Amidrazone Compounds for Combating Animal Pests

The present invention relates to new amidrazone compounds which are useful for combating animal pests, in particular insects, arachnids and nematodes. The invention also relates to a method for combating insects, nematodes and arachnids.

In spite of commercial pesticides available today, damage to crops, both growing and harvested, the damage of non-living material, in particular cellulose based materials such as wood or paper, caused by animal pests still occur. Therefore, there is continu- ing need to provide compounds which are useful for combating insects, nematodes and arachnids.

EP-A 604798 discloses inter alia compounds of the general formula

wherein n is 0, 1 or 2, W, B and A are each independently N or C-R ^a , Y and R ^a independently of each other are inter alia hydrogen, halogen, CN, NO ₂ , alkyl, haloalkyl, alkoxy or haloalkoxy, R ^x and R ^y , independently of each other are inter alia hydrogen or a C-bound radical such as optionally substituted alkyl, alkenyl, alkinyl or cycloalkyl, and R ^z is inter alia hydrogen, optionally substituted alkyl, cycloalkyl or phenyl. However, the activity of these compounds against the aforementioned pests is not always satisfactory.

It is an object of the present invention to provide further compounds having a good activity against insects, nematodes and/or arachnids and thus are useful for combating said pests.

The inventors of the present application surprisingly found that this object is achieved by compounds of formula I as defined below and the salts thereof. These compounds have not yet been described, except for the following compounds of formula I, wherein:

X and Y are both hydrogen, R ¹ and R ² are both methyl and Ar is 4-chlorophenyl;

X and Y are both hydrogen, R ¹ is ethyl or but-2-en-1yl, R ² is phenyl and Ar is 4- nitrophenyl; - X and Y form a chemical bond, R ¹ is methyl, Ar is phenyl, R ² is methyl, phenyl, 4- methylphenyl, 4-methoxy phenyl, 3-pyridyl or 4 pyridyl;

X and Y form a chemical bond, R ¹ is tert.-butoxymethyl, R ² is phenyl and Ar is phenyl or 4-methylphenyl;

X and Y form a chemical bond, R ¹ and R ² are identical and selected from phenyl, 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, 4-bromophenyl, 4- ethoxyphenyl and 4-ethoxycarbonylphenyl, and Ar is phenyl;

(see K.C. Kalia et al., Ind. J. Chem. 14B, (1976) p. 826; K.C. Kalia et al., Chem. Envi- ron. Res. 1994 (3) p. 59; A. S. Shawali, J.Heterocyclic Chem. 14 (1977), p. 185; B. N.

Misra et al., Ind. J. Chem. 23B, (1984) p. 728; A. R. Forrester, J. Chem. Soc. Perkin I,

1979, p. 637).

Therefore, the present invention relates to amidrazone compounds of the general for- mula I

including the tautomers of I and the salts thereof;

X and Y are hydrogen or together form a chemical bond;

Ar is an aromatic radical selected from phenyl and a 5- or 6-membered heteroaryl having 1, 2, 3 or 4 heteroatoms as ring members, which are selected, independ- ently of one another, from O, N and S, and where the aromatic radical may have

1 , 2, 3, 4 or 5 substituents R ^a ;

R ^a is (are) selected, independently of one another, from halogen, cyano, nitro, CrC ₁₀ -alkyl, C _r C ₁₀ -haloalkyl, C ₃ -C ₁₀ -cylcoalkyl, C ₃ -C ₁₀ -halocycloalkyl, C ₂ - C ₁₀ -alkenyl, C ₂ -C ₁₀ -haloalkenyl, C ₂ -C ₁₀ -alkynyl, C ₃ -C ₁₀ -haloalkynyl, C ₁ -C ₁₀ - alkoxy, CrC^-haloalkoxy, C ₂ -C ₁₀ -alkenyloxy, C ₂ -C ₁₀ -haloalkenyloxy, C ₂ - do-alkynyloxy, C ₃ -C ₁₀ -haloalkynyloxy, CrC^-alkylthio, CrC^-haloalkylthio, Ci-Cio-alkylsulfinyl, CrC ₁₀ -haloalkylsulfinyl, CrC ₁₀ -alkylsulfonyl, C ₁ -C ₁₀ - haloalkylsulfonyl, hydroxy, NR ³ R ⁴ , CrC^-alkoxycarbonyl, CrC ₁₀ -halo- alkoxycarbonyl, CrC^-alkenyloxycarbonyl, C ₂ -C ₁₀ -haloalkenyloxycarbonyl,

C _r C ₁₀ -alkylcarbonyl, Crdo-haloalkylcarbonyl, R ³ R ⁴ N-CO-, phenyl, benzyl and phenoxy, wherein phenyl, benzyl and phenoxy may be substituted by 1, 2, 3, 4 or 5 substituents R ^b as defined below,

wherein two radicals R ^a which are bound to adjacent carbon atoms may form a CH=CH-CH=CH moiety or a 0-CH ₂ -O moiety, where in these two moieties 1 or 2 hydrogen atoms may be replaced by a radical R ^b as defined below;

R ^b is (are) selected, independently of one another, from halogen, cyano, nitro, Ci-Cio-alkyl, CrC^-haloalkyl, C ₃ -C ₁₀ -cylcoalkyl, C ₃ -C ₁₀ -halocycloalkyl, C ₂ - Cio-alkenyl, C ₂ -Ci ₀ -haloalkenyl, C ₂ -C ₁₀ -alkynyl, C ₃ -C ₁₀ -haloalkynyl, C ₁ -C ₁₀ - alkoxy, CrC _1Q -haloalkoxy, C ₂ -C ₁₀ -alkenyloxy, C ₂ -C ₁₀ -haloalkenyloxy, C ₂ - C ₁₀ -alkynyloxy, C ₃ -C ₁₀ -haloalkynyloxy, Crdo-alkylthio, C _r Ci ₀ -haloalkylthio,

CrC ₁₀ -alkylsulfinyl, CrC ₁₀ -haloalkylsulfinyl, C _r C ₁₀ -alkylsulfonyl, Ci-C ₁₀ - haloalkylsulfonyl, hydroxy, NR ³ R ⁴ , CrC^-alkoxycarbonyl, CrC ₁₀ -halo- alkoxycarbonyl, C ₂ -C ₁₀ -alkenyloxycarbonyl, Crdo-haloalkenyloxycarbonyl, CrC ₁₀ -alkylcarbonyl, Crdo-haloalkylcarbonyl and R ³ R ⁴ N-CO-;

R ¹ is selected from the group consisiting of CrC ₁₀ -alkyl, CrC ₄ -alkoxy-CrC ₄ -alkyl, cyano-C _r C ₄ -alkyl, hydroxy-C ₁ -C ₄ -alkyl, CrC ₁₀ -haloalkyl, W-(C ₁ -C ₄ -BIkVl)-SiIyI-C ₁ - C ₄ -alkyl, C ₂ -C ₁₀ -alkenyl, C ₂ -C ₁₀ -haloalkenyl, C ₂ -C ₁₀ -alkynyl, C ₂ -C ₁₀ -haloalkynyl, C ₃ -C ₁₀ -cycloalkyl, phenyl, heteroaryl, C ₃ -C ₁₀ -CyClOaIkVl-C ₁ -C ₄ -BIkVl, phenyl-CrC ₄ - alkyl and heteroaryl-CrC ₄ -alkyl, wherein C ₃ -C ₁₀ -cycloalkyl, heteroaryl and phenyl in the last six mentioned radicals may be unsubstituted or carry 1 , 2, 3, 4 or 5 substituents R ^b as defined above and wherein heteroaryl has1 , 2, 3 or 4 heteroa- toms as ring members, which are selected, independently of one another, from O ₁ N and S and wherein CrC ₄ -alkyl in the last three mentioned substituents is unsubstituted or may carry 1 , 2, 3 or 4 substituents selected from OH, =0, halogen, C ₁ -C ₄ haloalkyl and C ₁ -C ₄ alkoxy. The substituent =0 denotes a carbonyl group;

R ² is selected from the group consisiting of Ci-C ₁₀ -alkyl, CrC ₄ -alkoxy- CrC ₄ -alkyl, Crdo-haloalkyl, C ₂ -C ₁₀ -alkenyl, C ₂ -C ₁₀ -haloalkenyl, C ₂ -C ₁₀ -alkynyl, C ₂ -C ₁₀ - haloalkynyl, C ₃ -C ₁₀ -cycloalkyl, phenyl, heteroaryl, C ₃ -C ₁₀ -cycloalkyl-CrC ₄ -alkyl, phenyl-C _r C ₄ -alkyl and heteroaryl-C _r C ₄ -alkyl, wherein C ₃ -C ₁₀ -cycloalkyl, heteroaryl and phenyl in the last six mentioned radicals may be unsubstituted or carry 1, 2, 3, 4 or 5 substituents R ^b as defined above, wherein one of the subsituents on C ₃ -C ₁₀ -cycloalkyl may also be phenyl which may carry 1 , 2, 3 or 4 substituents selected from the radicals R ^b as defined above, wherein C _r C ₄ -alkyl in the last three mentioned substituents is unsubstituted or may carry 1 , 2, 3 or 4 substituents selected from OH, =0, halogen C ₁ -C ₄ haloalkyl and C ₁ -C ₄ alkoxy, and wherein heteroaryl has1 , 2, 3 or 4 heteroatoms as ring members, which are selected, independently of one another, from O ₁ N and S. The substituent =0 denotes a carbonyl group;

R ³ , R ⁴ are selected independently of one another from H, C _r C ₁₀ -alkyl, d-C^-haloalkyl,

C ₃ -C ₁₀ -cylcoalkyl, C ₃ -C ₁₀ -halocycloalkyl, C ₂ -C ₁₀ -alkenyl, C ₂ -C ₁₀ -haloalkenyl, C ₂ - do-alkynyl, C ₃ -C ₁₀ -haloalkynyl, phenyl or benzyl wherein phenyl and benzyl may be substituted by 1 , 2, 3, 4 or 5 substituents which are selected, independently of

one another, from halogen, cyano, nitro, Ci-Ci _O -alkyl, C _r Ci ₀ -haloalkyl, C ₃ -C ₁₀ - cylcoalkyl, C ₃ -C ₁₀ -halocycloalkyl, C ₂ -C ₁₀ -alkenyl, C ₂ -C ₁₀ -haloalkenyl, C ₁ -Ci ₀ - alkoxy, C _r C ₁₀ -haloalkoxy, C _r Ci ₀ -alkylthio, C _r C ₁₀ -haloalkylthio, C ₁ -C ₁₀ - alkylsulfonyl, CrC ₁₀ -haloalkylsulfonyl, hydroxy, Crdo-alkoxycarbonyl, C ₁ -C ₁₀ - haloalkoxycarbonyl, Ca-C^-alkenyloxycarbonyl, C ₂ -C ₁₀ -haloalkenyloxycarbonyl,

CrC^-alkylcarbonyl and C _r C ₁₀ -haloalkylcarbonyl;

except for the following compounds of the formula I, wherein:

X and Y are both hydrogen, R ¹ and R ² are both methyl and Ar is 4-chlorophenyl; - X and Y are both hydrogen, R ¹ is ethyl or but-2-en-1yl, R ² is phenyl and Ar is A- nitrophenyl;

X and Y form a chemical bond, R ¹ is methyl, Ar is phenyl, R ² is methyl, phenyl, A- methylphenyl, 4-methoxyphenyl, 3-pyridyl or 4 pyridyl;

X and Y form a chemical bond, R ¹ is tert.-butoxymethyl, R ² is phenyl and Ar is phenyl or 4-methylphenyl;

X and Y form a Chemical bond, R ¹ and R ² are identical and selected from phenyl,

4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, 4-bromophenyl, A- ethoxyphenyl and 4-ethoxycarbonylphenyl, and Ar is phenyl; and except for the tautomer and the salts of these compounds.

Due to their excellent activity, the compounds of the general formula I can be used for controlling pests, selected from harmful insects, arachnids and nematodes. The compounds of the formula I are in particular useful from combating insects.

Accordingly, the invention further provides compositions for combating such pests, preferably in the form of directly sprayable solutions, emulsions, pastes, oil dispersions, powders, materials for scattering, dusts or in the form of granules, which comprises a pesticidally effective amount of at least one compound of the general formula I or at least a salt thereof and at least one carrier which may be liquid and/or solid and which is prefarably agronomically acceptable, and/or at least one surfactant.

Furthermore, the invention provides a method for combating such pests, which comprises contacting said pests, their habitat, 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 an attack of or infestation by said pest, with a pesticidally effective amount of a compound of the general formula I as defined herein or a salt thereof.

The invention provides in particular a method for protecting crops, including seeds, from attack or infestation by harmful insects, arachnids and/or nematodes, said method

comprises contacting a crop with a pesticidally effective amount of at least one compound of formula I as defined herein or with a salt thereof.

The invention also provides a method for protecting non-living materials from attack or infestation by the aforementioned pests, which method comprises contacting the nonliving material with a pesticidally effective amount of at least one compound of formula I as defined herein or with a salt thereof.

Suitable compounds of the general formula I encompass all possible stereoisomers (cis/trans isomers, enantiomers) which may occur and mixtures thereof. The present invention provides both the pure enantiomes or diastereomers or mixtures thereof, the pure cis- and trans-isomers and the mixtures thereof. The compounds of the general formula I may also exist in the form of different tautomers if Ar carries an amino or an- hydroxy group. The invention comprises the single tautomers, if seperable, as well as the tautomer mixtures.

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

Suitable agriculturally 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 barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH ₄ ⁺ ) and substituted ammonium in which one to four of the hydrogen atoms are replaced by Ci-C ₄ -alkyl, CrC ₄ -hydroxyalkyl, C _r C ₄ -alkoxy, C _r C ₄ -alkoxy-C _r C ₄ -alkyl, hydroxy-C ₁ -C ₄ -alkoxy-C _r C ₄ -alkyl, phenyl or benzyl. Examples of substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammonium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetraethyl- ammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxyethoxy)ethyl- ammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzyl- triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C ₄ - alkyl)sulfonium, and sulfoxonium ions, preferably tri(C _r C ₄ -alkyl)sulfoxonium.

Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hy- drogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C _r C ₄ -alkanoic acids, preferably formate, acetate, propionate and bu-

tyrate. They can be formed by reacting the compounds of the formulae Ia and Ib with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric 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 members. The prefix C _n -C _n , indicates in each case the possible number of carbon atoms in the group.

"Halogen" will be taken to mean fluoro, chloro, bromo and iodo.

The term "C _r C ₁₍ ralkyr as used herein (and also in CrCio-alkylsulfinyl and C ₁ -C ₁₀ - alkylsulfonyl) refers to a branched or unbranched saturated hydrocarbon group having 1 to 10 carbon atoms, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1- methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3- methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1 ,2- dimethylpropyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1- dimethylbutyl, 1,2-dimethylbutyi, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1 -methylpropyl, 1-ethyl-2-methylpropyl, heptyl, octyl, 2-ethylhexyl, nonyl and decyl and their isomers. C _r C ₄ -alkyl means for example methyl, ethyl, propyl, 1- methylethyl, butyl, 1 -methylpropyl, 2-methylpropyl or 1 ,1-dimethylethyl.

The term "CrC^-haloalkyl" as used herein (and also in C _r C ₁₀ -haloalkylsulfinyl and C ₁ - C ₁₀ -haloalkylsulfonyl) refers to a straight-chain or branched alkyl group having 1 to 10 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example C ₁ -C ₄ - haloalkyl, such as chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoro- methyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chloro- difluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2- dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl and the like. The term C ₁ - do-haloalkyl in particular comprises CrC ₂ -fluoroalkyl, which is synonym with methyl or ethyl, wherein 1 , 2, 3, 4 or 5 hydrogen atoms are substituted by fluorine atoms, such as fluoromethyl, difluoromethyl trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2- difluoroethyl, 2,2,2-trifluoroethyl and pentafluoromethyl.

Similarly, "CrC ₁₀ -alkoxy" and "CrCi ₀ -alkylthio" refer to straight-chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above) bonded through oxygen or sulfur linkages, respectively, at any bond in the alkyl group. Examples include C ₁ -C ₄ - alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy

and tert-butoxy, futher C ₁ -C ₄ -alkylthio such as methylthio, ethylthio, propylthio, isopro- pylthio, and n-butylthio.

Accordingly, the terms "C _r Ci ₀ -haloalkoxy" and " C _r C ₁₀ -haloalkylthio" refer to straight- chain or branched alkyl groups having 1 to 10 carbon atoms (as mentioned above) bonded through oxygen or sulfur linkages, respectively, at any bond in the alkyl group, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example CrC ₂ -haloalkoxy, such as chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 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 and pentafluoroethoxy, further CrC^haloalkylthio, such as chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichloro- fluoromethylthio, chlorodifluoromethylthio, 1-chloroethylthio, 1-bromoethylthio, 1- fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro- 2-fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2- trichloroethylthio and pentafluoroethylthio and the like. Similarly the terms C ₁ -C ₂ - fluoroalkoxy and C _r C ₂ -fluoroalkylthio refer to C _r C ₂ -fluoroalkyl which is bound to the remainder of the molecule via an oxygen atom or a sulfur atom, respectively.

The term "C ₂ -C ₁₀ -alkenyr as used herein intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any posi- tion, such as ethenyl, 1-propenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3- butenyl, 1-methyl-1-propenyl, 2-methyl- 1-propenyl, 1-methyl-2-propenyl, 2~methyl-2- propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl- 1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2- butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1 ,1-dimethyl-2- propenyl, 1,2-dimethyl-1-propenyl, 1 ,2-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-dimethy I- 1-butenyl, 1 ,2-dimethyl-2-butenyl, 1 ,2- dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3- butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 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 "C ₂ -C ₁₀ -haloalkenyr as used herein intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.

Similarly, the term "C ₂ -C ₁₀ -alkenyloxy" as used herein intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, the alkenyl group being bonded through oxygen linkages, respectively, at any bond in the alkenyl group, for example ethenyloxy, propenyloxy and the like.

Accordingly, the term "C ₂ -C ₁₀ -haloalkenyloxy" as used herein intends a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and a double bond in any position, the alkenyl group being bonded through oxygen linkages, respectively, at any bond in the alkenyl group, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above.

The term "C ₂ -C ₁₀ -alkynyl" as used herein refers to a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and containing at least one triple bond, such as ethynyl, propynyl, 1-butynyl, 2-butynyl, and the like.

The term "C ₃ -C ₁₀ -haioalkynyr as used herein refers to a branched or unbranched un- saturated hydrocarbon group having 3 to 10 carbon atoms and containing at least one triple bond, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, with the proviso that the halogen atom is not directly bound to the triple bond.

The term "C ₂ -C ₁₀ -alkynyloxy" as used herein refers to a branched or unbranched unsaturated hydrocarbon group having 2 to 10 carbon atoms and containing at least one triple bond, the alkynyl group being bonded through oxygen linkages at any bond in the alkynyl group.

Similarly, the term "C ₃ -Cio-haloalkynyloxy" as used herein refers to a branched or unbranched unsaturated hydrocarbon group having 3 to 10 carbon atoms and containing at least one triple bond, the group being bonded through oxygen linkages at any bond in the alkynyl group, where some or all of the hydrogen atoms in these group may be replaced by halogen atoms as mentioned above, with the proviso that the halogen atom is not directly bound to the triple bond.

The term "C ₃ -C ₁₍ rcycloalkyr as used herein refers to a monocyclic 3- to 10-membered saturated carbon atom ring, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo- heptyl, cyclooctyl and cyclodecyl.

The term "Ca-do-cycloalkyl-CrC^alkyl" as used herein refers to a monocyclic 3- to 10- membered saturated carbon atom ring which is attached to the remainder of the molecule by an C _r C ₄ -alkylene group, e.g. cyclopropylmethyl, 1-cyclopropyiethan-i-yl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctyl- methyl and cyclodecylmethyl.

The term "C ₃ -Ci ₀ -halocycloalkyr as used herein refers to a monocyclic 3- to 10- membered saturated carbon atom ring, e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclodecyl, where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, for example chloro-, dichloro- and trichlorocyclopropyl, fluoro-, difluoro- and trifluorocyclopropyl, chloro-, dichloro-, trichloro, tetrachloro-, pentachloro- and hexachlorocyclohexyl and the like.

The term "phenyl-CrC ₄ -alkyl" as used herein refers to an optionally substitueted phenyl group which is attached to the remainder of the molecule by an Ci-C ₄ -alkylene group, e.g. benzyl, 1-phenylethan-1-yl, 2-phenylethan-1-yl, 2-methyl-2-phenylethan-1-yl and the like.

The term "d-Cio-alkylcarbonyl" as used herein refers to Ci-Ci _O -alkyl which is bound to the remainder of the molecule via a carbonyl group. Examples include CO-CH ₃ , CO-C ₂ H ₅ , CO-CH ₂ -C ₂ H ₅ , CO-CH(CH ₃ ) ₂ , n-butylcarbonyl, CO-CH(CHg)-C ₂ H ₅ , CO-CH ₂ -CH(CHs) ₂ , CO-C(CH ₃ ) ₃ , n-pentylcarbonyl, 1- methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 2,2- dimethylpropylcarbonyl, 1-ethylpropylcarbonyl, n-hexylcarbonyl, 1 ,1- dimethylpropylcarbonyl, 1 ,2-dimethylpropylcarbonyl, 1-methylpentylcarbonyl, 2- methylpentylcarbonyl, 3-methylpentylcarbonyl, 4-methylpentylcarbonyl, 1 ,1- dimethylbutylcarbonyl, 1 ,2-dimethylbutylcarbonyl, 1 ,3-dimethylbutylcarbonyl, 2,2- dimethylbutylcarbonyl, 2,3-dimethylbutylcarbonyl, 3,3-dimethylbutylcarbonyl, 1- ethylbutylcarbonyl, 2-ethylbutylcarbonyl, 1 ,1 ,2-trimethylpropylcarbonyl, 1 ,2,2- trimethylpropylcarbonyl, 1-ethyl-1-methylpropylcarbonyl or 1 -ethyl-2- methylpropylcarbonyl.

The term "CrCio-haloalkylcarbonyl" as used herein refers to C _r C ₁₀ -haloalkyl which is bound to the remainder of the molecule via a carbonyl group. Examples include chloromethylcarbonyl, dichloromethylcarbonyl, trichloromethylcarbonyl, fluoromethylcarbonyl, difluoromethylcarbonyl, trifluoromethylcarbonyl etc.

The term "CrCio-alkoxycarbonyl" as used herein refers to C _r C ₁₀ -alkoxy which is bound to the remainder of the molecule via a carbonyl group. Examples include CO-OCH ₃ , CO-OC ₂ H ₅ , CO-OCH ₂ -C ₂ H ₅ , CO-OCH(CH ₃ ) ₂ , n-butoxycarbonyl, CO-OCH(CHg)-C ₂ H ₅ , CO-OCH ₂ -CH(CH ₃ ).:, CO-OC(CH ₃ ) ₃ , n-pentoxycarbonyl, 1- methylbutoxycarbonyl, 2-methylbutoxycarbonyl, 3-methylbutoxycarbonyl, 2,2- dimethylpropoxycarbonyl, 1-ethylpropoxycarbonyl, n-hexoxycarbonyl, 1,1- dimethylpropoxycarbonyl, 1 ,2-dimethylpropoxycarbonyl, 1-methylpentoxycarbonyl, 2- methylpentoxycarbonyl, 3-methylpentoxycarbonyl, 4-methylpentoxycarbonyl, 1,1- dimethylbutoxycarbonyl, 1 ,2-dimethylbutoxycarbonyl, 1,3-dimethylbutoxycarbonyl, 2,2- dimethylbutoxycarbonyl, 2,3-dimethylbutoxycarbonyl, 3,3-dimethylbutoxycarbonyl, 1- ethylbutoxycarbonyl, 2-ethylbutoxycarbonyl, 1 ,1 ,2-trimethylpropoxycarbonyl, 1,2,2- trimethylpropoxycarbonyl, 1-ethyl-1-methylpropoxycarbonyl or 1 -ethyl-2- methylpropoxycarbonyl .

The term "halo-Crdo-alkoxycarbonyl" as used herein refers to CrC ₁₀ -haloalkoxy which is bound to the remainder of the molecule via a carbonyl group.

The terms "halo-Crdo-alkoxy-Cr Cio-alkyl", "Crdo-alkoxycarbonyl-d-C^-alkyl", "halo-CrCio-alkoxycarbonyl-d-C^- alkyl" as used herein, refer to C _r C ₁₀ -alkyl, as defined herein, in particular to methyl, ethyl, 1 -propyl or 2-propyl, which is substituted by one radical selected from hydroxy, Ci-C ₁₀ -alkoxy, C ₁ -C ₁₀ - haloalkoxy, CrC^-alkoxycarbonyl or CrC ₁₀ -haloalkoxycarbonyl.

The term "5- or 6-membered heterocyclic radical with 1 , 2, 3 or 4 heteroatoms which are selected, independently of one another, from O, N and S " comprises monocyclic 5- or 6-membered heteroaromatic rings (heteroaryl) and nonaromatic saturated or partially unsaturated 5- or 6-membered mono-heterocycles, which carry 1 , 2, 3, or 4 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, pyr- rolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1 ,3-dioxolanyl, di- oxolenyl, thiolanyl, dihydrothienyl, oxazolidinyl, isoxazolidinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl, piperidinyl, piperaz- inyl, pyranyl, dihydropyranyl, tetrahydropyranyl, dioxanyl, thiopyranyl, dihy- drothiopyranyl, tetrahydrothiopyranyl, morpholinyl, thiazinyl and the like.

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

The term "heteroaryl-CrC ₄ -alkyr as used herein refers to an optionally substitueted heteroaryl group which is attached to the remainder of the molecule by an C ₁ -C ₄ - alkylene group, examples including triazinylmethyl, pyrazinylmethyl, pyrimidylmethyl, pyridazinylmethyl, pyridylmethyl, thienylmethyl, furylmethyl, pyrrolylmethyl, pyrazolyl- methyl, imidazolyl, triazolylmethyl, tetrazolylmethyl, thiazolylmethyl, oxazolylmethyl, thiadiazolylmethyl, oxadiazolylmethyl, isothiazolylmethyl and isoxazolylmethyl.

In a first aspect the invention relates to compounds of the formula I ₁ wherein both X and Y are hydrogen. These compounds are also referred to as compounds Ia. Compounds Ia may also exist in their tautomeric form Ia ¹ .

(Ia) (Ia ¹ )

In. a second aspect the invention relates to compounds of the formula I, wherein both X and Y form a chemical bond. These compounds are also referred to as compounds Ib.

With respect to the use according to the invention of the compounds of formula I (and likewise compounds Ia ₁ Ia ¹ and Ib), preference is given to the following meanings of the substituents, in each case on their own or in combination:

Preference is given to compounds of the formula I, wherein Ar in formula I is an option- ally substituted aromatic radical selected from phenyl or pyridyl, such as 2-, 3- or 4- pyridyl. The aromatic radical may be unsubstituted or preferably carries 1 , 2, 3, 4 or 5 substituents R ^a as defined above.

Preferred substuituents R ^a are selected, independently of one another, from halogen, CN ₁ OH ₁ NO ₂ , C _r C ₄ -alkyl, CrC ₄ -alkoxy, C _r C ₄ -haloalkoxy and C _r C ₄ -haloalkyl. In particular fluorine, chlorine, NO ₂ , CN, methyl, CHF ₂ , CF ₃ , CF ₂ CI, methoxy, OCHF ₂ , and OCF ₃ .

In a very preferred embodiment of the invention Ar is phenyl, which carries 1 , 2, 3, 4 or 5 substituents R ^a as defined above. Amongst these compounds those are preferred,

wherein at least one substituent R ^a is located in the ortho- and/or para-position of the phenyl ring, with particular preference given to those, wherein one or two substituents R ^a are located in the ortho-positions of the phenyl ring and one substituent R ^a is located in the para-position of the phenyl ring. In this embodiments particular preference is given to substuituents R ^a , which are selected, independently of one another, from halogen, CN, OH, NO ₂ , C _r C ₄ -alkyl, C _r C ₄ -alkoxy, C _r C ₄ -haloalkoxy and C ₁ -C ₄ - haloalkyl, in particular fluorine, chlorine, NO ₂ , CN, methyl, CHF ₂ , CF ₃ , CF ₂ CI, methoxy, OCHF ₂ , and OCF ₃ .

More preferably the radical Ar is of the formula A

wherein at least one, preferably at least two of the radicals R ^a1 , R ^a3 and R ^a5 are differ- ent from hydrogen, and wherein

R ^a1 is selected from the group consisting of hydrogen, halogen, CN, OH, NO ₂ , C ₁ -C ₄ - alkyl, Ci-C ₄ -a!koxy, CrC ₄ -haloalkoxy and CrC ₄ -haloalkyl, in particular hydrogen, methyl, fluorine, chlorine, NO ₂ , CN, CHF ₂ , CF ₃ , CF ₂ CI ₁ methoxy, OCHF ₂ , and OCF ₃ ;

R ^a2 is selected from the group consisting of hydrogen or halogen, in particular hydrogen, fluorine or chlorine;

R ^a3 is selected from the group consisting of hydrogen, halogen, CN, OH, NO ₂ , C ₁ -C ₄ - alkyl, C _r C ₄ -alkoxy, CrC ₄ -haloalkoxy and C _r C ₄ -haloalkyl, in particular hydrogen, halogen, C _r haloalkyl or C _r haloalkoxy, e.g. fluorine, chlorine, bromine, methyl, methoxy, trichloromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy;

R ^a4 is selected from the group consisting of hydrogen and halogen, in particular hydrogen, fluorine or chlorine; and

R ^a5 is selected from the group consisting of hydrogen, halogen, CN, OH, NO ₂ , C ₁ -C ₄ - alkyl, C _r C ₄ -alkoxy, C _r C ₄ -haloalkoxy and C _r C ₄ -haloalkyl, in particular hydrogen, methyl, fluorine, chlorine, NO ₂ , CN, CHF ₂ , CF ₃ , CF ₂ CI, methoxy, OCHF ₂ , and OCF ₃ .

Examples for radicals Ar of the formula A include 2-fluoro-6-chlorophenyl, 2,6-difluoro- phenyl, 2,6-dichlorophenyl, 2-fluoro-6-methylphenyl, 2,4,6-trifluorophenyl, pentafluoro- phenyl, 2-methyl-4-fluorophenyl, 2-trifluoromethylphenyl, 2-chlorophenyl, 2-fluoro- phenyl, 2,4-difluorophenyl, 2-fluoro-4-chlorophenyl, 2-methoxy-6-fluorophenyl, 2-chloro-4-flύorophenyl, 2-methyl-4-chlorophenyl, 2-trifluoromethyl-4-fluorophenyl,

2-chloro-4-trifluoromethyl, 2,6-dichloro-4-trifluoromethylpheπyl, 2-cyano-4-chlorophenyl, 2-nitro-4-chlorophenyl, 4-trifluoromethylphenyl, 2,4,6-trichlorophenyl, 4-bromo-2,6- dichlorophenyl, 2,6-dichloro-4-trifluoromethoxyphenyl, 2,6-dichloro-4-difluoromethoxy- phenyl, 2,6-dichloro-4-fluorophenyl, 2,6-dichloro-4-trichloromethylphenyl, 4-chloro-2,6- difluorophenyl, 4-bromo-2,6-difluorophenyl, 2,6-difluoro-4-trifluoromethylphenyl, 2,6-difluoro-4-trifluoromethoxyphenyl, 2,6-difluoro-4-difluoromethoxyphenyl, 2,6-difluoro-4-trichloromethylphenyl, 4-chloro-2-fluorophenyl, 2,4-dichlorophenyl, 2,3,4-trichlorophenyl, 2-nitro-4-trifluoromethylphenyl and 3,5-dichlorophenyl.

Preference is also given to compounds of the formula I (and likewise to compounds Ia, Ia' and Ib), wherein R ¹ is selected from the group consisting of CrC ₆ -alkyl, CrC ₆ -halo- alkyl, C ₃ -C ₆ -cycloalkyl, CrC ₄ -alkoxy-C ₂ -C ₄ -alkyl, C ₃ -C ₆ -alkenyl, C ₃ -C ₆ -alkynyl, C ₃ -C ₆ - haloalkenyl, C ₃ -C ₆ -haloalkynyl, Cs-Ce-cycloalkylmethyl, wherein C ₃ -C ₆ -cycloalkyl in the last two radicals may carry 1 , 2, 3 or 4 radicals R ^b as defined above and inparticular radicals R ^b which are selected from halogen and methyl. Particular preference is given to compounds of the formula I (and likewise to compounds Ia, Ia ¹ and Ib), wherein R ¹ is Ci-Cβ-alkyl, C ₃ -C ₆ -alkenyl and C ₃ -C ₆ -alkynyl, wherein these radicals may carry a halogen atom. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 2-butyl, tert.-butyl, 2-bromoethyl, 2-chloroethyl, 1-propen-3-yl, 1-chloro-1-propen-3-yl, 2-buten~1-yl, 3-methyl-2-buten-1-yl, 1-propin-3-yl, 1-butin-3-yl, cyclohexylmethyl, cyclopropylmethyl, 2-ethoxy-ethyl, 2-trimethylsilyl-ethyl, cyanomethyl, 2-chloro-1- propen-3-yl.

Likewise particular preference is given to compounds of the formula I (and likewise to compounds Ia, Ia ¹ and Ib), wherein R ¹ is phenyl-CrC ₄ -alkyl, in particular benzyl, 1- phenylethyl, 2-phenylethyl, 1-methyl-1-phenylethyl, wherein the phenyl ring in these radicals may be unsubstituted or substituted by a radical R ^b as defined above, with R ^b being particularly selected from methyl, halogen and methoxy.

Preference is also given to compounds of the formula I (and likewise to compounds Ia, Ia ¹ and Ib) ₁ wherein R ² is a radical, which is attached to the remainder of the molecule by a secondary or tertiary carbon atom. Amongst these, preference is given to those, wherein R ² is selected from secondary or tertiary CrCβ-alkyl, C ₃ -C ₆ -cycloalkyl and phenyl, wherein C ₃ -C ₆ -cycloalkyl and phenyl may be unsubstituted or carry 1 , 2, 3, 4 or 5 substituents selected from the radicals R ^b and wherein one of the subsituents on C ₃ -C ₆ -cycloaIkyl may also be phenyl that may carry 1 , 2, 3 or 4 substituents selected

from the radicals R ^bb wherein R ^bb has the one of the meanings of R ^b as defined above. Amongst these, preference is given to compounds wherein the radicals R ^b on phenyl are selected from methyl, trifluoromethyl, phenyl and halogen. Amongst these, preference is given to compounds wherein the radicals on cyloalkyl are selected from methyl, trifluoromethyl, phenyl, which may carry 1 , 2 or 3 radicals R ^bb , and halogen. R ^bb is preferably selected from halogen, C _r C ₄ -alkyl, C _r C ₄ -alkoxy, halo-C _r alkoxy and halo-C _r alkyl.

A particularly preferred embodiment of the invention relates to compounds of the for- mula I (and likewise to compounds Ia, Ia ¹ and Ib), wherein R ² is C ₃ -C ₆ -cycloalkyl in particular cyclopropyl which may be unsubstituted or carry 1 , 2, 3, 4 or 5 substituents selected from the radicals R ^b . Amongst these, preference is given to compounds wherein the radicals R ^b on the C ₃ -C ₆ -cycloalkyl radical are selected from methyl, trifluoromethyl, phenyl which may carry 1 , 2 or 3 halogen atoms and halogen. Exam- pies include 2,2-dichlorocyclopropyl, 2,2-dichloro-1-methylcyclopropyl, 1-trifluoro- methylcyclopropyl, 1-fluorocyclopropyl, 2,2-dichloro-3,3-dimethylcyclopropyl, 1-methyl- cyclopropyl, 2,2-dibromocyclopropyl, 2,2-dibromo-1-methylcyclopropyl, 2-chloro-2- fluoro-1-methylcyclopropyl, 2-chloro-1-methylcyclopropyl, 1-phenylcyclopropyl, 1-(4- methoxyphenyl)cyclopropyl, 1-(4-chlorophenyl)cyclopropyl, 1-((2,4-dichlorophenyl)- cyclopropyl and 2-methylcyclopropyl.

Examples of preferred compounds I are given in the following tables 1 to 37

Table 1 Compounds of the formulae Ia, Ia ¹ and Ib, wherein Ar is 2-fluoro-6-chlorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 2 Compounds of the formulae Ia, Ia' and Ib, wherein Ar is 2,6-difluorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 3 Compounds of the formulae Ia ₁ Ia ¹ and Ib, wherein Ar is 2,6-dichlorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 4 Compounds of the formulae Ia, Ia ¹ and Ib, wherein Ar is 2-fluoro-6-methylphenyi and

the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 5 Compounds of the formulae Ia, Ia' and Ib, wherein Ar is 2,4,6-trifluorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 6 Compounds of the formulae Ia, Ia' and Ib, wherein Ar is pentafluorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 7 Compounds of the formulae Ia, Ia' and Ib, wherein Ar is 2-methyl-4-fluorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 8 Compounds of the formulae Ia, Ia ¹ and Ib, wherein Ar is 2-trifluoromethylphenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 9 Compounds of the formulae Ia, Ia ¹ and Ib, wherein Ar is 2-methoxy-6-fluorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 10 Compounds of the formulae Ia, Ia ¹ and Ib, wherein Ar is 2-chlorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 11

Compounds of the formulae Ia, Ia' and Ib, wherein Ar is 2-fluorophenyl and the combi- nation of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 12

Compounds of the formulae Ia, Ia ¹ and Ib, wherein Ar is 2,4-difluorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 13

Compounds of the formulae Ia, Ia' and Ib, wherein Ar is 2-fluoro-4-chlorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 14

Compounds of the formulae Ia, Ia ¹ and Ib, wherein Ar is 2-chloro-4-fluorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 15

Compounds of the formulae Ia, Ia ¹ and Ib, wherein Ar is 2-methyl-4-chlorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 16

Compounds of the formulae Ia, Ia ¹ and Ib, wherein Ar is 2-trifluoromethyl-4-fluorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 17

Compounds of the formulae Ia, Ia' and Ib, wherein Ar is 2-chloro-4-trifluoromethyl- phenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 18

Compounds of the formulae Ia, Ia ¹ and Ib, wherein Ar is 2,6-dichloro-4-trifluoromethyl- phenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 19

Compounds of the formulae Ia, Ia ¹ and Ib, wherein Ar is 2-cyano-4-chlorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 20

Compounds of the formulae Ia, Ia ¹ and Ib, wherein Ar is 2-nitro-4-chlorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 21

Compounds of the formulae Ia, Ia ¹ and Ib, wherein Ar is 4-trifluoromethylphenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 22

Compounds of the formulae Ia, Ia ¹ and Ib, wherein Ar is 2,4,6-trichlorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 23

Compounds of the formulae Ia, Ia' and Ib, wherein Ar is 4-bromo-2,6-dichlorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 24

Compounds of the formulae Ia, Ia ¹ and Ib, wherein Ar is 2,6-dichloro-4-trifluoromethoxy- phenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A:

Table 25

Compounds of the formulae Ia, Ia' and Ib, wherein Ar is 2,6-dichloro-4-difluoromethoxy- phenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 26

Compounds of the formulae Ia, Ia' and Ib, wherein Ar is 2,6-dichloro-4-fluorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 27

Compounds of the formulae Ia, Ia ¹ and Ib, wherein Ar is 2,6-dichloro-4-trichloromethyl- phenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 28

Compounds of the formulae Ia, Ia ¹ and Ib, wherein Ar is 4-chloro-2,6-difluorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 29

Compounds of the formulae Ia, Ia ¹ and Ib ₁ wherein Ar is 4-bromo-2,6-difluorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 30

Compounds of the formulae Ia, Ia' and Ib, wherein Ar is 2,6-difluoro-4-trifluoromethyl- phenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 31

Compounds of the formulae Ia, Ia ^* and Ib, wherein Ar is 2,6-difluoro-4-trifluoromethoxy- phenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 32

Compounds of the formulae Ia, Ia ¹ and Ib, wherein Ar is 2,6-difluoro-4-difluoromethoxy- phenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 32

Compounds of the formulae Ia, Ia' and Ib, wherein Ar is 2,6-difluoro-4-trichloromethyl- phenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 33

Compounds of the formulae Ia, Ia ¹ and Ib, wherein Ar is 4-chloro-2-fluorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 34

Compounds of the formulae Ia, Ia ¹ and Ib, wherein Ar is 2,4-dichlorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 35

Compounds of the formulae Ia, Ia' and Ib, wherein Ar is 2,3,4-dichlorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 36

Compounds of the formulae Ia, Ia ¹ and Ib, wherein Ar is 2-nitro-4-trifluoromethylphenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table 37

Compounds of the formulae Ia ₁ Ia ¹ and Ib, wherein Ar is 3,5-dichlorophenyl and the combination of R ¹ and R ² for one compound corresponds in each case to one row of table A.

Table A:

The compounds of the general formulae I can be synthesized by techniques generally known in the art.

Compounds of the formula Ia (or their tautomers Ia') can be prepared by the synthesis shown in scheme 1.

Scheme 1:

(I") (IV) (Ia ¹ )

In scheme 1 , Ar, R ¹ and R ² have the abovementioned meanings, and Hal and Hal' are independently of each other halogen. Hal and Hal' have preferably the same meaning, especially Hal and Hal' denote chlorine.

In the first step of the synthesis depicted in scheme 1 an N-arylhydrazinoyl halide of the formula IV is prepared by reacting an acyl halide Il with an aryl hydrazine compound III in the presence of thionyl halide such as thionyl chloride. The reaction can be performed according to standard methods of organic chemistry well known in the art and disclosed e.g. in EP 0 604 798.

In the second step the N-arylhydrazinoyl halide IV is reacted with an hydroxylamine ether hydrohalide V. The reaction can be performed by analogy to the reaction of primary amines with hydrazinoyl halides as disclosed e.g. in EP 0 604 798.

In general, the compounds IV and V are reacted in equimolar amounts. It may, however, be advantageous to use compound V in excess, e.g. up to 10 mol per mol of compound IV.

Preferably, the reaction is carried out in the presence of a base. Suitable bases are tertiary amines such as trimethylamine, triethylamine, diisoproylethylamine (Hϋnig's base) or tripropylamine or pyridine or mixtures thereof; with triethylamine and Hϋnig's base being especially preferred. The molar ratio of the base to compound V is generally from 0.6:1 to 5:1.

It is preferred that the reaction is carried out in a solvent or diluent. Suitable organic solvents or diluents include ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dioxane or tetrahydrofuran, aromatic solvents, in particular alkylaromatic solvents such as tolu- ene, xylene etc., halogenated hydrocarbons, in particular haloalkanes such as tri-

chloromethane, dichloromethane, ethylenchloride, 1 ,2-dichloroethylene and mixtures thereof. Especially preferred solvents include diethyl ether and dichloromethane. Customary reaction temperatures are from 0 ⁰ C to 80 ⁰ C or.

The hydroxylamin ether hydrohalides V are commericially available or known from the literature or can be prepared by known methods.

Acyl halides Il can be prepared from the corresponding carboxylic acids Vl. The latter are commericially available or known from the literature or can be prepared by stan- dard methods. It is not necessary to isolate the acyl halide II, which can be reacted with compound III without purification.

The arylhydrazines of formula III are known in the art or may be obtained applying methods well known in the art, e.g., by diazotization of an appropiate aniline of the for- mula Ar-NH ₂ , wherein Ar has the abovementioned meanings, and reduction of the resulting diazonium salt.

An alternative route to compounds Ia ¹ (or Ia) is shown in scheme 2. In scheme 2, Ar, R ¹ and R ² have the above mentioned meanings, Hal is halogen, especially chlorine, and Ph denotes phenyl.

Scheme 2:

(Vi) 2. (R ¹ ONH ₃ ) ⁺ Hal- (V) (| _a -)

To this end, the carboxylic acid Vl is initially reacted with the hydrazine compound III in the presence of triphenylphosphine and a tetrahalomethane, such as tetrachloro- methane, to yield the N-arylhydrazinoyl halide compound Il (step 1), which can then be converted into the corresponding compound Ia by reacting an appropiate O-alkylated hydroxylamine-hydrohalide III (step 2) as described above. Accordingly, step 2 is carried out in the presence of a base. The reactions of steps 1 and 2 are carried out as a one-pot reaction.

Preferably, a polymer-supported triphenylphosphine is used in step 1. Suitable carriers for the polymer-supported triphenylphosphin are poly(ethylene glycol) or cross-linked polystyrene. The use of polymer-supported triphenylphosphine resins allows to easily

remove the triphenylphosphine oxide formed seperating the insoluble polymer materials from the reaction mixture.

Step 1 and step 2 are preferably carried out in the presence of a solvent. Suitable sol- vents are halogenated hydrocarbons such as trichloromethane, dichloromethane, ethylenchloride or 1 ,2-dichloroethylene, with dichloromethane being preferred. The solvent used in step 1 is usually used in step 2, too.

Step 1 can be carried out by mixing the carboxylic acid Vl, the hydrazine compound III, the triphenylphosphine, the tetrahalomethane and optionally the solvent in a reaction vessel. The reaction temperatures are usually in the range of 0 to 80°C. The reaction is usually carried out under atmospheric pressure. However elevated pressure or reduced pressure might also be applied.

After the reaction is completed, the reaction vessel is charged with the O-alkylated hydroxylamine-hydrohalide III and a base, if desired (step 2). Suitable bases includes those mentioned in scheme 1 , with Hϋnig's base being especially preferred. Step 2 is usually carried out at temperatures of from O ⁰ C to 80 ⁰ C.

The stoichiometric ratios are, for example, as follows: 1 to 10 equivalents of triphenylphosphine; 0.2 to 2 equivalents of carboxylic acid; 0.2 to 2 equivalents of arylhydrazine; 3 to 30 equivalents of halomethane; 0.4 to 4 equivalents of hydroxylamine ether hydro- halide; and 1 to 10 equivalents of base.

Work-up of the reaction mixture to isolate compound Ia or Ia', respectively, can be performed by conventional processes, including filtration, extraction and solvent removing. Purification can be achieved e.g. by crystallization and/or chromatography.

Compounds of the formula Ib can be prepared by dehydrogenation of a hydrazonamide Ia ¹ or the corresponding tautomer Ia, respectively, as shown in scheme 3. In scheme 3, Ar, R ¹ and R ² have the abovementioned meanings.

Scheme 3:

(Ia') (Ib)

The dehydrogenation of Ia or Ia ¹ , respectively, may be effected by using oxidants having high redox potentials and which are known to dehydrogenate hydrazine compounds. Suitable oxidandts include quinones, such as chloranil (2,3,5,6-tetrachloro-1 ,4- benzoquinone) or DDQ (2,3-dichloro-5,6-dicyano-1 ,4-benzoquinone), Pb(OAc) ₄ (lead (IV) acetate) (Uneyama et al, Bull. Chem. Soc. Jpn. 1995, 68, 1497-1507), MnO ₂ (manganese (IV) oxide) (Fusco et al, J. Heterocyclic Chem. 1987, 24, 773-778), KMnO ₄ (potassium permanganate), H ₂ O ₂ (hydrogen peroxide) (Buzykin et al, Synthesis 1993, 59-61) with DDQ being preferred.

In general, the oxidant and compound Ia or Ia' are reacted in at least equimolar amounts. It may be advantageous to employ the oxidant in excess, e.g. the molar ratio of compound Ia to oxidant is in the range from 1 :1 to 1:2.5.

The reaction is preferably carried out in the presence of an inert solvent. Suitable sol- vents include ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether or tetrahydrofuran, haloalkanes such as trichloromethane, dichloromethane or dichloro- ethane, aliphatic or aromatic hydrocarbons such as cyclohexane and petrol ether, benzene, toluene or o-, m- and p-xylene and mixtures thereof.

Preferably, the reaction is carried out in the presence of an organic base such as a tertiary amine e.g. a trialkylamine such as triethylamine or pyridine. The molar ratio of base to oxidant is usually in the range from 1 :0.8 to 1 :5. Customary reaction temperatures are from 0 ⁰ C to 120 ⁰ C.

Work-up of the reaction mixture to isolate compound Ib can be performed by conventional processes, including filtration, extraction and solvent removing. Purification can be achieved e.g. by crystallization and/or chromatography.

Some of the intermediates and end products are obtained in the form of colourless or slightly brownish viscous oils which can be purified or freed from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and the end products are obtained as solids, purification can also be carried out by recrystillization or digestion.

If individual compounds I can not be obtained by the routes described above, they can be prepared by derivatization of other compounds I.

If the synthesis yields a mixtures of isomers, a separation of the isomers is possible. However a separation is generally not necessary. In some cases the individual isomers will be interconverted during work-up for use or during application (for example under the action of light, acids or bases). Such conversions may also take place after use.

The compounds of the formula I are in particular suitable for efficiently controlling ar- thropodal pests such as arachnids and insects as well as nematodes..

In particular, they are suitable for controlling insect pests, such as

Insects: from the order of Lepidoptera, for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Den- drolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mel- lonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, HeIIuIa undalis, Hibernia defoliaria, Hyphantria cunea, Hypo- nomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, MaIa- cosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Pano- //s flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthori- maea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sito- troga cerealella, Sparganothis pilleriana, Spodoptera eridania, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni and Zeiraphera canadensis,

from the order of Coleoptera (beetles), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebu- losa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chae- tocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica Iongicornis, Diabrotica 12-punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, lps typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, MeI- olontha hippocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria,

from the order of Diptera, for example Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicu- laris, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hyso- cyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea and Tipula paludosa,

from the order of Thysanoptera (thrips), e.g. Dichromothrips spp., Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,

from the order of Hymenoptera e.g. Athalia rosae, Alia cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, So- lenopsis geminata and Solenopsis invicta,

from the order of Heteroptera, e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor,

from the order of Homoptera, e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis craccivora, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisa tabaci, Bemisa argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Bre- vicoryne 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, Macrosiphum avenae, Macrosiphum eu- phorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzodes persicae, Myzus ascalonicus, Myzus cerasi, Myzus varians, Na- sonovia ribis-nigri, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mail, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mall, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera aurantiiand, and Viteus vitifolii,

from the order of lsoptera (termites), e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus und Termes natalensis, and

from the order of Orthoptera, e.g. Acheta domestica, Blatta orientalis, Blattella ger- manica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asy- namorus.

They are also suitable for controlling Nematodes : plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species; cyst-forming nematodes, Globodera rosto- chiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Het- erodera 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, Mesocri- conema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dip- saci and other Ditylenchus species; AwI 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,

Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhyn- chus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species.

The compounds of the formula I and their salts 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 per- sicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus mou- bata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appen-

diculatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Acu- lus 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 cinnabaήnus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis.

Compounds of the formula I are particularly useful for controlling insects of the order Lepidoptera.

For use in a method according to the present invention, the compounds I can be converted into the customary formulations, e.g. solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular purpose; it is intended to ensure in each case a fine and uniform distribution of the compound according to the invention.

The formulations are prepared in a known manner, e.g. by extending the active ingredient with solvents and/or carriers, if desired using emulsifiers and dispersants. Solvents/auxiliaries, which are suitable, are essentially: - water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used. carriers such as ground natural minerals (e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g. highly disperse silica, silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin-sulfite waste liquors and methylcellulose.

Suitable surfactants are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic 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, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether,

tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methylcellulose.

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 NMR spectrum).

The following are examples of formulations: 1. Products for dilution with water

A Soluble concentrates (SL)

10 parts by weight of a compound according to the invention are dissolved in water or in a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active ingredient dissolves upon dilution with water.

B Dispersible concentrates (DC)

20 parts by weight of a compound according to the invention are dissolved in cyclohexanone with addition of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion.

C Emulsifiable concentrates (EC)

15 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5% strength). Dilution with water gives an emulsion.

D Emulsions (EW, EO)

40 parts by weight of a compound according to the invention are dissolved in xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5% strength). This mixture is introduced into water by means of an emulsifier (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion.

E Suspensions (SC, OD)

In an agitated ball mill, 20 parts by weight of a compound according to the invention are milled with addition of dispersant, wetters and water or an organic solvent to give a fine active ingredient suspension. Dilution with water gives a stable suspension of the active ingredient.

F Water-dispersible granules and water-soluble granules (WG, SG) 50 parts by weight of a compound according to the invention are ground finely with addition of dispersants and wetters and made into water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active ingredient.

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

75 parts by weight of a compound according to the invention are ground in a rotor- stator mill with addition of dispersant, wetters and silica gel. Dilution with water gives a stable dispersion or solution with the active ingredient.

2. Products to be applied undiluted

H Dustable powders (DP)

5 parts by weight of a compound according to the invention are ground finely and mixed intimately with 95% of finely divided kaolin. This gives a dustable product.

I Granules (GR, FG, GG, MG)

0.5 parts by weight of a compound according to the invention is ground finely and associated with 95.5% carriers. Current methods are extrusion, spray drying or the fluidized bed. This gives granules to be applied undiluted.

J ULV solutions (UL)

10 parts by weight of a compound according to the invention are dissolved in an organic solvent, for example xylene. This gives a product to be applied undiluted.

The active ingredients can be used as such, in the form of their formulations or the use forms prepared therefrom, eg. 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 intended purposes; it is intended to ensure in each case the finest possible distribution of the active ingredients according to the invention.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable 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 solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. 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.

Compositions of this invention may also contain other active ingredients, for example other pesticides such as insecticides and herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants 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.

These agents usually are admixed with the agents according to the invention in a weight ratio of 1 : 100 to 100: 1.

The following list of pesticides together with which the compounds according to the invention can be used, is intended to illustrate the possible combinations, but not to impose any limitation:

Organophosphates: Acephate, Azinphos-methyl, Chlorpyrifos, Chlorfenvinphos, Diazi- non, Dichlorvos, Dicrotophos, Dimethoate, Disulfoton, Ethion, Fenitrothion, Fenthion, Isoxathion, Malathion, Methamidophos, Methidathion, Methyl-Parathion, Mevinphos, Monocrotophos, Oxydemeton-methyl, Paraoxon, Parathion, Phenthoate, Phosalone, Phosmet, Phosphamidon, Phorate, Phoxim, Pirimiphos-methyl, Profenofos, Prothiofos, Sulprophos, Tetrachlorvinphos, Terbufos, Triazophos, Trichlorfon;

Carbamates: Alanycarb, Bendiocarb, Benfuracarb, Carbaryl, Carbofuran, Carbosulfan, Fenoxycarb, Furathiocarb, Indoxacarb, Methiocarb, Methomyl, Oxamyl, Pirimicarb, Propoxur, Thiodicarb, Triazamate;

Pyrethroids: Bifenthrin, Cyfluthrin, Cypermethrin, alpha-Cypermethrin, Deltamethrin, Esfenvalerate, Ethofenprox, Fenpropathrin, Fenvalerate, Cyhalothrin, Lambda- Cyhalothrin, Permethrin, Silafluofen, Tau-Fiuvalinate, Tefluthrin, Tralomethrin, Zeta- Cypermethrin;

Arthropod growth regulators: a) chitin synthesis inhibitors: benzoylureas: Chlorflua- zuron, Diflubenzuron, Flucycloxuron, Flufenoxuron, Hexaflumuron, Lufenuron, Novalu- ron, Teflubenzuron, Triflumuron; Buprofezin, Diofenolan, Hexythiazox, Etoxazole, Clofentazine; b) ecdysone antagonists: Halofenozide, Methoxyfenozide, Tebufenozide; c) juvenoids: Pyriproxyfen, Methoprene, Fenoxycarb; d) lipid biosynthesis inhibitors: Spirodiclofen;

various: Abamectin, Acequinocyl, Acetamiprid, Amitraz, Azadirachtin, Bifenazate, Car- tap, Chlorfenapyr, Chlordimeform, Cyromazine, Diafenthiuron, Diofenolan, Emamectin, Endosulfan, Ethiprole, Fenazaquin, Fipronil, Formetanate, Formetanate-hydrochlorid, Hydramethylnon Imidacloprid, Indoxacarb, Metaflumizon, Nitenpyram, Piperonylbu- toxid, Pyridaben, Pymetrozine, Spinosad, Tebufenpyrad, Thiamethoxam, Thiacloprid, Thiocyclam, Pyridalyl, Pyridalyl, Flonicamid, Fluacypyrim, Milbemectin, Spiromesifen, Spirodiclofen, Flupyrazofos, NC 512, Tolfenpyrad, Flubendiamide, Bistrifluron, Ben- clothiaz, Pyrafluprole, Pyriprole, Amidoflumet, Flufenerim, Cyflumetofen, Acequinocyl, Lepimectin, Profluthrin, Dimefluthrin, Amidrazone, Metaflumizone, N-Ethyl-2,2-dichlor- 1-methylcyclo-propanecarboxamid-2-(2,6-dichlor-α.α.α -tri-fluoro-p-tolyl)hydrazon, N-

ethyl-2,2-dimethylpropionamide-2-(2,6-dichlorq- α.α.α -trifluoro-p-tolyl)-hydrazon, and the pesticide of the following formula as described in WO 98/05638:

Aminoisothiazoles of the formula

wherein R = -CH ₂ O CH ₃ or H and R ¹ = -CF ₂ CF ₂ CF ₃ ;

Anthranilamides of the formula

and a compound of the formula

The aforementioned compositions are particularly useful for protecting plants against infestation of said pests or to combat these pests in infested plants.

However, the compounds of formula I are also suitable for the treatment of seeds. Application to the seeds is carried out before sowing, either directly on the seeds or after having pregerminated the latter.

Compositions which are 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 Dustable powders (DP, DS)

Preferred FS formulations of compounds of formula I for seed treatment usually comprise from 0.5 to 80% of the active ingredient, from 0,05 to 5 % of a wetter, from 0.5 to 15 % of a dispersing agent, from 0, 1 to 5 % of a thickener, from 5 to 20 % of an antifreeze agent, from 0,1 to 2 % of an anti-foam agent, from 1 to 20 % of a pigment and/or a dye, from 0 to 15 % of a sticker /adhesion agent, from 0 to 75 % of a filler/vehicle, and from 0,01 to 1 % of a preservative.

Suitable pigments or dyes for seed treatment formulations are 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 112, 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.

Stickers / adhesion agents are added to improve the adhesion of the active materials on the seeds after treatment. Suitable adhesives are block copolymers EO/PO surfac- tants but also polyvinylalcohols, polyvinylpyrrolidones, polyacrylates, polymethacry- lates, polybutenes, polyisobutylenes, polystyrene, polyethyleneamines, polyethyl- eneamides, polyethyleneimines (Lupasol®, Polymin®), polyethers and copolymers derived from these polymers.

For use against ants, termites, wasps, flies, mosquitos, crickets, or cockroaches, 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 particular necessities in terms of stickyness, moisture retention or aging characteristics.

The bait employed in the composition is a product which is sufficiently attractive to in- cite 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.

Formulations of compounds of formula I as aerosols (e.g in spray cans), oil sprays or pump sprays are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are preferably composed of the active compound, solvents such as lower alcohols (e.g. methanol, etha- nol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocarbons (e.g. kerosenes) having boiling ranges of approximately 50 to 250 ⁰ C, dimethyl- formamide, N-methylpyrrolidone, dimethyl sulfoxide, aromatic hydrocarbons 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 required, 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.

The compounds of formula I and its respective compositions can also be used in mos- quito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems.

The compounds of formula I and its compositions can be used for protecting non-living material, in particular cellulose-based materials such as wooden materials e.g. 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 protect 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.

In the methods according to the invention the pests are controlled by contacting the target parasite/pest, its food supply, habitat, breeding ground or its locus with a pesti- cidally effective amount of compounds of formula I or with a salt thereof or with a composition, containing a pesticidally effective amount of a compound of formula I or a salt thereof.

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

In general, "pesticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various compounds/compositions used in the invention. A pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.

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

The compounds of formula I may be also used to protect growing plants from attack or infestation by pests by contacting the plant with a pesticidally effective amount of com- pounds of formula I. 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).

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.

In the treatment of seed, the application rates of the mixture 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, in particular from 1 g to 200 g per 100 kg of seed.

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 m ² , preferably from 0.001 to 2O g per 100 m ² .

Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m ² treated material, desirably from 0.1 g to 50 g per m ² .

lnsecticidal 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 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.

For use in spray compositions, the content of active ingredient is from 0.001 to 80 weights %, preferably from 0.01 to 50 weight % and most preferably from 0.01 to 15 weight %.

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

The products were characterized by coupled High Performance Liquid Chromatogra- phy/mass spectrometry (HPLC/MS), by ¹ H-NMR or by their melting point.

For HPLC An analytical RP-18 column (Chromolith Speed ROD, dimensions 50 x 4.6 mm, from Merck KGaA, Germany), which was operated at 30 and 4O ⁰ C, at a flow-rate of 1.8 ml/min and an injection volume of 2 μl was used. The mobile phase used was acetonitrile/water with 0.1% trifluoroacetic acid in a ratio of 5:95 to 95:5 in 5 minutes). HPLC was carried out using either method A (high speed overview method; recorded on Agilent 1100 LC/MSD) or method B (slow method; recorded on Agilent 1100 LC/MSD). Mass spectrometry was carried out using a quadrupole mass spectrometer with electrospray ionization at 80V in the positive mode.

In the examples the following abbreviations are used: m.p. melting point RT retension time HPLC/MS eq. equivalent(s) Ex. Example

I. Preparation Examples

1.1 Preparation of N-oxy-amidrazones of the formula Ia

1.1 A Route A: general procedure

To a suspension of polymer supported triphenylphosphine (1.100 g, 5 eq., 2.5 mmol) in 10 ml of dichloromethane the appropiate cyclopropanecarboxylic acid

(0.5 mmol, 1 eq.), arylhydrazine (0.5 mmol, 1 eq.) and tetrachloromethane (0.63 ml, 7 mmol, 14 eq.) were successively added at room temperature. The mixture was shaked at 40 ⁰ C for 72 h. The mixture was allowed to cool to room temperature and the appropriate 0-(alkyl)-hydroxylamine-hydrochloride (1 mmol, 2 eq.) and diisopropylethylamin (Hϋnig's Base, 5 equiv., 2.5 mmol) were added. The mixture was shaked at room temperature over night. The mixture was filtered and the organic phase washed with citric acid and concentrated in vacuo. The resulting residue was finally purified by preparative HPLC (Purospher® STAR RP-18 endcapped, 5μ, 75x25, Merk KGaA, Germany, water/acetonitrile).

Alternatively, the N-oxy-amidrazones were prepared according to route B below.

1.1 B Route B

Example 1 : Preparation of 2,2-dichloro-N'-(2,6-dichloro-4-trifluoromethyl-phenyl)-1- methyl-N-propoxy-cyclo-propanecarbohydrazonamide

1.1 2,2-Dichloro-1 -methyl-cyclopropanecarbonyl chloride

432.5 ml of thionyl chloride were added to a solution of 501.0 g of 2,2-dichloro-1- methyl-cyclopropanecarbonic acid and 0.5 ml of N,N-dimethylformamide in 600 ml of dichloromethane at 30-40 ⁰ C. The mixture was refluxed over night. Excessive reactants were removed under reduced pressure (4O ⁰ C, 25 mbar). The re- suiting residue (+ 83.4 g of 75 % carbonyl chloride from a previous experiment)

was purified by fractional distillation (58-61 ⁰ C ₁ 15 mbar) to yield 601.7 g of 2,2- dichloro-1 -methyl-cyclopropanecarbonyl chloride.

1.2 N-[Chloro-(2,2-dichloro-1-methyl-cyclopropyl)methylene]-N'-( 2,6-dichloro-4- trifluoromethyl-phenyl)-hydrazine

To a solution of 250.0 g of (2,6-dichloro-4-trifluoromethyl-phenyl)-hydrazine in 3.5 I of toluene 195.1 g of 2,2-dichloro-1 -methyl-cyclopropanecarbonyl chloride were added dropwise at 15-25 ⁰ C. The mixture was stirred for 30 min and then ex- tracted with 2 L of an aqueous sodium hydroxide solution (3% strength) at 8O ⁰ C.

The organic phase was extracted twice with 11 of water and dried azeotropically. 104.2 ml of thionyl chloride were added at 110 ⁰ C and the mixture was refluxed for 3 h. Then excessive thionyl chloride and 2 I of toluene were distilled off. The solution was cooled to 25°C, filtered over 200 g of silica gel and washed with 0.7 I of toluene. The solvent was evaporated to yield 412.7 g of N-[chloro-(2,2- dichloro-1-methyl-cyclopropylmethylene]-N'-(2,6-dichloro-4-t rifluormethyl-phenyl)- hydrazine.

1.3 2,2-Dichloro-N'-(2,6-dichloro-4-trifluoromethyl-phenyl)-1-me thyl-N-propoxy-cyclo- propanecarbohydrazonamide

1.00 g of N-[chloro-(2,2-dichloro-1-methyl-cyclopropylmethylene]-N'-(2 ,6-dichloro- 4-trifluoromethyl-phenyl)-hydrazine were dissolved in 20 ml of diethyl ether. Successively, 0.9 ml of triethylamine and 3.00 g of 1-(aminooxy)propane- hydrochloride were added and the reaction mixture was stirred over night. The mixture was diluted with 20 ml ether and extracted three times with water. The organic phase was acidified with concentrated HCI and then evaporated. The resulting residue was taken up in 5 ml of toluene, filtered and the precipitate dissolved in water. The pH was adjusted to 8 using 50% strength by weight of an aqueous sodium hydroxide solution. The aqueous phase was then extracted with ether several times. The combined organic phases were washed with water, dried and evaporated to yield 0.42 g of 2,2-dichloro-N'-(2,6-dichloro-4- trifluoromethyl-phenyO-i-methyl-N-propoxy-cyclo-propanecarbo hydrazonamide.

Using essentially the same procedure as described above in route A or B and substituting the appropriate carboxylic acid, the appropiate arylhydrazine and the appropriate hydroxylamine ether hydrohalide, the compounds of the formula Ia shown in table I were prepared and identified by ¹ H-NMR or MS spectral analysis or melting point.

Table I: Compounds la/la'

00

έ

OI

1.2 Preparation of the diazene compounds of the formula Ib

Example 39: 1-[(2,2-dichloro-1-methyl-cyclopropyl)(propoxyimino)methyl]- 2-(2,6- dichloro-4-trifluoromethyl-phenyl)-diazene

0.41 g of 2,2-dichloro-N'-(2,6-dichloro-4-trifluoromethyl-phenyl)-1-me thyl-N- propoxy-cyclo-propanecarbohydrazonamide were dissolved in 10 ml of toluene and 0.09 ml of pyridine were added. After cooling to 0-5 ⁰ C, a solution of 0.25 g of 2,3-dichloro-5,6-dicyano-1 ,4-benzoquinone (DDQ) in 10 ml of toluene were added portionwise. The reaction mixture was allowed to warmed up to room temperature and then stirred over night. After dilution with 50 ml of ether, the organic phase was extracted three times with water, dried and concentrated. The residue was purified by column chromatography (silica gel, petrol ether/ethyl acetate) to yield 0.27 g of the title compound

Using essentially the same procedure as described in example 39 above and substituting the appropiate hydrazonamide compound Ia, the compounds of the formula Ib shown in table Il were prepared and identified by their ¹ H-NMR spectral data.

Table II:

The action of the compounds of the formula I against pests was demonstrated by the following experiments:

II. Assessment of the activity against animal pest

11.1 Brown planthopper (nilaparvata lugens)

The active compounds were formulated as a 20:80 acetone:water solution. Surfactant (Alkamuls EL 620) was added at the rate of 0.1% (vol/vol).

Potted rice plants of 3-4 weeks of age are sprayed with 10 ml of the test solution using air driven hand atomizer (Devillbis atomizer) at 1.7 bar. The treated plants are allowed to dry for about 1 hour and covered with Mylar cages. The plants are inoculated with 10 adults of the specie (5 male and 5 females) and kept at 25- 27°C and 50-60% humidity for 3 days. Mortality is assed after 24, 48 and 72 hours after treatment. Dead insects are usually found in the water surface. Each treatment is replicated once.

In this test, compounds of examples no. 5, 6, 9 and 17 at 300 ppm showed a mortality of at least 80% in comparison with untreated controls.

11.2 Cotton aphid (aphis gossypii), mixed life stages

The active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic ^® surfactant.

Cotton plants at the cotyledon stage (one plant per pot) were infested by placing a heavily infested leaf from the main colony on top of each cotyledon. The aphids were allowed to transfer to the host plant overnight, and the leaf used to transfer the aphids was removed. The cotyledons were dipped in the test solution and allowed to dry. After 5 days, mortality counts were made.

In this test, the compounds of example no. 3 and 6 at 300 ppm showed a mortality of at least 70% in comparison with untreated controls.

11.3 Cowpea Aphid (aphis craccivora)

The active compounds were formulated in 50:50 acetone:water and 0.1 % (vol/vol) Alkamuls EL 620 surfactant.

Potted cowpea beans of 7-10 days of age are inoculated with aphids 24 h before treatment by clipping a leaf infested with cowpea aphid approximately 30 individuals. The treated beans are sprayed with 5 ml of the test solution using air

driven hand atomizer (Devillbis atomizer) at 25 psi, allowed to air dry and kept at 25-27 ⁰ C and 50-60% humidity for 3 days. After 72 h, mortality was assessed.

In this test, the compound of example no. 4 at 300 ppm showed a mortality of at least 80% in comparison with untreated controls.

11.4 Diamondback 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 is 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 is inoculated with 10 third instar larvae and kept at 25-27°C and 50-60% humidity for 3 days. Mortality and feeding rate are assessed after 72 h of treatment.

In this test, the compounds of example no. 1 and 2 at 500 ppm showed a mortality of at least 80% mortality in comparison with untreated controls. In this test, the compounds of example no. 3, 4, 5, 6, and 8 at 300 ppm a mortality of at least 80% in comparison with untreated controls.

11.5 Green Peach Aphid (Myzus persicae), mixed life stages

The active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic ^® surfactant.

Pepper plants in the 2 ^nd leaf-pair stage (variety 'California Wonder') were infested with approximately 40 laboratory-reared aphids by placing infested leaf sections on top of the test plants. The leaf sections were removed after 24 hr. The leaves of the intact plants were dipped into gradient solutions of the test compound and allowed to dry. Test plants were maintained under fluorescent light (24 hour pho- toperiod) at about 25 ⁰ C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on check plants, was determined after 5 days.

In this test, compound of example no. 3 at 300 ppm showed a mortality of at least 70% in comparison with untreated controls.

11.6 Southern Armyworm (spodoptera eridania), 2 ^nd -3 ^rd instar larvae

The active compounds were formulated as a 10.000 ppm solution in a mixture of 35% acetone and water, which was diluted with water, if needed.

A Sieva lima bean leaf expanded to 7-8 cm in length is dipped in the test solution with agitation for 3 seconds and allowed to dry in a hood. The leaf is then placed in a 100 x 10 mm petri dish containing a damp filter paper on the bottom and ten 2nd instar caterpillars. At 4 days, observations are made of mortality, reduced feeding, or any interference with normal molting.

In this test, compounds of example no. 1 , 3, 4, 5, 6, 7, 8, 9, 10, 13, 15, 17 and 39 at 300 ppm showed a mortality of at least 80% in comparison with untreated controls.

11.7 Silverleaf Whitefly (bemisia argentifolii), adult

The active compounds were formulated in 50:50 acetone:water and 100 ppm Kinetic® surfactant.

Selected cotton plants were grown to the cotyledon state (one plant per pot). The cotyledons were dipped into the test solution to provide complete coverage of the foliage and placed in a well-vented area to dry. Each pot with treated seedling was placed in a plastic cup and 10 to 12 whitefly adults (approximately 3-5 day old) were introduced. The insects were colleted using an aspirator and an 0.6 cm, non-toxic 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. The cups were covered with a re-usable screened Hd (150 micron mesh polyester screen PeCap from Tetko Inc). Test plants were maintained in the holding room at about 25 ⁰ C and 20-40% relative humidity for 3 days avoiding direct exposure to the fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the cup. Mortality was assessed 3 days after treatment of the plants.

In this test, compound of example no. 6 at 300 ppm showed a mortality of at least 70% in comparison with untreated controls.

11.8 Orchid thrips (dichromothrips corbetti)

Dichromothrips corbetti adults used for bioassay were obtained from a colony maintained continuously under laboratory conditions. For testing purposes, the test compound was diluted to a concentration of 300 ppm (wt compound: vol diluent) in a 1 :1 mixture of acetone:water, plus 0.01% Kinetic ^® surfactant.

Thrips potency of each compound was evaluated by using a floral-immersion technique. Plastic petri dishes were used as test arenas. All petals of individual, intact orchid flowers were dipped into treatment solution for approximately 3 seconds and allowed to dry for 2 hours. Treated flowers were placed into individual petri dishes along with 10 - 15 adult thrips. The petri dishes were then covered with lids. All test arenas were held under continuous light and a temperature of about 28 ⁰ C for duration of the assay. After 4 days, the numbers of live thrips were counted on each flower, and along inner walls of each petri dish. The level of thrips mortality was extrapolated from pre-treatment thrips numbers.

In this test, compounds of example no. 4, 5, 9, and 17 at 300 ppm showed a mortality of at least 80% in comparison with untreated controls.

Comparative tests of the insecticidal activity

The compounds of examples 6 and 7 according to the present invention and comparative compounds A and B according to EP 0 604 798 were tested in greenhouse-assays for their ability to combat spodoptera eridania (southern armyworm) and plutella xylostella (diamondback moth), respectively, as described above. Comparative compounds A and B were prepared according to the methods given in EP 0 604 798.

Compounds that were examined:

example 6: R ¹ : CH ₂ CH=CH ₂ compound A: R ¹ : CH ₂ CH=CH ₂ example 7: R ¹ : C(CH ₃ ) ₃ compound B: R ¹ : C(CH ₃ J ₃

In the assay against spodoptera eridania (southern armyworm), compounds of the examples 6 and 7 according to the present invention at 300 ppm showed a mortality of at least 80 %, whereas comparison compounds A and B at 300 ppm showed no mortality.

In the assay against plutella xylostella (diamondback moth), the compound of the example 6 according to the present invention at 300 ppm showed a mortality of at least 80 %, whereas comparison compound A at 300 ppm showed no mortality.