Table 1 Compounds of formula I.A1 in which R 3 for a compound corresponds in each case to one row of Table B
  • Table 2 Compounds of formula I.A2 in which R 3 for a compound corresponds in each case to one row of Table B
  • Table 3 Compounds of formula I. A3 in which R 3 for a compound corresponds in each case to one row of Table B
  • Table 4 Compounds of formula I.A4 in which R 3 for a compound corresponds in each case to one row of Table B
  • Table 5 Compounds of formula I.A5 in which R 3 for a compound corresponds in each case to one row of Table B
  • Table 6 Compounds of formula I.A6 in which R 3 for a compound corresponds in each case one row of Table B
  • Table 8 Compounds of formula I.B1 in which R 3 for a compound corresponds in each case one row of Table B
  • Table 1 1 Compounds of formula I.B4 in which R 3 for a compound corresponds in each case one row of Table B
  • THF tetrahydrofuranyl
  • TET t ietanyl
  • the compounds of the present invention are suitable for use in protecting crops, plants, plant propagation materials, such as seeds, or soil or water, in which the plants are growing, from attack or infestation by animal pests. Therefore, the present invention also relates to a plant pro- tection method, which comprises contacting crops, plants, plant propagation materials, such as seeds, or soil or water, in which the plants are growing, to be protected from attack or infestation by animal pests, with a pesticidally effective amount of a compound of the present invention.
  • the compounds of the present invention are also suitable for use in combating or controlling animal pests. Therefore, the present invention also relates to a method of combating or controlling animal pests, which comprises contacting the animal pests, their habitat, breeding ground, or food supply, or the crops, plants, plant propagation materials, such as seeds, or soil, or the area, material or environment in which the animal pests are growing or may grow, with a pesticidally effective amount of a compound of the present invention.
  • the compounds of the present invention are effective through both contact and ingestion. Furthermore, the compounds of the present invention can be applied to any and all developmental stages, such as egg, larva, pupa, and adult.
  • the compounds of the present invention can be applied as such or in form of compositions comprising them as defined above. Furthermore, the compounds of the present invention can be applied together with a mixing partner as defined above or in form of compositions comprising said mixtures as defined above.
  • the components of said mixture can be applied simultaneously, jointly or separately, or in succession, that is immediately one after another and thereby creating the mixture "in situ" on the desired location, e.g. the plant, the sequence, in the case of separate application, generally not having any effect on the result of the control measures.
  • the application can be carried out both before and after the infestation of the crops, plants, plant propagation materials, such as seeds, soil, or the area, material or environment by the pests.
  • Suitable application methods include inter alia soil treatment, seed treatment, in furrow application, and foliar application.
  • Soil treatment methods include drenching the soil, drip irrigation (drip application onto the soil), dipping roots, tubers or bulbs, or soil injection.
  • Seed treatment techniques include seed dressing, seed coating, seed dusting, seed soaking, and seed pelleting.
  • furrow applications typically include the steps of making a furrow in cultivated land, seeding the furrow with seeds, applying the pesticidally active compound to the furrow, and closing the furrow.
  • Foliar application refers to the application of the pesticidally active compound to plant foliage, e.g. through spray equipment.
  • pheromones for specific crops and pests are known to a skilled person and publicly available from databases of pheromones and semiochemicals, such as http://www.pherobase.com.
  • the term "contacting” includes both direct contact (applying the com- pounds/compositions directly on the animal pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus, i.e. habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest is growing or may grow, of the animal pest or plant).
  • animal pest includes arthropods, gastropods, and nematodes.
  • Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, in particular insects.
  • Insects, which are of particular relevance for crops, are typically referred to as crop insect pests.
  • crop refers to both, growing and harvested crops.
  • plant includes cereals, e.g. durum and other wheat, rye, barley, triticale, oats, rice, or maize (fodder maize and sugar maize / sweet and field corn); beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g.
  • iceberg lettuce chicory, cabbage, asparagus, cabbages, carrots, onions, garlic, leeks, tomatoes, potatoes, cucurbits or sweet peppers; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rapeseed, sugar cane or oil palm; tobacco; nuts, e.g. walnuts; pistachios; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers (e.g.
  • Preferred plants include potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rapeseed, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • plant is to be understood as including wild type plants and plants, which have been modified by either conventional breeding, or mutagenesis or genetic engineering, or by a combination thereof.
  • Plants which have been modified by mutagenesis or genetic engineering, and are of particular commercial importance, include alfalfa, rapeseed (e.g. oilseed rape), bean, carnation, chicory, cotton, eggplant, eucalyptus, flax, lentil, maize, melon, papaya, petunia, plum, poplar, potato, rice, soybean, squash, sugar beet, sugarcane, sunflower, sweet pepper, tobacco, tomato, and cereals (e.g. wheat), in particular maize, soybean, cotton, wheat, and rice.
  • rapeseed e.g. oilseed rape
  • bean carnation
  • chicory cotton
  • eggplant eucalyptus
  • flax flax
  • lentil eucalyptus
  • melon melon
  • papaya petunia
  • plum poplar
  • potato rice
  • soybean zucchini
  • sugar beet sugarcane
  • sunflower sweet pepper
  • sweet pepper tobacco, tomato
  • the one or more mutagenized or integrated genes are preferably selected from pat, epsps, crylAb, bar, cry1 Fa2, crylAc, cry34Ab1 , cry35AB1 , cry3A, cryF, cryl F, mcry3a, cry2Ab2, cry3Bb1 , cry1A.105, dfr, barnase, vip3Aa20, barstar, als, bxn, bp40, asnl , and ppo5.
  • the mutagenesis or integration of the one or more genes is performed in order to improve certain properties of the plant.
  • Such properties include abiotic stress tolerance, altered growth/yield, disease resistance, herbi- cide tolerance, insect resistance, modified product quality, and pollination control.
  • herbicide tolerance e.g. imidazolinone tolerance, glyphosate tolerance, or glufosinate tolerance
  • mutagenesis for example Clearfield® oilseed rape being tolerant to imidazoli- nones, e.g. imazamox.
  • genetic engineering methods have been used to render plants, such as soybean, cotton, corn, beets and oil seed rape, tolerant to herbicides, such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate).
  • herbicides such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate).
  • glyphosate and glufosinate some of which are commercially available under the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate).
  • herbicides such as glyphosate and glufosinate
  • RoundupReady® glyphosate
  • LibertyLink® glufosinate
  • insect resistance is of importance, in particular lepidopteran insect resistance and coleopteran insect resistance.
  • Plants may be modified by mutagenesis or genetic engineering either in terms of one property (singular traits) or in terms of a combination of properties (stacked traits). Stacked traits, e.g. the combination of herbicide tolerance and insect resistance, are of increasing importance.
  • the pesticidal activity of the compounds of the present invention may be enhanced by the insecticidal trait of a modified plant. Furthermore, it has been found that the compounds of the present invention are suitable for preventing insects to become resistant to the insecticidal trait or for combating pests, which already have become resistant to the insecticidal trait of a modified plant. Moreover, the compounds of the present invention are suitable for combating pests, against which the insecticidal trait is not effective, so that a complementary insecticidal activity can advantageously be used.
  • plant propagation material refers to all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e.g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants. Seedlings and young plants, which are to be transplanted after germination or after emergence from soil, may also be included. These plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting.
  • seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like, and means in a preferred embodiment true seeds.
  • pesticidally effective amount means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism.
  • the pesticidally effective amount can vary for the various compounds/compositions used in the invention.
  • a pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, tar- get species, locus, mode of application, and the like.
  • the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m 2 , preferably from 0.001 to 20 g per 100 m 2 .
  • the rate of application of the active in- gredients of this invention may be in the range of 0.0001 g to 4000 g per hectare, e.g. from 1 g to 2 kg per hectare or from 1 g to 750 g per hectare, desirably from 1 g to 100 g per hectare, more desirably from 10 g to75 g per hectare, e.g., 10 to 20 g per hectare, 20 to 30 g per hectare, 30 to 40 g per hectare, 40 to 50 g per hectare, 50-60 g per hectare, or 60-75 g per hectare.
  • the compounds of the present invention are particularly suitable for use in the treatment of seeds in order to protect the seeds from insect pests, in particular from soil-living insect pests, and the resulting seedling's roots and shoots against soil pests and foliar insects.
  • the present invention therefore also relates to a method for the protection of seeds from insects, in particular from soil insects, and of the seedling's roots and shoots from insects, in particular from soil and foliar insects, said method comprising treating the seeds before sowing and/or after pregermina- tion with a compound of the present invention.
  • the protection of the seedling's roots and shoots is preferred. More preferred is the protection of seedling's shoots from piercing and sucking insects, chewing insects and nematodes.
  • seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking, seed pelleting, and in-furrow application methods.
  • seed treatment application of the active compound is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.
  • the present invention also comprises seeds coated with or containing the active compound.
  • coated with and/or containing generally signifies that the active ingredient is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application. When the said propagation product is (re)planted, it may absorb the active ingredient.
  • Suitable seed is for example seed of cereals, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucum- bers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.
  • the active compound may also be used for the treatment of seeds from plants, which have been modified by mutagenisis or genetic engineering, and which e.g. tolerate the action of herbicides or fungicides or insecticides. Such modified plants have been described in detail above.
  • Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, suspoemulsions (SE), powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter. Preferably, the formulations are applied such that germination is not included.
  • the active substance concentrations in ready-to-use formulations are preferably from 0.01 to 60% by weight, more preferably from 0.1 to 40 % by weight.
  • a FS formulation is used for seed treatment.
  • a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
  • Especially preferred FS formulations of the compounds of the present invention for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/l) of the active ingredient, from 0.1 to 20 % by weight (1 to 200 g/l) of at least one surfactant, e.g. 0.05 to 5 % by weight of a wetter and from 0.5 to 15 % by weight of a dispersing agent, up to 20 % by weight, e.g. from 5 to 20 % of an anti-freeze agent, from 0 to 15 % by weight, e.g. 1 to 15 % by weight of a pigment and/or a dye, from 0 to 40 % by weight, e.g.
  • a binder (sticker /adhesion agent), optionally up to 5 % by weight, e.g. from 0.1 to 5 % by weight of a thickener, optionally from 0.1 to 2 % of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1 % by weight and a filler/vehicle up to 100 % by weight.
  • a binder sticker /adhesion agent
  • a preservative such as a biocide, antioxidant or the like
  • the application rates of the compounds of the invention are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, more preferably from 1 g to 1000 g per 100 kg of seed and in particular from 1 g to 200 g per 100 kg of seed, e.g. from 1 g to 100 g or from 5 g to 100 g per 100 kg of seed.
  • the invention therefore also relates to seed comprising a compound of the present invention, or an agriculturally useful salt thereof, as defined herein.
  • the amount of the compound of the present invention or the agriculturally useful salt thereof will in general vary from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed. For specific crops such as lettuce the rate can be higher.
  • the compounds of the present invention may also be used for improving the health of a plant. Therefore, the present invention also relates to a method for improving plant health by treating a plant, plant propagation material and/or the locus where the plant is growing or is to grow with an effective and non-phytotoxic amount of a compound of the present invention.
  • an effective and non-phytotoxic amount means that the compound is used in a quantity which allows to obtain the desired effect but which does not give rise to any phyto- toxic symptom on the treated plant or on the plant grown from the treated propagule or treated soil.
  • Plant and “plant propagation material” are defined above.
  • Plant health is defined as a condition of the plant and/or its products which is determined by several aspects alone or in combination with each other such as yield (for example increased biomass and/or increased content of valuable ingredients), quality (for example improved content or composition of certain ingredients or shelf life), plant vigour (for example improved plant growth and/or greener leaves ("greening effect"), tolerance to abiotic (for example drought) and/or biotic stress (for example disease) and production efficiency (for example, harvesting efficiency, processability).
  • yield for example increased biomass and/or increased content of valuable ingredients
  • quality for example improved content or composition of certain ingredients or shelf life
  • plant vigour for example improved plant growth and/or greener leaves (“greening effect")
  • tolerance to abiotic for example drought
  • biotic stress for example disease
  • production efficiency for example, harvesting efficiency, processability
  • the above identified indicators for the health condition of a plant may be interdependent and may result from each other.
  • Each indicator is defined in the art and can be determined by meth- ods known to a skilled person.
  • the compounds of the invention are also suitable for use against non-crop insect pests.
  • compounds of the present invention can be used as bait composition, gel, general insect spray, aerosol, as ultra-low volume application and bed net (impreg- nated or surface applied).
  • drenching and rodding methods can be used.
  • non-crop insect pest refers to pests, which are particularly relevant for non-crop targets, such as ants, termites, wasps, flies, ticks, mosquitos, crickets, or cockroaches.
  • the bait can be a liquid, a solid or a semisolid preparation (e.g. a gel).
  • the bait employed in the composition is a product, which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it.
  • the attractiveness can be manipulated by using feeding stimulants or sex pheromones.
  • Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyor- ganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature (e.g. http://www.phero- base.com), and are known to those skilled in the art.
  • the typical content of active ingredient is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compound.
  • Formulations of the compounds of the present invention as aerosols are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches.
  • Aerosol recipes are preferably composed of the active compound, solvents, furthermore auxiliaries such as emulsifiers, perfume oils, if appropriate stabilizers, and, if required, propellants.
  • the oil spray formulations differ from the aerosol recipes in that no propellants are used.
  • the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.
  • the compounds of the present invention and its respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems.
  • Methods to control infectious diseases transmitted by insects e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis
  • compounds of the present invention and its respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like.
  • Insecticidal compositions for application to fibers, fabric, knitgoods, nonwovens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder.
  • the compounds of the present invention and its compositions can be used for protecting wooden materials such as trees, board fences, sleepers, frames, artistic artifacts, etc. and buildings, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities).
  • Customary application rates in the protection of materials are, for example, from 0.001 g to 2000 g or from 0.01 g to 1000 g of active compound per m 2 treated material, desirably from 0.1 g to 50 g per m 2 .
  • Insecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and/or insecticide.
  • the compounds of the present invention are especially suitable for efficiently combating animal pests such as arthropods, gastropods and nematodes including but not limited to:
  • insects from the order of Lepidoptera for example Achroia grisella, Acleris spp. such as A. fim- briana, A. gloverana, A. variana; Acrolepiopsis assectella, Acronicta major, Adoxophyes spp. such as A. cyrtosema, A. orana; Aedia leucomelas, Agrotis spp. such as A. exclamationis, A. fucosa, A. ipsilon, A. orthogoma, A. segetum, A.
  • Argyresthia conjugella Argyroploce spp., Argyrotaenia spp.
  • A. velutinana Athetis mindara, Austroasca viridi- grisea, Autographa gamma, Autographa nigrisigna, Barathra brassicae, Bedellia spp., Bonagota salubricola, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp. such as C. murinana, C.
  • Cactoblastis cactorum Cadra cautella, Calingo brazilien- sis, Caloptilis theivora, Capua reticulana, Carposina spp. such as C. niponensis, C. sasakii; Ce- phus spp., Chaetocnema aridula, Cheimatobia brumata, C ? spp. such as C. Indicus, C. sup- pressalis, C. partellus; Choreut/s par/ana, Choristoneura spp. such as C. conflictana, C. fumife- rana, C. longicellana, C. murinana, C.
  • kuehniella kuehniella; Epinotia aporema, Epiphyas postvittana, Erannis tiliaria, Erio- nota thrax, Etiella spp., Eu/ia spp., Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Faronta albilinea, Feltia spp. such as F. subterranean; Galleria mellonella, Gracillaria spp., Grapholita spp. such as G. funebrana, G.
  • H. armigera Heliothis armigera
  • H. zea Heliothis zea
  • Heliothis spp. such as H. assulta, H. subflexa, H. virescens
  • Hellula spp. such as H. undalis, H.
  • M. neustria constrictum, M. neustria; Mamestra spp. such as M. brassicae, M. configurata; Mam- stra brassicae, Manduca spp. such as M. quinquemaculata, M. sexta; Marasmia spp, Marmara spp., Maruca testulalis, Megalopyge lanata, Melanchra picta, Melanitis leda, Mods spp. such as M. lapites, M.
  • operculella Phyllocnistis citrella, Phyllonorycter spp. such as P. blancardella, P. crataegella, P. issikii, P. ringoniella; Pieris spp. such as P. brassicae, P. rapae, P. napi; Pilocrocis tripunctata, Plathypena scabra, Platynota spp. such as P. flavedana, P. idae- usalis, P.
  • Tecia soianivora Teiehin Iicus
  • the da spp. Theresimima ampelophaga, Thyrinteina spp, Tildenia inconspicuella, Tinea spp. such as T. cloacella, T. pellionella; Tineola bisselliella, Tortrix spp. such as T. viridana; Trichophaga ta- petzella, Trichoplusia spp. such as T.
  • insects from the order of Coleoptera for example Acalymma vittatum, Acanthoscehdes obtec- tus, Adoretus spp., Agelastica alni, Agrilus spp. such as A. anxius, A. planipennis, A. sinuatus; Agriotes spp. such as A. fuscicollis, A. lineatus, A. obscurus; Alphitobius diaperinus, Amphimal- lus solstitialis, Anisandrus dispar, Anisoplia austriaca, Anobium punctatum, Anomala diveren- ta, Anomala rufocuprea, Anoplophora spp. such as A.
  • Anthonomus spp. such as A. eugenii, A. grandis, A. pomorum; Anthrenus spp., Aphthona euphoridae, Apion spp., Apogo- nia spp. , Athous haemorrhoidalis, Atomaria spp. such as A. linearis; Attagenus spp. , Aulaco- phora femora/is, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp. such as B. lentis, B. pisorum, B.
  • C vespertinus such as C vespertinus; Conotrachelus nenuphar, Cosmopolites spp., Costelytra zealandica, Crioceris asparagi, Cryptolestes ferrugineus, Cryptorhyn- chus lapathi, Ctenicera spp. such as C destructor; Curculio spp., Cylindrocopturus spp., Cyclo- cephala spp., Dactylispa balyi, Dectes texanus, Dermestes spp., Diabrotica spp. such as D. un- decimpunctata, D. speciosa, D. longicornis, D. semipunctata, D.
  • insects from the order of Diptera for example Aedes spp. such as A. aegypti, A. albopictus, A. vexans; Anastrepha ludens, Anopheles spp. such as A. albimanus, A. crucians, A. freeborni, A. gambiae, A. leucosphyrus, A. maculipennis, A. minimus, A. quadrimaculatus, A. sinensis; Bac- trocera invadens, Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capi- tata, Chrysomyia spp. such as C.
  • Aedes spp. such as A. aegypti, A. albopictus, A. vexans
  • Anastrepha ludens Anopheles spp.
  • A. albimanus such as A.
  • insects from the order of Thysanoptera for example, Basothrips biformis, Dichromothrips cor- betti, Dichromothrips ssp., Echinothrips americanus, Enneothrips flavens, Frankliniella spp. such as F. fusca, F. occidentalis, F. tritici; Heliothrips spp., Hercinothrips femora/is, Kakothrips spp., Microcephalothrips abdominalis, Neohydatothrips samayunkur, Pezothrips kellyanus, Rhip- iphorothrips cruentatus, Scirtothrips spp.
  • T. imagi- nes such as S. citri, S. dorsalis, S. perseae
  • Stenchae- tothrips spp such as Taeniothrips cardamoni, Taeniothrips inconsequens, Thrips spp.
  • T. imagi- nes such as S. citri, S. dorsalis, S. perseae
  • Stenchae- tothrips spp such as Taeniothrips cardamoni, Taeniothrips inconsequens, Thrips spp.
  • T. imagi- nes such as S. citri, S. dorsalis, S. perseae
  • Stenchae- tothrips spp such as Taeniothrips cardamoni, Taeniothrips inconsequens, Thrips spp.
  • T. imagi- nes such as S. citri
  • insects from the order of Hemiptera for example, Acizzia jamatonica, Acrosternum spp. such as A. hilare; Acyrthosipon spp. such as A. onobrychis, A. pisum; Adelges laricis, Adelges tsu- gae, Adelphocoris spp., such as A. rapidus, A.
  • C hemipterus such as C hemipterus, C lectularius; Coccomytilus halli, Coccus spp. such as C hesperi- dum, C pseudomagnoliarum, Corythucha arcuata, Creontiades dilutus, Cryptomyzus ribis,
  • Euscelis bilobatus, Eu- schistus spp. such as E. heros, E. impictiventris, E. servus
  • Fiorinia theae Geococcus coffeae, Glycaspis brimblecombei, Halyomorpha spp. such as H. halys
  • Idiocerus spp. Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lecanoideus floccissimus, Lepidosaphes spp. such as L. ulmi; Leptocorisa spp., Lepto- glossus phyllopus, Lipaphis erysimi, Lygus spp. such as L. hesperus, L. lineolaris, L. pratensis; Maconellicoccus hirsutus, Marchalina hellenica, Macropes excavatus, Macrosiphum spp. such as M. rosae, M.
  • Nephotettix spp. such as N. malayanus, N. nigropictus, N. parvus, N. vires- cens; Nezara spp. such as N. viridula; Niiaparvata lugens, Nysius huttoni, Oebaius spp. such as O.
  • Oncometopia spp. Orthezia praelonga, Oxycaraenus hyalinipennis, Parabemisia myricae, Parlatoria spp., Parthenolecanium spp. such as P. corn/, P. persicae; Pemphigus spp. such as P. bursar/us, P. popu/ivenae; Peregrin us maidis, Perkinsiella saccharic/da, Phenaco- ccus spp. such as P. aceris, P.
  • Psylla spp. such as P. mali
  • Pteromalus spp. Pulvinaria amygdali, Pyrilla spp., Quadraspidiotus spp., such as Q. perniciosus
  • Quesada gigas Rastrococcus spp., Redu- vius senilis, Rhizoecus americanus, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosi- phum spp.
  • R. pseudobrassicas such as P. mali
  • Pteromalus spp. Pulvinaria amygdali, Pyrilla spp., Quadraspidiotus spp., such as Q. perniciosus
  • Quesada gigas Rastrococcus spp.
  • Redu- vius senilis Rhizoecus americanus
  • Rhodnius spp. Rhopalo
  • T. accerra, T. perditor Tibraca spp., Tomaspis spp., Toxoptera spp. such as T. aurantii; Trialeu- rodes spp. such as T. abutilonea, T. ricini, T. vaporariorum; Triatoma spp., Trioza spp., Typhlo- cyba spp., Unaspis spp. such as U. citri, U. yanonensis; and Viteus vitifolii,
  • Insects from the order Orthoptera for example Acheta domesticus, Calliptamus italicus, Chor- toicetes termini fera, Ceuthophilus spp., Diastrammena asynamora, Dociostaurus maroccanus, Gryllotalpa spp. such as G. africana, G. gryllotalpa; Gryllus spp., Hieroglyphus daganensis, Kraussaria angulifera, Locusta spp. such as L. migratoria, L. pardalina; Melanoplus spp. such as M. bivittatus, M. femurrubrum, M. mexicanus, M. sanguinipes, M.
  • Boophilus spp. such as B. annulatus, B. decoloratus, B. micro- plus, Dermacentor spp. such as D.silvarum, D. andersoni, D. variabilis, Hyalomma spp. such as H. truncatum, Ixodes spp. such as /. ricinus, I. rubicundus, I. scapularis, I. holocyclus, I. pacifi- cus, Rhipicephalus sanguineus, Ornithodorus spp. such as O. moubata, O. hermsi, O.
  • Aculus spp. such as A.
  • A. Dermata spp.
  • Colomerus vitis Epitrimerus pyri, Phyllocoptruta oleivora; Eriophytes ribis and Eriophyes spp.
  • Eriophyes sheldonr Family Tarsonemidae including Hemitarsonemus spp., Phytonemus pallidus and Polyphagotarsonemus latus, Steno- tarsonemus spp. Steneotarsonemus spinki, Family Tenuipalpidae including Brevipalpus spp. such as B.
  • Tetranych us spp. such as T. cinnabarinus, T. evansi, T. kan- zawai, T, pacificus, T. phaseulus, T. telarius and T. urticae; Bryobia praet/osa; Panonychus spp. such as P. ulmi, P. citri, Metatetranychus spp. and Oligonychus spp. such as 0. pratensis, O.
  • Pests from the Phylum Nematoda for example, plant parasitic nematodes such as root-knot nematodes, Meloidogyne spp. such as M. hapla, M. incognita, M. javanica; cyst-forming nematodes, Globodera spp. such as G. rostochiensis; Heterodera spp. such as H. avenae, H. glyci- nes, H. schachtii, H. trifolii; Seed gall nematodes, Anguina spp:, Stem and foliar nematodes,
  • Aphelenchoides spp. such as A. besseyi; Sting nematodes, Belonolaimus spp. such as B. longi- caudatus; Pine nematodes, Bursaphelenchus spp. such as B. lignicolus, B. xylophilus; Ring nematodes, Criconema spp., Criconemella spp. such as C. xenoplax and C. ornata; and, Crico- nemoides spp. such as Criconemoides in formis; Mesocriconema spp.; Stem and bulb nema- todes, Ditylenchus spp. such as £>.
  • Stunt nematodes Tylenchorhyn- chus spp. such as T. claytoni, T. dub/us
  • Citrus nematodes Tylenchulus spp. such as 7 ⁇ se/77/- penetrans
  • Dagger nematodes Xiphinema spp.
  • other plant parasitic nematode species Insects from the order Isoptera for example Calotermes flavicollis, Coptotermes spp. such as C. formosanus, C. gestroi, C. acinaciformis
  • Cornitermes cumulans Cry ptotermes spp. such as C. brevis, C.
  • Insects from the order Siphonoptera for example Cediopsylla simples, Ceratophyllus spp., Cte- nocephalides spp. such as C. felis, C. cam ' s, Xenopsylla cheopis, Pulex irritans, Trichodectes canis, Tunga penetrans, and Nosopsyllus fasciatus
  • Insects from the order Thysanura for example Lepisma saccharina, Ctenolepisma urbana, and Thermobia domestica
  • Pests from the class Chilopoda for example Geophilus spp., Scutigera spp.
  • Pests from the class Diplopoda for example Blaniulus guttulatus, Ju/us spp., Narceus spp.
  • Pests from the class Symphyla for example Scutigerella immaculata
  • Insects from the order Dermaptera for example Forficula auricularia
  • Insects from the order Collembola for example Onychiurus spp.
  • Onychiurus armatus Pests from the order Isopoda for example, Armadiiiidium vul- gare, Oniscus asellus, Porcellio scaber, Insects from the order Phthiraptera, for example Dama- linia spp., Pediculus spp.
  • Pediculus humanus capitis such as Pediculus humanus capitis, Pediculus humanus corporis, Pe- diculus humanus humanus; Pthirus pubis, Haematopinus spp. such as Haematopinus euryster- nus, Haematopinus suis; Linognathus spp.
  • Examples of further pest species which may be controlled by compounds of fomula (I) include: from the Phylum Mollusca, class Bivalvia, for example, Dre/ssena spp.; class Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea canaliclata, Succinea spp.; from the class of the helminths, for example, Ancy- lostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., As
  • Haemonchus contortus such as Haemonchus contortus; Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Op isth orchis spp., Onchocerca volvulus, Ostertagia spp., Paragonim us spp., Schistosomen spp., Strongyloides fuelleborni, Strongyloides stercora lis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti.
  • the present invention also relates to a mixture of at least one compound of the present invention with at least one mixing partner as defined herein after.
  • Preferred weight ratios for such binary mixtures are from 5000:1 to 1 :5000, preferably from 1000:1 to 1 :1000, more preferably from 100:1 to 1 :100, particularly preferably from 10:1 to 1 :10.
  • components I and II may be used in equal amounts, or an excess of component I, or an excess of component II may be used.
  • Mixing partners can be selected from pesticides, in particular insecticides, nematicides, and acaricides, fungicides, herbicides, plant growth regulators, fertilizers, and the like.
  • Preferred mixing partners are insecticides, nematicides and fungicides.
  • M.1 Acetylcholine esterase (AChE) inhibitors from the class of: M.1 A carbamates, for example aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofu- ran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC,
  • IRAC Insecticide Resistance Action Committee
  • GABA-gated chloride channel antagonists such as: M.2A cyclodiene organochlorine compounds, as for example endosulfan or chlordane; or M.2B fiproles (phenylpyrazoles), as for ex- ample ethiprole, fipronil, flufiprole, pyrafluprole and pyriprole;
  • M.3 Sodium channel modulators from the class of M.3A pyrethroids for example acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopent- enyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fen
  • M.6 Chloride channel activators from the class of avermectins and milbemycins, for example abamectin, emamectin benzoate, ivermectin, lepimectin or milbemectin;
  • M.7 Juvenile hormone mimics M.7A juvenile hormone analogues as hydroprene, kinoprene and methoprene; or others as M.7B fenoxycarb or M.7C pyriproxyfen;
  • M.8 miscellaneous non-specific (multi-site) inhibitors for example M.8A alkyl halides as methyl bromide and other alkyl halides, or M.8B chloropicrin, or M.8C sulfuryl fluoride, or M.8D borax, or M.8E tartar emetic;
  • M.9 Selective homopteran feeding blockers M.9B pymetrozine, or M.9C flonicamid;
  • M.10 Mite growth inhibitors M.10A clofentezine, hexythiazox and diflovidazin, or M.10B etoxa- zole;
  • M.1 1 Microbial disruptors of insect midgut membranes, for example bacillus thuringiensis or bacillus sphaericus, and the insecticdal proteins they produce such as bacillus thuringiensis subs p. israelensis, bacillus sphaericus, bacillus thuringiensis subs p. aizawai, bacillus thurin- giensis subsp. kurstakiand bacillus thuringiensis subsp. tenebrionis, or the Bt crop proteins: Cry-IAb, CrylAc, Cryl Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb and Cry34/35Ab1 ;
  • M.12 Inhibitors of mitochondrial ATP synthase M.12A diafenthiuron, or M.12B organotin miti- cides such as azocyclotin, cyhexatin or fenbutatin oxide, or M.12C propargite, or M.12D tetradi- fon;
  • chlorfenapyr DNOC or sulfluramid
  • Nicotinic acetylcholine receptor (nAChR) channel blockers for example nereistoxin ana- logues as bensultap, cartap hydrochloride, thiocyclam or thiosultap sodium;
  • benzoylureas as for example bistriflu- ron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novalu- ron, noviflumuron, teflubenzuron or triflumuron;
  • M.16 Inhibitors of the chitin biosynthesis type 1 as for example buprofezin;
  • Ecdyson receptor agonists such as diacylhydrazines, for example methoxyfenozide, tebufenozide, halofenozide, fufenozide or chromafenozide;
  • Octopamin receptor agonists as for example amitraz
  • M.20 Mitochondrial complex III electron transport inhibitors for example M.20A hydramethyl- non, or M.20B acequinocyl, or M.20C fluacrypyrim;
  • M.21 Mitochondrial complex I electron transport inhibitors for example M.21 A METI acaricides and insecticides such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad or tolfenpyrad, or M.21 B rotenone;
  • M.22 Voltage-dependent sodium channel blockers M.22A indoxacarb, or M.22B metaflumi- zone, or M.22B.1 : 2-[2-(4-Cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoro- methoxy)phenyl]-hydrazinecarboxamide or M.22B.2: N-(3-Chloro-2-methylphenyl)-2-[(4-chloro- phenyl)[4-[methyl(methylsulfonyl)amino]phenyl]methylene]-hydrazinecarboxamide;
  • M.23 Inhibitors of the of acetyl CoA carboxylase such as Tetronic and Tetramic acid derivatives, for example spirodiclofen, spiromesifen or spirotetramat;
  • M.24 Mitochondrial complex IV electron transport inhibitors for example M.24A phosphine such as aluminium phosphide, calcium phosphide, phosphine or zinc phosphide, or M.24B cyanide;
  • Mitochondrial complex II electron transport inhibitors such as beta-ketonitrile derivatives, for example cyenopyrafen or cyflumetofen;
  • M.28 Ryanodine receptor-modulators from the class of diamides: flubendiamide, chlorantranili- prole (rynaxypyr®), cyantraniliprole (cyazypyr®), tetraniliprole, or the phthalamide compounds M.28.1 : (R)-3-Chloro-N 1 - ⁇ 2-methyl-4-[1 ,2,2,2-tetrafluoro-1 -(trifluormethyl)ethyl]phenyl ⁇ -N2-(1 - methyl-2-methylsulfonylethyl)phthalamid and M.28.2: (S)-3-Chlor-N1 - ⁇ 2-methyl-4-[1 ,2,2,2-tetra- fluoro-1 -(trifluoromethyl)ethyl]phenyl ⁇ -N2-(1-methyl-2-methylsulfonylethyl)phthalamid, or the compound M.28.3: 3-bromo-N- ⁇ 2-bromo
  • M.29. insecticidal active compounds of unknown or uncertain mode of action as for example afidopyropen, afoxolaner, azadirachtin, amidoflumet, benzoximate, bifenazate, broflanilide, bro- mopropylate, chinomethionat, cryolite, dicloromezotiaz, dicofol, flufenerim, flometoquin, fluen- sulfone, fluhexafon, fluopyram, flupyradifurone, fluralaner, metoxadiazone, piperonyl butoxide, pyflubumide, pyridalyl, pyrifluquinazon, sulfoxaflor, tioxazafen, triflumezopyrim, or M.29.3: 1 1 -(4- chloro-2,6-dimethylphenyl)-12-hydroxy-1 ,4-dioxa-9-azad
  • M.29.10 5-[3-[2,6-dichloro-4-(3,3-di- chloroallyloxy)phenoxy]propoxy]-1 H-pyrazole; or a compound selected from M.29.1 1 , wherein the compound is selected from M.29.1 1 b) to M.29.1 1 p): M.29.1 1 .b) 3-(benzoylmethylamino)-N- [2-bromo-4-[1 ,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]-6-(trifluoromethyl)phenyl]-2-fluoro- benzamide; M.29.1 1 .c) 3-(benzoylmethylamino)-2-fluoro-N-[2-iodo-4-[1 ,2,2,2-tetrafluoro-1-(tri- fluoromethyl)ethyl]-6-(trifluoromethyl)phen
  • M.29.1 1.n) 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)pro- pyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; M.29.1 1 .o) 4-cyano-N-[2-cyano-5-[[2,6-di- chloro-4-[1 ,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]phenyl]-2-methyl-ben- zamide; M.29.1 1.p) N-[5-[[2-bromo-6-chloro-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]phe- nyl]carbamoyl]-2-cyano-phenyl]-4-cyan
  • M.29.12 selected from M.29.12a) to M.29.12m): M.29.12.a) 2-(1 ,3-Dioxan-2-yl)-6-[2-(3-pyridi- nyl)-5-thiazolyl]-pyridine; M.29.12.
  • M.29.14a 1 -[(6-Chloro-3-pyridinyl)methyl]-1 ,2,3,5,6,7-hexahydro-5-methoxy-7-methyl-8-nitro- imidazo[1 ,2-a]pyridine; or M.29.14b) 1-[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro- 1 ,2,3,5,6,7-hexahydroimidazo[1 ,2-a]pyridin-5-ol; or
  • M.29.16a 1 -isopropyl-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; or M.29.16b) 1- (1 ,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; M.29.16c) N,5- dimethyl-N-pyridazin-4-yl-1 -(2,2,2-trifluoro-1 -methyl-ethyl)pyrazole-4-carboxamide; M.29.16d) 1- [1 -(1 -cyanocyclopropyl)ethyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide;
  • M.29.16e N-ethyl-1-(2-fluoro-1-methyl-propyl)-5-methyl-N-pyridazin-4-yl-pyrazole-4-carbox- amide
  • M.29.16f 1 -(1 ,2-dimethylpropyl)-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide
  • M.29.16h N-methyl-1-(2-fluoro-1 -methyl-propyl]-5-methyl-N-pyridazin-4-yl-pyrazole-4- carboxamide
  • M.29.16i 1 -(4,4-difluorocyclohexyl)-N-ethyl-5-methyl
  • M.4 cycloxaprid is known from W010/069266 and W01 1/069456, M.4A.2, named as gua- dipyr, is known from W013/003977, and M.4A.3 (approved as paichongding in China) is known from WO07/101369.
  • M.22B.1 is described in CN10171577 and M.22B.2 in CN102126994.
  • Phthalamides M.28.1 and M.28.2 are known from WO07/101540.
  • M.28.3 is described in WO05/077934.
  • M.28.4 is described in WO07/043677.
  • M.28.5a) to M.28.5d) and M.28.5h) are described in WO07/006670, W013/024009 and W013/024010, ⁇ .28.5 ⁇ ) is described in
  • M.28.6 can be found in W012/034472.
  • M.29.3 is known from WO06/089633 and M.29.4 from WO08/06791 1.
  • M.29.5 is described in WO06/043635, and biological control agents on the basis of bacillus firmus are described in WO09/124707.
  • M.29.6a) to ⁇ .29.6 ⁇ ) listed under M.29.6 are described in W012/029672, and M.29.6j) and M.29.6k) in
  • M.29.8 is known from W013/055584.
  • M.29.9.a) is described in W013/050317.
  • M.29.9.b) is described in WO2014/126208.
  • M.29.10 is known from WO10/060379. Broflanilide and M.29.1 1. b) to M.29.1 1.h) are described in WO10/018714, and ⁇ .29.1 1 ⁇ ) to M.29.1 1 .p) in WO10/127926.
  • M.29.12.a) to M.29.12.c) are known from WO10/006713
  • M.29.12.d) and ⁇ .29.12. ⁇ ) are known from WO12/000896, and M.29.12. ⁇ ) to M.29.12.m) from WO10/129497.
  • M.29.14a) and M.29.14b) are known from WO07/101369.
  • M.29.16.a) to M.29.16h) are described in WO10/034737, WO12/084670, and W012/143317, respectively, and ⁇ .29.16 ⁇ ) and M.29.16j) are described in US 61/891437.
  • M.29.17a) to M.29.17J) are described in WO15/038503.
  • M.29.18a) to M.29.18d) are described in US2014/0213448.
  • M.29.19 is described in WO14/036056.
  • M.29.20 is known from WO14/090918.
  • Inhibitors of complex III at Q 0 site e. g. strobilurins: azoxystrobin (A.1 .1 ), coumethoxy- strobin (A.1 .2), coumoxystrobin (A.1.3), dimoxystrobin (A.1.4), enestroburin (A.1.5), fenamin- strobin (A.1.6), fenoxystrobin/flufenoxystrobin (A.1 .7), fluoxastrobin (A.1 .8), kresoxim-methyl (A.1 .9), mandestrobin (A.1 .10), metominostrobin (A.1 .1 1 ), orysastrobin (A.1 .12), picoxy.strobin (A.1 .13), pyraclostrobin (A.1.14), pyrametostrobin (A.1.15), pyraoxystrobin (A.1.16), trifloxystro- bin (A.1.1
  • inhibitors of complex III at Qi site cyazofamid (A.2.1 ), amisulbrom (A.2.2), [(3S,6S,7R,8R)- 8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan- 7-yl] 2-methylpropanoate (A.2.3), [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy- pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate (A.2.4), [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine-2-carbony
  • inhibitors of complex II e. g. carboxamides: benodanil (A.3.1 ), benzovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.1 1 ), isopyrazam (A.3.12), me- pronil (A.3.13), oxycarboxin (A.3.14), penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), tecloftalam (A.3.17), thifluzamide (A.3.18), N-(4'-trifluoromethylthiobiphenyl-2-yl)- 3-difluoromethyl-1-methyl-1 H-pyrazole
  • respiration inhibitors e. g. complex I, uncouplers: diflumetorim (A.4.1 ), (5,8-difluoro- quinazolin-4-yl)- ⁇ 2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl ⁇ -amine (A.4.2); ni- trophenyl derivates: binapacryl (A.4.3), dinobuton (A.4.4), dinocap (A.4.5), fluazinam (A.4.6); ferimzone (A.4.7); organometal compounds: fentin salts, such as fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.1 1 ); and silthiofam (A.4.12); B) Sterol biosynthesis inhibitors (SBI fungicides)
  • SBI fungicides Sterol bio
  • C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole (B.1 .1 ), bitertanol (B.1 .2), bromuconazole (B.1 .3), cyproconazole (B.1 .4), difenoconazole (B.1.5), diniconazole (B.1 .6), diniconazole-M (B.1 .7), epoxiconazole (B.1 .8), fenbuconazole (B.1.9), fluquinconazole (B.1 .10), flusilazole (B.1.1 1 ), flutriafol (B.1.12), hexaconazole (B.1.13), imibenconazole (B.1 .14), ipconazole (B.1.15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B
  • Delta 14-reductase inhibitors aldimorph (B.2.1 ), dodemorph (B.2.2), dodemorph-acetate (B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7), spirox- amine (B.2.8); Inhibitors of 3-keto reductase: fenhexamid (B.3.1 );
  • phenylamides or acyl amino acid fungicides benalaxyl (C.1 .1 ), benalaxyl-M (C.1.2), kiral- axyl (C.1.3), metalaxyl (C.1 .4), metalaxyl-M (mefenoxam, C.1 .5), ofurace (C.1.6), oxadixyl (C.1.7);
  • hymexazole C.2.1
  • octhilinone C.2.2
  • oxolinic acid C.2.3
  • bupirimate C.2.4
  • 5-fluorocytosine C.2.5
  • 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine C.2.6
  • 5-fluoro-2-(4- fluorophenylmethoxy)pyrimidin-4-amine C.2.7
  • tubulin inhibitors such as benzimidazoles, thiophanates: benomyl (D1.1 ), carbendazim (D1.2), fuberidazole (D1.3), thiabendazole (D1.4), thiophanate-methyl (D1 .5); triazolopyrim- idines: 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimi- dine (D1 .6);
  • diethofencarb (D2.1 ), ethaboxam (D2.2), pencycuron (D2.3), fluopicolide (D2.4), zoxamide (D2.5), metrafenone (D2.6), pyriofenone (D2.7);
  • methionine synthesis inhibitors anilino-pyrimidines: cyprodinil (E.1 .1 ), mepanipyrim (E.1 .2), pyrimethanil (E.1.3);
  • blasticidin-S (E.2.1 ), kasugamycin (E.2.2), kasugamycin hy- drochloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6), polyoxine (E.2.7), validamycin A (E.2.8);
  • MAP / histidine kinase inhibitors fluoroimid (F.1 .1 ), iprodione (F.1 .2), procymidone (F.1.3), vinclozolin (F.1 .4), fenpiclonil (F.1.5), fludioxonil (F.1.6);
  • quinoxyfen F.2.1 ;
  • Phospholipid biosynthesis inhibitors edifenphos (G.1 .1 ), iprobenfos (G.1 .2), pyrazophos (G.1 .3), isoprothiolane (G.1 .4);
  • lipid peroxidation dicloran (G.2.1 ), quintozene (G.2.2), tecnazene (G.2.3), tolclofos-methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), etridiazole (G.2.7);
  • phospholipid biosynthesis and cell wall deposition dimethomorph (G.3.1 ), flumorph (G.3.2), mandipropamid (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7) and N-(1-(1-(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4- fluorophenyl) ester (G.3.8);
  • inorganic active substances Bordeaux mixture (H.1.1 ), copper acetate (H.1.2), copper hydroxide (H.1.3), copper oxychloride (H.1 .4), basic copper sulfate (H.1 .5), sulfur (H.1.6);
  • thio- and dithiocarbamates ferbam (H.2.1 ), mancozeb (H.2.2), maneb (H.2.3), metam (H.2.4), metiram (H.2.5), propineb (H.2.6), thiram (H.2.7), zineb (H.2.8), ziram (H.2.9); organochlorine compounds (e. g.
  • phthalimides, sulfamides, chloronitriles anilazine (H.3.1 ), chlorothalonil (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.1 1 ), N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl- benzenesulfonamide (H.3.12);
  • guanidines and others guanidine (H.4.1 ), dodine (H.4.2), dodine free base (H.4.3), guazatine (H.4.4), guazatine-acetate (H.4.5), iminoctadine (H.4.6), iminoctadine-tri acetate (H.4.7), iminoctadine-tris(albesilate) (H.4.8), dithianon (H.4.9), 2,6-dimethyl-1 H,5H-[1 ,4]di- thiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone (H.4.10);
  • inhibitors of glucan synthesis validamycin (1.1.1 ), polyoxin B (1.1 .2);
  • melanin synthesis inhibitors pyroquilon (1.2.1 ), tricyclazole (I.2.2), carpropamid (1.2.3), di- cyclomet (I.2.4), fenoxanil (I.2.5);
  • bronopol K.1 .1
  • chinomethionat K.1.2
  • cyflufenamid K.1.3
  • cymoxanil K.1.4
  • dazomet K.1 .5
  • debacarb K.1.6
  • diclomezine K.1.7
  • difenzoquat K.1.8
  • difenzoquat-methylsulfate K.1 .9
  • diphenylamin K.1.10
  • fenpyrazamine K.1 .1 1
  • flumetover K.1 .12
  • flusulfamide K.1 .13
  • flutianil K.1 .14
  • methasulfocarb K.1.15), nitrapyrin (K.1.16), nitrothal-isopropyl (K.1 .18), oxathiapiprolin (K.1.19), tolprocarb (K.1 .20), oxin-copper (K.1.2
  • fungicides described by common names, their preparation and their activity e.g. against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available.
  • Suitable mixing partners for the compounds of the present invention also include biopesticides.
  • Biopesticides have been defined as a form of pesticides based on micro-organisms (bacteria, fungi, viruses, nematodes, etc.) or natural products (compounds, such as metabolites, proteins, or extracts from biological or other natural sources) (U.S. Environmental Protection Agency: http://www.epa.gov/pesticides/biopesticides/). Biopesticides fall into two major classes, microbial and biochemical pesticides:
  • Microbial pesticides consist of bacteria, fungi or viruses (and often include the metabolites that bacteria and fungi produce). Entomopathogenic nematodes are also classified as microbial pesticides, even though they are multi-cellular.
  • Biochemical pesticides are naturally occurring substances or or structurally-similar and functionally identical to a naturally-occurring substance and extracts from biological sources that control pests or provide other crop protection uses as defined below, but have non-toxic mode of actions (such as growth or developmental regulation, attractents, repellents or defence activators (e.g. induced resistance) and are relatively non-toxic to mammals.
  • Biopesticides for use against crop diseases have already established themselves on a variety of crops. For example, biopesticides already play an important role in controlling downy mildew diseases. Their benefits include: a 0-Day Pre-Harvest Interval, the ability to use under moderate to severe disease pressure, and the ability to use in mixture or in a rotational program with other registered pesticides.
  • Biopesticidal seed treatments are e.g. used to control soil borne fungal pathogens that cause seed rots, damping-off, root rot and seedling blights. They can also be used to control internal seed borne fungal pathogens as well as fungal pathogens that are on the surface of the seed.
  • Many biopesticidal products also show capacities to stimulate plant host defenses and other physiological processes that can make treated crops more resistant to a variety of biotic and abiotic stresses or can regulate plant growth. Many biopesticidal products also show capacities to stimulate plant health, plant growth and/or yield enhancing activity.
  • the invention also relates to agrochemical compositions comprising an auxiliary and at least one compound of the present invention or a mixture thereof.
  • An agrochemical composition comprises a pesticidally effective amount of a compound of the present invention or a mixture thereof.
  • the term "pesticidally effective amount” is defined below.
  • the compounds of the present invention or the mixtures thereof can be converted into customary types of agro-chemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g.
  • compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Mono- graph No. 2, 6th Ed. May 2008, CropLife International.
  • compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfac- tants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifi- ers and binders.
  • suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfac- tants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifi- ers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil frac- tions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclo-'hexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g.
  • mineral oil frac- tions of medium to high boiling point e.g. kerosene, diesel oil
  • oils of vegetable or animal origin oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e. g. toluene, paraffin, tetrahydrona
  • lactates carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
  • Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • mineral earths e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
  • polysaccharide powders e.g. cellulose, starch
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective col- loid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sul- fates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylaryl-sul- fonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkyhnaphthalenes, sulfosucci nates or sulfosuccinamates.
  • Examples of sul- fates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethox-ylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Exam-pies of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol eth-oxylates.
  • Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpoly- glucosides.
  • polymeric surfactants are homo- or copolymers of vinylpyrrolidone, vi- nylalcohols, or vinylacetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of poly- acrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyeth- yleneamines.
  • Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compounds of the present invention on the target.
  • examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazoli- nones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants are pigments of low water solubility and water- soluble dyes.
  • examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
  • composition types and their preparation are:
  • a compound I according to the invention 10-60 wt% of a compound I according to the invention and 5-15 wt% wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) up to 100 wt%.
  • the active substance dissolves upon dilution with water.
  • a compound I according to the invention 5-25 wt% of a compound I according to the invention and 1-10 wt% dispersant (e. g. polyvi- nylpyrrolidone) are dissolved in up to 100 wt% organic solvent (e.g. cyclohexanone). Dilution with water gives a dispersion.
  • dispersant e. g. polyvi- nylpyrrolidone
  • emulsifiers e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • water-insol- uble organic solvent e.g. aromatic hydrocarbon
  • Emulsions (EW, EO, ES)
  • emulsifiers e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • 20-40 wt% water-insoluble organic solvent e.g. aromatic hydrocarbon
  • a compound I according to the invention 20-60 wt% of a compound I according to the invention are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alco- hoi ethoxylate), 0,1 -2 wt% thickener (e.g. xanthan gum) and up to 100 wt% water to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alco- hoi ethoxylate
  • 0,1 -2 wt% thickener e.g. xanthan gum
  • up to 100 wt% water 100 wt% water
  • Dilution with water gives a stable suspension of the active substance.
  • binder e.g. polyvinylalcohol
  • 50-80 wt% of a compound I according to the invention are ground finely with addition of up to 100 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alcohol ethoxylate
  • wt% of a compound I according to the invention are ground in a rotor-stator mill with addition of 1-5 wt% dispersants (e.g. sodium lignosulfonate), 1 -3 wt% wetting agents (e.g. alcohol ethoxylate) and up to 100 wt% solid carrier, e.g. silica gel. Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants e.g. sodium lignosulfonate
  • 1 -3 wt% wetting agents e.g. alcohol ethoxylate
  • solid carrier e.g. silica gel
  • a compound I according to the invention In an agitated ball mill, 5-25 wt% of a compound I according to the invention are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1 -5 wt% thickener (e.g. car- boxymethylcellulose) and up to 100 wt% water to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
  • dispersants e.g. sodium lignosulfonate
  • 1 -5 wt% thickener e.g. car- boxymethylcellulose
  • 5-20 wt% of a compound I according to the invention are added to 5-30 wt% organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alko- hol ethoxylate and arylphenol ethoxylate), and water up to 100 %.
  • organic solvent blend e.g. fatty acid dimethylamide and cyclohexanone
  • surfactant blend e.g. alko- hol ethoxylate and arylphenol ethoxylate
  • An oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g. methyl- methacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radi-cal initiator results in the formation of poly(meth)acrylate microcapsules.
  • an oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insolu-ble organic solvent (e.g.
  • an isocyanate monomer e.g. diphenylme-thene-4,4'- diisocyanatae
  • a protective colloid e.g. polyvinyl alco- hoi
  • the addition of a polyamine results in the for-mation of a pol- yurea microcapsule.
  • the monomers amount to 1-10 wt%. The wt% relate to the total CS composition.
  • Dustable powders (DP, DS)
  • 1-10 wt% of a compound I according to the invention are ground finely and mixed intimately with up to 100 wt% solid carrier, e.g. finely divided kaolin.
  • 0.5-30 wt% of a compound I according to the invention is ground finely and associated with up to 100 wt% solid carrier (e.g. silicate). Granulation is achieved by extrusion, spray-drying or the fluidized bed.
  • solid carrier e.g. silicate
  • 1-50 wt% of a compound I according to the invention are dissolved in up to 100 wt% organic solvent, e.g. aromatic hydrocarbon.
  • organic solvent e.g. aromatic hydrocarbon.
  • compositions types i) to xi) may optionally comprise further auxiliaries, such as 0.1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1 -1 wt% anti-foaming agents, and 0.1 -1 wt% col- orants.
  • auxiliaries such as 0.1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1 -1 wt% anti-foaming agents, and 0.1 -1 wt% col- orants.
  • the agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active sub-stance.
  • the active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides may be added to the active substances or the compositions cormprising them as premix or, if appropriate not until immediately prior to use (tank mix).
  • pesticides e.g. herbicides, insecticides, fungicides, growth regulators, safeners
  • These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1 .
  • the user applies the composition according to the invention usually from a predosage de-vice, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained.
  • 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
  • composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
  • either individual components of the composition according to the invention or partially premixed components may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.
  • either individual components of the composition according to the invention or partially premixed components, e. g. components comprising compounds of the present invention and/or mixing partners as defined above, can be applied jointly (e.g. after tank mix) or consecutively.
  • the compounds of the present invention are suitable for use in treating or protecting animals against infestation or infection by parasites. Therefore, the present invention also relates to the use of a compound of the present invention for the manufacture of a medicament for the treatment or protection of animals against infestation or infection by parasites.
  • the present invention relates to a method of treating or protecting animals against infestation and infec- tion by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a compound of the present invention.
  • the present invention also relates to the non-therapeutic use of compounds of the present invention for treating or protecting animals against infestation and infection by parasites. Moreover, the present invention relates to a non-therapeutic method of treating or protecting animals against infestation and infection by parasites, which comprises applying to a locus a parasiticidally effective amount of a compound of the present invention.
  • the compounds of the present invention are further suitable for use in combating or controlling parasites in and on animals. Furthermore, the present invention relates to a method of combating or controlling parasites in and on animals, which comprises contacting the parasites with a parasitically effective amount of a compound of the present invention.
  • the present invention also relates to the non-therapeutic use of compounds of the present invention for controlling or combating parasites. Moreover, the present invention relates to a non- therapeutic method of combating or controlling parasites, which comprises applying to a locus a parasiticidally effective amount of a compound of the present invention.
  • the compounds of the present invention can be effective through both contact (via soil, glass, wall, bed net, carpet, blankets or animal parts) and ingestion (e.g. baits). Furthermore, the compounds of the present invention can be applied to any and all developmental stages.
  • the compounds of the present invention can be applied as such or in form of compositions comprising the compounds of the present invention.
  • the compounds of the present invention can also be applied together with a mixing partner, which acts against pathogenic parasites, e.g. with synthetic coccidiosis compounds, poly- etherantibiotics such as Amprolium, Robenidin, Toltrazuril, Monensin, Salinomycin, Madurami- cin, Lasalocid, Narasin or Semduramicin, or with other mixing partners as defined above, or in form of compositions comprising said mixtures.
  • the compounds of the present invention and compositions comprising them can be applied orally, parenterally or topically, e.g. dermally.
  • the compounds of the present invention can be systemically or non-systemically effective.
  • the application can be carried out prophylactically, therapeutically or non-therapeutically. Fur- thermore, the application can be carried out preventively to places at which occurrence of the parasites is expected.
  • the term "contacting" includes both direct contact (applying the compounds/compositions directly on the parasite, including the application directly on the animal or excluding the application directly on the animal, e.g. at it's locus for the latter) and indirect con- tact (applying the compounds/compositions to the locus of the parasite).
  • the contact of the parasite through application to its locus is an example of a non-therapeutic use of the compounds of the present invention.
  • locus means the habitat, food supply, breeding ground, area, material or environment in which a parasite is growing or may grow outside of the animal.
  • parasites includes endo- and ectoparasites. In some embodiments of the present invention, endoparasites can be preferred. In other embodiments, ectoparasites can be preferred. Infestations in warm-blooded animals and fish include, but are not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chig- gers, gnats, mosquitoes and fleas.
  • the compounds of the present invention are especially useful for combating parasites of the following orders and species, respectively:
  • fleas e.g. Ctenocephalides felis, Ctenocephalides cam ' s, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus
  • cockroaches e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Peri- planeta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis
  • flies mosquitoes (Diptera), e.g.
  • Pediculus humanus capitis Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bo vis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus; ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g.
  • Haematopinus spp. Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp.
  • Mallophagida suborders Arnblycerina and Ischnocerina
  • Trimenopon spp. Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Trichodectes spp., and Felicola spp.
  • Roundworms Nematoda Wipeworms and Trichinosis (Trichosyringida), e.g.
  • Trichinellidae Trichinella spp.
  • Rhabditida e.g. Rhabditis spp., Strongyloides spp., Helicephalobus spp.
  • Strongylida e.g. Strongylus spp., Ancylostoma spp., Necator americanus, Bunostomum spp.
  • Ascaris lumbricoides Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi; Camallanida, e.g. Dracunculus medinensis (guinea worm); Spirurida, e.g. Thelazia spp., Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp.
  • Faciola spp. Fascioloides magna, Paragonimus spp., Dicrocoelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilharzia spp., Alaria alata, Paragonimus spp., and Nanocyetes spp:, Cercomeromorpha, in particular Cestoda (Tape- worms), e.g.
  • Diphyllobothrium spp. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium caninum, Multi- ceps spp., Hymenolepis spp., Mesocestoides spp., Vampirolepis spp., Moniezia spp., Anoplo- cephala spp., Sirometra spp., Anoplocephala spp., and Hymenolepis spp..
  • animal includes warm-blooded animals (including humans) and fish.
  • mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rab- bits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur- bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels.
  • domestic animals such as dogs or cats.
  • parasiticidally effective amount means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism.
  • the parasiticidally effective amount can vary for the various compounds/compositions used in the invention.
  • a parasiticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired parasiticidal effect and duration, target species, mode of application, and the like.
  • the compounds of the present invention in total amounts of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50 mg/kg per day.
  • the formula I compounds may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules.
  • the formula I compounds may be administered to the animals in their drinking water.
  • the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula I compound, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
  • the formula I compounds may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection.
  • the formula I compounds may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection.
  • the formula I compounds may be formulated into an implant for subcutaneous administration.
  • the formula I compound may be transdermally administered to animals.
  • the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula I compound.
  • the formula I compounds may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or water-in-oil emulsions.
  • dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the formula I compound.
  • the formula I compounds may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.
  • Suitable preparations are:
  • Solutions such as oral solutions, concentrates for oral administration after dilution, solutions for use on the skin or in body cavities, pouring-on formulations, gels;
  • Solid preparations such as powders, premixes or concentrates, granules, pellets, tablets, boluses, capsules; aerosols and inhalants, and active compound-containing shaped articles.
  • compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and optionally adding further auxiliaries such as acids, bases, buffer salts, preserva- tives, and solubilizers.
  • auxiliaries for injection solutions are known in the art. The solutions are filtered and filled sterile.
  • Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the use concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being nec- essary.
  • Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on.
  • Solutions for use on the skin are prepared according to the state of the art and according to what is described above for injection solutions, sterile procedures not being necessary. Gels are applied to or spread on the skin or introduced into body cavities. Gels are prepared by treating solutions which have been prepared as described in the case of the injection solutions with sufficient thickener that a clear material having an ointment-like consistency results. Suitable thickeners are known in the art.
  • Pour-on formulations are poured or sprayed onto limited areas of the skin, the active compound penetrating the skin and acting systemically.
  • Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in suitable skin-compatible solvents or solvent mixtures.
  • suitable skin-compatible solvents or solvent mixtures If appropriate, other auxiliaries such as colorants, bioabsorption-promoting substances, antioxidants, light stabilizers, adhesives are added. Suitable such auxiliaries are known in the art.
  • Emulsions can be administered orally, dermally or as injections.
  • Emulsions are either of the water-in-oil type or of the oil-in-water type. They are prepared by dissolving the active compound either in the hydrophobic or in the hydrophilic phase and homogenizing this with the solvent of the other phase with the aid of suitable emulsifiers and, if appropriate, other auxiliaries such as colorants, absorption-promoting substances, preservatives, antioxidants, light stabilizers, viscosity-enhancing substances.
  • suitable hydrophobic phases (oils), suitable hydrophilic phases, suitable emulsifiers, and suitable further auxiliaries for emulsions are known in the art.
  • Suspensions can be administered orally or topically/dermally. They are prepared by suspending the active compound in a suspending agent, if appropriate with addition of other auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxidants, light stabilizers. Suitable suspending agents, and suitable other auxiliaries for suspensions including wetting agents are known in the art.
  • Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions described above only by their higher viscosity.
  • the active compound is mixed with suitable excipi- ents, if appropriate with addition of auxiliaries, and brought into the desired form.
  • auxiliaries for this purpose are known in the art.
  • compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the compound of the present invention.
  • Ready-to-use preparations contain the compounds acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80 per cent by weight, preferably from 0.1 to 65 per cent by weight, more preferably from 1 to 50 per cent by weight, most preferably from 5 to 40 per cent by weight.
  • Preparations which are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 per cent by weight, preferably of 1 to 50 per cent by weight.
  • the preparations comprise the compounds of formula I against endoparasites in concentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to 0.9 per cent by weight, very particularly preferably of 0.005 to 0.25 per cent by weight.
  • Topical application may be conducted with compound-containing shaped articles such as col- lars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.
  • compound-containing shaped articles such as col- lars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.
  • solid formulations which release compounds of the present invention in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks.
  • HPLC MS high performance liquid chromatography-coupled mass spectrometry
  • HPLC method Phenomenex Kinetex 1.7 ⁇ XB-C18 100A; 50 x 2.1 mm; mobile phase: A: water + 0.1 % trifluoroacetic acid (TFA); B: acetonitrile; gradient: 5-100% B in 1 .50 minutes; 100% B 0.25 min; flow: 0.8-1.Oml/min in 1.51 minutes at 60°C.
  • MS ESI positive, m/z 100-700.
  • the protocol for the synthesis of starting material 1 -methyl-3-(pentafluoroethyl)-4-(trifluorome- thyl)-5-fluoropyrazole (CAS 104315-28-8) is known from WO 2016/026789.
  • Step 1 Synthesis of tert-butyl 5-bromospiro[1 H-isobenzofuran-3,3'-azetidine]-1 '-carboxylate
  • a solution of isopropyl magnesium chloride-lithium chloride complex 90.9 mL of a 1.3 M solution in THF, 1 18.1 mmol
  • Step 2 Synthesis of tert-butyl 5-aminospiro[1 H-isobenzofuran-3,3'-azetidine]-1 '-carboxylate
  • a three necked flask was charged with a solution of the carboxylate from Step 1 (2.00 g, 5.88 mmol), benzophenone imine (1.278 g, 7.054 mmol) and NaOtBu (695 mg, 7.23 mmol) in tolu- ene (50 mL) under argon.
  • BINAP 366 mg, 588 mmol
  • Pd2(dba)3 were dissolved in toluene (15 mL) under argon.
  • Step 3 Synthesis of tert-butyl 5-[[2-methyl-5-(1 ,1 ,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)py- razole-3-carbonyl]amino]spiro[1 H-isobenzofuran-3,3'-azetidine]-1 '-carboxylate
  • Step 4 Synthesis of 2-methyl-5-(1 ,1 ,2,2,2-pentafluoroethyl)-N-spiro[1 H-isobenzofuran-3,3'- azetidin-1-ium]-5-yl-4-(trifluoromethyl)pyrazole-3-carboxamide trifluoroacetate
  • Step 5 Synthesis of 2-methyl-N-[1 '-(2-methylsulfonylacetyl)spiro[1 H-isobenzofuran-3,3'-azet- idine]-5-yl]-5-(1 ,1 ,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-carboxamide
  • Example 2 Synthesis of 1-[5-[1 -[2-methyl-5-(1 , 1 ,2,2, 2-pentafluoroethyl)-4-(trifluoromethyl)pyra- zol-3-yl]pyrazol-4-yl]spiro[1 H-isobenzofuran-3,3'-azetidine]-1 '-yl]propan-1-one (Compound I-2- 1 )-
  • Step 1 Synthesis of tert-butyl 5-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)spiro[1 H-isoben- zofuran-3,3'-azetidine]-1 '-carboxylate
  • Step 2 Synthesis of 5-(4-bromopyrazol-1-yl)-1 -methyl-3-(1 ,1 ,2,2,2-pentafluoroethyl)-4-(trifluo- romethyl)pyrazole
  • Step 3 Synthesis of tert-butyl 5-[1-[2-methyl-5-(1 ,1 ,2,2,2-pentafluoroethyl)-4-(trifluorome- thyl)pyrazol-3-yl]pyrazol-4-yl]spiro[1 H-isobenzofuran-3,3'-azetidine]-1 '-carboxylate
  • Step 4 Synthesis of 5-[1-[2-methyl-5-(1 ,1 ,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazol-3- yl]pyrazol-4-yl]spiro[1 H-isobenzofuran-3,3'-azetidin-1 -ium] trifluoroacetate
  • Step 5 Synthesis of 1 -[5-[1 -[2-methyl-5-(1 ,1 ,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazol- 3-yl]pyrazol-4-yl]spiro[1 H-isobenzofuran-3,3'-azetidine]-1 '-yl]propan-1 -one
  • the active compound was dissolved at the desired concentration in a mixture of 1 :1 (vohvol) distilled water : aceteone.
  • Surfactant Karl HV was added at a rate of 0.01 % (vol/vol).
  • the test solution was prepared at the day of use.
  • Leaves of cabbage were dipped in test solution and air-dried. Treated leaves were placed in petri dishes lined with moist filter paper and inoculated with ten 3rd instar larvae. Mortality was recorded 72 hours after treatment. Feeding damages were also recorded using a scale of 0- 100%.
  • the compounds 1-2-1 , I-2-2, 1-1 -3, I-2-3, I-2-4, I-2-5, and I-2-7, resp., at 300 ppm showed a mortality of at least 75% in comparison with untreated controls.
  • test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial mem brane.
  • the compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were pipetted into the aphid diet, using a custom built pipetter, at two replications.
  • aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at about 23 + 1 °C and about 50 + 5 % relative humidity for 3 days. Aphid mortality and fecundity was then visually assessed.
  • the compounds 1-1 -1 , 1-2-1 , 1-1 -2, I-2-2, 1-1-3, I-2-3, 1-1-4, I-2-4, 1-1 -5, I-2-5, 1-1-6, I-2-6, 1-1 -7, and I-2-7, resp., at 2500 ppm showed a mortality of at least 75% in comparison with untreated controls.
  • test unit For evaluating control of vetch aphid (Megoura viciae) through contact or systemic means the test unit consisted of 24-well-microtiter plates containing broad bean leaf disks. The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the leaf disks at 2.5 ⁇ , using a custom built micro atomizer, at two replications.
  • the leaf disks were air-dried and 5 - 8 adult aphids placed on the leaf disks inside the microtiter plate wells. The aphids were then allowed to suck on the treated leaf disks and incubated at about 23 + 1 °C and about 50 + 5 % relative humidity for 5 days. Aphid mortality and fecundity was then visually assessed.
  • the compounds 1-1 -1 , 1-2-1 , 1-1 -2, I-2-2, 1-1-3, I-2-3, 1-1-4, I-2-4, 1-1 -5, I-2-5, 1-1-6, I-2-6, 1-1 -7, and I-2-7, resp., at 2500 ppm showed a mortality of at least 75% in comparison with untreated controls.
  • test unit For evaluating control of tobacco budworm (Heliothis virescens) the test unit consisted of 96- well-microtiter plates containing an insect diet and 15-25 H. virescens eggs.
  • the compounds were formulated using a solution containing 75% v/v water and 25% v/v
  • microtiter plates were incubated at about 28 + 1 °C and about 80 + 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed.
  • test unit consisted of 96-well- microtiter plates containing an insect diet and 5-10 A. grandis eggs.
  • the compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 5 ⁇ , using a custom built micro atomizer, at two replications.
  • microtiter plates were incubated at about 25 + 1 °C and about 75 + 5 % rela- tive humidity for 5 days. Egg and larval mortality was then visually assessed.
  • Dichromothrips corbetti adults used for bioassay were obtained from a colony maintained continuously under laboratory conditions.
  • the test compound is diluted in a 1 :1 mixture of acetone:water (vohvol), plus Kinetic HV at a rate of 0.01 % v/v.
  • Thrips potency of each compound was evaluated by using a floral-immersion technique. All petals of individual, intact orchid flowers were dipped into treatment solution and allowed to dry in Petri dishes. Treated petals were placed into individual resealable plastic along with about 20 adult thrips. All test arenas were held under continuous light and a temperature of about 28°C for duration of the assay. After 3 days, the numbers of live thrips were counted on each petal. The percent mortality was recorded 72 hours after treatment. In this test, the compounds 1-2-1 , 1-1-2, I-2-2, 1-1 -3, I-2-3, I-2-4, I-2-5, I-2-6, and I-2-7, resp., at 300 ppm showed a mortality of at least 75% in comparison with untreated controls.
  • Rice seedlings were cleaned and washed 24 hours before spraying.
  • the active compounds were formulated in 1 :1 acetone:water (vohvol), and 0.01 % vol/vol surfactant (Kinetic HV) was added.
  • Potted rice seedlings were sprayed with 5-6 ml test solution, air dried, covered with Mylar cages cages and inoculated with 10 adults.
  • Treated rice plants were kept at about 28-29°C and relative humidity of about 50-60%. Percent mortality was recorded after 72 hours.
  • the compound I-2-3 at 300 ppm showed a mortality of at least 75% in comparison with untreated controls.
  • the active compound was dissolved at the desired concentration in a mixture of 1 :1 (vohvol) distilled water : acetone. Add surfactant (Kinetic HV) was added at a rate of 0.01 % (vol/vol). The test solution was prepared at the day of use.
  • Potted cowpea beans of 4-5 days of age were cleaned with tap water and sprayed with 1-2 ml of the test solution using air driven hand atomizer.
  • the treated plants were allowed to air dry and afterwards inoculated with 30 or more mites by clipping a cassava leaf section from rearing population.
  • Treated plants were placed inside a holding room at about 25-27°C and about 50- 60% relative humidity. Percent mortality was assessed 72 hours after treatment.

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Abstract

The present invention relates to novel spiro compounds of formula I, wherein the variables have the meanings as defined in the specification, to compositions comprising them, to active compound combinations comprising them, and to their use for protecting growing plants from attack or infestation by invertebrate pests, furthermore, to seed comprising such compounds.

Description

Spirocyclic derivatives
Description
The present invention relates to spirocyclic compounds of formula I
Figure imgf000002_0001
wherein
R11 is hydrogen, Ci-C6-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C6-halogenalkyl, C3-C6-cycloal- kyl, or C3-C6-halogencycycloalkyl;
R12, R13 independently from each other are halogen, cyano, NO2, Ci-C6-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C6-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycycloalkyl, Ci-C6-alk- oxy, Ci-C6-halogenalkoxy, S(0)n-Ci-C6-alkyl, S(0)n-Ci-C6-halogenalkyl;
n is 0, 1 , or 2;
is a group Wa, or Wb;
Figure imgf000002_0002
wherein
G1 , G2, G3 are independently from each other CRa, or N; wherein
Ra is halogen, OH, SH, NO2, cyano, isocyano, isothiocyanato, Ci-C6-alkyl, C3-C6-cyclo- alkyl, C2-C4-alkenyl, C3-C6-cycloalkenyl, C2-C4-alkynyl, Ci-C6-alkoxy, C2-C4-alkenyl- oxy, C2-C4-alkynyloxy, C3-C6-cycloalkoxy, C3-C6-cycloalkenyloxy, S(0)n-Ci-C6-alkyl, cycloalkylthio, C2-C4-alkenylthio, C3-C6-cycloalkenylthio, C2-C4-alkinylthio, C(0)NH2, SF5, S02-N(R33)R35, N(R33)R35, C(0)R35, C(0)OR35, N(R33)C(0)-Ci-C4-alkyl, alkyl- phosphinyl, alkylphosphonyl, C(0)N(R33)R35, phenyl, heterocyclyl, phenoxy, benzyl, benzyloxy, benzylthio, phenyl ylamino, benzylamino, and Si(CrC4-alkyl)3;
Figure imgf000002_0003
wherein
T is O or S;
R2 is H, Ci-C6-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C3-C7-cycloalkyl, or Ci-C6-alkylcar- bonyl, phenyl-Ci-C4-alkyl, hetaryl-Ci-C4-alkyl; and
# is the bond to pyrazole, and
§ is the bond to phenyl;
Z is O, or S(0)n;
R3 is selected from H, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6- alkynyl, C2-C6-haloalkynyl which aliphatic groups are unsubstituted or substituted by one or more radicals R31 ; C3-C6-cycloalkyl, C3-C6-halocycloalkyl which cyclic groups are unsubstituted or substituted with one or more radicals R32; C(=0)N(R33)R34, N(R33)R35, CH=NOR36; phenyl, heterocyclyl, or hetaryl which rings are unsubstituted or partially or fully substituted with RA;
R31 is independently OH, cyano, Ci-C6-alkoxy, Ci-C6-haloalkoxy, S(0)n-Ci-C6-alkyl, S(0)n-Ci-C6-haloalkyl, C(=0)N(R33)R34, C3-C6-cycloalkyl, or C3-C6-halocycloalkyl which cycles are unsubstitued or substituted with one or more R311; or
phenyl, heterocyclyl or hetaryl which rings are unsubstitued or partially or fully substituted with RA;
R311 is OH, cyano, Ci-C2-alkyl, or Ci-C2-haloalkyl;
R32 Ci-C6-alkyl, Ci-C6-haloalkyl, or a group as defined for R31 ;
R33 is H, or d-Ce-alkyl,
R34 is H, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl, or C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C3-C6-cycloalkylmethyl, or C3-C6-halocycloalkylmethyl which rings are unsubstituted or substituted with a cyano;
R35 H, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, CH2-CN, C3-C6-cycloal- kyl, C3-C6-halocycloalkyl, C3-C6-cycloalkylmethyl, C3-C6-halocycloalkylmethyl, phenyl and hetaryl which aromatic rings are unsubstituted or partially or fully substituted with RA;
R36 is H, Ci-C6-alkyl, or Ci-C6-haloalkyl;
RA is independently selected from halogen, cyano, N02, Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C C4-alkoxy, d-C4-haloalkoxy, S(0)n-Ci-C4- alkyl, S(0)n-Ci- C4-haloalkyl, Ci-C4-alkylcarbonyl, Ci-C4-haloalkylcarbonyl, C(=0)N(R33)R34; or two RA present on the same carbon atom of a saturated or partially saturated ring may form together =0 or =S; or
two RA present on the same S or SO ring member of a heterocyclic ring may together form a group =N(Ci-C6-alkyl), =NO(Ci-C6-alkyl), =NN(H)(Ci-C6-alkyl) or =NN(Ci-C6-alkyl)2; and the N-oxides, stereoisomers and agriculturally or veterinarily acceptable salts thereof.
Moreover, the invention relates to processes and intermediates for preparing the compounds of formula I, and also to active compound combinations, and compositions comprising them, and to their use for protecting growing plants from attack or infestation by invertebrate pests. Furthermore, the invention relates to methods of applying such compounds. The present inven- tion also relates to seed comprising such compounds.
Invertebrate pests and in particular arthropods and nematodes destroy growing and harvested crops and attack wooden dwelling and commercial structures, thereby causing large economic loss to the food supply and to property. There is an ongoing need for new agents for combating invertebrate pests such as insects, arachnids and nematodes.
WO 2013/092522, WO 2014/039422, WO 2016/026789, WO 2016/174049, and WO
2017/025590 describe pyrazoles or spirocyclic derivatives. These compounds are mentioned to be useful for combating invertebrate pests. Nevertheless, there remains a need for highly effective and versatile agents for combating invertebrate pests. It is therefore an object of the present invention to provide compounds having a good pesticidal activity and showing a broad activity spectrum against a large number of different invertebrate pests, especially against difficult to control pests, such as insects.
It has been found that these objects can be achieved by compounds of formula I as depicted and defined below, and by their stereoisomers, salts, tautomers and N-oxides, in particular their agriculturally acceptable salts.
Compounds of formula I, wherein W is a group Wa, correspond to formula I .A. Such com- pounds can be prepared starting from a halogenide of formula 11.3. a. The azetidine-N is protected by any suitable protecting group PG (e.g. Boc, or C(0)Rx, with Rx being Ci-C2-alkoxy, or benzyloxy), and X in formula I la is halogen, preferably bromine. Halogenides of formula I la can be prepared as follows: Halogenides of formula I la can be prepared from compounds of formula 11.1 . a (X is halogen, such as bromine or iodine, or a suitable leaving group like e.g. triflate; X' is halogen such as bromine or iodine; X" is a leaving group selected from halogen, mesylate, tosylate, or triflate) and II .2. a (Z is selected from oxygen or sulfur). Compounds of formula I I .2. a are known and are commercially available.
Figure imgf000004_0001
This transformation is usually carried out at temperatures of from -78°C to 60°C, preferably from -50°C to 20 °C, in an inert solvent, in the presence of a base [cf. WO 2014/039422].
Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and petrol ether, aromatic hydrocarbons such as toluene, o-, m-, and p-xylene, ethers such as diethyl- ether, Diisopropylether, tert.-butylmethylether, dioxane, anisole, 2-methyl-tetrahydrofuran and tetrahydrofurane, preferably ethers such as diethyl ether, tetrahydrofuran, tert.-butylmethylether, or 2-methyl-tetrahydrofuran. It is also possible to use mixtures of the solvents mentioned.
Suitable bases are, in general, organometallic compounds, such as alkali metal alkyls such as methyllithium, n-butyllithium, sec-butyllithium, tert.-butyllithium, phenyllithium, and alkaline earth metal alkyls, such as mehtylmagnesiumhalogenide, ethylmagnesiumhalide, isopropylmagnesi- umhalide, butylmagnesiumhalide, wherein the halide in the aforementioned terms can be selected from chlorine, bromine and iodine. Alternatively, alkali metal and alkaline earth metals, such as lithium, sodium, potassium or magnesium can be used. Particular preference is given to alkali metal alkyls, such as n-butyllithium or alkaline earth metal alkyls, such as isopropyl mag- nesium chloride or isopropyl magnesium bromide. The bases are generally employed in equimolar amounts, or in excess. The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of I I.2. a, based on 11.1 . a. Compounds of formula 11.1. a can be prepared from compounds of formula II.3. a by transformation of the hydroxy group into X". Compounds of formula II.3. a are known and are commercially available.
Figure imgf000005_0001
This transformation is usually carried out at temperatures of from -10°C to 120°C, preferably from 0°C to 80°C, in an inert solvent, in the presence or absence of a base depending on the nature of X". For transformations, where X" represents mesylate, tosylate or triflate, a sulfonyla- tion reagent and a base is required [cf. Freitas, Luiza B. de O. et al, European Journal of Medicinal Chemistry, 84, 595-604; 2014]; for transformations where X" represents a halogen, the re- actions do not require the addition of base but a halogenation reagent [cf. Lee, Choi Chuck et al, Journal of Organic Chemistry, 50(5), 705-7; 1985].
Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and petrol ether, aromatic hydrocarbons such as toluene, o-, m-, and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, and chlorobenzene, ethers such as diethylether, Diisopropylether, tert.-butylmethylether, dioxane, anisole, and tetrahydrofurane, esters, such as ethyl acetate and butyl acetate, nitrils such as acetonitrile, and propionitrile, moreover dimethyl sulphoxide, dimethyl formamide, and dimethylacetamide, preferably aromatic hydrocarbons such as toluene, or methylene chloride, dimethyl formamide, dimethylacetamide, ethyl acetate and butyl acetate. It is also possible to use mixtures of the solvents mentioned.
Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide, and magnesium oxide, alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal and al- kaline earth metal carbonates, such as lithium carbonate, sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, moreover, organic bases, for example tertiary amines, such as trimethylamine, triethylamine, triisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines. Particular preference is given to alkali metal and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate or tertiary amines such as triethylamine. The bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
Suitable sulfonylation reagents are methane sulfonyl chloride, toluenesulfonyl chloride or triflic anhydride.
Suitable halogenation reagents are for example chlorine, thionyl chloride, oxalyl chloride, phosphoryl chloride, phosphoryl bromide, phosphorus pentachloride and boron tribromide. The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of the sulfonylation reagent or the halo- genatin reagent based on II.3. a. Halogenide Ila is then transformed to boronic acid of formula I lia.
Figure imgf000006_0001
This transformation is usually carried out at temperatures of from -78°C to 80 °C, preferably from -10°C to 50 °C, in an inert solvent, in the presence of a base [cf. Hattori, Yoshihide et al, Bioorganic & Medicinal Chemistry, 14(10), 3258-3262; 2006 ].
Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and petrol ether, aromatic hydrocarbons such as toluene, o-, m-, and p-xylene, ethers such as diethyl- ether, Diisopropylether, tert.-butylmethylether, dioxane, anisole, 2-methyl-tetrahydrofuran and tetrahydrofurane, preferably ethers such as diethyl ether, tetrahydrofuran, tert.-butylmethylether, or 2-methyl-tetrahydrofuran. It is also possible to use mixtures of the solvents mentioned.
Suitable bases are, in general, organometallic compounds, such as alkali metal alkyls such as methyllithium, n-butyllithium, sec-butyllithium, tert.-butyllithium, phenyllithium, and alkaline earth metal alkyls, such as mehtylmagnesiumhalogenide, ethylmagnesiumhalide, isopropylmagnesi- umhalide, butylmagnesiumhalide, wherein the halide in the aforementioned terms can be se- lected from chlorine, bromine and iodine. Alternatively, alkali metal and alkaline earth metals, such as lithium, sodium, potassium or magnesium can be used. Particular preference is given to alkali metal alkyls, such as n-butyllithium or alkaline earth metal alkyls, such as isopropyl magnesium chloride or isopropyl magnesium bromide. The bases are generally employed in equimolar amounts, or in excess. The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of Ila, based on Ilia.
It may be advantageous to transform the boronic acid of formula Ilia to boronic acid esters of formula Illb, wherein A is Ci-C4-alkoxy, or both A groups form together a pinakolyl group §-0-C(RP)2-C(RP)2-0-§, wherein RP is Ci-C6-alkyl, and § denotes the bond to the boron atom.
Figure imgf000006_0002
This transformation can be performed as described by Broaders, Kyle E. et al, Journal of the American Chemical Society, 133(4), 756-758; 201 1 .
Boronic acid Ilia or its ester Illb is coupled with a pyrazole derivative of formula IVa, in which X is halogen, preferably bromine or iodine, and the other variables have the meaning as given for formula I. Pyrazole derivatives IVa are known from WO 2016/174049.
Figure imgf000006_0003
This transformation is usually carried out at temperatures of from 20°C to 180 °C, preferably from 25°C to 120 °C, in an inert solvent, in the presence of a base and a catalyst [cf. Kristensen, Jesper L. et al, Journal of Medicinal Chemistry, 53(19), 7021-7034; 2010 ].
Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and pet- rol ether, aromatic hydrocarbons such as toluene, o-, m-, and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, and chlorobenzene, ethers such as diethylether, Diisopropylether, tert.-butylmethylether, dioxane, anisole, and tetrahydrofurane, nitrils such as acetonitrile, and propionitrile, ketons such as acetone, methyl ethyl ketone, diethyl ketone, and tert. -butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-buta- nol, and tert.-butanol, moreover dimethyl sulphoxide, dimethyl formamide, and dimethylacetam- ide, and water; preferably aromatic hydrocarbons such as toluene, ethers such as tetrahydrofu- ran, nitriles such as acetonitrile, dimethyl formamide, and dimethylacetamide, and water. It is also possible to use mixtures of the solvents mentioned.
Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide, and magnesium oxide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, alkali metal phosphates, such as sodium phosphate or potassium phosphate, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, triisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines. Particular preference is given to alkali metal carbonates, such as sodium carbonate and potassium carbonate, alkali metal phosphates, such as sodium phosphate or potas- sium phosphate or tertiary amines, such as triethylamine.
The bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
Compounds of formula I wherein W is Wb correspond to formula I.B. They can be obtained by reaction of an amine I lie with a pyrazole carbonic acid of formula IVb.
The amine 111 is obtained from a halogenide of formula Ila by Buchwald-Hartwig Cross Coupling Reaction, e.g. with an imine lib under conditions known from WO 2015/049535.
Figure imgf000007_0001
This transformation is usually carried out at temperatures of from 10°C to 180 °C, preferably from 25°C to 120 °C, in an inert solvent, in the presence of a base and a catalyst.
Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and petrol ether, aromatic hydrocarbons such as toluene, o-, m-, and p-xylene, ethers such as diethylether, Diisopropylether, tert.-butylmethylether, dioxane, anisole, and tetrahydrofurane, nitrils such as acetonitrile, and propionitrile, moreover dimethyl sulphoxide, dimethyl formamide, and dimethylacetamide, preferably aromatic hydrocarbons such as toluene or ethers such as diethylether, Diisopropylether, tert.-butylmethylether and dioxane. It is also possible to use mixtures of the solvents mentioned. Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide, and magnesium oxide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate, cesium carbonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, triisopropylethylamine and N-methyl- piperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylamino- pyridine, and also bicyclic amines. Particular preference is given to alkali metal carbonates, such as potassium carbonate, cesium carbonate and amines, such as triethylamine, triisopropylethylamine and N-methylpiperidine, pyridine. The bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
Suitable catalysts are preferably Pd catalysts. The Pd catalysts used are generally produced in situ from at least one palladium(ll) salt or a palladium(O) compound and the corresponding phosphine ligands. However, they may also be used directly as palladium(O) compound without reducing the initial catalytic activity. Suitable palladium sources are for example palladium tri- fluoroacetate, palladium fluoroacetylacetonate, Pd(OAc)2, Pd(OCOCH2CH3)2, Pd(OH)2, PdCI2, PdBr2, Pd(acac)2 (acac=acetylacetonate), Pd(NC>3)2, Pd(dba)2, Pd2dba3 (dba=dibenzylideneace- tone), Pd(CH3CN)2CI2,Pd(PhCN)2CI2, Li[PdCI4], Pd/C, or palladium nanoparticles. Particularly preferred catalysts are selected from the following: Pd tetrakis, PdCI2(PPh3)2, CI2Pd(dppf), Pd2(dba)3, Pd(OAc)2, and PdCI2. Particularly preferred ligands are the following: PP i3, dppf, 2,2'-bis-(diphenylphosphino)-1 ,1 '- binaphthyl (BINAP), AsPh3, (tBu)3P, and tri(o-tolyl)phos- phine(tri(o-tol)P).
The starting materials are generally reacted with one another in equimolar amounts. In terms of yield, it may be advantageous to employ an excess of lib, based on lla.
For preparing compounds with R2 different from H the amine of formula I lie is alkylated or acyl- ated with an agent of formula R2-X, wherein X is a nucleophilic leaving group, such as a halo- gen, preferably CI or Br, or acetate, under reaction conditions generally known in the art [cf. Selva, Maurizio et al, Journal of Organic Chemistry, 68(19), 7374-7378; 2003].
This can be achieved by reacting the amine of formula 111 o with an excess of agent of formula R2-X either in an inert solvent, such as toluene, dimethyl formamide, tetrahydrofuran or in R2-X as the solvent for example if R2-X represents acetic anhydride. It may be advantageous to employ a base in either catalytic or stoichiometric or, if appropriate an excess amount. The reaction is generally at temperatures of from 0°C to 120 °C, preferably from 20°C to 1 10°C.
Alternatively the group R2 can analogously be introduced in R2=H compounds of formula Vb.
The amine 111 is reacted with a pyrazole carbonic acid of formula IVb, which is known from WO 2016/026789.
Figure imgf000009_0001
This transformation is usually carried out at temperatures of from -10°C to 120°C, preferably from 0°C to 1 10°C, in an inert solvent, in the presence of a base and a catalyst [cf. WO
2006/069155].
Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and petrol ether, aromatic hydrocarbons such as toluene, o-, m-, and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform, and chlorobenzene, ethers such as diethylether, Diisopropylether, tert.-butylmethylether, dioxane, anisole, and tetrahydrofurane, nitrils such as acetonitrile, and propionitrile, ketons such as acetone, methyl ethyl ketone, diethyl ketone, and tert. -butyl methyl ketone, esters, such as ethyl acetate and butyl acetate, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert.-butanol, moreover dimethyl sulphoxide, dimethyl formamide, and dimethylacetamide, preferably aromatic hydrocarbons such as toluene, dimethyl formamide, dimethylacetamide, ethyl acetate and butyl acetate. It is also possible to use mixtures of the solvents mentioned.
Suitable bases are, in general, inorganic compounds, such as alkali metal and alkaline earth metal hydroxides, such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides, such as lithium oxide, sodium oxide, calcium oxide, and magnesium oxide, alkali metal and alkaline earth metal hydrides, such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal and al- kaline earth metal carbonates, such as lithium carbonate, sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, triisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines.
Particular preference is given to alkali metal and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate or tertiary amines such as triethylamine.
The bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.
Suitable catalysts are acid activating reagents which form with the acid IVb an active ester species. They can be selected from dicyclohexyl carbodiimide, diisopropyl carbodiimide, car- bonyl diimidazole, 1-hydroxy-7-azabenzotriazole [HOAt], 1-hydroxy-7-benzotriazole [HOBt], 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, bromotripyrrolidinophosphonium hexafluorophosphate [PyBroP], 1 -[Bis(dimethylamino)methylene]-1 H-1 ,2,3-triazolo[4,5-b]pyri- dinium 3-oxid hexafluorophosphate [HATU]. The catalyst has to be added in equimolar amounts or in excess.
The protective group is then split off from compounds V (collectively for formulae Va and Vb) to yield the free azetidine of formula VI.
Figure imgf000010_0001
Compounds of formula VI can be obtained from compounds V by hydrolysis of the protective group. This transformation is usually carried out at temperatures of from -20°C to 100°C, preferably from 0°C to 40°C, using trifluoroacetic acid as a co-solvent in a solvent such as dichloro- methane or hydrochloric acid in ethers such as diethylether, Diisopropylether, tert.-butylmethylether, dioxane, and tetrahydrofurane (c.f. WO 2015/104422).
Figure imgf000010_0002
Compounds of formula I are obtained from compounds of formula VI in an amidation reaction. This transformation is usually carried out at temperatures of from -20°C to 100°C, preferably from 0°C to 40°C (c.f. WO 2015/104422).
Thereby compounds of formula VI are reacted with acid chloride R3-COCI in a solvent such as halogenated hydrocarbons such as methylene chloride, or ethers such as diethylether, diisopropylether, tert.-butylmethylether, dioxane, anisole, and THF, in the presence of an organic bases, for example tertiary amines, such as trimethylamine, triethylamine, triisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethyla- minopyridine, and also bicyclic amines.
The starting materials required for preparing the compounds I are commercially available or known from the literature, or can be prepared in accordance with the literature cited.
The reaction mixtures are worked up in a customary manner, for example by mixing with water, separating the phases and, if appropriate, chromatographic purification of the crude products. Some of the intermediates and end products are obtained in the form of colorless or slightly brownish viscous oils which are purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, purification can also be carried out by recrystallization or digestion.
If individual compounds I cannot be obtained by the routes described above, they can be prepared by derivatization of other compounds I.
However, if the synthesis yields mixtures of isomers, a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (for example under the action of light, acids or bases). Such conversions may also take place after use, for example in the treatment of plants in the treated plant, or in the harmful fungus to be controlled.
The radicals attached to the backbone of formula I may contain one or more centers of chirali- ty. In this case the compounds of formula I are present in the form of different enantiomers or diastereomers, depending on the substituents. The present invention relates to every possible stereoisomer of the formula I , i.e. to single enantiomers or diastereomers, as well as to mixtures thereof.
The compounds of formula I may be amorphous or may exist in one or more different crystal- line states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities. The present invention relates to amorphous and crystalline compounds of formula I , mixtures of different crystalline states of the respective compound I , as well as amorphous or crystalline salts thereof.
Salts of the compounds of the formula I are preferably veterinary and/or agriculturally accepta- ble salts, preferably agriculturally acceptable salts. They can be formed in a customary manner, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality.
Veterinary and/or agriculturally useful salts of the compounds of formula I encompass especially the acid addition salts of those acids whose cations and anions, respectively, have no ad- verse effect on the pesticidal action of the compounds of formula I.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting compounds of formula I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobro- mic acid, sulfuric acid, phosphoric acid or nitric acid.
The term "N-oxide" includes any compound of formula I which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety. The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix Cn-Cm indicates in each case the possible number of carbon atoms in the group.
The term "halogen" denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine.
The term "alkyl" as used herein and in the alkyl moieties of alkylamino, alkylcarbonyl, alkylthio, alkylsulfinyl, alkylsulfonyl and alkoxyalkyl denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably from 1 to 3 carbon atoms. Examples of an alkyl group are methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 1 -methyl- butyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, n-hexyl, 1 , 1 -dimethylpro- pyl, 1 ,2-dimethylpropyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 , 1 -dimethyl butyl , 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dime- thylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1 -ethyl-1 -methyl- propyl, and 1 -ethyl-2-methylpropyl.
The term "haloalkyl" as used herein and in the haloalkyl moieties of haloalkylcarbonyl, haloalk- oxycarbonyl, haloalkylthio, haloalkylsulfonyl, haloalkylsulfinyl, haloalkoxy and haloalkoxyalkyl, denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms. Preferred haloalkyl moieties are selected from Ci-C4- aloalkyl, more preferably from Ci-C3-haloalkyl or Ci-C2-haloalkyl, in particular from Ci-C2-fluoroalkyl such as fluoromethyl, difluoromethyl, trifluo- romethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and the like.
The term "alkoxy" as used herein denotes in each case a straight-chain or branched alkyl group which is bonded via an oxygen atom and has usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Examples of an alkoxy group are methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, 2-butyloxy, iso-butyloxy, tert.-butyloxy, and the like.
The term "alkoxyalkyl" as used herein refers to alkyl usually comprising 1 to 10, frequently 1 to 4, preferably 1 to 2 carbon atoms, wherein 1 carbon atom carries an alkoxy radical usually comprising 1 to 4, preferably 1 or 2 carbon atoms as defined above. Examples are CH2OCH3, CH2- OC2H5, 2-(methoxy)ethyl, and 2-(ethoxy)ethyl.
The term "haloalkoxy" as used herein denotes in each case a straight-chain or branched alk- oxy group having from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms, in particular fluorine atoms. Preferred haloalkoxy moieties include C1-C4- haloalkoxy, in particular Ci-C2-fluoroalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoro- methoxy, 1 -fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-flu- oroethoxy, 2-chloro-2,2-difluoro-ethoxy, 2,2dichloro-2-fluorethoxy, 2,2,2-trichloroethoxy, penta- fluoroethoxy and the like.
The term "alkylthio "(alkylsulfanyl: S-alkyl)" as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-alkylthio), more preferably 1 to 3 carbon atoms, which is attached via a sulfur atom. The term "haloalkylthio" as used herein refers to an alkylthio group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
The term "alkylsulfinyl" (alkylsulfoxyl: S(=0)-Ci-C6-alkyl), as used herein refers to a straight- chain or branched saturated alkyl group (as mentioned above) having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-alkylsulfinyl), more preferably 1 to 3 carbon atoms bonded through the sulfur atom of the sulfinyl group at any position in the alkyl group.
The term "haloalkylsulfinyl" as used herein refers to an alkylsulfinyl group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
The term "alkylsulfonyl" (S(=0)2-alkyl) as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-al- kylsulfonyl), preferably 1 to 3 carbon atoms, which is bonded via the sulfur atom of the sulfonyl group at any position in the alkyl group.
The term "haloalkylsulfonyl" as used herein refers to an alkylsulfonyl group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
The term "alkylcarbonyl" refers to an alkyl group as defined above, which is bonded via the carbon atom of a carbonyl group (C=0) to the remainder of the molecule. The term "haloalkylcarbonyl" refers to an alkylcarbonyl group as mentioned above, wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
The term "alkoxycarbonyl" refers to an alkylcarbonyl group as defined above, which is bonded via an oxygen atom to the remainder of the molecule.
The term "haloalkoxycarbonyl" refers to an alkoxycarbonyl group as mentioned above, wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
The term "alkenyl" as used herein denotes in each case a singly unsaturated hydrocarbon radical having usually 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms, e.g. vinyl, allyl (2- propen-1 -yl), 1-propen-1-yl, 2-propen-2-yl, methallyl (2-methylprop-2-en-1 -yl), 2-buten-1-yl, 3- buten-1 -yl, 2-penten-1-yl, 3-penten-1 -yl, 4-penten-1-yl, 1-methylbut-2-en-1-yl, 2-ethylprop-2-en- 1-yl and the like.
The term "haloalkenyl" as used herein refers to an alkenyl group as defined above, wherein the hydrogen atoms are partially or totally replaced with halogen atoms.
The term "alkynyl" as used herein denotes in each case a singly unsaturated hydrocarbon radical having usually 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms, e.g. ethynyl, pro- pargyl (2-propyn-1 -yl), 1-propyn-1-yl, 1-methylprop-2-yn-1 -yl), 2-butyn-1 -yl, 3-butyn-1-yl, 1-pen- tyn-1-yl, 3-pentyn-1-yl, 4-pentyn-1-yl, 1-methylbut-2-yn-1 -yl, 1-ethylprop-2-yn-1-yl and the like. The term "haloalkynyl" as used herein refers to an alkynyl group as defined above, wherein the hydrogen atoms are partially or totally replaced with halogen atoms.
The term "cycloalkyl" as used herein and in the cycloalkyl moieties of cycloalkoxy and cycloal- kylthio denotes in each case a monocyclic cycloaliphatic radical having usually from 3 to 10 or from 3 to 6 carbon atoms, such as cyclopropyl (C-C3H5), cyclobutyl (C-C4H7), cyclopentyl (c- C5H9), cyclohexyl (c-CeHu), cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl or cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The term "halocycloalkyl" as used herein and in the halocycloalkyl moieties of halocycloalkoxy and halocycloalkylthio denotes in each case a monocyclic cycloaliphatic radical having usually from 3 to 10 C atoms or 3 to 6 C atoms, wherein at least one, e.g. 1 , 2, 3, 4 or 5 of the hydrogen atoms, are replaced by halogen, in particular by fluorine or chlorine. Examples are 1 - and 2-fluo- rocyclopropyl, 1 ,2-, 2,2- and 2,3-difluorocyclopropyl, 1 ,2,2-trifluorocyclopropyl, 2,2,3,3-tetrafluo- rocyclpropyl, 1 - and 2-chlorocyclopropyl, 1 ,2-, 2,2- and 2,3-dichlorocyclopropyl, 1 ,2,2-trichloro- cyclopropyl, 2,2,3,3-tetrachlorocyclpropyl, 1 -,2- and 3-fluorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-difluorocyclopentyl, 1 -,2- and 3-chlorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-dichlo- rocyclopentyl and the like.
The term "cycloalkenyl" as used herein and in the cycloalkenyl moieties of cycloalkenyloxy and cycloalkenylthio denotes in each case a monocyclic singly unsaturated non-aromatic radical having usually from 3 to 10, e.g. 3 or 4 or from 5 to 10 carbon atoms, preferably from 3- to 8 carbon atoms. Exemplary cycloalkenyl groups include cyclopropenyl, cycloheptenyl or cycloocte- nyl.
The term "halocycloalkenyl" as used herein and in the halocycloalkenyl moieties of halocyclo- alkenyloxy and halocycloalkenylthio denotes in each case a monocyclic singly unsaturated non- aromatic radical having usually from 3 to 10, e.g. 3 or 4 or from 5 to 10 carbon atoms, preferably from 3- to 8 carbon atoms, wherein at least one, e.g. 1 , 2, 3, 4 or 5 of the hydrogen atoms, are replaced by halogen, in particular by fluorine or chlorine. Examples are 3,3-difluorocyclopropen- 1-yl and 3,3-dichlorocyclopropen-1-yl.
The term "cycloalkenylalkyl" refers to a cycloalkenyl group as defined above which is bonded via an alkylene group, such as a Ci-Cs-alkyl group or a Ci-C4-alkyl group, in particular a meth- ylene group (= cycloalkenylmethyl), to the remainder of the molecule.
The term "carbocycle" or "carbocyclyl" includes in general a 3- to 12-membered, preferably a 3- to 8-membered or a 5- to 8-membered, more preferably a 5- or 6-membered mono-cyclic, non-aromatic ring comprising 3 to 12, preferably 3 to 8 or 5 to 8, more preferably 5 or 6 carbon atoms. Preferably, the term "carbocycle" covers cycloalkyl and cycloalkenyl groups as defined above.
The term "heterocycle" or "heterocyclyl" includes in general 3- to 12-membered, preferably 5- or 6-membered, in particular 6-membered monocyclic heterocyclic non-aromatic radicals. The heterocyclic non-aromatic radicals usually comprise 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, wherein S-atoms as ring members may be present as S, SO or SO2. Examples of 5- or 6-membered heterocyclic radicals comprise saturated or unsaturated, non- aromatic heterocyclic rings, such as 2- and 3-azetidinyl, 2- and 3-oxetanyl, 2- and 3-thietanyl, 2- and 3-thietanyl-S-oxid (S-oxothietanyl), 2- and 3-thietanyl-S-dioxid (S-dioxothietanyl), 2- and 3- pyrrolidinyl, 2- and 3-tetrahydrofuranyl, 1 ,3-dioxolan-2-yl, thiolan-2-yl, S-oxothiolan-2-yl, S-diox- othiolan-2-yl, 4- and 5-oxazolidinyl, 1 ,3-dioxan-2-yl, 1 - and 3-thiopyran-2-yl, S-oxothiopyranyl, and S-dioxothiopyranyl.
The term "hetaryl" includes monocyclic 5- or 6-membered heteroaromatic radicals comprising as ring members 1 , 2, or 3 heteroatoms selected from N, O and S. Examples of 5- or 6-membered heteroaromatic radicals include pyridyl, i.e. 2-, 3-, and 4-pyridyl, pyrimidinyl, i.e. 2-, 4- and 5-pyrimidinyl, pyrazinyl, pyridazinyl, i.e. 3- and 4-pyridazinyl, thienyl, i.e. 2- and 3-thienyl, furyl, i.e. 2- and 3-furyl, pyrrolyl, i.e. 1 -, 2- and 3-pyrrolyl, oxazolyl, i.e. 2-, 4- and 5-oxazolyl, isoxa- zolyl, i.e. 3-, 4- and 5-isoxazolyl, thiazolyl, i.e. 2-, 3- and 5-thiazolyl, isothiazolyl, i.e. 3-, 4- and 5-isothiazolyl, pyrazolyl, i.e. 1-, 3-, 4- and 5-pyrazolyl, imidazolyl, i.e. 1-, 2-, 4- and 5-imidazolyl, oxadiazolyl, e.g. 2- and 5-[1 ,3,4]oxadiazolyl, thiadiazolyl, e.g. 1 ,3,4-thiadiazol-5-yl, 1 ,2,4-thiadia- zol-3-yl, triazolyl, e.g. 1 ,3,4-triazol-2-yl, and 1 ,2,4-triazol-3-yl.
The terms "heterocyclyolalkyl" and "hetarylalkyl" refer to heterocyclyl or hetaryl, resp., as defined above which are bound via a Ci-C4-alkyl group, in particular a methyl group (= heterocy- clylmethyl or hetarylmethyl, resp.), to the remainder of the molecule.
With respect to the variables, the particularly preferred embodiments of the intermediates cor- respond to those of the compounds of the formula I.
In a particular embodiment, the variables of the compounds of the formula I have the following meanings, these meanings, both on their own and in combination with one another, being particular embodiments of the compounds of the formula I. R11 is preferably Ci-C4-alkyl, C2-C3-alkenyl, C2-C3-alkynyl, or Ci-C2-halogenalkyl, in particular Ci-C4-alkyl, such as CH3, and C2H5.
R12 is preferably N02, Ci-C6-alkyl, C2-C3-alkenyl, C2-C3-alkynyl, Ci-C4-halogenalkyl, or S(0)n- Ci-C4-alkyl, in particular NO2, Ci-C4-halogenalkyl, or S(0)n-Ci-C4-alkyl, more preferably C1-C4- fluoroalkyl, such as CF3, and C2F5. R13 is preferably Ci-C4-alkyl, C2-C3-alkenyl, C2-C3-alkynyl, or Ci-C2-halogenalkyl, in particular Ci-C4-halogenalkyl, more preferably Ci-C4-fluoroalkyl, such as CF3, and C2F5.
A preferred embodiment relates to compounds wherein R11 is CH3, R12 is C2F5, and R13 is CF3.
One embodiment relates to compounds of formula I wherein W is a group Wa; such compounds correspond to formula I.A. Group Wa is preferably selected from W1 to W7, particularly Wa is a pyrazole:
Figure imgf000015_0001
One embodiment relates to compounds of formula IA wherein Wa is W1 ; such compounds correspond to formula I.A1 .
Another embodiment relates to compounds of formula IA wherein Wa is W2; such compounds correspond to formula I.A2.
Another embodiment relates to compounds of formula IA wherein Wa is W3; such compounds correspond to formula I. A3.
Another embodiment relates to compounds of formula IA wherein Wa is W4; such compounds correspond to formula I.A4.
Another embodiment relates to compounds of formula IA wherein Wa is W5; such compounds correspond to formula I.A5.
Another embodiment relates to compounds of formula IA wherein Wa is W6; such compounds correspond to formula I.A6.
Another embodiment relates to compounds of formula IA wherein Wa is W7; such compounds correspond to formula I.A7.
Ra as substituent of any of W1 to W7 is preferably H.
Another embodiment relates to compounds of formula I wherein W is a group Wb; such compounds correspond to formula I.B. In group Wb T is preferably O.
In group Wb R2 is preferably H. Z is preferably O.
R3 is preferably selected from H, Ci-C6-alkyl, Ci-C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl which aliphatic groups are unsubstituted or substituted by one radical R31, C3-C6-cycloalkyl, C3-C6-halocycloalkyl which cyclic groups are unsubstituted or sub- stituted by one radical R32; heterocycle, or hetaryl which rings are unsubstituted or partially or fully substituted by RA; R31 is independently OH, cyano, Ci-C4-alkoxy, Ci-C4-haloalkoxy, S(0)n-Ci-C4-alkyl, S(0)n-Ci- C4-haloalkyl, Cs-Cs-cycloalkyl, or Cs-Cs-halocycloalkyl which cycles are unsubstitued or substituted by one or more R31 1 ;
R311 is independently OH, cyano, Ci-C2-alkyl, or Ci-C2-haloalkyl;
n is 0, 1 , or 2;
R32 CrC2-alkyl, C C2-haloalkyl, OH, CN;
RA is independently selected from halogen, cyano, NO2, Ci-C2-alkyl, Ci-C2-haloalkyl, C2-C3- alkenyl, C2-C3-haloalkenyl, C2-C3-alkynyl, C2-C3-haloalkynyl, Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl, d-Cs-alkoxy, Ci-Cs-haloalkoxy, S(0)n-Ci-C3-alkyl, S(0)n-Ci-C3-haloalkyl; or two RA present on the same carbon atom of a saturated or partially saturated ring may form together =0.
More preferably R3 is selected from Ci-C4-alkyl, and Ci-C4-haloalkyl, which aliphatic groups are unsubstituted or substituted by one radical R31 ; and Cs-Cs-cycloalkyl, Cs-Cs-halocycloalkyl which cyclic groups are unsubstituted or substituted by one radical R32;
R31 is independently OH, cyano, Ci-C4-alkoxy, Ci-C4-haloalkoxy, S(0)n-Ci-C4-alkyl,
S(0)n-Ci-C4-haloalkyl, Cs-Cs-cycloalkyl, or Cs-Cs-halocycloalkyl which cycles are unsubstitued or substituted by one or more R311 ;
R311 is independently OH, cyano, Ci-C2-alkyl, or Ci-C2-haloalkyl;
n is O, 1 , or 2;
R32 CrC2-alkyl, C C2-haloalkyl, OH, CN.
Particularly preferred R3 is selected from Ci-Cs-alkyl, CH2CF3, CH2CH2CF3, CH2OH,
CH2-C-C3H5; C-C3H5, I -CN-C-C3H4, I -CF3-C-C3H4, I -OH-C-C3H4, 2,2,-F2-c-CsH3, CH2-C-C3H5, CH2OCH3, CH2OC2H5, CH2OCF3, CH2OCH2CF3, and CH2SOnCH3, CH2SOnC2H5, wherein n is 0, 1 , or 2; 1-pyrazolyl, 3-CH3-1 -pyrazolyl, 2-pyridyl, 3-thietan-yl, 3-thietan-yl-S-oxide, and 3-thietan- yl-S-dioxide.
In another particularly preferred embodiment R3 is Ci-C3-alkyl, particularly CH3, C2H5, n-propyl; CH2CF3; C2-C3-alkenyl, particularly CH=CH2, CH=CHCH3; C2-C3-alkynyl, particularly C≡CH; C-C3H5, C-C4H7, I -CF3-C-C3H4, CH2-C-C3H5; CH2SOnCH3, CH2SOnC2H5, wherein n is 0, 1 , or 2, and particularly n is 2; CH2-C(=0)NHC2H5; CH2-tetrahydrofuran-2-yl, CH2-1 ,3-dioxolan-2-yl,
CH2-1 ,3-dioxan-2-yl, 1 ,3-dioxolan-2-yl, 2-oxetanyl, 3-thietanyl, CH2-pyrimidin-2-yl, and 2-pyridyl.
In particular with a view to their use, preference is given to the compounds of formula I compiled in the tables below, which compounds correspond to formulae I.A1 to I.A7, and I.B1 to I.B
Figure imgf000016_0001
Figure imgf000017_0001
Compounds of formulae I.A1 , and I.B1 , resp., are particularly predferred.
Each of the groups mentioned for a substituent in the tables is furthermore per se, independently of the combination in which it is mentioned, a particularly preferred aspect of the substituent in question.
Table 1 : Compounds of formula I.A1 in which R3 for a compound corresponds in each case to one row of Table B
Table 2 : Compounds of formula I.A2 in which R3 for a compound corresponds in each case to one row of Table B
Table 3 : Compounds of formula I. A3 in which R3 for a compound corresponds in each case to one row of Table B
Table 4 : Compounds of formula I.A4 in which R3 for a compound corresponds in each case to one row of Table B
Table 5 : Compounds of formula I.A5 in which R3 for a compound corresponds in each case to one row of Table B Table 6 : Compounds of formula I.A6 in which R3 for a compound corresponds in each case one row of Table B
Table 7 : Compounds of formula I.A7 in which R3 for a compound corresponds in each case one row of Table B
Table 8 : Compounds of formula I.B1 in which R3 for a compound corresponds in each case one row of Table B
Table 9 : Compounds of formula I.B2 in which R3 for a compound corresponds in each case one row of Table B
Table 10 : Compounds of formula I.B3 in which R3 for a compound corresponds in each case one row of Table B
Table 1 1 : Compounds of formula I.B4 in which R3 for a compound corresponds in each case one row of Table B
Table 12 : Compounds of formula I.B5 in which R3 for a compound corresponds in each case one row of Table B
Table B
Figure imgf000018_0001
Figure imgf000018_0002
No. R3 DXL = dioxolanyl
B-54 OET-2 DXN = dioxanyl
B-55 OET-3 OET = oxetanyl
B-56 TET-3 PMD = pyrimidinyl
B-57 1-0-TET-3 PRD = pyridinyl
B-58 1 .1 -02-TET-3 PRZ = pyrazolyl
Abbreviations: THF = tetrahydrofuranyl TET " t ietanyl
The compounds of the present invention are suitable for use in protecting crops, plants, plant propagation materials, such as seeds, or soil or water, in which the plants are growing, from attack or infestation by animal pests. Therefore, the present invention also relates to a plant pro- tection method, which comprises contacting crops, plants, plant propagation materials, such as seeds, or soil or water, in which the plants are growing, to be protected from attack or infestation by animal pests, with a pesticidally effective amount of a compound of the present invention.
The compounds of the present invention are also suitable for use in combating or controlling animal pests. Therefore, the present invention also relates to a method of combating or controlling animal pests, which comprises contacting the animal pests, their habitat, breeding ground, or food supply, or the crops, plants, plant propagation materials, such as seeds, or soil, or the area, material or environment in which the animal pests are growing or may grow, with a pesticidally effective amount of a compound of the present invention.
The compounds of the present invention are effective through both contact and ingestion. Furthermore, the compounds of the present invention can be applied to any and all developmental stages, such as egg, larva, pupa, and adult.
The compounds of the present invention can be applied as such or in form of compositions comprising them as defined above. Furthermore, the compounds of the present invention can be applied together with a mixing partner as defined above or in form of compositions comprising said mixtures as defined above. The components of said mixture can be applied simultaneously, jointly or separately, or in succession, that is immediately one after another and thereby creating the mixture "in situ" on the desired location, e.g. the plant, the sequence, in the case of separate application, generally not having any effect on the result of the control measures. The application can be carried out both before and after the infestation of the crops, plants, plant propagation materials, such as seeds, soil, or the area, material or environment by the pests.
Suitable application methods include inter alia soil treatment, seed treatment, in furrow application, and foliar application. Soil treatment methods include drenching the soil, drip irrigation (drip application onto the soil), dipping roots, tubers or bulbs, or soil injection. Seed treatment techniques include seed dressing, seed coating, seed dusting, seed soaking, and seed pelleting. In furrow applications typically include the steps of making a furrow in cultivated land, seeding the furrow with seeds, applying the pesticidally active compound to the furrow, and closing the furrow. Foliar application refers to the application of the pesticidally active compound to plant foliage, e.g. through spray equipment. For foliar applications, it can be advantageous to modify the behavior of the pests by use of pheromones in combination with the compounds of the present invention. Suitable pheromones for specific crops and pests are known to a skilled person and publicly available from databases of pheromones and semiochemicals, such as http://www.pherobase.com.
As used herein, the term "contacting" includes both direct contact (applying the com- pounds/compositions directly on the animal pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus, i.e. habitat, breeding ground, plant, seed, soil, area, material or environment in which a pest is growing or may grow, of the animal pest or plant).
The term "animal pest" includes arthropods, gastropods, and nematodes. Preferred animal pests according to the invention are arthropods, preferably insects and arachnids, in particular insects. Insects, which are of particular relevance for crops, are typically referred to as crop insect pests.
The term "crop" refers to both, growing and harvested crops.
The term "plant" includes cereals, e.g. durum and other wheat, rye, barley, triticale, oats, rice, or maize (fodder maize and sugar maize / sweet and field corn); beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, nectarines, almonds, cherries, papayas, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as beans, lentils, peas, alfalfa or soybeans; oil plants, such as rapeseed (oilseed rape), turnip rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, pumpkins, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as eggplant, spinach, lettuce (e.g. iceberg lettuce), chicory, cabbage, asparagus, cabbages, carrots, onions, garlic, leeks, tomatoes, potatoes, cucurbits or sweet peppers; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rapeseed, sugar cane or oil palm; tobacco; nuts, e.g. walnuts; pistachios; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers (e.g. carnation, petunias, geranium/pelargoniums, pansies and impatiens), shrubs, broad-leaved trees (e.g. poplar) or evergreens, e.g. conifers; eucalyptus; turf; lawn; grass such as grass for animal feed or ornamental uses. Preferred plants include potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rapeseed, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
The term "plant" is to be understood as including wild type plants and plants, which have been modified by either conventional breeding, or mutagenesis or genetic engineering, or by a combination thereof.
Plants, which have been modified by mutagenesis or genetic engineering, and are of particular commercial importance, include alfalfa, rapeseed (e.g. oilseed rape), bean, carnation, chicory, cotton, eggplant, eucalyptus, flax, lentil, maize, melon, papaya, petunia, plum, poplar, potato, rice, soybean, squash, sugar beet, sugarcane, sunflower, sweet pepper, tobacco, tomato, and cereals (e.g. wheat), in particular maize, soybean, cotton, wheat, and rice. In plants, which have been modified by mutagenesis or genetic engineering, one or more genes have been mutagen- ized or integrated into the genetic material of the plant. The one or more mutagenized or integrated genes are preferably selected from pat, epsps, crylAb, bar, cry1 Fa2, crylAc, cry34Ab1 , cry35AB1 , cry3A, cryF, cryl F, mcry3a, cry2Ab2, cry3Bb1 , cry1A.105, dfr, barnase, vip3Aa20, barstar, als, bxn, bp40, asnl , and ppo5. The mutagenesis or integration of the one or more genes is performed in order to improve certain properties of the plant. Such properties, also known as traits, include abiotic stress tolerance, altered growth/yield, disease resistance, herbi- cide tolerance, insect resistance, modified product quality, and pollination control. Of these properties, herbicide tolerance, e.g. imidazolinone tolerance, glyphosate tolerance, or glufosinate tolerance, is of particular importance. Several plants have been rendered tolerant to herbicides by mutagenesis, for example Clearfield® oilseed rape being tolerant to imidazoli- nones, e.g. imazamox. Alternatively, genetic engineering methods have been used to render plants, such as soybean, cotton, corn, beets and oil seed rape, tolerant to herbicides, such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate). Furthermore, insect resistance is of importance, in particular lepidopteran insect resistance and coleopteran insect resistance. Insect resistance is typically achieved by modifying plants by integrating cry and/or vip genes, which were isolated from Bacillus thuringiensis (Bt), and code for the respective Bt toxins. Genetically modified plants with insect resistance are commercially available under trade names including WideStrike®, Bollgard®, Agrisure®, Herculex®, YieldGard®, Genuity®, and Intacta®. Plants may be modified by mutagenesis or genetic engineering either in terms of one property (singular traits) or in terms of a combination of properties (stacked traits). Stacked traits, e.g. the combination of herbicide tolerance and insect resistance, are of increasing importance. In general, all relevant modified plants in connection with singular or stacked traits as well as detailed information as to the mutagenized or integrated genes and the respective events are available from websites of the organizations "International Service for the Acquisition of Agri-biotech Applications (ISAAA)" (http://www.isaaa.org/gmapprovaldatabase) and "Center for Environmental Risk Assessment (CERA)" (http://cera-gmc.org/GMCropDatabase).
It has surprisingly been found that the pesticidal activity of the compounds of the present invention may be enhanced by the insecticidal trait of a modified plant. Furthermore, it has been found that the compounds of the present invention are suitable for preventing insects to become resistant to the insecticidal trait or for combating pests, which already have become resistant to the insecticidal trait of a modified plant. Moreover, the compounds of the present invention are suitable for combating pests, against which the insecticidal trait is not effective, so that a complementary insecticidal activity can advantageously be used.
The term "plant propagation material" refers to all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e.g. potatoes), which can be used for the multiplication of the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants. Seedlings and young plants, which are to be transplanted after germination or after emergence from soil, may also be included. These plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting.
The term "seed" embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains, cuttings, cut shoots and the like, and means in a preferred embodiment true seeds.
In general, "pesticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various compounds/compositions used in the invention. A pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, tar- get species, locus, mode of application, and the like.
In the case of soil treatment, in furrow application or of application to the pests dwelling place or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m2, preferably from 0.001 to 20 g per 100 m2.
For use in treating crop plants, e.g. by foliar application, the rate of application of the active in- gredients of this invention may be in the range of 0.0001 g to 4000 g per hectare, e.g. from 1 g to 2 kg per hectare or from 1 g to 750 g per hectare, desirably from 1 g to 100 g per hectare, more desirably from 10 g to75 g per hectare, e.g., 10 to 20 g per hectare, 20 to 30 g per hectare, 30 to 40 g per hectare, 40 to 50 g per hectare, 50-60 g per hectare, or 60-75 g per hectare. The compounds of the present invention are particularly suitable for use in the treatment of seeds in order to protect the seeds from insect pests, in particular from soil-living insect pests, and the resulting seedling's roots and shoots against soil pests and foliar insects. The present invention therefore also relates to a method for the protection of seeds from insects, in particular from soil insects, and of the seedling's roots and shoots from insects, in particular from soil and foliar insects, said method comprising treating the seeds before sowing and/or after pregermina- tion with a compound of the present invention. The protection of the seedling's roots and shoots is preferred. More preferred is the protection of seedling's shoots from piercing and sucking insects, chewing insects and nematodes.
The term "seed treatment" comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking, seed pelleting, and in-furrow application methods. Preferably, the seed treatment application of the active compound is carried out by spraying or by dusting the seeds before sowing of the plants and before emergence of the plants.
The present invention also comprises seeds coated with or containing the active compound. The term "coated with and/or containing" generally signifies that the active ingredient is for the most part on the surface of the propagation product at the time of application, although a greater or lesser part of the ingredient may penetrate into the propagation product, depending on the method of application. When the said propagation product is (re)planted, it may absorb the active ingredient.
Suitable seed is for example seed of cereals, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucum- bers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.
In addition, the active compound may also be used for the treatment of seeds from plants, which have been modified by mutagenisis or genetic engineering, and which e.g. tolerate the action of herbicides or fungicides or insecticides. Such modified plants have been described in detail above.
Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, suspoemulsions (SE), powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter. Preferably, the formulations are applied such that germination is not included.
The active substance concentrations in ready-to-use formulations, which may be obtained af- ter two-to-tenfold dilution, are preferably from 0.01 to 60% by weight, more preferably from 0.1 to 40 % by weight.
In a preferred embodiment a FS formulation is used for seed treatment. Typically, a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
Especially preferred FS formulations of the compounds of the present invention for seed treatment usually comprise from 0.1 to 80% by weight (1 to 800 g/l) of the active ingredient, from 0.1 to 20 % by weight (1 to 200 g/l) of at least one surfactant, e.g. 0.05 to 5 % by weight of a wetter and from 0.5 to 15 % by weight of a dispersing agent, up to 20 % by weight, e.g. from 5 to 20 % of an anti-freeze agent, from 0 to 15 % by weight, e.g. 1 to 15 % by weight of a pigment and/or a dye, from 0 to 40 % by weight, e.g. 1 to 40 % by weight of a binder (sticker /adhesion agent), optionally up to 5 % by weight, e.g. from 0.1 to 5 % by weight of a thickener, optionally from 0.1 to 2 % of an anti-foam agent, and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an amount from 0.01 to 1 % by weight and a filler/vehicle up to 100 % by weight. In the treatment of seed, the application rates of the compounds of the invention are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, more preferably from 1 g to 1000 g per 100 kg of seed and in particular from 1 g to 200 g per 100 kg of seed, e.g. from 1 g to 100 g or from 5 g to 100 g per 100 kg of seed.
The invention therefore also relates to seed comprising a compound of the present invention, or an agriculturally useful salt thereof, as defined herein. The amount of the compound of the present invention or the agriculturally useful salt thereof will in general vary from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed. For specific crops such as lettuce the rate can be higher. The compounds of the present invention may also be used for improving the health of a plant. Therefore, the present invention also relates to a method for improving plant health by treating a plant, plant propagation material and/or the locus where the plant is growing or is to grow with an effective and non-phytotoxic amount of a compound of the present invention.
As used herein "an effective and non-phytotoxic amount" means that the compound is used in a quantity which allows to obtain the desired effect but which does not give rise to any phyto- toxic symptom on the treated plant or on the plant grown from the treated propagule or treated soil.
The terms "plant" and "plant propagation material" are defined above. "Plant health" is defined as a condition of the plant and/or its products which is determined by several aspects alone or in combination with each other such as yield (for example increased biomass and/or increased content of valuable ingredients), quality (for example improved content or composition of certain ingredients or shelf life), plant vigour (for example improved plant growth and/or greener leaves ("greening effect"), tolerance to abiotic (for example drought) and/or biotic stress (for example disease) and production efficiency (for example, harvesting efficiency, processability).
The above identified indicators for the health condition of a plant may be interdependent and may result from each other. Each indicator is defined in the art and can be determined by meth- ods known to a skilled person.
The compounds of the invention are also suitable for use against non-crop insect pests. For use against said non-crop pests, compounds of the present invention can be used as bait composition, gel, general insect spray, aerosol, as ultra-low volume application and bed net (impreg- nated or surface applied). Furthermore, drenching and rodding methods can be used.
As used herein, the term "non-crop insect pest" refers to pests, which are particularly relevant for non-crop targets, such as ants, termites, wasps, flies, ticks, mosquitos, crickets, or cockroaches.
The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). The bait employed in the composition is a product, which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it. The attractiveness can be manipulated by using feeding stimulants or sex pheromones. Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyor- ganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature (e.g. http://www.phero- base.com), and are known to those skilled in the art.
For use in bait compositions, the typical content of active ingredient is from 0.001 weight % to 15 weight %, desirably from 0.001 weight % to 5% weight % of active compound.
Formulations of the compounds of the present invention as aerosols (e.g in spray cans), oil sprays or pump sprays are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are preferably composed of the active compound, solvents, furthermore auxiliaries such as emulsifiers, perfume oils, if appropriate stabilizers, and, if required, propellants.
The oil spray formulations differ from the aerosol recipes in that no propellants are used.
For use in spray compositions, the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.
The compounds of the present invention and its respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems.
Methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with compounds of the present invention and its respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like. Insecticidal compositions for application to fibers, fabric, knitgoods, nonwovens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder.
The compounds of the present invention and its compositions can be used for protecting wooden materials such as trees, board fences, sleepers, frames, artistic artifacts, etc. and buildings, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities).
Customary application rates in the protection of materials are, for example, from 0.001 g to 2000 g or from 0.01 g to 1000 g of active compound per m2 treated material, desirably from 0.1 g to 50 g per m2.
Insecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 weight %, preferably from 0.1 to 45 weight %, and more preferably from 1 to 25 weight % of at least one repellent and/or insecticide.
The compounds of the the present invention are especially suitable for efficiently combating animal pests such as arthropods, gastropods and nematodes including but not limited to:
insects from the order of Lepidoptera, for example Achroia grisella, Acleris spp. such as A. fim- briana, A. gloverana, A. variana; Acrolepiopsis assectella, Acronicta major, Adoxophyes spp. such as A. cyrtosema, A. orana; Aedia leucomelas, Agrotis spp. such as A. exclamationis, A. fucosa, A. ipsilon, A. orthogoma, A. segetum, A. subterranea; Alabama argillacea, Aleurodicus dispersus, Aisophiia pometaria, Ampelophaga rubiginosa, Amyeiois transiteiia, Anacampsis sar- cite/la, Anagasta kuehniella, Anarsia lineatella, Anisota senator/a, Antheraea pernyi, Anticarsia (=Thermesia) spp. such as A. gemma talis; Apamea spp., Aproaerema modicella, Arch ips spp. such as A. argyrospi/a, A. fuscocupreanus, A. rosana, A. xyloseanus; Argyresthia conjugella, Argyroploce spp., Argyrotaenia spp. such as A. velutinana; Athetis mindara, Austroasca viridi- grisea, Autographa gamma, Autographa nigrisigna, Barathra brassicae, Bedellia spp., Bonagota salubricola, Borbo cinnara, Bucculatrix thurberiella, Bupalus piniarius, Busseola spp., Cacoecia spp. such as C. murinana, C. podana; Cactoblastis cactorum, Cadra cautella, Calingo brazilien- sis, Caloptilis theivora, Capua reticulana, Carposina spp. such as C. niponensis, C. sasakii; Ce- phus spp., Chaetocnema aridula, Cheimatobia brumata, C ? spp. such as C. Indicus, C. sup- pressalis, C. partellus; Choreut/s par/ana, Choristoneura spp. such as C. conflictana, C. fumife- rana, C. longicellana, C. murinana, C. occidentalis, C. rosaceana; Chrysodeixis (=Pseudoplu- sia) spp. such as C. eriosoma, C. includens; Cirphis unipuncta, Clysia ambiguella, Cnaphaloce- rus spp., Cnaphalocrocis medinalis, Cnephasia spp., Cochylis hospes, Coleophora spp., Co/las eurytheme, Conopomorpha spp., Conotrachelus spp., Cop/tarsia spp., Corcyra cephalonica, Crambus caliginosellus, Crambus teterrellus, Crocidosema (=Epinotia) aporema, Cydalima (=Diaphania) perspectaiis, Cydia (=Carpocapsa) spp. such as C. pomoneiia, C. latiferreana; Da- laca noctuides, Datana integerrima, Dasychira pinicola, Dendrolimus spp. such as D. pini, D. spectabilis, D. sibiricus; Desmia funeralis, Diaphania spp. such as D. nitidalis, D. hyalinata; Di- atraea grandiosella, Diatraea saccharalis, Diphthera festiva, Earias spp. such as E. insulana, E. vittella; Ecdytolopha aurantianu, Egira (=Xylomyges) curia/is, E/asmopa/pus lignosellus, Eldana saccharine, Endopiza viteana, Ennomos subsignaria, Eoreuma loftini, Ephestia spp. such as E. cautella, E. elutella, E. kuehniella; Epinotia aporema, Epiphyas postvittana, Erannis tiliaria, Erio- nota thrax, Etiella spp., Eu/ia spp., Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Faronta albilinea, Feltia spp. such as F. subterranean; Galleria mellonella, Gracillaria spp., Grapholita spp. such as G. funebrana, G. molesta, G inopinata; Halysidota spp., Harrisina americana, Hedylepta spp., Helicoverpa spp. such as H. armigera (=Heliothis armigera), H. zea (=Heliothis zea); Heliothis spp. such as H. assulta, H. subflexa, H. virescens; Hellula spp. such as H. undalis, H. rogatalis; Helocoverpa gelotopoeon, Hemileuca oliviae, Her- petogramma licarsisalis, Hibernia defoliaria, Hofmannophila pseudospretella, Homoeosoma electellum, Homona magnanima, Hypena scabra, Hyphantria cunea, Hyponomeuta padella, Hyponomeuta malinellus, Kakivoria flavofasciata, Keiferia lycopersicella, Lambdina fiscellaria fiscellaria, Lambdina fiscellaria lugubrosa, Lamprosema indicata, Laspeyresia molesta, Legumi- nivora glycinivorella, Lerodea eufala, Leucinodes orbonalis, Leucoma salicis, Leucoptera spp. such as L. coffeella, L. scitella; Leuminivora lycinivorella, Lithocolletis blancardella, Lithophane antennata, Llattia octo (=Amyna axis), Lobes/a botrana, Lophocampa spp., Loxagrotis albicosta, Loxostege spp. such as L. sticticaiis, L. cereralis; Lyman tria spp. such as L. dispar, L. monacha; Lyonetia cierkeiia, Lyonetia prunifoiieiia, Malacosoma spp. such as M. americanum, M. californi- cum, M. constrictum, M. neustria; Mamestra spp. such as M. brassicae, M. configurata; Mam- stra brassicae, Manduca spp. such as M. quinquemaculata, M. sexta; Marasmia spp, Marmara spp., Maruca testulalis, Megalopyge lanata, Melanchra picta, Melanitis leda, Mods spp. such as M. lapites, M. repanda; Mods latipes, Monochroa fragariae, Mythimna separata, Nemapogon cloacella, Neoleucinodes elegantalis, Nepytia spp., Nymphula spp., Oiketicus spp., Omiodes indicata, Omphisa anastomosalis, Operophtera brumata, Orgy/a pseudotsugata, Or/a spp., Or- thaga thyrisa/is, Ostrinia spp. such as O. nubilalis; Oulema oryzae, Paleacrita vernata, Panolis flammea, Parnara spp., Papaipema nebris, Papilio cresphontes, Paramyelois transitella, Paran- threne regalis, Paysandisia archon, Pectinophora spp. such as P. gossypiella; Peridroma sau- cia, Perileucoptera spp., such as P. coffeella; Phalera bucephala, Phryganidia californica, Phthorimaea spp. such as P. operculella; Phyllocnistis citrella, Phyllonorycter spp. such as P. blancardella, P. crataegella, P. issikii, P. ringoniella; Pieris spp. such as P. brassicae, P. rapae, P. napi; Pilocrocis tripunctata, Plathypena scabra, Platynota spp. such as P. flavedana, P. idae- usalis, P. stultana; Platyptilia carduidactyla, Plebejus argus, Plodia interpunctella, Plusia spp, Plutella maculipennis, Plutella xylostella, Pontia protodica, Prays spp., Prodenia spp., Proxenus lepigone, Pseudaletia spp. such as P. sequax, P. unipuncta; Pyrausta nubilalis, Rachiplusia nu, Rich/a albicosta, Rhizobius ventralis, Rhyacionia frustrana, Sabulodes aegrotata, Schizura con- cinna, Schoenobius spp., Schreckensteinia festaliella, Scirpophaga spp. such as S. incertulas, S. innotata; Scot/a segetum, Sesamia spp. such as S. inferens, Seudyra subflava, Sitotroga ce- realella, Sparganothis pilleriana, Spilonota lechriaspis, S. ocellana, Spodoptera (=Lamphygma) spp. such as S. cosmoides, S. eridania, S. exigua, S. frugiperda, S. latisfascia, S. littoralis, S. litura, S. omithogalli; Stigmella spp., Stomopteryx subsecivella, Strymon bazochii, Sylepta derogata, Synanthedon spp. such as S. exitiosa, Tecia soianivora, Teiehin Iicus, Thaumatopoea pity oca m pa, Thaumatotibia (=Cryptophlebia) leucotreta, Thaumetopoea pityocampa, The da spp., Theresimima ampelophaga, Thyrinteina spp, Tildenia inconspicuella, Tinea spp. such as T. cloacella, T. pellionella; Tineola bisselliella, Tortrix spp. such as T. viridana; Trichophaga ta- petzella, Trichoplusia spp. such as T. ni; Tuta (=Scrobipalpula) absoluta, Udea spp. such as U. rubigalis, U. rubigalis; Virachola spp., Yponomeuta padella, and Zeiraphera canadensis;
insects from the order of Coleoptera, for example Acalymma vittatum, Acanthoscehdes obtec- tus, Adoretus spp., Agelastica alni, Agrilus spp. such as A. anxius, A. planipennis, A. sinuatus; Agriotes spp. such as A. fuscicollis, A. lineatus, A. obscurus; Alphitobius diaperinus, Amphimal- lus solstitialis, Anisandrus dispar, Anisoplia austriaca, Anobium punctatum, Anomala corpulen- ta, Anomala rufocuprea, Anoplophora spp. such as A. glabripennis; Anthonomus spp. such as A. eugenii, A. grandis, A. pomorum; Anthrenus spp., Aphthona euphoridae, Apion spp., Apogo- nia spp. , Athous haemorrhoidalis, Atomaria spp. such as A. linearis; Attagenus spp. , Aulaco- phora femora/is, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp. such as B. lentis, B. pisorum, B. rufimanus; Byctiscus betulae, Callidiellum rufipenne, Callopis- tria fioridensis, Caiiosobruchus chinensis, Cameraria ohridella, Cassida nebuiosa, Cerotoma tri- furcata, Cetonia aurata, Ceuthorhynchus spp. such as C assimilis, C. napi; Chaetocnema tibi- alis, Cleonus mendicus, Conoderus spp. such as C vespertinus; Conotrachelus nenuphar, Cosmopolites spp., Costelytra zealandica, Crioceris asparagi, Cryptolestes ferrugineus, Cryptorhyn- chus lapathi, Ctenicera spp. such as C destructor; Curculio spp., Cylindrocopturus spp., Cyclo- cephala spp., Dactylispa balyi, Dectes texanus, Dermestes spp., Diabrotica spp. such as D. un- decimpunctata, D. speciosa, D. longicornis, D. semipunctata, D. virgifera; Diaprepes abbrevi- ates, Dichocrocis spp., Dicladispa armigera, Diloboderus abderus, Diocalandra frumenti (Diocal- andra stigma ticollis), Enaphalodes rufulus, Epilachna spp. such as E. varivestis, E. vigintiocto- maculata; Epitrix spp. such as E. hirtipennis, E. simi/aris; Eutheoia humiiis, Eutinobothrus bras/i- iensis, Faustinus cubae, Gibbium psylloides, Gnathocerus cornutus, Hellula undalis, Heterony- chus arator, Hylamorpha elegans, Hylobius abietis, Hylotrupes bajulus, Hypera spp. such as H. brunneipennis, H. postica; Hypomeces squamosus, Hypothenemus spp., Ips typographus,
Lachnosterna consanguinea, Lasioderma serricorne, Latheticus oryzae, Lathridi us spp., Lema spp. such as L. bilineata, L. melanopus; Leptinotarsa spp. such as L. decemlineata; Leptispa pygmaea, Limonius californicus, Lissorhoptrus oryzophilus, Lixus spp., Luperodes spp., Lyctus spp. such as L. bruneus; Liogenys fuscus, Macrodactylus spp. such as M. subspinosus; Mal- adera matrida, Megaplatypus mutates, Megascelis spp., Melanotus communis, Meligethes spp. such as M. aeneus; Melolontha spp. such as M. hippocastani, M. melolontha; Metamasius he- mipterus, Microtheca spp., Migdolus spp. such as M. fryanus, Monochamus spp. such as M. alternates; Naupactus xanthographus, Nipt us hololeucus, Oberia b re vis, Oemona hirta, Oryctes rhinoceros, Oryzaephilus surinamensis, Oryzaphagus oryzae, Otiorrhynchus sulcatus, Otior- rhynchus ovatus, Otiorrhynchus sulcatus, Oulema melanopus, Oulema oryzae, Oxycetonia jucunda, Phaedon spp. such as P. brassicae, P. cochleariae; Phoracantha recurva, Phyllobius pyri, Phyllopertha horticola, Phyllophaga spp. such as P. helleri; Phyllotreta spp. such as P. chrysocephala, P. nemorum, P. striolata, P. vittula; Phyllopertha horticola, Pop/ilia japonica, Premnotry pes spp., Psacothea hilaris, Psylliodes chrysocephala, Prostephanus truncates, Psyl- liodes spp., Ptinus spp., Pulga saltona, Rhizopertha dominica, Rhynchophorus spp. such as R. billineatus, R. ferrugineus, R. palmarum, R. phoenicis, R. vulneratus; Saperda Candida, Scoly- tus schevyrewi, Scyphophorus acupunctatus, Sitona lineatus, Sitophilus spp. such as S. grana- ria, S. oryzae, S. zeamais; Sphenophorus spp. such as S. levis; Stegobium paniceum, Sterne- chus spp. such as S. subsignatus; Strophomorphus ctenotus, Symphyletes spp., Tanymecus spp., Tenebrio molitor, Tenebrioides mauretanicus, Tribolium spp. such as T. castaneum; Tro- goderma spp., Tychius spp., Xylotrech us spp. such as X. pyrrhoderus; and, Zabrus spp. such as Z. tenebrioides;
insects from the order of Diptera for example Aedes spp. such as A. aegypti, A. albopictus, A. vexans; Anastrepha ludens, Anopheles spp. such as A. albimanus, A. crucians, A. freeborni, A. gambiae, A. leucosphyrus, A. maculipennis, A. minimus, A. quadrimaculatus, A. sinensis; Bac- trocera invadens, Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Ceratitis capi- tata, Chrysomyia spp. such as C. bezziana, C. hominivorax, C. macellaria; Chrysops atlanticus, Chrysops discalis, Chrysops silacea, Cochliomyia spp. such as C. hominivorax; Contarinia spp. such as C. sorghicola; Cordylobia anthropophaga, Culex spp. such as C. nigripalpus, C. pipi- ens, C. quinquefasciatus, C. tarsalis, C. tritaeniorhynchus; Culicoides furens, Culiseta inornata, Culiseta melanura, Cuterebra spp., Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Dasi- neura oxycoccana, Delia spp. such as D. antique, D. coarctata, D. platura, D. radicum; Dermat- obia hominis, Drosophila spp. such as D. suzukii, Fannia spp. such as F. canicularis; Gastraphi- lus spp. such as G. intestinaiis; Geomyza tipunctata, Glossina spp. such as G. fuscipes, G. mor- sitans, G pa/pa/is, G. tach/noides; Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia spp. such as H. platura; Hypoderma spp. such as H. lineata; Hyppobosca spp., Hydrellia philippina, Leptoconops torrens, Liriomyza spp. such as L. sativae, L. trifolii; Lucilia spp. such as L. caprina, L. cuprina, L. sericata; Lycoria pectoraiis, Mansonia titiiianus, Mayetioia spp. such as M. destructor; Musca spp. such as M. autumnalis, M. domestica; Muscina stabu- lans, Oestrus spp. such as O. ovis; Opomyza florum, Oscinella spp. such as O. frit; Orseolia oryzae, Pegomya hysocyami, Phlebotomus argentipes, Phorbia spp. such as P. antiqua, P. brassicae, P. coarctata; Phytomyza gymnostoma, Prosimuiium mixtum, Psiia rosae, Psorophora columbiae, Psorophora discolor, Rhagoletis spp. such as R. cerasi, R. cingulate, R. indifferens, R. mendax, R. pomonella; Rivellia quadrifasciata, Sarcophaga spp. such as S. haemorrhoidalis; Simulium vittatum, Sitodiplosis mosellana, Stomoxys spp. such as S. calcitrans; Tabanus spp. such as T. atratus, T. bovinus, T. lineola, T. similis; Tannia spp., Thecodiplosis japonensis, Tip- ula oleracea, Tipula paludosa, and Wohlfahrtia spp;
insects from the order of Thysanoptera for example, Baliothrips biformis, Dichromothrips cor- betti, Dichromothrips ssp., Echinothrips americanus, Enneothrips flavens, Frankliniella spp. such as F. fusca, F. occidentalis, F. tritici; Heliothrips spp., Hercinothrips femora/is, Kakothrips spp., Microcephalothrips abdominalis, Neohydatothrips samayunkur, Pezothrips kellyanus, Rhip- iphorothrips cruentatus, Scirtothrips spp. such as S. citri, S. dorsalis, S. perseae; Stenchae- tothrips spp, Taeniothrips cardamoni, Taeniothrips inconsequens, Thrips spp. such as T. imagi- nes, T. hawaiiensis, T. oryzae, T. palmi, T. parvispinus, T. tabaci;
insects from the order of Hemiptera for example, Acizzia jamatonica, Acrosternum spp. such as A. hilare; Acyrthosipon spp. such as A. onobrychis, A. pisum; Adelges laricis, Adelges tsu- gae, Adelphocoris spp., such as A. rapidus, A. superbus; Aeneolamia spp., Agonoscena spp., Aulacorthum solani, Aleurocanthus woglumi, Aleurodes spp., Aleurodicus disperses, Aleurolo- bus barodensis, Aleurothrixus spp., Amrasca spp., Anasa tristis, Antestiopsis spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphidula nasturtii, Aphis spp. such as A. craccivora, A. fabae, A. forbesi, A. gossypii, A. grossulariae, A. maidiradicis, A. pomi, A. sambuci, A.
schneideri, A. spiraeco/a; Arbor/d/a apica/is, Ar/ius critatus, Aspidiella spp., Aspidiotus spp., Atari nus spp., Au/acasp/s yasumatsui, Aulacorthum so/an/, Bactericera cockerelli (Paratrioza cocker- elli), Bemisia spp. such as B. argentifolii, B. tabaci (Aleurodes tabaci); Blissus spp. such as B. leucopterus; Brachycaudus spp. such as B. cardui, B. helichrysi, B. persicae, B. prunicola; Bra- chycolus spp., Brachycorynella asparagi, Brevicoryne brassicae, Cacopsy I la spp. such as C. fulgu ralis, C. pyricola (Psylla plrlj; Calligypona margin ata, Calocoris spp., Campylomma livida, Capitophorus horn/, Carneocephala fulgida, Cavelerius spp., Ceraplastes spp., Ceratovacuna lanigera, Ceroplastes ceriferus, Cerosipha gossypii, Chaetosiphon fragaefolii, Chionaspis tega- lensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbiia, Cimex spp. such as C hemipterus, C lectularius; Coccomytilus halli, Coccus spp. such as C hesperi- dum, C pseudomagnoliarum, Corythucha arcuata, Creontiades dilutus, Cryptomyzus ribis,
Chrysomphalus aonidum, Cryptomyzus ribis, Ctenarytaina spatulata, Cyrtopeltis notatus, Dalbu- lus spp., Dasynus piperis, Dialeurodes spp. such as D. citrifolii; Dalbulus maidis, Diaphorina spp. such as D. citri; Diaspis spp. such as D. bromeliae; Dichelops furcatus, Diconocoris he- wetti, Dora/is spp., Dreyfusia nordmannianae, Dreyfusia piceae, Drosicha spp., Dysaphis spp. such as D. plantaginea, D. pyri, D. radicola; Dysaulacorthum pseudosolani, Dysdercus spp. such as D. cingulatus, D. intermedius; Dysmicoccus spp., Edessa spp., Geocoris spp., Empo- asca spp. such as E. fabae, E. so/ana; Ep/diaspis leperii, Eriosoma spp. such as E. lanigerum, E. pyricola; Erythroneura spp., Eurygaster spp. such as E. integriceps; Euscelis bilobatus, Eu- schistus spp. such as E. heros, E. impictiventris, E. servus; Fiorinia theae, Geococcus coffeae, Glycaspis brimblecombei, Halyomorpha spp. such as H. halys; Heliopeltis spp., Homalodisca vitripennis (=H. coagulata), Horcias nobiieiius, Hyaiopterus pruni, Hyperomyzus lactucae, Icerya spp. such as I. purchase; Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Lecanium spp., Lecanoideus floccissimus, Lepidosaphes spp. such as L. ulmi; Leptocorisa spp., Lepto- glossus phyllopus, Lipaphis erysimi, Lygus spp. such as L. hesperus, L. lineolaris, L. pratensis; Maconellicoccus hirsutus, Marchalina hellenica, Macropes excavatus, Macrosiphum spp. such as M. rosae, M. a venae, M. euphorbiae; Macrosteles quadrilineatus, Mahanarva fimbriolata, Megacopta cribraria, Megoura viciae, Melanaphis pyrarius, Melanaphis sacchari, Melanocallis (=Tinocallis) caryaefoliae, Metcafiella spp., Metopolophium dirhodum, Monellia costalis, Monel- liopsis pecanis, Myzocallis coryli, Murgantia spp., Myzus spp. such as M. ascalonicus, M. cera- si, M. nicotianae, M. persicae, M. varians; Nasonovia ribis-nigri, Neotoxoptera formosana, Neo- megalotomus spp, Nephotettix spp. such as N. malayanus, N. nigropictus, N. parvus, N. vires- cens; Nezara spp. such as N. viridula; Niiaparvata lugens, Nysius huttoni, Oebaius spp. such as O. pugnax; Oncometopia spp., Orthezia praelonga, Oxycaraenus hyalinipennis, Parabemisia myricae, Parlatoria spp., Parthenolecanium spp. such as P. corn/, P. persicae; Pemphigus spp. such as P. bursar/us, P. popu/ivenae; Peregrin us maidis, Perkinsiella saccharic/da, Phenaco- ccus spp. such as P. aceris, P. gossypii; Phloeomyzus passer/nil, Phorodon humu/i, Phylloxera spp. such as P. devastatrix, Piesma quadrata, Piezodorus spp. such as P. guildinii; Pinnaspis aspidistrae, Planococcus spp. such as P. citri, P. ficus; Prosapia bicincta, Protopulvinaria pyri- formis, Psallus seriatus, Pseudacysta persea, Pseudaulacaspis pentagona, Pseudococcus spp. such as P. comstocki; Psylla spp. such as P. mali; Pteromalus spp., Pulvinaria amygdali, Pyrilla spp., Quadraspidiotus spp., such as Q. perniciosus; Quesada gigas, Rastrococcus spp., Redu- vius senilis, Rhizoecus americanus, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosi- phum spp. such as R. pseudobrassicas, R. insertum, R. maidis, R. pad/; Sagatodes spp., Sahl- bergella singularis, Saissetia spp., Sappaphis mala, Sappaphis mali, Scaptocoris spp., Scaph- oides titan us, Schizaphis graminum, Schizoneura lanuginosa, Scotinophora spp., Selenaspidus articulatus, Sitobion avenae, Sogata spp., Sogatella furcifera, Solubea insularis, Spissistilus festinus (=Stictocephala festina), Stephanitis nashi, Stephanitis pyrioides, Stephanitis takeyai, Tenalaphara malayensis, Tetraleurodes perseae, Therioaphis maculate, Thyanta spp. such as T. accerra, T. perditor; Tibraca spp., Tomaspis spp., Toxoptera spp. such as T. aurantii; Trialeu- rodes spp. such as T. abutilonea, T. ricini, T. vaporariorum; Triatoma spp., Trioza spp., Typhlo- cyba spp., Unaspis spp. such as U. citri, U. yanonensis; and Viteus vitifolii,
Insects from the order Hymenoptera for example Acanthomyops interjectus, Athalia rosae, Atta spp. such as A. capiguara, A. cephalotes, A. cephalotes, A. laevigata, A. robusta, A. sex- dens, A. texana, Bombus spp., Brachymyrmex spp., Camponotus spp. such as C. floridanus, C. pennsylvanicus, C. modoc; Cardiocondyla nuda, Chalibion sp, Crematogaster spp., Dasymutilla occidentalis, Diprion spp., Dolichovespula maculata, Dorymyrmex spp., Dryocosmus kuriphilus, Formica spp., Hoplocampa spp. such as H. minuta, H. testudinea; Iridomyrmex humilis, Lasius spp. such as L. niger, Linepithema humile, Liometopum spp., Leptocybe invasa, Monomorium spp. such as M. pharaonis, Monomorium, Nylandria fulva, Pachycondyla chinensis, Paratrechi- na longicornis, Paravespula spp., such as P. germanica, P. pennsylvanica, P. vulgaris; Pheidole spp. such as P. megacephala; Pogonomyrmex spp. such as P. barbatus, P. californicus, Polis- tes rubiginosa, Prenolepis impairs, Pseudomyrmex gracilis, Schelipron spp., Sirex cyaneus, So- lenopsis spp. such as S. geminata, S.invicta, S. molesta, S. richteri, S. xyloni, Sphecius specio- sus, Sphexspp., Tapinoma spp. such as T. melanocephalum, T. sessile; Tetramorium spp. such as T. caespitum, T. bicarinatum, Vespa spp. such as V. crabro; Vespula spp. such as V. squamosal; Wasmannia auropunctata, Xylocopa sp;
Insects from the order Orthoptera for example Acheta domesticus, Calliptamus italicus, Chor- toicetes termini fera, Ceuthophilus spp., Diastrammena asynamora, Dociostaurus maroccanus, Gryllotalpa spp. such as G. africana, G. gryllotalpa; Gryllus spp., Hieroglyphus daganensis, Kraussaria angulifera, Locusta spp. such as L. migratoria, L. pardalina; Melanoplus spp. such as M. bivittatus, M. femurrubrum, M. mexicanus, M. sanguinipes, M. spretus; Nomadacris sep- temfasciata, Oedaleus senegalensis, Scapteriscus spp., Schistocerca spp. such as S. ameri- cana, S. gregaria, Stemopelmatus spp., Tachycines asynamorus, and Zonozerus variegatus; Pests from the Class Arachnida for example Acari,e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma spp. (e.g. A. americanum, A. variegatum, A. maculatum), Ar- gas spp. such as A. persicu), Boophilus spp. such as B. annulatus, B. decoloratus, B. micro- plus, Dermacentor spp. such as D.silvarum, D. andersoni, D. variabilis, Hyalomma spp. such as H. truncatum, Ixodes spp. such as /. ricinus, I. rubicundus, I. scapularis, I. holocyclus, I. pacifi- cus, Rhipicephalus sanguineus, Ornithodorus spp. such as O. moubata, O. hermsi, O. turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes spp. such as P. ovis, Rhipicephalus spp. such as R. sanguineus, R. appendiculatus, Rhipicephalus everts/, Rh/zog/y- phus spp., Sarcoptes spp. such asS. Scabiei, and Family Eriophyidae including Acer/a spp. such as A. she/doni, A. anthocoptes, Acallitus spp., Aculops spp. such as A. lycopersici, A. pel- ekassi, Aculus spp. such as A. schlechtendali; Colomerus vitis, Epitrimerus pyri, Phyllocoptruta oleivora; Eriophytes ribis and Eriophyes spp. such as Eriophyes sheldonr, Family Tarsonemidae including Hemitarsonemus spp., Phytonemus pallidus and Polyphagotarsonemus latus, Steno- tarsonemus spp. Steneotarsonemus spinki, Family Tenuipalpidae including Brevipalpus spp. such as B. phoenicisr, Family Tetranychidae including Eotetranychus spp., Eutetranychus spp., Oligonychus spp., Petrobia latens, Tetranych us spp. such as T. cinnabarinus, T. evansi, T. kan- zawai, T, pacificus, T. phaseulus, T. telarius and T. urticae; Bryobia praet/osa; Panonychus spp. such as P. ulmi, P. citri, Metatetranychus spp. and Oligonychus spp. such as 0. pratensis, O. perseae, Vasates lycopersici, Raoiella indica, /¾/77/7yCarpoglyphidae including Carpoglyphus spp.; Penthaleidae spp. such as Halotydeus destructor, Family Demodicidae with species such as Demodexspp.; Family Trombicidea including Trombicula spp.; Family Macronyssidae including Ornothonyssus spp.; Family Pyemotidae including Pyemotes tritici, Tyrophagus putrescen- tiae; Family Acaridae including Acarus siro, Family Araneida including Latrodectus mactans, Te- gen aria agrestis, Chiracanthium sp, Lycosa sp Achaearanea tepidariorum and Loxosceles re- c/usa;
Pests from the Phylum Nematoda, for example, plant parasitic nematodes such as root-knot nematodes, Meloidogyne spp. such as M. hapla, M. incognita, M. javanica; cyst-forming nematodes, Globodera spp. such as G. rostochiensis; Heterodera spp. such as H. avenae, H. glyci- nes, H. schachtii, H. trifolii; Seed gall nematodes, Anguina spp:, Stem and foliar nematodes,
Aphelenchoides spp. such as A. besseyi; Sting nematodes, Belonolaimus spp. such as B. longi- caudatus; Pine nematodes, Bursaphelenchus spp. such as B. lignicolus, B. xylophilus; Ring nematodes, Criconema spp., Criconemella spp. such as C. xenoplax and C. ornata; and, Crico- nemoides spp. such as Criconemoides in formis; Mesocriconema spp.; Stem and bulb nema- todes, Ditylenchus spp. such as £>. destructor, D. dipsaci;Aw\ nematodes, Dolichodorus spp.; Spiral nematodes, Heliocotylenchus multicinctus; Sheath and sheathoid nematodes, Hemicycli- ophora spp. and Hemicriconemoides spp.; Hirshmanniella spp.; Lance nematodes, Hoploaimus spp.; False rootknot nematodes, Nacobbus spp.; Needle nematodes, Longidorus spp. such as Z.. elongatus; Lesion nematodes, Pratylenchus spp. such as . brachyurus, P. neglectus, P. pe- netrans, P. curvitatus, P. goodeyi; Burrowing nematodes, Radopholus spp. such as R. similis; Rhadopholus spp.; Rhodopholus spp.; Reniform nematodes, Rotylenchus spp. such as R. ro- bustus, R. reniformis; Scutellonema spp.; Stubby-root nematode, Trichodorus spp. such as T. obtusus, T. primitivus; Paratrichodorus spp. such as P. minor; Stunt nematodes, Tylenchorhyn- chus spp. such as T. claytoni, T. dub/us; Citrus nematodes, Tylenchulus spp. such as 7^ se/77/- penetrans; Dagger nematodes, Xiphinema spp.; and other plant parasitic nematode species; Insects from the order Isoptera for example Calotermes flavicollis, Coptotermes spp. such as C. formosanus, C. gestroi, C. acinaciformis; Cornitermes cumulans, Cry ptotermes spp. such as C. brevis, C. cavifrons; Globitermes sulfureus, Heterotermes spp. such as H. aureus, H. longi- ceps, H. tenuis; Leucotermes flavipes, Odontotermes spp., I ncisitermes spp. such as /. minor, I. Snyder, Marginitermes hubbardi, Ma stotermes spp. such as M. darwiniensis Neocapritermes spp. such as N. opacus, N. parvus; Neotermes spp., Procornitermes spp., Zootermopsis spp. such as Z. angusticollis, Z. nevadensis, Reticulitermes spp. such as R. hesperus, R. tibialis, R. speratus, R. flavipes, R. grassei, R. lucifugus, R. santonensis, R. virgin icus; Termes natalensis, Insects from the order Blattaria for example Blattaspp. such as B. orientalis, B. lateralis; Blattella spp. such as B. asahinae, B. germanica; Leucophaea maderae, Panchlora nivea, Periplaneta spp. such as P. americana, P. australasiae, P. brunnea, P. fuligginosa, P. japonica; Supella long- ipalpa, Parcoblatta pennsylvanica, Eurycotis floridana, Pycnoscelus surinamensis,
Insects from the order Siphonoptera for example Cediopsylla simples, Ceratophyllus spp., Cte- nocephalides spp. such as C. felis, C. cam's, Xenopsylla cheopis, Pulex irritans, Trichodectes canis, Tunga penetrans, and Nosopsyllus fasciatus, Insects from the order Thysanura for example Lepisma saccharina, Ctenolepisma urbana, and Thermobia domestica, Pests from the class Chilopoda for example Geophilus spp., Scutigera spp. such as Scutigera co/eoptrata; Pests from the class Diplopoda for example Blaniulus guttulatus, Ju/us spp., Narceus spp., Pests from the class Symphyla for example Scutigerella immaculata, Insects from the order Dermaptera, for example Forficula auricularia, Insects from the order Collembola, for example Onychiurus spp., such as Onychiurus armatus, Pests from the order Isopoda for example, Armadiiiidium vul- gare, Oniscus asellus, Porcellio scaber, Insects from the order Phthiraptera, for example Dama- linia spp., Pediculus spp. such as Pediculus humanus capitis, Pediculus humanus corporis, Pe- diculus humanus humanus; Pthirus pubis, Haematopinus spp. such as Haematopinus euryster- nus, Haematopinus suis; Linognathus spp. such as Linognathus vituli; Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus, Trichodectes spp., Examples of further pest species which may be controlled by compounds of fomula (I) include: from the Phylum Mollusca, class Bivalvia, for example, Dre/ssena spp.; class Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Pomacea canaliclata, Succinea spp.; from the class of the helminths, for example, Ancy- lostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., As- caris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooper/a spp., Dicrocoelium spp., D/ctyocaulus filar/a, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp. such as Haemonchus contortus; Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Op isth orchis spp., Onchocerca volvulus, Ostertagia spp., Paragonim us spp., Schistosomen spp., Strongyloides fuelleborni, Strongyloides stercora lis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti.
The present invention also relates to a mixture of at least one compound of the present invention with at least one mixing partner as defined herein after. Preferred are binary mixtures of one compound of the present invention as component I with one mixing partner as defined herein after as component II. Preferred weight ratios for such binary mixtures are from 5000:1 to 1 :5000, preferably from 1000:1 to 1 :1000, more preferably from 100:1 to 1 :100, particularly preferably from 10:1 to 1 :10. In such binary mixtures, components I and II may be used in equal amounts, or an excess of component I, or an excess of component II may be used.
Mixing partners can be selected from pesticides, in particular insecticides, nematicides, and acaricides, fungicides, herbicides, plant growth regulators, fertilizers, and the like. Preferred mixing partners are insecticides, nematicides and fungicides.
The following list M of pesticides, grouped and numbered according the Mode of Action Classification of the Insecticide Resistance Action Committee (IRAC), together with which the com- pounds of the present invention can be used and with which potential synergistic effects might be produced, is intended to illustrate the possible combinations, but not to impose any limitation: M.1 Acetylcholine esterase (AChE) inhibitors from the class of: M.1 A carbamates, for example aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofu- ran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate; or from the class of M.1 B organophosphates, for example acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, dia- zinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O- (methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, me- carbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxyde- meton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phos- phamidon, phoxim, pirimiphos- methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyri- daphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thio- meton, triazophos, trichlorfon and vamidothion;
M.2. GABA-gated chloride channel antagonists such as: M.2A cyclodiene organochlorine compounds, as for example endosulfan or chlordane; or M.2B fiproles (phenylpyrazoles), as for ex- ample ethiprole, fipronil, flufiprole, pyrafluprole and pyriprole;
M.3 Sodium channel modulators from the class of M.3A pyrethroids, for example acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopent- enyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpro- pathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, heptafluthrin, imipro- thrin, meperfluthrin,metofluthrin, momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethylfluthrin, tetramethrin, tralo- methrin and transfluthrin; or M.3B sodium channel modulators such as DDT or methoxychlor; M.4 Nicotinic acetylcholine receptor agonists (nAChR) from the class of M.4A neonicotinoids: acetamiprid, clothianidin, cycloxaprid, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thi- amethoxam; or the compounds M.4A.2: (2E-)-1-[(6-Chloropyridin-3-yl)methyl]-N'-nitro-2-pentyli- denehydrazinecarboximidamide; or M4.A.3: 1 -[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro-5- propoxy-1 ,2,3,5,6,7-hexahydroimidazo[1 ,2-a]pyridine; or from the class M.4B nicotine;
M.5 Nicotinic acetylcholine receptor allosteric activators from the class of spinosyns: spinosad or spinetoram;
M.6 Chloride channel activators from the class of avermectins and milbemycins, for example abamectin, emamectin benzoate, ivermectin, lepimectin or milbemectin;
M.7 Juvenile hormone mimics: M.7A juvenile hormone analogues as hydroprene, kinoprene and methoprene; or others as M.7B fenoxycarb or M.7C pyriproxyfen;
M.8 miscellaneous non-specific (multi-site) inhibitors, for example M.8A alkyl halides as methyl bromide and other alkyl halides, or M.8B chloropicrin, or M.8C sulfuryl fluoride, or M.8D borax, or M.8E tartar emetic;
M.9 Selective homopteran feeding blockers: M.9B pymetrozine, or M.9C flonicamid;
M.10 Mite growth inhibitors: M.10A clofentezine, hexythiazox and diflovidazin, or M.10B etoxa- zole;
M.1 1 Microbial disruptors of insect midgut membranes, for example bacillus thuringiensis or bacillus sphaericus, and the insecticdal proteins they produce such as bacillus thuringiensis subs p. israelensis, bacillus sphaericus, bacillus thuringiensis subs p. aizawai, bacillus thurin- giensis subsp. kurstakiand bacillus thuringiensis subsp. tenebrionis, or the Bt crop proteins: Cry-IAb, CrylAc, Cryl Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb and Cry34/35Ab1 ;
M.12 Inhibitors of mitochondrial ATP synthase: M.12A diafenthiuron, or M.12B organotin miti- cides such as azocyclotin, cyhexatin or fenbutatin oxide, or M.12C propargite, or M.12D tetradi- fon;
M.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient:
chlorfenapyr, DNOC or sulfluramid;
M.14 Nicotinic acetylcholine receptor (nAChR) channel blockers, for example nereistoxin ana- logues as bensultap, cartap hydrochloride, thiocyclam or thiosultap sodium;
M.15 Inhibitors of the chitin biosynthesis type 0, such as benzoylureas as for example bistriflu- ron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novalu- ron, noviflumuron, teflubenzuron or triflumuron;
M.16 Inhibitors of the chitin biosynthesis type 1 , as for example buprofezin;
M.17 Moulting disruptors, Dipteran, as for example cyromazine;
M.18 Ecdyson receptor agonists such as diacylhydrazines, for example methoxyfenozide, tebufenozide, halofenozide, fufenozide or chromafenozide;
M.19 Octopamin receptor agonists, as for example amitraz;
M.20 Mitochondrial complex III electron transport inhibitors, for example M.20A hydramethyl- non, or M.20B acequinocyl, or M.20C fluacrypyrim;
M.21 Mitochondrial complex I electron transport inhibitors, for example M.21 A METI acaricides and insecticides such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad or tolfenpyrad, or M.21 B rotenone;
M.22 Voltage-dependent sodium channel blockers: M.22A indoxacarb, or M.22B metaflumi- zone, or M.22B.1 : 2-[2-(4-Cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoro- methoxy)phenyl]-hydrazinecarboxamide or M.22B.2: N-(3-Chloro-2-methylphenyl)-2-[(4-chloro- phenyl)[4-[methyl(methylsulfonyl)amino]phenyl]methylene]-hydrazinecarboxamide;
M.23 Inhibitors of the of acetyl CoA carboxylase, such as Tetronic and Tetramic acid derivatives, for example spirodiclofen, spiromesifen or spirotetramat;
M.24 Mitochondrial complex IV electron transport inhibitors, for example M.24A phosphine such as aluminium phosphide, calcium phosphide, phosphine or zinc phosphide, or M.24B cyanide;
M.25 Mitochondrial complex II electron transport inhibitors, such as beta-ketonitrile derivatives, for example cyenopyrafen or cyflumetofen;
M.28 Ryanodine receptor-modulators from the class of diamides: flubendiamide, chlorantranili- prole (rynaxypyr®), cyantraniliprole (cyazypyr®), tetraniliprole, or the phthalamide compounds M.28.1 : (R)-3-Chloro-N 1 -{2-methyl-4-[1 ,2,2,2-tetrafluoro-1 -(trifluormethyl)ethyl]phenyl}-N2-(1 - methyl-2-methylsulfonylethyl)phthalamid and M.28.2: (S)-3-Chlor-N1 -{2-methyl-4-[1 ,2,2,2-tetra- fluoro-1 -(trifluoromethyl)ethyl]phenyl}-N2-(1-methyl-2-methylsulfonylethyl)phthalamid, or the compound M.28.3: 3-bromo-N-{2-bromo-4-chloro-6-[(1-cyclopropylethyl)carbamoyl]phenyl}-1-(3- chloropyridin-2-yl)-1 H-pyrazole-5-carboxamide (cyclaniliprole), or the compound M.28.4: methyl- 2-[3,5-dibromo-2-({[3-bromo-1-(3-chloropyridin-2-yl)-1 H-pyrazol-5-yl]carbonyl}amino)benzoyl]- 1 ,2-dimethylhydrazinecarboxylate; or a compound selected from M.28.5a) to M.28.5d) and M.28.5h) to M.28.5I): M.28.5a) N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]- phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; M.28.5b) N-[4-chloro- 2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5 romethyl)pyrazole-3-carboxamide; M.28.5c) N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanyli- dene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-^ amide; M.28.5d) N-[4,6-dichloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3- chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; M.28.5h) N-[4,6-dibromo-2-[(di- ethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyra zole-3-carboxamide; M.28.5i) N-[2-(5-Amino-1 ,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3- bromo-1-(3-chloro-2-pyridinyl)-1 H-pyrazole-5-carboxamide; M.28.5j) 3-Chloro-1 -(3-chloro-2-pyri- dinyl)-N-[2,4-dichloro-6-[[(1 -cyano-1 -methylethyl)amino]carbonyl]phenyl]-1 H-pyrazole-5-carbox- amide; M.28.5k) 3-Bromo-N-[2,4-dichloro-6-(methylcarbamoyl)phenyl]-1-(3,5-dichloro-2-pyridyl)- 1 H-pyrazole-5-carboxamide; M.28.5I) N-[4-Chloro-2-[[(1 ,1-dimethylethyl)amino]carbonyl]-6- methylphenyl]-1-(3-chloro-2-pyridinyl)-3-(fluoromethoxy)-1 H-pyrazole-5-carboxamide; or
M.28.6: cyhalodiamide; or;
M.29. insecticidal active compounds of unknown or uncertain mode of action, as for example afidopyropen, afoxolaner, azadirachtin, amidoflumet, benzoximate, bifenazate, broflanilide, bro- mopropylate, chinomethionat, cryolite, dicloromezotiaz, dicofol, flufenerim, flometoquin, fluen- sulfone, fluhexafon, fluopyram, flupyradifurone, fluralaner, metoxadiazone, piperonyl butoxide, pyflubumide, pyridalyl, pyrifluquinazon, sulfoxaflor, tioxazafen, triflumezopyrim, or M.29.3: 1 1 -(4- chloro-2,6-dimethylphenyl)-12-hydroxy-1 ,4-dioxa-9-azadispiro[4.2.4.2]-tetradec-1 1-en-10-one, or M.29.4: 3-(4'-fluoro-2,4-dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-1-azaspiro[4.5]dec-3-en-2- one, or M.29.5: 1 -[2-fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)- 1 H-1 ,2,4-triazole-5-amine, or actives on basis of bacillus firmus (Votivo, 1-1582); or a compound selected from M.29.6, wherein the compound is selected from M.29.6a) to M.29.6k): M.29.6a) (E/Z)-N-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide; M.29.6b) (E/Z)- N-[1-[(6-chloro-5-fluoro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide; M.29.6c) (E/Z)-2,2,2-trifluoro-N-[1 -[(6-fluoro-3-pyridyl)methyl]-2-pyridylidene]acetamide; M.29.6d) (E/Z)-N- [1 -[(6-bromo-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide; M.29.6e) (E/Z)-N-[1-[1 - (6-chloro-3-pyridyl)ethyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide; M.29.6f) (E/Z)-N-[1-[(6-chlo- ro-3-pyridyl)methyl]-2-pyridylidene]-2,2-difluoro-acetamide; M.29.6g) (E/Z)-2-chloro-N-[1 -[(6- chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2-difluoro-acetamide; M.29.6h) (E/Z)-N-[1-[(2-chloro- pyrimidin-5-yl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide; M.29.6i) (E/Z)-N-[1 -[(6-chloro-3- pyridyl)methyl]-2-pyridylidene]-2,2,3,3,3-pentafluoro-propanamide.); M.29.6j) N-[1 -[(6-chloro-3- pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-thioacetamide; or M.29.6k) N-[1 -[(6-chloro-3-pyri- dyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-N'-isopropyl-acetamidine; or M.29.8: fluazaindolizine; or M.29.9. a): 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(1-ox- othietan-3-yl)benzamide; or M.29.9. b): fluxametamide; or M.29.10: 5-[3-[2,6-dichloro-4-(3,3-di- chloroallyloxy)phenoxy]propoxy]-1 H-pyrazole; or a compound selected from M.29.1 1 , wherein the compound is selected from M.29.1 1 b) to M.29.1 1 p): M.29.1 1 .b) 3-(benzoylmethylamino)-N- [2-bromo-4-[1 ,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]-6-(trifluoromethyl)phenyl]-2-fluoro- benzamide; M.29.1 1 .c) 3-(benzoylmethylamino)-2-fluoro-N-[2-iodo-4-[1 ,2,2,2-tetrafluoro-1-(tri- fluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]-benzamide; M.29.1 1 .d) N-[3-[[[2-iodo-4-[1 ,2,2,2- tetrafluoro-1-(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]amino]carbonyl]phenyl]-N-methyl- benzamide; M.29.1 1 .e) N-[3-[[[2-bromo-4-[1 ,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6-(trifluoro- methyl)phenyl]amino]carbonyl]-2-fluorophenyl]-4-fluoro-N-methyl-benzamide; M.29.1 1.f) 4-flu- oro-N-[2-fluoro-3-[[[2-iodo-4-[1 ,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6-(trifluorom
nyl]amino]carbonyl]phenyl]-N-methyl-benzamide; M.29.1 1 .g) 3-fluoro-N-[2-fluoro-3-[[[2-iodo-4- [1 ,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]amino]carbonyl]pheny^ methyl-benzamide; M.29.1 1.h) 2-chloro-N-[3-[[[2-iodo-4-[1 ,2,2,2-tetrafluoro-1 -(trifluorome- thyl)ethyl]-6-(trifluoromethyl)phenyl]amino]carbonyl]phenyl]- 3-pyridinecarboxamide; M.29.1 1 .i) 4-cyano-N-[2-cyano-5-[[2,6-dibromo-4-[1 ,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phe- nyl]carbamoyl]phenyl]-2-methyl-benzamide; M.29.1 1.j) 4-cyano-3-[(4-cyano-2-methyl-benzo- yl)amino]-N-[2,6-dichloro-4-[1 ,2,2,3,3,3-hexafluoro-1-(trifluoromethyl)propyl]phenyl]-2-fluoro- benzamide; M.29.1 1 .k) N-[5-[[2-chloro-6-cyano-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)pro- pyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; M.29.1 1 .1) N-[5-[[2-bromo- 6-chloro-4-[2,2,2-trifluoro-1-hydroxy-1 -(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano-phenyl]-
4- cyano-2-methyl-benzamide; M.29.1 1.m) N-[5-[[2-bromo-6-chloro-4-[1 ,2,2,3,3,3-hexafluoro-1- (trifluoromethyl)propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide;
M.29.1 1.n) 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[1 ,2,2,3,3,3-hexafluoro-1 -(trifluoromethyl)pro- pyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; M.29.1 1 .o) 4-cyano-N-[2-cyano-5-[[2,6-di- chloro-4-[1 ,2,2,2-tetrafluoro-1-(trifluoromethyl)ethyl]phenyl]carbamoyl]phenyl]-2-methyl-ben- zamide; M.29.1 1.p) N-[5-[[2-bromo-6-chloro-4-[1 ,2,2,2-tetrafluoro-1 -(trifluoromethyl)ethyl]phe- nyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; or
M.29.12, selected from M.29.12a) to M.29.12m): M.29.12.a) 2-(1 ,3-Dioxan-2-yl)-6-[2-(3-pyridi- nyl)-5-thiazolyl]-pyridine; M.29.12. b) 2-[6-[2-(5-Fluoro-3-pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimi- dine; M.29.12.C) 2-[6-[2-(3-Pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine; M.29.12.d) N-Methylsul- fonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carboxamide; M.29.12.e) N-Methylsulfonyl-6-[2-(3- pyridyl)thiazol-5-yl]pyridine-2-carboxamide; M.29.12.f) N-Ethyl-N-[4-methyl-2-(3-pyridyl)thiazol-
5- yl]-3-methylthio-propanamide; M.29.12.g) N-Methyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3- methylthio-propanamide; M.29.12.h) N,2-Dimethyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3-me- thylthio-propanamide; M.29.12.i) N-Ethyl-2-methyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3-me- thylthio-propanamide; M.29.12.j) N-[4-Chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-2-methyl-3-me- thylthio-propanamide; M.29.12.k) N-[4-Chloro-2-(3-pyridyl)thiazol-5-yl]-N,2-dimethyl-3-methyl- thio-propanamide; M.29.12.1) N-[4-Chloro-2-(3-pyridyl)thiazol-5-yl]-N-methyl-3-methylthio-pro- panamide; M.29.12. m) N-[4-Chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-3-methylthio-propanamide; or
M.29.14a) 1 -[(6-Chloro-3-pyridinyl)methyl]-1 ,2,3,5,6,7-hexahydro-5-methoxy-7-methyl-8-nitro- imidazo[1 ,2-a]pyridine; or M.29.14b) 1-[(6-Chloropyridin-3-yl)methyl]-7-methyl-8-nitro- 1 ,2,3,5,6,7-hexahydroimidazo[1 ,2-a]pyridin-5-ol; or
M.29.16a) 1 -isopropyl-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; or M.29.16b) 1- (1 ,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; M.29.16c) N,5- dimethyl-N-pyridazin-4-yl-1 -(2,2,2-trifluoro-1 -methyl-ethyl)pyrazole-4-carboxamide; M.29.16d) 1- [1 -(1 -cyanocyclopropyl)ethyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide;
M.29.16e) N-ethyl-1-(2-fluoro-1-methyl-propyl)-5-methyl-N-pyridazin-4-yl-pyrazole-4-carbox- amide; M.29.16f) 1 -(1 ,2-dimethylpropyl)-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; M.29.16g) 1-[1 -(1 -cyanocyclopropyl)ethyl]-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carbox- amide; M.29.16h) N-methyl-1-(2-fluoro-1 -methyl-propyl]-5-methyl-N-pyridazin-4-yl-pyrazole-4- carboxamide; M.29.16i) 1 -(4,4-difluorocyclohexyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4- carboxamide; or M.29.16j) 1-(4,4-difluorocyclohexyl)-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4- carboxamide, or
M.29.17: M.29.17a) to M.29.17j): M.29.17a) N-(1 -methylethyl)-2-(3-pyridinyl)-2H-indazole-4- carboxamide; M.29.17b) N-cyclopropyl-2-(3-pyridinyl)-2H-indazole-4-carboxamide; M.29.17c) N- cyclohexyl-2-(3-pyridinyl)-2H-indazole-4-carboxamide; M.29.17d) 2-(3-pyridinyl)-N-(2,2,2-trifluo- roethyl)-2H-indazole-4-carboxamide; M.29.17e) 2-(3-pyridinyl)-N-[(tetrahydro-2-furanyl)methyl]- 2H-indazole-5-carboxamide; M.29.17f) methyl 2-[[2-(3-pyridinyl)-2H-indazol-5-yl]carbonyl]hydra- zinecarboxylate; M.29.17g) N-[(2,2-difluorocyclopropyl)methyl]-2-(3-pyridinyl)-2H-indazole-5- carboxamide; M.29.17h) N-(2,2-difluoropropyl)-2-(3-pyridinyl)-2H-indazole-5-carboxamide;
Μ.29.17Ϊ) 2-(3-pyridinyl)-N-(2-pyrimidinylmethyl )-2H-indazole-5-carboxamide; M.29.17j) N-[(5- methyl-2-pyrazinyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide, or
M.29.18: M.29.18a) to M.29.18d): M.29.18a) N-[3-chloro-1 -(3-pyridyl)pyrazol-4-yl]-N-ethyl-3- (3,3,3-trifluoropropylsulfanyl)propanamide; M.29.18b) N-[3-chloro-1-(3-pyridyl)pyrazol-4-yl]-N- ethyl-3-(3,3,3-trifluoropropylsulfinyl)propanamide; M.29.18c) N-[3-chloro-1 -(3-pyridyl)pyrazol-4- yl]-3-[(2,2-difluorocyclopropyl)methylsulfanyl]-N-ethyl-propanamide; M.29.18d) N-[3-chloro-1-(3- pyridyl)pyrazol-4-yl]-3-[(2,2-difluorocyclopropyl)methylsulfinyl]-N-ethyl-propanamide; or M.29.19 sarolaner, or M.29.20 lotilaner.
The commercially available compounds of the group M listed above may be found in The Pes- ticide Manual, 16th Edition, C. MacBean, British Crop Protection Council (2013) among other publications. The online Pesticide Manual is updated regularly and is accessible through http://bcpcdata.com/pesticide-manual.html.
Another online data base for pesticides providing the ISO common names is http://www.alan- wood.net/pesticides.
The M.4 cycloxaprid is known from W010/069266 and W01 1/069456, M.4A.2, named as gua- dipyr, is known from W013/003977, and M.4A.3 (approved as paichongding in China) is known from WO07/101369. M.22B.1 is described in CN10171577 and M.22B.2 in CN102126994. Phthalamides M.28.1 and M.28.2 are known from WO07/101540. M.28.3 is described in WO05/077934. M.28.4 is described in WO07/043677. M.28.5a) to M.28.5d) and M.28.5h) are described in WO07/006670, W013/024009 and W013/024010, Μ.28.5Ϊ) is described in
W01 1/085575, M.28.5j) in WO08/134969, M.28.5k) in US201 1/046186 and M.28.5I) in
WO2012/034403. M.28.6 can be found in W012/034472. M.29.3 is known from WO06/089633 and M.29.4 from WO08/06791 1. M.29.5 is described in WO06/043635, and biological control agents on the basis of bacillus firmus are described in WO09/124707. M.29.6a) to Μ.29.6Ϊ) listed under M.29.6 are described in W012/029672, and M.29.6j) and M.29.6k) in
W013/129688. M.29.8 is known from W013/055584. M.29.9.a) is described in W013/050317. M.29.9.b) is described in WO2014/126208. M.29.10 is known from WO10/060379. Broflanilide and M.29.1 1. b) to M.29.1 1.h) are described in WO10/018714, and Μ.29.1 1 Ϊ) to M.29.1 1 .p) in WO10/127926. M.29.12.a) to M.29.12.c) are known from WO10/006713, M.29.12.d) and Μ.29.12.Θ) are known from WO12/000896, and M.29.12.†) to M.29.12.m) from WO10/129497. M.29.14a) and M.29.14b) are known from WO07/101369. M.29.16.a) to M.29.16h) are described in WO10/034737, WO12/084670, and W012/143317, respectively, and Μ.29.16Ϊ) and M.29.16j) are described in US 61/891437. M.29.17a) to M.29.17J) are described in WO15/038503. M.29.18a) to M.29.18d) are described in US2014/0213448. M.29.19 is described in WO14/036056. M.29.20 is known from WO14/090918.
The following list of fungicides, in conjunction with which the compounds of the present invention can be used, is intended to illustrate the possible combinations but does not limit them: A) Respiration inhibitors
Inhibitors of complex III at Q0 site (e. g. strobilurins): azoxystrobin (A.1 .1 ), coumethoxy- strobin (A.1 .2), coumoxystrobin (A.1.3), dimoxystrobin (A.1.4), enestroburin (A.1.5), fenamin- strobin (A.1.6), fenoxystrobin/flufenoxystrobin (A.1 .7), fluoxastrobin (A.1 .8), kresoxim-methyl (A.1 .9), mandestrobin (A.1 .10), metominostrobin (A.1 .1 1 ), orysastrobin (A.1 .12), picoxy.strobin (A.1 .13), pyraclostrobin (A.1.14), pyrametostrobin (A.1.15), pyraoxystrobin (A.1.16), trifloxystro- bin (A.1.17), 2-(2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneaminooxymethyl)-phenyl)-2-meth- oxyimino-N-methyl-acetamide (A.1.18), pyribencarb (A.1 .19), triclopyricarb/chlorodincarb (A.1 .20), famoxadone (A.1 .21 ), fenamidone (A.1.21 ), methyl-/V-[2-[(1 ,4-dimethyl-5-phenyl-pyra- zol-3-yl)oxylmethyl]phenyl]-N-methoxy-carbamate (A.1.22), 1-[3-chloro-2-[[1-(4-chlorophenyl)- 1 H-pyrazol-3-yl]oxymethyl]phenyl]-4-methyl-tetrazol-5-one (A.1 .23), 1-[3-bromo-2-[[1-(4-chloro- phenyl)pyrazol-3-yl]oxymethyl]phenyl]-4-methyl-tetrazol-5-one (A.1.24), 1-[2-[[1 -(4-chloro- phenyl)pyrazol-3-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one (A.1.25), 1-[2-[[1-(4- chlorophenyl)pyrazol-3-yl]oxymethyl]-3-fluoro-phenyl]-4-methyl-tetrazol-5-one (A.1 .26), 1 -[2-[[1 - (2,4-dichlorophenyl)pyrazol-3-yl]oxymethyl]-3-fluoro-phenyl]-4-methyl-tetrazol-5-one (A.1 .27), 1 - [2-[[4-(4-chlorophenyl)thiazol-2-yl]oxymethyl]-3-methyl-phenyl]-4-methyl-tetrazol-5-one (A.1.28), 1-[3-chloro-2-[[4-(p-tolyl)thiazol-2-yl]oxymethyl]phenyl]-4-methyl-tetrazol-5-one (A.1.29), 1-[3- cyclopropyl-2-[[2-methyl-4-(1 -methylpyrazol-3-yl)phenoxy]methyl]phenyl]-4-methyl-tetrazol-5- one (A.1 .30), 1 -[3-(difluoromethoxy)-2-[[2-methyl-4-(1-methylpyrazol-3-yl)phenoxy]methyl]phe- nyl]-4-methyl-tetrazol-5-one (A.1.31 ), 1-methyl-4-[3-methyl-2-[[2-methyl-4-(1 -methylpyrazol-3- yl)phenoxy]methyl]phenyl]tetrazol-5-one (A.1.32), 1-methyl-4-[3-methyl-2-[[1 -[3-(trifluorome- thyl)phenyl]-ethylideneamino]oxymethyl]phenyl]tetrazol-5-one (A.1.33), (Z;2£)-5-[1-(2,4-dichlo- rophenyl)pyrazol-3-yl]-oxy-2-methoxyimino-/V,3-dimethyl-pent-3-enamide (A.1 .34), (Z,2E)-5-[\- (4-chlorophenyl)pyrazol-3-yl]oxy-2-methoxyimino-/V,3-dimethyl-pent-3-enamide (A.1 .35), {Z,2E)- 5-[1-(4-chloro-2-fluoro-phenyl)pyrazol-3-yl]oxy-2-methoxyimino-/V,3-dimethyl-pent-3-enamide (A.1 .36),
inhibitors of complex III at Qi site: cyazofamid (A.2.1 ), amisulbrom (A.2.2), [(3S,6S,7R,8R)- 8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan- 7-yl] 2-methylpropanoate (A.2.3), [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy- pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate (A.2.4), [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine-2-carbonyl)amino]-6- methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate (A.2.5), [(3S,6S,7R,8R)-8-benzyl-3-[[3- (1 ,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5- dioxonan-7-yl] 2-methylpropanoate (A.2.6); (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridi- nyl)carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1 ,5-dioxonan-7-yl 2-methylpropanoate (A.2.7), (3S,6S,7R,8R)-8-benzyl-3-[3-[(isobutyryloxy)methoxy]-4-methoxypicolinamido]-6-me- thyl-4,9-dioxo-1 ,5-dioxonan-7-yl isobutyrate (A.2.8);
inhibitors of complex II (e. g. carboxamides): benodanil (A.3.1 ), benzovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.1 1 ), isopyrazam (A.3.12), me- pronil (A.3.13), oxycarboxin (A.3.14), penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), tecloftalam (A.3.17), thifluzamide (A.3.18), N-(4'-trifluoromethylthiobiphenyl-2-yl)- 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxamide (A.3.19), N-(2-(1 ,3,3-trimethyl-butyl)-phe- nyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide (A.3.20), 3-(difluoromethyl)-1 -methyl-N- (1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.21 ), 3-(trifluoromethyl)-1 -methyl-N- (1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.22), 1 ,3-dimethyl-N-(1 ,1 ,3-trimethylin- dan-4-yl)pyrazole-4-carboxamide (A.3.23), 3-(trifluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylin- dan-4-yl)pyrazole-4-carboxamide (A.3.24), 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole- 4-carboxamide (A.3.25), N-(7-fluoro-1 ,1 ,3-trimethyl-indan-4-yl)-1 ,3-dimethyl-pyrazole-4-carbox- amide (A.3.26), N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methyl-ethyl]-3-(difluoromethyl)-1 -me- thyl-pyrazole-4-carboxamide (A.3.27);
other respiration inhibitors (e. g. complex I, uncouplers): diflumetorim (A.4.1 ), (5,8-difluoro- quinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine (A.4.2); ni- trophenyl derivates: binapacryl (A.4.3), dinobuton (A.4.4), dinocap (A.4.5), fluazinam (A.4.6); ferimzone (A.4.7); organometal compounds: fentin salts, such as fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.1 1 ); and silthiofam (A.4.12); B) Sterol biosynthesis inhibitors (SBI fungicides)
C14 demethylase inhibitors (DMI fungicides): triazoles: azaconazole (B.1 .1 ), bitertanol (B.1 .2), bromuconazole (B.1 .3), cyproconazole (B.1 .4), difenoconazole (B.1.5), diniconazole (B.1 .6), diniconazole-M (B.1 .7), epoxiconazole (B.1 .8), fenbuconazole (B.1.9), fluquinconazole (B.1 .10), flusilazole (B.1.1 1 ), flutriafol (B.1.12), hexaconazole (B.1.13), imibenconazole (B.1 .14), ipconazole (B.1.15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1 .19), paclo- butrazole (B.1 .20), penconazole (B.1.21 ), propiconazole (B.1 .22), prothioconazole (B.1 .23), simeconazole (B.1.24), tebuconazole (B.1.25), tetraconazole (B.1.26), triadimefon (B.1 .27), tri- adimenol (B.1.28), triticonazole (B.1.29), uniconazole (B.1 .30), 1 -[reA(2^3 )-3-(2-chloro- phenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1 H-[1 ,2,4]triazolo (B.1.31 ), 2-\re (2^3 )-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-2H-[1 ,2,4]triazole-3-thiol (B.1 .32), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pentan-2-ol (B.1.33), 1-[4- (4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-cyclopropyl-2-(1 ,2,4-triazol-1 -yl)ethanol (B.1.34), 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1.35), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1 .36), 2-[4-(4-chloro- phenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1-(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1.37), 2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1 ,2,4-triazol-1-yl)propan-2-ol (B.1.38), 2-[2-chloro- 4-(4-chlorophenoxy)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1 .39), 2-[4-(4-chlorophe- noxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1-yl)pentan-2-ol (B.1.40), 2-[4-(4-fluorophen- oxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1-yl)propan-2-ol (B.1 .41 ), 2-[2-chloro-4-(4-chloro- phenoxy)phenyl]-1-(1 ,2,4-triazol-1 -yl)pent-3-yn-2-ol (B.1.51 ); imidazoles: imazalil (B.1.42), pe- furazoate (B.1.43), prochloraz (B.1.44), triflumizol (B.1 .45); pyrimidines, pyridines and pipera- zines: fenarimol (B.1 .46), nuarimol (B.1 .47), pyrifenox (B.1 .48), triforine (B.1.49), [3-(4-chloro-2- fluoro-phenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]-(3-pyridyl)methanol (B.1.50);
Delta 14-reductase inhibitors: aldimorph (B.2.1 ), dodemorph (B.2.2), dodemorph-acetate (B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7), spirox- amine (B.2.8); Inhibitors of 3-keto reductase: fenhexamid (B.3.1 );
C) Nucleic acid synthesis inhibitors
phenylamides or acyl amino acid fungicides: benalaxyl (C.1 .1 ), benalaxyl-M (C.1.2), kiral- axyl (C.1.3), metalaxyl (C.1 .4), metalaxyl-M (mefenoxam, C.1 .5), ofurace (C.1.6), oxadixyl (C.1.7);
others: hymexazole (C.2.1 ), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5-fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine (C.2.6), 5-fluoro-2-(4- fluorophenylmethoxy)pyrimidin-4-amine (C.2.7);
D) Inhibitors of cell division and cytoskeleton
- tubulin inhibitors, such as benzimidazoles, thiophanates: benomyl (D1.1 ), carbendazim (D1.2), fuberidazole (D1.3), thiabendazole (D1.4), thiophanate-methyl (D1 .5); triazolopyrim- idines: 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimi- dine (D1 .6);
other cell division inhibitors: diethofencarb (D2.1 ), ethaboxam (D2.2), pencycuron (D2.3), fluopicolide (D2.4), zoxamide (D2.5), metrafenone (D2.6), pyriofenone (D2.7);
E) Inhibitors of amino acid and protein synthesis
methionine synthesis inhibitors (anilino-pyrimidines): cyprodinil (E.1 .1 ), mepanipyrim (E.1 .2), pyrimethanil (E.1.3);
protein synthesis inhibitors: blasticidin-S (E.2.1 ), kasugamycin (E.2.2), kasugamycin hy- drochloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6), polyoxine (E.2.7), validamycin A (E.2.8);
F) Signal transduction inhibitors
MAP / histidine kinase inhibitors: fluoroimid (F.1 .1 ), iprodione (F.1 .2), procymidone (F.1.3), vinclozolin (F.1 .4), fenpiclonil (F.1.5), fludioxonil (F.1.6);
- G protein inhibitors: quinoxyfen (F.2.1 );
G) Lipid and membrane synthesis inhibitors
Phospholipid biosynthesis inhibitors: edifenphos (G.1 .1 ), iprobenfos (G.1 .2), pyrazophos (G.1 .3), isoprothiolane (G.1 .4);
lipid peroxidation: dicloran (G.2.1 ), quintozene (G.2.2), tecnazene (G.2.3), tolclofos-methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), etridiazole (G.2.7);
phospholipid biosynthesis and cell wall deposition: dimethomorph (G.3.1 ), flumorph (G.3.2), mandipropamid (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7) and N-(1-(1-(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4- fluorophenyl) ester (G.3.8);
- compounds affecting cell membrane permeability and fatty acides: propamocarb (G.4.1 ); fatty acid amide hydrolase inhibitors: oxathiapiprolin (G.5.1 ), 2-{3-[2-(1-{[3,5-bis(difluoro- methyl-1 H-pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5-yl}phenyl methanesulfonate (G.5.2), 2-{3-[2-(1 -{[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]acetyl}piperidin-4- yl) 1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate (G.5.3);
H) Inhibitors with Multi Site Action
inorganic active substances: Bordeaux mixture (H.1.1 ), copper acetate (H.1.2), copper hydroxide (H.1.3), copper oxychloride (H.1 .4), basic copper sulfate (H.1 .5), sulfur (H.1.6);
thio- and dithiocarbamates: ferbam (H.2.1 ), mancozeb (H.2.2), maneb (H.2.3), metam (H.2.4), metiram (H.2.5), propineb (H.2.6), thiram (H.2.7), zineb (H.2.8), ziram (H.2.9); organochlorine compounds (e. g. phthalimides, sulfamides, chloronitriles): anilazine (H.3.1 ), chlorothalonil (H.3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.1 1 ), N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl- benzenesulfonamide (H.3.12);
guanidines and others: guanidine (H.4.1 ), dodine (H.4.2), dodine free base (H.4.3), guazatine (H.4.4), guazatine-acetate (H.4.5), iminoctadine (H.4.6), iminoctadine-tri acetate (H.4.7), iminoctadine-tris(albesilate) (H.4.8), dithianon (H.4.9), 2,6-dimethyl-1 H,5H-[1 ,4]di- thiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone (H.4.10);
I) Cell wall synthesis inhibitors
inhibitors of glucan synthesis: validamycin (1.1.1 ), polyoxin B (1.1 .2);
melanin synthesis inhibitors: pyroquilon (1.2.1 ), tricyclazole (I.2.2), carpropamid (1.2.3), di- cyclomet (I.2.4), fenoxanil (I.2.5);
J) Plant defence inducers
- acibenzolar-S-methyl (J.1.1 ), probenazole (J.1 .2), isotianil (J.1 .3), tiadinil (J.1 .4), prohexa- dione-calcium (J.1.5); phosphonates: fosetyl (J.1.6), fosetyl-aluminum (J.1 .7), phosphorous acid and its salts (J.1.8), potassium or sodium bicarbonate (J.1 .9);
K) Unknown mode of action
bronopol (K.1 .1 ), chinomethionat (K.1.2), cyflufenamid (K.1.3), cymoxanil (K.1.4), dazomet (K.1 .5), debacarb (K.1.6), diclomezine (K.1.7), difenzoquat (K.1.8), difenzoquat-methylsulfate (K.1 .9), diphenylamin (K.1.10), fenpyrazamine (K.1 .1 1 ), flumetover (K.1 .12), flusulfamide (K.1 .13), flutianil (K.1 .14), methasulfocarb (K.1.15), nitrapyrin (K.1.16), nitrothal-isopropyl (K.1 .18), oxathiapiprolin (K.1.19), tolprocarb (K.1 .20), oxin-copper (K.1.21 ), proquinazid
(K.1 .22), tebufloquin (K.1 .23), tecloftalam (K.1 .24), triazoxide (K.1.25), 2-butoxy-6-iodo- 3-propylchromen-4-one (K.1.26), 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1-[4-(4-{5-[2-(prop- 2-yn-1-yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone (K.1 .27), 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1-yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2-yn-1-yl- oxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1-yl]ethanone (K.1 .28), 2-[3,5- bis(difluoromethyl)-1 H-pyrazol-1-yl]-1 -[4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihy- dro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1-yl]ethanone (K.1 .29), N-(cyclopropylmethoxy- imino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide (K.1 .30), N'-(4-(4- chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine (K.1.31 ), N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine (K.1 .32), N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine (K.1.33), N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N- ethyl-N-methyl formamidine (K.1 .34), methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl- quinolin-4-yl ester (K.1 .35), 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (K.1 .36), 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (pyrisoxazole) (K.1 .37), N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide (K.1.38), 5-chloro-1 -(4,6-di- methoxy-pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole (K.1.39), 2-(4-chloro-phenyl)-N-[4-(3,4- dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide, ethyl (Z)-3-amino-2-cyano-3-phe- nyl-prop-2-enoate (K.1 .40), picarbutrazox (K.1.41 ), pentyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phe- nyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate (K.1.42), 2-[2-[(7,8-difluoro-2-methyl-3- quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol (K.1 .43), 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quino- lyl)oxy]phen-yl]propan-2-ol (K.1 .44), 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)- quinoline (K.1 .45), 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline (K.1.46), 3- (4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline (K.1 .47), 9-fluoro-2,2-dimethyl- 5-(3-quinolyl)-3H-1 ,4-benzoxazepine (K.1 .48).
The fungicides described by common names, their preparation and their activity e.g. against harmful fungi is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available.
The fungicides described by lUPAC nomenclature, their preparation and their pesticidal activ- ity is also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968; EP-A 141 317; EP-A 152 031 ; EP-A
226 917; EP-A 243 970; EP-A 256 503; EP-A 428 941 ; EP-A 532 022; EP-A 1 028 125; EP-A
1 035 122; EP-A 1 201 648; EP-A 1 122 244, JP 2002316902; DE 19650197; DE 10021412;
DE 102005009458; US 3,296,272; US 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413;
WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501 ; WO 01/56358; WO 02/22583; WO 02/40431 ; WO 03/10149; WO 03/1 1853; WO 03/14103; WO 03/16286;
WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491 ; WO 04/49804; WO 04/83193;
WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721 ; WO 05/87772; WO 05/87773;
WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07/90624, WO 1 1/028657,
WO2012/168188, WO 2007/006670, WO 201 1/77514; W013/047749, WO 10/069882, WO 13/047441 , WO 03/16303, WO 09/90181 , WO 13/007767, WO 13/010862, WO 13/127704,
WO 13/024009, WO 13/024010 and WO 13/047441 , WO 13/162072, WO 13/092224, WO
1 1/135833).
Suitable mixing partners for the compounds of the present invention also include biopesticides.
Biopesticides have been defined as a form of pesticides based on micro-organisms (bacteria, fungi, viruses, nematodes, etc.) or natural products (compounds, such as metabolites, proteins, or extracts from biological or other natural sources) (U.S. Environmental Protection Agency: http://www.epa.gov/pesticides/biopesticides/). Biopesticides fall into two major classes, microbial and biochemical pesticides:
(1 ) Microbial pesticides consist of bacteria, fungi or viruses (and often include the metabolites that bacteria and fungi produce). Entomopathogenic nematodes are also classified as microbial pesticides, even though they are multi-cellular.
(2) Biochemical pesticides are naturally occurring substances or or structurally-similar and functionally identical to a naturally-occurring substance and extracts from biological sources that control pests or provide other crop protection uses as defined below, but have non-toxic mode of actions (such as growth or developmental regulation, attractents, repellents or defence activators (e.g. induced resistance) and are relatively non-toxic to mammals.
Biopesticides for use against crop diseases have already established themselves on a variety of crops. For example, biopesticides already play an important role in controlling downy mildew diseases. Their benefits include: a 0-Day Pre-Harvest Interval, the ability to use under moderate to severe disease pressure, and the ability to use in mixture or in a rotational program with other registered pesticides.
A major growth area for biopesticides is in the area of seed treatments and soil amendments. Biopesticidal seed treatments are e.g. used to control soil borne fungal pathogens that cause seed rots, damping-off, root rot and seedling blights. They can also be used to control internal seed borne fungal pathogens as well as fungal pathogens that are on the surface of the seed. Many biopesticidal products also show capacities to stimulate plant host defenses and other physiological processes that can make treated crops more resistant to a variety of biotic and abiotic stresses or can regulate plant growth. Many biopesticidal products also show capacities to stimulate plant health, plant growth and/or yield enhancing activity.
The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound of the present invention or a mixture thereof.
An agrochemical composition comprises a pesticidally effective amount of a compound of the present invention or a mixture thereof. The term "pesticidally effective amount" is defined below. The compounds of the present invention or the mixtures thereof can be converted into customary types of agro-chemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Mono- graph No. 2, 6th Ed. May 2008, CropLife International.
The compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Examples for suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfac- tants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifi- ers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil frac- tions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclo-'hexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective col- loid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sul- fates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl-sul- fonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkyhnaphthalenes, sulfosucci nates or sulfosuccinamates. Examples of sul- fates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethox-ylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Exam-pies of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol eth-oxylates.
Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpoly- glucosides. Examples of polymeric surfactants are homo- or copolymers of vinylpyrrolidone, vi- nylalcohols, or vinylacetate.
Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of poly- acrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyeth- yleneamines.
Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compounds of the present invention on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazoli- nones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants). Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
Examples for composition types and their preparation are:
i) Water-soluble concentrates (SL, LS)
10-60 wt% of a compound I according to the invention and 5-15 wt% wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) up to 100 wt%. The active substance dissolves upon dilution with water.
ii) Dispersible concentrates (DC)
5-25 wt% of a compound I according to the invention and 1-10 wt% dispersant (e. g. polyvi- nylpyrrolidone) are dissolved in up to 100 wt% organic solvent (e.g. cyclohexanone). Dilution with water gives a dispersion.
iii) Emulsifiable concentrates (EC)
15-70 wt% of a compound I according to the invention and 5-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in up to 100 wt% water-insol- uble organic solvent (e.g. aromatic hydrocarbon). Dilution with water gives an emulsion.
iv) Emulsions (EW, EO, ES)
5-40 wt% of a compound I according to the invention and 1 -10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% water-insoluble organic solvent (e.g. aromatic hydrocarbon). This mixture is introduced into up to 100 wt% water by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion.
v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20-60 wt% of a compound I according to the invention are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alco- hoi ethoxylate), 0,1 -2 wt% thickener (e.g. xanthan gum) and up to 100 wt% water to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt% binder (e.g. polyvinylalcohol) is added.
vi) Water-dispersible granules and water-soluble granules (WG, SG)
50-80 wt% of a compound I according to the invention are ground finely with addition of up to 100 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)
50-80 wt% of a compound I according to the invention are ground in a rotor-stator mill with addition of 1-5 wt% dispersants (e.g. sodium lignosulfonate), 1 -3 wt% wetting agents (e.g. alcohol ethoxylate) and up to 100 wt% solid carrier, e.g. silica gel. Dilution with water gives a stable dispersion or solution of the active substance.
viii) Gel (GW, GF)
In an agitated ball mill, 5-25 wt% of a compound I according to the invention are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1 -5 wt% thickener (e.g. car- boxymethylcellulose) and up to 100 wt% water to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance. ix) Microemulsion (ME)
5-20 wt% of a compound I according to the invention are added to 5-30 wt% organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alko- hol ethoxylate and arylphenol ethoxylate), and water up to 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
x) Microcapsules (CS)
An oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g. methyl- methacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radi-cal initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insolu-ble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylme-thene-4,4'- diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alco- hoi). The addition of a polyamine (e.g. hexamethylenediamine) results in the for-mation of a pol- yurea microcapsule. The monomers amount to 1-10 wt%. The wt% relate to the total CS composition.
xi) Dustable powders (DP, DS)
1-10 wt% of a compound I according to the invention are ground finely and mixed intimately with up to 100 wt% solid carrier, e.g. finely divided kaolin.
xii) Granules (GR, FG)
0.5-30 wt% of a compound I according to the invention is ground finely and associated with up to 100 wt% solid carrier (e.g. silicate). Granulation is achieved by extrusion, spray-drying or the fluidized bed.
xiii) Ultra-low volume liquids (UL)
1-50 wt% of a compound I according to the invention are dissolved in up to 100 wt% organic solvent, e.g. aromatic hydrocarbon.
The compositions types i) to xi) may optionally comprise further auxiliaries, such as 0.1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1 -1 wt% anti-foaming agents, and 0.1 -1 wt% col- orants.
The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active sub-stance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the active substances or the compositions cormprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1 .
The user applies the composition according to the invention usually from a predosage de-vice, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising compounds of the present invention and/or mixing partners as defined above, may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.
In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising compounds of the present invention and/or mixing partners as defined above, can be applied jointly (e.g. after tank mix) or consecutively. The compounds of the present invention are suitable for use in treating or protecting animals against infestation or infection by parasites. Therefore, the present invention also relates to the use of a compound of the present invention for the manufacture of a medicament for the treatment or protection of animals against infestation or infection by parasites. Furthermore, the present invention relates to a method of treating or protecting animals against infestation and infec- tion by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a compound of the present invention.
The present invention also relates to the non-therapeutic use of compounds of the present invention for treating or protecting animals against infestation and infection by parasites. Moreover, the present invention relates to a non-therapeutic method of treating or protecting animals against infestation and infection by parasites, which comprises applying to a locus a parasiticidally effective amount of a compound of the present invention.
The compounds of the present invention are further suitable for use in combating or controlling parasites in and on animals. Furthermore, the present invention relates to a method of combating or controlling parasites in and on animals, which comprises contacting the parasites with a parasitically effective amount of a compound of the present invention.
The present invention also relates to the non-therapeutic use of compounds of the present invention for controlling or combating parasites. Moreover, the present invention relates to a non- therapeutic method of combating or controlling parasites, which comprises applying to a locus a parasiticidally effective amount of a compound of the present invention.
The compounds of the present invention can be effective through both contact (via soil, glass, wall, bed net, carpet, blankets or animal parts) and ingestion (e.g. baits). Furthermore, the compounds of the present invention can be applied to any and all developmental stages.
The compounds of the present invention can be applied as such or in form of compositions comprising the compounds of the present invention.
The compounds of the present invention can also be applied together with a mixing partner, which acts against pathogenic parasites, e.g. with synthetic coccidiosis compounds, poly- etherantibiotics such as Amprolium, Robenidin, Toltrazuril, Monensin, Salinomycin, Madurami- cin, Lasalocid, Narasin or Semduramicin, or with other mixing partners as defined above, or in form of compositions comprising said mixtures. The compounds of the present invention and compositions comprising them can be applied orally, parenterally or topically, e.g. dermally. The compounds of the present invention can be systemically or non-systemically effective.
The application can be carried out prophylactically, therapeutically or non-therapeutically. Fur- thermore, the application can be carried out preventively to places at which occurrence of the parasites is expected.
As used herein, the term "contacting" includes both direct contact (applying the compounds/compositions directly on the parasite, including the application directly on the animal or excluding the application directly on the animal, e.g. at it's locus for the latter) and indirect con- tact (applying the compounds/compositions to the locus of the parasite). The contact of the parasite through application to its locus is an example of a non-therapeutic use of the compounds of the present invention.
The term "locus" means the habitat, food supply, breeding ground, area, material or environment in which a parasite is growing or may grow outside of the animal.
As used herein, the term "parasites" includes endo- and ectoparasites. In some embodiments of the present invention, endoparasites can be preferred. In other embodiments, ectoparasites can be preferred. Infestations in warm-blooded animals and fish include, but are not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chig- gers, gnats, mosquitoes and fleas.
The compounds of the present invention are especially useful for combating parasites of the following orders and species, respectively:
fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides cam's, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus; cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica, Peri- planeta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis; flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes aibopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimacula- tus, Calliphora vicina, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops siiacea, Chrysops atianticus, Cochiiomyia hominivorax, Cordylobia anthropophaga, Culicoides furens, Culex pip/ens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dermatobia hominis, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Glossina pa/pa/is, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hipp elates spp., Hypoderma lineata, Leptoconops torrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Manso- nia spp., Musca domes tica, Muscina stabulans, Oestrus ovis, Phlebotomus argentipes, Psoro- phora columbiae, Psorophora discolor, Prosimulium mixtum, Sarcophaga haemorrhoidalis, Sar- cophaga sp., Simuiium vittatum, Stomoxys caicitrans, Tabanus bovinus, Tabanus atratus, Taba- nus lineola, and Tabanus similis; lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bo vis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus; ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocy- clus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum, Ornithodorus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Ornithonyssus bacoti and Dermanyssus galli- nae; Actinedida (Prostigmata) und Acaridida (Astigmata), e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listro- phorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Kne- midocoptes spp., Cytodites spp., and Laminosioptes spp; Bugs (Heteropterida): Cimex lectular- ius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius ssp., Panstrongyius ssp., and Ari/us cr/tatus; Anop\ur\da, e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp.; Mallophagida (suborders Arnblycerina and Ischnocerina), e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Trichodectes spp., and Felicola spp.; Roundworms Nematoda: Wipeworms and Trichinosis (Trichosyringida), e.g. Trichinellidae (Trichinella spp.), ( richuridae^ Trichuris spp., Capillaria spp.; Rhabditida, e.g. Rhabditis spp., Strongyloides spp., Helicephalobus spp.; Strongylida, e.g. Strongylus spp., Ancylostoma spp., Necator americanus, Bunostomum spp. (Hookworm), Tri- chostrongylus spp., Haemonchus contortus, Ostertagia spp., Cooper/a spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oesophagostomum spp., Stephanurus dentatus, Ollu- lanus spp., Chabertia spp., Stephanurus dentatus, Syngamus trachea, Ancylostoma spp., Unci- naria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Proto- strongylus spp., Angiostrongylus spp., Parelaphostrongylus spp., Aleurostrongylus abstrusus, and Dioctophyma renale; Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., and Oxyuris equi; Camallanida, e.g. Dracunculus medinensis (guinea worm); Spirurida, e.g. Thelazia spp., Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp. a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Habronema spp.; Thorny headed worms (Acanthocephala), e.g. Acanthocephalus spp., Macracanthorhynchus hirudinaceus and Oncicola spp.; Planarians (Plathelminthes): Flukes (Trematoda), e.g. Faciola spp., Fascioloides magna, Paragonimus spp., Dicrocoelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilharzia spp., Alaria alata, Paragonimus spp., and Nanocyetes spp:, Cercomeromorpha, in particular Cestoda (Tape- worms), e.g. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium caninum, Multi- ceps spp., Hymenolepis spp., Mesocestoides spp., Vampirolepis spp., Moniezia spp., Anoplo- cephala spp., Sirometra spp., Anoplocephala spp., and Hymenolepis spp..
As used herein, the term "animal" includes warm-blooded animals (including humans) and fish. Preferred are mammals, such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rab- bits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur- bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels. Particularly preferred are domestic animals, such as dogs or cats.
In general, "parasiticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The parasiticidally effective amount can vary for the various compounds/compositions used in the invention. A parasiticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired parasiticidal effect and duration, target species, mode of application, and the like.
Generally, it is favorable to apply the compounds of the present invention in total amounts of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50 mg/kg per day.
For oral administration to warm-blooded animals, the formula I compounds may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. In addition, the formula I compounds may be administered to the animals in their drinking water. For oral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula I compound, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
Alternatively, the formula I compounds may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The formula I compounds may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the formula I compounds may be formulated into an implant for subcutaneous administration. In addition, the formula I compound may be transdermally administered to animals. For parenteral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula I compound.
The formula I compounds may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or water-in-oil emulsions. For topical application, dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the formula I compound. In addition, the formula I compounds may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.
Suitable preparations are:
- Solutions such as oral solutions, concentrates for oral administration after dilution, solutions for use on the skin or in body cavities, pouring-on formulations, gels;
- Emulsions and suspensions for oral or dermal administration; semi-solid preparations;
- Formulations in which the active compound is processed in an ointment base or in an oil-in- water or water-in-oil emulsion base;
- Solid preparations such as powders, premixes or concentrates, granules, pellets, tablets, boluses, capsules; aerosols and inhalants, and active compound-containing shaped articles.
Compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and optionally adding further auxiliaries such as acids, bases, buffer salts, preserva- tives, and solubilizers. Suitable auxiliaries for injection solutions are known in the art. The solutions are filtered and filled sterile.
Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the use concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being nec- essary.
Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on. Solutions for use on the skin are prepared according to the state of the art and according to what is described above for injection solutions, sterile procedures not being necessary. Gels are applied to or spread on the skin or introduced into body cavities. Gels are prepared by treating solutions which have been prepared as described in the case of the injection solutions with sufficient thickener that a clear material having an ointment-like consistency results. Suitable thickeners are known in the art.
Pour-on formulations are poured or sprayed onto limited areas of the skin, the active compound penetrating the skin and acting systemically. Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in suitable skin-compatible solvents or solvent mixtures. If appropriate, other auxiliaries such as colorants, bioabsorption-promoting substances, antioxidants, light stabilizers, adhesives are added. Suitable such auxiliaries are known in the art.
Emulsions can be administered orally, dermally or as injections. Emulsions are either of the water-in-oil type or of the oil-in-water type. They are prepared by dissolving the active compound either in the hydrophobic or in the hydrophilic phase and homogenizing this with the solvent of the other phase with the aid of suitable emulsifiers and, if appropriate, other auxiliaries such as colorants, absorption-promoting substances, preservatives, antioxidants, light stabilizers, viscosity-enhancing substances. Suitable hydrophobic phases (oils), suitable hydrophilic phases, suitable emulsifiers, and suitable further auxiliaries for emulsions are known in the art.
Suspensions can be administered orally or topically/dermally. They are prepared by suspending the active compound in a suspending agent, if appropriate with addition of other auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxidants, light stabilizers. Suitable suspending agents, and suitable other auxiliaries for suspensions including wetting agents are known in the art.
Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions described above only by their higher viscosity.
For the production of solid preparations, the active compound is mixed with suitable excipi- ents, if appropriate with addition of auxiliaries, and brought into the desired form. Suitable auxiliaries for this purpose are known in the art.
The compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the compound of the present invention.
Ready-to-use preparations contain the compounds acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80 per cent by weight, preferably from 0.1 to 65 per cent by weight, more preferably from 1 to 50 per cent by weight, most preferably from 5 to 40 per cent by weight.
Preparations which are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 per cent by weight, preferably of 1 to 50 per cent by weight.
Furthermore, the preparations comprise the compounds of formula I against endoparasites in concentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to 0.9 per cent by weight, very particularly preferably of 0.005 to 0.25 per cent by weight.
Topical application may be conducted with compound-containing shaped articles such as col- lars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.
Generally it is favorable to apply solid formulations which release compounds of the present invention in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks. Examples
A. Preparation examples
With appropriate modification of the starting materials, the procedures given in the synthesis description were used to obtain further compounds I. The compounds obtained in this manner are listed in the table that follows, together with physical data.
The products shown below were characterized by melting point determination, by NMR spectroscopy or by the masses ([m/z]) or retention time (RT; [min.]) determined by HPLC MS or HPLC spectrometry.
HPLC MS = high performance liquid chromatography-coupled mass spectrometry;
HPLC method: Phenomenex Kinetex 1.7 μηι XB-C18 100A; 50 x 2.1 mm; mobile phase: A: water + 0.1 % trifluoroacetic acid (TFA); B: acetonitrile; gradient: 5-100% B in 1 .50 minutes; 100% B 0.25 min; flow: 0.8-1.Oml/min in 1.51 minutes at 60°C. MS: ESI positive, m/z 100-700. The protocol for the synthesis of starting material 1 -methyl-3-(pentafluoroethyl)-4-(trifluorome- thyl)-5-fluoropyrazole (CAS 104315-28-8) is known from WO 2016/026789. Likewise, 1 -methyl- 3-(pentafluoroethyl)-4-(trifluoromethyl)-1 H-pyrazole-5-carboxylic acid (CAS 1226890-61 -4) is known from WO 2015/181 139. Example 1 : Synthesis of 2-methyl-N-[1 '-(2-methylsulfonylacetyl)spiro[1 H-isobenzofuran-3,3'- azetidine]-5-yl]-5-(1 ,1 ,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-carboxamide (Compound 1-1-7)
Step 1 : Synthesis of tert-butyl 5-bromospiro[1 H-isobenzofuran-3,3'-azetidine]-1 '-carboxylate To a mixture of 4-bromo-1 -(chloromethyl)-2-iodo-benzene (26.10 g, 78.76 mmol) in THF (100 mL) was added a solution of isopropyl magnesium chloride-lithium chloride complex (90.9 mL of a 1.3 M solution in THF, 1 18.1 mmol) at -30°C. After 1 h at this temperature, a solution of tert- butyl 3-oxoazetidine-1 -carboxylate (18.88 g, 1 10.3 mmol) in THF (50 mL) was added keeping the temperature at -30°C. After the completed addition, the mixture was allowed to slowly warm to 20-25°C and left over night. Aqueous citric acid (1 M) was added and the mixture was stirred into MTBE. The organic layer was separated and washed with water and brine. After drying over Na2S04, the solvent was evaporated and the residue was taken up in n-heptane to form a precipitate which was collected via filtration. The title compound (10.2 g) was obtained as a solid and used in the next step as such.
1H-NMR (400 MHz, CDCI3): δ = 1 .50 (s, 9H), 4.12 (d, 2H), 4.37 (d, 2H), 5.06 (s, 2H), 7.12 (d, 1 H), 7.47 (d, 1 H), 7.63 (s, 1 H) ppm.
Step 2: Synthesis of tert-butyl 5-aminospiro[1 H-isobenzofuran-3,3'-azetidine]-1 '-carboxylate A three necked flask was charged with a solution of the carboxylate from Step 1 (2.00 g, 5.88 mmol), benzophenone imine (1.278 g, 7.054 mmol) and NaOtBu (695 mg, 7.23 mmol) in tolu- ene (50 mL) under argon. In a second flask, BINAP (366 mg, 588 mmol) and Pd2(dba)3 were dissolved in toluene (15 mL) under argon. This mixture was transferred drop wise to the reaction mixture in the first flask and heated to 80°C. After 4 h the mixture was cooled to 20-25°C and diluted with ethyl acetate. Filtration removed the solids and the filtrate was evaporated to form a residue (2.6 g) which was taken up in methanol (25 mL). Sodium acetate 1 .21 g, 14.7 mmol) and hydroxylammonium chloride (746 mg, 10.7 mmol) were added and stirred over night. After concentration in vacuum, the residue was taken up in ethyl acetate and washed with aqueous NaOH (0.1 M). The organic layer was dried over Na2S04 and concentrated in vacuum. Silica gel chromatography of the residue yielded the title compound (1.0 g).
H-NMR (400 MHz, CDCI3): δ = 1 .48 (s, 9H), 4.12 (d, 2H), 4.26 (d, 2H), 5.03 (s, 2H), 6.67 (d, 1 H), 6.76 (s, 1 H), 6.92 (d, 1 H) ppm.
Step 3: Synthesis of tert-butyl 5-[[2-methyl-5-(1 ,1 ,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)py- razole-3-carbonyl]amino]spiro[1 H-isobenzofuran-3,3'-azetidine]-1 '-carboxylate
A mixture of 1 -methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1 H-pyrazole-5-carboxylic acid (CAS 1226890-61-4, 6.80 g, 0.022 mol, 1 .36 equiv.), the carboxylate from Step 2 (6.69 g with 90% purity, 0.022 mol) and dichloromethane (200 ml.) was charged into a flask. To this mixture, PyBroP (9.335 g, 20.03 mmol) was added. At 0-5°C, Hiinig Base (10.9 ml_, 8.28 g, 64.1 mmol) was added slowly and allowed to reach 20-25°C. After completion of the reaction, water was added. The mixture was extracted with dichloromethane three times. Combined organic layers were washed with water and dried over Na2S04. Concentration in vacuum yielded a residue which was purified via column chromatography on silica gel to give the title compound (7.10 g).
1H-NMR (400 MHz, CDC ): δ = 1 .42 (s, 9H), 4.10 (s, 3H), 4.15 (d, 2H), 4.30 (d, 2H), 5.10 (s, 2H), 7.27 (d, 1 H), 7.59 (s, 1 H), 7.79 (d, 1 H) 8.93 (s, 1 H) ppm.
Step 4: Synthesis of 2-methyl-5-(1 ,1 ,2,2,2-pentafluoroethyl)-N-spiro[1 H-isobenzofuran-3,3'- azetidin-1-ium]-5-yl-4-(trifluoromethyl)pyrazole-3-carboxamide trifluoroacetate
To a solution of the carboxylate from Step 3 (7.10 g, 0.012 mol) in dichloromethane (100 ml.) was added trifluoroacetic acid (50 ml.) at 0°C. After 2 h at this temperature, all volatiles were re- moved in vacuum and the residue (8.3 g) was used in the next step without further purification.
Step 5: Synthesis of 2-methyl-N-[1 '-(2-methylsulfonylacetyl)spiro[1 H-isobenzofuran-3,3'-azet- idine]-5-yl]-5-(1 ,1 ,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazole-3-carboxamide
To a solution of the trifluoroacetate from Step 4 (560 mg, 958 mmol) in THF (15 ml.) was added DMAP (1 1 .7 mg, 0.096 mmol) and Hiinig Base (0.98 ml_, 5.8 mmol). After 30 min, the mixture was cooled to 0°C and 2-methylsulfonylacetyl chloride (277 mg, 1.15 mmol) in THF (2 ml.) was added. The mixture was gradually warmed to 20-25°C and stirred over night. All volatiles were removed in vacuum and the residue was taken up in ethyl acetate. The organic layer was washed with aqueous hydrochloric acid (1 M), water and saturated sodium bicarbonate, fol- lowed by brine. Drying over Na2S04 and evaporation in vacuum gave a residue that was purified via column chromatography on silica gel to yield the title compound (282 mg).
H-NMR (400 MHz, CDCb): δ = 3.85 (m, 2H), 4.09 (s, 3H), 4.39 (m, 2H), 4.66 (s, 2H), 5.14 (s, 2H), 7.27 (s, 1 H), 7.63 (s, 1 H), 7.80 (d, 1 H) 8.30 (s, 1 H) ppm.
In analogy to Example 1 , compounds 1-1-1 to 1-1-7 of table I were prepared.
Figure imgf000054_0001
Table I - compounds of formula I.B1
Figure imgf000054_0002
Example 2: Synthesis of 1-[5-[1 -[2-methyl-5-(1 , 1 ,2,2, 2-pentafluoroethyl)-4-(trifluoromethyl)pyra- zol-3-yl]pyrazol-4-yl]spiro[1 H-isobenzofuran-3,3'-azetidine]-1 '-yl]propan-1-one (Compound I-2- 1 )-
Step 1 : Synthesis of tert-butyl 5-(4,4,5,5-tetramethyl-1 ,3,2-dioxaborolan-2-yl)spiro[1 H-isoben- zofuran-3,3'-azetidine]-1 '-carboxylate
To a mixture of tert-butyl 5-bromospiro[1 H-isobenzofuran-3,3'-azetidine]-1 '-carboxylate (Example 1 , Step 1 , 5.20 g, 15.3 mmol), potassium acetate (4.50 g, 45.9 mmol) and bis(pina- colato)diboron (4.658 g, 18.34 mmol) in acetonitrile (80 mL) was added under argon Xphos (437 mg, 0.917 mmol) and palladium(ll) acetate (103 mg, 0.459 mmol) and the mixture was stirred at 80°C for 16 h. After completion of the reaction, Kieselguhr was added and all solids were removed via filtration. The filtrate was concentrated in vacuum and taken up in MTBE. The or- ganic layer was washed with water and brine, dried over Na2S04 and concentrated in vacuum. The residue was taken up in n-heptane, where a precipitate formed. The solids were collected through filtration and dried to obtain the title compound (6.2 g), which was used in the next step without further purification.
H-NMR (400 MHz, CDCI3): δ = 1 .47 (s, 12H), 1 .49 (s, 9H), 4.19 (d, 2H), 4.30 (d, 2H), 5.12 (s, 2H), 7.22 (d, 1 H), 7.80 (d, 1 H), 7.91 (s, 1 H) ppm.
Step 2: Synthesis of 5-(4-bromopyrazol-1-yl)-1 -methyl-3-(1 ,1 ,2,2,2-pentafluoroethyl)-4-(trifluo- romethyl)pyrazole
A mixture of 1 -methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-5-fluoropyrazole (CAS 104315- 28-8, 5.61 g, 19.6 mmol), 4-bromo-1 H-pyrazole (2.88 g, 19.6 mmol), Cs2C03 (12.8 g, 0.039 mol) in acetonitrile (80 mL) was stirred at 65°C for 5 h. After cooling, all solids were removed via filtration and the residue was washed with acetonitrile. The filtrate was concentrated in vacuum and taken up in ethyl acetate. The organic layer was washed with water, dried over Na2S04 and concentrated in vacuum. The residue was purified via column chromatography on silica gel to obtain the title compound (7.70 g).
1H-NMR (400 MHz, CDCI3): δ = 3.81 (s, 3H), 7.71 (s, 1 H), 7.85 (s, 1 H) ppm. Step 3: Synthesis of tert-butyl 5-[1-[2-methyl-5-(1 ,1 ,2,2,2-pentafluoroethyl)-4-(trifluorome- thyl)pyrazol-3-yl]pyrazol-4-yl]spiro[1 H-isobenzofuran-3,3'-azetidine]-1 '-carboxylate
A mixture of the pyrazole from Step 2 (248 mg, 0.602 mmol), the carboxylate from Step 1 (233 mg, 0.602 mmol), K2CO3 (249 mg, 1.80 mmol), palladium tetrakis(triphenylphosphine) (7 mg, 6 μηηοΙ), THF (6 mL) and water (2 mL) was heated at 80°C for 16 h. After cooling, water was added and the mixture was extracted with ethyl acetate. Combined organic layers were washed with brine and dried over Na2S04. After concentration in vacuum, the residue was triturated with n-heptane to yield the title compound (245 mg).
1H-NMR (400 MHz, CDC ): δ = 1 .50 (s, 9H), 3.87 (s, 3H), 4.18 (d, 2H), 4.36 (d, 2H), 5.16 (s, 2H), 7.28 (s, 1 H), 7.52 (d, 1 H), 7.61 (s, 1 H), 7.95 (s, 1 H) 8.19 (s, 1 H) ppm.
Step 4: Synthesis of 5-[1-[2-methyl-5-(1 ,1 ,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazol-3- yl]pyrazol-4-yl]spiro[1 H-isobenzofuran-3,3'-azetidin-1 -ium] trifluoroacetate
A solution of the carboxylate from Step 3 (8.880 g, 14.96 mmol) in dichloromethane (150 mL) was cooled to 0°C and trifluoroacetic acid (60 mL) was added slowly. After 2 h at 0°C, the mixture was concentrated at 20°C in vacuum. The residue was triturated with diisopropyl ether to yield the title compound (7.90 g).
1H-NMR (400 MHz, CDCb): δ = 3.84 (s, 3H), 4.41 (m, 2H), 4.58 (m, 2H), 5.17 (s, 2H), 7.31 (d, 1 H), 7.62 (d, 1 H), 8.15 (s, 1 H), 8.25 (s, 1 H) 8.29 (s, 1 H), 9.72 (br. s, 1 H), 10.67 (br. s, 1 H) ppm.
Step 5: Synthesis of 1 -[5-[1 -[2-methyl-5-(1 ,1 ,2,2,2-pentafluoroethyl)-4-(trifluoromethyl)pyrazol- 3-yl]pyrazol-4-yl]spiro[1 H-isobenzofuran-3,3'-azetidine]-1 '-yl]propan-1 -one
To a solution of the trifluoroacetate from Step 4 (500 mg, 0.82 mmol) in THF (15 mL) was added DMAP (10 mg, 0.08 mmol) and Hiinig Base (0.84 mL, 0.63 g, 4.94 mmol). After 30 min at 20-25°C, the mixture was cooled to 0°C and propionic acid chloride (86 μί, 91 mg, 0.99 mmol) in THF (2 mL) was added. The ice bath was removed and the mixture was stirred over night. After concentration in vacuum, the residue was taken up in ethyl acetate and washed successively with aqueous 1 M HCI, water, saturated aqueous NaHCC and brine. The organic layer was separated, dried over Na2S04 and evaporated. The residue was subjected to column chromatography on silica gel to yield the title compound (428 mg).
1H-NMR (500 MHz, CDCI3): δ = 1 .20 (t, 3H), 2.24 (q, 2H), 3.88 (s, 3H), 4.33 (d, 2H), 4.36 (m, 2H), 5.18 (s, 2H), 7.30 (d, 1 H), 7.54 (d, 1 H), 7.55 (s, 1 H), 7.94 (s, 1 H), 8.18 (s, 1 H) ppm. In analogy to Example 2, compounds 1-2-1 to I-2-7 of table II were prepared.
Figure imgf000055_0001
Table II - compounds of formula I.A1
Figure imgf000056_0001
II. Evaluation of pesticidal activity:
The activity of the compounds of formula I of the present invention can be demonstrated and evaluated by the following biological test.
B.1 Diamond back moth (Plutella xylostella)
The active compound was dissolved at the desired concentration in a mixture of 1 :1 (vohvol) distilled water : aceteone. Surfactant (Kinetic HV) was added at a rate of 0.01 % (vol/vol). The test solution was prepared at the day of use.
Leaves of cabbage were dipped in test solution and air-dried. Treated leaves were placed in petri dishes lined with moist filter paper and inoculated with ten 3rd instar larvae. Mortality was recorded 72 hours after treatment. Feeding damages were also recorded using a scale of 0- 100%.
In this test, the compounds 1-2-1 , I-2-2, 1-1 -3, I-2-3, I-2-4, I-2-5, and I-2-7, resp., at 300 ppm showed a mortality of at least 75% in comparison with untreated controls.
B.2 Green Peach Aphid (Myzus persicae)
For evaluating control of green peach aphid (Myzus persicae) through systemic means the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial mem brane.
The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were pipetted into the aphid diet, using a custom built pipetter, at two replications.
After application, 5 - 8 adult aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at about 23 + 1 °C and about 50 + 5 % relative humidity for 3 days. Aphid mortality and fecundity was then visually assessed.
In this test, the compounds 1-1 -1 , 1-2-1 , 1-1 -2, I-2-2, 1-1-3, I-2-3, 1-1-4, I-2-4, 1-1 -5, I-2-5, 1-1-6, I-2-6, 1-1 -7, and I-2-7, resp., at 2500 ppm showed a mortality of at least 75% in comparison with untreated controls.
B.3 Vetch aphid (Megoura viciae)
For evaluating control of vetch aphid (Megoura viciae) through contact or systemic means the test unit consisted of 24-well-microtiter plates containing broad bean leaf disks. The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the leaf disks at 2.5 μΙ, using a custom built micro atomizer, at two replications.
After application, the leaf disks were air-dried and 5 - 8 adult aphids placed on the leaf disks inside the microtiter plate wells. The aphids were then allowed to suck on the treated leaf disks and incubated at about 23 + 1 °C and about 50 + 5 % relative humidity for 5 days. Aphid mortality and fecundity was then visually assessed.
In this test, the compounds 1-1 -1 , 1-2-1 , 1-1 -2, I-2-2, 1-1-3, I-2-3, 1-1-4, I-2-4, 1-1 -5, I-2-5, 1-1-6, I-2-6, 1-1 -7, and I-2-7, resp., at 2500 ppm showed a mortality of at least 75% in comparison with untreated controls.
B.4 Tobacco budworm (Heliothis virescens)
For evaluating control of tobacco budworm (Heliothis virescens) the test unit consisted of 96- well-microtiter plates containing an insect diet and 15-25 H. virescens eggs.
The compounds were formulated using a solution containing 75% v/v water and 25% v/v
DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 10 μΙ, using a custom built micro atomizer, at two replications.
After application, microtiter plates were incubated at about 28 + 1 °C and about 80 + 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed.
In this test, the compounds 1-2-1 , I-2-2, I-2-3, I-2-4, and I-2-5, resp., at 2500 ppm showed a mortality of at least 75% in comparison with untreated controls.
B.5 Boll weevil (Anthonomus grandis)
For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of 96-well- microtiter plates containing an insect diet and 5-10 A. grandis eggs.
The compounds were formulated using a solution containing 75% v/v water and 25% v/v DMSO. Different concentrations of formulated compounds were sprayed onto the insect diet at 5 μΙ, using a custom built micro atomizer, at two replications.
After application, microtiter plates were incubated at about 25 + 1 °C and about 75 + 5 % rela- tive humidity for 5 days. Egg and larval mortality was then visually assessed.
In this test, the compounds 1-1 -1 , 1-2-1 , 1-1 -2, I-2-2, 1-1-3, I-2-3, 1-1-4, I-2-4, 1-1 -5, I-2-5, 1-1-6, I-2-6, 1-1 -7, and I-2-7, resp., at 2500 ppm showed a mortality of at least 75% in comparison with untreated controls. B.7 Orchid thrips {dichromothrips corbetti)
Dichromothrips corbetti adults used for bioassay were obtained from a colony maintained continuously under laboratory conditions. For testing purposes, the test compound is diluted in a 1 :1 mixture of acetone:water (vohvol), plus Kinetic HV at a rate of 0.01 % v/v.
Thrips potency of each compound was evaluated by using a floral-immersion technique. All petals of individual, intact orchid flowers were dipped into treatment solution and allowed to dry in Petri dishes. Treated petals were placed into individual resealable plastic along with about 20 adult thrips. All test arenas were held under continuous light and a temperature of about 28°C for duration of the assay. After 3 days, the numbers of live thrips were counted on each petal. The percent mortality was recorded 72 hours after treatment. In this test, the compounds 1-2-1 , 1-1-2, I-2-2, 1-1 -3, I-2-3, I-2-4, I-2-5, I-2-6, and I-2-7, resp., at 300 ppm showed a mortality of at least 75% in comparison with untreated controls.
B.8 Rice green leafhopper (Nephotettix virescens)
Rice seedlings were cleaned and washed 24 hours before spraying. The active compounds were formulated in 1 :1 acetone:water (vohvol), and 0.01 % vol/vol surfactant (Kinetic HV) was added. Potted rice seedlings were sprayed with 5-6 ml test solution, air dried, covered with Mylar cages cages and inoculated with 10 adults. Treated rice plants were kept at about 28-29°C and relative humidity of about 50-60%. Percent mortality was recorded after 72 hours.
In this test, the compound I-2-3 at 300 ppm showed a mortality of at least 75% in comparison with untreated controls.
B.9 Red spider Mite (Tetranychus kanzawai)
The active compound was dissolved at the desired concentration in a mixture of 1 :1 (vohvol) distilled water : acetone. Add surfactant (Kinetic HV) was added at a rate of 0.01 % (vol/vol). The test solution was prepared at the day of use.
Potted cowpea beans of 4-5 days of age were cleaned with tap water and sprayed with 1-2 ml of the test solution using air driven hand atomizer. The treated plants were allowed to air dry and afterwards inoculated with 30 or more mites by clipping a cassava leaf section from rearing population. Treated plants were placed inside a holding room at about 25-27°C and about 50- 60% relative humidity. Percent mortality was assessed 72 hours after treatment.
In this test, the compounds 1-1 -1 , 1-2-1 , and 1-1-3, resp., at 300 ppm, showed a mortality of at least 75% in comparison with untreated controls.

Claims

Claims
1 . Spiro compounds of formula I
Figure imgf000059_0001
wherein
R11 is hydrogen, Ci-C6-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C6-halogenalkyl, C3-C6- cycloalkyl, or C3-C6-halogencycycloalkyl;
R12, R13 independently from each other are halogen, cyano, NO2, Ci-C6-alkyl, C2-C4- alkenyl, C2-C4-alkynyl, Ci-C6-halogenalkyl, C3-C6-cycloalkyl, C3-C6-halogencycyclo- alkyl, Ci-C6-alkoxy, Ci-C6-halogenalkoxy, S(0)n-Ci-C6-alkyl, S(0)n-CrC6-halogen- alkyl;
n is 0, 1 , or 2;
W is a group Wa, or Wb;
-1 ^2
N' O V
SG3 §
wherein
G1 , G2, G3 are independently from each other CRa, or N; wherein
Ra is halogen, OH, SH, NO2, cyano, isocyano, isothiocyanato, Ci-C6-alkyl, C3-C6- cycloalkyl, C2-C4-alkenyl, C3-C6-cycloalkenyl, C2-C4-alkynyl, Ci-C6-alkoxy, C2- C4-alkenyloxy, C2-C4-alkynyloxy, C3-C6-cycloalkoxy, C3-C6-cycloalkenyloxy, S(0)n-Ci-C6-alkyl, cydoalkylthio, C2-C4-alkenylthio, C3-C6-cycloalkenylthio, C2- C4-alkinylthio, C(0)NH2, SF5, S02-N(R33)R35, N(R33)R35, C(0)R35, C(0)OR35, N(R )C(0)-CrC4-alkyl, alkylphosphinyl, alkylphosphonyl, C(0)N(R )R35, phenyl, heterocyclyl, phenoxy, benzyl, benzyloxy, benzylthio, phenylthio, phenyla- mino, benzylamino, and Si(Ci-C4-alkyl)3;
Figure imgf000059_0002
wherein
T is O or S;
R2 is H, Ci-C6-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C3-C7-cycloalkyl, or Ci-C6-alkylcar- bonyl, phenyl-Ci-C4-alkyl, hetaryl-Ci-C4-alkyl; and
# is the bond to pyrazole, and
§ is the bond to phenyl;
Z is O, or S(0)n; R3 is selected from H, Ci-C6-alkyl, CrC6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-alkynyl, C2-C6-haloalkynyl which aliphatic groups are unsubstituted or substituted by one or more radicals R31 ; C3-C6-cycloalkyl, C3-C6-halocycloalkyl which cyclic groups are unsubstituted or substituted with one or more radicals R32;
C(=0)N(R33)R34, N(R33)R35, CH=NOR36; phenyl, heterocyclyl, or hetaryl which rings are unsubstituted or partially or fully substituted with RA;
R31 is independently OH , cyano, Ci-C6-alkoxy, Ci-C6-haloalkoxy, S(0)n-Ci-C6-al- kyl, S(0)n-Ci-C6-haloalkyl, C(=0)N(R33)R34, C3-C6-cycloalkyl, or C3-C6-halocy- cloalkyl which cycles are unsubstitued or substituted with one or more R311 ; or phenyl, heterocyclyl or hetaryl which rings are unsubstitued or partially or fully substituted with RA;
R311 is OH, cyano, Ci-C2-alkyl, or Ci-C2-haloalkyl;
R32 Ci-C6-alkyl, Ci-C6-haloalkyl, or a group as defined for R31 ;
R33 is H, or Ci-Ce-alkyl,
R34 is H, Ci-Ce-alkyl, C C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C2-C6-al- kynyl, C2-C6-haloalkynyl, or C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C3-C6-cy- cloalkylmethyl, or C3-C6-halocycloalkylmethyl which rings are unsubstituted or substituted with a cyano;
R35 H, Ci-Ce-alkyl, Ci-C6-haloalkyl, C2-C4-alkenyl, C2-C4-alkynyl, CH2-CN, C3-C6- cycloalkyl, C3-C6-halocycloalkyl, C3-C6-cycloalkylmethyl, C3-C6-halocycloalkyl- methyl, phenyl and hetaryl which aromatic rings are unsubstituted or partially or fully substituted with RA;
R36 is H, Ci-Ce-alkyl, or Ci-C6-haloalkyl;
RA is independently selected from halogen, cyano, NO2, Ci-C4-alkyl, Ci-C4-haloal- kyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, C2-C4-haloalkynyl, C3-C6- cycloalkyl, C3-C6-halocycloalkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy, S(0)n-Ci-C4- alkyl, S(0)n-Ci-C4-haloalkyl, Ci-C4-alkylcarbonyl, Ci-C4-haloalkylcarbonyl, C(=0)N(R33)R34; or
two RA present on the same carbon atom of a saturated or partially saturated ring may form together =0 or =S; or
two RA present on the same S or SO ring member of a heterocyclic ring may together form a group =N(Ci-C6-alkyl), =NO(Ci-C6-alkyl), =NN(H)(Ci-C6-alkyl) or =NN(Ci-C6-alkyl)2;
and the N-oxides, stereoisomers and agriculturally or veterinarily acceptable salts thereof. Compounds of formula I according to claim 1 , wherein W is Wa. Compounds of formula I according to claim 2, wherein Wa is selected from
Figure imgf000060_0001
Figure imgf000061_0001
Compounds of formula I according to claim 1 , wherein W is Wb.
Compounds of formula I according to claim 4, wherein R2 is H.
Compounds of formula I according to any of claims 1 to 5, wherein Z is O.
Compounds of formula I according to any of claims 1 to 6, wherein R11 is Ci-C4-alkyl, R12 and R13 are N02, Ci-C4-halogenalkyl, or S(0)n-Ci-C4-alkyl.
Compounds of formula I according to any of claims 1 to 7, wherein
R3 is selected from Ci-C4-alkyl, and CrC4-haloalkyl, which aliphatic groups are unsub- stituted or substituted by one radical R31; and C3-C5-cycloalkyl, C3-C5-halocycloalkyl which cyclic groups are unsubstituted or substituted by one radical R32;
R31 is independently OH, cyano, Ci-C4-alkoxy, Ci-C4-haloalkoxy, S(0)n-Ci-C4-al- kyl, S(0)n-Ci-C4-haloalkyl, Cs-Cs-cycloalkyl, or Cs-Cs-halocycloalkyl which cycles are unsubstitued or substituted by one or more R311 ;
R311 is independently OH, cyano, Ci-C2-alkyl, or Ci-C2-haloalkyl;
n is 0, 1 , or 2; and
R32 is independently Ci-C4-alkyl, Ci-C4-haloalkyl, or a group as defined for R31.
9. Compounds of formula I according to any of claims 1 to 8, wherein
R3 is selected from Ci-C3-alkyl, CH2CF3, CH2CH2CF3, CH2OH, CH2-c-C3H5, c-C3H5, 1 -CN- c-C3H4, 1 -CF3-c-C3H4, 1-OH-c-C3H4, 2,2-F2-c-C3H3, CH2OCH3, CH2OC2H5, CH2OCF3,
CH2OCH2CF3, and CH2S(0)nCH3, CH2S(0)nC2H5, wherein n is 0, 1 , or 2; 1-pyrazolyl, 3- CH3-1 -pyrazolyl, 2-pyridyl,3-thietan-yl, 3-thietan-yl-S-oxide, and 3-thietan-yl-S-dioxide.
10. Intermediate compounds of formula Ila
Figure imgf000061_0002
wherein Z is as defined in claims 1 or 6,
X is halogen, and
PG is Boc, or C(0)Rx, with Rx being Ci-C2-alkoxy, or benzyloxy. 1 1. A composition comprising at least one compound according to any one of claims 1 to 9 and at least one inert liquid and/or solid carrier.
12. An agricultural composition for combating animal pests comprising at least one compound as defined in any of claims 1 to 9 and at least one inert liquid and/or solid acceptable carrier and, if desired, at least one surfactant.
The composition according to claim 1 1 or 12, comprising additionally a further active substance.
A method for combating or controlling invertebrate pests, which method comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound as defined in any one of claims 1 to 9.
A method for protecting growing plants from attack or infestation by invertebrate pests, which method comprises contacting a plant, or soil or water in which the plant is growing, with a pesticidally effective amount of at least one compound as defined in any of claims 1 to 9.
16. Seed comprising a compound as defined in any of claims 1 to 9, or the enantiomers, dia- stereomers or salts thereof, in an amount of from 0.1 g to 10 kg per 100 kg of seed. 17. The use of the compounds as defined in any of claims 1 to 9 for protecting growing plants from attack or infestation by invertebrate pests.
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