WO1994001432A1

WO1994001432A1 - Imidazole derivatives

Info

Publication number: WO1994001432A1
Application number: PCT/EP1993/001682
Authority: WO
Inventors: Christof Hildenbrand; Jean-Claude Gehret; Olivier Tinembart
Original assignee: Ciba-Geigy Ag
Priority date: 1992-07-13
Filing date: 1993-06-30
Publication date: 1994-01-20
Also published as: JPH06511260A; CA2116455A1; EP0603377A1; AU4561993A

Abstract

Novel 4,5-dicyanoimidazole derivatives of formula (I), wherein X is oxygen, sulfur, SO or SO2; R1 is hydrogen, C1-C6alkyl, C1--C6haloalkyl, C1-C6hydroxyalkyl, C1-C6cyanoalkyl, or a C1-C6alkylene substituted by C1-C6alkoxy, C1-C6haloalkoxy, C1-C6alkylthio, C1-C6haloalkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, C1-C6hydroxyalkyl, C1-C6alkyloxycarbonyl, C1-C6alkylcarbonyl, C1-C6alkylcarbonyloxy or by COOH; R2 is hydrogen, halogen, CN, C1-C6alkyl, C1-C6haloalkyl, C1-C6cyanoalkyl, C1-C6hydroxyalkyl, C1-C6alkoxy, C1-C6haloalkoxy, C1-C6alkylthio, C1-C6haloalkylthio or C3-C7cycloalkyl; R3 is hydrogen, halogen, C1-C6alkyl, C1-C6haloalkyl, cyano or nitro; R4 is hydrogen, halogen, nitro, cyano, NCS, C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy or C1-C6haloalkoxy; and R5 is hydrogen, halogen, nitro, C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy or C1-C6haloalkoxy; or R4 and R5 together form a -O-(CH2)m-O- bridge, wherein m is an integer selected from the group consisting of 1, 2 and 3, with the proviso that R4 and R5 are located at adjacent carbon atoms; including the physiologically tolerable addition compounds, can be used against insects and representatives of the order Acarina that are harmful to animals and plants, as well as against helminths in warm-blooded animals.

Description

Imidazole derivatives

The present invention relates to novel 4,5-dicyanoimidazolyl derivatives of formula I below, which have anthelmintic, acaricidal and insecticidal activity. The invention relates also to pharmaceutical compositions and pesticides based on the compounds of formula I. It relates also to the preparation of the active ingredients and compositions and to the use thereof for controlling helminths, especially nematodes, cestodes and trematodes in warm-blooded animals, especially in domestic animals and productive livestock, and to the use thereof for controlling pests of the order Arthropoda, especially for controlling insects and representatives of the order Acarina. The present invention relates likewise to valuable intermediates which can be used for the preparation of active ingredients, especially those of formula I below.

The novel 4,5-dicyanoimidazolyl derivatives have the following formula I

wherein

X is oxygen, sulfur, SO or SO₂;

R₁ is hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁ -C₆hydroxyalkyl, C₁-C₆cyanoalkyl, or a C₁-C₆alkylene substituted by C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylthio, C₁-C₆-haloalkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆-haloalkylsulfonyl, C₁-C₆hydroxyalkyl, C₁-C₆alkyloxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆alkylcarbonyloxy or by COOH;

R₂ is hydrogen, halogen, CN, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆cyanoalkyl, C₁-C₆-hydroxyalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylthio, C₁-C₆haloalkylthio or

C₃-C₇cycloalkyl;

R₃ is hydrogen, halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, cyano or nitro;

R₄ is hydrogen, halogen, nitro, cyano, NCS, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy or C₁-C₆haloalkoxy; and R₅ is hydrogen, halogen, nitro, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy or C₁-C₆haloalkoxy; or

R₄ and R₅ together form a -O-(CH₂)_m -O- bridge, wherein m is an integer selected from the group consisting of 1, 2 and 3, with the proviso that R₄ and R₅ are located at adjacent carbon atoms;

including the physiologically tolerable addition compounds.

In the definition of formula I according to the invention, the individual generic terms are to be understood as having the following meanings:

Within the scope of the present invention, the term alkyl by itself or as part of another substituent is to be understood as meaning, for example, the following straight-chained and branched groups, depending on the number of carbon atoms indicated: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, etc.. Haloalkyl by itself or as part of haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl is a mono- to per-halogenated alkyl substituent, for example CH₂CI, CHCI₂, CCI₃, CH₂F, CHF₂, CF₃, CH₂Br, CHBr₂, CBr₃, CH₂I, CI₃, CHClF, CHBrCl, CFBrCl, C₂F₅, CH₂CH₂Cl,

CHCICH₃, C₂CI₅, CHFCHCI₂, etc., but preferably CF₃. Here and in the following, halogen is to be understood as meaning fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, but especially chlorine. NCS is N≡C-S-; alkylthio is alkyl-S-; alkylsulfinyl is alkyl-S(O)-; alkylsulfonyl is alkyl-S(O)₂-; alkylcarbonyl is alkyl-C(O)-; alkylcarbonyloxy is alkyl-C(O)-O-; alkyloxycarbonyl is alkyl-O-C(O)-;

alkylene is a saturated aliphatic bridge member that is unbranched or branched, for example -CH₂-; -CH₂CH₂-; -CH₂CH(CH₃)-; -CH₂CH(CH₃)CH₂-; -CH₂C(CH₃)₂-; etc..

Cycloalkyl by itself or as part of a substituent is, depending on the number of carbon atoms indicated, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.. Cyanoalkyl is an alkyl group in which from one to three hydrogen atoms have been substituted by CN, preferably an alkyl group in which a CN group is located at the terminal carbon atom. Accordingly, hydroxyalkyl is an alkyl group in which from one to three hydrogen atoms have been substituted by OH, preferably an alkyl group in which an OH group is located at the terminal carbon atom.

The expression "physiologically tolerable addition compounds" is to be understood as meaning complexes or salts of a compound of formula I with an inorganic or organic base, which are formed by the addition of an equivalent amount of a salt-forming base to the base molecule of formula I, or with solvents such as dimethylformamide (DMF) or dimethylacetamide (DMA). Examples of suitable inorganic bases are oxides, hydroxides, carbonates and hydrogen carbonates of alkali metals and alkaline earth metals (e.g. CaO, BaO, NaOH, KOH, Ca(OH)₂, KHCO₃, NaHCO₃, K₂CO₃ or Na₂CO₃). Typical representatives of suitable organic bases are tetrabutylammonium hydroxide; trialkylamines, such as triethylamine, or dialkylamines, such as diethyl- or dipropyl-amine.

The following sub-groups within the scope of formula I, inter alia, are preferred on account of their pronounced activity:

Group (A): Compounds of formula I wherein

X is oxygen or sulfur;

R₁ is hydrogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃hydroxyalkyl, or a Ci~C4alkylene substituted by C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio, C₁-C₃alkylsulfinyl, C₁-C₃haloalkylsulfinyl, C₁-C₃alkylsulfonyl, C₁-C₃haloalkylsulfonyl, C₁-C₃hydroxyalkyl, C₁-C₃alkyloxycarbonyl, C₁-C₃alkylcarbonyl or by COOH;

R₂ is hydrogen, halogen, CN, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃cyanoalkyl, C₁-C₃-alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio or C₃-C₆cycloalkyl;

R₃ is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, cyano or nitro;

R₄ is hydrogen, halogen, nitro, cyano, NCS, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy or C₁-C₃haloalkoxy; and

R₅ is hydrogen, halogen, nitro, C₁-C₃alkyl, C₁-C₃-ιaloalkyl, C₁-C₃alkoxy or C₁-C₃haloalkoxy; or

R₄ and R₅ together form a -O-(CH₂)_m-O- bridge, wherein m is an integer selected from the group consisting of 1, 2 and 3, with the proviso that R₄ and R₅ are located at adjacent carbon atoms;

including the physiologically tolerable addition compounds.

Group (B): Compounds of formula I wherein

X is oxygen or sulfur;

R₁ is hydrogen, C₁- C₃alkyl, C₁-C₃haloalkyl, C₁-C₃ hydroxyalkyl, or a C₁-C₄alkylene substituted by C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio, C₁-C₃alkylsulfinyl, C₁-C₃haloalkylsulfinyl, C₁-C₃alkylsulfonyl, C₁-C₃haloalkylsulfonyl, C₁-C₃hydroxyalkyl, C₁-C₃alkyloxycarbonyl, C₁-C₃alkylcarbonyl or by COOH;

R₂ is hydrogen, halogen, C₁-C₂haloalkyl or C₁ -C₂alkoxy; R₃ is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, cyano or nitro;

R₄ is hydrogen, halogen, C₁-C₂alkyl or OCF₃; and

R₅ is hydrogen, halogen, nitro, C₁-C₂alkyl, OCF₃ or CF₃;

including the physiologically tolerable addition compounds.

Group (C): Compounds of formula I wherein

X is oxygen or sulfur;

R₁ is hydrogen;

R₂ is hydrogen, fluorine, chlorine, bromine, CN, C₁-C₂haloalkyl or C₁-C₂alkoxy;

R₃ is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, cyano or nitro;

R₄ is hydrogen, halogen, C₁-C₂alkyl or OCF₃; and

R₅ is hydrogen, halogen, nitro, C₁-C₂alkyl, OCF₃ or CF₃;

including the physiologically tolerable addition compounds.

Group (D): Compounds of formula I wherein

X is oxygen or sulfur;

R₁ is C₁-C₂alkyl, preferably methyl;

R₂ is hydrogen, halogen, C₁-C₂haloalkyl or C₁-C₂alkoxy;

R₃ is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, cyano or nitro;

R₄ is hydrogen, halogen, C₁-C₂alkyl or OCF₃; and

R₅ is hydrogen, halogen, nitro, C₁-C₂alkyl, OCF₃ or CF₃;

including the physiologically tolerable addition compounds.

Group (E): Compounds of formula I wherein

X is oxygen;

R₁ is hydrogen, C₁-C₃alkyl, C₁-C₃haloalkyl, or a C₁-C4alkylene substituted by C₁-C₃-alkoxy, Ci^haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio, C₁-C₃alkylsulfιnyl, C₁-C₃haloalkylsulfinyl, C₁-C₃alkylsulfonyl, C₁-C₃haloalkylsulfonyl, C₁-C₃hydroxyalkyl, C₁-C₃alkyloxycarbonyl, C₁-C₃alkylcarbonyl or by COOH;

R₂ is hydrogen, halogen, C₁-C₂haloalkyl, C₁-C₂haloalkoxy or C₁-C₂ alkoxy;

R₃ is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, cyano or nitro;

R₄ is hydrogen, halogen, C₁-C₂alkyl or OCF₃; and

R₅ is hydrogen, halogen, nitro, C₁-C₂alkyl, OCF₃ or CF₃; including the physiologically tolerable addition compounds.

Group (F): Compounds of formula I wherein

X is oxygen or sulfur;

R₁ is hydrogen, C₁-C₃alkyl or C₁-C₂hydroxyalkyl;

R₂ is hydrogen, fluorine, chlorine, CF₃, CN, C₁-C₂alkyl or C₁-C₂alkoxy;

R₃ is hydrogen, fluorine or chlorine;

R₄ is hydrogen; and

R₅ is hydrogen, fluorine, chlorine, nitro, C₁-C₂alkoxy, OCF₃ or CF₃; or

R₄ and R₅ together form a -O-CH₂CH₂-O- group which links the carbon atoms C-5 and

C-6 of the benzothiazole group;

including the physiologically tolerable addition compounds.

Group (G): Compounds of formula I wherein

X is oxygen or sulfur;

R₁ is C₁-C₃ haloalkyl, or a C₁-C₄alkylene substituted by C₁-C₃alkoxy, C₁-C₃ haloalkoxy, C₁-C₃hydroxyalkyl or by COOH;

R₂ is hydrogen, halogen, CN, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃cyanoalkyl, C₁-C₃-alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio or C₃-Cgcycloalkyl;

R₃ is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, cyano or nitro;

R₅ is hydrogen, halogen, nitro, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy or C₁-C₃haloalkoxy; or

R₄ and R₅ together form a -O-(CH₂)_m-O- bridge, wherein m is an integer selected from the group consisting of 2 and 3, with the proviso that R₄ and R₅ are located at adjacent carbon atoms;

including the physiologically tolerable addition compounds.

Group (H): Compounds of formula I wherein

X is oxygen or sulfur;

R₁ is C₁-C₃haloalkyl, or a C₁-C₄alkylene substituted by C₁-C₃alkoxy;

R₂ is hydrogen, halogen, C₁-C₂haloalkyl or C₁-C₂alkoxy; R₃ is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, cyano or nitro;

R₄ is hydrogen, halogen, C₁-C₂alkyl or OCF₃; and

R₅ is hydrogen, halogen, nitro, C₁-C₂alkyl, OCF₃ or CF₃;

including the physiologically tolerable addition compounds.

Within groups A to H, special preference is given to those compounds of formula I wherein the benzothiazolyl-X- group is bonded in the para-position.

Within groups A to H, special preference is given also to those compounds of formula I wherein X is oxygen.

Especially preferred individual representatives of the compounds of formula I include:

2-[4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-phenyl]-4,5-dicyanoimidazole;

2-[4-(6-chloro-benzothiazolyl-2-oxy)-phenyl]-4,5-dicyanoimidazole;

2-[2-chloro-4-(6-chloro-benzothiazolyl-2-oxy)-phenyl]-4,5-dicyanoimidazole;

2-[4-(5-trifluoromethyl-benzothiazolyl-2-oxy)-phenyl]-4,5-dicyanoimidazole;

1-methyl-2-[4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-phenyl]-4,5-dicyanoimidazole; and

1-ethoxymethyl-2-[4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-3-chlorophenyl]- 4,5-dicyanoimidazole.

Other interesting representatives from groups G and H are, for example:

2-[4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-3,5-dichlorophenyl]-1-ethoxymethyl-4,5-dicy anoimidazole;

2-[4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-2-chlorophenyl]-1-ethoxymethyl-4,5-dicyanoimidazole;

2-[4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-3-fluorophenyl]-1-ethoxymethyl- 4,5-dicyanoimidazole;

2-[4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-3-chlorophenyl]-1-ethoxymethyl- 4,5-dicyanoimidazole;

2-[4-(5-trifluoromethyl-benzothiazolyl-2-oxy)-phenyl]-1-ethoxymethyl-4,5-dicyanoimidazole;

2-[4-(5-trifluoromethyl-benzothiazolyl-2-oxy)-phenyl]-1-carboxymethyl-4,5-dicyanoimidazole; and 2-[4-(5-trifluoromethyl-benzothiazolyl-2-oxy)-phenyl]-1-(3,3,3-trifluoropropyl)- 4,5-dicyanoimidazole.

The compounds of formula I are prepared either

(a) by cyclising a compound of formula II

,

wherein the substituents R₁, R₂, R₃, R₄, R₅ and X are as defined under formula I, with a suitable oxidising agent and, in those cases in which R₁ in the compound of formula II is hydrogen, introducing an alkyl radical mentioned under Ri in formula I by subsequent alkylation, or

(b) by reacting a compound of formula III ,

wherein the substituents R₁, R₂, R₃ and X are as defined under formula I, with a compound of formula IV ,

wherein R₄ and R₅ are as defined under formula I and Y is a customary leaving group.

The cyclisation of variant (a) may be carried out using cyclising agents known per se. Examples of suitable cyclising agents are:

Lead tetraacetate in glacial acetic acid or a mixture of glacial acetic acid and an aromatic inert hydrocarbon, for example benzene, toluene or xylene [cf. F.F. Stephens et al., J. Chem. Soc, 2971 (1949) and 1722 (1950)].

Iodine in a polar organic solvent, for example N-methyl-2-pyrrolidone, with the addition of an inorganic base, such as sodium acetate, and at elevated temperature [cf.

EP-269 238].

Organic oxidising agents, such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), in a polar inert solvent, such as acetonitrile, and at elevated temperature [cf. EP-283 173].

Aqueous organic oxidising agents, such as sodium hypochlorite [cf. Jpn. Kokai Tokhyo koko 79, 112, 861] or N-chlorosuccinimide in a polar organic solvent, such as N,N- dimethylformamide (DMF), with the addition of a soluble organic base, such as nicotinamide [cf. Synthesis 1058 (1984)].

In the cyclisation, the reaction temperatures are customarily from +20° to +100°C, preferably from +40° to +90°C.

In variant (a), a compound of formula II wherein Ri is hydrogen is preferably used as starting material and one of the alkyl substituents mentioned under Ri from the group C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆hydroxyalkyl, C₁-C₆cyanoalkyl, and a C₁-C₅-alkylene substituted by C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₁-C₆alkylsulfmyl, C₁-C₆haloalkylsulfmyl, C₁-C₆alkylsulfonyl, C₁-C₆haloalkylsulfonyl, C₁-C₆haloalkoxy, C₁-C₆hydroxyalkyl, C₁-C₆alky loxycarbonyl, C₁-C₆-alkylcarbonyl, C₁-C₆alkylcarbonyloxy or by COOH, is subsequently introduced by means of one of the customary alkylating methods.

Variant (b) [reaction of III with IV] is preferably carried out in the presence of an inert polar organic solvent, such as dimethyl sulfoxide (DMSO), N,N-dimethylacetamide (DMAA) or DMF, the reaction advantageously being carried out in the presence of an inorganic base at temperatures of from 0° to +180°C, preferably from +20° to +160°C. Examples of suitable inorganic bases are oxides, hydroxides, carbonates and hydrogen carbonates of alkali metals and alkaline earth metals (e.g. CaO, BaO, NaOH, KOH, Ca(OH)₂, KHCO₃, NaHCO₃, K₂CO₃ and Na₂CO₃), and also acetates, for example CH₃COONa and CH₃COOK. Also suitable as bases are alkali metal alcoholates, for example sodium ethanolate, sodium propanolate, potassium tert-butanolate and sodium methanolate. The base is advantageously added in an amount of from 10 to 100 % of the equimolar amount, based on the reactants. The water of reaction formed in this reaction may optionally be removed from the reaction mixture by means of a customary entrainer, for example methylene chloride, benzene or toluene.

Customary leaving groups in connection with reaction (b) are to be understood as being, for example, halogen, especially chlorine, bromine or iodine, preferably chlorine, or sulfonyl radicals, such as benzoylsulfonyl, paratosyl or lower-alkylsulfonyl, especially mesyl.

The compounds of formula IV are known or can be prepared analogously to known representatives.

The compounds of formula II are novel and, on account of their structure, are especially suitable for the preparation of the active end products of formula I or of other active substances having that partial structure. They therefore form an important part of the present invention.

The compounds of formula III wherein R₁=H are prepared by cyclising a compound of formula V

,

wherein R₂, R₃ and X are as defined under formula I and R₁ is H, as described under reaction (a) in the case of formula II and, in those cases in which R₁ in the compound of formula V is hydrogen, introducing an alkyl radical mentioned under R₁ in formula I by subsequent alkylation.

In that reaction it is especially advantageous to use iodine/N-methylpyrrolidone as cyclising agent.

In the cyclisation of compounds of formula V, a compound of formula V wherein R₁ is hydrogen is preferably used as starting material and one of the alkyl substituents mentioned under R₁ from the group C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆hydroxyalkyl, C₁-C₆cyanoalkyl, and a C₁-C₆alkylene substituted by C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆-alkylsulfonyl, C₁-C₆haloalkylsulfonyl, C₁-C₆haloalkoxy, C₁-C₆hydroxyalkyl, C₁-C₆-alkyloxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆alkylcarbonyloxy or by COOH, is subsequently introduced by means of one of the customary alkylating methods.

The compounds of formula III may also be prepared from compounds of formula VI ,

wherein R₁, R₂- R₃ and X may have all the meanings given under formula I, by demethylation at the CH₃-X- group. There may be used as demethylating agent, for example, aluminium chloride in chlorobenzene, it being possible to proceed analogously to J.W. ApSimon et al., Can. J. Chem. 60, 308 (1982). The compounds of formula VI may in turn be prepared according to methods known in the literature.

The compounds of formula II are prepared by reacting compounds of formula VII ,

wherein R₂, R₃, R₄, R₅ and X are as defined under formula I, with 2,3-diamino-maleic acid dinitrile (DAMN) of formula IX ,

wherein R₁ is as defined under formula I, and, in those cases in which R₁ in the compound of formula IX is hydrogen, introducing an alkyl radical mentioned under R₁ in formula I by subsequent alkylation. The compounds of formula V are prepared in a completely analogous manner, namely by reacting a compound of formula VIII ,

wherein R₂, R₃ and X are as defined under formula I, with DAMN (of formula IX).

The reactions with DAMN may be carried out analogously to the reactions described in the literature, for example analogously to DE 3 726 044 or R.W. Begland et al., J. Org. Chem. 39, 2341 (1974).

In the reactions with a compound of formula IX, a compound of formula IX wherein R₁ is hydrogen is preferably used as starting material and one of the alkyl substituents mentioned under Ri from the group C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆hydroxyalkyl, C₁-C₆cyanoalkyl, and a C₁-C₆alkylene substituted by C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylthio, C₁-C₆haloalkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆-alkylsulfonyl, C₁-C₆haloalkylsulfonyl, C₁-C₆haloalkoxy, C₁-C₆hydroxyalkyl, C₁-C₆-alkyloxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆alkylcarbonyloxy or by COOH, is subsequently introduced by means of one of the customary alkylating methods.

The compounds of formula VIII are known or can be prepared analogously to the known representatives, for example as described in J. Chem. Eng. Data 28, 39 (1983);

R.N. Young et al., Tetrahedron Letters 25, 1753 (1984) or L.C. Raiford et al., J. Amer. Chem. Soc. 52, 4576 (1930).

The compounds of formula VII are novel, and the invention relates also to them. They are valuable precursors in the preparation of the active compounds of formula I. In them there is already a partial structure that is important for the activity of the end products. The compounds of formula VII are prepared by reacting compounds of formula VIII with compounds of formula IV, the reaction preferably being carried out in an inert polar solvent, such as DMSO or DMF, and advantageously in the presence of an inorganic base at temperatures of from 0° to +180°C, preferably from +20° to +160°C. Examples of suitable inorganic bases are oxides, hydroxides, carbonates and hydrogen carbonates of alkali metals and alkaline earth metals (e.g. CaO, BaO, NaOH, KOH, Ca(OH)₂, KHCO₃, NaHCO₃, K₂CO₃ and Na₂CO₃), and also acetates, for example CH₃COONa and

CH₃COOK. Also suitable as bases are alkali metal alcoholates, for example sodium ethanolate, sodium propanolate, potassium tert-butanolate and sodium methanolate. The base is advantageously added in an amount of from 10 to 100 % of the equimolar amount, based on the reactants. The water of reaction formed in this reaction may optionally be removed from the reaction mixture by means of a customary entrainer, for example methylene chloride, benzene or toluene.

It has now been found that the compounds of formula I according to the invention are valuable active ingredients in pest control while being well tolerated by warm-blooded animals, fish and plants. Thus, they not only exhibit a broad activity spectrum against helminths, such as nematodes, cestodes and trematodes, that parasitise the animal organism, especially mammals, their action being directed especially against nematodes (roundworms), but they may also be used equally successfully against phytopathogenic insects and arachnids which occur on useful plants and ornamentals in agriculture, especially in cotton, vegetable and fruit crops, in forestry, in the protection of stored goods and material stocks, and in the hygiene sector, especially on domestic animals and productive livestock. They are effective against all or individual development stages of normally sensitive and also resistant species of insects and arachnids.

As a particular feature of the compounds of formula I attention is drawn to their surprisingly high tolerability by warm-blooded animals, as a result of which they are superior to many other anthelmintics. The practical handling thereof in the treatment of worm-infested animals is extraordinarily simplified by the fact that they are tolerated by the treated animals without symptoms even at relatively high doses.

As anthelmintics, the novel compounds of formula I according to the invention are suitable, for example, for controlling parasitic nematodes of the orders (according to

K.I. Skrajabin)

Rhabditida

Ascaridida

Spirurida

Trichocephalida

or for controlling cestodes of the orders (according to Wardle & McLeod)

Cyclophyllidae

Pseudophyllidae or for controlling trematodes of the order

Digenea

in domestic animals and productive livestock, such as cattle, sheep, goats, horses, pigs, red deer, cats, dogs and fowl. They may be administered to the animals either as a single dose or repeatedly, the single doses preferably being from 1 to 50 mg per kg of body weight, depending on the species of animal. In many cases, protracted administration may result in an improved action or may permit the use of smaller total doses.

In the case of the animal pests from the group of the insects and Acarina, the activity of the compounds of formula I according to the invention may manifest itself in the death of the pests immediately or only at a later date, for example at moulting, or in reduced oviposition and/or a reduced hatching rate. The above-mentioned animal pests include: of the order Lepidoptera for example

Acleris spp., Adoxophyes spp., Aegeria spp., Agrotis spp., Alabama argillaceae, Amylois spp., Anticarsia gemmatalis, Archips spp., Argyrotaenia spp., Autographa spp., Busseola fusca, Cadra cautella, Carposina nipponensis, Chilo spp., Choristoneura spp., Clysia ambiguella, Cnaphalocrocis spp., Cnephasia spp., Cochylis spp., Coleophora spp.,

Crocidolomia binotalis, Cryptophlebia leucotreta, Cydia spp., Diatraea spp., Diparopsis castanea, Earias spp., Ephestia spp., Eucosma spp., Eupoecilia ambiguella, Euproctis spp.,

Euxoa spp., Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana,

Lymantria spp., Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta,

Operophtera spp., Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea,

Pectinophora gossypiella, Phthorimaea operculella, Pieris rapae, Pieris spp., Plutella xylostella, Prays spp., Scirpophaga spp., Sesamia spp., Sparganothis spp., Spodoptera spp.,

Synanthedon spp., Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.;

of the order Coleoptera for example

Agriotes spp., Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp.,

Leptinotarsa decemlineata, Lissorhoptrus spp., Melolontha spp., Orycaephilus spp.,

Otiorhynchus spp., Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp.,

Scarabeidae, Sitophilus spp., Sitotroga spp., Tenebrio spp., Tribolium spp. and

Trogoderma spp.;

of the order Orthoptera for example Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp.,

Periplaneta spp. and Schistocerca spp.;

of the order Isoptera for example

Reticulitermes spp.;

of the order Psocoptera for example

Liposcelis spp.;

of the order Anoplura for example

Haematopinus spp., Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.;

of the order Mallophaga for example

Damalinea spp. and Trichodectes spp.;

of the order Thysanoptera for example

Frankliniella spp., Hercinothrips spp., Taeniothrips spp., Thrips palmi, Thrips tabaci and

Scirtothrips aurantii;

of the order Heteroptera for example

Cimex spp., Distantiella theobroma, Dysdercus spp., Euchistus spp., Eurygaster spp.,

Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis,

Scotinophara spp. and Triatoma spp.;

of the order Homoptera for example

Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp.,

Aspidiotus spp., Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium,

Chrysomphalus dictyospermi, Coccus hesperidum, Empoasca spp., Eriosoma larigerum,

Erythroneura spp., Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp.,

Macrosiphus spp., Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp.,

Pemphigus spp., Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp.,

Pulvinaria aethiopica, Quadraspidiotus spp., Rhopalosiphum spp., Saissetia spp.,

Scaphoideus spp., Schizaphis spp., Sitobion spp., Trialeurodes vaporariorum, Trioza erytreae and Unaspis citri;

of the order Hymenoptera for example

Acromyrmex, Atta spp., Cephus spp., Diprion spp., Diprionidae, Gilpinia polytoma,

Hoplocampa spp., Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.;

of the order Diptera for example

Aedes spp., Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster,

Fannia spp., Gastrophilus spp., Glossina spp., Hypoderma spp., Hyppobosca spp., Liriomyza spp., Lucilia spp., Melanagromyza spp., Musca spp., Oestrus spp., Orseolia spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Rhagoletis pomonella, Sciara spp.,

Stomoxys spp., Tabanus spp., Tannia spp. and Tipula spp.;

of the order Siphonaptera for example

Ceratophyllus spp. and Xenopsylla cheopis;

of the order Acarina for example

Acarus siro, Aceria sheldoni, Aculus schlechtendali, Amblyomma spp., Argas spp.,

Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp.,

Dermanyssus gallinae, Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora,

Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp.,

Sarcoptes spp., Tarsonemus spp. and Tetranychus spp.; and

of the order Thysanura for example

Lepisma saccharina.

The compounds of formula I according to the invention are therefore highly suitable inter alia for controlling pests from the group of the insects and arachnids in cotton, fruit, maize, soybean, citrus and vegetable crops. In particular, plant-eating insects, such as Anthonomus grandis, plant-eating insect larvae, such as the larvae of Spodoptera littoralis or Heliothis virescens, sucking insects, such as Aphis craccivora or Bemisia tabaci, and soil insects, such as Diabrotica balteata, are controlled.

The compounds of formula I may also be used as dressing agents for protecting seeds (fruit, tubers, grains) and plant cuttings against noxious insects as well as against phytopathogenic noxious insects that occur in the soil. The invention relates also to

compositions comprising compounds of formula I as active ingredient, especially cropprotecting compositions, and to their use in the agricultural sector, including farming, horticulture and forestry, or related fields.

Furthermore, the present invention relates also to the preparation of those compositions, which comprises homogeneously mixing and/or grinding the active ingredient with one or more substances or groups of substances described herein. The formulation stages can be supplemented by kneading, granulating (in the case of granules) and, optionally, compressing (in the case of pellets). Also included is a prophylactic and/or curative method of controlling plant pests and/or helminths in mammals, which comprises applying the compounds of formula I according to the invention, or the compositions according to the invention, to the locus of the pest.

Target subjects for the use as anthelmintics are all warm-blooded animals which may be infested with helminths, especially mammals and fowl, but most especially domestic animals, productive livestock and pet animals, such as cows, horses, donkeys, sheep, goats, llamas, camels, red deer, pigs, dogs, cats, rabbits, chickens, turkeys, ducks, geese, pheasants, partridges, etc., as well as all fur-producing breeding animals. Of course, infested zoo animals may also be treated successfully.

It is generally known that of the endoparasites occuring in warm-blooded animals it is particularly the helminths that cause great damage to the animals infested with them. Where there is chronic and especially epidemic occurrence of worm-related disorders in herds of animals, such damage caused by helminthiases can assume serious economic proportions. In the animals affected, the damage manifests itself inter alia as losses of productivity, reduced resistance to other diseases, and increased mortality. Especially dangerous worm-related disorders are caused by helminths parasitising the gastrointestinal tract and other organs and, despite numerous prophylactic measures, still occur relatively frequently in ruminants, such as cattle, sheep and goats, as well as in horses, pigs, fowl, red deer, dogs and cats.

In this description the term "helminths" is to be understood as meaning especially parasitic worms that belong to the Platyhelminthes (cestodes, trematodes) and Nemathelminthes (nematodes and related species), that is to say tapeworms, sucker worms and roundworms of the gastrointestinal tract and other organs (e.g. the liver, lungs, kidneys, lymph vessels, blood, etc.).

There is therefore an urgent need to provide therapeutic compositions suitable for controlling helminths in all their development stages and for guarding against attack by such parasites.

Although a number of substances having anthelmintic activity are known that have been proposed for controlling the various species of helminth, these have not proved completely satisfactory, either because at a tolerable dose it is not possible to make full use of their activity spectrum, or because at therapeutically effective doses they exhibit undesired side-effects or properties. In this respect the resistance to certain classes of substances, which occurs more and more today, is also increasingly significant. "Albendazol", which is described, for example, in the literature (British Pat. No. 1 464 326; Am. J. Vet. Res. 38, 1425-1426 (1977); Am. J. Vet. Res. 37, 1515-1516 (1976); Am. J. Vet. Res. 38, 807-808 (1977); Am. J. Vet. Res. 38, 1247-1248 (1977)), has only a limited anthelmintic activity spectrum in ruminants. Its action against benzimidazole-resistant nematodes and adult liver flukes is completely inadequate, and in particular the pathogenically important immature migrating forms of the latter are not affected at doses tolerated by the host animal.

It has surprisingly been found that the novel compounds of formula I have a broad activity spectrum against helminths, such as nematodes, cestodes and trematodes, that parasitise the animal organism, especially warm-blooded animals, their action being directed especially against nematodes (roundworms).

Target crops to be protected against phytopathogenic pests within the scope of the present invention comprise e.g. the following species of plants:

cereals (wheat, barley, rye, oats, rice, maize, sorghum and related crops), beet (sugar beet and fodder beet), pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries), leguminous plants (beans, lentils, peas, soybeans), oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts), cucumber plants (cucumber, marrows, melons), fibre plants (cotton, flax, hemp, jute), citrus fruit (oranges, lemons, grapefruit, mandarins), vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika), lauraceae (avocados, cinnamon, camphor), or plants such as tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas and natural rubber plants, as well as ornamentals.

The compounds of formula I are normally applied in the form of compositions and can be applied to the crop area or plant to be treated, simultaneously or in succession, with further compounds. These further compounds can be fertilisers or micronutrient donors or other preparations that inf.πence plant growth. They can also be selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or other

application-promoting adjuvants customarily employed in formulation technology.

The good pesticidal activity of the compounds of formula I according to the invention corresponds to a mortality of at least 50-60 % of the mentioned pests. The activity of the compounds of the invention and of the compositions comprising them against animal pests can be substantially broadened and adapted to prevailing circumstances by the addition of other insecticides and/or acaricides. Examples of suitable additives include representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenols and derivatives thereof, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons, and Bacillus thuringiensis

preparations.

The compounds of formula I are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology, and can therefore be formulated in known manner e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.

A preferred method of applying a compound of formula I, or an agrochemical composition which comprises at least one of said compounds, is foliar application. The number of applications and the rate of application depend on the risk of infestation by the

corresponding pathogen. However, the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) if the locus of the plant is impregnated with a liquid formulation, or if the compounds are applied in solid form to the soil, e.g. in granular form (soil application). In paddy rice crops, such granules may be applied in metered amounts to the flooded rice field. The compounds of formula I may, however, also be applied to seeds (coating), either by impregnating the seeds with a liquid formulation comprising a compound of formula I, or by coating them with a solid formulation.

The formulations, i.e. the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I, or combinations of those compounds with other agrochemical active ingredients, and, where appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface- active compounds (surfactants).

Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms of alkylbenzenes, e.g. xylene mixtures or alkylated naphthalenes, aliphatic or cycloaliphatic hydrocarbons, such as cyclohexane, paraffins or tetrahydronaphthalene, alcohols such as ethanol, propanol and butanol, and glycols and their ethers and esters, such as propylene glycol, dipropylene glycol ether, ethylene glycol, ethylene glycol mono-methyl or monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetonol alcohol, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, or water, vegetable oils, such as rape oil, castor oil, coconut oil or soybean oil; and, where appropriate, also silicone oils.

The solid carriers used, e.g. for dusts and dispersible powders, are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are calcite or sand. In addition, a great number of granulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulverised plant residues.

Depending on the nature of the compound of formula I to be formulated, or of the combinations of those compounds with other insecticides or acaricides, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term "surfactants" will also be understood as comprising mixtures of surfactants.

Both so-called water-soluble soaps and also water-soluble synthetic surface-active compounds are suitable anionic surfactants.

Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C₁₀-C₂₂), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tall oil. Fatty acid methyltaurin salts may also be mentioned as surfactants.

More frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates. The fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and generally contain a

C₈-C₂₂alkyl radical, which also includes the alkyl moiety of acyl radicals, e.g. the sodium or calcium salt of lignosulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing approximately 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or of a condensate of naphthalenesulfonic acid and formaldehyde. Also suitable are corresponding phosphates, e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids.

Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, or saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols. Further suitable non-ionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of non-ionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.

Cationic surfactants are preferably quaternary ammonium salts which contain, as N-substituent, at least one C₈-C₂₂alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals. The salts are preferably in the form of halides, methyl sulfates or ethyl sulfates, e.g. stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.

The surfactants customarily employed in formulation technology are described, for example, in the following publications:

"McCutcheon's Detergents and Emulsifiers Annual", MC Publishing Corp., Glen Rock, NJ, USA, 1988,

H. Stache, "Tensid-Taschenbuch", 2nd edition, C. Hanser Verlag, Munich, Vienna, 1981,

M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-1981.

The pesticidal compositions for crop protection usually comprise 0.1 to 99 %, preferably 0.1 to 95 %, of a compound of formula I or of combinations of that compound with other insecticides or acaricides, 1 to 99.9 % of a solid or liquid adjuvant, and 0 to 25 %, preferably 0.1 to 25 %, of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations, which have considerably lower concentrations of active ingredient. Typical application concentrations are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm. The rates of application per hectare are generally from 1 to 2000 g of active ingredient per hectare, preferably from 10 to 1000 g/ha, especially from 20 to 600 g/ha.

Preferred forms of administration for use in warm-blooded animals for controlling helminths include solutions, emulsions, suspensions (drenches), feed additives, powders, tablets, including effervescent tablets, boli, capsules and microencapsulations. Care must be taken to ensure that the formulation adjuvants are physiologically tolerable.

Suitable binders for tablets and boli are chemically modified, water- or alcohol-soluble, polymeric natural substances, such as starch, cellulose or protein derivatives (e.g. methylcellulose, carboxymethylcellulose, ethylhydroxyethylcellulose, proteins such as zein, gelatine and the like) as well as synthetic polymers, for example polyvinyl alcohol, polyvinylpyrrolidone, etc.. Tablets also comprise fillers (e.g. starches, microcrystalline cellulose, sugars, lactose, etc.), lubricants and disintegrators.

If the anthelmintic compositions are in the form of feed concentrates, then there are used as carriers, for example, high-performance feed, fodder grain or protein concentrates. In addition to the active ingredients, such feed concentrates or compositions may comprise additives, vitamins, antibiotics, chemotherapeutics, or other pesticides, especially bacteriostats, fungistats, coccidiostats, or hormone preparations, substances having an anabolic action, or substances that promote growth, affect the meat quality of animals for slaughter, or that are otherwise beneficial to the organism. If the compositions or the compounds of formula I contained therein are added directly to the feed or to the animal's drinking water, then the finished feed or the finished drinking water preferably comprises the active ingredients in a concentration of approximately from 0.0005 to 0.02 % by weight (5-200 ppm).

The compositions according to the invention may be administered to the animals to be treated perorally, parenterally or subcutaneously, the compositions being in the form of solutions, emulsions, suspensions (drenches), powders, tablets, boli and capsules.

The anthelmintic compositions according to the invention usually comprise 0.1 to 99 % by weight, preferably 0.1 to 95 % by weight, of a compound of formula I, Ia or mixtures thereof, 99.9 to 1 % by weight, preferably 99.8 to 5 % by weight, of a solid or liquid adjuvant, including 0 to 25 % by weight, preferably 0.1 to 25 % by weight, of a surfactant.

Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.

Such compositions may also comprise further additives, such as stabilisers, antifoams, viscosity regulators, binders, tackifiers, as well as other active ingredients for obtaining special effects.

The present invention relates also to such anthelmintic compositions employed by the end user.

In each of the methods of pest control according to the invention, or in each of the pesticidal compositions according to the invention, the compounds of formula I may be used in all their spatial configurations, their mixtures, or in the form of their salts.

The invention relates also to a method for the prophylactic protection of warm-blooded animals, especially domestic animals, productive livestock and pet animals, against parasitic helminths, which method comprises administering the compounds of formula I, or the active ingredient formulations prepared therefrom, to the animals in the form of an additive to their feed or their drinking water, or in solid or liquid form orally, by injection or parenterally. The invention relates also to the compounds of formula I according to the invention for use in one of the mentioned methods.

The following Examples serve solely to illustrate the invention, without limiting it.

Preferred formulations are composed especially of the following constituents (throughout, percentages are by weight):

Emulsifiable concentrates:

active ingredient: 1 to 90 %, preferably 5 to 20 %

surface-active agent: 1 to 30 %, preferably 10 to 20 %

liquid carrier: 5 to 94 %, preferably 70 to 85 %

Dusts:

active ingredient: 0.1 to 10 %, preferably 0.1 to 1 %

solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %

Suspension concentrates:

active ingredient: 5 to 75 %, preferably 10 to 50 %

water: 94 to 24 %, preferably 88 to 30 %

surface-active agent: 1 to 40 %, preferably 2 to 30 %

Wettable powders:

active ingredient: 0.5 to 90 %, preferably 1 to 80 %

surface-active agent: 0.5 to 20 %, preferably 1 to 15 %

solid carrier: 5 to 95 %, preferably 15 to 90 %

Granules:

active ingredient: 0.5 to 30 %, preferably 3 to 15 %

solid carrier: 99.5 to 70 %, preferably 97 to 85 %

The compositions may also comprise further additives, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers, as well as fertilisers or other active ingredients for obtaining special effects. The following Examples serve to illustrate the invention, but they do not limit it. The symbol "h" stands for hour, "min." stands for minute, and "N" means normality. 1. Preparation Examples

1.1. Preparation of 4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-benzaldehyde (precursor)

A mixture of 20.3 g of 2-chloro-6-trifluoromethoxy-benzothiazole, 9.8 g of 4-hydroxybenzaldehyde, 22.1 g of anhydrous K₂CO₃ and 100 ml of DMSO is stirred for 24 h at +60°C under a nitrogen atmosphere. Then the internal temperature is increased to +80°C and the mixture is stirred for a further 7 h. After cooling to room temperature, the mixture is filtered, and the filtrate is poured onto ice-water and extracted several times with ethyl acetate. The combined organic phases are washed in succession with 2N hydrochloric acid, 2N sodium hydroxide solution and saturated sodium chloride solution, dried over sodium sulfate and concentrated by evaporation. The crystalline crude product is dissolved in diethyl ether and the solution is purified with active carbon. Approximately half the solvent is evaporated off, n-hexane is added to the residue that remains, and the mixture is cooled in an ice-bath for the purpose of crystal formation. The crystalline product is isolated by filtration and dried, yielding 12.4 g of 4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-benzaldehyde having a melting point of 67-68°C.

1.2. Preparation of the Schiff's base of 4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-benzaldehyde (precursor)

A mixture of 18.7 g of 4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-benzaldehyde, 5.9 g of DAMN and 150 ml of ethanol is heated under reflux for 50 h. The reaction mixture is brought to room temperature and then concentrated completely by evaporation under reduced pressure. The crystal mass that remains is taken up in ethyl acetate, and activated carbon is added. After filtration, the ester solution is concentrated slightly, and n-hexane is added for the purpose of crystallisation. The crystalline product is isolated by filtration and again dissolved in ethyl acetate, again purified with activated carbon, as described, and again precipitated by means of n-hexane. Drying yields 14.3 g of the Schiff's base of 4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-benzaldehyde having a melting point of 204-206°C. As the NMR spectrum shows, it is a mixture of the E/Z isomers having the following structure:

1.3. Preparation of 2-[4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-phenyl]-4,5-dicyanoimidazole (end product)

14.3 g of the Schiff's base of 4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-benzaldehyde prepared according to Procedure 1.2. and 4.9 g of nicotinic acid amide are dissolved under a nitrogen atmosphere in 150 ml of DMF; 5.3 g of N-chlorosuccinimide are added in portions, and the mixture is slowly heated in an oil bath. When a temperature of +50°C is reached, the heat source is removed. The internal temperature nevertheless continues to rise to approximately +70°C, whereupon a solid precipitates. After cooling the reaction mixture to room temperature, the precipitate is filtered off and the filtrate is diluted with ethyl acetate. The organic phase is washed several times with water and saturated sodium chloride solution and is dried over magnesium sulfate, and the solvent is removed in vacuo. The crystalline crude product is further dried in vacuo for 24 h at +80°C in order to remove final traces of DMF and is then dissolved in ethyl acetate, and the ester solution is purified with activated carbon. A portion of the ester is removed by concentration by evaporation and the solution that remains is made to crystallise by the addition of n-hexane. The crystalline phase is isolated by filtration and dried, yielding 10.4 g of 2-[4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-phenyl]-4,5-dicyanoimidazole having a melting point of 186-189°C.

The compounds mentioned in the following Tables may also be prepared analogously to the above-described methods.

2. Formulation Examples

2.1. Emulsifiable concentrates a) b) c) a compound of Table 1 25% 40% 50% calcium dodecylbenzenesulfonate 5% 8% 6% castor oil polyethylene glycol ether

(36 mol of ethylene oxide) 5% - - tributylphenol polyethylene glycol

ether (30 mol of ethylene oxide) - 12% 4% cyclohexanone - 15% 20% xylene mixture 65% 25% 20%

Emulsions of any desired concentration can be produced from such concentrates by dilution with water.

2.2. Emulsifiable concentrates a) b) c) a compound of Table 1 10% 8% 60% octylphenol polyethylene glycol ether

(4-5 mol of ethylene oxide) 3% 3% 2% calcium dodecylbenzenesulfonate 3% 4% 4% castor oil polyethylene glycol ether

(35 mol of ethylene oxide) 4% 5% 4% cyclohexanone 30% 40% 15% xylene mixture 50% 40% 15%

2.3. Suspension concentrate

a compound of Table 1 40 %

ethylene glycol 10 %

nonylphenol polyethylene glycol ether

(15 mol of ethylene oxide) 6 %

sodium lignosulfonate 10 %

carboxymethylcellulose 1 %

37 % aqueous formaldehyde solution 0.2 %

silicone oil in the form of a 75 %

aqueous emulsion 0.8 %

water 32 %

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

2.4. Water-dispersible powder mixtures a) b) c) a compound of Table 1 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % - oleic acid 3 % - 5 % sodium diisobutylnaphthalenesulfonate - 6 % 10 % octylphenol polyethylene glycol ether

(7-8 mol of ethylene oxide) - 2 % - highly dispersed silicic acid 5 % 10 % 10 % kaolin 62 % 27 % _

The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.

2.5. Dusts a) b)

a compound of Table 1 2 % 5 %

highly dispersed silicic acid 1 % 5 %

talcum 97 % - kaolin - 90 % Ready-for-use dusts are obtained by intimately mixing the carriers with the active ingredient and grinding the mixture.

2.6. Granules a) b)

a compound of Table 1 5 % 10 %

kaolin 94 % - highly dispersed silicic acid 1 % - attapulgite - 90 %

The active ingredient is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo. Such granules can be mixed with the animal feed.

2.7. Granules

a compound of Table 1 10 %

sodium lignosulfonate 2 %

carboxymethylcellulose 1 %

kaolin 87 %

The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

2.8. Granules

a compound of Table 1 3 %

polyethylene glycol (mol. wt. 200) 3 %

kaolin 94 %

The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner. 2.9. Tablets or boli

I a compound of Table 1 33.00 %

methylcellulose 0.80 %

highly dispersed silicic acid 0.80 %

maize starch 8.40 %

II crystalline lactose 22.50 %

maize starch 17.00 %

microcrystalline cellulose 16.50 %

magnesium stearate 1.00 %

I The methylcellulose is stirred into water. When the material has swollen, the silicic acid is stirred in and the mixture is suspended homogeneously. The active ingredient and the maize starch are mixed. The aqueous suspension is incorporated into that mixture, and the mixture is kneaded to form a dough. The mass so obtained is granulated through a 12 M sieve and dried.

II All four adjuvants are mixed thoroughly.

III The pre-mixtures obtained according to I and II are mixed and compressed to form tablets or boli.

2.4. Injectables

A. Oily vehicle (slow release)

a compound of Table 1 0.1 - 1.0 g

groundnut oil ad 100 ml a compound of Table 1 0.1 - 1.0 g

sesame oil ad 100 ml

Preparation: The active ingredient is dissolved in some of the oil with stirring and, optionally, with slight heating. After cooling, the solution is made up to the desired volume and sterile-filtered through a suitable 0.22 μm membrane filter. B. Water-miscible solvent (moderate release rate)

a compound of Table 1 0.1 - 1.0 g

4-hydroxymethyl-1,3-dioxolan

(glycerol formal) 40 g

1,2-propanediol ad 100 ml

a compound of Table 1 0.1 - 1.0 g

glyceroldimethyl ketal 40 g

1,2-propanediol ad 100 ml

Preparation: The active ingredient is dissolved in some of the solvent, with stirring; the solution is made up to the desired volume and sterile-filtered through a suitable 0.22 μm membrane filter.

C. Aqueous solubilisate (rapid release)

a compound of Table 1 0.1 - 1.0 g

polyethoxylated castor oil

(40 ethylene oxide units) 10 g

1,2-propanediol 20 g benzyl alcohol 1 g

aqua ad inject. ad 100 ml a compound of Table 1 0.1 - 1.0 g

polyethoxylated sorbitan monooleate

(20 ethylene oxide units) 8 g

4-hydroxymethyl-1,3-dioxolan

(glycerol formal) 20 g benzyl alcohol 1 g

aqua ad inject. ad 100 ml

Preparation: The active ingredient is dissolved in the solvents and the surfactant, and the solution is made up to the desired volume with water. Sterile filtration through a suitable membrane filter having a pore diameter of 0.22 μm.

The aqueous systems may also be used preferably for oral and/or intraruminal administration. 3. Biological Examples The anthelmintic activity is demonstrated by means of the following tests:

3.1. Test on sheep infested with nematodes such as Haemonchus contortus and

Trichostrongylus colubriformis

The active ingredient is administered in the form of a suspension, by means of a stomach probe or by rumen injection, to sheep which have previously been artificially infested with nematodes such as Haemonchus contortus and Trichostrongylus colubriformis. From 1 to 3 animals are used per test or per dose. Each sheep is treated with only a single dose.

A first evaluation is made by comparing the number of worm eggs excreted in the sheep's faeces before and after treatment.

Seven to ten and after the treatment, the sheep are sacrificed and dissected. Evaluation istrade by counting the number of worms remaining in the intestine after the treatment, untreated sheep infested at the same time and in the same manner are used as control orcomparison. In this test, compounds of formula I of Table 1 achieve a marked reduction in nematode infestation. For example, when 20 mg of active ingredient are used per kg of body weight, compounds 1.1, 1.2, 1.5, 1.7 and 1.8 achieve a reduction of approximately 90-100 % in nematode infestation. With some compounds, that result is also achieved with an even lower dose, for example with 10 mg of active ingredient per kg of body weight or even smaller amounts of active ingredient.

3.2. Test on sheep infested with Fasciola hepatica

The active ingredient is administered in the form of a suspension, by means of a stomach probe or by rumen injection, to sheep which have previously been artificially infested with Fasciola hepatica. 3 animals are used per test or per dose. Each animal is treated with only a single dose.

A first evaluation is made by comparing the number of worm eggs excreted in the sheep's faeces before and after treatment. Three to four weeks after the treatment, the sheep are sacrificed and dissected. Evaluation is made by counting the number of liver flukes remaining in the bile duct after the treatment. Untreated sheep infested at the same time and in the same manner are used as control or comparison. The difference in the number of liver flukes found in the two groups indicates the level of activity of the test compound.

In this test, compounds of Table 1 exhibit good activity against Fasciola hepatica at doses of less than 50 mg of active ingredient per kg of body weight. Of those compounds, compound no. 1.1 proves to be particularly effective against Fasciola hepatica.

The insecticidal and acaricidal activity of the compounds of formula I is demonstrated by means of the following tests:

3.3. Ovicidal/larvicidal action against Heliothis virescens

Egg deposits of Heliothis virescens on cotton are sprayed with an aqueous emulsion comprising the test compound in a concentration of 400 ppm. 8 days later, the percentage of eggs which have hatched and the survival rate of the caterpillars are evaluated in comparison with untreated controls (% reduction in the population).

Compounds of Table 1 exhibit good activity against Heliothis virescens in this test.

Compounds 1.5, 1.6, 1.8 and 1.33 and exhibit especially a pronounced development-inhibiting activity.

3.4. Action against Aphis craccivora

Pea seedlings are infested with Aphis craccivora and then sprayed with a spray mixture comprising the test compound in a concentration of 400 ppm, and incubated at 20°C. Evaluation is made 3 and 6 days later. The percentage reduction in the population (% activity) is determined by comparing the number of dead aphids on the treated plants with that on untreated plants.

Compounds of Table 1 exhibit good activity against Aphis craccivora in this test. In particular, compound 1.1 is more than 80 % effective. 3.5. Action against Tetranychus urticae

Young bean plants are populated with a mixed population of Tetranychus urticae and sprayed one day later with an aqueous emulsion comprising the test compound in a concentration of 400 ppm. The plants are then incubated for 6 days at 25°C and then evaluated. The percentage reduction in the population (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with that on untreated plants.

For example, compound 1.4 from Table 1 is more than 80 % effective against Tetranychus urticae in this test.

Claims

What is claimed is:

1. A 4,5-dicyanoimidazole derivative of formula I

wherein

X is oxygen, sulfur, SO or SO₂;

R₁ is hydrogen, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆hydroxyalkyl, C₁-C₆cyanoalkyl, or a C₁-C₆alkylene substituted by C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylthio, C₁-C₆-haloalkylthio, C₁-C₆alkylsulfinyl, C₁-C₆haloalkylsulfinyl, C₁-C₆alkylsulfonyl, C₁-C₆-haloalkylsulfonyl, C₁-C₆hydroxyalkyl, C₁-C₆alkyloxycarbonyl, C₁-C₆alkylcarbonyl, C₁-C₆alkylcarbonyloxy or by COOH;

R₂ is hydrogen, halogen, CN, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆cyanoalkyl, C₁-C₆-hydroxyalkyl, C₁-C₆alkoxy, C₁-C₆haloalkoxy, C₁-C₆alkylthio, C₁-C₆haloalkylthio or C₃-C₇cycloalkyl;

R₃ is hydrogen, halogen, C₁-C₆alkyl, C₁-C₆haloalkyl, cyano or nitro;

R₄ is hydrogen, halogen, nitro, cyano, NCS, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy or C₁-C₆haloalkoxy; and

R₅ is hydrogen, halogen, nitro, C₁-C₆alkyl, C₁-C₆haloalkyl, C₁-C₆alkoxy or C₁-C₆haloalkoxy; or

including a physiologically tolerable addition compound.

2. A compound of formula I according to claim 1 wherein

X is oxygen or sulfur;

R₁ is hydrogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃_ιydroxyalkyl, or a C₁-C4alkylene substituted by C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio, C₁-C₃alkylsulfinyl, C₁-C₃haloalkylsulfinyl, C₁-C₃alkylsulfonyl, C₁-C₃haloalkylsulfonyl, C₁-C₃hydroxyalkyl, C₁-C₃alkyloxycarbonyl, C₁-C₃alkylcarbonyl or by COOH; R₂ is hydrogen, halogen, CN, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃cyanoalkyl, C₁-C₃-alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio or C₃-C6cycloalkyl; R₃ is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, cyano or nitro;

R₅ is hydrogen, halogen, nitro, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy or C₁-C₃ haloalkoxy; or

including a physiologically tolerable addition compound.

3. A compound of formula I according to claim 1 wherein

X is oxygen or sulfur;

R₁ is hydrogen, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃hydroxyalkyl, or a C₁-C₄alkylene substituted by C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio, C₁-C₃alkylsulfinyl, C₁-C₃haloalkylsulfinyl, C₁-C₃alkylsulfonyl, C₁-C₃haloalkylsulfonyl, C₁-C₃hydroxyalkyl, C₁-C₃alkyloxycarbonyl, C₁-C₃alkylcarbonyl or by COOH; R₂ is hydrogen, halogen, C₁-C₂haloalkyl or C₁-C₂alkoxy;

R₃ is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, cyano or nitro;

R₄ is hydrogen, halogen, C₁-C₂alkyl or OCF₃; and

R₅ is hydrogen, halogen, nitro, C₁-C₂alkyl, OCF₃ or CF₃;

including a physiologically tolerable addition compound.

4. A compound of formula I according to claim 1 wherein

X is oxygen or sulfur;

R₁ is hydrogen;

R₃ is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, cyano or nitro;

R₄ is hydrogen, halogen, C₁-C₂alkyl or OCF₃; and

R₅ is hydrogen, halogen, nitro, C₁-C₂alkyl, OCF₃ or CF₃;

including a physiologically tolerable addition compound.

5. A compound of formula I according to claim 1 wherein

X is oxygen or sulfur;

R₁ is C₁-C₂alkyl, preferably methyl; R₂ is hydrogen, halogen, C₁-C₂haloalkyl or C₁-C₂alkoxy;

R₃ is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, cyano or nitro;

R₄ is hydrogen, halogen, C₁-C₂alkyl or OCF₃; and

R₅ is hydrogen, halogen, nitro, C₁-C₂alkyl, OCF₃ or CF₃;

including a physiologically tolerable addition compound.

6. A compound of formula I according to claim 1 wherein

X is oxygen;

R₁ is hydrogen, C₁-C₃alkyl, C₁-C₃haloalkyl, or a C₁-C₄alkylene substituted by C₁-C₃-alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio, C₁-C₃alkylsulfinyl, C₁-C₃haloalkylsulfinyl, C₁-C₃alkylsulfonyl, C₁-C₃haloalkylsulfonyl, C₁-C₃hydroxyalkyl, C₁-C₃alkyloxycarbonyl, C₁-C₃alkylcarbonyl or by COOH;

R₂ is hydrogen, halogen, C₁-C₂haloalkyl, C₁-C₂haloalkoxy or C₁-C₂alkoxy;

R₃ is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, cyano or nitro;

R₄ is hydrogen, halogen, C₁-C₂alkyl or OCF₃; and

R₅ is hydrogen, halogen, nitro, C₁-C₂alkyl, OCF₃ or CF₃;

including a physiologically tolerable addition compound.

7. A compound of formula I according to claim 1 wherein

X is oxygen or sulfur;

R₁ is hydrogen, C₁-C₃alkyl or C₁-C₂hydroxyalkyl;

R₃ is hydrogen, fluorine or chlorine;

R₄ is hydrogen; and

C-6 of the benzothiazole group;

including a physiologically tolerable addition compound.

8. A compound of formula I according to claim 1 wherein

X is oxygen or sulfur;

R₁ is C₁-C₃haloalkyl, or a C₁-C₄alkylene substituted by C₁-C₃alkoxy, C₁-C₃haloalkoxy, C₁-C₃hydroxyalkyl or by COOH;

R₂ is hydrogen, halogen, CN, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃cyanoalkyl, C₁-C₃-alkoxy, C₁-C₃haloalkoxy, C₁-C₃alkylthio, C₁-C₃haloalkylthio or C₃-C6cycloalkyl;

R₃ is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, cyano or nitro; R₄ is hydrogen, halogen, nitro, cyano, NCS, C₁-C₃alkyl, C₁-C₃haloalkyl, C₁-C₃alkoxy or C₁-C₃haloalkoxy; and

including a physiologically tolerable addition compound.

9. A compound of formula I according to claim 8 wherein

X is oxygen or sulfur;

R₁ is C₁-C₃haloalkyl, or a C₁-C4alkylene substituted by C₁-C₃alkoxy;

R₂ is hydrogen, halogen, C₁-C₂haloalkyl or C₁-C₂ alkoxy;

R₃ is hydrogen, halogen, C₁-C₃alkyl, C₁-C₃haloalkyl, cyano or nitro;

R₄ is hydrogen, halogen, C₁-C₂alkyl or OCF₃; and

R₅ is hydrogen, halogen, nitro, C₁-C₂alkyl, OCF₃ or CF₃;

including a physiologically tolerable addition compound.

10. A compound of formula I according to either claim 8 or claim 9 wherein the benzothiazolyloxy group is in the para-position with respect to the imidazole radical.

11. A compound of formula I according to claim 1 selected from the group:

2-[4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-phenyl]-4,5-dicyanoimidazole;

2-[4-(6-chloro-benzothiazolyl-2-oxy)-phenyl]-4,5-dicyanoimidazole;

2-[2-chloro-4-(6-chloro-benzothiazolyl-2-oxy)-phenyl]-4,5-dicyanoimidazole;

2-[4-(5-trifluoromethyl-benzothiazolyl-2-oxy)-phenyl]-4,5-dicyanoimidazole;

1-ethoxymethyl-2-[4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-3-chlorophenyl]-4,5-dicyanoimidazole.

12. A compound of formula I according to claim 8 selected from the group:

2-[4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-3,5-dichlorophenyl]-1-ethoxymethyl-4,5-dicyanoimidazole;

2-[4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-2-chlorophenyl]-1-ethoxymethyl-4,5-dicyanoimidazole; 2-[4-(6-trifluoromethoxy-benzothiazolyl-2-oxy)-3-fluorophenyl]-1-ethoxymethyl- 4,5-dicyanoimidazole;

2-[4-(5-trifluoromethyl-benzothiazolyl-2-oxy)-phenyl]-1-carboxymethyl-4,5-dicyanoimidazole; and

2-[4-(5-trifluoromethyl-benzothiazolyl-2-oxy)-phenyl]-1-(3,3,3-trifluoropropyl)- 4,5-dicyanoimidazole.

13. A process for the preparation of a compound of formula I according to claim 1, which comprises either

(a) cyclising a compound of formula II

,

wherein the substituents R₁, R₂, R₃, R₄, R₅ and X are as defined under formula I, with a suitable oxidising agent and, in those cases in which R₁ in the compound of formula II is hydrogen, introducing an alkyl radical mentioned under R₁ in formula I by subsequent alkylation, or

(b) reacting a compound of formula III ,

14. A pesticidal composition which comprises, in addition to at least one formulation adjuvant, a 4,5-dicyanoimidazole of formula I according to any one of claims 1 to 12.

15. A method of controlling parasites of the order of the arthropods that are harmful to animals or plants, especially insects and representatives of the order Acarina that are harmful to animals and plants, or of controlling helminths in warm-blooded animals, which method comprises treating the pests or their locus with an effective amount of a 4,5-dicyanoimidazole of formula I according to any one of claims 1 to 12.

16. The use of a 4,5-dicyanoimidazole of formula I according to any one of claims 1 to 12 for controlling arthropods that are harmful to animals and plants, especially insects and representatives of the order Acarina, or for controlling helminths in warm-blooded animals.

17. A 4,5-dicyanoimidazole of formula I according to any one of claims 1 to 12 for use in a method of controlling arthropods that are harmful to animals, especially insects and representatives of the order Acarina, or of controlling helminths in warm-blooded animals.

18. The use of a 4,5-dicyanoimidazole of formula I according to any one of claims 1 to 12 for the preparation of a pharmaceutical, especially an anthelmintic.

19. A compound of formula II

wherein the substituents R₁, R₂, R₃, R₄, R₅ and X are as defined under formula I in claim 1.

20. A compound of formula VII

wherein R₂, R₃, R₄, R₅ and X are as defined under formula I in claim 1.

21. A process for the preparation of a compound of formula II according to claim 19, which comprises reacting a compound of formula VII ,

wherein R₁ is as defined under formula I, and, in those cases in which R₁ in the compound of formula IX is hydrogen, introducing an alkyl radical mentioned under R₁ in formula I by subsequent alkylation.

22. A process for the preparation of a compound of formula VII according to claim 20, which comprises reacting a compound of formula VIII ,

wherein R₂, R₃ and X are as defined under formula I in claim 1, with a compound of formula IV ,

wherein R₄ and R₅ are as defined under formula I in claim 1 and Y is a customary leaving group.

23. The use of a compound of formula II according to claim 19 or of a compound of formula VII according to claim 20 for the preparation of an active ingredient for pest control or of an active ingredient for controlling helminths.