WO2011064188A1 - Insecticidal methods using nitrogen-containing heteroaromatic compounds - Google Patents

Abstract

Insectical methods using nitrogen containing heteroaromatic compounds The present invention relates to new insecticidal methods of using nitrogen-containing heteroaromatic compounds of the formula (I), wherein A, E, G, M, W, Y, X, R¹ and R² are defined as in the description, and to their enantiomers, diastereomers and agriculturally and veterinary acceptable salts. The present invention relates to methods of administering and applying such Pyridine compounds of formula I for insecticidal use and purposes in agriculture and in the veterinary field. The invention relates also to new derivatives of Pyridine compounds of formula I.

Description

Insecticidal methods using nitrogen-containing heteroaromatic compounds

The present invention relates to new insecticidal methods of using nitrogen- containing heteroaromatic compounds and salts thereof. The present invention relates also to new nitrogen-containing heteroaromatic derivatives and their uses in the agricultural field.

Animal pests destroy growing and harvested crops, as well as the seeds and attack wooden dwelling and commercial structures, causing damage in the agricultural field, large economic loss to the food supply and to the property. While a large number of pesticidal agents are known, due to the ability of target pests to develop resistance to said agents, there is an ongoing need for new agents for combating animal pests. In particular, animal pests such as insects and acaridae are difficult to be effectively controlled.

It is therefore an object of the present invention to provide new methods and compounds having a good pesticidal activity. Moreover it is an object of the present invention to provide methods and compounds specially against difficult to control insects and acaridae.

It has been found that these objects can be solved by nitrogen-containing heteroaromatic derivatives of the

wherein

A, E, G, M are N or C-R^c, wherein one or two of these groups being N,

and wherein

R^c is hydrogen or R^a,

and wherein

R^a is selected independently of one another from the group consisting of Z- CN , Z-OH, Z-NO2, Z-halogen, Ci-Cs-alkyl, Ci-C₄-haloalkyl, C₂-C₈-alkenyl, C₂-C₈- alkynyl, Z-d-Ce-alkoxy, Z-d-Ce-haloalkoxy, Z-C3-Cio-cycloalkyl,

0-Z-C₃-Cio-cycloalkyl, Z-C(=0)-R^a2, NR'R", Z-(tri-Ci-C₄-alkyl)silyl, Z-phenyl and S(0)_nR^bb,

wherein

n is 0, 1 or 2;

Z is a covalent bond or Ci-C4-alkylene;

R^a2 is d-Ce-alkyl, Ci-C₄-haloalkyl, Z-Ci-C₆-alkoxy, Z-Ci-C₄-haloalkoxy or NR'R"; R',R"are selected, independently of one another, from hydrogen, Ci-Ce-alkyl,

Ci-C₄-haloalkyl, C₃-C₈-alkenyl, C₃-C₈-alkynyl, Z-C₃-C₆-cycloalkyl, Z-Ci-C₈- alkoxy, Z-Ci-Cs-haloalkoxy,

or wherein

R' and R" together with the nitrogen atom to which they are attached may also form a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic heterocycle which may contain, in addition to the nitrogen atom they are bound to, 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S;

R^bb is Ci-Cs-alkyl or Ci-C₆-haloalkyl;

or wherein

R^a together with the group R^a optionally attached to the adjacent carbon atom may also form a five- or six-membered saturated or partially or fully unsaturated ring which, in addition to carbon atoms, may contain 1 , 2 or 3 heteroatoms selected from the group consisting of O, N and S;

W is O or S;

X is O, S or N-R;

Y is R¹ or NH-R, wherein

R¹ is OR or SR,

and wherein

R is selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C4-ha- loalkyl, C2-C6-alkenyl, C3-C6-alkynyl, Z-C3-Cio-cycloalkyl, Ci-C6-alkoxy-Ci-

Cs-alkyl, Ci-C6-cyanoalkyl, Z-phenyl, a 5- or 6 membered monocyclic het- erocycle attached via Z, which contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S and which may be attached via a carbon or a nitrogen atom of the heterocycle and wherein the heterocycle my be fully or partially substitiuted by R^a,

Z-C(=0)-R^a2, Z-S0₂R^a2 and tri-Ci-C₄-alkylsilyl;

and wherein in the group R and its subsubtituents, the carbon chains and/or the (hetero)cyclic groups may be partially or fully substituted by groups R^a;

R² is phenyl, naphthyl or a 5- or 6-membered monocyclic or 9- or 10-membered bicyclic aromatic heterocycle which comprises 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S, wherein the cyclic groups are unsubsti- tuted or substituted by 1 , 2, 3, 4 or 5 groups R^a;

or an N-oxide, enantiomer, diastereomer or an agriculturally or veterinarily suitable salt thereof.

The present invention relates to following insecticidal methods applying such compounds of formula I.

It was an object of the present invention to provide methods of combating and controlling animal pests which methods comprise contacting the animal pests, their habit, breeding ground, food supply, plant, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of at least one nitrogen-containing heteroaromatic compound of formula I and/or an N-oxide, enantiomer, diastereomer or agriculturally acceptable salt thereof;

It was further an object of the present invention to provide methods for protecting crops and growing plants from attack or infestation by animal pests, which methods comprise contacting a crop or a growing plant with a pesticidally effective amount of at least one nitrogen-containing heteroaromatic compound of formula I and/or an N-oxide, enantiomer, diastereomer or agriculturally acceptable salt thereof;

Another object of the present invention was to provide methods for protecting plant propargation material, especially seeds, from soil insects and seedlings' roots and shoots from soil and foliar insects, which methods comprise contacting the seeds before sowing and/or after pregermination with at least one nitrogen-containing heteroaromatic compound of formula I and/or an N-oxide, enantiomer, diastereomer or agriculturally acceptable salt thereof;

And another object of the present invention was to provide methods for treating, controlling, preventing or protecting animals against infestation or infection by parasites, which methods comprise administering or applying to the animals and/or to their enviroment a parasitically effective amount of at least one nitrogen-containing heteroaromatic compound of formula I and/or an N-oxide, enantiomer, diastereomer or a veterinary acceptable salt thereof.

Object of the invention are also methods of using at least one compound of the formula I and/or an N-oxide, enantiomer, diastereomer and/or a veterinary acceptable salts thereof, for combating parasites in and on animals by treating the parasites with an parasitical active amount thereof.

In this field it was further an object of the present invention to use nitrogen-con- taining heteroaromatic compound of formula I and/or an N-oxide, enantiomer, diastereomer or a veterinary acceptable salt thereof for the preparation of a medicament for treating animals against infestion and infection by parasites.

Furthermore, the present invention relates also to new nitrogen-containing heteroaromatic compounds of the general formulae II and III, their N-oxides, enantiomers, diastereomers or agricultural or veterinary useful salts thereof and to veterinary or agricultural compositions comprising them and at least one inert liquid and/or solid agronomically acceptable carrier, as well as to their uses as described above for compounds of formula I.

The present invention relates also to nitrogen-containing heteroaromatic compounds of formula I, which are of formula II:

wherein

X, W are as defined for formula I;

Y is OR or SR, wherein

R is selected from hydrogen, Ci-C6-alkyl, Ci-C4-haloalkyl, C2-C6-alkenyl, C3-C6- alkynyl, Z-C3-Cio-cycloalkyl, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-cyanoalkyl, Z- phenyl, Z-C(=0)-R^a2 or tri-Ci-C4-alkylsilyl, and wherein

R^a2 is selected from Ci-C₆-alkyl, Ci-C₄-haloalkyl, Z-Ci-C₆-alkoxy, Z-Ci-C₄-halo- alkoxy or NR'R", and R', R" are selected independently of one another from hydrogen, d-Ce-alkyl,

Ci-C₄-haloalkyl, C₃-C₈-alkenyl, C₃-C₈-alkynyl, Z-C₃-C₆-cycloalkyl, Z-Ci-C₈- alkoxy or Z-Ci-Cs-haloalkoxy;

and wherein

in the group R and its subsubtituents, the carbon chains and/or the cyclic groups may be partially or fully substituted by halogen, Ci-Cs-alkyl or Ci-C6-haloalky;

R¹ is hydrogen or Ci-C6-alkoxy;

and

R^c2, R^c3, R^c3, R^a3, R^a4 and R^a5 are selected independently from one another from the group consisting of hydrogen, OH, CN , NO2, halogen, Ci-C₄-alkyl, Ci-C₄-haloalkyl, Ci- C₄-alkoxy and Ci-C4-haloalkoxy;

and/or at least an N-oxide, an enantiomer, diastereomer or agriculturally or veterinary acceptable salt thereof. The present invention relates also to nitrogen-containing heteroaromatic compounds of formula I, which are of formula III:

wherein

X, W are as defined for formula (I) in claiml ;

R¹ is hydrogen or Ci-C6-alkoxy;

R² is phenyl or pyridyl, which may carry one or more substitutents selected from the group consisting of OH , CN , NO2, halogen, Ci-C₄-alkyl, Ci-C₄-haloalkyl, Ci-C₄-alkoxy and Ci-C₄-haloalkoxy;

R^c2, R^c3, R^ are selected independently from one another from the group consist- ing of hydrogen, OH , CN , NO2, halogen, Ci-C₄-alkyl, Ci-C₄-haloalkyl, Ci-C₄- alkoxy and Ci-C₄-haloalkoxy;

and

R is a 5- or 6-membered monocyclic heterocycle attached via Z and selected from the group consisting of pyridyl, thiazolyl, isothiazolyl, pyrazolyl, oxazolyl and isoxazolyl, wherein the heterocycle may be attached via a carbon or a nitrogen atom of the heterocycle and which may carry one or more substitutents selected from the group consisting of OH , CN , NO2, halogen, Ci-C₄-alkyl, Ci- C₄-haloalkyl, Ci-C₄-alkoxy and Ci-C₄-haloalkoxy, wherein

Z is a covalent bond or Ci-C₄-alkylene chain, wherein the carbon chain may op- tionally carry one or more substituents selected from d-Ce-alkyl or Ci-C₄- haloalkyl;

and/or at least an N-oxide, an enantiomer, diastereomer or agriculturally or veterinary acceptable salt thereof. The compounds of the formulae I, II or III, wherein X would represent O or S (both characterized by X¹ in the following tautomeric formulae), and their precursors can be present in two tautomeric forms. The invention relates to both tautomers. For the sake of clarity, only one tautomer is generally mentioned in th

tautomer 1 tautomer 2

Nitrogen-containing heteroaromatic compounds are described for herbicidal uses in WO 2010/069802.

However, no insectidial uses and applications are to be found for such nitrogen- containing heteroaromatic compounds of formula I. Neither the compounds of formula II and III, nor their insecticidal activity as well as methods of applications and uses thereof were described previously. The compounds of the formula I, II and III, their N-oxides, enantiomers, diastereo- mers and their agriculturally or veterinary acceptable salts thereof are highly active against animal pest, i.e. harmful arthropodes and nematodes. They may be used against difficult to control insects and acaridae.

Thus, the present invention relates to and includes the following embodiments: - agricultural and veterinary compositions comprising an amount of at least one compound of the formula I, II or III, or an N-oxide, enantiomer, diasteromer or salt thereof;

- the use of a compound of formula 1, 11 or III, or an N-oxide, enantiomer, diasteromer or salt thereof for combating or controlling animal pests;

- a method of combating animal pests which comprises contacting the animal pests, their habit, breeding ground, food supply, plant, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of at least one compound of the formula I, II or III, or an N- oxide, enantiomer, diasteromer or salt thereof;

- a method for protecting crops from attack or infestation by animal pests, which comprises contacting a crop with a pesticidally effective amount of at least one compound of the formula I, II or III, or an N-oxide, enantiomer, diasteromer or salt thereof;

- a method for the protection of plant propargation material, especially seeds, from soil insects and of the seedlings' roots and shoots from soil and foliar insects comprising contacting the plant propargation material, especially the seeds, before sowing and/or after pregermination with at least one compound of the formula 1, 11 or III, or the N-oxide, enantiomers, diastereomers or salts thereof;

- seeds comprising a compound of the formula I , II or III, or an N-oxide, enanti- omer, diasteromer or salt thereof; - the use of compounds of formula 1,11 or III, or the N-oxide, enantiomers, diastereomers or veterinary acceptable salts thereof for combating parasites in and on animals;

- a method for treating, controlling, preventing or protecting animals against infes- tation or infection by parasites which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of an compound of formula I, II or III, or the N-oxide, enantiomers, diastereomers and/or veterinary acceptable salt thereof;

- the use of compounds of formula I, II or III, or the N-oxide, enantiomers, dia- stereomers or veterinary acceptable salts thereof for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites, wherein the composition comprisess a parasiticidally effective amount of an compound of formula I, II or III, or the enantiomers, diastereomers and/or veterinary acceptable salt thereof.

Depending on the substitution pattern, the compounds of the present invention can contain one or more chiral centers, in which case they are present as enantiomer or diastereomer mixtures. Subject matter of this invention are not only compositions containing these mixtures but also those containing the pure enantiomers or diastereo- mers.

The compounds of the present invention may be amorphous or may exist in one ore more different crystalline states (polymorphs) which may have a different macroscopic properties such as stability or show different biological properties such as activities. The present invention includes both amorphous and crystalline compounds of the for- mula I, II or III or as well mixtures of their different crystalline states.

Salts of the compounds of formulae I, II and III are preferably agriculturally and veterinary acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formulae I, II or III has a basic functionality or by reacting an acidic compound of formulae I, II or III with a suitable base.

Suitable agriculturally useful salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention. Suit-able cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and bar-ium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH⁴⁺) and substituted ammonium in which one to four of the hydrogen atoms are replaced by Ci-C4-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy- Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylam- monium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetra- ethylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxy- ethoxy)ethylammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyl-triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sulfoxonium. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydro- gen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hy-drogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and bu- tyrate. They can be formed by reacting a compound of the present invention with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sul- furic acid, phosphoric acid or nitric acid.

By the term "veterinarily acceptable salts" is meant salts of those cations or anions which are known and accepted in the art for the formation of salts for veterinary use. Suitable acid addition salts, e.g. formed by compounds of the present invention containing a basic nitrogen atom, e.g. an amino group, include salts with inorganic acids, for example hydrochlorids, sulphates, phosphates, and nitrates and salts of organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.

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 mem- bers.

The prefix C_n-C_m 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.

Examples of other meanings are:

The term "Ci-C6-alkyl" as used herein and in the alkyl moieties of Ci-C6-alkoxy, Ci-C6-alkylamino, di(CrC6-alkyl)amino, Ci-C6-alkylthio, Ci-C6-alkylcarbonyl, Ci-C6-alk- oxycarbonyl, 0-C6-alkylaminocarbonyl and di(Ci-C6-alkyl)aminocarbonyl refers to a saturated straight-chain or branched hydrocarbon group having 1 to 6 carbon atoms, especially 1 to 3 carbon groups (= Ci-C3-alkyl). Examples for Ci-C3-alkyl are methyl, ethyl, propyl and 1 -methylethyl (isopropyl). Examples for C1-C6 alkyl further encompass, butyl, 1 -methyl propyl (sec-butyl, 2-butyl), 2-methylpropyl (iso-butyl), 1 ,1-dimethyl- ethyl (tert-butyl), pentyl, 1 -methylbutyl, 2-methylbutyl, 3 methylbutyl, 2,2-dimethylpropyl, 1 -ethyl propyl, hexyl, 1 ,1 -dimethyl propyl, 1 ,2 dimethylpropyl, 1-methylpentyl, 2-methyl- pentyl, 3 methylpentyl, 4-methylpentyl, 1 ,1 dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-di- methylbutyl, 2,2-dimethylbutyl, 2,3 dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2- ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1-ethyl-1 -methylpropyl, 1 -ethyl-2 methylpropyl.

The term "Ci-C6-haloalkyl" as used herein and in the haloalkyl moieties of C1-C6- haloalkoxy, Ci-C6-haloalkylthio, Ci-C6-haloalkylcarbonyl and Ci-C6-haloalkoxycarbonyl refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example Ci-C3-haloalkyl, such as chloromethyl, bromo- methyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chloro-fluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, 1 -bromo- ethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-flu- oroethyl, 2 chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pen- tafluoroethyl and the like.

The term "Ci-C6-alkoxy" as used herein and in the term Ci-C6-alkoxycarbonyl refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms (= Ci-C3-alkoxy) which is attached via an oxygen atom. Examples for Ci-C3-alkoxy include methoxy, ethoxy, OCH2-C2H5 (propoxy) and

OCH(CH3)2 (isopropoxy). Examples for Ci-C6-alkoxy further encompass n-butoxy, OCH(CH₃)C₂H₅ (sec-butoxy), OCH₂CH(CH₃)₂ (isobutoxy), OC(CH₃)₃ (tert-butoxy), n- pentoxy, 1 methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1 , 1 -dimethylpropoxy, 1 ,2- dimethylpropoxy, 2,2-dimethylpropoxy, 1 -ethyl propoxy, n-hexoxy, 1 methylpentoxy, 2- methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1 ,1 -dimethylbutoxy, 1 ,2-dimethyl- butoxy, 1 ,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbut- oxy, 1 -ethylbutoxy, 2-ethylbutoxy, 1 , 1 ,2-trimethylpropoxy, 1 ,2,2 trimethylpropoxy, 1 - ethyl-1 -methylpropoxy, 1 -ethyl-2-methylpropoxy and the like.

The term "Ci-C6-haloalkoxy" as used herein and in the term Ci-C6-haloalkoxy- carbonyl refers to a Ci-C6-alkoxy group as men-tioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine. Preferred are Ci-C₃-haloalkoxy groups, i.e. Ci-C₃-alkoxy groups as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoro- methoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2- iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro- 2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroeth- oxy, 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chlo- ropropoxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3 trichloropropoxy, 2,2,3,3,3-pentafluoropropoxy, hepta- fluoropropoxy, 1 -(fluoromethyl)-2-fluoroethoxy, 1 -(chloromethyl)-2-chloroethoxy and 1 (bromomethyl)-2-bromoethoxy. Examples for Ci-C6-haloalkoxy further encompass 4- fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy, nonafluorobutoxy, 5-fluoro-1 -pentoxy, 5- chloro-1 -pentoxy, 5 bromo-1 -pentoxy, 5-iodo-1 -pentoxy, 5,5,5-trichloro-1 -pentoxy, un- decafluoropentoxy, 6-fluoro-1 -hexoxy, 6-chloro-1 -hexoxy, 6-bromo-1 -hexoxy, 6-iodo-1 - hexoxy, 6,6,6 trichloro-1 -hexoxy and dodecafluorohexoxy. Particularly preferred are chloromethoxy, fluorometh-oxy, difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 2 chloroethoxy and 2,2,2-trifluoroethoxy.

The term "Ci-C6-alkylcarbonyl" as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms

(= Ci-C4-alkylcarbonyl) bonded via the carbon atom of the carbonyl group at any bond in the alkyl group. Examples for Ci-C4-alkyl carbonyl include C(=0)CH₃, C(0)C2H₅, n-propylcarbonyl, 1 -methylethylcarbonyl, n-butylcarbonyl, 1 -methylpropylcarbonyl, 2- methylpropylcarbonyl and 1 ,1 -dimethylethylcarbonyl. Examples for Ci-C6-alkylcar- bonyl further encompass n-pentylcarbonyl, 1 -methylbutylcarbonyl, 2-methylbutylcar- bonyl, 3-methylbutylcarbonyl, 1 ,1-dimethylpropylcarbonyl, 1 ,2-dimethylpropylcarbonyl, 2,2-dimethylpropylcarbonyl, 1 -ethylpropylcarbonyl, n-hexylcarbonyl, 1-methylpentylcar- bonyl, 2-methylpentylcarbonyl, 3-methylpentylcarbonyl, 4-methylpentylcarbonyl, 1 ,1-di- methylbutylcarbonyl, 1 ,2-dimethylbutylcarbonyl, 1 ,3-dimethylbutylcarbonyl, 2,2-di- methylbutylcarbonyl, 2,3-dimethylbutylcarbonyl, 3,3-dimethylbutylcarbonyl, 1-ethyl- butylcarbonyl, 2-ethylbutylcarbonyl, 1 ,1 ,2 tnmethylpropylcarbonyl, 1 ,2,2-trimethylpropyl- carbonyl, 1-ethyl-1 -methylpropylcarbonyl or 1 -ethyl-2-methylpropylcarbonyl and the like.

The term "Ci-C6-alkoxycarbonyl" as used herein refers to a straight-chain or branched alkoxy group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (= Ci-C4-alkoxycarbonyl) attached via the carbon atom of the carbonyl group (R-O- C(O)-; R = alkyl). Examples for Ci-C₄-alkoxycarbonyl include -C(0)OCH₃, -C(0)OC₂H₅, -C(0)0-CH₂-C₂H₅, -C(0)OCH(CH₃)₂, n-butoxycarbonyl, -C(0)OCH(CH₃)-C₂H₅,

-C(0)-OCH₂CH(CH₃)₂ and C(0)OC(CH₃)3. Examples for Ci-C₆-alkoxycarbonyl further encompass n-pentoxycarbonyl, 1-methylbutoxycarbonyl, 2-methylbutoxycarbonyl,

3- methylbutoxycarbonyl, 2,2-dimethylpropoxycarbonyl, 1-ethylpropoxycarbonyl, n-hex- oxycarbonyl, 1 ,1 -dimethylpropoxycarbonyl, 1 ,2-dimethylpropoxycarbonyl, 1 -methyl- pentoxycarbonyl, 2-methylpentoxycarbonyl, 3-methylpentoxycarbonyl, 4-methylpent- oxycarbonyl, 1 ,1 -dimethylbutoxycarbonyl, 1 ,2-dimethylbutoxycarbonyl, 1 ,3-dimethyl- butoxycarbonyl, 2,2-dimethylbutoxycarbonyl, 2,3-dimethylbutoxycarbonyl, 3,3-dimethyl- butoxycarbonyl, 1 -ethylbutoxycarbonyl, 2-ethylbutoxycarbonyl, 1 ,1 ,2-trimethylpropoxy- carbonyl, 1 ,2,2-trimethylpropoxycarbonyl, 1 -ethyl-1-methylpropoxycarbonyl or 1-ethyl- 2-methylpropoxycarbonyl.

The term "Ci-C6-alkylthio "(Ci-C6-alkylsulfanyl: Ci-C6-alkyl-S-)" as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms, pref- era-bly 1 to 3 carbon atoms (= Ci-C3-alkylthio) which is attached via a sulfur atom. Examples for Ci-C3-alkylthio include methylthio, ethylthio, propylthio and 1 methylethyl- thio. Examples for Ci-C6-alkylthio further encompass butylthio, 1 -methylpropylthio,

2-methylpropylthio and 1 ,1 -dimethylethylthio. n-pentylthio, 1-methylbutylthio, 2-methyl- butylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, n-hexylthio, 1 ,1 - dimethylpropylthio, 1 ,2-dimethylpropylthio, 1 -methylpentylthio, 2-methylpentylthio, 3- methylpentylthio, 4-methylpentylthio, 1 ,1 -dimethylbutylthio, 1 ,2-dimethylbutylthio, 1 ,3- dimethylbutythio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1 - ethylbutlthio, 2-ethylbutylthio, 1 ,1 ,2-trimethylpropylthio, 1 ,2,2-trimethylpropylthio, 1 - ethyl-1 -methylpropylthio and 1 -ethyl-2-methylpropylthio.

In analogy to the above, the term "Ci-C6-alkylsulfonyl" (Ci-C6-alkyl-S0₂-)" as used herein refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms (= Ci-C3-alkylthio) which is attached via a sul- fonyl group S0₂.

In case when in the term "NR'R"" one of R' or R" is Ci-Cs-alkyl or d-Ce-alkylcar- bonyl, this is represented by the term "Ci-C6-alkylamino" or the term "Ci-C6-alkylamino- carbonyl", or when both of R' and R" are Ci-C6-alkyl or Ci-C6-alkylcarbonyl this represented by the term "di(Ci-C6-alkyl)amino)" or the term "di(Ci-C6-alkylamino)-carbonyl".

In such cases the term "Ci-C6-alkylamino" as used herein and the term "Ci-C6-alkyl" refers to a secondary amino group carrying one alkyl group as defined above, e.g. me- thylamino, ethylamino, propylamino, 1-methylethylamino, butylamino, 1 -methylpropyl- amino, 2-methylpropylamino, 1 ,1-dimethylethylamino, pentylamino, 1 -methylbutylami- no, 2-methylbutylamino, 3-methylbutylamino, 2,2-dimethylpropylamino, 1-ethylpropyl- amino, hexylamino, 1 ,1-dimethylpropylamino, 1 ,2-dimethylpropylamino, 1 -methylpentyl- amino, 2-methylpentylamino, 3-methylpentylamino, 4-methylpentylamino, 1 ,1 -dimethyl- butylamino, 1 ,2-dimethylbutylamino, 1 ,3-dimethylbutylamino, 2,2-dimethylbutylamino, 2,3-dimethylbutylamino, 3,3-dimethylbutylamino, 1-ethylbutylamino, 2-ethylbutylamino, 1 ,1 ,2-trimethylpropylamino, 1 ,2,2-trimethylpropylamino, 1 -ethyl-1-methylpropylamino or 1-ethyl-2-methylpropylamino.

And the term "di(Ci-C6-alkyl)amino)" as used herein and the term "di(Ci-C6-alkyl- amino)-carbonyl" refers to a tertiary amino group carrying two alkyl radicals as defined above, e.g. dimethylamino, diethylamino, di-n-propylamino, diiso-propylamino, N-ethyl- N-methylamino, N-(n-propyl)-N-methylamino, N-(isopropyl)-N methylamino, N-(n-butyl)- N-methylamino, N-(n-pentyl)-N-methylamino, N-(2-butyl)-N methylamino, N-(isobutyl)- N-methylamino, N-(n-pentyl)-N-methylamino, N-(n-propyl)-N ethylamino, N-(isopropyl)- N-ethylamino, N-(n-butyl)-N-ethylamino, N-(n-pentyl)-N ethylamino, N-(2-butyl)-N- ethylamino, N-(isobutyl)-N-ethylamino and the like.

The term "C2-C6-alkenyl" as used herein and in the alkenyl moieties of C2-C6-al- kenyloxy, C2-C6-alkenylamino and C2-C6-alkenylcarbonyl refers to a straight-chain or branched unsaturated hydrocarbon group having 2 to 6 carbon atoms and a double bond in any position, such as ethenyl, 1 -propenyl, 2-propenyl, 1-methyl-ethenyl, 1-but- enyl, 2-butenyl, 3-butenyl, 1 -methyl-1 -propenyl, 2 methyl-1-propenyl, 1-methyl-2-pro- penyl, 2-methyl-2-propenyl; 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1- butenyl, 2-methyl-1-butenyl, 3-methyl-1 -butenyl, 1-methyl-2-butenyl, 2-methyl-2-but- enyl, 3-methyl-2-butenyl, 1 -methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1 ,1-dimethyl-2-propenyl, 1 ,2-dimethyl-1 -propenyl, 1 ,2-dimethyl-2-propenyl, 1 -ethyl-1 - propenyl, 1-ethyl-2-propenyl, 1 -hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1- methyl-1 -pentenyl, 2-methyl-1-pentenyl, 3-methyl-1 -pentenyl, 4-methyl-1-pentenyl, 1- methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1- methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1- methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1 ,1- dimethyl-2-butenyl, 1 ,1-dimethyl-3-butenyl, 1 ,2-dimethyl-1-butenyl, 1 ,2-dimethyl-2-but- enyl, 1 ,2-dimethyl-3-butenyl, 1 ,3-dimethyl-1 -butenyl, 1 ,3-dimethyl-2-butenyl, 1 ,3-di- methyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1 -butenyl, 2,3-dimethyl-2-but- enyl, 2,3-dimethyl-3-butenyl, 3,3 dimethyl-1 -butenyl, 3,3-dimethyl-2-butenyl, 1 -ethyl-1 - butenyl, 1 -ethyl-2-butenyl, 1 ethyl-3-butenyl, 2-ethyl-1 -butenyl, 2-ethyl-2-butenyl, 2- ethyl-3-butenyl, 1 ,1 ,2 trimethyl-2-propenyl, 1 -ethyl-1 -methyl-2-propenyl, 1 -ethyl-2- methyl-1 -propenyl and 1 -ethyl-2-methyl-2-propenyl. The term, "C2-C6-alkenyloxy" as used herein refers to a straight-chain or branched al-kenyl group having 2 to 6 carbon atoms which is attached via an oxygen atom, such as vinyloxy, allyloxy (propen-3-yloxy), methallyloxy, buten-4-yloxy and the like.

The term "C2-C6-alkynyl" as used herein and in the alkynyl moieties of

C2-C6-alkynyloxy, C2-C6-alkynylamino, C2-C6-alkynylthio and C2-C6-alkynylcarbonyl refers to a straight-chain or branched unsaturated hydrocarbon group having 2 to 6 carbon atoms and containing at least one triple bond, such as ethynyl, prop-1-yn-1-yl, prop-2-yn-1 -yl, n-but-1 -yn-1 -yl, n-but-1 -yn-3-yl, n-but-1 -yn-4-yl, n-but-2-yn-1-yl, n-pent- 1 -yn-1 -yl, n-pent-1 -yn-3-yl, n-pent-1-yn-4-yl, n-pent-1-yn-5-yl, n-pent-2-yn-1-yl, n-pent- 2-yn-4-yl, n-pent-2-yn-5-yl, 3-methylbut-1 -yn-3-yl, 3-methylbut-1-yn-4-yl, n-hex-1-yn-1- yl, n-hex-1 -yn-3-yl, n-hex-1 yn-4-yl, n-hex-1 -yn-5-yl, n-hex-1-yn-6-yl, n-hex-2-yn-1-yl, n-hex-2-yn-4-yl, n-hex-2-yn-5-yl, n-hex-2-yn-6-yl, n-hex-3-yn-1 -yl, n-hex-3-yn-2-yl, 3-methylpent-1-yn-1-yl, 3 methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl, 3-methylpent-1 - yn-5-yl, 4-methylpent-1-yn-1-yl, 4-methylpent-2-yn-4-yl or 4-methylpent-2-yn-5-yl and the like.

The term, "C2-C6-alkynyloxy" as used herein refers to a straight-chain or branched al-kynyl group having 2 to 6 carbon atoms (as mentioned above) which is attached via an oxygen atom, such as propargyloxy (propyn-3-yloxy), butyn-3-yloxy, butyn-4-yloxy and the like.

The term "C3-Ci2-cycloalkyl" as used herein refers to a mono- or bi- or polycyclic hydrocarbon radical having 3 to 12 (= C3-Ci2-cycloalkyl), frequently 3 to 8 carbon atoms (= C3-C8-cycloalkyl), in particular 3 to 6 carbon atoms (= C3-C6-cycloalkyl). Examples of monocyclic radicals comprise cyclo-propyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo- heptyl, cyclooctyl, cyclononyl and cyclodecyl. Examples of bicyclic radicals comprise bicyclo[2.2.1 ]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.2]octyl and bicyclo[3.2.1]octyl. Phenyl fused to benzene is naphthyl.

Phenyl fused to a 5- or 6-membered non-aromatic (i.e. saturated or partially unsaturated) heterocyclic ring is for example 2,3-dihydrobenzofuranyl, benzoxolanyl,

2,3-dihydrobenzothienyl, indolinyl, chromanyl, chromenyl, benzodioxanyl and the like. Examples for phenyl fused to a 5- or 6-membered aromatic heterocyclic ring (= fused to a 5- or 6-membered heteroaromatic ring) are given below.

The term "saturated or (partially) unsaturated heterocycle" comprises nonaromatic saturated or partially unsaturated heterocyclic rings having 5 or 6 ring members and 1 , 2, 3 or 4, preferably 1 , 2 or 3 heteroatoms as ring members. The heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member. Examples for non-aromatic rings include pyrrolidinyl, pyrazolinyl, imidazolinyl, pyrrolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1 ,3- dioxolanyl, dioxolenyl, thiolanyl, dihydrothienyl, oxazolidinyl, isoxazolidinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl, piperi- dinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, 1 ,3- and 1 ,4-dioxanyl, thiopyranyl, dihydrothiopyranyl, tetrahydrothiopyranyl, morpholinyl, thiazinyl and the like. Examples for heterocyclic ring also comprising 1 or 2 carbonyl groups as ring members comprise pyrrolidin-2-onyl, pyrrolidin-2,5-dionyl, imidazolidin-2-onyl, oxa- zolidin-2-onyl, thiazolidin-2-onyl and the like.

The term "aromatic heterocycle" or "heteroaryl" ("mono or bicyclic 5- to 10-mem- bered") as used herein refers to a monocyclic heteroaromatic radical which has 5 or 6 ring members, which may be fused to a carbocyclic or heterocyclic 5, 6 or 7 membered ring thus having a total number of ring members from 8 to 10, wherein in each case 1 , 2, 3 or 4, preferably 1 , 2 or 3, of these ring members are heteroatoms selected, independently from each other, from the group consisting of oxygen, nitrogen and sulfur. The heteraryl radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member. The carbocyclic or heterocyclic fused ring is selected from C5-C7-cycloalkyl, 5 to 7 membered heterocyclyl and phenyl.

Examples for monocyclic 5- to 6-membered heteroaromatic rings include triazinyl, pyrazinyl, pyrimidyl, pyridazinyl, pyridyl, thienyl, furyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, isothiazolyl and isoxa- zolyl.

Examples for 5- to 6-membered heteroaromatic rings being fused to a phenyl ring (or for benzene fused to a 5- to 6-membered heteroaromatic ring) are quinolinyl, iso- quinolinyl, indolyl, indolizinyl, isoindolyl, indazolyl, benzofuryl, benzthienyl,

benzo[b]thiazolyl, benzoxazolyl, benzthiazolyl, benzoxazolyl, and benzimidazolyl. Ex- amples for 5- to 6-membered heteroaromatic rings being fused to a cycloalkenyl ring are dihydroindolyl, dihydroindolizinyl, dihydroisoindolyl, dihydrochinolinyl, dihydroiso- chinolinyl, chromenyl, chromanyl and the like.

The term "linear or branched Ci-C6-alkanediyl" as used herein and in the term

Ci-C6-alkanediyloxy refers to a straight-chain or branched saturated alkyl group having 1 to 6 carbon atoms (as mentioned above) in particular 1 to 4 carbon atoms

(= Ci-C4-alkanediyl), where one of the hydrogen atoms in these groups is replaced by a further bonding position. Examples for linear Ci-C6-alkanediyl comprise methyldiyl, ethane-1 ,2-diyl, propane-1 ,3-diyl, butane-1 ,4-diyl, pentane-1 ,5-diyl, hexane-1 ,6-diyl. Examples for branched Ci-C6-alkanediyl comprise ethyl-1 ,1-diyl, propyl-1 ,1 -diyl, butyl- 1 ,1-diyl, 1 -methylethane-1 ,2 diyl, 1 ,2-dimethylethane-1 ,2-diyl, 1 -ethyl etna ne-1 ,2 diyl, 1-methylpropane-1 ,3-diyl, 2-methylpropan-1 ,3-diyl and the like.

With respect to the different methods and uses according to the invention, particular preference is given to the following meanings of the substituents and variables of the Nitrogen-containing heteroaromatic compounds of formula I used, in each case on their own or in combination.

In the methods and uses according to present invention, preferably the compounds of formula I used are characterized in that

A is N; and

E, G, M are C-R^c.

In the methods and uses according to present invention, preferably the compounds of formula I used are characterized in that Y is OR, and wherein

R is selected from hydrogen, Ci-C6-alkyl, Ci-C4-haloalkyl, C2-C6-alkenyl, C3-C6- alkynyl, Z-C3-Cio-cycloalkyl, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-cyanoalkyl, Z-phenyl, Z-C(=0)-R^a2 or tri-C 1 -C₄-a I ky I si lyl ,

wherein

R^a2 is selected from d-Ce-alkyl, Ci-C4-haloalkyl, Z-d-Ce-alkoxy, Z-Ci-d-halo- alkoxy or NR'R", and

R', R" are selected independently of one another from hydrogen, Ci-Cs-alkyl,

Ci-C4-haloalkyl, d-Cs-alkenyl, Ca-Cs-alkynyl, Z-C3-C6-cycloalkyl, Z-Ci-Cs-alkoxy or Z-d-Ce-haloalkoxy;

and wherein

in the group R and its subsubtituents, the carbon chains and/or the cyclic groups may be partially or fully substituted by halogen, Ci-Cs-alkyl or Ci-C6-haloalkyl. In the methods and uses according to present invention, preferably the compounds of formula I used are characterized in that

Y is SR, and wherein

R is selected from hydrogen, Ci-C6-alkyl, Ci-C4-haloalkyl, C2-C6-alkenyl, C3-C6- alkynyl, Z-C3-Cio-cycloalkyl, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-cyanoalkyl, Z-phenyl, Z-C(=0)-R^a2 or tri-Ci-C₄-alkylsilyl,

wherein

R^a2 is selected from Ci-Ce-alkyl, Ci-C₄-haloalkyl, Z-Ci-Ce-alkoxy, Z-Ci-C₄-halo- alkoxy or NR'R", and

R', R" are selected independently of one another from hydrogen, Ci-Cs-alkyl, Ci-C₄-haloalkyl, C₃-C₈-alkenyl, C₃-C₈-alkynyl, Z-C₃-C₆-cycloalkyl, Z-Ci-Cs-alkoxy or Z-Ci-Ce-haloalkoxy;

and wherein

in the group R and its subsubtituents, the carbon chains and/or the cyclic groups may be partially or fully substituted by halogen, Ci-Cs-alkyl or Ci-C6-haloalkyl.

In the methods and uses according to present invention, preferably the compounds of formula I used are characterized in that

Y is NH-R, and wherein

R is selected from hydrogen, Ci-C6-alkyl, Ci-C4-haloalkyl, C2-C6-alkenyl, C3-C6- alkynyl, Z-C3-Cio-cycloalkyl, Ci-C6-alkoxy-Ci-C6-alkyl, Ci-C6-cyanoalkyl, Z-phenyl, Z-C(=0)-R^a2 or tri-C 1 -C₄-a I ky I si lyl ,

wherein

R^a2 is selected from d-Ce-alkyl, Ci-d-haloalkyl, Z-Ci-Ce-alkoxy, Z-Ci-d-halo- alkoxy or NR'R";

and wherein

in the group R and its subsubtituents, the carbon chains and/or the cyclic groups may be partially or fully substituted by halogen, Ci-Cs-alkyl or Ci-C6-haloalkyl. In the methods and uses according to present invention, preferably the compounds of formula I used are characterized in that

Y is NH-R, and wherein

R is a 5- or 6-membered monocyclic heterocycle attached via Z and selected from the group consisting of pyrimidyl, pyridyl, thienyl, furyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl, oxazolyl, isothiazolyl, isoxazolyl, quinolinyl, isoquinolinyl, indolyl, benzofuryl, benzthienyl, benzoxazolyl, benzthiazolyl and benzimidazolyl, wherein the heterocycle may be attached via a carbon or a nitrogen atom of the heterocycle and wherein the heterocycle may carry one or more substitutents selected from the group consisting of OH, CN, N0₂, halogen, Ci-C₄-alkyl, Ci-C₄-haloalkyl, Ci-C₄-alkoxy or Ci-C₄-haloalkoxy.

In the methods and uses according to present invention, preferably the compounds of formula I used are characterized in that W is O.

In the methods and uses according to present invention, preferably the compounds of formula I used are characterized in that X is O.

In the methods and uses according to present invention, preferably the compounds of formula I used are characterized in that X is S.

In the methods and uses according to present invention, preferably the compounds of formula I used are chara nds are of formula I.A

wherein

X, Y, W, R¹ and R^a are as defined for formula I above,

R^c2 , R^c3 and R^c4 are as defined for R^c, and

m is 0, 1 , 2, 3 or 4.

The above embodiments preferred for formula I apply also to compounds of formulae II, and III, resp., insofar applicable to formulae II, and III, resp.

In particular with view to the compounds themselves and their use as insecticides, preference is given to the compounds of the formula I, which are of formula II compiled in the examples below, whe o the formula ll-A below:

wherein Y, R¹, R^c2, R^c3 and R^c4 are defined as in table II below, and R^a3, R^a4 and R³ are defined as in tables lla to tables Mm thereinafter.

The groups mentioned for a substituent in the tables are furthermore per se, independently of the combination in which they are mentioned, a particularly preferred aspect of the substituent in question. Table II:

No. Y R¹ _{Rc2 Rc3 R}c4

11-1 OH OH H H H

II-2 OH OC(0)CH₃ H H H

II-3 OH OC(0)CH₂CH₃ H H H

II-4 OH OC(0)CH(CH₃)₂ H H H

II-5 OH OC(0)C(CH₃)₃ H H H

II-6 OH OC(0)-C₆H₅ H H H

II-7 OH OC(0)-CH₂C₆H₅ H H H

II-8 OH OC(0)-OCH₃ H H H

II-9 OH OC(0)-N(CH₃)₂ H H H

11-10 OH 0C(0)-0CH₂CH₃ H H H

11-1 1 OH OS(0)₂-CH₃ H H H

11-12 OH OS(0)₂-N(CH₃)₂ H H H

11-13 OH OS(0)₂-C₆H₄-4-CH₃ H H H

11-14 OH OH H H F

11-15 OH OC(0)CH₃ H H F

11-16 OH OC(0)CH₂CH₃ H H F

11-17 OH OC(0)CH(CH₃)₂ H H F

11-18 OH OC(0)C(CH₃)₃ H H F

11-19 OH OC(0)-C₆H₅ H H F

II-20 OH OC(0)-CH₂C₆H₅ H H F

11-21 OH OC(0)-OCH₃ H H F

11 -22 OH OC(0)-N(CH₃)₂ H H F

II-23 OH OC(0)-OCH₂CH₃ H H F

11 -24 OH OS(0)₂-CH₃ H H F

II-25 OH OS(0)₂-N(CH₃)₂ H H F

II-26 OH OS(0)2-C₆H₄-4-CH₃ H H F

II-27 OH OH H H CI

II-28 OH OC(0)CH₃ H H CI

II-29 OH OC(0)CH₂CH₃ H H CI

II-30 OH OC(0)CH(CH₃)₂ H H CI

11-31 OH OC(0)C(CH₃)₃ H H CI

II-32 OH OC(0)-C₆H₅ H H CI

II-33 OH OC(0)-CH₂C₆H₅ H H CI

II-34 OH OC(0)-OCH₃ H H CI

II-35 OH OC(0)-N(CH₃)₂ H H CI

II-36 OH OC(0)-OCH₂CH₃ H H CI

II-37 OH OS(0)₂-CH₃ H H CI

II-38 OH OS(0)₂-N(CH₃)₂ H H CI No. Y R¹ _{Rc2 Rc3 R}c4

II-39 OH OS(0)2-C₆H₄-4-CH₃ H H CI

II-40 OH OH H H Br

11-41 OH OC(0)CH₃ H H Br

11 -42 OH OC(0)CH₂CH₃ H H Br

II-43 OH OC(0)CH(CH₃)₂ H H Br

11 -44 OH OC(0)C(CH₃)₃ H H Br

II-45 OH OC(0)-C₆H₅ H H Br

II-46 OH OC(0)-CH₂C₆H₅ H H Br

II-47 OH OC(0)-OCH₃ H H Br

II-48 OH OC(0)-N(CH₃)₂ H H Br

II-49 OH OC(0)-OCH₂CH₃ H H Br

II-50 OH OS(0)₂-CH₃ H H Br

11-51 OH OS(0)₂-N(CH₃)₂ H H Br

11 -52 OH OS(0)₂-C₆H₄-4-CH₃ H H Br

II-53 OH OH H H CF₃

11 -54 OH OC(0)CH₃ H H CF₃

II-55 OH OC(0)CH₂CH₃ H H CF₃

II-56 OH OC(0)CH(CH₃)₂ H H CF₃

II-57 OH OC(0)C(CH₃)₃ H H CF₃

II-58 OH OC(0)-C₆H₅ H H CF₃

II-59 OH OC(0)-CH₂C₆H₅ H H CF₃

II-60 OH OC(0)-OCH₃ H H CF₃

11-61 OH OC(0)-N(CH₃)₂ H H CF₃

II-62 OH OC(0)-OCH₂CH₃ H H CF₃

II-63 OH OS(0)₂-CH₃ H H CF₃

11 -64 OH OS(0)₂-N(CH₃)₂ H H CF₃

II-65 OH OS(0)₂-C₆H₄-4-CH₃ H H CF₃

II-66 OH OH H H CHF₂

II-67 OH OC(0)CH₃ H H CHF₂

II-68 OH OC(0)CH₂CH₃ H H CHF₂

II-69 OH OC(0)CH(CH₃)₂ H H CHF₂

II-70 OH OC(0)C(CH₃)₃ H H CHF₂

11-71 OH OC(0)-C₆H₅ H H CHF₂

11 -72 OH OC(0)-CH₂C₆H₅ H H CHF₂

II-73 OH OC(0)-OCH₃ H H CHF₂

11 -74 OH OC(0)-N(CH₃)₂ H H CHF₂

II-75 OH OC(0)-OCH₂CH₃ H H CHF₂

II-76 OH OS(0)₂-CH₃ H H CHF₂

II-77 OH OS(0)₂-N(CH₃)₂ H H CHF₂

II-78 OH OS(0)₂-C₆H₄-4-CH₃ H H CHF₂ No. Y R¹ _{Rc2 Rc3 R}c4

II-79 OH OH H H OCH₃

II-80 OH OC(0)CH₃ H H OCH₃

11-81 OH OC(0)CH₂CH₃ H H OCH₃

11 -82 OH OC(0)CH(CH₃)₂ H H OCH₃

II-83 OH OC(0)C(CH₃)₃ H H OCH₃

II-84 OH OC(0)-C₆H₅ H H OCH₃

II-85 OH OC(0)-CH₂C₆H₅ H H OCH₃

II-86 OH OC(0)-OCH₃ H H OCH₃

II-87 OH OC(0)-N(CH₃)₂ H H OCH₃

II-88 OH OC(0)-OCH₂CH₃ H H OCH₃

II-89 OH OS(0)₂-CH₃ H H OCH₃

II-90 OH OS(0)₂-N(CH₃)₂ H H OCH₃

11-91 OH OS(0)₂-C₆H₄-4-CH₃ H H OCH₃

II-92 OH OH H H OCF₃

II-93 OH OC(0)CH₃ H H OCF₃

II-94 OH OC(0)CH₂CH₃ H H OCF₃

II-95 OH OC(0)CH(CH₃)₂ H H OCF₃

II-96 OH OC(0)C(CH₃)₃ H H OCF₃

II-97 OH OC(0)-C₆H₅ H H OCF₃

II-98 OH OC(0)-CH₂C₆H₅ H H OCF₃

II-99 OH OC(0)-OCH₃ H H OCF₃-100 OH OC(0)-N(CH₃)₂ H H OCF₃-101 OH OC(0)-OCH₂CH₃ H H OCF₃-102 OH OS(0)₂-CH₃ H H OCF₃-103 OH 0S(0)₂-N(CH₃)₂ H H OCF₃-104 OH OS(0)₂-C₆H₄-4-CH₃ H H OCF₃-105 OH OH H H SCF₃-106 OH OC(0)CH₃ H H SCF₃-107 OH OC(0)CH₂CH₃ H H SCF₃-108 OH OC(0)CH(CH₃)₂ H H SCF₃-109 OH OC(0)C(CH₃)₃ H H SCF₃-1 10 OH OC(0)-C₆H₅ H H SCF₃-1 1 1 OH OC(0)-CH₂C₆H₅ H H SCF₃-1 12 OH OC(0)-OCH₃ H H SCF₃-1 13 OH OC(0)-N(CH₃)₂ H H SCF₃-1 14 OH 0C(0)-0CH₂CH₃ H H SCF₃-1 15 OH OS(0)₂-CH₃ H H SCF₃-1 16 OH OS(0)₂-N(CH₃)₂ H H SCF₃-1 17 OH OS(0)₂-C₆H₄-4-CH₃ H H SCF₃-1 18 OH OH H H CN

No. Y R¹ _{Rc2 Rc3 R}c4

11-199 OH OC(0)CH(CH₃)₂ H OCH₃ H

II-200 OH OC(0)C(CH₃)₃ H OCH₃ H

11-201 OH OC(0)-C₆H₅ H OCH₃ H

II-202 OH OC(0)-CH₂C₆H₅ H OCH₃ H

II-203 OH OC(0)-OCH₃ H OCH₃ H

II-204 OH OC(0)-N(CH₃)₂ H OCH₃ H

II-205 OH OC(0)-OCH₂CH₃ H OCH₃ H

II-206 OH OS(0)₂-CH₃ H OCH₃ H

II-207 OH OS(0)₂-N(CH₃)₂ H OCH₃ H

II-208 OH OS(0)₂-C₆H₄-4-CH₃ H OCH₃ H

II-209 OH OH H OCF₃ H

11-210 OH OC(0)CH₃ H OCF₃ H

11-21 1 OH OC(0)CH₂CH₃ H OCF₃ H

11-212 OH OC(0)CH(CH₃)₂ H OCF₃ H

11-213 OH OC(0)C(CH₃)₃ H OCF₃ H

11-214 OH OC(0)-C₆H₅ H OCF₃ H

11-215 OH OC(0)-CH₂C₆H₅ H OCF₃ H

11-216 OH OC(0)-OCH₃ H OCF₃ H

11-217 OH OC(0)-N(CH₃)₂ H OCF₃ H

11-218 OH OC(0)-OCH₂CH₃ H OCF₃ H

11-219 OH OS(0)₂-CH₃ H OCF₃ H

II-220 OH OS(0)₂-N(CH₃)₂ H OCF₃ H

11-221 OH OS(0)₂-C₆H₄-4-CH₃ H OCF₃ H

11 -222 OH OH H SCF₃ H

II-223 OH OC(0)CH₃ H SCF₃ H

11 -224 OH OC(0)CH₂CH₃ H SCF₃ H

II-225 OH OC(0)CH(CH₃)₂ H SCF₃ H

II-226 OH OC(0)C(CH₃)₃ H SCF₃ H

II-227 OH OC(0)-C₆H₅ H SCF₃ H

II-228 OH OC(0)-CH₂C₆H₅ H SCF₃ H

II-229 OH OC(0)-OCH₃ H SCF₃ H

II-230 OH OC(0)-N(CH₃)₂ H SCF₃ H

11-231 OH OC(0)-OCH₂CH₃ H SCF₃ H

II-232 OH OS(0)₂-CH₃ H SCF₃ H

II-233 OH OS(0)₂-N(CH₃)₂ H SCF₃ H

II-234 OH OS(0)₂-C₆H₄-4-CH₃ H SCF₃ H

II-235 OH OH H CN H

II-236 OH OC(0)CH₃ H CN H

II-237 OH OC(0)CH₂CH₃ H CN H

II-238 OH OC(0)CH(CH₃)₂ H CN H No. Y R¹ _{Rc2 Rc3 R}c4

II-239 OH OC(0)C(CH₃)₃ H CN H

II-240 OH OC(0)-C₆H₅ H CN H

11-241 OH OC(0)-CH₂C₆H₅ H CN H

11 -242 OH OC(0)-OCH₃ H CN H

II-243 OH OC(0)-N(CH₃)₂ H CN H

11 -244 OH 0C(0)-0CH₂CH₃ H CN H

II-245 OH OS(0)₂-CH₃ H CN H

II-246 OH OS(0)₂-N(CH₃)₂ H CN H

II-247 OH OS(0)₂-C₆H₄-4-CH₃ H CN H

II-248 SH OH H H H

II-249 SH OC(0)CH₃ H H H

II-250 SH OC(0)CH₂CH₃ H H H

11-251 SH OC(0)CH(CH₃)₂ H H H

11 -252 SH OC(0)C(CH₃)₃ H H H

II-253 SH OC(0)-C₆H₅ H H H

11 -254 SH OC(0)-CH₂C₆H₅ H H H

II-255 SH OC(0)-OCH₃ H H H

II-256 SH OC(0)-N(CH₃)₂ H H H

II-257 SH OC(0)-OCH₂CH₃ H H H

II-258 SH OS(0)₂-CH₃ H H H

II-259 SH OS(0)₂-N(CH₃)₂ H H H

II-260 SH OS(0)₂-C₆H₄-4-CH₃ H H H

11-261 SH OH H H F

11 -262 SH OC(0)CH₃ H H F

II-263 SH OC(0)CH₂CH₃ H H F

11 -264 SH OC(0)CH(CH₃)₂ H H F

II-265 SH OC(0)C(CH₃)₃ H H F

II-266 SH OC(0)-C₆H₅ H H F

II-267 SH OC(0)-CH₂C₆H₅ H H F

II-268 SH OC(0)-OCH₃ H H F

II-269 SH OC(0)-N(CH₃)₂ H H F

II-270 SH OC(0)-OCH₂CH₃ H H F

11-271 SH OS(0)₂-CH₃ H H F

11 -272 SH OS(0)₂-N(CH₃)₂ H H F

II-273 SH OS(0)₂-C₆H₄-4-CH₃ H H F

11 -274 SH OH H H CI

II-275 SH OC(0)CH₃ H H CI

II-276 SH OC(0)CH₂CH₃ H H CI

II-277 SH OC(0)CH(CH₃)₂ H H CI

II-278 SH OC(0)C(CH₃)₃ H H CI No. Y R¹ _{Rc2 Rc3 R}c4

11-279 SH OC(0)-C₆H₅ H H CI

11-280 SH OC(0)-CH₂C₆H₅ H H CI

11-281 SH OC(0)-OCH₃ H H CI

11 -282 SH OC(0)-N(CH₃)₂ H H CI

II-283 SH OC(0)-OCH₂CH₃ H H CI

11 -284 SH OS(0)₂-CH₃ H H CI

II-285 SH OS(0)₂-N(CH₃)₂ H H CI

II-286 SH OS(0)2-C₆H₄-4-CH₃ H H CI

II-287 SH OH H H Br

II-288 SH OC(0)CH₃ H H Br

II-289 SH OC(0)CH₂CH₃ H H Br

II-290 SH OC(0)CH(CH₃)₂ H H Br

11-291 SH OC(0)C(CH₃)₃ H H Br

II-292 SH OC(0)-C₆H₅ H H Br

II-293 SH OC(0)-CH₂C₆H₅ H H Br

II-294 SH OC(0)-OCH₃ H H Br

II-295 SH OC(0)-N(CH₃)₂ H H Br

II-296 SH OC(0)-OCH₂CH₃ H H Br

II-297 SH OS(0)₂-CH₃ H H Br

II-298 SH OS(0)₂-N(CH₃)₂ H H Br

II-299 SH OS(0)₂-C₆H₄-4-CH₃ H H Br

II-300 SH OH H H CF₃

11-301 SH OC(0)CH₃ H H CF₃

II-302 SH OC(0)CH₂CH₃ H H CF₃

II-303 SH OC(0)CH(CH₃)₂ H H CF₃

II-304 SH OC(0)C(CH₃)₃ H H CF₃

II-305 SH OC(0)-C₆H₅ H H CF₃

II-306 SH OC(0)-CH₂C₆H₅ H H CF₃

II-307 SH OC(0)-OCH₃ H H CF₃

II-308 SH OC(0)-N(CH₃)₂ H H CF₃

II-309 SH OC(0)-OCH₂CH₃ H H CF₃

11-310 SH OS(0)₂-CH₃ H H CF₃

11-31 1 SH OS(0)₂-N(CH₃)₂ H H CF₃

11-312 SH OS(0)₂-C₆H₄-4-CH₃ H H CF₃

11-313 SH OH H H CHF₂

11-314 SH OC(0)CH₃ H H CHF₂

11-315 SH OC(0)CH₂CH₃ H H CHF₂

11-316 SH OC(0)CH(CH₃)₂ H H CHF₂

11-317 SH OC(0)C(CH₃)₃ H H CHF₂

11-318 SH OC(0)-C₆H₅ H H CHF₂ No. Y R¹ _{Rc2 Rc3 R}c4

11-319 SH OC(0)-CH₂C₆H₅ H H CHF₂

II-320 SH OC(0)-OCH₃ H H CHF₂

11-321 SH OC(0)-N(CH₃)₂ H H CHF₂

II-322 SH OC(0)-OCH₂CH₃ H H CHF₂

II-323 SH OS(0)₂-CH₃ H H CHF₂

II-324 SH OS(0)₂-N(CH₃)₂ H H CHF₂

II-325 SH OS(0)₂-C₆H₄-4-CH₃ H H CHF₂

II-326 SH OH H H OCH₃

II-327 SH OC(0)CH₃ H H OCH₃

II-328 SH OC(0)CH₂CH₃ H H OCH₃

II-329 SH OC(0)CH(CH₃)₂ H H OCH₃

II-330 SH OC(0)C(CH₃)₃ H H OCH₃

11-331 SH OC(0)-C₆H₅ H H OCH₃

II-332 SH OC(0)-CH₂C₆H₅ H H OCH₃

II-333 SH OC(0)-OCH₃ H H OCH₃

II-334 SH OC(0)-N(CH₃)₂ H H OCH₃

II-335 SH OC(0)-OCH₂CH₃ H H OCH₃

II-336 SH OS(0)₂-CH₃ H H OCH₃

II-337 SH OS(0)₂-N(CH₃)₂ H H OCH₃

II-338 SH OS(0)₂-C₆H₄-4-CH₃ H H OCH₃

II-339 SH OH H H OCF₃

II-340 SH OC(0)CH₃ H H OCF₃

11-341 SH OC(0)CH₂CH₃ H H OCF₃

II-342 SH OC(0)CH(CH₃)₂ H H OCF3

II-343 SH OC(0)C(CH₃)₃ H H OCF₃

II-344 SH OC(0)-C₆H₅ H H OCF₃

II-345 SH OC(0)-CH₂C₆H₅ H H OCF₃

II-346 SH OC(0)-OCH₃ H H OCF₃

II-347 SH OC(0)-N(CH₃)₂ H H OCF₃

II-348 SH OC(0)-OCH₂CH₃ H H OCF₃

II-349 SH OS(0)₂-CH₃ H H OCF3

II-350 SH OS(0)₂-N(CH₃)₂ H H OCF₃

11-351 SH OS(0)₂-C₆H₄-4-CH₃ H H OCF₃

II-352 SH OH H H SCF₃

II-353 SH OC(0)CH₃ H H SCF₃

II-354 SH OC(0)CH₂CH₃ H H SCF₃

II-355 SH OC(0)CH(CH₃)₂ H H SCF₃

II-356 SH OC(0)C(CH₃)₃ H H SCF₃

II-357 SH OC(0)-C₆H₅ H H SCF₃

II-358 SH OC(0)-CH₂C₆H₅ H H SCF₃ No. Y R¹ _{Rc2 Rc3 R}c4

11-359 SH OC(0)-OCH₃ H H SCF₃

11-360 SH OC(0)-N(CH₃)₂ H H SCF₃

11-361 SH OC(0)-OCH₂CH₃ H H SCF₃

II-362 SH OS(0)₂-CH₃ H H SCF₃

II-363 SH OS(0)₂-N(CH₃)2 H H SCF₃

II-364 SH OS(0)₂-C₆H₄-4-CH₃ H H SCF₃

II-365 SH OH H H CN

II-366 SH OC(0)CH₃ H H CN

II-367 SH OC(0)CH₂CH₃ H H CN

II-368 SH OC(0)CH(CH₃)₂ H H CN

II-369 SH OC(0)C(CH₃)₃ H H CN

II-370 SH OC(0)-C₆H₅ H H CN

11-371 SH OC(0)-CH₂C₆H₅ H H CN

II-372 SH OC(0)-OCH₃ H H CN

11-373 SH OC(0)-N(CH₃)₂ H H CN

11-374 SH OC(0)-OCH₂CH₃ H H CN

11-375 SH OS(0)₂-CH₃ H H CN

11-376 SH 0S(0)₂-N(CH₃)₂ H H CN

11-377 SH OS(0)₂-C₆H₄-4-CH₃ H H CN

11-378 SH OH H F H

11-379 SH OC(0)CH₃ H F H

11-380 SH OC(0)CH₂CH₃ H F H

11-381 SH OC(0)CH(CH₃)₂ H F H

II-382 SH OC(0)C(CH₃)₃ H F H

II-383 SH OC(0)-C₆H₅ H F H

II-384 SH OC(0)-CH₂C₆H₅ H F H

II-385 SH OC(0)-OCH₃ H F H

II-386 SH OC(0)-N(CH₃)₂ H F H

II-387 SH OC(0)-OCH₂CH₃ H F H

II-388 SH OS(0)₂-CH₃ H F H

II-389 SH OS(0)₂-N(CH₃)₂ H F H

II-390 SH OS(0)₂-C₆H₄-4-CH₃ H F H

11-391 SH OH H CI H

II-392 SH OC(0)CH₃ H CI H

II-393 SH OC(0)CH₂CH₃ H CI H

II-394 SH OC(0)CH(CH₃)₂ H CI H

II-395 SH OC(0)C(CH₃)₃ H CI H

II-396 SH OC(0)-C₆H₅ H CI H

II-397 SH OC(0)-CH₂C₆H₅ H CI H

II-398 SH OC(0)-OCH₃ H CI H No. Y R¹ _{Rc2 R}c3 _Rc4

11-399 SH OC(0)-N(CH₃)₂ H CI H

11-400 SH OC(0)-OCH₂CH₃ H CI H

11-401 SH OS(0)₂-CH₃ H CI H

II-402 SH OS(0)₂-N(CH₃)₂ H CI H

II-403 SH OS(0)₂-C₆H₄-4-CH₃ H CI H

II-404 SH OH H Br H

II-405 SH OC(0)CH₃ H Br H

II-406 SH OC(0)CH₂CH₃ H Br H

II-407 SH OC(0)CH(CH₃)₂ H Br H

II-408 SH OC(0)C(CH₃)₃ H Br H

II-409 SH OC(0)-C₆H₅ H Br H

11-410 SH OC(0)-CH₂C₆H₅ H Br H

11-41 1 SH OC(0)-OCH₃ H Br H

11-412 SH OC(0)-N(CH₃)₂ H Br H

11-413 SH OC(0)-OCH₂CH₃ H Br H

11-414 SH OS(0)₂-CH₃ H Br H

11-415 SH OS(0)₂-N(CH₃)₂ H Br H

11-416 SH 0S(0)₂-C₆H₄-4-CH₃ H Br H

11-417 SH OH H CF₃ H

11-418 SH OC(0)CH₃ H CF₃ H

11-419 SH OC(0)CH₂CH₃ H CF₃ H

II-420 SH OC(0)CH(CH₃)₂ H CF₃ H

11-421 SH OC(0)C(CH₃)₃ H CF₃ H

11 -422 SH OC(0)-C₆H₅ H CF₃ H

II-423 SH OC(0)-CH₂C₆H₅ H CF₃ H

11 -424 SH OC(0)-OCH₃ H CF₃ H

II-425 SH OC(0)-N(CH₃)₂ H CF₃ H

II-426 SH OC(0)-OCH₂CH₃ H CF₃ H

II-427 SH OS(0)₂-CH₃ H CF₃ H

II-428 SH OS(0)₂-N(CH₃)₂ H CF₃ H

II-429 SH OS(0)₂-C₆H₄-4-CH₃ H CF₃ H

II-430 SH OH H CHF₂ H

11-431 SH OC(0)CH₃ H CHF₂ H

II-432 SH OC(0)CH₂CH₃ H CHF₂ H

II-433 SH OC(0)CH(CH₃)₂ H CHF₂ H

II-434 SH OC(0)C(CH₃)₃ H CHF₂ H

II-435 SH OC(0)-C₆H₅ H CHF₂ H

II-436 SH OC(0)-CH₂C₆H₅ H CHF₂ H

II-437 SH OC(0)-OCH₃ H CHF₂ H

II-438 SH OC(0)-N(CH₃)₂ H CHF₂ H No. Y R¹ _{Rc2 Rc3 R}c4

11-439 SH OC(0)-OCH₂CH₃ H CHF₂ H

11-440 SH OS(0)₂-CH₃ H CHF₂ H

11-441 SH OS(0)₂-N(CH₃)₂ H CHF₂ H

11 -442 SH OS(0)₂-C₆H₄-4-CH₃ H CHF₂ H

II-443 SH OH H OCH₃ H

11 -444 SH OC(0)CH₃ H OCH₃ H

II-445 SH OC(0)CH₂CH₃ H OCH₃ H

II-446 SH OC(0)CH(CH₃)₂ H OCH₃ H

II-447 SH OC(0)C(CH₃)₃ H OCH₃ H

II-448 SH OC(0)-C₆H₅ H OCH₃ H

II-449 SH OC(0)-CH₂C₆H₅ H OCH₃ H

II-450 SH OC(0)-OCH₃ H OCH₃ H

11-451 SH OC(0)-N(CH₃)₂ H OCH₃ H

11 -452 SH OC(0)-OCH₂CH₃ H OCH₃ H

II-453 SH OS(0)₂-CH₃ H OCH₃ H

11 -454 SH 0S(0)₂-N(CH₃)₂ H OCH₃ H

II-455 SH OS(0)₂-C₆H₄-4-CH₃ H OCH₃ H

II-456 SH OH H OCF₃ H

II-457 SH OC(0)CH₃ H OCF₃ H

II-458 SH OC(0)CH₂CH₃ H OCF₃ H

II-459 SH OC(0)CH(CH₃)₂ H OCF₃ H

II-460 SH OC(0)C(CH₃)₃ H OCF₃ H

11-461 SH OC(0)-C₆H₅ H OCF₃ H

11 -462 SH OC(0)-CH₂C₆H₅ H OCF₃ H

II-463 SH OC(0)-OCH₃ H OCF₃ H

11 -464 SH OC(0)-N(CH₃)₂ H OCF₃ H

II-465 SH OC(0)-OCH₂CH₃ H OCF₃ H

II-466 SH OS(0)₂-CH₃ H OCF₃ H

II-467 SH OS(0)₂-N(CH₃)₂ H OCF₃ H

II-468 SH 0S(0)₂-C₆H₄-4-CH₃ H OCF₃ H

II-469 SH OH H SCF₃ H

II-470 SH OC(0)CH₃ H SCF₃ H

11-471 SH OC(0)CH₂CH₃ H SCF₃ H

11 -472 SH OC(0)CH(CH₃)₂ H SCF₃ H

II-473 SH OC(0)C(CH₃)₃ H SCF₃ H

11 -474 SH OC(0)-C₆H₅ H SCF₃ H

II-475 SH OC(0)-CH₂C₆H₅ H SCF₃ H

II-476 SH OC(0)-OCH₃ H SCF₃ H

II-477 SH OC(0)-N(CH₃)₂ H SCF₃ H

II-478 SH OC(0)-OCH₂CH₃ H SCF₃ H No. Y R¹ _{Rc2 Rc3 R}c4

11-479 SH OS(0)₂-CH₃ H SCF₃ H

11-480 SH OS(0)₂-N(CH₃)2 H SCF₃ H

11-481 SH OS(0)2-C₆H4-4-CH₃ H SCF₃ H

11 -482 SH OH H CN H

II-483 SH OC(0)CH₃ H CN H

11 -484 SH OC(0)CH₂CH₃ H CN H

II-485 SH OC(0)CH(CH₃)₂ H CN H

II-486 SH OC(0)C(CH₃)₃ H CN H

II-487 SH OC(0)-C₆H₅ H CN H

II-488 SH OC(0)-CH₂C₆H₅ H CN H

II-489 SH OC(0)-OCH₃ H CN H

II-490 SH OC(0)-N(CH₃)₂ H CN H

11-491 SH OC(0)-OCH₂CH₃ H CN H

II-492 SH OS(0)₂-CH₃ H CN H

II-493 SH OS(0)₂-N(CH₃)₂ H CN H

II-494 SH OS(0)₂-C₆H₄-4-CH₃ H CN H

Table I la:

Compounds II.1a to ll.494a of the formula ll-A, in which R^a3 is CI, R^a4 is H, R^a5 is H and the combination of Y, R¹, R^c2, R^c3 and R^c4 for a compound corresponds in each case to one row of Table II.

Table Mb:

Compounds 11.1 b to 11.494b of the formula ll-A, in which R^a3 is F, R^a4 is H, R^a5 is H and the combination of Y, R¹, R^c2, R^c3 and R^c4 for a compound corresponds in each case to one row of Table II

Table lie:

Compounds II.1 c to ll.494c of the formula ll-A, in which R^a3 is Br, R^a4 is H, R^a5 is H and the combination of Y, R¹, R^c2, R^c3 and R^c4 for a compound corresponds in each case to one row of Table II

Table lid:

Compounds 11.1 d to ll.494d of the formula ll-A, in which R^a3 is CF₃, R^a4 is H, R^a5 is H and the combination of Y, R¹, R^c2, R^c3 and R^c4 for a compound corresponds in each case to one row of Table II

Table lie:

Compounds II.1e to ll.494e of the formula ll-A, in which R^a3 is CHF₂, R^a4 is H, R^a5 is H and the combination of Y, R¹, R^c2, R^c3 and R^c4 for a compound corresponds in each case to one row of Table II

Table I If:

Compounds 11.1 f to 11.494f of the formula ll-A, in which R^a3 is OCF₃, R^a4 is H, R^a5 is H and the combination of Y, R¹, R^c2, R^c3 and R^c4 for a compound corresponds in each case to one row of Table II Table llg:

Compounds ll.1g to ll.494g of the formula ll-A, in which R^a3 is H, R^a4 is CI, R^a5 is H and the combination of Y, R¹, R^c2, R^c3 and R^c4 for a compound corresponds in each case to one row of Table II

Table llh:

Compounds 11.1 h to ll.494h of the formula ll-A, in which R^a3 is H, R^a4 is F R^a5 is H and the combination of Y, R , R^c2, R^c3 and R^c4 for a compound corresponds in each case to one row of Table II

Table Mi:

Compounds 11.1 i to ΙΙ.494Ϊ of the formula ll-A, in which R^a3 is H, R^a4 is Br R^a5 is H and the combination of Y, R¹, R^c2, R^c3 and R^c4 for a compound corresponds in each case to one row of Table II

Table llj:

Compounds II.1j to ll.494j of the formula ll-A, in which R^a3 is H, R^a4 is CF₃, R^a5 is H and the combination of Y, R¹ , R^c2, R°³ and R^c4 for a compound corresponds in each case to one row of Table II

Table Ilk:

Compounds II.1 k to ll.494k of the formula ll-A, in which R^a3 is H, R^a4 is CHF₂, R^a5 is H and the combination of Y, R¹, R^c2, R^c3 and R^c4 for a compound corresponds in each case to one row of Table II

Table II I:

Compounds 11.11 to 11.4941 of the formula for ll-A, in which R^a3 is H, R^a4 is OCF₃, R^a5 is H and the combination of Y, R¹, R^c2, R^c3 and R^c4 a compound corresponds in each case to one row of Table II

Table Mm:

Compounds 11.1 m to ll.494m of the formula for ll-A, in which R^a3 is H, R^a4 is H, R^a5 is H and the combination of Y, R¹, R^c2, R^c3 and R^c4 a compound corresponds in each case to one row of Table II In particular with view to the compounds themselves and their use as insecticides, preference is given to the compounds of the formula III compiled in the examples below, wherein the compounds elow:

wherein R¹, R^a2, R^a3 and R^a4 are defined as in table III below, and R is defined as in tables Ilia to Nip thereinafter.

The groups mentioned for a substituent in the tables are furthermore per se, independently of the combination in which they are mentioned, a particularly preferred aspect of the substituent in question. Table III:

No. R¹ _{Ra2 Ra3 R}a4

-1 OH H H H

-2 OC(0)CH₃ H H H

-3 OC(0)CH₂CH₃ H H H

-4 0C(0)CH(CH₃)₂ H H H

-5 OC(0)C(CH₃)₃ H H H

-6 OC(0)-C₆H₅ H H H

-7 OC(0)-CH₂C₆H₅ H H H

-8 OC(0)-OCH₃ H H H

-9 OC(0)-N(CH₃)₂ H H H

-10 OC(0)-OCH₂CH₃ H H H

-11 OS(0)₂-CH₃ H H H

-12 OS(0)₂-N(CH₃)₂ H H H

-13 OS(0)₂-C₆H₄-4-CH₃ H H H

-14 OH H H F

-15 OC(0)CH₃ H H F

-16 OC(0)CH₂CH₃ H H F

-17 OC(0)CH(CH₃)₂ H H F

-18 OC(0)C(CH₃)₃ H H F

-19 OC(0)-C₆H₅ H H F

-20 OC(0)-CH₂C₆H₅ H H F

-21 OC(0)-OCH₃ H H F

-22 OC(0)-N(CH₃)₂ H H F

-23 OC(0)-OCH₂CH₃ H H F

-24 OS(0)₂-CH₃ H H F

-25 OS(0)₂-N(CH₃)₂ H H F

-26 OS(0)₂-C₆H₄-4-CH₃ H H F

-27 OH H H CI

-28 OC(0)CH₃ H H CI

-29 OC(0)CH₂CH₃ H H CI

-30 OC(0)CH(CH₃)₂ H H CI

-31 OC(0)C(CH₃)₃ H H CI

-32 OC(0)-C₆H₅ H H CI

-33 OC(0)-CH₂C₆H₅ H H CI

-34 OC(0)-OCH₃ H H CI

-35 OC(0)-N(CH₃)₂ H H CI

-36 OC(0)-OCH₂CH₃ H H CI

-37 OS(0)₂-CH₃ H H CI

-38 OS(0)₂-N(CH₃)₂ H H CI No. R¹ _{Ra2 Ra3 R}a4

II -39 OS(0)2-C₆H4-4-CH₃ H H CI

II -40 OH H H Br

II -41 OC(0)CH₃ H H Br

II -42 OC(0)CH₂CH₃ H H Br

II -43 OC(0)CH(CH₃)₂ H H Br

II -44 OC(0)C(CH₃)₃ H H Br

II -45 0C(0)-C₆H₅ H H Br

II -46 OC(0)-CH₂C₆H₅ H H Br

II -47 OC(0)-OCH₃ H H Br

II -48 OC(0)-N(CH₃)₂ H H Br

II -49 OC(0)-OCH₂CH₃ H H Br

II -50 OS(0)₂-CH₃ H H Br

II -51 OS(0)₂-N(CH₃)₂ H H Br

II -52 0S(0)₂-C₆H₄-4-CH₃ H H Br

II -53 OH H H CF₃

II -54 OC(0)CH₃ H H CF₃

II -55 OC(0)CH₂CH₃ H H CF₃

II -56 OC(0)CH(CH₃)₂ H H CF₃

II -57 OC(0)C(CH₃)₃ H H CF₃

II -58 OC(0)-C₆H₅ H H CF₃

II -59 OC(0)-CH₂C₆H₅ H H CF₃

II -60 OC(0)-OCH₃ H H CF₃

II -61 OC(0)-N(CH₃)₂ H H CF₃

II -62 OC(0)-OCH₂CH₃ H H CF₃

II -63 OS(0)₂-CH₃ H H CF₃

II -64 OS(0)₂-N(CH₃)₂ H H CF₃

II -65 OS(0)₂-C₆H₄-4-CH₃ H H CF₃

II -66 OH H H CHF₂

II -67 OC(0)CH₃ H H CHF₂

II -68 OC(0)CH₂CH₃ H H CHF₂

II -69 OC(0)CH(CH₃)₂ H H CHF₂

II -70 OC(0)C(CH₃)₃ H H CHF₂

II -71 OC(0)-C₆H₅ H H CHF₂

II -72 OC(0)-CH₂C₆H₅ H H CHF₂

II -73 OC(0)-OCH₃ H H CHF₂

II -74 OC(0)-N(CH₃)₂ H H CHF₂

II -75 OC(0)-OCH₂CH₃ H H CHF₂

II -76 OS(0)₂-CH₃ H H CHF₂

II -77 OS(0)₂-N(CH₃)₂ H H CHF₂

II -78 OS(0)₂-C₆H₄-4-CH₃ H H CHF₂ No. R¹ _{Ra2 Ra3 R}a4

I I-79 OH H H OCH₃

I I -80 OC(0)CH₃ H H OCH₃

I 1-81 OC(0)CH₂CH₃ H H OCH₃

I I -82 OC(0)CH(CH₃)₂ H H OCH₃

I I -83 OC(0)C(CH₃)₃ H H OCH₃

I I-84 OC(0)-C₆H₅ H H OCH₃

I I -85 0C(0)-CH₂C₆H₅ H H OCH₃

I I-86 OC(0)-OCH₃ H H OCH₃

I I -87 0C(0)-N(CH₃)₂ H H OCH₃

I I-88 0C(0)-0CH₂CH₃ H H OCH₃

I I -89 OS(0)₂-CH₃ H H OCH₃

I I-90 OS(0)₂-N(CH₃)₂ H H OCH₃

I 1-91 OS(0)₂-C₆H₄-4-CH₃ H H OCH₃

I I -92 OH H H OCF₃

I I-93 OC(0)CH₃ H H OCF₃

I I -94 0C(0)CH₂CH₃ H H OCF₃

I I-95 OC(0)CH(CH₃)₂ H H OCF₃

I I-96 OC(0)C(CH₃)₃ H H OCF₃

I I-97 OC(0)-C₆H₅ H H OCF₃

I I-98 OC(0)-CH₂C₆H₅ H H OCF₃

I I-99 OC(0)-OCH₃ H H OCF₃I -100 OC(0)-N(CH₃)₂ H H OCF3I -101 OC(0)-OCH₂CH₃ H H OCF₃I -102 OS(0)₂-CH₃ H H OCF₃I -103 0S(0)₂-N(CH₃)₂ H H OCF₃I -104 OS(0)₂-C₆H₄-4-CH₃ H H OCF₃I -105 OH H F HI -106 OC(0)CH₃ H F HI -107 OC(0)CH₂CH₃ H F HI -108 OC(0)CH(CH₃)₂ H F HI -109 OC(0)C(CH₃)₃ H F HI -110 0C(0)-C₆H₅ H F HI -11 1 OC(0)-CH₂C₆H₅ H F HI -112 OC(0)-OCH₃ H F HI -113 OC(0)-N(CH₃)₂ H F HI -114 OC(0)-OCH₂CH₃ H F HI -115 OS(0)₂-CH₃ H F HI -116 OS(0)₂-N(CH₃)₂ H F HI -117 0S(0)₂-C₆H₄-4-CH₃ H F HI -118 OH H CI H No. R¹ _{Ra2 Ra3 R}a4

II -119 OC(0)CH₃ H CI H

II -120 OC(0)CH₂CH₃ H CI H

II -121 OC(0)CH(CH₃)₂ H CI H

II -122 OC(0)C(CH₃)₃ H CI H

II -123 OC(0)-C₆H₅ H CI H

II -124 OC(0)-CH₂C₆H₅ H CI H

II -125 OC(0)-OCH₃ H CI H

II -126 OC(0)-N(CH₃)₂ H CI H

II -127 OC(0)-OCH₂CH₃ H CI H

II -128 OS(0)₂-CH₃ H CI H

II -129 OS(0)₂-N(CH₃)₂ H CI H

II -130 OS(0)₂-C₆H₄-4-CH₃ H CI H

II -131 OH H Br H

II -132 OC(0)CH₃ H Br H

II -133 OC(0)CH₂CH₃ H Br H

II -134 0C(0)CH(CH₃)₂ H Br H

II -135 OC(0)C(CH₃)₃ H Br H

II -136 OC(0)-C₆H₅ H Br H

II -137 OC(0)-CH₂C₆H₅ H Br H

II -138 OC(0)-OCH₃ H Br H

II -139 0C(0)-N(CH₃)₂ H Br H

II -140 0C(0)-0CH₂CH₃ H Br H

II -141 0S(0)₂-CH₃ H Br H

II -142 OS(0)₂-N(CH₃)₂ H Br H

II -143 OS(0)₂-C₆H₄-4-CH₃ H Br H

II -144 OH H CF₃ H

II -145 OC(0)CH₃ H CF₃ H

II -146 OC(0)CH₂CH₃ H CF₃ H

II -147 OC(0)CH(CH₃)₂ H CF₃ H

II -148 OC(0)C(CH₃)₃ H CF₃ H

II -149 OC(0)-C₆H₅ H CF₃ H

II -150 0C(0)-CH₂C₆H₅ H CF₃ H

II -151 OC(0)-OCH₃ H CF₃ H

II -152 OC(0)-N(CH₃)₂ H CF₃ H

II -153 OC(0)-OCH₂CH₃ H CF₃ H

II -154 OS(0)₂-CH₃ H CF₃ H

II -155 OS(0)₂-N(CH₃)₂ H CF₃ H

II -156 OS(0)2-C₆H₄-4-CH₃ H CF₃ H

II -157 OH H CHF₂ H

II -158 OC(0)CH₃ H CHF₂ H No. R¹ _{Ra2 Ra3 R}a4

II -159 OC(0)CH₂CH₃ H CHF₂ H

II -160 OC(0)CH(CH₃)₂ H CHF₂ H

II -161 OC(0)C(CH₃)₃ H CHF₂ H

II -162 OC(0)-C₆H₅ H CHF₂ H

II -163 OC(0)-CH₂C₆H₅ H CHF₂ H

II -164 OC(0)-OCH₃ H CHF₂ H

II -165 OC(0)-N(CH₃)₂ H CHF₂ H

II -166 OC(0)-OCH₂CH₃ H CHF₂ H

II -167 OS(0)₂-CH₃ H CHF₂ H

II -168 OS(0)₂-N(CH₃)₂ H CHF₂ H

II -169 OS(0)₂-C₆H₄-4-CH₃ H CHF₂ H

II -170 OH H OCH₃ H

II -171 OC(0)CH₃ H OCH₃ H

II -172 OC(0)CH₂CH₃ H OCH₃ H

II -173 OC(0)CH(CH₃)₂ H OCH₃ H

II -174 OC(0)C(CH₃)₃ H OCH₃ H

II -175 OC(0)-C₆H₅ H OCH₃ H

II -176 OC(0)-CH₂C₆H₅ H OCH₃ H

II -177 OC(0)-OCH₃ H OCH₃ H

II -178 OC(0)-N(CH₃)₂ H OCH₃ H

II -179 OC(0)-OCH₂CH₃ H OCH₃ H

II -180 OS(0)₂-CH₃ H OCH₃ H

II -181 OS(0)₂-N(CH₃)₂ H OCH₃ H

II -182 OS(0)₂-C₆H₄-4-CH₃ H OCH₃ H

II -183 OH H OCF₃ H

II -184 OC(0)CH₃ H OCF₃ H

II -185 OC(0)CH₂CH₃ H OCF₃ H

II -186 OC(0)CH(CH₃)₂ H OCF₃ H

II -187 OC(0)C(CH₃)₃ H OCF₃ H

II -188 OC(0)-C₆H₅ H OCF₃ H

II -189 OC(0)-CH₂C₆H₅ H OCF₃ H

II -190 OC(0)-OCH₃ H OCF₃ H

II -191 OC(0)-N(CH₃)₂ H OCF₃ H

II -192 OC(0)-OCH₂CH₃ H OCF₃ H

II -193 OS(0)₂-CH₃ H OCF₃ H

II -194 OS(0)₂-N(CH₃)₂ H OCF₃ H

II -195 OS(0)₂-C₆H₄-4-CH₃ H OCF₃ H

II -196 OH F H H

II -197 OC(0)CH₃ F H H

II -198 OC(0)CH₂CH₃ F H H No. R¹ _{Ra2 Ra3 R}a4

II -199 OC(0)CH(CH₃)₂ F H H

II -200 OC(0)C(CH₃)₃ F H H

II -201 OC(0)-C₆H₅ F H H

II -202 OC(0)-CH₂C₆H₅ F H H

II -203 OC(0)-OCH₃ F H H

II -204 OC(0)-N(CH₃)₂ F H H

II -205 OC(0)-OCH₂CH₃ F H H

II -206 OS(0)₂-CH₃ F H H

II -207 OS(0)₂-N(CH₃)₂ F H H

II -208 OS(0)₂-C₆H₄-4-CH₃ F H H

II -209 OH CI H H

II -210 OC(0)CH₃ CI H H

II -21 1 OC(0)CH₂CH₃ CI H H

II -212 OC(0)CH(CH₃)₂ CI H H

II -213 OC(0)C(CH₃)₃ CI H H

II -214 OC(0)-C₆H₅ CI H H

II -215 OC(0)-CH₂C₆H₅ CI H H

II -216 OC(0)-OCH₃ CI H H

II -217 OC(0)-N(CH₃)₂ CI H H

II -218 OC(0)-OCH₂CH₃ CI H H

II -219 OS(0)₂-CH₃ CI H H

II -220 OS(0)₂-N(CH₃)₂ CI H H

II -221 OS(0)₂-C₆H₄-4-CH₃ CI H H

II -222 OH Br H H

II -223 OC(0)CH₃ Br H H

II -224 OC(0)CH₂CH₃ Br H H

II -225 OC(0)CH(CH₃)₂ Br H H

II -226 OC(0)C(CH₃)₃ Br H H

II -227 OC(0)-C₆H₅ Br H H

II -228 OC(0)-CH₂C₆H₅ Br H H

II -229 OC(0)-OCH₃ Br H H

II -230 OC(0)-N(CH₃)₂ Br H H

II -231 OC(0)-OCH₂CH₃ Br H H

II -232 OS(0)₂-CH₃ Br H H

II -233 OS(0)₂-N(CH₃)₂ Br H H

II -234 OS(0)₂-C₆H₄-4-CH₃ Br H H

II -235 OH CF₃ H H

II -236 OC(0)CH₃ CF₃ H H

II -237 OC(0)CH₂CH₃ CF₃ H H

II -238 OC(0)CH(CH₃)₂ CF₃ H H No. R¹ _{Ra2 Ra3 R}a4

II -239 OC(0)C(CH₃)₃ CF₃ H H

II -240 OC(0)-C₆H₅ CF₃ H H

II -241 OC(0)-CH₂C₆H₅ CF₃ H H

II -242 OC(0)-OCH₃ CF₃ H H

II -243 OC(0)-N(CH₃)₂ CF₃ H H

II -244 OC(0)-OCH₂CH₃ CF₃ H H

II -245 OS(0)₂-CH₃ CF₃ H H

II -246 OS(0)₂-N(CH₃)₂ CF₃ H H

II -247 OS(0)₂-C₆H₄-4-CH₃ CF₃ H H

II -248 OH CHF₂ H H

II -249 OC(0)CH₃ CHF₂ H H

II -250 OC(0)CH₂CH₃ CHF₂ H H

II -251 OC(0)CH(CH₃)₂ CHF₂ H H

II -252 0C(0)C(CH₃)₃ CHF₂ H H

II -253 OC(0)-C₆H₅ CHF₂ H H

II -254 0C(0)-CH₂C₆H₅ CHF₂ H H

II -255 OC(0)-OCH₃ CHF₂ H H

II -256 OC(0)-N(CH₃)₂ CHF₂ H H

II -257 OC(0)-OCH₂CH₃ CHF₂ H H

II -258 OS(0)₂-CH₃ CHF₂ H H

II -259 0S(0)₂-N(CH₃)₂ CHF₂ H H

II -260 OS(0)₂-C₆H₄-4-CH₃ CHF₂ H H

II -261 OH OCH₃ H H

II -262 OC(0)CH₃ OCH₃ H H

II -263 OC(0)CH₂CH₃ OCH₃ H H

II -264 OC(0)CH(CH₃)₂ OCH₃ H H

II -265 OC(0)C(CH₃)₃ OCH₃ H H

II -266 OC(0)-C₆H₅ OCH₃ H H

II -267 OC(0)-CH₂C₆H₅ OCH₃ H H

II -268 OC(0)-OCH₃ OCH₃ H H

II -269 OC(0)-N(CH₃)₂ OCH₃ H H

II -270 OC(0)-OCH₂CH₃ OCH₃ H H

II -271 OS(0)₂-CH₃ OCH₃ H H

II -272 OS(0)₂-N(CH₃)₂ OCH₃ H H

II -273 OS(0)₂-C₆H₄-4-CH₃ OCH₃ H H

II -274 OH OCF₃ H H

II -275 OC(0)CH₃ OCF₃ H H

II -276 OC(0)CH₂CH₃ OCF₃ H H

II -277 OC(0)CH(CH₃)₂ OCF₃ H H

II -278 OC(0)C(CH₃)₃ OCF₃ H H No. R¹ _Ra2 _{Ra3 R}a4

111-279 OC(0)-C₆H₅ OCF₃ H H

111-280 OC(0)-CH₂C₆H₅ OCF₃ H H

111-281 OC(0)-OCH₃ OCF₃ H H

III-282 OC(0)-N(CH₃)₂ OCF₃ H H

III-283 OC(0)-OCH₂CH₃ OCF₃ H H

III-284 OS(0)₂-CH₃ OCF₃ H H

III-285 OS(0)₂-N(CH₃)₂ OCF₃ H H

III-286 OS(0)₂-C₆H₄-4-CH₃ OCF3 H H

Table Ilia:

a to III.286a of the formula lll-A, in which R is

and the combination of R¹, R^a2 , R^a3 and R^a4 for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.

Table lllb:

b to lll.286b of the formula lll-A, in which R is

and the combination of R¹, R^a2 , R^a3 and R^a4 for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.

Table I lie:

c to III.286c of the formula lll-A, in which R is

and the combination of R¹, R^a2 , R^a3 and R^a4 for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.

Table llld:

d to lll.286d of the formula lll-A, in which R is

and the combination of R¹, R^a2 , R^a3 and R^a4 for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule. Table llle:

Compounds lll.l e to lll.286e of the formula lll-A, in which R is

and the combination of R¹, R² , R^a3 and R^a4 for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.

Table lllf:

f to 111.286f of the formula lll-A, in which R is

and the combination of R , R^a2, R^a3 and R^a4 for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.

Table lllg:

Compounds lll.lg to lll.286g of the formula lll-A, in which R is

^ and the combination of R¹, R^a2, R^a3 and R^a4 for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.

Table lllh:

Compounds lll.lh to lll.286h of the formula lll-A, in which R is

and the combination of R¹, R^a2 , R^a3 and R^a4 for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.

Table UN:

Compounds 111.1 i to lll.286i of the formula lll-A, in which R is

H₃C^^_rCH₂*

^ and the combination of R¹, R^a2 , R^a3 and R^a4 for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.

Table lllj:

Compounds lll.lj to lll.286j of the formula lll-A, in which R is ^H3C! ~^CHCH₃

and the combination of R¹, R^a2 , R^a3 and R^a4 for a compound corresponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.

Table lllk:

Compounds 111.1k to 111.286k of the formula lll-A, in which R is

^ and the combination of R¹, R^a2, R^a3 and R^a4 for a compound corre- sponds in each case to one row of Table III, and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.

Table I I I I:

to 111.2861 of the formula for l ll-A, in which R is

and the combination of R¹ , R^a2 , R^a3 and R^a4 for a compound cor- responds in each case to one row of Table I II , and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.

Tablell lm:

m to III .286m of the formula ll l-A , in which R is

_anc| ^_{e com D}j_nation of R¹ , R^a2 , R^a3 and R^a4 for a compound corresponds in each case to one row of Table III , and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.

Table l l ln:

Compounds 111.1 η to l ll.286n of the formula ll l-A, in which R is

O— N 3

and the combination of R¹ , R^a2 , R^a3 and R^a4 for a compound corresponds in each case to one row of Table I II , and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.

Table l l lo:

ο to l ll.286o of the formula ll l-A, in which R is

and the combination of R¹ , R^a2 , R^a3 and R^a4 for a compound corresponds in each case to one row of Table I II , and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.

Table l l lp:

Compounds l ll. l p to l ll.286p of the formula ll l-A, in which R is

and the combination of R¹ , R^a2 , R^a3 and R^a4 for a compound corresponds in each case to one row of Table I II , and wherein the asterisk denotes the attachment point of the fragment to the remainder of the molecule.

The compounds according to the present invention can be prepared analogously to the synthesis routes described in unpublished EP application 08172182.1 and according to standard processes of organic chemistry, for example according to the following synthesis route:

Scheme 1A:

Carboxylic acids of the formula IV can be reacted with compounds of the formula V to give compounds of the formula VI. In the formulae VI and V, the variables have the meaning given for formula I. The group R' is Ci-C4-alkoxy, Y' is O, S or NH, Hal is a halogen atom or another suitable leaving group, such as sulfonates, phosphoric esters and the like and SG in this context is a protective group which decreases the reactivity of Y, suc

This reaction is usually carried out at temperatures of from -78°C to 120°C, preferably from -20°C to 50°C, in an inert organic solvent in the presence of a base, (cf.

Greene's Protective Groups in Organic Synthesis, Wiley).

Scheme 1 B:

Alternatively, carboxylic acids of the formula IVb can be reacted with compounds of the formula Vb to give compounds of the formula VI. In the formulae VI band Vb, the variables have the meaning given for formula I. The group R' is Ci-C4-alkoxy, Y' is O, S or NH, Hal is a halogen atom or another suitable nucleophilic leaving group, such as alkoxy or phenoxy and SG in this context is a protective group which decreases the reactivity of Y, such as, for example, optionally substituted benzyl, or a group R, wherein R has the meaning given for formula I.

This reaction is usually carried out at temperatures of from -78°C to 120°C, preferably from -20°C to 50°C, in an inert organic solvent in the presence of a base, (cf. Chi- nese Journal of Chemistry 2007, 25(6), 839-842).

Alternatively, compounds of formula VI wherein Y -NH and the protective group SG remains in the molecule till the final preparation of compounds of formula I, SG can be selected from the group R, wherein group R is as defined above for formula I. In such cases, compounds of formula VI, or precursors thereof, can be prepared according to generally known methods (cf. R.C. Larock, Comprehensive Organic Transformations)." Suitable solvents in scheme 1 and 1 B are aliphatic hydrocarbons, such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propioni- trile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene. It is also possible to use mixtures of the solvents mentioned. Suitable bases in scheme 1 and 1 B 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 amides, such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbon- ates, such as lithium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls, such as methyllithium, butyllithium and phenyllithium, al- kylmagnesium halides, such as methylmagnesium chloride, and also alkali metal and alkaline earth metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, tributylamine, diiso- propylethylamine and N-methylpiperidine, pyridine, substituted pyridines, such as col- lidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines. Preference is given to alkali metal and alkaline earth metal hydrides, particularly preferably sodium hydride. The bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvents.

In both schemes, the starting materials are generally reacted with one another in equimolar amounts.

Scheme 2:

The corresponding acid of the formula Via is released from the compounds of the formula VI. This reaction is usually carried out at temperatures of from -78°C to 120°C, preferably from -20°C to 50°C, in an inert organic solvent in the presence of a base (cf. Bioorganic and M ).

Suitable solvents are water, alcohols, such as methanol, ethanol, isopropanol, a- liphatic 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 diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisol and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and also dimethyl sulfoxide, di- methylformamide and dimethylacetamide, particularly preferably halogenated hydrocarbons, such as methylene chloride, chloroform and chlorobenzene. 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 amides, such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbon- ates, such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls, such as methyllithium, butyllithium and phenyllithium, alkyl magnesium halides, such as methylmagnesium chloride, and also alkali metal and alkaline earth metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, tributylamine, diisopropylethyl- amine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and also bicyclic amines. Preference is given to alkali metal and alkaline earth metal hydroxides, particularly preferably lithum hydroxide. The bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvent.

Scheme 3:

The compounds of the formula Via are activated by introducing a leaving group L¹. Suitable leaving groups L¹ in this context are, in general, groups which increase the electrophilicity of the carbonyl group, for example O-alkyl, O-aryl, halides, activated esters or aldehydes (such as, for example, Weinreb amide), in particular pentafluoro- phenoxy.

This reaction is usually carried out at temperatures of from -78°C to 120°C, preferably from -20°C to 50°C, in an inert organic solvent in the presence of a base, such as, for example, triethylamine (cf. J. Agric. and Food Chem. 1994, 42(4), 1019-1025), a catalyst, such as, for example, dicyclohexylcarbodiimide (cf. Egyptian Journal of Chem- istry 1994, 37(3), 273-282) or other known coupling agents.

Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohex- ane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chloroben- zene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably methylene chloride and toluene. 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 amides, such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates, such as lithium carbonate, potassium carbonate and calcium carbonate, and also alkali metal bicarbon- ates, such as sodium bicarbonate, organometallic compounds, in particular alkali metal alkyls, such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides, such as methylmagnesium chloride, and also alkali metal and alkaline earth metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium, moreover organic bases, for example tertiary amines, such as trimethylamine, triethylamine, tributylamine, diisopropylethyl- amine 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 lithium carbonate, potassium carbonate, calcium carbonate, cesium carbonate and rubidium carbonate. The bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvents.

The starting materials are generally reacted with one another in equimolar amounts.

Suitable agents H-L¹ in this context are alcohols, optionally subst. phenols, Ν,Ο- dialkyl hydroxylamine, in particular pentafluorophenol or Ν,Ο-dimethylhydroxylamine.

Scheme 4:

The compounds of the formula VII are reacted with acetic acid derivatives of the fo

This reaction is usually carried out at temperatures of from -78°C to 120°C, preferably from -20°C to 50°C, in an inert organic solvent in the presence of a base or a Lewis acid or a catalyst [cf. Bioorganic & Medicinal Chemistry (2004) Vol. 12(6), 1357-1366].

Suitable solvents are aliphatic hydrocarbons, such as pentane, hexane, cyclohex- ane and petroleum ether, aromatic hydrocarbons, such as toluene, o-, m- and p-xylene, halogenated hydrocarbons, such as methylene chloride, chloroform and chloroben- zene, ethers, such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles, such as acetonitrile and propionitrile, ketones, such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and also dimethyl sulfoxide, dimethylformamide and dimethylacetamide, particularly preferably acetonitrile and dimethylformamide. 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 amides, such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates, such as lithium car- bonate, potassium carbonate, calcium carbonate, cesium carbonate and rubidium carbonate, and also alkali metal bicarbonates, such as sodium bicarbonate, organometal- lic compounds, in particular alkali metal alkyls, such as methyllithium, butyllithium and phenyllithium, alkylmagnesium halides, such as methylmagnesium chloride, and also alkali metal and alkaline earth metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and dimethoxymagnesium, moreover organic bases, for example tertiary amines, such as trimethylamine, triethyl- amine, tributylamine, diisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines, such as collidine, lutidine and 4-dimethylaminopyridine, and also bi- cyclic amines. Preference is given to alkali metal and alkaline earth metal alkoxides, particularly preferably potassium tert-butoxide.

The bases are generally employed in catalytic amounts; however, they can also be used in equimolar amounts, in excess or, if appropriate, as solvents.

The starting materials are generally reacted with one another in equimolar amounts.

Scheme 5:

The compounds of the formula Γ can be released from the compounds of the formula IX by re

The reaction conditions depend on the nature of the protective group SG; the removal of an optionally substituted benzyl group can be achieved, for example, using trifluoroacetic acid at temperatures of from -78°C to 100°C, preferably from -20°C to 50°C, in an inert organic solvent [cf. Greene's Protective Groups in Organic Synthesis,

The introduction of the group X different from oxygen into the compounds of the formula Γ or precursors thereof is carried out according to generally known methods. Scheme 6:

Tautomer 2 of the compounds of the formula I can be alkylated, acylated or sulfonated by reaction with, respectively, an alkylating, acylating or sulfonating agent of formula VIII a

Tautomer 2

In the formula X of scheme 6, R^v is d-Cs-alkyl, Ci-Cs-alkylcarbonyl, Ci-Cs-alkyl- sulfonyl, C-i-Ce-arylcarbonyl, C-i-Cs-arylsulfonyl, wherein the alkyl and aryl groups may be partially or fully substituted by groups R^a, and L in this context is a nucleophilic leaving group, for example halogen, alkoxy, alkylcarbonyloxy or arylcarbonyloxy. Useful acylating or sulfonating agents include, in particular, acetyl chloride, pivaloyl chloride, tosyl chloride or methylsulfonyl chloride.

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, the purification can also be carried out by recrystallization or digestion.

If individual compounds of formula I cannot be obtained by the routes described above, they can be prepared by derivatization of other compounds of formula I. Same applies to compounds of formula II or of formula III.

If the synthesis yields mixtures of isomers, a separation is generally however 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 application, for example in the case of the treatment of plants in the treated plant or in the harmful plant to be controlled.

In order to obtain salts, which are suitable for agricutural or veterinary use, the compounds of formula I, II and III can be reacted with conventional salt builders as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, benzene sulfonic acid, p-toluol-sulfonic acid, dodecylben- zene sulfonic acid, methyl bromide, dimethyl sulfate or diethyl sulfate in temperature range of 0 to 150°C, preferably 20 to 120 °C.

The formation of the salt is usually conducted in a dissolving or diluting agent. Suitable are e.g. aliphatic hydrocarbons as n-pentane, n-hexane or petrol ether, aromatic hydrocarbons, as benzole, toluole or xylole, benzine or ethers as diethyl ether, methyl- tert. -butyl ether, tetrahydrofurane or dioxane, further ketones, as acetone, methyl-ethyl- ketone or methyl-isopropyl-ketone, as well as halogenated hydrocarbons as chloroben- zole, methylene chloride, ethylenen chloride, chloroform or tetrachlor ethylene. Also mixtures of those solvents can be used.

For the preparation of salts of compounds of the present invention the educts are employed usually in a stoichiometric ratio. The excess of one or the other component can be useful.

In the sense of the present invention, "animal pests" are preferably selected from arthropods and nematodes, more preferably from harmful insects, arachnids and nematodes, and even more preferably from insects, acarids and nematodes.

The compounds of the present invention are in particular suitable for efficiently controlling arthropodal pests such as arachnids, myriapedes and insects as well as nematodes. Animal pests controlled by the compounds of the present invention include for example:

Insects from the order of the lepidopterans (Lepidoptera), for example Agrotis ypsi- lon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia con- jugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandi- osella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bou- liana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha mo- lesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lamb- dina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocol- letis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseu- dotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, hyacionia frus- trana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis;

beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes ob- scurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blasto- phagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata,

Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabrotica longicornis, Diabrotica semipunctata, Diabrotica 12-punctata Diabrotica speciosa, Diabrotica virgifera, Epila- chna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus,

Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sito- philus granaria;

flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albi- manus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbi- tae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gaster- ophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia titillanus, Mayetiola destructor, Musca autumnalis, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phor- bia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis, Sarcophaga spp., Simulium vittatum, Sto- moxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea, and Tipula paludosa;

thrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips ssp., Frank- liniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,

termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Re- ticulitermes santonensis, Reticulitermes grassei, Termes natalensis, and Coptotermes formosanus;

cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Pe- riplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuliggi- nosa, Periplaneta australasiae, and Blatta orientalis;

bugs, aphids, leafhoppers, whiteflies, scale insects, cicadas (Hemiptera), e.g. Acros- ternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysder- cus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyl- lopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis , Thyanta perditor, Acyrthosiphon onobrychis, Adelges laricis, Aphidula nastur- tii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum so- lani, Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosi- pha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plan- taginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzus persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rho- palomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, Viteus vitifolii, Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., and Arilus critatus;

ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampa minuta, Hoplocampa testudinea, Lasius niger,

Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidole megacephala, Dasymutilla occidentalis, Bombus spp., Vespula squamosa,

Paravespula vulgaris, Paravespula pennsylvanica, Paravespula germanica,

Dolichovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepithema humile;

crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroc- canus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus, Hiero- glyphus daganensis, Kraussaria angulifera, Calliptamus italicus, Chortoicetes terminif- era, and Locustana pardalina;

arachnoidea, such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Ambry- omma maculatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Ornithodorus moubata, Ornithodorus hermsi, Orni- thodorus turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Pso- roptes ovis, Rhipicephalus sanguineus, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyl- locoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kan- zawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panony- chus ulmi, Panonychus citri, and Oligonychus pratensis; Araneida, e.g. Latrodectus mactans, and Loxosceles reclusa;

fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,

silverfish, firebrat (Thysanura), e.g. Lepisma saccharina and Thermobia domestica, centipedes (Chilopoda), e.g. Scutigera coleoptrata,

millipedes (Diplopoda), e.g. Narceus spp.,

Earwigs (Dermaptera), e.g. forficula auricularia,

lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovi- cola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus. Collembola (springtails), e.g. Onychiurus ssp.. They are also suitable for controlling Nematodes : plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne ja- vanica, and other Meloidogyne species; cyst-forming nematodes, Globodera rosto- chiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Hete- rodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocrico- nema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; Awl nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nema- todes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longi- dorus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorus species, Paratri- chodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species. The compounds of the present invention are also useful for controlling arachnids (Arachnoidea), such as acarians (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persi- cus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus mou- bata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendi- culatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpus phoenicis; Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis.

Compounds of the present invention are particularly useful for controlling insects, preferably sucking or piercing insects such as insects from the genera Thysanoptera, Diptera and Hemiptera, in particular the following species:

Thysanoptera : Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scir- tothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,

Diptera, e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gam- biae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chryso- mya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia an- thropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefascia- tus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radi- cum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachin- oides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia titillanus, Maye- tiola destructor, Musca autumnalis, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomo- nella, Sarcophaga haemorrhoidalis, Sarcophaga spp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea, and Tipula paludosa;

Hemiptera, in particular aphids: Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea,

Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosi- phum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzodes persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rho- palomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, and Viteus vitifolii;

Compounds of the present invention are particularly useful for controlling insects of the orders Hemiptera and Thysanoptera.

For use in a method according to the present invention, the compounds of the present invention can be converted into the customary formulations, e.g. solutions, emul- sions, suspensions, dusts, powders, pastes, granules and directly sprayable solutions. The use form depends on the particular purpose and application method. Formulations and application methods are chosen to ensure in each case a fine and uniform distribution of the compound of the present invention. The formulations are prepared in a known manner (see e.g. for review US

3,060,084, EP-A 707 445 (for liquid concentrates), Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and et seq. WO 91/13546, US

4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701 , US 5,208,030, GB 2,095,558, US 3,299,566, Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961 , Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989 and Mollet, H., Grubemann, A., Formulation technology, Wiley VCH Verlag GmbH, Weinheim (Germany), 2001 , 2. D. A. Knowles, Chemistry and Technology of Agrochemical Formulations, Kluwer Academic Publishers, Dordrecht, 1998 (ISBN 0-7514-0443-8), for example by extending the active compound with auxiliaries suitable for the formulation of agrochemicals, such as solvents and/or carriers, if desired emulsifiers, surfactants and dispersants, preservatives, anti- foaming agents, anti-freezing agents, for seed treatment formulation also optionally colorants and/or binders and/or gelling agents.

Solvents/carriers, which are suitable, are e.g.:

solvents such as water, aromatic solvents (for example Solvesso products, xylene and the like), paraffins (for example mineral fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (N-metyhl-pyrrolidone (NMP),N-octylpyrrolidone NOP), acetates (glycol diacetate), alkyl lactates, lactones such as g-butyrolactone, glycols, fatty acid dimethylamides, fatty acids and fatty acid esters, triglycerides, oils of vegetable or animal origin and modified oils such as alkylated plant oils. In principle, solvent mixtures may also be used.

- carriers such as ground natural minerals and ground synthetic minerals, such as silica gels, finely divided silicic acid, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.

Suitable emulsifiers are nonionic and anionic emulsifiers (for example polyoxyethyl- ene fatty alcohol ethers, alkylsulfonates and arylsulfonates).

Examples of dispersants are lignin-sulfite waste liquors and methylcellulose.

Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalene- sulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, poly- oxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide conden- sates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropyl- ene, lauryl alcohol polyglycol ether acetal, sorbitol esters,

Also anti-freezing agents such as glycerin, ethylene glycol, propylene glycol and bactericides such as can be added to the formulation.

Suitable antifoaming agents are for example antifoaming agents based on silicon or magnesium stearate.

Suitable preservatives are for example dichlorophen und benzyl alcohol hemiformal Suitable thickeners are compounds which confer a pseudoplastic flow behavior to the formulation, i.e. high viscosity at rest and low viscosity in the agitated stage. Men- tion may be made, in this context, for example, of commercial thickeners based on polysaccharides, such as Xanthan Gum^® (Kelzan^® from Kelco), hodopol^®23 (Rhone Poulenc) or Veegum^® (from R.T. Vanderbilt), or organic phyllosilicates, such as Atta- clay^® (from Engelhardt). Antifoam agents suitable for the dispersions according to the invention are, for example, silicone emulsions (such as, for example, Silikon^® SRE, Wacker or Rhodorsil^® from Rhodia), long-chain alcohols, fatty acids, organofluorine compounds and mixtures thereof. Biocides can be added to stabilize the compositions according to the invention against attack by microorganisms. Suitable biocides are, for example, based on isothiazolones such as the compounds marketed under the trademarks Proxel^® from Avecia (or Arch) or Acticide^® RS from Thor Chemie and Kathon^® MK from Rohm & Haas. Suitable antifreeze agents are organic polyols, for example ethylene glycol, propylene glycol or glycerol. These are usually employed in amounts of not more than 10% by weight, based on the total weight of the active compound composition. If appropriate, the active compound compositions according to the invention may comprise 1 to 5% by weight of buffer, based on the total amount of the formulation prepared, to regulate the pH, the amount and type of the buffer used depending on the chemical properties of the active compound or the active compounds. Examples of buffers are alkali metal salts of weak inorganic or organic acids, such as, for example, phosphoric acid, boronic acid, acetic acid, propionic acid, citric acid, fumaric acid, tartaric acid, oxalic acid and succinic acid.

Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone and water.

Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.

In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active ingredient. The active ingredients are employed in a purity of from 90% to 100%, preferably 95% to 100% (according to NM spectrum).

For seed treatment purposes, respective formulations can be diluted 2-10 fold leading to concentrations in the ready to use preparations of 0,01 to 60% by weight active compound by weight, preferably 0,1 to 40% by weight.

The compound of formula I or formula II can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the in- tended purposes; they are intended to ensure in each case the finest possible distribution of the active compounds according to the invention.

The following are examples of formulations:

1. Products for dilution with water. For seed treatment purposes, such products may be applied to the seed diluted or undiluted.

A) Water-soluble concentrates (SL, LS)

10 parts by weight of the active compound is dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active compound dissolves upon dilution with water, whereby a formulation with 10 % (w/w) of active compound is obtained.

B) Dispersible concentrates (DC)

20 parts by weight of the active compound is dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion, whereby a formulation with 20% (w/w) of active compounds is obtained.

C) Emulsifiable concentrates (EC)

15 parts by weight of the active compounds is dissolved in 7 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion, whereby a formulation with 15%) (w/w) of active compounds is obtained.

D) Emulsions (EW, EO, ES)

25 parts by weight of the active compound is dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifier machine (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion, whereby a formulation with 25% (w/w) of active compound is obtained.

E) Suspensions (SC, OD, FS)

In an agitated ball mill, 20 parts by weight of the active compound is comminuted with addition of 10 parts by weight of dispersants, wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound suspension. Dilution with water gives a stable suspension of the active compound, whereby a formulation with 20% (w/w) of active compound is obtained.

F) Water-dispersible granules and water-soluble granules (WG, SG)

50 parts by weight of the active compound is ground finely with addition of 50 parts by weight of dispersants and wetters and made as water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluid- ized bed). Dilution with water gives a stable dispersion or solution of the active com- pound, whereby a formulation with 50% (w/w) of active compound is obtained.

G) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS)

75 parts by weight of the active compound are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound, whereby a formulation with 75% (w/w) of active compound is obtained.

H) Gel-Formulation (GF)

In an agitated ball mill, 20 parts by weight of the active compound is comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of a gelling agent wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound suspension. Dilution with water gives a stable suspension of the active compound, whereby a formulation with 20% (w/w) of active compound is obtained.

2. Products to be applied undiluted for foliar applications. For seed treatment purposes, such products may be applied to the seed diluted or undiluted.

I) Dustable powders (DP, DS)

5 parts by weight of the active compound are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable product having 5% (w/w) of active compound.

J) Granules (GR, FG, GG, MG)

0.5 part by weight of the active compound is ground finely and associated with 95.5 parts by weight of carriers, whereby a formulation with 0.5% (w/w) of active compound is obtained. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted for foliar use.

K) ULV solutions (UL)

10 parts by weight of the active compound is dissolved in 90 parts by weight of an or- ganic solvent, for example xylene. This gives a product having 10% (w/w) of active compound, which is applied undiluted for foliar use.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wet- table powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or sol- vent, can be homogenized in water by means of a wetter, tackifier, dispersant or emul- sifier. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water. The active ingredient concentrations in the ready-to-use products can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1 %.

The active ingredients may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active ingredient, or even to apply the active ingredient without additives.

Formulations of 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 control- ling pests such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are preferably composed of the active compound, solvents such as lower alcohols (e.g. methanol, ethanol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g. kerosenes) having boiling ranges of approximately 50 to 250 °C, dimethylformamide, N-methylpyrrolidone, dimethyl sulfoxide, aromatic hydro- carbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of ethylene oxide, fatty alcohol ethoxylate, perfume oils such as ethereal oils, esters of medium fatty acids with lower alcohols, aromatic carbonyl compounds, if appropriate stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if re- quired, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases.

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 %.

In the method of this invention compounds of the present invention may be applied with other active ingredients, for example with other pesticides, insecticides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxi- cants and plant growth regulators, safeners and nematicides. These additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.

The following list M of pesticides together with which the compounds according to the 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. Organo(thio)phosphate compounds: acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyri- fos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, fam- phur, fenamiphos, fenitrothion, fenthion, flupyrazophos, fosthiazate, heptenophos, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfo- tep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, tri- chlorfon, vamidothion;

M.2. Carbamate compounds: aldicarb, alanycarb, bendiocarb, benfuracarb, buto- carboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobu- carb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate; M.3. Pyrethroid compounds: acrinathrin, allethrin, d-cis-trans allethrin, d-trans al- lethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cyclo- prothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta- cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fen- propathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, metofluthrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), res- methrin, silafluofen, tefluthrin, tetramethrin, tralomethrin, transfluthrin;

M.4. Juvenile hormone mimics: hydroprene, kinoprene, methoprene, fenoxycarb, pyriproxyfen;

M.5. Nicotinic receptor agonists/antagonists compounds: acetamiprid, bensultap, cartap hydrochloride, clothianidin, dinotefuran, imidacloprid, thiamethoxam, niten- pyram, nicotine, spinosad (allosteric agonist), spinetoram (allosteric agonist), thiaclo- prid, thiocyclam, thiosultap-sodium and AKD1022.

M.6. GABA gated chloride channel antagonist compounds: chlordane, endosulfan, gamma-HCH (lindane); ethiprole, fipronil, pyrafluprole, pyriprole

M.7. Chloride channel activators: abamectin, emamectin benzoate, milbemectin, le- pimectin;

M.8. METI I compounds: fenazaquin, fenpyroximate, pyrimidifen, pyridaben, te- bufenpyrad, tolfenpyrad, flufenerim, rotenone;

M.9. METI II and III compounds: acequinocyl, fluacyprim, hydramethylnon;

M.10. Uncouplers of oxidative phosphorylation: chlorfenapyr, DNOC;

M.1 1. Inhibitors of oxidative phosphorylation: azocyclotin, cyhexatin, diafenthiuron, fenbutatin oxide, propargite, tetradifon;

M.12. Moulting disruptors: cyromazine, chromafenozide, halofenozide, methoxy- fenozide, tebufenozide;

M.13. Synergists: piperonyl butoxide, tribufos;

M.14. Sodium channel blocker compounds: indoxacarb, metaflumizone;

M.15. Fumigants: methyl bromide, chloropicrin sulfuryl fluoride;

M.16. Selective feeding blockers: crylotie, pymetrozine, flonicamid;

M.17. Mite growth inhibitors: clofentezine, hexythiazox, etoxazole; M.18. Chitin synthesis inhibitors: buprofezin, bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, novif- lumuron, teflubenzuron, triflumuron;

M.19. Lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;

M.20. Octapaminergic agonsits: amitraz;

M.21 . Ryanodine receptor modulators: flubendiamide and the phtalamid compound (R)-, (S)- 3- Chlor-N1-{2-methyl-4-[1 , 2,2,2 - tetrafluor-1-(trifluormethyl)ethyl]phenyl}- N2-(1 -methyl-2-methylsulfonylethyl)phthalamid (M21.1 )

M.22. Isoxazoline compounds: 4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5-di- hydro-isoxazol-3-yl]-2-methyl-N-pyridin-2-ylmethyl-benzamide (M22.1 ), 4-[5-(3,5-Di- chloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N-(2,2,2-trifluoro- ethyl)-benzamide (M22.2), 4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro- isoxazol-3-yl]-2-methyl-N-[(2,2,2-trifluoro-ethylcarbamoyl)-methyl]-benzamide (M22.3), 4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-naphthalene-1 - carboxylic acid [(2,2,2-trifluoro-ethylcarbamoyl)-methyl]-amide (M22.4)4-[5-(3,5-Dichlo- rophenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-N-[(methoxyimino)methyl]-2- methylbenzamide (M22.5), 4-[5-(3-Chloro-5-trifluoromethyl-phenyl)-5-trifluoromethyl- 4,5-dihydro-isoxazol-3-yl]-2-methyl-N-[(2,2,2-trifluoro-ethylcarbamoyl)-methyl]-benz- amide (M22.6), 4-[5-(3-Chloro-5-trifluoromethyl-phenyl)-5-trifluoromethyl-4,5-dihydro- isoxazol-3-yl]-naphthalene-1 -carboxylic acid [(2,2,2-trifluoro-ethylcarbamoyl)-methyl]- amide (M22.7) and 5-[5-(3,5-Dichloro-4-fluoro-phenyl)-5-trifluoromethyl-4,5-dihydro- isoxazol-3-yl]-2-[1 ,2,4]triazol-1 -yl-benzonitrile (M22.8);

M.23. Anthranilamide compounds: chloranthraniliprole, cyantraniliprole, 5-Bromo-2- (3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [4-cyano-2-(1 -cyclopropyl-ethyl- carbamoyl)-6-methyl-phenyl]-amide (M23.1 ), 5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-py- razole-3-carboxylic acid [2-chloro-4-cyano-6-(1 -cyclopropyl-ethylcarbamoyl)-phenyl]- amide (M23.2), 5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2-bro- mo-4-cyano-6-(1 -cyclopropyl-ethylcarbamoyl)-phenyl]-amide(M23.3), 5-Bromo-2-(3- chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2-bromo-4-chloro-6-(1-cyclopropyl- ethylcarbamoyl)-phenyl]-amide(M23.4), 5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole- 3-carboxylic acid [2,4-dichloro-6-(1-cyclopropyl-ethylcarbamoyl)-phenyl]-amide (M23.5), 5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [4-chloro-2- (1 -cyclopropyl-ethylcarbamoyl)-6-methyl-phenyl]-amide (M23.6), N'-(2-{[5-Bromo-2-(3- chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-5-chloro-3-methyl-benzoyl)-hydra- zinecarboxylic acid methyl ester (M23.7), N'-(2-{[5-Bromo-2-(3-chloro-pyridin-2-yl)-2H- pyrazole-3-carbonyl]-amino}-5-chloro-3-methyl-benzoyl)-N'-methyl-hydrazinecarboxylic acid methyl ester (M23.8), N'-(2-{[5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-car- bonyl]-amino}-5-chloro-3-methyl-benzoyl)-N,N'-dimethyl-hydrazinecarboxylic acid methyl ester (M23.9), N'-(3,5-Dibromo-2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyra- zole-3-carbonyl]-amino}-benzoyl)-hydrazinecarboxylic acid methyl ester (M23.10), N'- (3,5-Dibromo-2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}- benzoyl)-N'-methyl-hydrazinecarboxylic acid methyl ester (M23.1 1 ) and N'-(3,5-Di- bromo-2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-benzoyl)- Ν,Ν'-dimethyl-hydrazinecarboxylic acid methyl ester (M23.12);

M.24. Malononitrile compounds: 2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,3-triflu- oro-propyl)malononitrile (CF₂H-CF2-CF2-CF2-CH2-C(CN)2-CH2-CH2-CF3) (M24.1 ) and 2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,4,4,4-pentafluorobutyl)-malonodinitrile (CF2H-CF2-CF2-CF2-CH2-C(CN)2-CH2-CH2-CF2-CF₃) (M24.2);

M.25. Microbial disruptors: Bacillus thuringiensis subsp. Israelensi, Bacillus sphaeri- cus, Bacillus thuringiensis subsp. Aizawai, Bacillus thuringiensis subsp. Kurstaki, Bacillus thuringiensis subsp. Tenebrionis;

M.26. Aminofuranone compounds:

4-{[(6-Bromopyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on (M26.1 ), 4-{[(6-Fluoropyrid-3-yl)methyl](2,2-difluoroethyl)amino}furan-2(5H)-on (M26.2), 4-{[(2-Chloro1 ,3-thiazolo-5-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on (M26.3), 4-{[(6-Chloropyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on (M26.4), 4-{[(6-Chloropyrid-3-yl)methyl](2,2-difluoroethyl)amino}furan-2(5H)-on (M26.5), 4-{[(6-Chloro-5-fluoropyrid-3-yl)methyl](methyl)amino}furan-2(5H)-on (M26.6), 4-{[(5,6-Dichloropyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on (M26.7), 4-{[(6-Chloro-5-fluoropyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-on (M26.8), 4-{[(6-Chloropyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-on (M26.9) and 4-{[(6-Chloropyrid-3-yl)methyl](methyl)amino}furan-2(5H)-on (M26.10);

M.27. Various compounds: aluminium phosphide, amidoflumet, benclothiaz, ben- zoximate, bifenazate, borax, bromopropylate, cyanide, cyenopyrafen, cyflumetofen, chinomethionate, dicofol, fluoroacetate, phosphine, pyridalyl, pyrifluquinazon, sulfur, organic sulfur compounds, tartar emetic, sulfoxaflor, N-R'-2,2-dihalo-1-R"cyclo-pro- panecarboxamide-2-(2,6-dichloro-a ,a ,a -trifluoro-p-tolyl)hydrazone or N-R'-2,2- di(R"')propionamide-2-(2,6-dichloro-a ,a ,a -trifluoro-p-tolyl)-hydrazone, wherein R' is methyl or ethyl, halo is chloro or bromo, R" is hydrogen or methyl and R'" is methyl or ethyl, 4-But-2-ynyloxy-6-(3,5-dimethyl-piperidin-1-yl)-2-fluoro-pyrimidine (M27.1), Cyclopropaneacetic acid , 1 ,1 '-[(3S,4R,4aR,6S,6aS, 12R, 12aS, 12bS)-4-[[(2-cyclopro- pylacetyl)oxy]methyl]-1 ,3,4,4a,5,6,6a,12,12a,12b-decahydro-12-hydroxy-4,6a,12b-tri- methyl-1 1 -oxo-9-(3-pyridinyl)-2H , 1 1 H-naphtho[2, 1 -b]pyrano[3,4-e]pyran-3,6-diyl] ester (M27.2) and 8-(2-Cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl- pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane(M27.3).

The commercially available compounds of the group M may be found in The Pesti- cide Manual, 13th Edition, British Crop Protection Council (2003) among other publications.

Paraoxon and their preparation have been described in Farm Chemicals Handbook, Volume 88, Meister Publishing Company, 2001. Flupyrazofos has been described in Pesticide Science 54, 1988, p.237-243 and in US 4822779. AKD 1022 and its prepara- tion have been described in US 6300348. The anthranilamides M23.1 to M23.6 have been described in WO 08/72743 and WO 200872783, those M23.7 to M23.12 in WO 07/043677. The phthalamide M 21.1 is known from WO 07/101540. -The alkynylether compound M27.1 is described e.g. in JP 2006131529. Organic sulfur compounds have been described in WO 07/060839. The isoxazoline compounds M 22.1 to M 22.8 have been described in e.g. WO 05/085216, WO 07/079162, WO 07/026965, WO

09/126668 and WO 09/051956. The aminofuranone compounds M 26.1 to M 26.10 have been described eg. in WO 07/1 15644. The pyripyropene derivative M 27.2 has been described in WO 08/66153 and WO 08/108491. The pyridazin compound M 27.3 has been described in JP 2008/1 15155. Malononitrile compounds as those (M24.1 ) and (M24.2) have been described in WO 02/089579, WO 02/090320, WO 02/090321 , WO 04/006677, WO 05/068423, WO 05/068432 and WO 05/063694.

The following list of fungicidal active substances which, in combination with the compounds of the present invention, can be used in pesticidal mixtures is intended to illustrate the possible combinations, but does not limit them:

F.I) Respiration Inhibitors

F.I-1) Inhibitors of complex III at Qo site (e.g. strobilurins)

strobilurins: azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxy- strobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, triclopyricarb/ chlorodincarb, trifloxystrobin, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3-methoxy- acrylic acid methyl ester and 2 (2-(3-(2,6-dichlorophenyl)-1-methyl-allylideneamino- oxymethyl)-phenyl)-2-methoxyimino-N methyl-acetamide;

oxazolidinediones and imidazolinones: famoxadone, fenamidone;

F.I-2) Inhibitors of complex II (e.g. carboxamides):

carboxanilides: benodanil, bixafen, boscalid, carboxin, fenfuram, fenhexamid, flu- opyram, flutolanil, furametpyr, isopyrazam, isotianil, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, tiadinil, 2-amino-4 methyl-thiazole-5- carboxanilide, N-(3',4',5' trifluorobiphenyl-2 yl)-3-difluoromethyl-1-methyl-1 H-pyrazole-4 carboxamide, N-(4'-trifluoromethylthiobiphenyl-2-yl)-3 difluoromethyl-1 -methyl-1 H pyra- zole-4-carboxamide and N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5 fluoro-1 H- pyrazole-4 carboxamide;

F.I-3) Inhibitors of complex III at Qi site: cyazofamid, amisulbrom;

F.I-4) Other respiration inhibitors (complex I, uncouplers)

diflumetorim; tecnazen; ferimzone; ametoctradin; silthiofam;

nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam, nitrthal-isopropyl, organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide;

F.ll) Sterol biosynthesis inhibitors (SBI fungicides)

F.II-1 ) C14 demethylase inhibitors (DMI fungicides, e.g. triazoles, imidazoles) triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusila- zole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebu- conazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole;

imidazoles: imazalil, pefurazoate, oxpoconazole, prochloraz, triflumizole;

pyrimidines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine; F.11-2) Delta14-reductase inhitors (Amines, e.g. morpholines, piperidines) morpholines: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tride- morph;

piperidines: fenpropidin, piperalin;

spiroketalamines: spiroxamine;

F.II-3) Inhibitors of 3-keto reductase: hydroxyanilides: fenhexamid;

F.lll) Nucleic acid synthesis inhibitors

F.I 11-1 ) RNA, DNA synthesis

phenylamides or acyl amino acid fungicides: benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl;

isoxazoles and iosothiazolones: hymexazole, octhilinone;

F.III-2) DNA topisomerase inhibitors: oxolinic acid;

F.III-3) Nucleotide metabolism (e.g. adenosin-deaminase)

hydroxy (2-amino)-pyrimidines: bupirimate;

F.IV) Inhibitors of cell division and or cytoskeleton

F.IV-1) Tubulin inhibitors: benzimidazoles and thiophanates: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl;

triazolopyrimidines: 5-chloro-7 (4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)- [1 ,2,4]triazolo[1 ,5 a]pyrimidine

F.IV-2) Other cell division inhibitors

benzamides and phenyl acetamides: diethofencarb, ethaboxam, pencycuron, fluopi- colide, zoxamide;

F.IV-3) Actin inhibitors: benzophenones: metrafenone;

F.V) Inhibitors of amino acid and protein synthesis

F.V-1) Mmethionine synthesis inhibitors (anilino-pyrimidines)

anilino-pyrimidines: cyprodinil, mepanipyrim, nitrapyrin, pyrimethanil;

F.V-2) Protein synthesis inhibitors (anilino-pyrimidines)

antibiotics: blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildio- mycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;

F.VI) Signal transduction inhibitors

F.VI-1) MAP / Histidine kinase inhibitors (e.g. anilino-pyrimidines)

dicarboximides: fluoroimid, iprodione, procymidone, vinclozolin;

phenylpyrroles: fenpiclonil, fludioxonil;

F.VI-2) G protein inhibitors: quinolines: quinoxyfen;

F.VII) Lipid and membrane synthesis inhibitors

F.VI 1-1 ) Phospholipid biosynthesis inhibitors

organophosphorus compounds: edifenphos, iprobenfos, pyrazophos;

dithiolanes: isoprothiolane;

F.VII-2) Lipid peroxidation

aromatic hydrocarbons: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole;

F.VII-3) Carboxyl acid amides (CAA fungicides) cinnamic or mandelic acid amides: dimethomorph, flumorph, mandiproamid, pyri- morph;

valinamide carbamates: benthiavalicarb, iprovalicarb, pyribencarb, valifenalate and N-(1-(1-(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester; F.VII-4) Compounds affecting cell membrane permeability and fatty acides carbamates: propamocarb, propamocarb-hydrochlorid

F.VIII) Inhibitors with Multi Site Action

F.VIII-1) Inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;

F.VIII-2) Thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, methasul- phocarb, metiram, propineb, thiram, zineb, ziram;

F.VIII-3) Organochlorine compounds (e.g. phthalimides, sulfamides, chloronitriles): anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusul- famide, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, N- (4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide;

F.VIII-4) Guanidines: guanidine, dodine, dodine free base, guazatine, guazatine- acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate);

F.VIII-5) Ahtraquinones: dithianon;

F.IX) Cell wall synthesis inhibitors

F.IX-1) Inhibitors of glucan synthesis: validamycin, polyoxin B;

F.IX-2) Melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamide, di- cyclomet, fenoxanil;

F.X) Plant defence inducers

F.X-1) Salicylic acid pathway: acibenzolar-S-methyl;

F.X-2) Others: probenazole, isotianil, tiadinil, prohexadione-calcium;

phosphonates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts;

F.XI) Unknown mode of action:

bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclo- mezine, difenzoquat, difenzoquat-methylsulfate, diphenylamin, flumetover, flusul- famide, flutianil, methasulfocarb, oxin-copper, proquinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen-4-one, N-(cyclopropylmethoxyimino-(6- difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3- trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N methyl formamidine, N' (4-(4- fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, N'-(5-difluoromethyl-2 methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N- ethyl-N-methyl formamidine, 2-{1-[2-(5-methyl-3-trifluoromethyl-pyrazole-1 -yl)-acetyl]- piperidin-4-yl}-thiazole-4-carboxylic acid methyl-(1 ,2,3,4-tetrahydro-naphthalen-1-yl)- amide, 2-{1-[2-(5-methyl-3-trifluoromethyl-pyrazole-1-yl)-acetyl]-piperidin-4-yl}-thiazole- 4-carboxylic acid methyl-(R)-1 ,2,3,4-tetrahydro-naphthalen-1-yl-amide, methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester and N-Methyl-2-{1-[(5-methyl- 3-trifluoromethyl-1 H-pyrazol-1-yl)-acetyl]-piperidin-4-yl}-N-[(1 R)-1 ,2,3,4-tetrahydro- naphthalen-1-yl]-4-thiazolecarboxamide, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazoli- din-3 yl]-pyridine, 3-[5-(4-methyl-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (pyris- oxazole), 5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-dihydro-pyrazole-1 carbothioic acid S-allyl ester, N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide, 5- chloro-1 (4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole, 2-(4-chloro- phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;

F.XI) Growth regulators:

abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegu- lac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid , maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N 6 benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5 tri iodobenzoic acid , trinexapac-ethyl and uniconazole;

F. XII) Biological control agents

antifungal biocontrol agents: Bacillus substilis strain with NRRL No. B-21661 (e.g. RHAPSODY®, SERENADE® MAX and SERENADE® ASO from AgraQuest, Inc., USA.), Bacillus pumilus strain with NRRL No. B-30087 (e.g. SONATA® and BALLAD® Plus from AgraQuest, Inc., USA), Ulocladium oudemansii (e.g. the product BOTRY- ZEN from BotriZen Ltd., New Zealand), Chitosan (e.g. ARMOUR-ZEN from BotriZen Ltd., New Zealand).

Accordingly, the present invention provides a method for controlling animal pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a cultivated plant, plant propagation materials (such as seed), soil, area, material or environment in which the pests are growing or may grow, or the materials, cultivated plants, plant propagation materials (such as seed), soils, surfaces or spaces to be protected from pest attack or infestation with a pesticidally effective amount of a compound of the present invention or a salt thereof or a composition as defined above.

Preferably, the method of the invention serves for protecting plant propagation material (such as seed) and the plant which grows therefrom from animal pest attack or infestation and comprises treating the plant propagation material (such as seed) with a pesticidally effective amount of a compound of the present invention or an agriculturally acceptable salt thereof as defined above or with a pesticidally effective amount of an agricultural composition as defined above and below. The method of the invention is not limited to the protection of the "substrate" (plant, plant propagation materials, soil material etc.) which has been treated according to the invention, but also has a preventive effect, thus, for example, according protection to a plant which grows from a treated plant propagation materials (such as seed), the plant itself not having been treated. The invention further provides an agricultural composition for combating such animal pests, which comprises such an amount of at least one compound of the present invention or at least one agriculturally useful salt thereof and at least one inert liquid and/or solid agronomically acceptable carrier that has a pesticidal action and, if desired, at least one surfactant.

Such a composition may contain a single active compound of the present invention or a salt thereof or a mixture of several active compounds of the present invention or their salts according to the present invention. The composition according to the present invention may comprise an individual isomer or mixtures of isomers as well as individ- ual tautomers or mixtures of tautomers.

The animal pest, i.e. the insects, arachnids and nematodes, the plant, soil or water in which the plant is growing can be contacted with the compounds of the present invention or composition(s) containing them by any application method known in the art. As such, "contacting" includes both direct contact (applying the compounds/compo- sitions 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 of the animal pest or plant).

The compounds of the present invention or the pesticidal compositions comprising them may be used to protect growing plants and crops from attack or infestation by animal pests, especially insects, acaridae or arachnids by contacting the plant/crop with a pesticidally effective amount of compounds of the present invention. The term "crop" refers both to growing and harvested crops.

The compounds of the present invention and the compositions comprising them are particularly important in the control of a multitude of insects on various cultivated plants, such as cereal, root crops, oil crops, vegetables, spices, ornamentals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.

The compounds of the present invention are employed as such or in form of compositions by treating the insects or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from insecticidal attack with a insecti- cidally effective amount of the active compounds. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the insects.

The present invention also includes a method of combating animal pests which comprises contacting the animal pests, their habit, breeding ground, food supply, cultivated plants, seed, soil, area, material or environment in which the animal pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from animal attack or infestation with a pesticidally effective amount of a mix- ture of at least one active compound of the present invention.

Moreover, animal pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of compounds of the present invention. As such, the application may be carried out before or after the infection of the locus, growing crops, or harvested crops by the pest.

The compounds of the invention can also be applied preventively to places at which occurrence of the pests is expected.

The compounds of the present invention may be also used to protect growing plants from attack or infestation by pests by contacting the plant with a pesticidally effective amount of compounds of the present invention. As such, "contacting" includes both direct contact (applying the compounds/compositions directly on the pest and/or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the pest and/or plant).

"Locus" means a habitat, breeding ground, plant, seed, soil, area, material or envi- ronment in which a pest or parasite is growing or may grow.

The term "plant propagation material" is to be understood to denote 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 "cultivated plants" is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering. Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-transtional modification of protein(s) (oligo- or polypeptides) poly for example by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties(e.g. as disclosed in Biotechnol Prog. 2001 Jul- Aug;17(4):720-8., Protein Eng Des Sel. 2004 Jan;17(1 ):57-66, Nat Protoc.

2007;2(5):1225-35., Curr Opin Chem Biol. 2006 Oct;10(5):487-91. Epub 2006 Aug 28., Biomaterials. 2001 Mar;22(5):405-17, Bioconjug Chem. 2005 Jan-Feb;16(1 ):1 13-21 ).

The term "cultivated plants" is to be understood also including plants that have been rendered tolerant to applications of specific classes of herbicides, such as hydroxy- phenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonyl ureas (see e. g. US 6,222,100, WO 01/82685, WO 00/26390, WO

97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) or imidazolinones (see e. g. US

6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073); enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate (see e. g. WO 92/00377); glutamine synthetase (GS) inhibitors, such as glufosinate (see e. g. EP-A 242 236, EP-A 242 246) or oxynil herbicides (see e. g. US 5,559,024) as a result of conventional methods of breeding or genetic engineering. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), for example Clearfield® summer rape (Canola) being tolerant to imidazolinones, e. g. imazamox. Genetic engineering methods have been used to render cultivated plants, such as soybean, cotton, corn, beets and rape, tolerant to herbicides, such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate).

The term "cultivated plants" is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as a-endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal pro- teins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, for example WO 02/015701 ). Further examples of such toxins or genetically-modified plants capable of synthesizing such toxins are dis-closed, for example, in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/018810 und WO 03/052073. The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins protection from harmful pests from certain taxonomic groups of arthro- pods, particularly to beetles (Coleoptera), flies (Diptera), and butterflies and moths (Lepidoptera) and to plant parasitic nematodes (Nematoda).

The term "cultivated plants" is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called " pathogenesis-related proteins" (PR proteins, see, for example EP-A 0 392 225), plant disease resistance genes (for example potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum) or T4- lyso-zym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.

The term "cultivated plants" is to be understood also including plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting envi- ron-mental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.

The term "cultivated plants" is to be understood also including plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, for ex-ample oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera® rape).

The term "cultivated plants" is to be understood also including plants that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, for example potatoes that produce increased amounts of amylopectin (e. g. Amflora® potato). 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 ef- fective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.

In the case of soil treatment 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.

Customary application rates in the protection of materials are, for example, 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. For use in treating crop plants, the rate of application of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.

The compounds of formula I and II are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part).

The compounds of the invention may also be applied against non-crop insect pests, such as ants, termites, wasps, flies, mosquitos, crickets, or cockroaches. For use against said non-crop pests, compounds of formula I are preferably used in a bait composition.

The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks. Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources. Gels can be based on aqueous or oily matrices and can be formulated to par- ticular necessities in terms of stickyness, moisture retention or aging characteristics.

The bait employed in the composition is a product, which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it. The attractiveness can be manipulated by using feeding stimulants or sex pheromones. Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature 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.

The compounds of the present invention and their 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 formula I 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, nonwov- ens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder. Suitable repellents for example are Ν,Ν-Diethyl-meta-toluamide (DEET), Ν,Ν-diethylphenylacetamide (DEPA), 1 - (3-cyclohexan-1-yl-carbonyl)-2-methylpiperine, (2-hydroxymethylcyclohexyl) acetic acid lactone, 2-ethyl-1 ,3-hexandiol, indalone, Methylneodecanamide (MNDA), a pyrethroid not used for insect control such as {(+/-)-3-allyl-2-methyl-4-oxocyclopent-2-(+)-enyl-(+)- trans-chrysantemate (Esbiothrin), a repellent derived from or identical with plant extracts like limonene, eugenol, (+)-Eucamalol (1 ), (-)-l-epi-eucamalol or crude plant extracts from plants like Eucalyptus maculata, Vitex rotundifolia, Cymbopogan martinii, Cymbopogan citratus (lemon grass), Cymopogan nartdus (citronella). Suitable binders are selected for example from polymers and copolymers of vinyl esters of aliphatic acids (such as such as vinyl acetate and vinyl versatate), acrylic and methacrylic esters of alcohols, such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate, mono- and di-ethylenically unsaturated hydrocarbons, such as styrene, and aliphatic diens, such as butadiene.

The impregnation of curtains and bednets is done in general by dipping the textile material into emulsions or dispersions of the insecticide or spraying them onto the nets.

The compounds of the present invention and their compositions can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, 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). The compounds of formula I are applied not only to the surrounding soil surface or into the under-floor soil in order to pro- tect wooden materials but it can also be applied to lumbered articles such as surfaces of the under-floor concrete, alcove posts, beams, plywoods, furniture, etc., wooden articles such as particle boards, half boards, etc. and vinyl articles such as coated electric wires, vinyl sheets, heat insulating material such as styrene foams, etc. In case of application against ants doing harm to crops or human beings, the ant controller of the present invention is applied to the crops or the surrounding soil, or is directly applied to the nest of ants or the like.

The compounds of the present invention are also suitable for the treatment of seeds in order to protect the seed from insect pest, in particular from soil-living insect pests and the resulting plant's roots and shoots against soil pests and foliar insects.

The compounds of the present invention are particularly useful for the protection of the seed from soil pests and the resulting plant's roots and shoots against soil pests and foliar insects. The protection of the resulting plant's roots and shoots is preferred. More preferred is the protection of resulting plant's shoots from piercing and sucking insects, wherein the protection from aphids is most preferred.

The present invention therefore comprises a method for the protection of seeds from insects, in particular from soil insects and of the seedlings' roots and shoots from insects, in particular from soil and foliar insects, said method comprising contacting the seeds before sowing and/or after pregermination with a compound of the general for- mula I or II or a salt thereof. Particularly preferred is a method, wherein the plant's roots and shoots are protected, more preferably a method, wherein the plants shoots are protected form piercing and sucking insects, most preferably aa method, wherein the plants shoots are protected from aphids. 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.

The term seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.

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 ingredi- ent 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 seed of cereals, root crops, oil crops, vegetables, spices, ornamen- tals, for example seed of durum and other wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn), soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias, geranium/pelargoniums, pansies and impatiens.

In addition, the active compound may also be used for the treatment seeds from plants, which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods.

For example, the active compound can be employed in treatment of seeds from plants, which are resistant to herbicides from the group consisting of the sulfonylureas, imida- zolinones, glufosinate-ammonium or glyphosate-isopropylammonium and analogous active substances (see for example, EP-A 242 236, EP-A 242 246) (WO 92/00377) (EP-A 257 993, U.S. Pat. No. 5,013,659) or in transgenic crop plants, for example cot- ton, with the capability of producing Bacillus thuringiensis toxins (Bt toxins) which make the plants resistant to certain pests (EP-A 142 924, EP-A 193 259),

Furthermore, the active compound can be used also for the treatment of seeds from plants, which have modified characteristics in comparison with existing plants consist, which can be generated for example by traditional breeding methods and/or the gen- eration of mutants, or by recombinant procedures). For example, a number of cases have been described of recombinant modifications of crop plants for the purpose of modifying the starch synthesized in the plants (e.g. WO 92/11376, WO 92/14827, WO 91/19806) or of transgenic crop plants having a modified fatty acid composition (WO 91/13972).

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. Compositions which are especially useful for seed treatment are e.g.:

A Soluble concentrates (SL, LS) D Emulsions (EW, EO, ES)

E Suspensions (SC, OD, FS)

F Water-dispersible granules and water-soluble granules (WG, SG)

G Water-dispersible powders and water-soluble powders (WP, SP, WS)

H Gel-Formulations (GF)

I Dustable powders (DP, DS)

Conventional seed treatment formulations include for example flowable concentrates FS, solutions LS, powders for dry treatment DS, water dispersible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel for- mulation 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

In a preferred embodiment a FS formulation is used for seed treatment. Typcially, 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 compounds of formula I 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.

Seed Treatment formulations may additionally also comprise binders and optionally colorants.

Binders can be added to improve the adhesion of the active materials on the seeds after treatment. Suitable binders are homo- and copolymers from alkylene oxides like ethylene oxide or propylene oxide, polyvinylacetate, polyvinylalcohols, polyvinylpyrrolidones, and copolymers thereof, ethylene-vinyl acetate copolymers, acrylic homo- and copolymers, polyethyleneamines, polyethyleneamides and polyethyleneimines, polysaccharides like celluloses, tylose and starch, polyolefin homo- and copolymers like olefin/maleic anhydride copolymers, polyurethanes, polyesters, polystyrene homo and copolymers

Optionally, also colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 1 12, C.I. Solvent Red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 1 12, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.

Example of a gelling agent is carrageen (Satiagel^®).

In the treatment of seed, the application rates of the compounds I 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.

The invention therefore also relates to seed comprising a compound of the formula I, or an agriculturally useful salt of I, as defined herein. The amount of the compound I 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 or the veterinarily acceptable salts thereof are in particular also suitable for being used for combating parasites in and on animals. An object of the present invention is therfore also to provide new methods to control parasites in and on animals. Another object of the invention is to provide safer pesticides for animals. Another object of the invention is further to provide pesticides for animals that may be used in lower doses than existing pesticides. And another object of the invention is to provide pesticides for animals, which provide a long residual control of the parasites.

The invention also relates to compositions containing a parasiticidally effective amount of compounds of formula I or the enantiomers or veterinarily acceptable salts thereof and an acceptable carrier, for combating parasites in and on animals.

The present invention also provides a method for treating, controlling, preventing and protecting animals against infestation and infection 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 or the veterinarily acceptable salts thereof or a composition comprising it.

The present invention also provides a non-therapeutic method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises applying to a locus a parasiticidally effective amount of a compound of formula I or the enantiomers or veterinarily acceptable salts thereof or a composition comprising it.

The invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises including a parasiticidally effective amount of a compound of formula I or the enantiomers or veterinarily acceptable salts thereof in a composition comprising it.

The invention relates further to the use of compounds of the present invention for treating, controlling, preventing or protecting animals against infestation or infection by parasites. The invention relates also to the use of a compound of the present invention, or a composition comprising it, for the manufacture of a medicament for the therapeutic treatment of animals against infections or infestions by parasites.

Activity of compounds against agricultural pests does not suggest their suitability for control of endo- and ectoparasites in and on animals which requires, for example, low, non-emetic dosages in the case of oral application, metabolic compatibility with the animal, low toxicity, and a safe handling.

Surprisingly it has now been found that compounds of the present invention are suitable for combating endo- and ectoparasites in and on animals. The compounds of formula I or the enantiomers or veterinarily acceptable salts thereof and compositions comprising them are suitable for systemic and/or non-systemic control of ecto- and/or endoparasites. They are active against all or some stages of development.

Compounds of the present invention or veterinarily acceptable salts thereof and compositions comprising them are preferably used for controlling and preventing infes- tations and infections animals including warm-blooded animals (including humans) and fish. They are for example suitable for controlling and preventing infestations and infections in mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, 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.

Compounds of the present invention or veterinarily acceptable salts thereof and compositions comprising them are preferably used for controlling and preventing infestations and infections in domestic animals, such as dogs or cats.

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, chiggers, gnats, mosquitoes and fleas.

The compounds of the present invention are especially useful for combating ectoparasites.

The compounds of the present invention are especially useful for combating endoparasites.

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 canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,

cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Pe- riplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuliggi- nosa, Periplaneta australasiae, and Blatta orientalis,

flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albi- manus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Chrysomya bezziana, Chry- somya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Cu- liseta inornata, Culiseta melanura, Dermatobia hominis, Fannia canicularis, Gastero- philus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Leptoconops torrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia spp., Musca domestica, Muscina stabulans, Oestrus ovis, Phle- botomus argentipes, Psorophora columbiae, Psorophora discolor, Prosimulium mixtum, Sarcophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis,

lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovi- cola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus. ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor ander- soni, Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum, Orni- thodorus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Orni- thonyssus bacoti and Dermanyssus gallinae,

Actinedida (Prostigmata) und Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., and Laminosioptes spp, Bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduvius senilis, Tria- toma spp., Rhodnius ssp., Panstrongylus ssp. and Arilus critatus,

Anoplurida, e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp,

Mallophagida (suborders Arnblycerina and Ischnocerina), e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Trichodectes spp., and Felicola spp,

Roundworms Nematoda:

Wipeworms and Trichinosis (Trichosyringida), e.g. Trichinellidae (Trichinella spp.), (Trichuridae) Trichuris spp., Capillaria spp,

Rhabditida, e.g. Rhabditis spp, Strongyloides spp., Helicephalobus spp,

Strongylida, e.g. Strongylus spp., Ancylostoma spp., Necator americanus,

Bunostomum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus., Os- tertagia spp. , Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oesophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stephanurus dentatus , Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globo- cephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongy- lus spp., Angiostrongylus spp., Parelaphostrongylus spp. Aleurostrongylus abstrusus, and Dioctophyma renale, Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, As- caridia 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., Dirofi- lari spp. a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Hab- ronema spp.,

Thorny headed worms (Acanthocephala), e.g. Acanthocephalus spp., Macracantho- rhynchus hirudinaceus and Oncicola spp,

Planarians (Plathelminthes):

Flukes (Trematoda), e.g. Faciola spp., Fascioloides magna, Paragonimus spp., Di- crocoelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobil- harzia spp., Alaria alata, Paragonimus spp., and Nanocyetes spp,

Cercomeromorpha, in particular Cestoda (Tapeworms), e.g. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium caninum, Multiceps spp., Hymenolepis spp., Mesocestoides spp., Vampirolepis spp., Moniezia spp., Anoplocephala spp., Sirometra spp., Anoplocephala spp., and Hymenolepis spp.

The present invention relates to the therapeutic and the non-therapeutic use of compounds of the present invention for controlling and/or combating parasites in and/or on animals.

The compounds of the present invention may be used to protect the animals from attack or infestation by parasites by contacting them with a parasitically effective amount of compounds of the present invention. As such, "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 contact (applying the compounds/compositions to the locus of the parasite). The contact of the parasite through application to its locus is an example of a non-therapeutic use of compounds of formula I.

"Locus" as defined above means the habitat, food supply, breeding ground, area, material or environment in which a parasite is growing or may grow outside of the animal. The compounds of the invention can also be applied preventively to places at which occurrence of the pests or parasites is expected.

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). The administration can be carried out prophylactically, therapeutically or non- therapeutically.

Administration of the active compounds is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally.

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 formula I 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 compounds the present invention may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and cap- sules. 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 active compound, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.

Alternatively, the compounds the present invention may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The compounds the present invention may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the compounds the present invention may be formulated into an implant for subcutaneous administration. In addition the compound the present invention may be transdermal^ ad- ministered to animals. For parenteral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the active compound.

The compounds the present invention 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 compound the present invention. In addition, the compounds the present invention 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 ingredients such as acids, bases, buffer salts, preservatives, and solubilizers. The solutions are filtered and filled sterile. Suitable solvents are physiologically tolerable solvents such as water, alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycols, N- methyl-pyrrolidone, 2-pyrrolidone, and mixtures thereof.

The active compounds can optionally be dissolved in physiologically tolerable vege- table or synthetic oils which are suitable for injection.

Suitable solubilizers are solvents which promote the dissolution of the active compound in the main solvent or prevent its precipitation. Examples are polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan ester.

Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid esters, and n-butanol.

Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the use concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being necessary.

Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on.

Solutions for use on the skin are prepared according to the state of the art and according to what is described above for injection solutions, sterile procedures not being necessary.

Further suitable solvents are polypropylene glycol, phenyl ethanol, phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate, ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether, ketons such as acetone, methyl- ethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylformamide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof.

It may be advantageous to add thickeners during preparation. Suitable thickeners are inorganic thickeners such as bentonites, colloidal silicic acid, aluminium mono- stearate, organic thickeners such as cellulose derivatives, polyvinyl alcohols and their copolymers, acrylates and methacrylates.

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 ointmentlike consistency results. The thickeners employed are the thickeners given above. 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 solvents which are: water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyethanol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as alkylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, di- ethylene glycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone, cyclic carbonates such as propylene carbonate, ethylene carbonate, aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, n-alkylpyrrolidones such as methylpyrrolidone, n-butylpyrrolidone or n-octylpyrrolidone, N-methylpyrroli- done, 2-pyrrolidone, 2,2-dimethyl-4-oxy-methylene-1 ,3-diox- olane and glycerol formal.

Suitable colorants are all colorants permitted for use on animals and which can be dissolved or suspended.

Suitable absorption-promoting substances are, for example, DMSO, spreading oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils and copoly- mers thereof with polyethers, fatty acid esters, triglycerides, fatty alcohols.

Suitable antioxidants are sulfites or metabisulfites such as potassium metabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole, tocopherol.

Suitable light stabilizers are, for example, novantisolic acid.

Suitable adhesives are, for example, cellulose derivatives, starch derivatives, poly- acrylates, natural polymers such as alginates, gelatin.

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) are:

liquid paraffins, silicone oils, natural vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides such as caprylic/capric biglyceride, triglyceride mixture with vegetable fatty acids of the chain length C8-C12 or other specially selected natural fatty acids, partial glyceride mixtures of saturated or unsaturated fatty acids possibly also containing hydroxyl groups, mono- and diglycerides of the Cs-Cio fatty acids, fatty acid esters such as ethyl stearate, di-n-butyryl adipate, hexyl laurate, dipropyl- ene glycol perlargonate, esters of a branched fatty acid of medium chain length with saturated fatty alcohols of chain length C16-C18, isopropyl myristate, isopropyl palmitate, caprylic/capric acid esters of saturated fatty alcohols of chain length C12-C18, isopropyl stearate, oleyl oleate, decyl oleate, ethyl oleate, ethyl lactate, waxy fatty acid esters such as synthetic duck coccygeal gland fat, dibutyl phthalate, diisopropyl adipate, and ester mixtures related to the latter, fatty alcohols such as isotridecyl alcohol, 2-octyl- dodecanol, cetylstearyl alcohol, oleyl alcohol, and fatty acids such as oleic acid and mixtures thereof.

Suitable hydrophilic phases are: water, alcohols such as propylene glycol, glycerol, sorbitol and mixtures thereof.

Suitable emulsifiers are:

non-ionic surfactants, e.g. polyethoxylated castor oil, polyethoxylated sorbitan monooleate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, al- kylphenol polyglycol ether; ampholytic surfactants such as di-sodium N-lauryl-p-iminodipropionate or lecithin; anionic surfactants, such as sodium lauryl sulfate, fatty alcohol ether sulfates, mono/dialkyl polyglycol ether orthophosphoric acid ester monoethanolamine salt; cation-active surfactants, such as cetyltrimethylammonium chloride.

Suitable further auxiliaries are: substances which enhance the viscosity and stabilize the emulsion, such as carboxymethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, waxes, colloidal silicic acid or mixtures of the substances mentioned.

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.

Liquid suspending agents are all homogeneous solvents and solvent mixtures. Suitable wetting agents (dispersants) are the emulsifiers given above.

Other auxiliaries which may be mentioned are those given above.

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 excipients, if appropriate with addition of auxiliaries, and brought into the desired form. Suitable excipients are all physiologically tolerable solid inert substances. Those used are inorganic and organic substances. Inorganic substances are, for example, sodium chloride, carbonates such as calcium carbonate, hydrogencarbonates, aluminium oxides, titanium oxide, silicic acids, argillaceous earths, precipitated or colloidal silica, or phosphates. Organic substances are, for example, sugar, cellulose, foodstuffs and feeds such as milk powder, animal meal, grain meals and shreds, starches.

Suitable auxiliaries are preservatives, antioxidants, and/or colorants which have been mentioned above.

Other suitable auxiliaries are lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose.

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 ec- toparasites 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 the present invention 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.

The compositions comprising the compounds of the present invention them can be applied orally, parenterally or topically, respectively dermally. For example, optionally the topical application is conducted in the form of compound-containing shaped articles such as collars, 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 formula I 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.

For the preparation of the shaped articles, thermoplastic and flexible plastics as well as elastomers and thermoplastic elastomers are used. Suitable plastics and elastomers are polyvinyl resins, polyurethane, polyacrylate, epoxy resins, cellulose, cellulose de- rivatives, polyamides and polyester which are sufficiently compatible with the compounds of the present invention. A detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in WO 03/086075.

The active compounds can also be used as a mixture with synergists or with other active compounds which act against pathogenic endo- and ectoparasites.

The active compounds can be applied solely or in a mixture with synergists or with other active compounds which act against pathogenic endo- and ectoparasites.

For example, the active compounds of the present invention can be applied in mixtures with synthetic coccidiosis compounds, polyetherantibiotics as Amprolium, Ro- benidin, Toltrazuril, Monensin, Salinomycin, Maduramicin, Lasalocid, Narasin or Sem- duramicin or with other pesticides which are described in the list M above.

Examples

The present invention is now illustrated in further details by the following examples.

S.1. Preparation of methyl 3-(3-hydroxypyridin-2-yl)-3-oxo-2-(2-trifluoromethyl- phenyl)propionate [1-1]

Step 1 : Methyl 3-(4-methoxybenzyloxy)pyridine-2-carboxylate

4 g of NaH were added to a solution of 15.2 g of methyl 3-hydroxypyridine-2-carb- oxylate in 200 ml of dimethyl formamide (DMF) and the mixture was stirred at 20-25°C for 30 min. 15.4 g of para-methoxybenzyl chloride were then added. The mixture was stirred at 40°C for about 15 hours and then added to water. After extraction with ethyl acetate, phase separation and washing of the combined organic phases with water and saturated NaCI solution followed by drying and removal of the solvent, the residue was subjected to column chromatography. This gave 20 g of the title compound as a yellow oil.

Step 2: 3-(4-Methoxybenzyloxy)pyridine-2-carboxylic acid

A solution of 7 g of the ester from step 1 and 2.2 g of LiOH in 60 ml of methanol and 40 ml of water was stirrred at 20-25°C for about 15 hours. 100 ml of water and 7 ml of acetic acid were then added. The mixture was extracted with ethyl acetate. The combined organic phases were dried and freed from the solvent. This gave 5 g of the title compound as a yellowish solid.

Step 3: Pentafluorophenyl 3-(4-methoxybenzyloxy)pyridine-2-carboxylate 2.4 g of Ν,Ν'-diisopropylcarbodiimide were added dropwise to a solution of 5 g of the acid from step 2 and 3.5 g of pentafluorophenol in 100 ml of CH2CI2. The mixture was stirred at 20-25°C for about 1 hour, then washed with saturated NaCI solution and dried under reduced pressure. Purification of the residue by column chromatography (petroleum ether: ethyl acetate 5:1 ) gave 4.6 g of the title compound.

Step 4: Methyl 3-[3-(4-methoxybenzyloxy)pyridin-2-yl]-3-oxo-2-(2-trifluoromethyl- phenyl)propionate

0.74 g of potassium tert-butoxide was added to a solution of 1.2 g of the ester from step 3 in 10 ml DMF. The mixture was stirred at 20-25°C for about 30 min. A solution of 2.25 g of methyl (2-trifluoromethylphenyl)acetate in 5 ml of DMF was then added. After 30 min of stirring at 20-25°C, the reaction was ended by addition of saturated NH4CI solution. The mixture was extracted with ethyl acetate. The combined organic phases were washed with saturated NaCI solution and then dried and freed from the solvent. Purification of the residue by column chromatography (petroleum ether: ethyl acetate 5:1) gave 0.23 g of the title compound.

Step 5: Methyl 3-(3-hydroxypyridin-2-yl)-3-oxo-2-(2- trifluoromethylphenyl)propionate

At 0°C, 1 ml of trifluoroacetic acid was added to 160 mg of the ester from step 4, and the reaction mixture was stirred at 0°C for 20 min. Saturated NaHCOa solution was then added. Extraction with ethyl acetate, removal of the solvent under reduced pressure and preparative HPLC gave 83 mg of the title compound.

Characterization by ¹H NMR (CDCI₃): δ 1 1.05 (brs, 1 H); 8.26-8.24 (m, 1 H); 7.73 (d, 1 H); 7.61-7.58 (m, 2H); 7.48-7.34 (m, 3H); 6.64 (s, 1 H); 3.76 (s, 3H). S.2. Preparation of methyl 3-(3-mercaptopyridin-2-yl)-3-oxo-2-(2- trifluoromethylphenyl)propionate [I-3]

Step 1 : Methyl 3-(4-methoxy-benzylsulfanyl)-pyridine-2-carboxylate

3.18 g of (4-methoxy-phenyl)-methanethiol were dissolved in 40 ml_ of DMSO and treated with 1 .65 g NaH under nitrogen-atmosphere at 0 °C. The mixture was stirred at reflux for 2 h and subsequently a solution of 4.06 g methyl 3-bromo-pyridine-2-carb- oxylate in DMSO was added. The mixture was stirred at 90 °C overnight and allowed to cool down to r.t. afterwards. Aqueous NaCI-solution was then added and the mixture was extracted with EtOAc. The combined organic phases were dried with anhydrous Na2S04 and concentrated under reduced pressure to give 1.7 g of the title compound. Step 2: 3-(4-Methoxy-benzylsulfanyl)-pyridine-2-carboxylic acid

0.58 mg of the ester from step 1 were dissolved in a 1 :1-mixture of methanol and water and 0.17 g LiOH were added. The mixture was stirred at r.t. for 4 h and the organic solvent was evaporated afterwards. The remaining aqueous phase was acidified to pH 5-6 with hydrochloric acid and extracted with EtOAc. The combined organic phases were dried with Na2S04. Evaporation of the solvent under reduced pressure gave 0.5 g of the title compound.

Step 3: Methyl 3-[3-(4-methoxy-benzylsulfanyl)-pyridin-2-yl]-3-oxo-2-(2-trifluoro- methyl-phenyl)-propionate

0.76 g of methyl (2-trifluoromethyl-phenyl)-acetate were dissolved in 30 ml_ of DMF, followed by the the addition of 0.94 g CDI. After the mixture was stirred at r.t. for 1 h, 0.80 g of the carboxylic acid from step 2 and 0.47 g NaH were added and stirring was continued for 2 h. Then the reaction mixture was quenched with saturated N H4CI- solution and extracted with EtOAc. The combined organic phases were washed with EtOAc, washed with saturated NaCI-solution, dried with anhydrous Na2SC>4 and concentrated under reduced pressure. The crude material thus obtained was purified by column-chromatography on silica to give 0.60 g of the title compound.

Step 4: Methyl 3-(3-mercaptopyridin-2-yl)-3-oxo-2-(2-trifluoromethylphenyl)propio- nate [l-3]

To a solution of 0.20 g of the product from step 3 in 10 ml. of CH2CI2 10 mL TFA were added. The mixture was cooled to 0 °C and 0.51 g CF3SO3H were added drop- wise. After 20 min the purple-colored mixture was partitioned between ice-water and CH2CI2. The aqueous phase was extracted with CH2CI2 and the combined organic phases were washed with saturated NaCI-solution, dried with Na2S04 and concentrated under reduced pressure. The resulting crude product was purified by preparative HPLC to give 60 mg of the title compound.

S.3. Preparation of methyl 3-oxo-3-[3-(2,2,2-trifluoro-ethylamino)-pyridin-2-yl]-2- (2-trifluoromethyl-phenyl)-propionate [I-8]

Step 1 : N-(2-Chloro-pyridin-3-yl)-2,2,2-trifluoro-acetamide

To a solution of 10 g 2-chloro-pyridin-3-ylamine in 150 mL CH2CI2 was added 16.3 g trifluoroacetic anhydride over a period of 20 min and the mixture was stirred for 2 h. The reaction mixture was then quenched with saturated aqueous NaHCC -solution and extracted with CH2CI2. The combined organic phases were washed with saturated NaCI-solution, dried with Na2SC>4 and concentrated under reduced pressure to give 16 g of the title compound.

Step 2: 2-Chloro-pyridin-3-ylamine

3.4 g IJAIH4 was added portionwise to a solution of 10 g of the amide from step 1 at 0 °C under nitrogen-atmosphere. After 10 min at 0 °C the reaction mixture was allowed to reach r.t. and stirring was continued for 6 h. The mixture was quenched with water at 0 °C and extracted with CH2CI2. The aqueous phase was was washed with saturated NaCI-solution, dried with Na2SC>4 and concentrated under reduced pressure. The crude product was purified by column-chromatography on silica (petroleum ether: ethyl ace- tate 10:1 ) to give 6.4 g of the title compound.

Step 3: Methyl 3-(2,2,2-trifluoro-ethylamino)-pyridine-2-carboxylate

2.0 g PdCl2(dppf)2 was added to a solution of 6.4 g of the chloride from step 2 and 6.2 g ΝΕΪ3 in 80 mL MeOH and 160 mL toluene under nitrogen-atmosphere. The mix- ture was heated to 80 °C under a CO-atmosphere (50 psi) for 12 h. Then the mixture was filtrated and the solvent was evaporated unter reduced pressure. The residue was purified by column-chromatography on silica (petroleum ether: ethyl acetate 1 :1 ) to give 5.8 g of the title compound.

Step 4: 3-(2,2,2-Trifluoro-ethylamino)-pyridine-2-carboxylic acid

4.68 g methyl 3-(2,2,2-trifluoro-ethylamino)-pyridine-2-carboxylate were dissolved in a 1 :1 -mixture of methanol and water and 1.72 g LiOH were added. The mixture was stirred at r.t. for 4 h and the organic solvent was evaporated afterwards. The remaining aqueous phase was acidified to pH 5-6 with hydrochloric acid and extracted with EtOAc. The combined organic phases were dried with Na2S0₄. Evaporation of the solvent under reduced pressure gave 3.7 g of the title compound.

Step 5: Methyl 3-oxo-3-[3-(2,2,2-trifluoro-ethylamino)-pyridin-2-yl]-2-(2-trifluoro- methyl-phenyl)-propionate [I-8]

2.20 g of methyl (2-trifluoromethyl-phenyl)-acetate were dissolved in 20 ml_ of DMF, followed by the the addition of 1.94 g CDI. After the mixture was stirred at r.t. for 1 h, 2.60 g of the carboxylic acid from step 4 and 0.80 g NaH were added and stirring was continued for 2 h. Then the reaction mixture was quenched with saturated NH4CI- solution and extracted with EtOAc. The combined organic phases were washed with EtOAc, washed with saturated NaCI-solution, dried with anhydrous Na2S04 and con- centrated under reduced pressure. The crude material thus obtained was purified by column-chromatography on silica to give 0.30 g of the title compound.

Compounds of the present invention are listed in the following table C.1 with their physical data and illustrate examples without imposing any limitation.

The compounds were characterized by ¹H-NMR spectroscopy or HPLC (High Performance Liquid Chromatography Mass Spectrometry). HPLC was carried out using an analytic RP-18 column (Chromolith Speed ROD from Merck KgaA, Germany) which was operated at 40°C. Acetonitrile with 0.1 % by volume of a trifluoroacetic acid/water mixture and 0.1 % by volume of trifluoroacetic acid served as mobile phase; flow rate: 1.8 mL/min and injection volume: 2 μΙ.

¹H-NMR: The signals are characterized by chemical shift (ppm) vs. tetramethylsi- lane, by their multiplicity and by their integral (relative number of hydrogen atoms given). The following abbreviations are used to characterize the multiplicity of the signals: m = multiplett, q = quartett, t = triplett, d = doublet and s = singulett.

Table d

¹> Phys. Data: M = CD₃OD; C = CDC ; D = DMSO-de

B. Biological examples The pesticidal activity can be demonstrated in the following biological test examples.

B.1 Activity against Cotton aphid (Aphis gossypii, mixed life stages)

The active compounds were formulated in cyclohexanone as a 10,0000 ppm solution supplied in 1.3 ml ABgene® tubes. These tubes were inserted into an automated elec-trostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone:50% water (v/v). A nonionic sur-factant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v).

Cotton plants at the cotyledon stage were infested with aphids prior to treatment by placing a heavily infested leaf from the main aphid colony on top of each cotyledon. Aphids were allowed to transfer overnight to accomplish an infestation of 80-100 aphids per plant and the host leaf was removed. The infested plants were then sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood, removed from the sprayer, and then maintained in a growth room under fluorescent lighting in a 24-hr photoperiod at 25°C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on untreated control plants, was determined after 5 days.

In this test, the compounds I-2 and I-7 of table C.1 at 500 ppm showed a mortality of at least 50% in comparison with untreated controls. B.2 Activity against Green Peach Aphid (Myzus persicae, mixed life stages) The active compounds were formulated in cyclohexanone as a 10,0000 ppm solution supplied in 1.3 ml ABgene® tubes. These tubes were inserted into an automated elec-trostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone:50% water (v/v). A nonionic sur-factant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v).

Bell pepper plants at the first true-leaf stage were infested prior to treatment by placing heavily infested leaves from the main colony on top of the treatment plants. Aphids were allowed to transfer overnight to accomplish an infestation of 30-50 aphids per plant and the host leaves were removed. The infested plants were then sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood, removed, and then maintained in a growth room under fluorescent lighting in a 24-hr photoperiod at 25°C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on untreated control plants, was determined after 5 days.

In this test, the compound 1-7 of table C.1 at 500 ppm showed a mortality of at least 50% in comparison with untreated controls.

B.3 Activity against Silverleaf Whitefly (Bemisia argentifolii, adult)

The active compounds were formulated in cyclohexanone as a 10,0000 ppm solu- tion supplied in 1.3 ml ABgene® tubes. These tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 50% acetone:50% water (v/v). A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v). Cotton plants at the cotyledon stage (one plant per pot) were sprayed by an automated elec- trostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer. Each pot was placed into a plastic cup and 10 to 12 whitefly adults (approximately 3-5 days old) were introduced. The insects were collected using an aspirator and 0.6 cm, nontoxic Tygon® tubing (R-3603) connected to a barrier pipette tip. The tip, containing the collected insects, was then gently inserted into the soil containing the treated plant, allowing insects to crawl out of the tip to reach the foliage for feeding. Cups were covered with a reusable screened lid (150-micron mesh polyester screen PeCap from Tetko, Inc.). Test plants were maintained in a growth room at 25°C and 20-40% relative humidity for 3 days, avoiding direct exposure to fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the cup. Mortality was assessed 3 days after treatment, compared to untreated control plants.

In this test compounds I-2 and I-7 of table C.1 at 500 ppm showed a mortality of at least 50% in comparison with untreated controls. B.4 Activity against Cowpea Aphid (Aphis craccivora)

The active compounds were formulated in 50:50 (vol:vol) acetone:water. The test solution was prepared at the day of use.

Potted cowpea plants colonized with 100 - 150 aphids of various stages were sprayed after the pest population had been recorded. Population reduction was as- sessed after 24, 72, and 120 hours.

In this test, the compound I-7 of table C.1 at 500 ppm showed a mortality of at least 50 % in comparison with untreated controls.

B.5 Activity against Diamond back moth (Plutella xylostella)

The active compounds were formulated in 50:50 acetone:water and 0.1 % (vol/vol) Alkamuls EL 620 surfactant. A 6 cm leaf disk of cabbage leaves was dipped in the test solution for 3 seconds and allowed to air dry in a Petri plate lined with moist filter paper. The leaf disk was inoculated with 10 third instar larvae and kept at 25-27°C and 50- 60% humidity for 3 days. Mortality was assessed after 72 h of treatment.

In this test, the compounds I-8, I-9 and 1-10 of table C.1 at 500 ppm showed a mortality of at least 50% in comparison with untreated controls.

B.6 Activity against Orchid thrips (Dichromothrips corbetti)

The active compounds were formulated as a 50:50 (vohvol) acetone:water solution. Surfactant (Alkamuls EL 620) was added at the rate of 0.1 % (vol/vol). Vanda orchids petals were cleaned, washed and air dried prior to spraying. Petals were dipped into the test solution for 3 seconds, air dried, placed inside a resealable plastic and inoculated with 20 adults. The treated petals were kept inside the holding room at 28-29 °C and relative humidity of 50-60%. Percent mortality was recorded after 72 hours.

In this test the compounds I-2 and I-6 of table C.1 at 500 ppm showed a mortality of at least 50% in comparison with untreated controls.

B.7 Rice plant hopper (Nilaparvata lugens)

Rice seedlings were cleaned and washed 24 hours before spraying. The active corn-pounds were formulated in 50:50 acetone:water and 0.1 % vol/vol surfactant (EL 620) was added. Potted rice seedlings were sprayed with 5 ml test solution, air dried, placed in cages and inoculated with 10 adults. Treated rice plants were kept at 28-29°C and relative humidity of 50-60%. Percent mortality was recorded after 72 hours.

In this test compounds I-2, I-6 and I-7 of table C.1 at 500 ppm showed a mortality of at least 50% in comparison with untreated controls. B.8 Rice green leafhopper (Nephotettix virescens)

Rice seedlings were cleaned and washed 24 hours before spraying. The active corn-pounds were formulated in 50:50 acetone:water, and 0.1 % vol/vol surfactant (EL 620) was added. Potted rice seedlings were sprayed with 5 ml test solution, air dried, placed in cages and inoculated with 10 adults. Treated rice plants were kept at 28-29°C and relative humidity of 50-60%. Percent mortality was recorded after 72 hours.

In this test compounds I-2, I-6 and I-7 of table C.1 at 500 ppm showed a mortality of at least 50% in comparison with untreated controls.

B.9 Activity against Vetch aphid (Megoura viciae)

The active compounds were formulated in 1 :3 (vohvol) DMSO : water with different concentrations of formulated compounds. Bean leaf disks were placed into microtiter- plates filled with 0.8% agar-agar and 2.5 ppm OPUS™. The leaf disks were sprayed with 2.5 μΙ of the test solution and 5 to 8 adult aphids were placed into the microtiter- plates which were then closed and kept at 23 ± 1 °C and 50 ± 5% relative humidity un- der fluorescent light for 6 days. Mortality was assessed on the basis of vital, reproduced aphids. Aphid mortality and fecundity was then visually assessed.

In this test, the compounds I-2, I-6, I-7 and 1-12 of table C.1 at 2500 ppm showed a mortality of at least 50%. B.10 Activity against Green Peach Aphid (Myzus persicae, mixed life stages) 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 membrane. 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 to 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 I-2, I-6, I-7, 1-10, 1-12, 1-13, 1-14 and 1-15 of table C.1 at 2500 ppm showed a mortality of at least 50%. B.1 1 Activity against Mexican Boll Weevil (Anthonomus grandis)

For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of 24-well-microtiter plates containing an insect diet and 20-30 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 in- sect diet at 20 μΙ, using a custom built micro atomizer, at two replications. After application, microtiter plates were incubated at about 23 + 1 °C and about 50 + 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed.

In this test the compounds 1-17 and 1-18 of table C.1 at 2500 ppm showed a mortality of at least 50%.

Claims

ims:

A method for combating or controlling insects, arachnids or nematodes comprising contacting an insect, arachnid or nematode or their food supply, habitat or breeding grounds with a nitrogen-containing heteroaromatic compound of formula I or a composition comprising at least a compound of formula I:

wherein

A, E, G, M are N or C-R^c, wherein one or two of these groups being N,

R^c is hydrogen or R^a,

R^a is selected independently of one another from the group consisting of Z-CN, Z-OH, Z-NO2, Z-halogen, d-Cs-alkyl, Ci-C4-haloalkyl, C2-Ce-alkenyl, C2-Ce-alkynyl,

Z-d-Cs-alkoxy, Z-d-Cs-haloalkoxy, Z-C3-Cio-cycloalkyl, 0-Z-C₃-Cio-cycloalkyl, Z-C(=0)-R^a2, NR'R", Z-(tri-d-d- alkyl)silyl, Z-phenyl and S(0)_nR^b , n is 0, 1 or 2;

Z is a covalent bond or Ci-C4-alkylene;

R^a2 is d-Ce-alkyl, Ci-d-haloalkyl, Z-d-C₆-alkoxy, Z-d- d-haloalkoxy or NR'R'';

R', R" are selected, independently of one another from hydrogen, d-Cs-alkyl, d-d-haloalkyl, d-Cs-alkenyl, C3-Ce-alkynyl, Z-C3-C6-cycloalkyl, Z-Ci-Ce-alkoxy, Z-d-Cs-haloalkoxy,

R' and R" together with the nitrogen atom to which they are attached may also form a 5- or 6- membered monocyclic or 9- or 10-membered bicyclic heterocycle which may contain, in addition to the nitrogen atom they are bound to, 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S;

R^bb is d-Cs-alkyl or d-C₆-haloalkyl;

R^a together with the group R^a optionally attached to the adjacent carbon atom may also form a five- or six-membered saturated or partially or fully unsaturated ring which, in addition to carbon atoms, may contain 1 , 2 or 3 heteroatoms selected from the group consisting of O, N and S;

W is O or S;

X is O, S or N-R; Y is R¹ or NH-R, wherein

R¹ is OR or SR,

R is selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C4-haloalkyl, C2-C6-alkenyl, C3-C6-alkynyl, Z-C3-Cio-cyclo- alkyl, CrC6-alkoxy-Ci-C6-alkyl, Ci-C6-cyanoalkyl, Z-phenyl, a 5- or 6 membered monocyclic heterocycle attached via Z, which contains 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S and which may be attached via a carbon or a nitrogen atom of the heterocycle and wherein the heterocycle my be fully or partially substitiuted by R^a;

Z-C(=0)-R^a2, Z-S0₂R^a2 and tri-Ci-C₄-alkylsilyl;

and wherein in the group R and its subsubtituents, the carbon chains and/or the (hetero)cyclic groups may be partially or fully substituted by groups R^a;

R² is phenyl, naphthyl or a 5- or 6-membered monocyclic or 9- or 10- membered bicyclic aromatic heterocycle which comprises 1 , 2, 3 or 4 heteroatoms selected from the group consisting of O, N and S, wherein the cyclic groups are unsubstituted or substituted by 1 , 2, 3, 4 or 5 groups R^a; or an N-oxide, enantiomer, diastereomer or an agriculturally or veterinarily suitable salt thereof.

A method for protecting crops and growing plants from attack or infestation by insects, arachnids or nematodes comprising contacting a plant, or soil or water in which the plant is growing, with an nitrogen-containing heteroaromatic compound of formula I or a composition comprising at least such a compound of formula I as defined in claim 1 , or an N-oxide, enantiomer, diastereomer or an agriculturally suitable salt thereof.

3. A method for protecting plant propagation material, especially seeds, from soil insects and seedlings' roots and shoots from soil and foliar insects comprising contacting the plant propagation material, especially the seeds, before sowing and/or after pregermination with at least one nitrogen-containing heteroaromatic compound of formula I or a composition comprising at least such a compound of formula I as defined in claim 1 , or an N-oxide, enantiomer, diastereomer or an ag- riculturally suitable salt thereof.

4. A method for treating, controlling, preventing or protecting animals against infestation or infection by parasites by administering or applying orally, topically or parenterally to the animals a nitrogen-containing heteroaromatic compound of formula I or a composition comprising at least such a compound of formula I as defined in claim 1 , or an N-oxide, enantiomer, diastereomer or veterinarily suitable salt thereof. A method according to any one of claims 1 to 4, characterized in that in formula I A is N; and E, G, M are C-R^c.

A method according to any of claims 1 to 5, characterized in that in formula I

Y is OR, and wherein

R is selected from hydrogen, Ci-C6-alkyl, Ci-C4-haloalkyl, C2-C6-alkenyl, C3-C6-alkynyl, Z-C3-Cio-cycloalkyl, Ci-C6-alkoxy-Ci-C6-alkyl, C1-C6- cyanoalkyl, Z-phenyl, Z-C(=0)-R^a2 or t ri-C i -C₄-a I ky Is i lyl ,

R^a2 is selected from Ci-C6-alkyl, Ci-C4-haloalkyl, Z-Ci-C6-alkoxy, Z-Ci-C₄-haloalkoxy or NR'R", and

R', R" are selected independently of one another from hydrogen, d-Ce-alkyl, Ci-C4-haloalkyl, C3-Ce-alkenyl, C3-Ce-alkynyl, Z-C3-C6-cycloalkyl, Z-Ci-Ce-alkoxy or Z-Ci-Cs-haloalkoxy; in the group R and its subsubtituents, the carbon chains and/or the cyclic groups may be partially or fully substituted by halogen or groups R ^b.

A method according to any of the claims 1 to 5, characterized in that in formula I

Y is SR, and wherein

R is selected from hydrogen, Ci-Cs-alkyl, Ci-C4-haloalkyl, C2-C6-alkenyl, C3-C6-alkynyl, Z-C3-Cio-cycloalkyl, Ci-C6-alkoxy-CrC6-alkyl, CrC6- cyanoalkyl, Z-phenyl, Z-C(=0)-R^a2 or tri-Ci-C₄-alkylsilyl,

R^a2 is selected from Ci-C6-alkyl, Ci-C4-haloalkyl, Z-Ci-C6-alkoxy, Z-Ci-C₄-haloalkoxy or NR'R", and

R', R" are selected independently of one another from hydrogen, d-Cs-alkyl, Ci-C4-haloalkyl, C3-Cs-alkenyl, C3-Cs-alkynyl, Z-C3-C6-cycloalkyl, Z-Ci-Cs-alkoxy or Z-d-Cs-haloalkoxy; in the group R and its subsubtituents, the carbon chains and/or the cyclic groups may be partially or fully substituted by halogen or groups R .

A method according to any of claims 1 to 5, characterized in that in formula I

Y is N H-R, and wherein

R is selected from hydrogen, Ci-C6-alkyl, Ci-C4-haloalkyl, C2-C6-alkenyl, C3-C6-alkynyl, Z-C3-Cio-cycloalkyl, Ci-C6-alkoxy-Ci-C6-alkyl, C1-C6- cyanoalkyl, Z-phenyl, Z-C(=0)-R^a2 or t ri-C i -C₄-a I ky Is i lyl ,

R^a2 is selected from Ci-C6-alkyl, Ci-C4-haloalkyl, Z-Ci-C6-alkoxy,

Z-Ci-C₄-haloalkoxy or NR'R";

in the group R and its subsubtituents, the carbon chains and/or the cyclic groups may be partially or fully substituted by halogen or groups R^bb. A method according to any of claims 1 to 5, characterized in that in formula I

Y is NH-R, and wherein

R is a 5- or 6-membered monocyclic heterocycle attached via Z and selected from the group consisting of pyrimidyl, pyridyl, thienyl, furyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl, oxazolyl, isothiazolyl, isoxa- zolyl, quinolinyl, isoquinolinyl, indolyl, benzofuryl, benzthienyl, ben- zoxazolyl, benzthiazolyl and benzimidazolyl, wherein the heterocycle may be attached via a carbon or a nitrogen atom of the heterocycle and wherein the heterocycle may carry one or more substitutents selected from the group consisting of OH, CN, N02, halogen, C1-C4- alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy or Ci-C4-haloalkoxy.

A method according to any of claims 1 to 9, characterized in that in formula I W is O.

1 1. A method according to any of claims 1 to 10, characterized in that in formula I X is O.

A method according to any of claims 1 to 10, characterized in that in formula X is S.

13. A method according to any of claims 1 to 12, characterized in that the compounds of formula I are

wherein

X, Y, W, R¹ and R^a are as defined for formula I;

R^c2 , R^c3 and R^c4 are as defined for R^c, and

m is 0, 1 , 2, 3 or 4.

A compound of formula I, which is of formula II

wherein X, W are as defined for formula I in claim 1 ;

Y is OR or SR, wherein

R is selected from hydrogen, Ci-C6-alkyl, Ci-C4-haloalkyl, C2-C6-alkenyl, C3-C6-alkynyl, Z-C3-Cio-cycloalkyl, Ci-C6-alkoxy-Ci-C6-alkyl, C1-C6- cyanoalkyi, Z-phenyl, Z-C(=0)-R^a2 or tri-Ci-C4-alkylsilyl, and wherein

R^a2 is selected from Ci-C6-alkyl, Ci-C4-haloalkyl, Z-Ci-C6-alkoxy, Z- Ci-C₄-haloalkoxy or N R'R", and

R\ R" are selected independently of one another from hydrogen, d-Ce-alkyl, Ci-C4-haloalkyl, C3-Ce-alkenyl, C3-Ce-alkynyl, Z-C3-C6-cycloalkyl, Z-Ci-Cs-alkoxy or Z-d-Cs-haloalkoxy; in the group R and its subsubtituents, the carbon chains and/or the cyclic groups may be partially or fully substituted by halogen, Ci-Ce- alkyl or Ci-C6-haloalky;

R¹ is hydroxy or Ci-C6-alkoxy; and

R^c2, R^c3, R^c3, R^a3, R^a4 and R^a5 are selected independently from one another from the group consisting of hydrogen, OH , CN , N0₂, halogen, Ci-C₄-alkyl, Ci-C₄-halo- alkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy; and/or at least an N-oxide, an enantiomer, diastereomer or agriculturally or vet- erinary acceptable salt thereof.

15. A compound of formula I , which is of formula

wherein

X, W are as defined for formula I in claim 1 ;

R¹ is hydroxy or Ci-C6-alkoxy;

R² is phenyl or pyridyl, which may carry one or more substitutents selected from the group consisting of OH , CN , NO2, halogen, C1-C4- alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy;

R^c2, R^c3, R^c4 are selected independently from one another from the group consisting of hydrogen, OH , CN, NO2, halogen, Ci-C4-alkyl, C1-C4- haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy; and

R is a 5- or 6-membered monocyclic heterocycle attached via Z and selected from the group consisting of pyridyl, thiazolyl, isothiazolyl, pyrazolyl, oxazolyl and isoxazolyl, wherein the heterocycle may be attached via a carbon or a nitrogen atom of the heterocycle and which may carry one or more substitutents selected from the group consisting of OH, CN , NO2, halogen, Ci-C4-alkyl, C1-C4- haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy, Z is a covalent bond or Ci-C4-alkylene chain, wherein the carbon chain may optionally carry one or more substituents selected from d-Cs-alkyl or C1-C4- haloalkyl;

and/or at least an N-oxide, an enantiomer, diastereomer or agriculturally or veterinary acceptable salt thereof.

16. An agricultural or verterinary composition comprising at least one nitrogen- containing heteroaromatic compound of formula I, II or III as defined in any of claims 1 or 5 to 15, or the N-oxide, enantiomer, diastereomer or agriculturally or veterinary acceptable salt thereof and at least one inert liquid and/or solid carrier.

17. A method according to claim 4 which comprises orally, topically or parenterally administering or applying to the animals a nitrogen-containing heteroaromatic compound of formula I, II or III or the N-oxide, enantiomer, diastereomer or veterinary acceptable salt thereof as defined in any one of claims 4 to 15.

18. A method according to claim 3, wherein the nitrogen-containing heteroaromatic compound of the formula I, II or III or its N-oxide, enantiomer diastereomer or ag- riculturally acceptable salt as defined in any of claims 3 or 5 to 15 is applied in an amount of from 100 mg to 10 kg per 100 kg of seeds.

19. A method according to claim 3, wherein of the resulting plant's roots and shoots are protected.

20. Seed comprising a nitrogen-containing heteroaromatic compound of formula I, II or III, or its N-oxide, enantiomer, diastereomer or agriculturally useful salt as defined in any of claims 3 or 5 to 15 in an amount of from 0.1 g to 10 kg per 100 kg of seed.

21. Use of a nitrogen-containing heteroaromatic compound of formula I, II or III as defined in any one of claims 4 to 15 for the preparation of an orally, topically or parenterally applicable or administrable veterinary medicament for treating, controlling, preventing or protecting animals against infestation or infection by para- sites.