EP0986534A2

EP0986534A2 - Organic compounds

Info

Publication number: EP0986534A2
Application number: EP98932100A
Authority: EP
Inventors: Peter Maienfisch; Tibor GÖGH; Manfred Böger; Thomas Pitterna
Original assignee: Novartis Erfindungen Verwaltungs GmbH; Novartis AG
Current assignee: Novartis Pharma GmbH; Novartis AG
Priority date: 1997-06-03
Filing date: 1998-05-29
Publication date: 2000-03-22
Also published as: WO1998055448A2; CA2291441A1; AU8211698A; AU734489B2; BR9809912A; CN1259118A; WO1998055448A3; JP2002502405A

Abstract

The invention relates to fluoroalkene carboxylic acid derivatives of general formula (I), in which R1 and R2 are hydrogen (independently of each other), or alkyl, a group of formula (II), cycloalkyl, alkenyl or alkynyl, which are optionally substituted; R3 is hydrogen, fluorine, or methyl; m is 0, 1, 2, 3, 4 or 5; n is 0 or 1; X is oxygen or NR4 and R4 is hydrogen or C1-C6-alkyl or benzyl, which are optionally substituted. The invention also relates to a method for their production, to insecticides containing the new fluoroalkene carboxylic derivatives as active agent, and their use against harmful insects and acarians.

Description

Organic compounds

The present invention relates to new fluoroalkenecarboxylic acid derivatives, processes for their preparation, insecticidal compositions which comprise the new fluoroalkenecarboxylic acid derivatives as active ingredient, and the use of the new fluoroalkenecarboxylic acid derivatives for controlling harmful insects and acarids.

The present invention relates to compounds of the formula

wherein

R ₁ and R _{2 are} independently hydrogen; or alkyl, a group N =, aryl,

Cycloalkyl, alkenyl or alkynyl, which are optionally substituted; R _{3 is} hydrogen, fluorine or methyl; m 0, 1, 2, 3, 4 or 5; n O or l;

X is oxygen or NR, and

R _{4 represents} hydrogen or CrC ₆ alkyl or benzyl, which are optionally substituted, and optionally their possible E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in salt form, with the proviso that that a) R _{3 is} not hydrogen or fluorine and m and n are not both 0 when X is oxygen and R ₁ and R _{2 are} independently hydrogen or unsubstituted or substituted alkyl, alkenyl, cycloalkyl, aryl or heteroaryl; b) R _{3 is} not hydrogen or fluorine and m and n are not both 0 when R _{4 is} hydrogen and R ^ and R _{2 are} independently hydrogen or unsubstituted or substituted alkyl, aryl or heteroaryl; c) m is not 0, 1 or 2 and R _{4 is} not hydrogen, alkyl or haloalkyl if one of the radicals R 1 or R _{2 is} 4-alkylsulfonyloxyphenyl, 4-haloalkysulfonyloxypphenyl or 4-haloalkoxysulfonyloxyphenyl, which can optionally carry further substituents, and the others represent optionally substituted phenyl; and d) m is not 0, 1 or 2 and R, is not hydrogen, alkyl or haloalkyl and n is not 0 if one of the radicals R 1 and R _{2 is} 4-perhaloalkoxyphenyl which may optionally carry further substituents and the other for optionally substituted phenyl; a method of making and using these compounds, E / Z isomers and tautomers; Pesticides, the active ingredient of which is selected from these compounds, E / Z isomers and tautomers; and a method of making and using these agents; Intermediates, and optionally their possible E / Z isomers, E / Z isomer mixtures and / or tautomers, in free form or in salt form, for the preparation of these compounds, optionally tautomers, in free form or in salt form, of these intermediates; and a process for making and using these intermediates and their tautomers.

Preferred groups of compounds of the formula (I) - taking into account the above-mentioned measures - are those in which

Ri and R _{2 are} independently hydrogen or alkyl, cycloalkyl, alkenyl or

Alkynyl, which are optionally substituted, mean R _{3 represents} hydrogen, fluorine or methyl, m 0, 1, 2, 3, 4 or 5; n is 0 or 1, X is oxygen or NR ₄ , and R _{4 is} hydrogen or unsubstituted or substituted CC ₆ alkyl or benzyl; wherein Ri is hydrogen or unsubstituted or substituted alkyl, alkenyl, alkynyl or

Are cycloalkyl, R _{2 is} hydrogen or unsubstituted or substituted aryl or heteroaryl, R _{3 is} hydrogen, fluorine or methyl, m is 0, 1, 2, 3, 4 or 5; n is 0 or 1, X is oxygen or NR ₄ , and R _{4 is} hydrogen or unsubstituted or substituted dC ₆ alkyl or benzyl; and in which R 1 and R ₂ independently of one another denote H or aryl, which are optionally substituted, or R _{3 represents} hydrogen, fluorine or methyl, m 0, 1, 2, 3, 4 or 5; n is 0 or 1,

X represents oxygen or NR ₄ , and

R _{4 represents} hydrogen or unsubstituted or substituted C ₁ -C ₆ -alkyl or benzyl, the general terms used in the above definitions of the substituents R 1, R ₂ , R and R ₄ are defined below as follows:

Halogen means fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, especially fluorine or chlorine and especially chlorine.

Alkyl means straight-chain or branched alkyl radicals having 1 to 20 carbon atoms, which can be unsubstituted or substituted one or more times. R 1 and R ₂ as alkyl groups are preferably straight-chain or branched alkyl radicals having 1 to 8 carbon atoms and particularly preferably alkyl radicals having 1 to 4 carbon atoms. Suitable substituents of R _T and R ₂ as alkyl groups are hydroxyl, halogen, alkoxy, haloalkoxy, alkoxyalkoxy, alkythio, haloalkylthio, alkylsulfinyl, alkylsulfonyl, alkylsulfonyloxy, alkylcarbonyl, dialkylamino, pyrrolidino, piperidino, morphoiino, alkoxycarbonyl, alkylcarbonyloxy , Aryl, aryloxy, arylthio, arylsulfonyl, arylsulfonyloxy, arylcarbonyl or heteroaryl, where aryl or heteroaryl groups in turn are substituted one or more times by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or halophenyl could be. The alkyl radicals present as alkyl groups in the substituents of R 1 and R ₂ preferably have 1 to 4 carbon atoms. These alkyl radicals are particularly preferably methyl or ethyl radicals. Examples of R <and R ₂ as alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2,2-dimethylpropyl , Isopentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 1, 3-dimethylbutyl, 2-ethylbutyl, n-heptyl, n-octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, hexadecyl and octadecyl. Preferred substituents of R *. and R ₂ as alkyl groups are hydroxy, halogen, alkoxy, haloalkoxy, alkoxyalkoxy, alkythio, haloalkylthio, alkylsulfinyl, alkylsulfonyl, alkylsulfonyloxy, alkylcarbonyl, dialkylamino, pyrrolidino, piperidino, morphoiino, alkoxycarbonyl, alkylcarbonyloxy, cycloalkyl, phenyl, phenyl, phenoxy, phenyl, phenoxy , Phenylsulfonyloxy, benzoyl and pyridyl can be substituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, nitro or cyano. A single or multiple substitution of a radical R- or R ₂ means in particular a 1 to 4-fold, preferably a 1 to 2-fold and particularly preferably a 1-fold substitution, with R and R ₂ in particular as lower alkyl radicals , such as methyl or ethyl, can be perhalogenated, in particular perfluorinated, when substituted by halogen. In the case of multiple substitution, the respective substituents can be the same or different.

Aryl means phenyl or naphthyl, preferably phenyl.

Heteroaryl denotes aromatic radicals with 5 or 6 ring members and 1 or 2 heteroatoms, which are selected from the group consisting of nitrogen, oxygen and sulfur. Examples of heteroaryl radicals are pyrrolyl, furyl, thienyl, imidazolyl, pyrrazolyl, oxazolyl, thiazolyl, pyridyl, pyridazinyl, pyrimidinyl and pyrazinyl, the radicals R 1 and R ₂ as heteroaryl radicals each being bonded via a carbon atom and optionally a benzene ring being fused to these radicals can. Preferred heteroaryl radicals are pyridyl, pyrimidinyl, quinolyl, furyl and thienyl.

Aryl residues and heteroaryl residues can be unsubstituted or one or more times by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfonyloxy, haloalkylsulfonyloxy, haloalkoxysulfonyloxy, nitro, cyano, benzoyl, phenyl, phenoxy, phenylthyl, benzylkinoamino, dialylyloxylamino, dialylyloxylamino, trialyl , Pyrrolidino, piperidino, morphoiino, anilino, cycloalkylalkoxy or halocycloalkylalkoxy, heteroaryl or heteroaryloxy, where benzoyl, phenyl, phenoxy, phenylthio, benzyloxy, anilino, heteroaryl and heteroaryloxy radicals on their own or as substituents can be substituted several times by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio, halophenylthio, cycloalkylalkoxy or halocycloalkylalkoxy. The alkyl groups occurring as or in the substituents of R 1 and R ₂ as aryl or heteroaryl groups preferably have 1 to 4 carbon atoms. These alkyl groups are particularly preferably methyl or ethyl groups.

Alkenyl means straight-chain or branched alkenyl radicals having 3 to 20, preferably 3 to 8 carbon atoms and particularly preferably alkenyl radicals having 3 to 5 carbon atoms, which can be unsubstituted or substituted one or more times by halogen. Alkenyl preferably denotes those alkenyl radicals which are bonded via a saturated carbon atom, ie alkenyl radicals with a central or terminal double bond. Examples for alkenyl radicals are allyl, methallyl, 2-buten-1-yl, 3-butene-1-yl, 2-penten-1-yl, 3-penten-1-yl, 4-penten-1-yl, 2-methyl -2-buten-1-yl, 2-hexen-1-yl, 3-hexen-1-yl, 4-hexen-1-yl, 5-hexen-1yl, 2-hepten-1-yl, 2-octene -1-yl and 2-decen-1 -yl. Allyl and methallyl are particularly preferred alkenyl radicals.

Alkynyl means straight-chain or branched alkynyl radicals having 3 to 20, preferably 3 to 8 carbon atoms and particularly preferably alkynyl radicals having 3 to 5 carbon atoms, which may be unsubstituted or substituted one or more times by halogen. Alkynyl preferably denotes those alkynyl radicals which are bonded via a saturated carbon atom, i.e. H. Alkynyl residues with a middle or terminal triple bond. Examples of alkynyl radicals are propargyl, 2-butyn-1-yl, 3-butyn-1-yl, 2-, 3- or 4-pentyn-1-yl, 2-, 3-, 4- or 5-hexyn-1 -yl, 2-, 3-, 4-, 5- or 6 heptin-1-yl and 2-, 3-, 4-, 5-, 6- or 7-octin-1yl. A particularly preferred alkynyl radical is the propargyl radical.

Cycloalkyl means cycloalkyl radicals having 3 to 7 carbon atoms, which may be unsubstituted or substituted one or more times by halogen, alkyl or haloalkyl, alkyl and haloalkyl radicals preferably containing 1 to 4 carbon atoms and particularly preferably 1 to 2 carbon atoms. Examples of cycloalkyl radicals are cyclopropyl, 2-methylcyclopropyl, cyclobutyl, cyclopentyl, 2-methylcyclopentyl, 3,4-dimethylcyclopentyl, cyclohexyl, 2-methylcylohexyl, 4-methylcyclohexyl, 3,4-dimethylcyclohexyl, 2,4-dimethylcyclohexyl and cycloheptyl.

The meaning of the general terms used in the definition of the general terms used applies, unless expressly deviated therefrom, to the entire present description.

The present invention relates in particular to compounds of the general formula (I) in which, taking into account the above-mentioned measures,

Ri and R ₂ independently

Hydrogen; C Cao-alkyl, which is straight-chain or branched and one to four times by hydroxy, halogen, alkoxy, haloalkoxy, alkoxyalkoxy, alkythio, haloalkylthio, alkylsulfinyl, alkylsulfonyl, alkylsulfonyloxy, alkylcarbonyl, dialkylamino, pyrrolidino, piperidino, morphoino, alkoxycarbonylcycloalkylcarbonyl , Phenyl, Naphthyl, Phenoxy, Naphthoxy, Phenylthio, Naphthylthio, Phenylsulfonyl, Naphthylsulfonyl, Phenylsulfonyloxy, Naphthylsulfonyloxy, Benzoyl, Naphthoyl, Heteroaryl or Heteroaryloxy with 5 to 6 ring members or substituted by 5, 6 O or S and is 1 to 2 heteroatoms and S 1, 2, or 3 heteroaryl atoms and is 1, 2, or 3 heteroaryl atoms and has 1, 2, or 3-membered groups and is 1 to 2 heteroarytes and can be substituted by 1, 2 or 3 heteroaryl atoms and 1 to 2, or 1 and 2 heteroaryl atoms and 1 to 2, or 1 and 2 heteroaryl groups mentioned aryl or heteroaryl groups in turn one or two times by halogen, alkyl,

Haloalkyl, alkoxy, haloalkoxy, alkylthio, nitro, cyano, phenoxy, halophenoxy,

Phenylthio or halophenylthio may be substituted;

C ₃ -C ₂ o-alkenyl which can be straight-chain or branched and can be substituted one to four times by halogen;

C ₃ -C ₂ o-alkynyl which can be straight-chain or branched and can be substituted one to four times by halogen;

C ₃ -C ₇ cycloalkyl, which can be substituted one to four times by halogen, alkyl or haloalkyl;

Phenyl or naphthyl which is one to four times by halogen, alkyl, haloalkyl, alkoxy,

Haloalkoxy, cycloalkylalkoxy, halocycloalkylalkoxy, alkylthio, haloalkylthio,

Alkylsulfonyloxy, haloalkylsulfonyloxy, haloalkoxysulfonyloxy, alkyiamino, dialkylamino,

Pyrrolidino, piperidino, morphoiino, nitro, cyano, trialkylsilyl, phenyl, phenoxy, phenylthio,

Benzoyl, benzyloxy, anilino, naphthyl, heteroaryl or heteroaryloxy with 5 to 6

Ring members and 1 to 2 heteroatoms N, O or S can be substituted, with phenyl,

Phenoxy, phenylthio, benzoyl, benzyloxy, anilino, naphthyl, heteroaryl and

Heteroaryloxy radicals as substituents, in turn, one or two times by halogen, alkyl,

Haloalkyl, alkoxy, haloalkoxy, alkylthio, nitro, cyano, phenoxy, phenylthio,

Halogenphenylthio, Cycloalkylalkoxy or Halogencycloalkylalkoxy can be substituted,

Heteroaryl with 5 to 6 ring members and 1 to 2 heteroatoms N, O or S, which is mono- to tetravalent by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cycloalkylalkoxy,

Halocycloalkylalkoxy, alkylthio, haloalkylthio, alkyiamino, dialkylamino, pyrrolidino,

Piperidino, Morphoiino, Nitro, Cyano, Trialkylsilyl, Phenyl, Phenoxy, Phenylthio, Benzoyl,

Benzyloxy, anilino, naphthyl, heteroaryl or heteroaryloxy with 5 to 6 ring members and 1 to 2 heteroatoms N, O or S can be substituted, phenyl, phenoxy,

Phenylthio, benzoyl, benzyloxy, anilino, naphthyl, heteroaryl and heteroaryloxy radicals as substituents, in turn, one or two times by halogen, alkyl, haloalkyl, alkoxy,

Haloalkoxy, alkylthio, nitro, cyano, phenoxy, phenylthio, halophenylthio,

Cycloalkylalkoxy or Halogencycloalkylalkoxy may be substituted;

R _{3 is} hydrogen, fluorine or methyl; m 0, 1, 2, 3, 4 or 5; n 0 or 1; and

X represents oxygen or NR ₄ , where R represents hydrogen, CC-alkyl, which can be substituted one or more times by halogen, C 1 -C ₄ -alkoxy or di-C C -alkylamino, or stands for benzyl, one or more times by halogen, CC ₄ -Alkyl, halogen-C C -alkyl, dd-alkoxy, nitro or cyano may be substituted.

Compounds of the formula (I) are preferred, taking into account the measures listed above, in which R 1 and R ₂ independently of one another are hydrogen, C 1 -C ₈ -alkyl, which is straight-chain or branched and mono- or disubstituted by hydroxyl, halogen, CrC ₄ - Alkoxy, halogen-dC -alkoxy, CC -alkoxyalkoxy, C ₁ -C ₄ -alkylthio, halogen-C C ₄ -alkylthio, CrC -alkylsulfinyl, Cι-C ₄ -alkylsulfonyl, CrC lkylsulfonyloxy, d- C ₄ -alkylcarbonyl, Di -Crd-alkyiamino, pyrrolidino, piperidino, morphoiino, dC -alkoxycarbonyl, -C-C ₄ -alkylcarbonyioxy, C ₃ -C ₆ -cycloalkyl, phenyl, naphthyl, phenoxy, naphthoxy, phenylthio, naphthylthio, phenylsulfonyl, naphthylsulfonyl, naphthylsulfonyl, naphthylsulfonyl, naphthylsulfonyl Naphthylsulfonyioxy, benzoyl, naphthoyl, heteroaryl or heteroaryloxy with 5 to 6 ring members and 1 or 2 heteroatoms N, O or S may be substituted, the aryl or heteroaryl groups mentioned being in turn mono- or disubstituted by halogen, C 1 -C ₄ -alkyl, Halogen-CrC ₄ -alkyl, CrC-alkoxy, halog en-CrC ₄ -alkoxy, CC -alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or halophenylthio may be substituted; C ₃ -C ₈ alkenyl which can be straight-chain or branched and can be mono- or disubstituted by halogen;

C ₃ -C ₈ alkynyl, which can be straight-chain or branched and can be mono- or disubstituted by halogen;

C ₃ -C cycloalkyl, which can be mono- or disubstituted by halogen, CC-alkyl or halogen-C C ₄ - alkyl;

Phenyl or naphthyl which is mono- or disubstituted by halogen, CrC ₄ -alkyl, halogen-C C-alkyl, CC ₄ -alkoxy, halogen-C C ₄ -alkoxy, C ₃ -C ₆ -cycloalkyl-C C ₄ - alkoxy, halogen-C C ₄ - cycloalkyl -CC -alkoxy, CC ₄ -alkylthio, halogen-

CC ₄ -alkylthio, CrC ₄ -alkylsulfonyloxy, halo-CrC ₄ -alkylsulfonyloxy, halo-dd-alkoxy-sulfonyloxy, Cι-C -alkylamino, di-CrC ₄ -alkylamino, pyrrolidino, piperidino, morphoiino, nitro, cyano, tri- CrC -alkylsilyl, phenyl, phenoxy, phenylthio, benzoyl, benzyloxy, anilino, naphthyl, heteroaryl or heteroaryloxy with 5 to 6 ring members and 1 or 2 heteroatoms N, O or S can be substituted, phenyl, phenoxy, phenylthio, benzoyl -, Benzyloxy, anilino, naphthyl, heteroaryl and heteroaryloxy radicals as substituents, in turn, one or two times by halogen, CrC ₄ -alkyl, halogen-C C ₄ -alkyI, CrC ₄ -alkoxy, halogen-C C ₄ -alkoxy , CrC ₄ alkylthio, nitro, cyano, phenoxy, phenylthio, halogen phenylthio, C ₃ -C ₆ cycloalkyl -CC ₄ -alkoxy or halogen-C ₃ -C ₆ -cycloalkyl -CC ₄ -alkoxy may be substituted,

Heteroaryl with 5 to 6 ring members and 1 to 2 heteroatoms N, O or S, the one or two times by halogen, C ₁ -C ₄ alkyl, halogen-dC ^ alkyl, -C-C alkoxy, halogen-CrC - alkoxy , QrCe-cycloalkyl-dd-alkoxy, halogen-C ₃ -C ₆ -cycloalkyl-dC -alkoxy, C -C ₄ -

Alkylthio, halo -CC ₄ -alkylthio, CrC-alkylamino, di-CrC ₄ -alkylamino, pyrrolidino,

Piperidino, Morphoiino, Nitro, Cyano, Tri-Cι-C ₄ alkylsilyl, phenyl, phenoxy, phenylthio,

Benzoyl, benzyloxy, anilino, naphthyl, heteroaryl or heteroaryloxy with 5 to 6

Ring members and 1 to 2 heteroatoms N, O or S can be substituted, with phenyl,

Phenoxy, phenylthio, benzoyl, benzyloxy, anilino, naphthyl, heteroaryl and

Heteroaryloxy radicals as substituents, in turn, one or two times by halogen, CrC ₄ -

Alkyl, halogen-dC ₄ -alkyl, CC ₄ -alkoxy, halogen-CrC ₄ -alkoxy, -C-C ₄ -alkylthio, nitro,

Cyano, phenoxy, phenylthio, halophenylthio, C ₃ -C ₆ cycloalkyl -CC ₄ -alkoxy or

Halogen-C ₃ -C ₆ -cycloalkyl -CC-C ₄ alkoxy may be substituted,

R _{3 is} hydrogen, fluorine or methyl, m 0, 1, 2, 3 or 4, n 0 or 1 and

X represents oxygen or NR, where

R _{4 is} hydrogen, dC ₄ alkyl, which can be mono- or disubstituted by halogen, CrC ₄ alkoxy or di-dC ₄ alkylamino, or for

Benzyl is the one to two times by halogen, dd-alkyl, halogen-dC ₄ -alkyl, dC ₄ -

Alkoxy, nitro or cyano can be substituted.

The preferred meanings defined above for the radicals R _{1 f} R, R ₃ and R which occur in general apply analogously to those defined above

Subgroups of compounds of formula (I).

Among the compounds of the formula (I), preference is furthermore given to those in which a) R _{3 is} hydrogen; b) m denotes 0, 1, 2, 3 or 4, particularly preferably 1 or 4; c) n denotes 0; d) R _{4 represents} hydrogen; e) Ri and R _{2 have} the meaning given above, R _{3 represents} hydrogen, m is 0, 1, 2, 3 or 4, n represents 0 or 1, and X represents oxygen or NH; f) Ri and R _{2 have} the meaning given above, R ₃ stands for hydrogen, m is 1 or 4, n means 0 and X represents oxygen or NH: g) Ri has the meaning given above, R ₃ stands for hydrogen and R _{2 is} a group

means where Alk is methyl or ethyl and the phenyl ring is optionally substituted.

Particularly preferred individual compounds are compounds of the formula (I) in which R _{3 is} hydrogen and a) Ri is hydrogen, R _{2 is} hydrogen, X is oxygen, m 1 and n 0; b) Ri methyl, R ₂ methyl, X oxygen, m 1 and n 0; c) Ri methyl, R ₂ phenyl, X oxygen, m 1 and n 0; d) Ri methyl, R ₂ 4-trifluoromethylphenyl, X oxygen, m 1 and n 0; e) Ri methyl, R ₂ 4-nitrophenyl, X oxygen, m 1 and n 0; f) R _! Methyl, R ₂ 4-tert-butylphenyl, X oxygen, m 1 and n 0; g) R _T phenyl, R ₂ phenyl, X oxygen, m 1 and n 0; h) Ri hydrogen, R ₂ phenyl, X oxygen, m 1 and n 0; i) R _T phenyl, R ₂ benzyl, X oxygen, m 1 and n 0; j) Ri ethyl, R ₂ 4-chlorophenyl, X oxygen, m 1 and n 0; k) R _T hydrogen, R ₂ methyl, X NH, m 1 and n 0;

I) R, methyl, R ₂ methyl, X NH, m 1 and n 0; m) Ri methyl, R ₂ phenyl, X NH, m 1 and n 0; n) Ri methyl, R ₂ 3-trifluoromethylphenyl, X NH, m 1 and n 0; o) R _T methyl, R ₂ 4-tert-butylphenyl, X NH, m 1 and n 0; p) Ri phenyl, R ₂ phenyl, X NH, m 1 and n 0; q) Ri hydrogen, R ₂ phenyl, X oxygen, m 1 and n 0; r) R _T phenyl, R ₂ benzyl, X NH, m 1 and n 0; s) Ri ethyl, R ₂ 4-chlorophenyl, X NH, m 1 and n 0; t) Ri hydrogen, R ₂ hydrogen, X NH, m 1 and n 1; u) Ri methyl, R ₂ methyl, X NH, m 1 and n 1; v) R, methyl, R ₂ phenyl, X NH, m 1 and n 1; w) R _T methyl, R 3-trifluoromethylphenyl, X NH, m 1 and n 1; x) Ri methyl, R ₂ 4-tert-butylphenyl, X NH, m 1 and n 1; y) Ri phenyl, R ₂ phenyl, X NH, m 1 and n 1; z) Ri hydrogen, R ₂ phenyl, X oxygen, m 1 and n 1; aa) R _T phenyl, R ₂ benzyl, X NH, m 1 and n 1; or bb) R 1 is ethyl, R _{2 is} 4-chlorophenyl, X is NH, m 1 and n 1.

The present invention further provides a process for the preparation of a compound of the formula (I), characterized in that a) for the preparation of a compound of the formula (I), in which n is 0 and R 1, R ₂ , R ₃ , X and m have the meaning given above under formula (I), a compound of the formula

in which R ₃ and m have the meaning given under formula (I) and Y _{2 is} Cl, Br or OSO ₂ alkyl, with a compound of the formula

/

HX - N - (III)

\ in which R _{1 (} R ₂ and X have the meaning given under formula (I); b) compounds of the formula (I) in which n is 0, X is NR ₄ , and R _{1 f} R ₂ , R ₃ and m have the meaning given above under formula (I), prepared by using a compound of formula

in which R ₃ , R ₄ and m have the meaning given under formula (I), with a compound of the formula

(V)

\

implements in which R 1 and R _{2 have} the meaning given under formula (I). c) Compounds of formula (I), wherein n is 1 and R _{1 (} R ₂ , R ₃ , R, X and m have the meaning given above under formula (I), by preparing a compound of

formula

in which R ₃ and m have the meaning given above under formula (I), with a compound of the formula

implemented in which Y _{1 is} Cl, Br or OSO ₂ alkyl and X, Ri and R _{2 have} the meaning given above under formula (I).

The starting materials of the formulas (II) and (VI) are known or can be prepared analogously to known processes.

The starting materials of the formula (III) can be prepared in a manner known per se by reacting a ketone of the above formula (V) with hydrazine, a hydrazine monosubstituted by R _{4 as} defined above or with hydroxylamine, the ketones of the formula (V) in turn are accessible by the known processes customary for the production of ketones.

The starting materials of formula (II) can be obtained by using an acid halide of the formula

in which shark means chlorine or bromine, is reacted with a hydrazine monosubstituted by R ₄ according to the meaning given above.

The starting materials of formula (VII) can be obtained by using a chloroacetic acid halide, e.g. B. chloroacetyl chloride, with a compound of formula (III) as defined above. Process a) is preferably not carried out in an inert, hydroxyl-free solvent in the presence of an organic base, such as, for example, pyridine, 4-dimethylaminopyridine, 4-pyrrolidinopyridine, lutidine, coilidine, trialkylamine, N, N-dialkylaniline, or a bicyclic one nucleophilic base such as 1,4-diazabicyclo [2.2.2] octane (DABCO),

1,5-diazabicyclo [4.3.0] non-5-ene (DBN) or 1,8-diazabicyclo [5.4.0] undec-7-ene (1,5-5) (DBU). The reaction is generally carried out at temperatures from -30 ° C. to + 70 ° C., preferably from -10 ° C. to + 50 ° C. The procedure is expediently carried out in the presence of an inert solvent or solvent mixture. Aliphatic and aromatic hydrocarbons such as benzene, toluene, xylenes, petroleum ether, hexane are suitable for this purpose; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachlorethylene; Ethers and ethereal compounds such as dialkyl ether (diethyl ether, diisopropyl ether, tert-butyl methyl ether, etc.) anisole, dioxane, tetrahydrofuran; Nitriles such as acetonitrile, propionitrile; Esters such as ethyl acetate (ethyl acetate), propyl acetate or butyl acetate; Ketones such as acetone, diethyl ketone, methyl ethyl ketone; and mixtures of such solvents with one another. However, the reaction can also be carried out in excess of one of the bases mentioned above, or a second equivalent or a larger excess of the compound of I can also be used instead of the base. The reaction is carried out under the pressure of the environment, although it could also be carried out under increased or reduced pressure.

The reaction of process b) is advantageously carried out in an inert solvent at a temperature of 20 ° C. to 150 ° C., preferably at 40 ° C. to 120 ° C., optionally in the presence of a catalytic amount of an acid, such as acetic acid or p-toluenesulfone. acid. Preferred inert solvents are lower alkanols, especially methanol and ethanol.

The reaction of process c) is advantageously carried out in an inert solvent in the presence of a base and, if appropriate, in the presence of a catalyst, such as NaI or CsF, with polar aprotic solvents such as N, N-dimethylformamide, dimethyl sulfoxide, dioxane being preferred as the inert solvent and tetrahydrofuran. In particular, pyridine, 4-dimethylaminopyridine, 4-pyrrolidinopyridine, lutidine, coilidine, trialkylamine, N, N-dialkylaniline, or a bicyclic base are not bases nucleophilic base such as 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,5-diazabicyclo [4.3.O] non-5-ene (DBN) or 1,8-diazabicyclo [5.4.0] undec-7 -en (1, 5-5) (DBU), suitable.

The reactions described above and below are carried out in a manner known per se, e.g. in the absence or, where appropriate, in the presence of a suitable solvent or diluent or a mixture thereof, with cooling, at room temperature or with heating, e.g. in a temperature range from about -80 ° C to the boiling temperature of the reaction mixture, preferably from about -20 ° C to about + 150 ° C, and, if necessary, in a closed vessel, under pressure, in an inert gas atmosphere and / or under anhydrous Conditions works. Particularly advantageous reaction conditions can be found in the examples.

The compounds of the formula (I) according to the invention are valuable active ingredients in the field of pest control, while being well tolerated by warm-blooded animals, fish and plants. In particular, the active compounds according to the invention act against insects and arachnids, as they occur on useful and ornamental plants in agriculture and horticulture, in particular in rice, cotton, vegetable and fruit plantations, and in the forest. The compounds of the formula (I) are particularly suitable for controlling insects in rice, fruit and vegetable crops, in particular insects which damage plants, such as Aphis craccivora, Nilaparvata lugens and Nephotettix cincticeps. Further areas of application of the active compounds according to the invention are the protection of stored goods and materials, and in the hygiene sector in particular the protection of domestic and farm animals. The compounds of the formula (I) are active against all or individual stages of development of normally sensitive, but also of resistant types of pests. Their effect can be such. B. in a killing of the pests, which occurs immediately or only after some time, for example when molting, or in a reduced egg laying and / or hatching rate.

The animal pests mentioned include, for example, those which are mentioned in European patent application EP-A-736'252. EP-A-736'252 is therefore included by reference in the present subject matter.

The compounds of the formula (I) are particularly suitable as active compounds for controlling pests from the Homoptera order and from the Akarina order.

The compounds of the formula (I) are particularly suitable for controlling the pests in cotton, vegetable, fruit and rice crops, such as spider mites, aphids, and caterpillars and rice cicadas. Mainly spider mites like Panonychus ulmi, aphids like Aphis craccivora, caterpillars like those of Heliothis virescens and rice leafhoppers like Nilaparvata lugens or Nephotettix cincticeps can be checked.

The good pesticidal activity of the compounds of the formula (I) according to the invention corresponds to a mortality rate of at least 50-60% of the pests mentioned.

The action of the compounds of the formula (I) according to the invention and the compositions comprising them can be broadened considerably by adding other insecticides and / or acaricides and adapted to the given circumstances. Representatives of the following classes of active substances are suitable as additives: organic phosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons and Bacillus thuringiensis preparations.

The compounds of the formula (I) are used in unchanged form or, preferably, together with the auxiliaries customary in formulation technology and can therefore, for example, also to emulsifiable concentrates, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts, granules Encapsulations in polymeric substances are processed in a known manner. The application methods, such as spraying, atomizing, dusting, scattering or pouring, as well as the agents, are chosen in accordance with the desired goals and the given conditions.

The formulation, that is to say an active ingredient (I), or combinations of these active ingredients with other insecticides or acaricides, and, if appropriate, agents, preparations or compositions comprising a solid or liquid additive are prepared in a known manner, for example by intimate mixing and / or Grinding the active ingredients with extenders, such as with solvents, solid carriers, and optionally surface-active compounds (surfactants).

The auxiliaries such as solvents, solid carriers, surface-active compounds, nonionic surfactants, cationic surfactants, anionic surfactants and other auxiliaries in the agents used according to the invention are, for example, the same as those described in EP-A-736'252.

The pesticidal preparations generally contain 0.1 to 99%, in particular 0.1 to 95%, of active ingredient I or of the combination of this active ingredient with other insecticides and / or acaricides and 1 to 99.9%, in particular 5 to 99.9%, of a solid or liquid auxiliary, it being possible for the preparations to be, as a rule, 0 to 25%, in particular 0.1 to 20%, surfactants (% means weight percent). While concentrated products are preferred as a commercial product, the end user generally uses diluted preparations which have significantly lower active substance concentrations. Typical application concentrations are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm. The application rates per hectare are generally 1 to 1000 g of active ingredient per hectare, preferably 25 to 500 g / ha.

In particular, preferred formulations are composed as follows (% = weight percent):

Emulsifiable concentrates:

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

Surfactant: 1 to 30%, preferably 10 to 20% liquid carrier: 5 to 94%, preferably 70 to 85%

Dusts:

Active ingredient: 0.1 to 10%, preferably 0.1 to 1% solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension concentrates:

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

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

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 95%, preferably 15 to 90%

Granules:

Active ingredient: 0.5 to 30%, preferably 3 to 15% solid carrier 99.5 to 70%, preferably 97 to 85%

The preparations can also contain other auxiliaries, such as stabilizers, e.g. B. optionally epoxidized vegetable oils (e.g. epoxidized coconut oil, rapeseed oil or soybean oil), defoamers, z. B. silicone oil, preservatives, viscosity regulators, binders and / or adhesives, as well as fertilizers or other active ingredients to achieve special effects.

The following examples serve to illustrate the invention. They do not limit the invention. Temperatures are given in degrees Celsius.

Example H1

0.73 g (10 mmol) of acetone oxime and 1.01 g (10 mmol) of triethylamine are dissolved in 30 ml of anhydrous benzene. 1.68 g (10 mmol) of 6,6-difluoro-5-hexenoyl chloride (DAHSCI) is added to the solution at 5-10 ° C. for 30 minutes while stirring internally, and stirring is continued for 10 hours at room temperature, then filtered through a glass suction filter and the filtrate was concentrated in a rotary evaporator. The crude product obtained is separated by column chromatography on silica gel (ethyl acetate: isohexane = 20:80). The title compound is obtained with an n _D ²⁰ = 1.6893.

Example H2:

6 ¹ '5

H ^CκK

F ₂ C = CH - ^ CH ^ - C - NH - N = C

C ₆ H ₅

1.5 g (7.6 mmol) of benzophenone hydrazone and 0.77 g (7.6 mmol) of triethylamine are dissolved in 30 ml of anhydrous benzene and the solution at 5-10 ° C. with 1.29 g (7.6 mmol) 6 , 6-difluoro-5-hexenoyl chloride (DAHSCI) was added over 30 minutes. The mixture is stirred for a further 10 hours at room temperature, filtered through a glass suction filter and the filtrate is concentrated in a rotary evaporator. The crude product obtained is separated by column chromatography on silica gel (ethyl acetate: isohexane = 20:80). The title compound is obtained with a melting point of 70-71 ° C.

Example H3

0.5 g (10 mmol) of the hydrazine hydrate is added to 1.64 g (10 mmol) of 6,6-difluoro-5-hexenic acid, methyl ester in 10 ml of methanol. The solution is heated under reflux for 10 minutes on a water bath and then concentrated in a rotary evaporator. The back is suspended in 20 ml of methylene chloride, 0.445 g (10 mmol) of acetaldehyde is added at 0 ° C. and stirring is continued for 10 hours at room temperature. After evaporation of methylene chloride, the crude product is separated by column chromatography on silica gel (methyl acetate: isohexane = 20:80). The title compound is obtained with a melting point of 78-79 ° C.

Example H4

3.6 g (18.4 mmol) benzophenone hydrazone and 1.85 g (18.3 mmol) triethylamine are dissolved in 50 ml benzene and cooled to 5 ° C. 2.06 g (18.2 mmol) of chloroacetyl chloride are slowly added dropwise with thorough stirring, so that the temperature can always be kept at 5 to 10 ° C. After the chloroacetyl chloride has been added, the mixture is stirred at room temperature for a further 14 hours. It is filtered off and the filtrate is evaporated. The residue is washed with a small amount of isohexane: acetic acid = 80:20, filtered and dried. The title compound is obtained with a melting point of 92-93 ° C.

A mixture of 1.7 g (6.2 mmol) of chloroacetic benzophenone hydrazide, 0.93 g (6.2 mmol) of 6,6-difluoro-5-hexenoic acid, 0.63 g (6.2 mmol) of triethylamine and 0 is stirred , 2 g NaI in 10 ml dimethylformamide at room temperature for 14 hours. The reaction mixture is poured onto ice, extracted with chloroform and dried over Na ₂ SO ₄ . After the solvent has been distilled off, the crude product is dried on silica gel (isohexane: ethyl acetate = 80:20). The title compound is obtained with an n _D ²⁰ = 1.5678.

Example H5

0.5 g (10 mmol) of the hydrazine hydrate is added to a solution of 0.9 g (10 mmol) of methyl glycolate in 10 ml of methanol. The solution is heated under reflux on the water bath for 10 minutes and then concentrated in a rotary evaporator. The residue is reslurried in 10 ml of methanol, mixed with 0.58 g (10 mmol) of acetone and stirred for a further 10 hours at room temperature. After evaporating off the methanol, the residue is slurried in 20 ml of dichloromethane-tetrahydrofuran. 1.5 g (10 mmol) of 6,6-difluoro-5-hexenoic acid, 406 g (10 mmol) of DCC and 0.1 g of 4-dimethylaminopyridine were added, the mixture was stirred for 14 hours, then filtered through a glass suction filter and the filtrate was concentrated in a rotary evaporator. The crude product obtained is purified by column chromatography on silica gel (ethyl acetate: isohexane = 20:80). The title compound is obtained with an n _D ²⁰ = 1.6768.

The compounds of the formula (I) listed in Tables 1 to 20 can be prepared in a manner analogous to that described in Examples H1 to H5.

Table 1: Compounds of the formula

H O

I II

^F v

^' C CH. 0 c II

F

Verb.No. Ri R ₂ Phys. Data

1.01 H H

1 .02 H CH ₃

1.03 HC ₂ H ₅

1,04 HC ₃ H ₇ -n

1.05 HC ₃ H ₇ -i

1.06 HC ₄ H ₉ -n

1.10 H CH ₂ C (CH ₃ ) ₃

1.1 1 CH ₃ H

1.12 CH ₃ CH ₃

1.13 CH ₃ C ₂ H ₅

1.14 CH ₃ C ₃ H ₇ -n

1.15 CH ₃ C ₃ H ₇ -i

1.16 CH ₃ C ₄ H ₉ -n

1.20 CH ₃ CH ₂ C (CH ₃ ) ₃ Verb.No. Ri R ₂ Phys. Data

1.22 CH ₃ C ₆ H ₄ -2-CI

1.23 CH ₃ C ₆ H ₄ -3-CI

1.24 CH ₃ C ₆ H ₄ -4-CI

1.27 CH ₃ C ₆ H ₄ -4-CF ₃

1.28 CH ₃ C ₆ H ₄ -2-CN

1.29 CH ₃ C ₆ H ₄ -3-CN

1.30 CH ₃ C ₆ H ₄ -4-CN

1.31 CH ₃ C ₆ H ₄ -2-NO ₂

1.32 CH ₃ C ₆ H ₄ -3-NO ₂

1.33 CH ₃ C ₆ H ₄ -4-NO ₂

1.34 CH ₃ C ₆ H ₄ -4-CeH ₅

1.35 CH ₃ C ₆ H ₄ -4-OC ₆ H ₅

1.36 CH ₃ C ₆ H ₄ -4-C (CH ₃ ) ₃

1.37 CH ₃ C ₆ H ₄ -4-OCF ₃

1.38 CH ₃ C ₆ H ₄ -4-COOC ₂ H ₅

1.39 CH ₃ C ₆ F ₅

1.40 CH ₃ -C ₆ H2-3,4,5- (OCH ₃ ) 3

Verb.No. Ri R2 Phys. Data

1.50 CβHs cyclopropyl

1.51 CβHs cyclopentyl

1.52 CβHβ cyclohexyl

1.59 C-βHs C ₆ H ₄ -4-OC ₆ H ₅

1.60 CβHδ C ₆ H ₄ -4-C (CH ₃ ) ₃

1.64 C ₆ H ₄ - ^• 4-CI C ₃ H ₇ -n

1.67 CeH ₄ - ^• 4-CI C ₄ H ₉ -n

1.68 CeH ₄ - -4-CI CH ₂ C ₆ H ₅

1.69 CeH ₄ - -4-CI CH ₂ C ₆ H ₄ -4-CH ₃

1.70 CβH ₄ - ^• 4-CI C ₆ H ₄ -4-CI

1.71 CβH ₄ - -4-CI C ₆ H ₄ -4-OH

1.72 CeH ₄ - -4-CI CeH ₄ -2-CH ₃

1.73 CβH ₄ '-4-CI C ₆ H ₄ -2-CI

1.74 CeH ₄ - -4-CI C ₆ H ₄ -4-Br

1.75 CβH ₄ '-4-CI 4-pyridyl

1.76 CβH ₄ -4-CI C ₆ H ₄ -4-OCH ₂ -C ₆ H ₄ -3-CF ₃ Verb.No. Ri R ₂ Phys. Data

1.80 C ₂ H ₅ -C ₆ H ₄ -4-CI

Table 2: Compounds of the formula

Verb.No. Ri R ₂ Phys. Data

2.01 H H

2.02 H CH ₃

2.03 HC ₂ H _δ

2.04 HC ₃ H ₇ -n

2.05 HC ₃ H ₇ -i

2.06 HC ₄ H ₉ -n

2.09 H CιoH ₂ ι-n

2.10 H CH ₂ C (CH ₃ ) ₃

2.11 CH ₃ H

2.12 CH ₃ CH ₃

2.13 CH ₃ C ₂ H ₅

2.14 CH ₃ C ₃ H ₇ -n

2.15 CH ₃ C ₃ H ₇ -i

2.16 CH ₃ C ₄ H ₉ -n

2.18 CH ₃ CeHι ₃ -n Verb No. R, Phys. Data

2.20 CH ₃ CH ₂ C (CH ₃ ) ₃

2.22 CH ₃ C ₆ H ₄ -2-CI

2.23. CH ₃ C ₆ H ₄ -3-CI

2.24 CH ₃ C ₆ H ₄ -4-CI

2.27 CH ₃ C ₆ H ₄ -4-CF ₃

2.28 CH ₃ C ₆ H ₄ -2-CN

2.29 CH ₃ C ₆ H ₄ -3-CN

2.30 CH ₃ C ₆ H ₄ -4-CN

2.31 CH ₃ C ₆ H ₄ -2-NO ₂

2.32 CH ₃ C ₆ H ₄ -3-NO ₂

2.33 CH ₃ C ₆ H ₄ -4-NO ₂

2.35 CH ₃ C ₆ H ₄ -4-OC ₆ H ₅

2.36 CH ₃ C ₆ H ₄ -4-C (CH ₃ ) ₃

2.37 CH ₃ C ₆ H ₄ -4-OCF ₃

2.38 CH ₃ C ₆ H ₄ -4-COOC ₂ H ₅

2.39 CH ₃ C ₆ F ₅

2.40 CH ₃ C ₆ H ₂ -3,4,5- (OCH ₃ ) ₃

Verb.No. Ri R ₂ Phys. Data

2.50 CβHs cyclopropyl

2.51 CβH _δ cyclopentyl

2.52 CβHs cyclohexyl

2.56 dHs C ₆ H ₄ -4-CN

2.60 CβHs C ₆ H ₄ -4-C (CH ₃ ) ₃

2.62 C _δ H ₄ - ^• 4-CI CF ₃

2.68 CeH ₄ - -4-CI CH ₂ C ₆ H ₅

2.69 CeH ₄ - -4-CI CH ₂ CeH ₄ -4-CH ₃

2.70 CeH ₄ - -4-CI C ₆ H ₄ -4-CI

2.71 CβH ₄ - -4-CI C ₆ H ₄ -4-OH

2.72 CβH ₄ - -4-CI CβH ₄ -2-CH ₃

2.73 CβH ₄ - -4-CI C ₆ H ₄ -2-CI

2.74 CeH - -4-CI C ₆ H ₄ -4-Br

2.75 CβH ₄ '-4-CI 4-pyridyl

2.76 CβH ₄ '-4-CI -C ₆ H ₄ -4-OCH ₂ -C ₆ H ₄ -3-CF ₃ Verb.No. Ri R ₂ Phys. Data

2.80 C ₂ H _δ -C ₆ H ₄ -4-CI

Table 3: Compounds of the formula

H 0 H R. 1 II II ^C ^. CH ₂ ^, N ^ ^ C ^

^F -c ^C - CH, OCN ^ R, 1 II

F 0

Verb.No. Ri R ₂ Phys. Data

3.01 H H

3.02 H CH ₃

3.03 HC ₂ ms

3.04 HC ₃ H ₇ -n

3.05 HC ₃ H ₇ -i

3.06 HC ₄ H ₉ -n

3.08 H CeHι ₃ -n

3.09 H CιoH ₂ ι-n

3.10 H CH ₂ C (CH ₃ ) ₃

3.11 CH ₃ H

3.12 CH ₃ CH ₃

3.13 CH ₃ C ₂ ms

3.14 CH ₃ C ₃ H ₇ -n

3.15 CH ₃ C ₃ H ₇ -i

3.16 CH ₃ C ₄ H ₉ -n

3.19 CH ₃ CιoH ₂ ι-n

3.20 CH ₃ CH ₂ C (CH ₃ ) ₃ Verb No. R, Phys. Data

3.22 CH ₃ C ₆ H ₄ -2-CI

3.23 CH ₃ C ₆ H ₄ -3-CI

3.24 CH ₃ C ₆ H ₄ -4-CI

3.26 CH ₃ CeH ₄ -3-CF ₃

3.27 CH ₃ C ₆ H ₄ -4-CF ₃

3.28 CH ₃ C ₆ H ₄ -2-CN

3.29 CH ₃ C ₆ H ₄ -3-CN

3.30 CH ₃ C ₆ H ₄ -4-CN

3.31 CH ₃ C ₆ H ₄ -2-NO ₂

3.32 CH ₃ C ₆ H ₄ -3-NO ₂

3.33 CH ₃ C ₆ H ₄ -4-NO ₂

3.35 CH ₃ C ₆ H ₄ -4-OC ₆ H ₅

3.36 CH ₃ C ₆ H ₄ -4-C (CH ₃ ) ₃

3.37 CH ₃ C ₆ H ₄ -4-OCF ₃

3.38 CH ₃ C ₆ H ₄ -4-COOC ₂ H ₅

3.39 CH ₃ C ₆ F ₅

3.40 CH ₃ C ₆ H ₂ -3,4,5- (OCH ₃ ) ₃

Verb.No. Ri R ₂ Phys. Data

3.50 CβHs cyclopropyl

3.51 CβH5 cyclopentyl

3.52 CβHδ cyclohexyl

3.60 CβHs C ₆ H ₄ -4-C (CH ₃ ) ₃

3.63 CeH ₄ - ^• 4-CI C ₂ Hs

3.69 CeH ₄ - ^• 4-CI CH2CeH ₄ -4-CH ₃

3.70 CβH - -4-CI C ₆ H ₄ -4-CI

3.71 CβH - -4-CI C ₆ H ₄ -4-OH

3.72 CδH - -4-CI CβH ₄ -2-CH ₃

3.73 CβH ₄ '-4-CI C ₆ H ₄ -2-CI

3.74 CβH ₄ '-4-CI C ₆ H ₄ -4-Br

3.75 CβH '-4-CI 4-pyridyl

3.76 CβH ₄ '-4-CI C ₆ H ₄ -4-OCH ₂ -C ₆ H ₄ -3-CF ₃ Verb.No. Ri R ₂ Phys. Data

Table 4: Compounds of the formula

Verb.Nr. Ri R ₂ Phys. Data

4.1 H H

4.2 H CH ₃ no 20 = 1.6869

4.4 HC ₃ H ₇ -n

4.5 HC ₃ H ₇ -i

4.6 HC ₄ H ₉ -n

4.8 H eHι ₃ -n

4.11 CH ₃ H

4.12 CH ₃ CH ₃ no 20 = 1, 6893

4.14 CH ₃ C ₃ H ₇ -n

4.15 CH ₃ C ₃ H ₇ -i

4.16 CH ₃ C ₄ H ₉ -n

Verb.Nr. Ri R ₂ Phys. Data

4.20 CH ₃ CH ₂ C (CH ₃ ) ₃

4.21 CH ₃ CβHs n _D ²⁰ = 1.50731

4.22 CH ₃ C ₆ H ₄ -2-CI oil

4.23 CH ₃ C ₆ H ₄ -3-CI n _D ²⁰ = 1.6883

4.24 CH ₃ C ₆ H ₄ -4-CI oil

4.25 CH ₃ CβH ₄ -2-CF ₃ n _D ²⁰ = 1.4667

4.26 CH ₃ C ₆ H ₄ -3-CF ₃ n _D ²⁰ = 1.6765

4.27 CH ₃ C ₆ H ₄ -4-CF ₃

4.28 CH ₃ C ₆ H ₄ -2-CN

4.29 CH ₃ C ₆ H ₄ -3-CN amorphous

4.30 CH ₃ C ₆ H ₄ -4-CN m.p .: 121-128 ° C

4.31 CH ₃ C ₆ H ₄ -2-NO ₂ n _D ²⁰ = 1.6888

4.32 CH ₃ C ₆ H ₄ -3-NO ₂ n _D ²⁰ = 1.6897

4.33 CH ₃ C ₆ H ₄ -4-NO ₂ n _D ²⁰ = 1.6853

4.34 CH ₃ CβH ₄ -4-C ₆ H ₅ m.p .: 51-52 ° C

4.35 CH ₃ C ₆ H ₄ -4-OC ₆ H ₅ oil

4.36 CH ₃ C ₆ H ₄ -4-C (CH ₃ ) ₃ n _D ²⁰ = 1.6754

4.37 CH ₃ C ₆ H ₄ -4-OCF ₃ n _D ²⁰ = 1.6843

4.38 CH ₃ C ₆ H ₄ -4-COOC ₂ H ₅ amorphous

4.39 CH ₃ C ₆ F ₅ oil

4.40 CH ₃ C ₆ H ₂ -3.4.5- (OCH ₃ ) ₃ n _D ²⁰ = 1, 5207

4.41 CH ₃ amorphous

Verb.Nr. Phys. Data

₄ Hg-t 20

4.48 CβHβ C rio = 1.4850

Cyclopropyl 20

4.50 CβHδ n _D = 1.5132

4.51 CβHs cyclopentyl

4.52 CβHs cyclohexyl

4.53 CδHδ CβHδ n _D ²⁰ = 1.5503

4.55 CβHs C ₆ H ₄ -4-CF ₃ n _D ²² = 1.5130

4.57 CβHδ C ₆ H ₄ -4-NO ₂ amorphous

4.60 CβHs C ₆ H ₄ -4-C (CH ₃ ) ₃

4.62 CeH - 4-CI CF ₃ n _D 2'0 ^u = 1, 4709

4.68 CeH ₄ - ^• 4-CI CHoOβHs

4.69 CβH ₄ - ^• 4-CI CH ₂ C ₆ H ₄ -4-CH ₃

4.70 CβH ₄ - ^• 4-CI C ₆ H ₄ -4-CI mp: 66-67 ° C

4.71 CβH ₄ - -4-CI C ₆ H ₄ -4-OH

4.72 CβH - -4-CI CeH ₄ -2-CH ₃

4.73 CβH ₄ '-4-CI C ₆ H ₄ -2-CI

4.74 CeH ₄ - -4-CI C ₆ H ₄ -4-Br

20th

4.75 CβH ₄ -4-CI 4-pyridyl ΠD * ¹ = 1.5575 Verb.Nr. R, R ₂ Phys. Data

4.76 C ₆ H ₄ -4-CI C ₆ H ₄ -4-OCH ₂ -C ₆ H ₄ -3-CF ₃

20th

4.79 CβHs CH2C6H5 Γ.D = 1.6744

20th

4.80 C ₂ Hs -C ₆ H ₄ -4-CI no = 1, 6768 ₃ -3.5- (CF ₃ ) ₂ 20

4.81 CH ₃ C- ₆ H no = 1, 4509

4.82 Cyclopropyl -C ₆ H ₃ -4-CI no 20 = 1.6820

Verb.Nr. Phys. Data

4.95 -CβHs C ₆ H ₃ -2.4-F ₂ 26 n _D = 1, 5267

4.97 -C ₆ H ₄ -4-FC ₆ H ₄ -4-F m.p .: 55-57 ° C

4.98 -CβHs CβH ₄ -3-CF ₃ 22 n _D "= 1.5143

4.99 -CeH ₄ -3-CF ₃ CβH ₄ -3-CF ₃ 22 n _D "= 1.4831

4,100 -C6H5 C ₆ H ₄ -2-CI 22 n _D "= 1.5523

4.103 -CβHs -C ₆ H ₃ * 4-CI-3-NO ₂ m.p .: 72-75 ° C

4,104 -C-βHs -C ₆ H ₄ -3-NO ₂ r n. _D ²² = 1, 5615

4,105 -CβHs -C ₆ H ₃ -2,4-CI _{2 r} n, 2 =: 1, 5490

4,106 -C-6H ₅ -C ₆ H ₄ -4-SC ₆ H ₄ -4-CI n, _D 23 =: 1, 5757 Verb.Nr. R, Phys. Data

4.107 -C ₆ 6Hrl5 n _D 2 "3 = 1.5058

4,108 2 ₄

-C ₆ H ₄ -4-OCH ₃ -C ₆ H ₄ -4-O-CH ₃ no = 1.578

Table 5: Compounds of the formula

RT R ₂ Phys. Data

5.1 H H

5.2 H CH ₃ mp 78-79 ° C

5.3 HC ₂ ms

5.4 HC ₃ H ₇ -n

5.5 HC ₃ H ₇ -i

5.6 HC ₄ H ₉ -n

5.9 H CιoH ₂ ι-n

5.11 CH ₃ H

5.12 CH ₃ CH ₃ n _D ²⁰ = 1.7589

5.13 CH ₃ C ₂ ms

5.14 CH ₃ C ₃ H ₇ -n

5.15 CH ₃ C ₃ H ₇ -i

5.16 CH ₃ C ₄ H ₉ -n

5.19 CH ₃ CιoH ₂ ι-n

5.20 CH ₃ CH ₂ C (CH ₃ ) ₃

5.21 CH ₃ C ₆ H ₅ m.p .: 64-66 ° C

5.22 CH ₃ C ₆ H ₄ -2-CI m.p .: 79-82 ° C

5.23 CH ₃ C ₆ H ₄ -3-CI m.p .: 75-78 ° C

5.24 CH ₃ C ₆ H ₄ -4-CI mp: 104-106 ° C

5.25 CH ₃ C ₆ H ₄ -2-CF ₃ n _D ²⁰ = 1.4941

5.26 CH ₃ C ₆ H ₄ -3-CF ₃ mp 82-83 ° C

Verb.No. Ri R ₂ Phys. Data

5.52 -CβHs cyclohexyl

5.53 -C-βHs CβHs mp 70-71 ° C

5.54 -CβHs C ₆ H ₄ -4-CI mp 129-131 ° C

5.55 -CβHs C ₆ H ₄ -4-CF ₃ mp 119-120 ° C

5.57 -CβHs C ₆ H ₄ -4-NO ₂ mp 88-90 ° C

5.58 -C _δ Hs CβH ₄ -4-C ₆ H ₅ mp 130-132 ° C

5.59 -CβHs C ₆ H ₄ -4-OC ₆ H ₅

5.60 -CβH _δ C ₆ H ₄ -4-C (CH ₃ ) ₃

5.61 -CeH ₅ C ₆ H ₄ -4-OCF ₃

5.62 -C ₆ H ₄ -4-CI CF ₃

5.63 -C ₆ H ₄ -4-CI C ₂ H _δ

5.64 -C ₆ H ₄ -4-CI C ₃ H ₇ -n

5.65 -C ₆ H ₄ -4-CI C ₃ H ₇ -i

5.67 -C ₆ H ₄ -4-CI C ₄ H ₉ -n

5.68 -C ₆ H ₄ -4-CI CH ₂ CβH ₅

5.69 -C ₆ H ₄ -4-CI CH ₂ CgH ₄ -4-CH ₃

5.70 -C ₆ H ₄ -4-CI -C ₆ H ₄ -4-CI mp 114-116 ° C

5.71 -C ₆ H ₄ -4-CI -C ₆ H ₄ -4-OH

5.72 -C ₆ H ₄ -4-CI -CeH -2-CH ₃

5.73 -C ₆ H ₄ -4-CI -C ₆ H ₄ -2-CI

5.74 -C ₆ H ₄ -4-CI -C ₆ H ₄ -4-Br

5.75 -C ₆ H ₄ -4-CI 4-pyridyl mp 144-148 ° C

5.76 -C ₆ H ₄ -4-CI -C ₆ H ₄ -4-OCH ₂ -C ₆ H ₄ -3-CF3 resin

5.78 H -CβHs mp 60-63 ° C

5.79 -CβHδ -CH ₂ C ₆ H ₅ mp 95-96 ° C

5.80 -C ₂ H ₅ -C ₆ H ₄ -4-CI mp 106-107 ° C

5.81 -C ₆ H ₄ -4-CI -C ₆ H ₄ -4-OSO ₂ N (CH ₃ ) ₂ mp 105-115 ° C Verb No. R, Phys. Data

5.83 -CβHs cyclopropyl mp 80-82 ° C

5.84 -CH ₃ -CeH ₃ -3.5- (CF ₃ ) ₂ mp 103-105 ° C

5.85 -CβHs -C ₆ H ₄ -4-F mp 77-78 ° C

5.86 -CβHö -C ₆ H ₃ -2.4-F ₂ mp 109-110 ° C

5.87 -CβH _δ -C ₆ H ₄ -4-F mp 99-101 ° C

5.88 -C ₆ H ₄ -4-F -C ₆ H ₄ -4-F mp 76-77 ° C

5.92 -C _{6 6} HIT5 mp 81-82 ° C

5.93 -CβH ₄ -3-CF ₃ -CβH ₄ -3-CF ₃ mp 62-63 ° C

5.94 -C ₆ H ₄ -4-OCH ₃ -C ₆ H ₄ -4-OCH ₃ mp 82-83 ° C

5.95 -C ₆ H ₄ -4-OCH ₃ -CH ₂ -C ₆ H ₄ -4-OCH ₃ mp 123-124 ° C

5.96 -CβHs -C ₆ H ₄ -2-CI mp 69-70 ° C

5.97 -CβHs -C ₆ H ₃ -2.4-CI ₂ mp 117-118 ° C

5.98 -C ₆ H ₄ -4-N (CH ₃ ) ₂ -C ₆ H ₄ -4-N (CH ₃ ) ₂ mp 93-94 ° C

5.99 -CβH _δ -C ₆ H ₄ -4-SC ₆ H ₄ -4-CH ₃ mp 112-113 ° C

5,100 -C ₆ 6Hπ5 n _D ²⁰ = 1.5510

5.101 -C _{6 6} HIT5 n _D ²⁰ = 1, 5355

Verb.No. Ri R2 Phys. Data

6.53 CβHs CβHs m.p. 50-53 ° C

6.54 CβH _δ C ₆ H ₄ -4-CI mp 102-102 ° C

6.59 CeHs C ₆ H ₄ -4-OC ₆ H ₅

6.60 CβHs C ₆ H ₄ -4-C (CH ₃ ) ₃

6.62 C ₆ H ₄ -4-CI CF ₃

6.64 C ₆ H ₄ -4-CI C ₃ H ₇ -n

6.65 C ₆ H ₄ -4-CI C ₃ H ₇ -i

6.67 C ₆ H ₄ -4-CI C ₄ H ₉ -n

6.69 C ₆ H ₄ -4-CI CH ₂ CeH ₄ -4-CH ₃

6.70 C ₆ H ₄ -4-CI C ₆ H ₄ -4-CI mp 73-75 ° C

6.71 C ₆ H ₄ -4-CI C ₆ H ₄ -4-OH

6.72 C ₆ H ₄ -4-CI CeH ₄ -2-CH ₃

6.73 C ₆ H ₄ -4-CI C ₆ H ₄ -2-CI

6.74 C ₆ H ₄ -4-CI C ₆ H ₄ -4-Br

6.75 C ₆ H ₄ -4-CI 4-pyridyl

6.76 C ₆ H ₄ -4-CI C ₆ H ₄ -4-OCH ₂ -C ₆ H ₄ -3-CF ₃

6.78 H -CβHs mp 72-75 ° C

6.79 CβH ₅ -CH ₂ CβH ₅ mp 104-106 ° C

6.80 C2H5 -C ₆ H ₄ -4-CI mp 79-80 ° C

6.81 CH ₃ -CeH ₃ -3.5- (CF ₃ ) ₂ mp 148-150 ° C

6.82 C ₂ H ₅ -C ₆ H ₄ -4-CI mp 79-80 ° C

Verb.No. Ri R ₂ Phys. Data

8.51 CβHs cyclopentyl

8.52 CβHs cyclohexyl

8.56 C ₆ Hs C ₆ H ₄ -4-CN

8.59 C-βHs C ₆ H ₄ -4-OC ₆ H ₅

8.60 C ₆ Hs C ₆ H ₄ -4-C (CH ₃ ) ₃

8.62 C ₆ H ₄ -4-CI CF ₃

8.63 C ₆ H ₄ -4-CI C ₂ H _δ

8.64 C ₆ H ₄ -4-CI C ₃ H ₇ -n

8.65 C ₆ H ₄ -4-CI C ₃ H ₇ -i

8.68 C ₆ H ₄ -4-CI CH ₂ CeHs

8.69 C ₆ H ₄ -4-CI CH ₂ CeH ₄ -4-CH ₃

8.70 C ₆ H ₄ -4-CI C ₆ H ₄ -4-CI

8.71 C ₆ H ₄ -4-CI C ₆ H ₄ -4-OH

8.72 C ₆ H ₄ -4-CI CβH ₄ -2-CH ₃

8.73 C ₆ H ₄ -4-CI C ₆ H ₄ -2-CI

8.74 C ₆ H ₄ -4-CI C ₆ H ₄ -4-Br

8.75 C ₆ H ₄ -4-CI 4-pyridyl

8.76 C ₆ H ₄ -4-CI C ₆ H ₄ -4-OCH ₂ -C ₆ H ₄ -3-CF ₃

8.78 H -CeH ₅

8.80 C ₂ Hs -C ₆ H ₄ -4-CI- Table 9: Compounds of the formula

Verb No. R, Phys. Data

9.01 H H

9.02 H CH ₃

9.03 HC ₂ H _δ

9.04 HC ₃ H ₇ -n

9.05 HC ₃ H ₇ -i

9.06 HC ₄ H ₉ -n

9.09 H CιoH ₂ ι-n

9.10 H CH ₂ C (CH ₃ ) ₃

9.1 1 CH ₃ H

9.12 CH ₃ CH ₃

9.13 CH ₃ C ₂ H _δ

9.14 CH ₃ C ₃ H ₇ -n

9.15 CH ₃ C ₃ H ₇ -i

9.16 CH ₃ C ₄ H ₉ -n

9.19 CH ₃ CιoH ₂ ι-n

9.20 CH ₃ CH ₂ C (CH ₃ ) ₃

9.22 CH ₃ C ₆ H ₄ -2-CI

9.23 CH ₃ C ₆ H ₄ -3-CI

9.24 CH ₃ C ₆ H ₄ -4-CI

co co o CO CD O o CD CO O co co co co co co co co co co co o co co co

CJl 45.45.45.45-45.45.45.45. CO CO o co co co ω co co co ho ro ro o CD 00 v | cn CO ro o co oo vi cn CJI 45. co ro -> ■ o CO 00 v |

o o o o o o o o o o O O O O O O O O O O O O O O

X X X X X X X X X X X X X X X X X X X X X X X X X

Table 11: Compounds of the formula

^FF

Verb No. R, Phys. Data

11.01 H H

11.02 H -CH ₃

11.03 H -C ₂ H ₅

11.04 H -C ₃ H ₇ -n

11.05 H -C ₃ H ₇ -i

11.06 H -C ₄ H ₉ -n

11.08 H -CeHι ₃ -n

11.09 H -CιoH ₂ ι-n

11.10 H -CH ₂ C (CH ₃ ) ₃

11.11 CH ₃ H

1 1.12 CH ₃ -CH ₃

11.13 CH ₃ -C ₂ ms

11.14 CH ₃ -C ₃ H ₇ -n

11.15 CH ₃ -C ₃ H ₇ -i

11.16 CH ₃ -C ₄ H ₉ -n

11.19 CH ₃ -CιoH ₂ ι-n

11.20 CH ₃ -CH ₂ C (CH ₃ ) ₃

11.22 CH ₃ -C ₆ H ₄ -2-CI

11.23 CH ₃ -C ₆ H ₄ -3-CI

11.24 CH ₃ -C ₆ H ₄ -4-CI

11.25 CH ₃ -CeH ₄ -2-CF ₃

11.26 CH ₃ -C ₆ H ₄ -3-CF ₃

ro ro vl

xo

45.

00 O

rό o

X

Verb No. R, Phys. Data

20.16 CH ₃ -C ₆ H ₄ -4-CI NH 3

20.17 CH ₃ -C ₆ H ₄ -4-CI NH 4

20.18 CH ₃ -C ₆ H ₄ -4-CI NH 5

20.19 CH ₃ -C ₆ H ₄ -4-CI O 0

20.20 CH ₃ -C ₆ H ₄ -4-CI O 1

20.21 CH ₃ -C ₆ H ₄ -4-CI O 2

20.22 CH ₃ -C ₆ H ₄ -4-CI O 3

20.23 CH ₃ -C ₆ H ₄ -4-CI O 4

20.24 CH ₃ -C ₆ H ₄ -4-CI O 5

20.25 -CβH ₄ -4-CI -C ₆ H ₄ -4-CI NH 1

20.26 -CβH ₄ -4-CI -C ₆ H ₄ -4-CI O 1

Biological examples

Example B1: Ovicidal action on Heliothis virescens

Eggs from Heliothis virescens deposited on filter paper are briefly immersed in an acetonic-aqueous test solution containing 400 ppm of the active ingredient to be tested. After the test solution has dried on, the eggs are incubated in petri dishes. After 6 days, the percentage hatching of the eggs is evaluated in comparison to untreated control batches (% hatching reduction).

Compounds according to Tables 1-20 show good activity against Heliothis virescens in this test. In particular, the connections 4.80, 4.53, 4.78, 4.12, 4.21, 4.79, 4.02, 4.36, 4.26, 5.76, 5.77, 5.53, 5.21, 5.78, 5.02, 5.12, 5.79, 5.36, 5.26, 5.80, 6.53, 6.21, 6.78 , 6.79, 6.12, 6.02, 6.36, 6.26 and 6.80 show an effect over 80%.

Example B2: Action against Nilaparvata luoens

Rice plants are treated with an aqueous emulsion spray mixture which contains 400 ppm of the active ingredient. After the spray coating has dried on, the rice plants are colonized with 2nd and 3rd stage larvae of Nilaparvata lugens. Evaluation takes place 21 days later. The percentage reduction in population (% action) is determined by comparing the number of surviving cicadas on the treated plants with those on the untreated plants. The compounds of Tables 1-20 show a good activity against Nilaparvata lugens in this test. In particular, the connections 4.80, 4.53, 4.78, 4.12, 4.21, 4.79, 4.02, 4.36, 4.26, 5.76, 5.77, 5.53, 5.21, 5.78, 5.02, 5.12, 5.79, 5.36, 5.26, 5.80, 6.53, 6.21, 6.78 , 6.79, 6.12, 6.02, 6.36, 6.26 and 6.80 show an effect over 80%.

Example B3: Activity against Diabrotica balteata larvae

Corn seedlings are sprayed with an aqueous emulsion spray mixture which contains 400 ppm of the active ingredient. After the spray coating has dried on, the maize seedlings are populated with 10 larvae of Diabrotica balteata of the second stage and placed in a plastic container. Evaluation takes place 6 days later. The percentage reduction in the population (% activity) is determined by comparing the number of dead larvae on the treated plants with those on the untreated plants.

The compounds of Tables 1-20 show good activity against Diabrotica balteata in this test. In particular, the connections 4.80, 4.53, 4.78, 4.12, 4.21, 4.79, 4.02, 4.36, 4.26, 5.76, 5.77, 5.53, 5.21, 5.78, 5.02, 5.12, 5.79, 5.36, 5.26, 6.53, 6.21, 6.78, 6.79 , 6.12, 6.02, 6.26 and 6.80 show an effect over 80%.

Example B4: Action against Tetranychus urticae

Young bean plants are populated with a mixed population of Tetranychus urticae and sprayed with an aqueous emulsion spray mixture containing 400 ppm of the active ingredient 1 day later. The plants are then incubated at 25 ° C. for 6 days and then evaluated. The percentage reduction in the population (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with those on the untreated plants.

The compounds of Tables 1-20 show a good activity against Tetranychus urticae in this test. In particular, the connections 4.80, 4.53, 4.78, 4.12, 4.21, 4.79, 4.02, 4.36, 4.26, 5.76, 5.77, 5.53, 5.21, 5.78, 5.02, 5.12, 5.79, 5.36, 5.26, 5.80, 6.53, 6.21, 6.78 , 6.12, 6.02, 6.36, 6.26 and 6.80 show an effect over 80%.

Example B5: Activity against Spodoptera littoralis caterpillars

Young soybean plants are sprayed with an aqueous emulsion spray mixture which contains 400 ppm of the active ingredient. After the spray coating has dried on, the soy plants are populated with 10 caterpillars of the third stage of Spodoptera littoralis and placed in a plastic container. The evaluation is carried out three days later. From the comparison the number of dead caterpillars and the feeding damage on the treated to those on the untreated plants is the percentage reduction in the population or. determines the percentage reduction in feeding damage (% effect).

The compounds of Tables 1-20 show a good activity against Spodoptera littoralis in this test. In particular, the compounds 4.80, 4.53, 4.12, 4.21, 4.36, 5.77, 5.53, 5.21, 5.78, 5.79, 5.36, 5.26, 5.80, 6.53, 6.21, 6.12, 6.02, 6.36, 6.26 and 6.80 show an effect above 80%.

Example B6: Action against Plutella xylostella caterpillars

Young cabbages are sprayed with an aqueous emulsion spray mixture which contains 400 ppm of the active ingredient. After the spray coating has dried on, the cabbages are populated with 10 caterpillars of the third stage of Plutella xylostella and placed in a plastic container. Evaluation is carried out 3 days later. By comparing the number of dead caterpillars and the damage caused by feeding on the treated plants to those on the untreated plants, the percentage reduction in the population or determines the percentage reduction in feeding damage (% effect).

The compounds of Tables 1-20 show good activity against Plutella xylostella in this test. The compounds 4.80, 4.53, 4.78, 4.12, 4.21, 4.79, 4.02, 4.36, 4.26, 5.77, 5.53, 5.78, 5.36, 5.26, 5.80, 6.53, 6.21, 6.78, 6.12, 6.02 and 6.80 in particular show an effect 80%.

Example B7: Action against Aphis craccivora

Pea seedlings are infected with Aphis craccivora and then sprayed with a spray mixture containing 400 ppm of the active ingredient and incubated at 20 ° C. Evaluation is carried out 3 and 6 days later. The percentage reduction in the population (% action) is determined by comparing the number of dead leaves on the treated plants with those on the untreated plants.

The compounds of Tables 1-20 show good activity against Aphis craccivora in this test. Especially the compounds 4.80, 4.53, 4.78, 4.12, 4.21, 4.79, 4.36, 4.26, 5.77, 5.53, 5.21, 5.78, 5.26, 5.80, 6.53, 6.21, 6.78, 6.12, 6.02 and 6.80 show an effect over 80% . Example B8: Action against Mvzus persicae

Pea seedlings are infected with Myzus persicae and then sprayed with a spray mixture containing 400 ppm of the active ingredient and incubated at 20 ^Λ C. Evaluation is carried out 3 and 6 days later. The percentage reduction in population (% activity) is determined by comparing the number of dead aphids on the treated plants with those on the untreated plants.

The compounds of Tables 1-20 show a good activity against Myzus persicae in this test. Compounds 4.80, 4.53, 4.78, 4.12, 4.21, 4.79, 4.36, 4.26, 5.21, 5.78, 5.26, 5.80, 6.53, 6.21, 6.78, 6.12, 6.02 and 6.80 in particular show an activity above 80

%.

Example B9: Systemic action against Mvzus persicae

Pea seedlings are infected with Myzus persicae, then placed with the roots in a spray mixture containing 400 ppm of the active ingredient and incubated at 20 ^% C. Evaluation is carried out 3 and 6 days later. The percentage reduction in population (% activity) is determined by comparing the number of dead aphids on the treated plants with those on the untreated plants.

The compounds of Tables 1-20 show a good activity against Myzus persicae in this test. In particular, the compounds 4.80, 4.53, 4.78, 4.12, 4.21, 4.79, 4.02, 4.36, 5.21, 5.78, 5.02, 5.12, 6.21, 6.78, 6.79, and 6.80 show an activity above 80%.

Example B10: Ovo / Iarvizide effect on Heliothis virescens

Eggs of Heliothis virescens deposited on cotton are sprayed with an aqueous emulsion spray mixture which contains 400 ppm of the active ingredient. After 8 days, the percentage hatching of the eggs and the survival rate of the caterpillars are evaluated in comparison to untreated control batches (% reduction in the population).

Example B11: Action against Tetranychus urticae ovizid

Young bean plants are populated with Tetranychus urticae females, which are removed after 24 hours. The plants populated with eggs are with a sprayed aqueous emulsion broth containing 400 ppm of the active ingredient. The plants are then incubated for 6 days at 25 ° C. and then evaluated. The percentage reduction in the population (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with those on the untreated plants.

The compounds of Tables 1-20 show a good activity against Tetranychus urticae in this test. In particular, the connections 4.53, 4.78, 4.12, 4.21, 4.79, 4.02, 4.36, 4.26, 5.76, 5.77, 5.53, 5.21, 5.78, 5.12, 5.79, 5.36, 5.26, 5.80, 6.53, 6.21, 6.78, 6.12, 6.02 , 6.36, 6.26 and 6.80 show an effect above 80%.

Example B12: Action against Panonvchus ulmi (OP and carb. Resistant)

Apple seedlings are colonized with adult Panonychus ulmi females. After seven days, the infected plants are sprayed to runoff point with an aqueous emulsion spray liquor containing 400 ppm of the compound to be tested and cultured in a greenhouse. The evaluation is carried out after 14 days. The percentage reduction in population (% activity) is determined by comparing the number of dead spider mites on the treated plants with those on the untreated plants.

Compounds in Tables 1-20 show good activity in the above test. In particular the connections 4.53, 4.78, 4.12, 4.21, 4.79, 4.36, 4.26, 5.76, 5.77, 5.53, 5.21, 5.78, 5.12, 5.79, 5.36, 5.26, 5.80, 6.53, 6.21, 6.78, 6.12, 6.02, 6.36 , 6.26 and 6.80 show an effect above 80%.

Claims

claims

1. A connection of the general

in which

\

Ri and R _{2 are} independently hydrogen; or alkyl, a group Aryl,

Cycloalkyl, alkenyl or alkynyl, which are optionally substituted;

R _{3 is} hydrogen, fluorine or methyl; m 0, 1, 2, 3, 4 or 5; n 0 or 1;

X is oxygen or NR ₄ ; and

R _{4 represents} hydrogen or CrC ₆ alkyl or benzyl, which are optionally substituted, and optionally their possible E / Z isomers, E / Z isomer mixtures and / or tautomers, in each case in free form or in salt form. with the proviso that a) R _{3 is} not hydrogen or fluorine and m and n are not both 0 when X is oxygen and R 1 and R _{2 are} independently hydrogen or unsubstituted or substituted alkyl, alkenyl, cycloalkyl, aryl or heteroaryl ; b) R _{3 is} not hydrogen or fluorine and m and n are not both 0 when R _{4 is} hydrogen and R 1 and R _{2 are} independently hydrogen or unsubstituted or substituted alkyl, aryl or heteroaryl; c) m is not 0, 1 or 2 and R is hydrogen, alkyl or haloalkyl if one of the radicals R 1 or R _{2 is} 4-alkylsulfonyloxyphenyl, 4-haloalkylsulfonyloxypphenyl or 4-haloalkoxysulfonyloxyphenyl, which can optionally carry further substituents, and that others represent optionally substituted phenyl; and d) m is not 0, 1 or 2 and R _{4 is} not hydrogen, alkyl or haloalkyl and n is not 0 if one of the radicals R 1 and R _{2 is} 4-perhaloalkoxyphenyl which may optionally carry further substituents and the other is optionally substituted phenyl.

2. A compound according to claim 1 of formula (I) in free form.

3. A compound according to claim 1 of formula (I) in which

Ri and R _{2 are} independently hydrogen; Cι-C ₂ o-alkyl, which is straight-chain or branched and one to four times by hydroxy, halogen, alkoxy, haloalkoxy, alkoxyalkoxy, alkythio, haloalkylthio, alkylsulfinyl, alkylsulfonyl, alkylsulfonyloxy, alkylcarbonyl, dialkylamino, pyrrolidino, piperidino, morphoiino, alkoxycarbonyl be alkyl carbonyloxy, cycloalkyl, phenyl, naphthyl, phenoxy, naphthoxy, phenylthio, naphthylthio, phenylsulfonyl, naphthylsulfonyl, phenylsulfonyloxy, naphthylsulfonyloxy, benzoyl, naphthoyl, heteroaryl or heteroaryloxy with 5 or 6 ring members and 1 to 2 heteroatoms N, O or S substituted may, where the aryl or heteroaryl groups mentioned may in turn be mono- or disubstituted by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, nitro, cyano, phenoxy, halophenoxy, phenylthio or halophenylthio;

Phenyl or naphthyl, which is mono- to tetra-fold by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cycloalkylalkoxy, halocycloalkylalkoxy, alkylthio, haloalkylthio, alkylsulfonyloxy, haloalkylsulfonyloxy, haloalkoxysulfonyloxy, alkyiamino, dialkylamino, pyrrolidino, piperidyl, piperidino, piperidino, piperidino Phenyl, phenoxy, phenylthio, benzoyl, benzyloxy, anilino, naphthyl, heteroaryl or heteroaryloxy with 5 to 6 ring members and 1 or 2 heteroatoms N, O or S can be substituted, phenyl-, phenoxy, phenylthio-, benzoyl-, benzyloxy- , Anilino, naphthyl, heteroaryl and heteroaryloxy radicals as substituents may in turn be substituted one or two times by halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio, nitro, cyano, phenoxy, phenylthio, halophenylthio, cycloalkylalkoxy or halocycloalkylalkoxy, with heteroaryl 5 to 6 ring members and 1 to 2 heteroatoms N, O or S, one to four times by halogen, alkyl, halogenal kyl, alkoxy, haloalkoxy, cycloalkylalkoxy, halocycloalkylalkoxy, alkylthio, haloalkylthio, alkyiamino, dialkylamino, pyrrolidino, piperidino, morphoiino, nitro, cyano, trialkylsilyl, phenyl, phenoxy, phenylthio, benzoyl, Benzyloxy, anilino, naphthyl, heteroaryl or heteroaryloxy with 5 to 6 ring members and 1 to 2 heteroatoms N, O or S can be substituted, phenyl, phenoxy,

Haloalkoxy, alkylthio, nitro, cyano, phenoxy, phenylthio, halophenylthio,

Cycloalkylalkoxy or Halogencycloalkylalkoxy may be substituted;

R _{3 is} hydrogen, fluorine or methyl; m 0, 1, 2, 3, 4 or 5; n 0 or 1; and

X represents oxygen or NR, where

R _{4 represents} hydrogen, C 1 -C ₄ -alkyl, which can be substituted one or more times by halogen, CrC ₄ alkoxy or di-C 1 -C ₄ -alkylamino, or represents benzyl which has one or more times by halogen, CrC ₄ -alkyl, halogen-dC ₄ -alkyl, -CC alkoxy, nitro or cyano may be substituted.

4. A compound according to any one of claims 1 or 2 of formula (I) in which

Ri and R _{2 are} independently hydrogen or unsubstituted or substituted

Alkyl, cycloalkyl, alkenyl or alkynyl,

R _{3 is} hydrogen, fluorine or methyl, m is 0, 1, 2, 3, 4 or 5; n 0 or 1,

X is oxygen or NR ₄ , and

R _{4 represents} hydrogen or unsubstituted or substituted dC ₆ alkyl or benzyl.

5. A compound according to claim 1 or 2 of formula (I) in which

Ri is hydrogen or unsubstituted or substituted alkyl, alkenyl, alkynyl or

Mean cycloalkyl,

R _{2 represents} hydrogen or unsubstituted or substituted aryl or heteroaryl,

R _{3 represents} hydrogen, fluorine or methyl, m is 0, 1, 2, 3, 4 or 5 and n is 0 or 1,

X represents oxygen or NR ₄ , and

R represents hydrogen or unsubstituted or substituted CrC ₆ alkyl or benzyl.

6. A compound according to claim 1 or 2 of formula (I) in which

Ri and R _{2 are} independently hydrogen or unsubstituted or substituted

Aryl or mean

X represents oxygen or NR, and

R _{4 represents} hydrogen or unsubstituted or substituted C ₁ -C ₆ alkyl or benzyl.

7. A compound according to any one of claims 1-5 of formula (I), in which R _{3 is} hydrogen and R _{1 (} R ₂ , R ₄ , m, n and X have the meaning given.

8. A compound according to any one of claims 1-5 of formula (I), in which m is 0, 1, 2, 3 or 4 and R _{1 (} R ₂ , R ₃ , R, n and X have the meaning given.

9. A compound according to claims 1-5 of formula (I) in which m is 1 or 4 and R 1, R ₂ , R ₃ , R, n and X have the meaning given.

10. A compound according to any one of claims 1-5 of formula (I), in which n is 0 and R 1, R ₂ , R ₃ , R ₄ , m and X have the meaning given.

11. A compound according to any one of claims 1-5 of formula (I), in which n is 0 and m is 1 or 4 and R 1, R ₂ , R ₃ , R ₄ and X have the meaning given.

12. A compound according to any one of claims 1-5 of formula (I), in which R _{3 is} hydrogen, n is 0 and m is 1 or 4, X is NH or oxygen, and R 1 and R _{2 have} the meaning given .

13. A process for the preparation of a compound as defined in claim 1, formula (I), characterized in that a) compounds of the formula (I) in which n is 0 and R _{1 (} R ₂ , R ₃ , X and m have the meaning given above under formula (I), by using a compound of formula in which R ₃ and m have the meaning given under formula (I) and Y _{2 is} Cl, Br or OSO ₂ alkyl, with a compound of the formula

, ^R 1

/

HX - N: (III) \ in which R _{1 (} R ₂ and X have the meaning given under formula (I); b) compounds of the formula (I) in which n is 0 and X is NR ₄ , and R _1? R ₂ , R ₃ and m have the meaning given under formula (I), by using a compound of the formula

in which R ₃ , R ₄ and m have the meaning given below, with a compound of the formula

, ^R 1

/

(V)

\ implements in which R _Ϊ and R _{2 have} the meaning given under the formula (I); and c) compounds of the formula (I) in which n is 1 and R _{1 (} R ₂ , R ₃ , R, X and m have the meaning given under the formula (I), by preparing a compound of the formula

in which R ₃ and m have the meaning given above under, with a compound of the formula implements in which Yi is Cl, Br or OSO ₂ alkyl and X, Ri and R _{2 are} those listed above under

Formula (I) have the meaning given.

14. pesticide, characterized in that it contains, in addition to inert auxiliaries and carriers, at least one compound as claimed in claim 1 of the formula (I) as active substance.

15. A process for the preparation of a pesticide according to claim 14, characterized in that a compound according to claim 1 of the formula (I) is mixed with inert auxiliaries and carriers.

16. A method for controlling pests, characterized in that a compound as described in claim 1, the formula (I), or an agent as described in claim 14, is applied to the pests or their habitat.

17. Use of a compound as described in claim 1, of formula (I), or optionally an E / Z isomer or tautomer thereof, in free form or in agrochemically usable salt form, for the preparation of an agent as described in claim 14.

18. The method according to claim 14 for the protection of plant propagation material, characterized in that the propagation material or the place where the propagation material is applied is treated.

19. Use of a compound as described in claim 1, the formula (I), or an agent as described in claim 14, for controlling pests.