WO1995029889A1

WO1995029889A1 - Perhaloalkoxybenzenophenone hydrazones and their use as pesticides

Info

Publication number: WO1995029889A1
Application number: PCT/EP1995/001424
Authority: WO
Inventors: Alfons Pascual; Roger Graham Hall; Dieter DÜRR
Original assignee: Ciba-Geigy Ag
Priority date: 1994-04-29
Filing date: 1995-04-15
Publication date: 1995-11-09
Also published as: SK138396A3; CN1147246A; HU9602972D0; EP0757671A1; HUT75200A; JPH10504799A; CA2189035A1; CZ313996A3; AU2446595A; IL113435A0; ZA953446B; BR9501849A; MX9605193A

Abstract

Compounds of formula (I) in which X is (a) or (b), n is 0, 1, 2, 3, 4 or 5, where if n is greater than 1, the radicals R2 are identical or different; o is 0, 1, 2, 3 or 4, where if o is greater than 1, the radicals R3 are identical or different; R1 is perhalo-C1-C4alkoxy; R2 is halogen, C1-C8alkyl, halo-C1-C8alkyl, C1-C8alkoxy, halo-C1-C8alkoxy, C1-C8alkylthio, halo-C1-C8alkylthio, C1-C8alkylsulfynyl, halo-C1-C8alkylsulfynyl, C1-C8alkylsulfonyl, halo-C1-C8alkylsulfonyl, CN or phenyl; R3 is halogen, C1-C8alkyl, halo-C1-C8alkyl or halo-C1-C8alkoxy; R4 is H, halogen, C1-C8alkyl, C3-C6cycloalkyl, halo-C1-C8alkyl, C1-C8alkoxy, C1-C8alkoxy-C1-C8alkyl, C1-C8alkoxy-C1-C8alkoxy, C1-C8alkylthio or NR8R9; R5 is C1-C8alkyl, NR10R11, OR20, SR20 or SO2R20; R6 is H, C1-C8alkyl, C3-C6cycloalkyl, halo-C1-C8alkyl, C1-C8alkenyl, C1-C8alkynyl, C1-C8acyl or phenyl; R7 is H, an unsubstituted or substituted C1-C8alkyl, C3-C6cycloakyl, C3-C6cycloalkyl-C1-C8alkyl, C1-C8alkenyl, C1-C8alkynyl, C3-C6cycloalkenyl, C3-C6cycloalkenyl-C1-C8alkyl or C3-C6cycloalkyl-C1-C8alkenyl group, it being possible for the substituents to be selected from the group consisting of halogen, C1-C8alkyl, halo-C1-C8alkyl, C1-C8alkoxy, halo-C1-C8alkoxy, C1-C8alkyl-S(O)p, it being possible for p to be 0, 1 or 2, C1-C8alkoxycarbonyl, di(C1-C8alkyl)amino and C1-C8alkanoyloxy; an unsubstituted or substituted phenyl or heteroaryl group, it being possible for the substituents to be selected from the group consisting of C1-C6alkyl and halogen; C1-C8alkoxy, NR16R17, COOR6 or SR6; R8 and R9 independently of one another are H, C1-C8alkyl or OH; R10 is H, C1-C8alkyl, C3-C6cycloalkyl, halo-C1-C8alkyl, halo-C1-C8alkoxy-C1-C8alkyl, phenyl, OR12, S(O)mR13, m being 0, 1 or 2, or NR14R15; R11 is H, C1-C8alkyl, C3-C6cycloalkyl, halo-C1-C8alkyl, C1-C8alkoxy-C1-C8alkyl, allyl, C1-C8alkylallyl, haloallyl or propargyl; R12 is H, C1-C8alkyl, halo-C1-C8alkyl, C1-C8alkoxy-C1-C8alkyl, C3-C6cycloalkyl, C2-C8alkenyl, halo-C2-C8alkenyl or propargyl; R13 is H, C1-C8alkyl, halogen-C1-C8alkyl, phenyl or NR14R15; R14 and R15 independently of one another are H, C1-C8alkyl, halo-C1-C8alkyl, phenyl, C1-C8alkylamido, di(C1-C8alkyl)amido or NH2; R16 and R17 independently of one another are H, C1-C8alkyl, halo-C1-C8alkyl, C2-C8alkenyl, C1-C8alkoxy or NH2; R18 is S(O)mR19, m being 0, 1 or 2, NO2 or CN; R19 is C1-C8alkyl, halo-C1-C8alkyl, C3-C6cycloalkyl, phenyl, benzyl or NR14R15; R20 is C1-C8alkyl, halo-C1-C8alkyl or C3-C6cycloalkyl; Y is O, S, NR18 or CHC(O)R21; and R21 is H, C1-C8alkyl, halo-C1-C8alkyl, C1-C8alkoxy or phenyl, and if appropriate, E/Z isomers and tautomers thereof, in each case in free form or in salt form, can be used as agrochemical active ingredients and may be prepared in a manner known per se.

Description

PERHALOALKOXYBENZENOPHENONE HYDRAZONES AND THEIR USE AS PESTICIDES The invention relates to compounds of the formula

in which X is or ,

n is 0, 1, 2, 3, 4 or 5, where, if n is greater than 1, the radicals R₂ are identical or different; o is 0, 1, 2, 3 or 4, where, if o is greater than 1, the radicals R₃ are identical or different;

R₁ is perhalo-C₁-C₄alkoxy;

R₂ is halogen, C₁-C₈alkyl, halo-C₁-C₈alkyl, C₁-C₈alkoxy, halo-C₁-C₈alkoxy,

C₁-C₈alkylthio, halo-C₁-C₈alkylthio, C₁-C₈alkylsulfynyl, halo-C₁-C₈alkylsulfynyl,

C₁-C₈alkylsulfonyl, halo-C₁-C₈alkylsulfonyl, CN or phenyl;

R₃ is halogen, C₁-C₈alkyl, halo-C₁-C₈alkyl or halo-C₁-C₈alkoxy;

R₄ is H, halogen, C₁-C₈alkyl, C₃-C₆cycloalkyl, halo-C₁-C₈alkyl, C₁-C₈alkoxy,

C₁-C₈alkoxy-C₁-C₈alkyl, C₁-C₈alkoxy-C₁-C₈alkoxy, C₁-C₈alkylthio or NR₈R₉;

R₅ is C₁-C₈alkyl, NR₁₀R₁₁, OR₂₀, SR₂₀ or SO₂R₂₀;

R₆ is H, C₁-C₈alkyl, C₃-C₆cycloalkyl, halo-C₁-C₈alkyl, C₁-C₈alkenyl, C₁-C₈alkynyl,

C₁-C₈acyl or phenyl;

R₇ is H, an unsubstituted or substituted C₁-C₈alkyl, C₃-C₆cycloalkyl,

C₃-C₆cycloalkyl-C₁-C₈alkyl, C₁-C₈alkenyl, C₁-C₈alkynyl, C₃-C₆cycloalkenyl,

C₃-C₆cycloalkenyl-C₁-C₈alkyl or C₃-C₆cycloalkyl-C₁-C₈alkenyl group, it being possible for the substituents to be selected from the group consisting of halogen, C₁-C₈alkyl, halo-C₁-C₈alkyl, C₁-C₈alkoxy, halo-C₁-C₈alkoxy, C₁-C₈alkyl-S(O)_p, it being possible for p to be 0, 1 or 2, C₁-C₈alkoxycarbonyl, di(C₁-C₈alkytyamino and C₁-C₈alkanoyloxy; an unsubstituted or substituted phenyl or heteroaryl group, it being possible for the substituents to be selected from the group consisting of C₁-C₆alkyl and halogen;

C₁-C₈alkoxy, NR₁₆R₁₇, COOR₆ or SR₆;

R₈ and R₉ independently of one another are H, C₁-C₈alkyl or OH;

R₁₀ is H, C₁-C₈alkyl, C₃-C₆cycloalkyl, halo-C₁-C₈alkyl, halo-C₁-C₈alkoxy-C₁-C₈alkyl, phenyl, OR₁₂, S(O)_mR₁₃, m being 0, 1 or 2, or NR₁₄R₁₅;

R₁₁ is H, C₁-C₈alkyl, C₃-C₆cycloalkyl, halo-C₁-C₈alkyl, C₁-C₈alkoxy-C₁-C₈alkyl, allyl, C₁-C₈alkylallyl, haloallyl or propargyl;

R₁₂ is H, C₁-C₈alkyl, halo-C₁-C₈alkyl, C₁-C₈alkoxy-C₁-C₈alkyl, C₃-C₆cycloalkyl,

C₂-C₈alkenyl, halo-C₂-C₈alkenyl or propargyl;

R₁₃ is H, C₁-C₈alkyl, halogen-C₁-C₈alkyl, phenyl or NR₁₄R₁₅;

R₁₄ and R₁₅ independently of one another are H, C₁-C₈alkyl, halo-C₁-C₈alkyl, phenyl,

C₁-C₈alkylamido, di(C₁-C₈alkyl)amido or NH₂;

R₁₆ and R₁₇ independendy of one another are H, C₁-C₈alkyl, halo-C₁-C₈alkyl,

C₂-C₈alkenyl, C₁-C₈alkoxy or NH₂;

R₁₈ is S(O)_mR₁₉, m being 0, 1 or 2, NO₂ or CN;

R₁₉ is C₁-C₈alkyl, halo-C₁-C₈alkyl, C₃-C₆cycloalkyl, phenyl, benzyl or NR₁₄R₁₅;

R₂₀ is C₁-C₈alkyl, halo-C₁-C₈alkyl or C₃-C₆cycloalkyl;

Y is O, S, NR₁₈ or CHC(O)R₂₁; and

R₂₁ is H, C₁-C₈alkyl, halo-C₁-C₈alkyl, C₁-C₈alkoxy or phenyl,

with the proviso that in the compounds of the formula I, in which X is -N=C(R₄)R₅, R₁ is

OCF₃, o is 0, n is 1, R₄ is CH₃ and R₅ is -N(CH₃)OCH₃, R₂ is other than fluorine and chlorine, and E/Z isomers and tautomers thereof, in each case in free form or in salt form; to a process for the preparation and to the use of these compounds and tautomers, to pesticides whose active ingredient is selected from amongst these compounds and tautomers, in each case in free form or in agrochemically utilizable salt form, and to a process for the preparation and to the use of these compositions.

Certain hydrazone derivatives are proposed in the literature as insecticidally active ingredients in pesticides. However, the biological properties of these known compounds are not entirely satisfactory in the field of pest control, which is why there is a need to provide other compounds having pesticidal properties, in particular for controlling insects, this object being achieved according to the invention by provision of the present compounds I.

The compounds I can exist as E/Z isomers, for example in the following two isomeric forms

and

Accordingly, the compounds I are, if appropriate, also to be understood as meaning hereinbelow appropriate E/Z isomers, even if the latter are not specifically mentioned in each case.

Some of the compounds I may exist as tautomers, for example, if R₆ is H then

corresponding compounds I, i.e. those in which X is a substructure -N(H)-C(R₇)=Y, may be in equilibrium with the respective tautomers comprising a substructure -N=C(R₇)-YH. Accordingly, the compounds I hereinbelow are, if appropriate, also to be understood as meaning corresponding tautomers, even if the latter are not mentioned specifically in each case.

The compounds I and, if appropriate, their E/Z isomers and tautomers can exist as salts. Compounds I which have at least one basic centre can form, for example, acid addition salts. These acid addition salts are formed, for example, with strong inorganic acids, such as mineral acids, for example sulfuric acid, a phosphorus acid or a hydrohalic acid, with strong organic carboxylic acids, such as unsubstituted or substituted, for example halogen-substituted, C₁-C₄alkanecarboxylic acids, for example acetic acid, such as saturated or unsaturated dicarboxylic acids, for example oxalic acid, malonic acid, maleic acid, fumaric acid or phthalic acid, such as hydroxycarboxylic acids, for example ascorbic acid, lactic acid, malic acid, tartaric acid or citric acid, or such as benzoic acid, or with organic sulfonic acids such as unsubstituted or substituted, for example

halogen-substituted, C₁-C₄alkane- or arylsulfonic acids, for example methane- or p-toluenesulfonic acid. Furthermore, compounds I having at least one acidic group can form salts with bases. Examples of suitable salts with bases are metal salts, such as alkali metal salts or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower-alkylamine, for example ethyl-, diethyl-, triethyl- or dimethylpropylamine, or a mono-, di- or trihydroxy-lower-alkylamine, for example mono-, di- or triethanolamine. Furthermore, appropriate internal salts may be formed, if appropriate. Preferred within the scope of the invention are agrochemically advantageous salts; however, salts which are disadvantageous for agrochemical purposes, for example salts which are toxic to bees or fish, and which are employed, for example, for the isolation or purification of free compounds I or their agrochemically utilizable salts, are also embraced by the invention. Due to the close relationship between the compounds I in free form and in the form of their salts, the free compounds I or their salts hereinabove and hereinbelow are, analogously, also to be understood as meaning the corresponding salts or the free compounds I, if appropriate. This also applies correspondingly to E/Z isomers and tautomers of compounds I and their salts. Unless otherwise defined, the general terms used hereinabove and hereinbelow have the meanings given below.

Halogen - as a group per se and as structural element of other groups and compounds, such as haloalkyl, haloalkoxy, haloalkoxyalkyl and haloalkenyl - is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine.

Unless otherwise defined, carbon-containing groups and compounds have in each case at least 1 but not more than 8, preferably at least 1 but not more than 4, in particular 1 or 2, carbon atoms.

C₃-C₆Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Alkyl - as a group per se and as structural element of other groups and compounds, such as haloalkyl, alkoxy, alkoxyalkyl, alkylthio, alkylsulfynyl or alkylsulfonyl - is, in each case with due consideration of the number of carbon atoms existing in each case in the particular group or compound, either straight-chain, i.e. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, or branched, for example isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isooctyl.

Halogen-substituted carbon-containing groups and compounds, such as haloalkyl, haloalkoxy or haloalkenyl, can be partially halogenated or perhalogenated, it being possible for the halogen substituents to be identical or different in the case of

polyhalogenations. Examples of haloalkyl - as a group per se and as structural element of other groups and compounds, such as halocycloalkylalkyl and haloalkenyl - are methyl which is mono- to trisubstituted by fluorine, chlorine and/or bromine, such as CHF₂ or CF₃; ethyl which is mono- to pentasubstituted by fluorine, chlorine and/or bromine, such as CH₂CF₃, CF₂CF₃, CF₂CC1₃, CF₂CHCl₂, CF₂CHF₂, CF₂CFCl₂, CF₂CHBr₂, CF₂CHClF, CF₂CHBrF or CClFCHClF; propyl or isopropyl, mono- to heptasubstituted by fluorine, chlorine and/or bromine, such as CH₂CHBrCH₂Br, CF₂CHFCF₃, CH₂CF₂CF₃ or

CH(CF₃)₂; and butyl or one of the isomers thereof, mono- to nonasubstituted by fluorine, chlorine and/or bromine, such as CF(CF₃)CHFCF₃ or CH₂(CF₂)₂CF₃.

Acyl groups can be formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, hexanoyl, heptanoyl, octanoyl, aroyl, for example benzoyl, or heteroaroyl, for example thienoyl. Examples of heteroaryl radicals are thienyl, pyrryl, imidazolyl, pyrazolyl, triazolyl, thiazolyl, isothiazolyl, pyridyl, indolyl, benzo[b]thienyl or benzo[b]furyl.

Taking into consideration the abovementioned proviso, preferred embodiments within the scope of the invention are:

(1) a compound of the formula I in which n is 0, 1, 2, 3 or 4, preferably 1, 2, or 3, in particular 1 or 2, very particularly 1, where, if n is greater than 1, the radicals R₂ are identical or different, or, if appropriate, an E/Z isomer or tautomer thereof;

(2) a compound of the formula I in which o is 0, 1, 2 or 3, preferably 0, 1 or 2, in particular 0 or 1, very particularly 0, where, if m is greater than 1, the radicals R₃ are identical or different, or, if appropriate, an E/Z isomer or tautomer thereof;

(3) a compound of the formula I in which R₁ is perhalo-C₁-C₃alkoxy, preferably perhalo-C₁-C₂alkoxy, in particular perhalomethoxy, or, if appropriate, an E/Z isomer or tautomer thereof;

(4) a compound of the formula I in which R₂ is halogen, C₁-C₆alkyl, halo-C₁-C₆alkyl, C₁-C₆alkoxy or halo-C₁-C₆alkoxy, preferably halogen, C₁-C₄alkyl, halo-C₁-C₄alkyl or halo-C₁-C₄alkoxy, in particular halogen, C₁-C₂alkyl, halo-C₁-C₂alkyl or

halo-C₁-C₂alkoxy, very particularly halogen, methyl, halomethyl or halomethoxy, or, if appropriate, an E/Z isomer or tautomer thereof;

(5) a compound of the formula I in which R₃ is H, halogen, C₁-C₄alkyl, halo-C₁-C₄alkyl or halo-C₁-C₄alkoxy, preferably H, halogen, C₁-C₂alkyl or halo-C₁-C₂alkyl, in particular H, halogen or methyl, very particularly H, chlorine or fluorine, or, if appropriate, an E/Z isomer or tautomer thereof;

(6) a compound of the formula I in which R₄ is H, halogen, C₁-C₆alkyl, C₃-C₆cycloalkyl, halo-C₁-C₄alkyl, C₁-C₄alkoxy, C₁-C₄alkoxy-C₁-C₄alkyl, C₁-C₄alkoxy-C₁-C₄alkoxy, C₁-C₄alkylthio or NR₈R₉, preferably H, halogen, C₁-C₄alkyl, C₃-C₆cycloalkyl, halo-C₁-C₂alkyl or C₁-C₂alkoxy, in particular H or C₁-C₄alkyl, or, if appropriate, an E/Z isomer or tautomer thereof;

(7) a compound of the formula I in which R₅ is C₁-C₄alkyl, NR₁₀R_{1 1}, OR₂₀, SR₂₀ or SO₂R₂₀, preferably NR₁₀Rn or OR₂₀, in particular NR₁₀R₁₁ , or, if appropriate, an E/Z isomer or tautomer thereof;

(8) a compound of the formula I in which R₆ is H, C₁-C₆alkyl, C₃-C₆cycloalkyl,

C₁-C₆alkenyl, C₁-C₆alkynyl or C₁-C₆acyl, preferably H, C₁-C₄alkyl, C₃-C₆cycloalkyl or C₁-C₆acyl, in particular H or C₁-C₄alkyl, or, if appropriate, an E/Z isomer or tautomer thereof;

(9) a compound of the formula I in which R₇ is H, unsubstituted or substituted

C₁-C₆alkyl, C₃-C₆cycloalkyl, C₃-C₆cycloalkyl-C₁-C₄alkyl, C₁-C₆alkenyl, C₁-C₆alkynyl, it being possible for the substituents to be selected from the group consisting of halogen, C₁-C₄alkyl, halo-C₁-C₄alkyl, C₁-C₄alkoxy, halo-C₁-C₄alkoxy, C₁-C₄alkyl-S(O)_p, it being possible for p to be 0, 1 or 2, C₁-C₄-alkoxycarbonyl, di(C₁-C₄alkyl)amino and

C₁-C₄alkanoyloxy; phenyl or heteroaryl, unsubstituted or mono- or polysubstituted by substituents from the group consisting of C₁-C₄alkyl and halogen; C₁-C₄alkoxy, NR₁₆R₁₇, COOR₆ or SR₆; preferably H, unsubstituted or substituted C₁-C₆alkyl, C₃-C₆cycloalkyl, it being possible for the substituents to be selected from the group consisting of halogen, C₁-C₂alkyl, halo-C₁-C₂alkyl, C₁-C₂alkoxy, halo-C₁-C₂alkoxy, C₁-C₂alkyl-S(O)_p, it being possible for p to be 0, 1 or 2, C₁-C₂alkoxycarbonyl, di(C₁-C₂alkyl)amino and

C₁-C₂alkanoyloxy; phenyl or heteroaryl, unsubstituted or mono- or polysubstituted by substituents from the group consisting of C₁-C₂alkyl and halogen; C₁-C₂alkoxy, NR₁₆R₁₇ or SR₆; in particular H, unsubstituted or substituted C₁-C₆alkyl, C₃-C₆cycloalkyl, it being possible for the substituents to be selected from the group consisting of halogen,

C₁-C₂alkyl and C₁-C₂alkoxy; phenyl or heteroaryl, unsubstituted or substituted by halogen; C₁-C₂alkoxy, NR₁₆R₁₇ or SR₆; very particularly C₁-C₄alkyl, C₃-C₆cycloalkyl; phenyl or heteroaryl, unsubstituted or substituted by halogen; C₁-C₂alkoxy or NR₁₆R₁₇, or, if appropriate, an E/Z isomer or tautomer thereof;

(10) a compound of the formula I in which R₈ is H or C₁-C₆alkyl, preferably H or

C₁-C₄alkyl, in particular H or methyl, or, if appropriate, an E/Z isomer or tautomer thereof;

(11) a compound of the formula I in which R₉ is H or C₁-C₆alkyl, preferably H or

(12) a compound of the formula I in which R₁₀ is H, C₁-C₄alkyl, C₃-C₆cycloalkyl, halo-C₁-C₄alkyl, phenyl, OR₁₂, S(O)_mR₁₃, m being 0 or 2, or NR₁₄R₁₅, preferably H, C₁-C₂alkyl, phenyl or OR₁₂, in particular H, C₁-C₂alkyl or OR₁₂, or, if appropriate, an E/Z isomer or tautomer thereof;

(13) a compound of the formula I in which R₁₁ is H, C₁-C₄alkyl, C₃-C₆cycloalkyl, halo-C₁-C₄alkyl, C₁-C₄alkoxy-C₁-C₄alkyl, allyl, C₂-C₄alkylallyl, haloallyl or propargyl, preferably H, C₁-C₂alkyl, C₃-C₆cycloalkyl, allyl or C₁-C₄alkylallyl, in particular H or C₁-C₂alkyl, or, if appropriate, an E/Z isomer or tautomer thereof;

(14) a compound of the formula I in which R₁₂ is H, C₁-C₄alkyl, halo-C₁-C₄alkyl, C₁-C₄alkoxy-C₁-C₄alkyl, C₃-C₆cycloalkyl, C₂-C₄alkenyl, halo-C₂-C₄alkenyl or propargyl, preferably H, C₁-C₄alkyl, C₃-C₆cycloalkyl, C₂-C₄alkenyl or propargyl, in particular H, C₁-C₂alkyl or C₃-C₆cycloalkyl, or, if appropriate, an E/Z isomer or tautomer thereof;

(15) a compound of the formula I in which R₁₃ is H, C₁-C₄alkyl, halo-C₁-C₄alkyl, phenyl or NR₁₄R₁₅, preferably C₁-C₂alkyl, halo-C₁-C₂alkyl or phenyl, in particular C₁-C₂alkyl or halo-C₁-C₂alkyl, or, if appropriate, an E/Z isomer or tautomer thereof;

(16) a compound of the formula I in which R₁₄ is H, C₁-C₄alkyl, halo-C₁-C₄alkyl, phenyl, C₁-C₈alkylamido, di(C₁-C₄alkyl)amido or NH₂, preferably H, C₁-C₂alkyl or phenyl, in particular C₁-C₂alkyl or phenyl, or, if appropriate, an E/Z isomer or tautomer thereof;

(17) a compound of the formula I in which R₁₅ is H, C₁-C₄alkyl, halo-C₁-C₄alkyl, phenyl, C₁-C₈alkylamido, di(C₁-C₄alkyl)amido or NH₂, preferably H, C₁-C₂alkyl or phenyl, in particular C₁-C₂alkyl or phenyl, or, if appropriate, an E/Z isomer or tautomer thereof;

(18) a compound of the formula I in which R₁₆ is H, C₁-C₄alkyl, halo-C₁-C₄alkyl or C₁-C₈alkoxy, preferably H or C₁-C₄alkyl, in particular C₁-C₂alkyl, or, if appropriate, an E/Z isomer or tautomer thereof;

(19) a compound of the formula I in which R₁₇ is H, C₁-C₄alkyl, halo-C₁-C₄alkyl or C₁-C₈alkoxy, preferably H or C₁-C₄alkyl, in particular C₁-C₂alkyl, or, if appropriate, an E/Z isomer or tautomer thereof;

(20) a compound of the formula I in which R₁₈ is SO₂R₁₉, NO₂ or CN, preferably SO₂R₁₉, or, if appropriate, an E/Z isomer or tautomer thereof; (21) a compound of the formula I in which R₁₉ is C₁-C₄alkyl, halo-C₁-C₄alkyl,

C₃-C₆cycloalkyl, phenyl, benzyl or NR₁₄R₁₅, preferably C₁-C₂alkyl, phenyl, benzyl or NR₁₄R₁₅, in particular C₁-C₂alkyl or benzyl, or, if appropriate, an E/Z isomer or tautomer thereof;

(22) a compound of the formula I in which R₂₀ is C₁-C₄alkyl, halo-C₁-C₄alkyl or

C₃-C₆cycloalkyl, preferably C₁-C₂alkyl or C₃-C₆cycloalkyl, in particular C₁-C₂alkyl, and if appropriate an E/Z isomer or tautomer thereof;

(23) a compound of the formula I in which Y is O, S or NR₁₈, preferably O or NR₁₈, in particular O, and if appropriate an E/Z isomer or tautomer thereof;

(24) a compound of the formula I, in which R₂₁ is H, C₁-C₄alkyl, halo-C₁-C₄alkyl or C₁-C₄alkoxy, preferably C₁-C₂alkyl, halo-C₁-C₂alkyl or C₁-C₂alkoxy, in particular methyl, trifluoromethyl, methoxy or ethoxy, and if appropriate an E/Z isomer or tautomer thereof;

(25) a compound of the formula I in which n is 1, 2 or 3, where, if n is greater than 1, the radicals R₂ are identical or different, o is 0, 1 or 2, where, if o is greater than 1, the radicals R₃ are identical or different, R₁ is perhalo-C₁-C₃alkoxy, R₂ is halogen,

C₁-C₆alkyl, halo-C₁-C₆alkyl or halo-C₁-C₆alkoxy, R₃ is H, halogen, C₁-C₂alkyl or halo-C₁-C₂alkyl, R₄ is H, halogen, C₁-C₄alkyl, C₃-C₆cycloalkyl, halo-C₁-C₂alkyl or C₁-C₂alkoxy, R₅ is C₁-C₄alkyl, NR₁₀R₁₁, OR₂₀, SR₂₀ or SO₂R₂₀, R₆ is H, C₁-C₆alkyl, C₃-C₆cycloalkyl, C₁-C₆alkenyl, C₁-C₆alkynyl or C₁-C₆acyl, R₇ is H, unsubstituted or substituted C₁-C₆alkyl, C₃-C₆cycloalkyl, it being possible for the substituents to be selected from the group consisting of halogen, C₁-C₂alkyl, halo-C₁-C₂alkyl, C₁-C₂alkoxy, halo-C₁-C₂alkoxy, C₁-C₂alkyl-S(O)_p, it being possible for p to be 0, 1 or 2,

C₁-C₂alkoxycarbonyl, di(C₁-C₂alkyl)amino and C₁-C₂alkanoyloxy; phenyl or heteroaryl, unsubstituted or mono- or polysubstituted by substituents from the group consisting of C₁-C₂alkyl and halogen; C₁-C₂alkoxy, NR₁₆R₁₇ or SR₆, R₁₀ is H, C₁-C₄alkyl,

C₃-C₆cycloalkyl, halo-C₁-C₄alkyl, phenyl, OR₁₂, S(O)_mR₁₃, where m is 0 or 2, or NR₁₄R₁₅, R₁₁ is H, C₁-C₄alkyl, C₃-C₆cycloalkyl, halo-C₁-C₄alkyl,

C₁-C₄alkoxy-C₁-C₄alkyl, allyl, C₁-C₄alkylallyl, haloallyl or propargyl, R₁₂ is H,

C₁-C₄alkyl, halo-C₁-C₄alkyl, C₁-C₄alkoxy-C₁-C₄alkyl, C₃-C₆cycloalkyl, C₂-C₄alkenyl, halo-C₂-C₄alkenyl or propargyl, R₁₃ is H, C₁-C₄alkyl, halo-C₁-C₄alkyl, phenyl or NR₁₄R₁₅, R₁₄ and R₁₅ independently of one another are H, C₁-C₄alkyl, halo-C₁-C₄alkyl, phenyl, C₁-C₈alkylamido, di(C₁-C₄alkyl)amido or NH₂, R₁₆ and R₁₇ independently of one another are H, C₁-C₄alkyl, halo-C₁-C₄alkyl or C₁-C₈alkoxy, R₁₈ is SO₂R₁₉, NO₂ or CN, R₁₉ is C₁-C₂alkyl, phenyl, benzyl or NR₁₄R₁₅, R₂₀ is C₁-C₂alkyl or C₃-C₆cycloalkyl, and Y is O, S or NR₁₈, or, if appropriate, an E/Z isomer or tautomer thereof;

(26) a compound of the formula I in which n is 1 or 2, where, if n is greater than 1, the radicals R₂ are identical or different, o is 0 or 1, R₁ is perhalo-C₁-C₂alkoxy, R₂ is halogen, C₁-C₄alkyl, halo-C₁-C₄alkyl or halo-C₁-C₄alkoxy, R₃ is H, halogen or methyl, R₄ is H or C₁-C₄alkyl, R₅ is C₁-C₄alkyl, NR₁₀R₁₁, OR₂₀, SR₂₀ or SO₂R₂₀, R₆ is H, C₁-C₄alkyl, C₃-C₆cycloalkyl or C₁-C₆acyl, R₇ is H, C₁-C₆alkyl, C₃-C₆cycloalkyl, unsubstituted or substituted phenyl or heteroaryl, it being possible for the substituents to be selected from the group consisting of halogen, C₁-C₂alkyl and C₁-C₂alkoxy, or is C₁-C₂alkoxy or NR₁₆R₁₇, R₁₀ is H, C₁-C₂alkyl, phenyl or OR₁₂, R₁₁ is H, C₁-C₂alkyl, C₃-C₆cycloalkyl, allyl or C₁-C₄alkylallyl, R₁₂ is H, C₁-C₄alkyl, C₃-C₆cycloalkyl, C₂-C₄alkenyl or propargyl, R₁₆ and R₁₇ independently of one another are H or C₁-C₄alkyl, R₁₈ is SO₂R₁₉, NO₂ or CN, R₁₉ is C₁-C₂alkyl or benzyl, R₂₀ is C₁-C₂alkyl or C₃-C₆cycloalkyl, and Y is O, S or NR₁₈, or, if appropriate, an E/Z isomer or tautomer thereof;

(27) a compound of the formula I in which n is 1, o is 0 or 1, R₁ is perhalomethoxy, R₂ is halogen, C₁-C₂alkyl, halo-C₁-C₂alkyl or halo-C₁-C₂alkoxy, R₃ is H, chlorine or fluorine, R₄ is H or C₁-C₄alkyl, R₅ is NR₁₀R₁₁ or OR₂₀, R₆ is H or C₁-C₄alkyl, R₇ is H, C₁-C₄alkyl, C₃-C₆cycloalkyl, phenyl, unsubstituted or halogen-substituted heteroaryl, C₁-C₂alkoxy or NR₁₆R₁₇, R₁₀ and R₁₁ independently of one another are H, C₁-C₂alkyl or OR₁₂, R₁₂ is H, C₁-C₂alkyl or C₃-C₆cycloalkyl, R₁₆ and R₁₇ independently of one another are C₁-C₂alkyl, R₁₈ is SO₂R₁₉, R₁₉ is C₁-C₂alkyl or benzyl, R₂₀ is C₁-C₂alkyl, and Y is O or NR₁₈, or, if appropriate, an E/Z isomer or tautomer thereof;

(28) a compound of the formula I in which n is 1, o is 0 or 1, Rj is perhalomethoxy, R₂ is halogen, methyl, halomethyl or halomethoxy, R₃ is H, chlorine or fluorine, R₄ is H or C₁-C₄alkyl, R₅ is NR₁₀R₁₁, R₆ is H or C₁-C₄alkyl, R₇ is H, C₁-C₄alkyl, C₃-C₆cycloalkyl, phenyl, unsubstituted or halogen-substituted heteroaryl, C₁-C₂alkoxy or NR₁₆R₁₇, R₁₀ and R₁₁ independently of one another are H, C₁-C₂alkyl or OR₁₂, R₁₂ is H, C₁-C₂alkyl or C₃-C₆cycloalkyl, R₁₆ and R₁₇ independently of one another are C₁-C₂alkyl, R₁₈ is SO₂R₁₉, R₁₉ is C₁-C₂alkyl or benzyl, R₂₀ is C₁-C₂alkyl, and Y is O or NR₁₈, or, if appropriate, an E/Z isomer or tautomer thereof.

Particularly preferred compounds of the formula I within the scope of the invention are those mentioned in Tables 1, 2 and 3, and very particularly preferred such compounds are those mentioned in Examples H3, H5 to H7 and H10 and, if appropriate, the E/Z isomers or tautomers thereof.

Specifically preferred within the scope of the invention is 4-chloro-4'-trifluoromethoxybenzophenone N-cyclopropylcarbonylhydrazone and the E/Z isomer thereof (Compound 1.5 in Table 1).

The invention furthermore relates to the process for the preparation of the compounds of the formula I and, if appropriate, the E/Z isomers and tautomers thereof, taking into consideration the abovementioned proviso, in each case in free form or in salt form, which comprises, for example, a) to prepare a compound of the formula I in which Y is O, reacting a compound of the formula

,

which is known or which can be prepared in analogy to corresponding known compounds and in which n, o, R₁, R₂, R₃ and R₆ are as defined in formula I, or, if appropriate, an E/Z isomer or tautomer thereof, in free form or in salt form, with a compound of the formula R₇COX₁ in which X₁ is a leaving group, preferably halogen, in particular chlorine, and R₇ is as defined in formula I, preferably in the presence of a base, or b) to prepare a compound of the formula I in which Y is O or S, reacting a compound of the formula ,

which is known or which can be prepared in analogy to corresponding known compounds and in which n, o, R₁, R₂ and R₃ are as defined in formula I, with a compound of the formula ,

which is known or which can be prepared in analogy to corresponding known compounds and in which Y is O or S and R₆ and R₇ are as defined in formula I, in free form or in salt form, preferably in the presence of an acid, or c) to prepare a compound of the formula I in which Y is S, reacting a compound of the formula I in which Y is O and R₆ is preferably a C₁-C₈alkyl group, with phosphorus pentasulfide, or d) to prepare a compound of the formula I in which Y is S and R₆ is H, reacting a compound of the formula

,

which is known or which can be prepared in analogy to corresponding known compounds and in which n, o, R₁, R₂, R₃ and R₇ are as defined in formula I, or, if appropriate, an E/Z isomer thereof, in free form or in salt form, with H₂S, preferably in the presence of a base, or e) reacting a compound of the formula I in which R₆ is H, with R₆X₂ in which X₂ is a leaving group, for example halogen, trifluoromethylsulfonyl, toluenesulfonyl or benzenesulfonyl, preferably halogen, if appropriate in the presence of a base, or f) to prepare a compound of the formula I in which Y is NR₁₈, reacting a compound of the formula II with a compound of the formula ,

which is known or which can be prepared in analogy to corresponding known compounds and in which R₇ and R₁₈ are as defined in formula I and X₃ is a leaving group, for example halogen or C₁-C₄alkoxy, preferably ethoxy, or, if appropriate, an E/Z isomer thereof, in free form or in salt form, preferably in the presence of a base or of an acid, or g) to prepare a compound of the formula I in which R₅ is NR₁₀R₁₁, reacting a compound of the formula II in which R₆ is H with a compound of the formula ,

which is known or which can be prepared in analogy to corresponding known compounds and in which R₄, R₁₀ and R₁₁ are as defined in formula I and R is a C₁-C₄alkyl group, or h) to prepare a compound of the formula I in which R₅ is NR₁₀R₁₁, reacting a compound of the formula

,

which is known or which can be prepared in analogy to corresponding known compounds, for example by reacting a compound of the formula I in which Y is O and R₆ is H with phosphorus pentachloride, and in which n, o, R₁, R₂, R₃ and R₄ are as defined in formula I, or, if appropriate, an E/Z isomer thereof, in free form or in salt form, with NHR₁₀R₁₁, preferably in the presence of a base,

and in each case, if desired, converting a compound of the formula I or a tautomer thereof which can be obtained according to the process or via a different route, in each case in free form or in salt form, into a different compound of the formula I or an E/Z isomer or tautomer thereof, resolving an isomer mixture which can be obtained according to the process and isolating the desired isomer and/or converting a free compound of the formula I or a tautomer or an E/Z isomer thereof which can be obtained according to the process into a salt or a salt which can be obtained according to the process, of a compound of the formula I or of a tautomer or an E/Z isomer thereof, into the free compound of the formula I or a tautomer or an E/Z isomer thereof or into a different salt. The invention furthermore relates to the process for the preparation of the compounds of the formula II, in each case in free form or in salt form, which comprises, for example, i) reacting a compound of the formula ,

which is known or which can be prepared in analogy to corresponding known compounds and in which R₁ is as defined in formula I and X₄ is halogen, preferably chlorine, with benzene which is mono- or polysubstituted by R₂ which is as defined in formula I under the customary conditions of a Friedel-Crafts reaction, or j) reacting a compound of the formula ,

which is known or which can be prepared in analogy to corresponding known compounds and in which R₁ is as defined in formula I with phenylmagnesium halide which is mono- or polysubstituted by R₂ which is as defined in formula I, preferably phenylmagnesium bromide, under the customary conditions of a Grignard reaction, or k) reacting a compound of the formula ,

which is known or which can be prepared in analogy to corresponding known compounds and in which n, o, R₂ and R₃ are as defined in formula I, with Br(CF₂)_pBr, in which p is 1,

2, 3 or 4, preferably in the presence of a strong base, for example sodium hydride, potassium hydride or potassium t-butoxide,

or,

to prepare a compound of the formula II in which R₁ is OCF₃, reacting this compound XI with CCl₄ in the presence of HF, or

to prepare a compound of the formula II in which R₁ is OCF₂Cl, reacting this

compound XI with CI₃COCOCI in the presence of HF and, if appropriate, reacting the product further with HF to prepare a compound of the formula II in which R₁ is OCF₃, or 1) to prepare a compound of the formula II in which R₁ is OCF₃, reacting a compound of the formula .

which is known or which can be prepared in analogy to corresponding known compounds and in which n, o, R₂ and R₃ are as defined in formula I with HF, preferably in the presence of an oxidant, preferably 1,3-dibromo-5,5-dimethylhydantoin, and a base, preferably pyridine, or m) to prepare a compound of the formula II in which R₁ is OCF₃, reacting a compound of the formula ,

which is known or which can be prepared in analogy to corresponding known compounds and in which n, o, R₂ and R₃ are as defined in formula I and R is C₁-C₄alkyl, with PCl₅ and Cl₂, further reacting the resulting product with SbF₃ and SbCl₅, followed by hydrolysis,

and subsequently reacting the resulting benzophenone derivative with R₆NHNH₂ and/or, if desired, converting a compound of the formula II which can be obtained according to the process or via a different route into a different compound of the formula II and/or resolving an isomer mixture which can be obtained according to the process and isolating the desired isomer.

What has been said above for tautomers and E/Z isomers or salts of compounds I with regard to the tautomers and E/Z isomers or salts thereof applies analogously to starting materials mentioned hereinabove and hereinbelow.

The reactions described hereinabove and hereinbelow are carried out in a manner known per se, for example in the absence or, conventionally, in the presence of a suitable solvent or diluent or a mixture of these, the process being carried out, as required, with cooling, at room temperature or with heating, for example in a temperature range from approximately -80°C to the boiling point of the reaction medium, preferably from approximately 0°C to approximately +150°C, and, if required, in a sealed vessel, underpressure, under an inert gas atmosphere and/or under anhydrous conditions. Particularly advantageous reaction conditions can be found in the examples.

The starting materials mentioned hereinabove and hereinbelow which are used for the preparation of the compounds I and, if appropriate, the tautomers or E/Z isomers thereof, in each case in free form or in salt form, are known or can be prepared by methods known per se, for example in accordance with the information given below.

Variant a):

Examples of suitable bases for facilitating the reaction are alkylamines, alkylenediamines, free or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples which may be mentioned are triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine,

N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)-pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,5-diazabicyclo[5.4.0]undec-5-ene (DBU).

The reactants can be reacted with each other as such, i.e. without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or a mixture of these will be advantageous. Examples of such solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; amides, such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, bases employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, can also act as solvent or diluent. The reaction is advantageously carried out in a temperature range from approximately 0°C to approximately +100°C, preferably from approximately 10°C to approximately +40°C.

In a preferred embodiment of variant a), a compound II is reacted with an acyl halide at 10° to 40°, preferably 20°, in an aromatic hydrocarbon, preferably in toluene, and in the presence of a base as catalyst, preferably triethylamine.

Variant b:

Examples of suitable acid catalysts for facilitating the reaction are those acids, employed in catalytic amounts, which have been listed above as being suitable for the formation of acid addition salts with compounds I.

The reactants can be reacted with each other as such, i.e. without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or a mixture of these will be advantageous. Examples of such solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol

monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxane; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides, such as

N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide,

N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of an acid catalyst, acids employed in excess, for example strong organic carboxylic acids, such as unsubstituted or substituted, for example halogen-substituted, C₁-C₄alkanecarboxylic acids, for example formic acid, acetic acid or propionic acid, can also act as solvent or diluent.

The reaction is advantageously carried out in a temperature range from approximately 0°C to approximately +100°C, preferably from approximately 10°C to approximately +40°C. Variant c):

The reactants can be reacted with one another as such, i.e. without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or a mixture of these will be advantageous. Examples of such solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane,

dichloroethane, trichloroethene or tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxane; and sulfoxides, such as dimethyl sulfoxide.

The reaction is advantageously carried out in a temperature range from approximately 20°C to approximately +120°C, preferably from approximately 40°C to approximately +100°C.

Variant d):

N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)- pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,5-diazabicyclo[5.4.0]undec-5-ene (DBU).

The reactants can be reacted with each other as such, i.e. without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or a mixture of these will be advantageous. Examples of such solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxane; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, bases employed in excess, such as triethylamine, pyridine,

N-methylmorpholine or N,N-diethylaniline, can also act as solvent or diluent.

The reaction is advantageously carried out in a temperature range from approximately 0°C to approximately +100°C, preferably from approximately 10°C to approximately +40°C.

Variant e):

Examples of bases which are suitable for facilitating the reaction are alkylamines, alkylenediamines, free or N-alkylated, saturated or unsaturated cycloalkylamines and carbocyclic amines. Examples which may be mentioned are triethylamine,

diisopropylethylamine, triethylenediamine, N-cyclohexyl-N,N-dimethylamine and

N,N-diethylaniline.

The reactants can be reacted with each other as such, i.e. without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or a mixture of these will be advantageous. Examples of such solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxane; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, bases employed in excess, such as triethylamine or N,N-diethylaniline, can also act as solvents or diluents.

Variant f):

Examples of bases which are suitable for facilitating the reaction are alkylamines, alkylenediamines, free or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides as well as carbocyclic amines. Examples which may be mentioned are triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,5-diazabicyclo[5.4.0]undec-5-ene (DBU).

Examples of acid catalysts which are suitable for facilitating the reaction are those acids, employed in catalytic amounts, which are mentioned above as being suitable for the formation of acid addition salts with compounds I.

N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide,

N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, then bases employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also act as solvents or diluents. If the reaction is carried out in the presence of an acid catalyst, acids employed in excess, for example strong organic carboxylic acids, such as unsubstituted or substituted, for example halogen-substituted, C₁-C₄alkanecarboxylic acids, such as formic acid, acetic acid or propionic acid, may also act as solvents or diluents.

The reaction is advantageously carried out in a temperature range from approximately 20°C to approximately +100°C, preferably from approximately 50°C to approximately +80°C. Variant g):

monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxane; alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides, such as

N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide,

N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide.

The reaction is advantageously carried out in a temperature range from approximately 20°C to approximately +120°C, preferably from approximately 50°C to approximately +110°C.

Variant h):

Examples of bases which are suitable for facilitating the reaction are alkylamines, alkylenediamines, free or N-alkylated, saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides as well as carbocyclic amines. Examples which may be mentioned are triethylamine, diisopropylethylamine, triethylenediamine,

cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and 1,5-diazabicyclo[5.4.0]undec-5-ene (DBU).

The reactants can be reacted with each other as such, i.e. without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or a mixture of these will be advantageous. Examples of such solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran or dioxane; alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; amides, such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or hexamethylphosphoric triamide; nitriles, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide. If the reaction is carried out in the presence of a base, then bases employed in excess, such as triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, may also act as solvents or diluents.

Salts of compounds I can be prepared in a manner known per se. For example, acid addition salts of compounds I are obtained by treatment with a suitable acid or a suitable ion-exchanger reagent, and salts with bases are obtained by treatment with a suitable base or a suitable ion-exchanger reagent.

Salts of compounds I can be converted in the customary manner to give the free compounds I, acid addition salts for example by treatment with a suitable basic agent or with a suitable ion-exchanger reagent, and salts with bases for example by treatment with a suitable acid or a suitable ion-exchanger reagent.

Salts of compounds I can be converted in a manner known per se to give other salts of compounds I, for example acid addition salts can be converted to other acid addition salts, for example by treating a salt of an inorganic acid, such as a hydrochloride, with a suitable metal salt, such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus separates out from the reaction mixture.

Depending on the procedure and on the reaction conditions, the compounds I which have salt-forming properties can be obtained in free form or in the form of salts.

The compounds I and II can exist in the form of one of the isomers which are possible or in the form of a mixture of these, for example depending on the number and the absolute and relative configuration of the asymmetric carbon atoms as pure isomers, such as antipodes and/or diastereomers, or as isomer mixtures, such as enantiomer mixtures, for example racemates, diastereomer mixtures or racemate mixtures; the invention relates to the pure isomers as well as to all isomer mixtures which are possible and is to be understood accordingly hereinabove and hereinbelow even when stereochemical details are not mentioned specifically in each case.

Diastereomer mixtures and racemate mixtures of compounds I and II which can be obtained according to the process - depending on the selection of starting materials and procedures - or via other routes can be separated in a known manner by virtue of the physico-chemical differences of the components to give the pure diastereomers or racemates, for example by fractional crystallization, distillation and/or chromatography.

Enantiomer mixtures which can thus be obtained, such as racemates, can be resolved by known methods to give the optical antipodes, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-pressure liquid chromatography (HPLC) on acetylcellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, only one enantiomer being complexed in the process.

Pure diastereomers or enantiomers can be obtained according to the invention not only by separating suitable isomer mixtures, but also by generally known methods of

diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention using starting materials with correspondingly suitable stereochemistry.

If individual components differ with regard to their biological activity, it is advantageous to isolate, or synthesize, in each case the biologically more active isomer, for example enantiomer, or isomer mixture, for example enantiomer mixture.

The compounds I and II can also be obtained in the form of their hydrates and/or include other solvents, for example those which may need to be used for crystallizing compounds which are in solid form.

The invention relates to all those embodiments of the process by which, starting with a compound which can be obtained during any stage of the process as starting material or intermediate, all or some of the missing steps are carried out or a starting material is used in the form of a derivative or salt and/or a racemate or antipode thereof or, in particular, is formed under the reaction conditions.

In the process of the present invention, starting substances and intermediates which are preferably used are those which lead to the compounds I which have been described at the outset as being particularly valuable.

In particular, the invention relates to the preparation processes described in Examples H1 to H10.

The invention also provides starting materials and intermediates, in each case in free form or in salt form, which are novel and are used according to the invention for the preparation of the compounds I or the salts thereof, their use as well as processes for their preparation.

The compounds I according to the invention are valuable preventive and/or curative active ingredients in the field of pest control, even when applied in low concentrations, while being well tolerated by warm-blooded species, fish and plants and having a highly favourable biocidal spectrum. The active ingredients according to the invention are active against all or individual development stages of normally-sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina. The insecticidal or acaricidal activity of the active ingredients according to the invention may become apparent directly, for example from a destruction of the pests, either immediately or only after some time has elapsed, for example during molting, or indirectly, for example from a reduced oviposition and/or hatching rate, a good activity corresponding to a mortality of at least 50 to 60 %.

The abovementioned animal pests include, for example:

from 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.;

from 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.;

from the order Orthoptera, for example,

Blatta spp., Blattella spp., Gryllotalpa spp., Leucophaea maderae, Locusta spp.,

Periplaneta spp. and Schistocerca spp.;

from the order Isoptera, for example,

Reticulitermes spp.;

from the order Psocoptera, for example,

Liposcelis spp.;

from the order Anoplura, for example,

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

from the order Mallophaga, for example,

Damalinea spp. and Trichodectes spp.;

from the order Thysanoptera, for example,

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

Scirtothrips aurantii;

from 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.;

from 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;

from 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.;

from 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.;

from the order Siphonaptera, for example,

Ceratophyllus spp. and Xenopsylla cheopis;

from the order Thysanura, for example,

Lepisma saccharina and

from 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..

The active ingredients according to the invention are particularly suitable for controlling, i.e. containing or destroying, pests of the abovementioned type which are found in particular on plants, mainly on useful plants and ornamentals in agriculture, horticulture and forestry, or on parts of such plants, such as fruits, flowers, foliage, stalks, tubers or roots, and, in some cases, the protective effect is also extended to newly-forming parts of the plants.

Target crops which are suitable are, in particular, cereals such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar beet or fodder beet; fruit, for example pomaceous fruit, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; pulses, such as beans, lentils, peas or soya beans; oil crops such as oilseed rape, mustard, poppy, olives, sunflowers, coconut, castor oil, cocoa or groundnuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruits such as oranges, lemons, grapefruit or tangerines; vegetables such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; the laurel family, such as avocado, cinnamon or camphor; and also tobacco, nuts, coffee, egg plants, sugar cane, tea, pepper, grapevines, hops, the plantain family, natural latex plants and ornamentals.

The active ingredients according to the invention are particularly suitable for controlling Boophilus microplus, Nilaparvata lugens, Panonychus ulmi and Tetranychus urticae in vegetable, fruit and rice plants.

Other fields of application for the active ingredients according to the invention are the protection of stored products and stores and materials, and, in the hygiene field, in particular the protection of domestic animals and productive livestock against pests of the abovementioned type.

The invention therefore also relates to pesticides such as emulsifiable concentrates, suspension concentrates, ready-to-spray or ready-to-dilute solutions, spreadable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances, all of which comprise - at least - one of the active ingredients according to the invention and are to be selected according to the intended aims and prevailing circumstances.

In these compositions, the active ingredient is employed in pure form, a solid active ingredient for example in a specific particle size, or, preferably, together with - at least - one of the auxiliaries conventionally used in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants).

Solvents which are suitable are, for example: unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably the fractions C₈ to C₁₂ of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols, such as ethanol, propanol or butanol, glycols as well as their ethers and esters, such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl or monoethyl ether, ketones such as cyclohexanone, isophorone or diacetanol alcohol, strongly polar solvents such as N-methylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, unepoxidized or epoxidized vegetable oils, such as unepoxidized or epoxidized rapeseed oil, castor oil, coconut oil or soya oil, and silicone oils.

Solid carriers which are used, for example for dusts and dispersible powders, are, as a rule, ground natural minerals, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly-disperse silicas or highly-disperse absorptive polymers. Suitable paniculate, adsorptive carriers for granules are porous types, such as pumice, brick grit, sepiolite or bentonite, and suitable

non-sorptive carriers are calcite or sand. Moreover, a large number of granulated materials of inorganic or organic nature can be used, especially dolomite or comminuted plant residues.

Suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants or surfactant mixtures which have good emulsifying, dispersing and wetting properties, depending on the nature of the active ingredient to be formulated. The surfactants listed below are only to be considered as examples; the specialist literature describes a large number of other surfactants which are conventionally used in the art of formulation and suitable according to the invention.

Suitable non-ionic surfactants are mainly polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can comprise 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols. Other suitable non-ionic surfactants are water-soluble polyethylene oxide adducts with polypropylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol which have 1 to 10 carbon atoms in the alkyl chain and comprise 20 to

250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. The abovementioned compounds customarily comprise 1 to 5 ethylene glycol units per propylene glycol unit. Examples which may be mentioned are

nonylphenolpolyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and

octylphenoxypolyethoxyethanol. Other substances which are suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are mainly quaternary ammonium salts which comprise, as substituents, at least one alkyl radical having 8 to 22 carbon atoms and as further substituents lower, halogenated or unhalogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, for example stearyltrimethylammonium chloride and benzyldi(2-chloroethyl)ethylammonium bromide.

Suitable anionic surfactants can be either water-soluble soaps or water-soluble, synthetic surface-active compounds. Soaps which are suitable are the alkali metal salts, alkaline earth metal salts and substituted or unsubstituted ammonium salts of higher fatty acids (C₁₀-C₂₂), such as the sodium salts or potassium salts of oleic or stearic acid, or of natural mixtures of fatty acids which can be obtained from, for example, coconut oil or tall oil; other surfactants which may be mentioned are the fatty acid methyltaurides. However, synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates. The fatty sulfonates or fatty sulfates are, as a rule, in the form of alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammonium salts and have, as a rule, an alkyl radical having 8 to 22 carbon atoms, alkyl also including the alkyl moiety of acyl radicals; examples which may be mentioned are the sodium or calcium salts of lignosulfonic acid, of the

dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives comprise preferably 2 sulfonic acid groups and a fatty acid radical having approximately 8 to 22 carbon atoms. Alkylarylsulfonates are, for example, the sodium salts, calcium salts or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensation product. Suitable phosphates, for example salts of the phosphoric ester of a p-nonylphenol/(4-14)ethylene oxide adduct, or phospholipids, are also suitable.

As a rule, the compositions comprise 0.1 to 99%, in particular 0.1 to 95%, of active ingredient and 1 to 99.9%, in particular 5 to 99.9%, of - at least - one solid or liquid auxiliary, it being possible, as a rule, for 0 to 25%, in particular 0.1 to 20%, of the compositions to be surfactants (% in each case meaning per cent by weight). While concentrated compositions are more preferred as commercial products, the end user employs, as a rule, dilute preparations with considerably lower concentrations of active ingredients. Preferred compositions are, in particular, composed as follows (% = per cent by weight): Emulsifiable concentrates:

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

Surfactant: 1 to 30%, preferably 10 to 20 %

Solvent: 5 to 98%, 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%

Surfactant: 1 to 40%, preferably 2 to 30%

Wettable powders:

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

Surfactant: 0.5 to 20%, preferably 1 to 15%

Solid carrier: 5 to 99%, preferably 15 to 98%

Granules:

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

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

By adding other insecticidal active ingredients, the action of the compositions according to the invention can be broadened considerably and adapted to prevailing circumstances. Suitable active ingredients which are added are, for example, representatives of the following classes of active ingredients: organophosphorus compounds, nitrophenols and derivatives, formamidines, acylureas, carbamates, pyrethroids, nitroenamines and derivatives, pyrroles, thioureas and derivatives, chlorinated hydrocarbons and Bacillus thuringiensis preparations. The compositions according to the invention can also comprise other solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, as well as fertilizers and other active ingredients for achieving specific effects, for example acaricides, bactericides, fungicides, nematicides, molluscicides or selective herbicides. The compositions according to the invention are prepared in a known manner, for example in the absence of auxiliaries by grinding, screening and/or compressing a solid active ingredient or mixture of active ingredients, for example to obtain a particular particle size, and in the presence of at least one auxiliary, for example by intimately mixing and/or grinding the active ingredient or mixture of active ingredients with the auxiliary(ies). The invention also provides these processes for the preparation of the compositions according to the invention and the use of the compounds I for the preparation of these compositions.

Other subjects of the invention are the methods of application for the compositions, that is to say the methods for controlling pests of the abovementioned type, such as spraying, atomizing, dusting, brushing on, seed-dressing, scattering or pouring, to be chosen according to the intended aims and the prevailing circumstances, and the use of the compositions for controlling pests of the abovementioned type. Typical use concentrations are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm, of active ingredient. As a rule, the rates of application per hectare are 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 20 to 600 g/ha.

A preferred method of application in the field of crop protection is application to the foliage of the plants (foliar application), it being possible to match frequency and rates of application to the danger of infestation with the pest in question. Alternatively, the active ingredient may reach the plants via the root system (systemic action), by drenching the locus of the plants with a liquid composition or by introducing the active ingredient in solid form into the locus of the plants, for example in the soil, for example in granular form (soil application). In the case of paddy rice, such granules may be metered into the flooded paddy field.

The compositions according to the invention are also suitable for the protection of plant propagation material, for example seed, such as fruits, tubers or kernels, or nursery plants, against animal pests. The propagation material can be treated with the composition before planting, for example seed before sowing. Alternatively, the active ingredients according to the invention can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by coating them with a solid composition. Alternatively, the composition can be applied to the planting site when the propagation material is planted, for example into the seed furrow during sowing. The invention also provides these treatment methods for plant propagation material and the plant propagation material which has been treated in this manner. The examples which follow are intended to illustrate the invention. They do not restrict the invention. Temperatures are given in degrees celcius.

Preparation examples

General notes

The compounds are obtained as mixtures of isomers, in most cases in the form of viscous oils. They can be purified by column chromatography. NMR spectra and elementary analyses confirm the claimed structures.

Example H1: 4-Chloro-4' -trifluoromethoxybenzophenone

10.8 g of 4-trifluoromethoxybenzonitrile are added dropwise to a solution of

4-chlorophenylmagnesium bromide in ether (from 22.9 g of 1-bromo-4-chlorobenzene and 2.88 g of magnesium filings in 80 ml of ether) and the mixture is subsequently refluxed for 24 hours. After cooling, 50 ml of 50% sulfuric acid are added at 20-30°C; after the exothermal reaction has subsided, stirring of the batch is continued for 1 hour at room temperature. The phases are separated, and the aqueous phase is extracted repeatedly by shaking with ether. The combined organic phases are worked up using saturated NaHCO₃ solution and saturated NaCl solution. The solid crude product is purified by means of flash chromatography (ethyl acetate/hexane 1:20). This gives 14.3 g of the title compound in crystalline form with an m.p. of 74-75°C.

Example H2: 4- Chloro-4' -trifluoromethoxybenzophenone hydrazone

10.0 g of 4-chloro-4'-trifluoromethoxybenzophenone, 9.70 g of hydrazine hydrate and 2 ml of acetic acid are refluxed gently for 10 hours in 270 ml of absolute alcohol. The solution is then evaporated, the residue is taken up in dichloromethane, and the mixture is washed with water. Evaporation of the dry organic phase gives 9.34 g of the title compound as white, greasy crystals.

Example H3: 4-Chloro-4'-trifluoromethoxybenzophenone N-acetylhydrazone (Compound 1.1 in Table 1)

2.24 g of 4-chloro-4'-trifluoromethoxybenzophenone hydrazone, 0.52 ml of acetyl chloride and 1.04 ml of triethylamine are stirred overnight at room temperature in 40 ml of toluene. After the addition of ether, the organic phase is washed with water, dried over MgSO₄ and evaporated. The residue is stirred with cold hexane and filtered. The title compound is obtained as an isomer mixture in the form of white crystals of m.p. 129-131°C. Example H4: 4-Chloro-4^,-trifluoromethoxybenzophenone N-methylhydrazone

1.50 g of 4-chloro-4'-trifluoromethoxybenzophenone, 1.25 g of methylhydrazine and 0.4 ml of acetic acid are refluxed gently for 24 hours in 45 ml of ethanol. After the mixture has been evaporated, the residue is taken up in dichloromethane and the mixture is washed with water. After drying over MgSO₄ and evaporation, 1.48 g of the title compound remain as a yellow oil.

Example H5: 4-Chloro-4^,-rrifluoromethoxybenzophenone N-formyl-N-methylhydrazone (Compound 1.6 in Table 1)

15 g of sodium formate are introduced into 12.5 ml of ether with stirring and with the exclusion of moisture, and 14.7 g of acetyl chloride are added dropwise at 0°C. Stirring is continued for several hours at room temperature, and sodium chloride is filtered off and the mixture is washed with dry ether. This gives a solution of approximately 14.22 g of formyl acetate in ether.

Some of this solution, containing approximately 0.38 g of formyl acetate, is added dropwise to a solution of 1.48 g of 4-chloro-4'-trifluoromethoxybenzophenone

N-methylhydrazone in 20 ml of ether. After a few hours, the reaction has ended, and the mixture is treated with ice-water, and the organic phase is collected, again washed with water and dried over MgSO₄. After evaporation, the residue is purified by means of flash chromatography (ethyl acetate/hexane 1:3). The product is obtained as an isomer mixture in the form of a yellow oily-waxy substance.

Example H6: 1-(4-Chlorophenyl)-4-dimethylamino-1-(4-trifluoromethoxyphenyl)-2,3-diaza-1,3-pentadiene (Compound 2.1 in Table 2)

A solution of 0.85 g of 4-chloro-4'-trifluoromethoxybenzophenone hydrazone in 15 ml of toluene is treated with 0.66 g of N,N-dimethylacetamide dimethyl acetal. The mixture is subsequently refluxed for 18 hours. After the mixture has been cooled and the solvent evaporated completely, the brown residue is purified by means of flash chromatography (ethyl acetate/hexane 1:5). The title compound is obtained as an isomer mixture in the form of yellow crystals of m.p. 52-54°C.

Example H7: 5-Ethanesulfonyl-1-(4-chlorophenyl)-1-(4-trifluoromethoxyphenyl)-2,3,5-triazapenta-1,3-diene or 5-ethanesulfonyl-1-(4-chlorophenyl-1-(4-trifluoromethoxyphenyl)-2,3,5-triazapenta-1,4-diene. (Compound 3.1 in Table 3)

0.75 g of 1-ethanesulfonyl-1-aza-3-oxa-1-pentene and 0.85 g of N-ethyldiisopropylamine are added to a solution of 0.85 g of 4-chloro-4'-trifluoromethoxybenzophenone hydrazone in 15 ml of toluene. The mixture is stirred for 20 hours under reflux. After the mixture has been cooled, the solvent is evaporated completely and the residue purified by means of flash chromatography (ethyl acetate/hexane 1:2). The title compound is obtained as an isomer mixture in the form of a yellow wax.

Example H8: 4-Bromodifluoromethoxy-4'-chlorobenzophenone

2.58 g of 80% sodium hydride in oil are added in three equally- sized portions at 25-30°C to a stirred solution of 25 g of 4-chloro-4'-hydroxybenzophenone in 150 ml of

dimethylformamide. 27 g of dibromodifluoromethane are then added dropwise at 25 °C, and the mixture is stirred for 16 hours at room temperature. The reaction mixture is subsequently poured into 800 ml of H₂O and extracted three times using in each case 300 ml of ethyl acetate. The organic phase is evaporated and the residue purified by column chromatography (silica gel; hexane/ethyl acetate 20:1). This gives white crystals of a melting point 52-55°C.

Example H9: 4-Bromodifluoromethoxy-4'-chlorobenzophenone hydrazone

7.15 g of 4-bromodifluoromethoxy-4'-chlorobenzophenone, 5.45 g of hydrazine hydrate and 1.5 ml of glacial acetic acid are stirred for 6 hours at 60°C in 150 ml of ethanol. The reaction mixture is concentrated and the concentrate extracted using water and ethyl acetate. The organic phase is evaporated and the residue purified by column

chromatography (silica gel; hexane/ethyl acetate 7:1). This gives yellowish crystals which melt at 45-49°C.

Example H10: 4-Bromodifluoromethoxy-4'-chlorobenzophenone N-acetylhydrazone (Compound 1.27 in Table 1)

0.30 g of triethylamine is added dropwise at 20-25°C to a solution of 1.0 g of

4-bromodifluoromethoxy-4'-chlorobenzophenonehydrazone and 0.23 g of acetyl chloride in 20 ml of tetrahydrofuran, and the mixture is stirred for 90 minutes at room temperature. The reaction mixture is concentrated and the concentrate extracted using water and ethyl acetate. The organic phase is evaporated and purified by column chromatography (silica gel; hexane/ethyl acetate 3:1). This gives the product, which melts at 118-120°C.

Example H11:

The other compounds listed in Tables 1, 2, 3 and 5 may also be prepared analogously to the procedures described in Examples H3, H6, H7 and H10. The compounds listed in Table 4 may be prepared analogously to the procedures described in Examples H2 and H9. In the column "physical data" of these tables, the figures indicate the melting point.

Formulation examples (% = per cent by weight)

Example Fl: Emulsion concentrates a) b) c)

Active ingredient 25% 40% 50%

Calcium dodecylbenzenesulfonate 5% 8% 6%

Castor oil polyethylene glycol ether

(36 mol of EO) 5% - -

Tributylphenol polyethylene glycol ether

(30 mol of EO) - 12% 4%

Cyclohexanone - 15% 20%

Xylene mixture 65% 25% 20%

Mixing finely ground active ingredient and additives gives an emulsion concentrate from which emulsions of any desired concentration can be obtained by diluting it with water.

Example F2: Solutions a) b) c) d)

Active ingredient 80% 10% 5% 95%

Ethylene glycol monomethyl

ether 20% - - -

Polyethylene glycol (MW 400) - 70% - -

N-Methylpyrrolid-2-one - 20% - -

Epoxidized coconut oil - - 1% 5%

Petroleum spirit

(boiling range: 160-190°) - - 94% -

Mixing finely ground active ingredient and additives gives a solution which is suitable for use in the form of microdrops.

Example F3: Granules a) b) c) d)

Active ingredient 5% 10% 8% 21%

Kaolin 94% - 79% 54%

Highly disperse

silica 1% - 13% 7%

Attapulgite - 90% - 18% The active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier mixture and the solvent is evaporated in vacuo.

Example F4: Dusts a) b)

Active ingredient 2% 5%

Highly disperse

silica 1% 5%

Talc 97% -

Kaolin - 90%

Ready-to-use dusts are obtained by mixing active ingredient and carriers.

Example F5: Wettable powders a) b) c)

Active ingredient 25% 50% 75%

Sodium lignosulfonate 5% 5% -

Sodium lauryl sulfate 3% - 5%

Sodium diisobutylnaphthalenesulfonate - 6% 10% Octylphenol polyethylene glycol

ether (7-8 mol of EO) - 2% -

Highly disperse silica 5% 10% 10%

Kaolin 62% 27% -

Active ingredient and additives are mixed and the mixture is ground in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.

Example F6: Emulsion concentrate

Active ingredient 10%

Octylphenol polyethylene glycol

ether (4-5 mol of EO) 3%

Calcium dodecylbenzenesulfonate 3%

Castor oil polyethylene glycol

ether (36 mol of EO) 4%

Cyclohexanone 30%

Xylene mixture 50%

Example F7: Dusts a) b)

Active ingredient 5% 8%

Talc 95% -

Kaolin - 92%

Ready-to-use dusts are obtained by mixing active ingredient and carrier and grinding the mixture in a suitable mill.

Example F8: Extruder granules

Active ingredient 10%

Sodium lignosulfonate 2%

Carboxymethylcellulose 1%

Kaolin 87%

Active ingredient and additives are mixed, the mixture is ground, moistened with water, extruded and granulated, and the granules are dried in a stream of air.

Example F9: Coated granules

Active ingredient 3%

Polyethylene glycol

(MW 200) 3%

Kaolin 94%

Uniformly applying, in a mixer, the finely ground active ingredient to the kaolin which has been moistened with polyethylene glycol gives dust-free coated granules.

Example F10: Suspension concentrate

Active ingredient 40%

Ethylene glycol 10%

Nonylphenol polyethylene glycol ether

(15 mol of EO) 6%

Sodium lignosulfonate 10%

Carboxymethylcellulose 1%

Aqueous formaldehyde solution (37%) 0.2%

Aqueous silicone oil emulsion (75%) 0.8% Water 32%

Mixing finely ground active ingredient and additives gives a suspension concentrate from which suspensions of any desired concentration can be obtained by diluting it with water.

Biological examples:

Example Bl: Action against Spodoptera littoralis caterpillars

Young soya bean plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of the active ingredient. After the spray coating has dried on, the soya bean plants are populated with 10 third instar caterpillars of Spodoptera littoralis and introduced into a plastic container. 3 days later, the test is evaluated. The percentage reduction in population, or the percentage reduction in feeding damage (% action), is determined by comparing the number of dead caterpillars and the feeding damage on the treated to those on the untreated plants.

In this test, the compounds of Tables 1, 2, 3, 4 and 5 exhibit a good activity against Spodoptera littoralis. An activity of over 80% is shown, in particular, by compounds 1.1, 1.3 to 1.14, 1.58, 1.60, 1.61, 1.63, 1.66, 1.67, 1.69, 1.70, 1.76 to 1.79, 1.81 to 1.85, 1.107 to 1.111, 1.114, 1.117, 1.121 to 1.123, 1.131 to 1.133, 1.135 to 1.138, 1.140, 2.3, 2.17 and 2.19.

Example B2: Activity against Heliothis virescens caterpillars

Young soya bean plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of the active ingredient. After the spray coating has dried on, the soya bean plants are populated with 10 first instar caterpillars of Heliothis virescens and introduced into a plastic container. 6 days later, the test is evaluated. The percentage reduction in population, or the percentage reduction in feeding damage (% action), is determined by comparing the number of dead caterpillars and the feeding damage on the treated to those on the untreated plants.

In this test, the compounds of Tables 1, 2, 3, 4 and 5 exhibit a good activity against Heliothis virescens. An activity of over 80% is shown, in particular, by compounds 1.1 to 1.14, 1.58, 1.60, 1.61, 1.63, 1.66, 1.67, 1.69, 1.70, 1.76 to 1.79, 1.81 to 1.85, 1.107 to 1.112, 1.114, 1.116, 1.117, 1.120 to 1.123, 1.125, 1.131 to 1.133, 1.135 to 1.138, 1.140, 2.1 to 2.3, 2.16, 2.17, 2.19, 4.1 and 4.4. Example B3: Ovicidal activity against Heliothis virescens

Heliothis virescens eggs deposited on filter paper are briefly immersed in a test solution comprising 400 ppm of the active ingredient to be tested in acetone/water. After the test solution has dried on, the eggs are incubated in Petri dishes. After 6 days, the percentage hatching rate of the eggs is evaluated in comparison with untreated control batches (% reduction in hatching).

In this test, compounds of Tables 1, 2, 3, 4 and 5 show a good activity against Heliothis virescens. An activity of over 80% is shown, in particular, by compounds 1.1 to 1.14, 1.58,

1.60, 1.61, 1.63, 1.66, 1.67, 1.69, 1.70, 1.76 to 1.79, 1.81 to 1.85, 1.107 to 1.112, 1.114 to

1.117, 1.120 to 1.123, 1.125, 1.126, 1.131 to 1.133, 1.135 to 1.138, 1.140, 2.1 to 2.3, 2.16,

2.17, 2.19, 3.2, 3.3, 4.1, 4.2, 4.4 and 4.5.

Example B4: Activity against Diabrotica balteata larvae

Maize seedlings are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of the active ingredient. After the spray coating has dried on, the maize seedlings are populated with 10 second instar larvae of Diabrotica balteata and introduced into a plastic container. 6 days later, the test is evaluated. The percentage reduction in population (% activity) is determined by comparing the number of dead larvae on the treated to those on the untreated plants.

In this test, the compounds of Tables 1, 2, 3, 4 and 5 show a good activity against

Diabrotica balteata. An activity of over 80% is shown, in particular, by compounds 1.1, 1.2, 1.4, 1.6, 1.58, 1.61, 1.66, 1.67, 1.76 to 1.79, 1.81 to 1.84, 1.107, 1.108, 1.111, 1.112, 1.114, 1.121, 1.122, 1.125, 1.132, 1.133, 1.137, 1.138, 1.140, 2.2, 2.3, 2.17, 2.19, 4.2, 4.4 and 4.5.

Example B5: Activity against Plutella xylostella caterpillars

Young cabbage plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of the active ingredient. After the spray coating has dried on, the cabbage plants are populated with 10 third instar caterpillars of Plutella xylostella and introduced into a plastic container. 3 days later, the test is evaluated. The percentage reduction in population, or the percentage reduction in feeding damage (% action), is determined by comparing the number of dead caterpillars and the feeding damage on the treated to those on the untreated plants. In this test, the compounds of Tables 1, 2, 3, 4 and 5 exhibit a good activity against Plutella xylostella. An activity of over 80% is shown, in particular, by compounds 1.1, 1.3 to 1.14, 1.58, 1.60, 1.61, 1.63, 1.66, 1.67, 1.69, 1.70, 1.76 to 1.79, 1.81 to 1.85, 1.107 to 1.111, 1.114, 1.117, 1.121 to 1.123, 1.132, 1.133, 1.135 to 1.138, 1.140, 2.2, 2.3, 2.17 and 2.19.

Claims

What is claimed is:

1. A compound of the formula

in which X is or ,

R₁ is perhalo-C₁-C₄alkoxy;

C₁-C₈alkylsulfonyl, halo-C₁-C₈alkylsulfonyl, CN or phenyl;

R₃ is halogen, C₁-C₈alkyl, halo-C₁-C₈alkyl or halo-C₁-C₈alkoxy;

R₅ is C₁-C₈alkyl, NR₁₀R₁₁, OR₂₀, SR₂₀ or SO₂R₂₀;

R₆ is H, C₁-C₈alkyl, C₃-C₆cycloalkyl, halo-C₁-C₈alkyl, C₁-C₈alkenyl, C₁-C₈alkynyl, C₁-C₈acyl or phenyl;

R₇ is H, an unsubstituted or substituted C₁-C₈alkyl, C₃-C₆cycloalkyl,

C₃-C₆cycloalkenyl-C₁-C₈alkyl or C₃-C₆cycloalkyl-C₁-C₈alkenyl group, it being possible for the substituents to be selected from the group consisting of halogen, C₁-C₈alkyl, halo-C₁-C₈alkyl, C₁-C₈alkoxy, halo-C_C-C₈alkoxy, C₁-C₈alkyl-S(O)_p, it being possible for p to be 0, 1 or 2, C₁-C₈alkoxycarbonyl, di(C₁-C₈alkyl)amino and C₁-C₈alkanoyloxy; an unsubstituted or substituted phenyl or heteroaryl group, it being possible for the substituents to be selected from the group consisting of C₁-C₆alkyl and halogen;

C₁-C₈alkoxy, NR₁₆R₁₇, COOR₆ or SR₆;

R₈ and R₉ independently of one another are H, C₁-C₈alkyl or OH;

C₂-C₈alkenyl, halo-C₂-C₈alkenyl or propargyl;

R₁₄ and R₁₅ independently of one another are H, C₁-C₈alkyl, halo-C₁-C₈alkyl, phenyl, C₁-C₈alkylamido, di(C₁-C₈alkyl)amido or NH₂;

R₁₆ and R₁₇ independently of one another are H, C₁-C₈alkyl, halo-C₁-C₈alkyl,

C₂-C₈alkenyl, C₁-C₈alkoxy or NH₂;

R₁₈ is S(O)_mR₁₉, m being 0, 1 or 2, NO₂ or CN;

R₂₀ is C₁-C₈alkyl, halo-C₁-C₈alkyl or C₃-C₆cycloalkyl;

Y is O, S, NR₁₈ or CHC(O)R₂₁; and

R₂₁ is H, C₁-C₈alkyl, halo-C₁-C₈alkyl, C₁-C₈alkoxy or phenyl,

OCF₃, o is 0, n is 1, R₄ is CH₃ and R₅ is -N(CH₃)OCH₃, R₂ is other than fluorine and chlorine, or an E/Z isomer or tautomer thereof, in each case in free form or in salt form.

2. A compound according to claim 1 of the formula I in which n is 1 or 2 where, if n is greater than 1, the radicals R₂ are identical or different, or, if appropriate, an E/Z isomer or tautomer thereof.

3. A compound according to claim 1 of the formula I in which o is 0 or 1, or, if appropriate, an E/Z isomer or tautomer thereof.

4. A compound according to claim 1 of the formula I in which R₁ is perhalo-C₁-C₂alkoxy, or, if appropriate, an E/Z isomer or tautomer thereof.

5. A compound according to claim 1 of the formula I in which R₂ is halogen, or, if appropriate, an E/Z isomer or tautomer thereof.

6. A compound according to claim 1 of the formula I in which n is 1 or 2, where, if n is greater than 1, the radicals R₂ are identical or different, o is 0 or 1, R₁ is

perhalo-C₁-C₂alkoxy, R₂ is halogen, C₁-C₄alkyl, halo-C₁-C₄alkyl or halo-C₁-C₄alkoxy, R₃ is H, halogen or methyl, R₄ is H or C₁-C₄alkyl, R₅ is C₁-C₄alkyl, NR₁₀R₁₁, OR₂₀, SR₂₀ or SO₂R₂₀, R₆ is H, C₁-C₄alkyl, C₃-C₆cycloalkyl or C₁-C₆acyl, R₇ is H, C₁-C₆alkyl,

C₃-C₆cycloalkyl, unsubstituted or substituted phenyl or heteroaryl, it being possible for the substituents to be selected from the group consisting of halogen, C₁-C₂alkyl and C₁-C₂alkoxy, or is C₁-C₂alkoxy or NR₁₆R₁₇, R₁₀ is H, C₁-C₂alkyl, phenyl or OR₁₂, R₁₁ is H, C₁-C₂alkyl, C₃-C₆cycloalkyl, allyl or C₁-C₄alkylallyl, R₁₂ is H, C₁-C₄alkyl,

C₃-C₆cycloalkyl, C₂-C₄alkenyl or propargyl, R₁₆ and R₁₇ independently of one another are H or C₁-C₄alkyl, R₁₈ is SO₂R₁₉, NO₂ or CN, R₁₉ is C₁-C₂alkyl or benzyl, R₂₀ is

C₁-C₂alkyl or C₃-C₆cycloalkyl, and Y is O, S or NR₁₈, or, if appropriate, an E/Z isomer or tautomer thereof.

7. A compound according to claim 1 of the formula I in which n is 1, o is 0 or 1, R₁ is perhalomethoxy, R₂ is halogen, C₁-C₂alkyl, halo-C₁-C₂alkyl or halo-C₁-C₂alkoxy, R₃ is H, chlorine or fluorine, R₄ is H or C₁-C₄alkyl, R₅ is NR₁₀Rn or OR₂₀, R_δ is H or

C₁-C₄alkyl, R₇ is H, C₁-C₄alkyl, C₃-C₆cycloalkyl, phenyl, unsubstituted or

halogen-substituted heteroaryl, C₁-C₂alkoxy or NR₁₆R₁₇, R₁₀ and R₁₁ independently of one another are H, C₁-C₂alkyl or OR₁₂, R₁₂ is H, C₁-C₂alkyl or C₃-C₆cycloalkyl, R₁₆ and R₁₇ independently of one another are C₁-C₂alkyl, R₁₈ is SO₂R₁₉, R₁₉ is C₁-C₂alkyl or benzyl, R₂₀ is C₁-C₂alkyl, and Y is O or NR₁₈, or, if appropriate, an E/Z isomer or tautomer thereof.

8. A compound according to claim 1 of the formula I in which n is 1, o is 0 or 1, R₁ is perhalomethoxy, R₂ is halogen, methyl, halomethyl or halomethoxy, R₃ is H, chlorine or fluorine, R₄ is H or C₁-C₄alkyl, R₅ is NR₁₀R₁₁, R₆ is H or C₁-C₄alkyl, R₇ is H, C₁-C₄alkyl, C₃-C₆cycloalkyl, phenyl, unsubstituted or halogen-substituted heteroaryl, C₁-C₂alkoxy or NR₁₆R₁₇, R₁₀ and R₁₁ independently of one another are H, C₁-C₂alkyl or OR₁₂, R₁₂ is H, C₁-C₂alkyl or C₃-C₆cycloalkyl, R₁₆ and R₁₇ independently of one another are C₁-C₂alkyl, R₁₈ is SO₂R₁₉, R₁₉ is C₁-C₂alkyl or benzyl, R₂₀ is C₁-C₂alkyl, and Y is O or NR₁₈, or, if appropriate, an E/Z isomer or tautomer thereof.

9. 4-Chloro-4'-trifluoromethoxybenzophenone N-cyclopropylcarbonylhydrazone or an E/Z isomer thereof according to claim 1.

10. A process for the preparation of a compound according to claim 1 of the formula I or, if appropriate, an E/Z isomer or tautomer thereof, in each case in free form or in salt form, taking into consideration the abovementioned proviso, which comprises a) to prepare a compound of the formula I in which Y is O, reacting a compound of the formula ,

which is known or which can be prepared in analogy to corresponding known compounds and in which n, o, R₁, R₂, R₃ and R₆ are as defined in formula I, or, if appropriate, an E/Z isomer or tautomer thereof, in free form or in salt furm, with a compound of the formula R₇COX₁ in which X₁ is a leaving group, preferably halogen, in particular chlorine, and R₇ is as defined in formula I, preferably in the presence of a base, or b) to prepare a compound of the formula I in which Y is O or S, reacting a compound of the formula ,

which is known or which can be prepared in analogy to corresponding known compounds and in which Y is O or S and R₆ and R₇ are as defined in formula I, in free form or in salt form, preferably in the presence of an acid, or c) to prepare a compound of the formula I in which Y is S, reacting a compound of the formula I in which Y is O and R₆ is preferably a C₁-C₈alkyl group, with phosphorus pentasulfide, or d) to prepare a compound of the formula I in which Y is S and R₆ is H, reacting a compound of the formula ,

which is known or which can be prepared in analogy to corresponding known compounds and in which R₄, R₁₀ and R₁₁ are as defined in formula I and R is a C₁-C₄alkyl group, or h) to prepare a compound of the formula I in which R₅ is NR₁₀R_{1 1}, reacting a compound of the formula ,

and in each case, if desired, converting a compound of the formula I or a tautomer thereof which can be obtained according to the process or via a different route, in each case in free form or in salt form, into a different compound of the formula I or an E/Z isomer or tautomer thereof, resolving an isomer mixture which can be obtained according to the process and isolating the desired isomer and/or converting a free compound of the formula I or a tautomer or an E/Z isomer thereof which can be obtained according to the process into a salt or a salt which can be obtained according to the process, of a compound of the formula I or of a tautomer or an E/Z isomer thereof, into the free compound of the formula I or a tautomer or an E/Z isomer thereof or into a different salt.

11. A pesticide which comprises at least one compound according to claim 1 of the formula I, in free form or in agrochemically utilizable salt form, as active ingredient and, if appropriate, at least one auxiliary.

12. A composition according to claim 11 for controlling insects or representatives of the order Acarina.

13. A process for the preparation of a composition according to claim 11 comprising at least one auxiliary, which process comprises intimately mixing and/or grinding the active ingredient with the auxiliary(ies).

14. The use of a compound according to claim 1 of the formula I in free form or in agrochemically utilizable salt form for the preparation of a composition according to claim 11.

15. The use of a composition according to claim 11 for controlling pests.

16. The use according to claim 15 for the protection of plant propagation material.

17. A method of controlling pests, which comprises applying a composition according to claim 11 to the pests or to their environment.

18. A process according to claim 17 for the protection of plant propagation material, which comprises treating the propagation material or the site where the propagation material is planted.

19. Plant propagation material treated in accordance with the process described in claim 18.

20. A compound of the formula , in which n, o, R₁, R₂, R₃ and R₆ are as defined in formula I, or, if appropriate, an E/Z isomer or tautomer thereof, in free form or in salt form.

21. A process for the preparation of a compound according to claim 20, of the formula II, in free form or in salt form, which comprises i) reacting a compound of the formula ,

or,

compound XI with Cl₃COCOCI in the presence of HF and, if appropriate, reacting the product further with HF to prepare a compound of the formula II in which R₁ is OCF₃, or l) to prepare a compound of the formula II in which R₁ is OCF₃, reacting a compound of the formula ,

22. The use of a compound according to claim 20 of the formula II, in free form or in salt form, for the preparation of a compound according to claim 1.