DE10204116A1 - DELTA · 1 · -pyrrolines - Google Patents

Abstract

The invention relates to novel Δ<sp>1</sp>-pyrrolines of formula (I), in which R<sp>1</sp>, R<sp>2</sp>, R<sp>3</sp>, R<sp>4</sp>, m, R<sp>5</sp>, n and R<sp>6</sp> are defined as per the description, to several methods for producing said substances and to the use thereof as pesticides for combating pests.

Description

The present invention relates to new Δ ¹ -pyrrolines, several processes for their preparation and their use as pesticides.

It is already known that numerous Δ ¹ -pyrrolines have insecticidal properties (cf. WO 00/21958, WO 99/59968, WO 99/59967 and WO 98/22438). The effectiveness of these substances is good, but leaves something to be desired in some cases.

New Δ ¹ pyrrolines of the formula (I)


found in which
R ¹ , R ² and R ³ independently of one another represent hydrogen, halogen or methyl,
R ^{4 represents} halogen, alkoxy or alkylthio,
m represents 0, 1, 2, 3 or 4, where the substituents R ^{4 are} identical or different if m represents 2, 3 or 4,
R ^{5 represents} alkyl,
n stands for 0, 1, 2, 3 or 4, where the substituents R ^{5 are} identical or different if n stands for 2, 3 or 4,
R ^{6 represents} hydrogen, cyano, formyl, -SOR ⁷ , -SO ₂ R ⁷ , -COR ⁷ , -CO ₂ R ⁷ , -CONR ⁸ R ⁹ , or -C (R ¹⁰ ) = N-OR ¹¹ ,
R ^{7 represents} optionally substituted one or more times, identically or differently, by halogen, alkoxy, alkylthio, haloalkoxy, haloalkylthio, alkylamino and / or dialkylamino;
or represents cycloalkyl, aryl or arylalkyl which is optionally mono- or polysubstituted, identically or differently, by halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and / or haloalkylthio,
R ⁸ and R ^{9 are} independently hydrogen, -SO ₂ R ⁷ ; for alkyl or alkenyl which is optionally mono- or polysubstituted, identically or differently, by halogen, alkylamino, dialkylamino, alkoxy and / or alkylthio;
or in each case optionally mono- or polysubstituted, identically or differently, by halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and / or haloalkylthio, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, saturated or unsaturated, 5- to 10-membered heterocyclyl or heterocyclylalkyl stand,
R ⁸ and R ⁹ together also represent alkylene which is optionally mono- or polysubstituted, identically or differently, by halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and / or haloalkylthio,
R ¹⁰ and R ^{11 are} independently hydrogen, alkyl, alkenyl, haloalkyl or haloalkenyl.

The compounds of formula (I) may optionally, depending on the type and number of substituents as geometric and / or optical isomers or Regioisomers or their isomer mixtures in different compositions available. Both the pure isomers and the isomer mixtures are claimed according to the invention.

• A) Δ¹-Pyrroline der Formel (II)
  
  
  in welcher
  R¹, R², R³, R⁴ und m die oben angegebenen Bedeutungen haben,
  mit Piperazin-Derivaten der Formel (III)
  
  
  in welcher
  R⁵, n und R⁶ die oben angegebenen Bedeutungen haben,
  in Gegenwart eines Katalysators, in Gegenwart von 2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl (BINAP), gegebenenfalls in Gegenwart einer Base und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt.

It was also found that Δ ¹ -pyrrolines of the formula (I) can be prepared by

• A) Δ ¹ -pyrrolines of the formula (II)
  
  
  in which
  R ¹ , R ² , R ³ , R ⁴ and m have the meanings given above,
  with piperazine derivatives of the formula (III)
  
  
  in which
  R ⁵ , n and R ^{6 have} the meanings given above,
  in the presence of a catalyst, in the presence of 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl (BINAP), optionally in the presence of a base and optionally in the presence of a diluent.

Finally, it was found that the compounds of the formula (I) have very good insecticidal properties and are useful both in crop protection as well as in material protection to combat unwanted pests, such as Insects, let use.

The Δ ¹ -pyrrolines according to the invention are generally defined by the formula (I).

Preferred are Δ ¹ -pyrrolines of the formula (I), in which
R ^{1 represents} hydrogen, fluorine, chlorine, bromine or methyl,
R ² and R ³ independently of one another represent hydrogen, fluorine, chlorine or bromine,
R ^{4 represents} fluorine, chlorine, bromine, C ₁ -C ₆ alkoxy or C ₁ -C ₆ alkylthio,
m represents 0, 1, 2 or 3, where the substituents R ^{4 are} identical or different if m represents 2 or 3,
R ^{5 represents} C ₁ -C ₆ alkyl,
n represents 0, 1, 2, 3 or 4; where the substituents R ^{5 are the} same or different when n is 2, 3 or 4,
R ^{6 represents} hydrogen, cyano, formyl, -SOR ⁷ , -SO ₂ R ⁷ , -COR ⁷ , -CO ₂ R ⁷ , -CONR ⁸ R ⁹ or -C (R ¹⁰ ) = N-OR ¹¹ ,
optionally mono- or polysubstituted by identical or different halogen, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ - Alkylamino and / or di- (C ₁ -C ₆ alkyl) amino substituted C ₁ -C ₂₀ alkyl;
or for each optionally optionally up to eight times, identical or different, by halogen, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ - C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio substituted C ₃ -C ₆ cycloalkyl, aryl or aryl-C ₁ -C ₄ alkyl,
R ⁸ and R ^{9 are} independently hydrogen, -SO ₂ R ⁷ ; in each case optionally substituted once to thirteen times by identical or different halogen, C ₁ -C ₆ - alkylamino, di- (C ₁ -C ₆ alkyl) amino, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio substituted C ₁ -C ₆ alkyl or C ₂ - C ₆ alkenyl;
or for each optionally one to four times, identically or differently, by halogen, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ - C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio substituted C ₃ -C ₇ cycloalkyl, C ₃ -C ₇ cycloalkyl-C ₁ -C ₄ alkyl, aryl, aryl-C ₁ -C ₄ alkyl, saturated or unsaturated, 5- to 10-membered heterocyclyl or heterocyclyl-C ₁ -C ₄ -alkyl having 1 to 4 heteroatoms which contain 0 to 4 nitrogen atoms, 0 to 2 non-adjacent oxygen atoms and / or 0 to 2 non-adjacent sulfur atoms ( in particular tetrazolyl, furyl, furfuryl, benzofuryl, tetrahydrofuryl, thienyl, thenyl, benzothienyl, thiolanyl, pyrrolyl, indolyl, pyrrolinyl, pyrrolidinyl, oxazolyl, benzoxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiazolyl, pyridolidyl, pyridine , Piperidinyl, morpholinyl, thiomorpholinyl, triazinyl, triazolyl, quinolinyl or isoquinolinyl) stand,
R ⁸ and R ⁹ furthermore together for optionally single to quadruple, identical or different by halogen, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ Haloalkoxy, C ₁ -C ₆ -alkylthio, C ₁ -C ₆ -haloalkylthio substituted C ₃ -C ₆ -alkylene,
R ¹⁰ and R ¹¹ independently of one another represent hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₁ -C ₆ haloalkyl or C ₂ -C ₆ haloalkenyl.

Δ ¹ -Pyrrolines of the formula (I), in which
R ^{1 represents} fluorine, chlorine or methyl,
R ^{2 represents} hydrogen, fluorine or chlorine, where R ² is bonded in the 6-position of the phenyl ring,
R ^{3 represents} hydrogen,
R ^{4 represents} fluorine, chlorine, bromine, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkylthio,
m represents 0, 1 or 2, where the substituents R ^{4 are} identical or different if m represents 2,
R ^{5 represents} C ₁ -C ₄ alkyl,
n stands for 0, 1 or 2, where the substituents R ^{5 are} identical or different if n stands for 2,
R ^{6 represents} hydrogen, cyano, formyl, -SOR ⁷ , -SO ₂ R ⁷ , -COR ⁷ , -CO ₂ R ⁷ or -CONR ⁸ R ⁹ ,
R ⁷ is optionally mono- or polysubstituted by identical or different fluorine, chlorine, bromine, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ -haloalkoxy, C ₁ -C ₄ haloalkylthio, Methylamino, ethylamino and / or di- (C ₁ -C ₆ alkyl) amino substituted C ₁ -C ₁₀ alkyl;
or for each optionally one to four times, identical or different, by fluorine, chlorine, bromine, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ - Haloalkoxy, C ₁ -C ₄ alkylthio and / or C ₁ -C ₄ haloalkylthio substituted cyclopropyl, cyclopentyl, cyclohexyl, phenyl or benzyl,
R ⁸ and R ^{9 are} independently hydrogen, -SO ₂ R ⁷ ; for in each case optionally up to nine times, identically or differently, by fluorine, chlorine and / or bromine, C ₁ -C ₄ -alkylamino, di- (C ₁ -C ₄ -alkyl) amino, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio substituted C ₁ -C ₄ alkyl or C ₂ -C ₆ alkenyl;
or for each optionally single to triple, identical or different by fluorine, chlorine and / or bromine, C ₁ -C ₄ alkyl, cyano, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C _4- haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio substituted C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ cycloalkyl-C ₁ -C ₄ alkyl, phenyl, benzyl, phenylethyl, Tetrazolyl, furyl, furfuryl, benzofuryl, tetrahydrofuryl, thienyl, thenyl, benzothienyl, thiolanyl, pyrrolyl, indolyl, pyrrolinyl, pyrrolidinyl, oxazolyl, benzoxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiazolyl, pyridolidyl, pyridine Piperidinyl, morpholinyl, thiomorpholinyl, triazinyl, triazolyl, quinolinyl or isoquinolinyl,
R ⁸ and R ⁹ also together for optionally single to quadruple, identical or different by fluorine, chlorine, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ - C ₄ -C ₅ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio substituted C ₄ -C ₅ alkylene.

Δ ¹ -pyrrolines of the formula (I), in which
R ^{1 represents} fluorine or chlorine,
R ^{2 represents} hydrogen or fluorine, where R ² is bonded in the 6-position of the phenyl ring,
R ^{3 represents} hydrogen,
R ^{4 represents} fluorine, chlorine, bromine, methoxy, ethoxy, methylthio or ethylthio,
m represents 0 or 1,
R ^{5 represents} methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl or t-butyl,
n stands for 0, 1 or 2, where the substituents R ^{5 are} identical or different if n stands for 2,
R ^{6 represents} hydrogen, -SOR ⁷ , -SO ₂ R ⁷ , -COR ⁷ , -CO ₂ R ⁷ , -CONR ⁸ R ⁹ ,
R ^{7 is} methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, hexyl, -CF ₃ , -CHF ₂ , -CCl ₃ , -CCl ₂ F, methoxymethyl, trifluoromethoxymethyl, methylthiomethyl, trifluoromethylthiomethyl, dimethylaminomethyl, dimethylaminoethyl, diethylaminomethyl, diethylaminoethyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl or benzyl,
R ⁸ and R ^{9 are} independently hydrogen, -SO ₂ CF ₃ ; for methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, hexyl, -CF ₃ , -CH ₂ CF ₃ , - (CF ₂ ) ₃ CF ₃ ;
stand for cyclopropyl, cyclopentyl, cyclohexyl, methoxymethyl, methoxyethyl, or for phenyl or benzyl substituted in each case optionally up to three times, identically or differently by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, trifluoromethoxy,
R ⁸ and R ⁹ also together for - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ - or -CH ₂ -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -CH ₂ - stand.

Also preferred are compounds of formula (I) in which R ¹ and R ² each represent fluorine.

Also preferred are compounds of formula (I) in which R ¹ , R ² and R ³ each represent hydrogen.

Preference is furthermore given to compounds of the formula (I) in which m represents 0.

Also preferred are compounds of formula (I) in which n is 0 or I, particularly preferably represents 0.

Also preferred are compounds of formula (I) in which R ^{6 represents} -COR ⁷ , -CO ₂ R ⁷ or -CONR ⁸ R ⁹ , where R ⁷ , R ⁸ and R ^{9 have} the meanings given above.

Compounds of the formula (Ia) are also very particularly preferred


in which
R ^{1 represents} fluorine or chlorine,
R ^{2 represents} hydrogen or fluorine and
R ⁵ , n and R ^{6 have} the meanings given above.

Compounds of the formula (Ia) are emphasized in which
R ^{1 represents} fluorine or chlorine,
R ^{2 represents} hydrogen or fluorine,
R ^{5 represents} methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl or t-butyl,
n stands for 0, 1 or 2, where the substituents R ^{5 are} identical or different if n stands for 2, and
R ^{6 represents} hydrogen, -SOR ⁷ , -SO ₂ R ⁷ , -COR ⁷ , -CO ₂ R ⁷ , -CONR ⁸ R ⁹ ,
R ^{7 is} methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, hexyl, -CF ₃ , -CHF ₂ , -CCl ₃ , -CCl ₂ F, methoxymethyl, trifluoromethoxymethyl, methylthiomethyl, trifluoromethylthiomethyl, dimethylaminomethyl, dimethylaminoethyl, diethylaminomethyl, diethylaminoethyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl or benzyl,
R ⁸ and R ^{9 are} independently hydrogen, -SO ₂ CF ₃ ; for methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, hexyl, -CF ₃ , -CH ₂ CF ₃ , - (CF ₂ ) ₃ CF ₃ ;
stand for cyclopropyl, cyclopentyl, cyclohexyl, methoxymethyl, methoxyethyl, or for phenyl or benzyl substituted in each case optionally up to three times, identically or differently by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, trifluoromethoxy,
R ⁸ and R ⁹ also together for - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ - or -CH ₂ -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -CH ₂ - stand.

Also highlighted are compounds of the formula (Ia), in which
R ^{1 represents} fluorine,
R ^{2 represents} fluorine,
R ^{5 represents} methyl,
n represents 0 or 1,
R ^{6 represents} -COR ⁷ , -CO ₂ R ⁷ or -CONR ⁸ R ⁹ ,
R ^{7 represents} methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, hexyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl or benzyl,
R ⁸ and R ^{9 are} independently hydrogen, -SO ₂ CF ₃ ; for methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, hexyl, -CF ₃ , -CH ₂ CF ₃ , - (CF ₂ ) ₃ CF ₃ ;
stand for cyclopropyl, cyclopentyl, cyclohexyl, methoxymethyl, methoxyethyl, or for phenyl or benzyl substituted in each case optionally up to three times, identically or differently by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, trifluoromethoxy.

Also preferred are compounds of formula (Ia) in which R ¹ and R ² each represent fluorine.

Also preferred are compounds of formula (I-a) in which m is 0.

Preference is furthermore given to compounds of the formula (I-a) in which n is 0 or 1, particularly preferably represents 0.

Also preferred are compounds of formula (Ia) in which R ^{6 represents} -COR ⁷ , -CO ₂ R ⁷ or -CONR ⁸ R ⁹ , where R ⁷ , R ⁸ and R ^{9 have} the meanings given above.

Also very particularly preferred are (R) -configured compounds of the formula (Ib)


in which
R ¹ , R ² , R ³ , R ⁴ , m, R ⁵ , n and R ^{6 have} the general, preferred, particularly preferred, very particularly preferred or particularly very particularly preferred meanings given above.

Compounds of the formula (I-b) are obtained by customary processes for Racemate resolution, such as by chromatography of the corresponding racemates a chiral stationary phase. It is possible to use both the racemic End products or racemic intermediates in this way into the two enantiomers disassemble.

Saturated hydrocarbon residues such as alkyl can, also in combination with Heteroatoms such as B. in alkoxy, as far as possible, in each case straight-chain or be branched.

Halogen-substituted radicals, e.g. B. haloalkyl, are single or multiple to halogenated to the maximum possible number of substituents. With multiple Halogenation, the halogen atoms can be the same or different. Halogen stands for Fluorine, chlorine, bromine or iodine, especially for fluorine, chlorine or bromine.

With radicals substituted by alkyl, e.g. B. dialkylamino, can Alkyl groups are each straight-chain or branched and the same or different.

The general or preferred areas listed above Residual definitions or explanations can, however, also be used with one another, i.e. between the respective areas and preferred areas can be combined as desired. they seem for the end products as well as for the preliminary and intermediate products accordingly.

If 5- (2,6-difluorophenyl) -2- (4-bromophenyl) -3,4-dihydro-2H-pyrrole and isobutyl-1-piperazinecarboxylate are used as starting materials as well as a catalyst and BINAP, the course of the process according to the invention can be used (A) can be illustrated by the following formula scheme.

Explanation of the processes and intermediates Procedure (A)

Formula (II) provides a general definition of the Δ ¹ -pyrrolines required as starting materials when carrying out process (A) according to the invention. In this formula, R ¹ , R ² , R ³ , R ⁴ and m are preferred, particularly preferred or very particularly preferred for those meanings which are already preferred for these radicals in connection with the description of the substances of the formula (I) according to the invention , particularly preferred, etc. were mentioned.

Δ ¹ -pyrrolines of the formula (II) are known and / or can be prepared by known processes (cf. WO 98/22438).

Formula (III) provides a general definition of the piperazine derivatives required as starting materials when carrying out process (A) according to the invention. In this formula, R ⁵ , n and R ^{6 are} preferably, particularly preferably or very particularly preferably those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention were.

• a) tertyl- 1 -piperazincarboxylat-Derivate der Formel (III-a)
  
  
  in welcher
  R⁵ und n die oben angegebenen Bedeutungen haben,
  in einer ersten Stufe mit Chloriden der Formel (IV)
  
  Cl-R⁶ (IV)
  
  in welcher
  R⁶ die oben angegebenen Bedeutungen hat,
  gegebenenfalls in Gegenwart eines Verdünnungsmittels (z. B. Dioxan) und gegebenenfalls in Gegenwart eines Säurebindemittels (z. B. Triethylamin) umsetzt und die so erhaltenen Produkte der Formel (V)
  
  
  in welcher
  R⁵, n und R⁶ die oben angegebenen Bedeutungen haben
  in einer zweiten Stufe mit einer Säure (z. B. Trifluroessigsäure) gegebenenfalls in Gegenwart eines Verdünnungsmittels (z. B. Dichlormethan) umsetzt.

Piperazine derivatives of the formula (III) are known in some cases. They can be made by

• a) tertyl-1-piperazine carboxylate derivatives of the formula (III-a)
  
  
  in which
  R ⁵ and n have the meanings given above,
  in a first stage with chlorides of the formula (IV)
  
  Cl-R ⁶ (IV)
  
  in which
  R ^{6 has} the meanings given above,
  if appropriate in the presence of a diluent (for example dioxane) and if appropriate in the presence of an acid binder (for example triethylamine), and the products of the formula (V) thus obtained
  
  
  in which
  R ⁵ , n and R ^{6 have} the meanings given above
  in a second stage with an acid (e.g. trifluroacetic acid), if appropriate in the presence of a diluent (e.g. dichloromethane).

Formula (III-a) provides a general definition of the tert-butyl-1-piperazinecarboxylate derivatives required as starting materials in carrying out process (a). In this formula, R ⁵ and n are preferably, particularly preferably or very particularly preferably, those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention.

Tert-butyl-1-piperazine carboxylate derivatives of the formula (III-a) are known.

Formula (IV) provides a general definition of the chlorides required as starting materials when carrying out process (a). In this formula, R ^{6 is} preferably, particularly preferably or very particularly preferably those meanings which have already been mentioned as preferred, particularly preferred, etc. for these radicals in connection with the description of the substances of the formula (I) according to the invention.

Chlorides of the formula (IV) are known.

When carrying out process (A) according to the invention, preference is given to using a palladium catalyst which in turn can be used with or without the addition of further ligands. PdCl ₂ (dppf) [dppf = 1,1'-bis (diphenylphosphino) ferrocenes], Pd (PPh3) ₄ , PdCl ₂ (PPh3) ₂ , PdCl ₂ (CH ₃ CN) ₂ , Pd2 (dba ) ₃ [dba = dibenzylidene acetone] or Pd (OAc) ₂ , particularly preferably Pd (OAc) ₂ .

Triarylphosphines, trialkylphosphines or arsines are suitable as ligands. Dppf, PPh ₃ , P (tert-Bu) ₃ , Pcy ₃ or AsPh _{3 are} preferably used, particularly preferably dppf.

Suitable diluents for carrying out the process according to the invention Process (A) all the usual inert, organic solvents in question. Halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, Methylcyclohexane, benzene, toluene, xylene or decalin; Chlorobenzene, dichlorobenzene, Dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, Methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or Anisole. Dioxane, tetrahydrofuran or toluene are particularly preferably used.

The bases used in carrying out process (A) according to the invention are all inorganic and organic bases customary for such reactions in Consideration. Alkaline earth or alkali metal hydroxides, such as Sodium hydroxide, calcium hydroxide, potassium hydroxide, or also Ammonium hydroxide, alkali metal carbonates, such as sodium carbonate, potassium carbonate, cesium carbonate, Potassium hydrogen carbonate, sodium hydrogen carbonate, alkali or Alkaline earth metal acetates such as sodium acetate, potassium acetate, calcium acetate, alkali metal fluorides, and tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, Pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyelooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU). It is however, also possible to work without additional acid binder, or the Amine component in an excess, so that they simultaneously as Acid binder acts. Cesium carbonate is particularly preferably used.

The reaction temperatures can be carried out when carrying out the inventive Process (A) can be varied over a wide range. Generally works one at temperatures between 0 ° C and 140 ° C, preferably between 20 ° C and 120 ° C, particularly preferably between 60 ° C and 100 ° C.

When carrying out process (A) according to the invention, the starting point is 1 mol Compound of formula (II) generally 1 mole or a slight excess a compound of formula (III) and 0.1 to 50 mol% of a catalyst. It However, it is also possible to use the reaction components in other ratios use. The processing takes place according to usual methods. Generally done one in such a way that the reaction mixture is diluted with water and with extracted an organic diluent. The organic phase will washed, dried, filtered and concentrated. The residue will eventually by conventional methods, such as chromatography or recrystallization, from possibly contaminants still present.

When performing all of the methods according to the invention one works in generally under atmospheric pressure. But it is also possible, in each case under increased or to work under reduced pressure.

The active compounds according to the invention are suitable, with good plant tolerance and favorable warm-blood toxicity, for combating animal pests, in particular insects, arachnids and nematodes which occur in agriculture, in forests, in the protection of stored products and materials, and in the hygiene sector. They can preferably be used as pesticides. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The pests mentioned above include:
From the order of the Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
From the order of the Diplopoda z. B. Blaniulus guttulatus.
From the order of the Chilopoda z. B. Geophilus carpophagus, Scutigera spp.
From the order of the Symphyla z. B. Scutigerella immaculata.
From the order of the Thysanura z. B. Lepisma saccharina.
From the order of the Collembola z. B. Onychiurus armatus.
From the order of the Orthoptera z. B. Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria.
From the order of the Blattaria z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica.
From the order of the Dermaptera z. B. Auricular Forficula.
From the order of the Isoptera z. B. Reticulitermes spp.
From the order of the Phthiraptera z. B. Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp.
From the order of the Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella accidentalis.
From the order of the Heteroptera z. B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus sppe, Phosiphodumumpp., Macrosiphumum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.
From the order of the Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiisppina, Fpp , Heliothis spp., Mamestra brassicae, Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Hofeamannellellaella, Hofeamannellaellaella, Tinea pellionella Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae.
From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephppis, Orphusus spp. , Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Giptusibbium psol. Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica, Lissorhoptrus oryzophilus.
From the order of the Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
From the order of the Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomox ., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa, Hylemyia spp., Liriomyza spp.
From the order of the Siphonaptera z. B. Xenopsylla cheopis, Ceratophyllus spp. From the class of the Arachnida z. B. Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommodes spp., I ., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp., Brevipalpus spp.

Plant parasitic nematodes include e.g. B. Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaphelenchus spp.

The compounds of formula (I) according to the invention are particularly noteworthy through an excellent effect against caterpillars, beetle larvae, spider mites, Aphids and leaf flies.

The compounds according to the invention can optionally be used in certain Concentrations or application rates also as herbicides and microbicides, for example as fungicides, antifungals and bactericides. You leave optionally as intermediates or precursors for the synthesis of further Use active ingredients.

According to the invention, all plants and parts of plants can be treated. Under Plants are understood here as all plants and plant populations desired and undesirable wild plants or crops (including naturally occurring crops). Cultivated plants can be plants that by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these Methods can be obtained, including transgenic plants and including those that can or cannot be protected by plant variety rights Plant varieties. Plant parts should include all above-ground and underground parts and organs of the plants, such as sprout, leaf, flower and root are understood, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes are listed. To the Plant parts also include crops as well as vegetative and generative Propagation material, for example cuttings, tubers, rhizomes, cuttings and seeds.

The treatment of the plants and plant parts according to the invention with the Active substances take place directly or by influencing their environment, habitat or Storage room according to the usual treatment methods, e.g. B. by diving, spraying, Evaporation, atomization, scattering, spreading and in the case of propagation material, especially in the case of seeds, further by single or multi-layer coating.

The active compounds according to the invention can be converted into the customary formulations such as solutions, emulsions, wettable powders, suspensions, powders, Dusts, pastes, soluble powders, granules, suspension emulsion concentrates, Active ingredient-impregnated natural and synthetic substances as well as very fine encapsulation in polymeric fabrics.

These formulations are prepared in a known manner, e.g. B. by mixing of the active compounds according to the invention with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foaming agents.

In the case of the use of water as an extender, e.g. B. also organic Solvents are used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or Alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as Chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. petroleum fractions, mineral and vegetable Oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as Acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar Solvents such as dimethylformamide and dimethyl sulfoxide, and water.

The following are suitable as solid carriers:
z. B. ammonium salts and natural rock powders, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders, such as highly disperse silica, aluminum oxide and silicates, are suitable as solid carriers for granules: z. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems;
as emulsifying and / or foam-generating agents come into question: z. B. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for. B. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates;
as dispersants come into question: z. B. lignin sulfite and methyl cellulose.

In the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural Phospholipids such as cephalins and lecithins and synthetic phospholipids. Further Additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, Ferrocyan blue and organic dyes such as alizarin, azo and Metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, Molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95% by weight Active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be in commercially available formulations and in the use forms prepared from these formulations in a mixture with other active ingredients, such as insecticides, attractants, sterilants, bactericides, Acaricides, nematicides, fungicides, growth regulators or Herbicides are present. Insecticides include, for example, phosphoric acid esters, Carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms u. a.

Particularly cheap mixing partners are e.g. B. the following: fungicides aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin,
Benalaxyl, benodanil, benomyl, benzamacril, benzamacrylic isobutyl, bialaphos, binapacrylic, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,
Calcium polysulfide, capsimycin, captafol, captan, carbendazim, carboxin, carvone, quinomethionate (quinomethionate), chlobenthiazone, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyphodinconol, cypodinconol, cypodinconol
Debacarb, dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazol-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithorphoxin, dithorphononodine,
Edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,
Famoxadone, Fenapanil, Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fenpropimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzon, Fluazinam, Flumetover, Fluoromid, Fluquinconazol, Flurprimolol, Flusulfazolutol, Flusulfazolutol, Flusulfazolutol, Flusulfazolutol, Flusulfazolutol, Flusulfazolutol, Flusulfazolutol, Flusulfosolutol, Flusulfazolutol, Flusulfazolutol, Flusulfazolutol, Flusulfazolutol, Flusulfidol, Flusilazolutol, Flusulfidol, Flusilazolutol, Flusulfidol, Flusilazolutol, Flusulfazolutol, Flusulfidol, Flusilazolutol, Flusulfidol, Flusilazolutol Fosetyl sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis, furmecyclox,
Guazatin, hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan, Isovaledione,
Kasugamycin, Kresoxim-methyl, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,
Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,
Paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidone, propamocarb, propanosine sodium, propiconazole, propineb, pyrazophos, pyrifen, pyifenox, pyrroyilonil
Quinconazole, quintozen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, tecloftalam, tecnazene, Tetcyclacis, tetraconazole, thiabendazole, Thicyofen, Thifluzamide, thiophanate-methyl, thiram, Tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, Triazbutil, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
Uniconazole, validamycin A, vinclozolin, viniconazole,
Zarilamid, Zineb, Ziram as well
Dagger G, OK-8705, OK-8801,
α- (1,1-dimethylethyl) -β- (2-phenoxyethyl) -1H-1,2,4-triazole-1-ethanol,
α- (2,4-dichlorophenyl) -β-fluoro-β-propyl-1H-1,2,4-triazole-1-ethanol,
α- (2,4-dichlorophenyl) -β-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol,
a- (5-methyl-1,3-dioxan-5-yl) -β - [[4- (trifluoromethyl) phenyl] methylene] -1H-1,2,4-triazol-1-ethanol,
(5RS, 6RS) -6-hydroxy-2,2,7,7-tetramethyl-5- (1H-1,2,4-triazol-1-yl) -3-octanone,
(E) -α- (methoxyimino) -N-methyl-2-phenoxy-phenylacetamide,
{2-Methyl-1 - [[[1- (4-methylphenyl) ethyl] amino] carbonyl] propyl} carbamic acid 1-isopropyl ester
1- (2,4-dichlorophenyl) -2- (1H-1,2,4-triazol-1-yl) -ethanone-O- (phenylmethyl) oxime,
1- (2-methyl-1-naphthalenyl) -1H-pyrrole-2,5-dione,
1- (3,5-dichlorophenyl) -3- (2-propenyl) -2,5-pyrrolidinedione,
1 - [(diiodomethyl) sulphonyl] -4-methylbenzene,
1 - [[2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl] -1H-imidazole,
1 - [[2- (4-chlorophenyl) -3-phenyloxiranyl] methyl] -1H-1,2,4-triazole,
1- [1- [2 - [(2,4-dichlorophenyl) methoxy] phenyl] ethenyl] -1H-imidazole,
1-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol,
2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-1,3-thiazol-5-carboxanilide,
2,2-dichloro-N- [1- (4-chlorophenyl) ethyl] -1-ethyl-3-methyl-cyclopropanecarboxamide,
2,6-dichloro-5- (methylthio) -4-pyrimidinyl thiocyanate,
2,6-dichloro-N- (4-trifluoromethylbenzyl) -benzamide,
2,6-dichloro-N - [[4- (trifluoromethyl) phenyl] methyl] benzamide,
2- (2,3,3-triiodo-2-propenyl) -2H-tetrazole,
2 - [(1-methylethyl) sulphonyl] -5- (trichloromethyl) -1,3,4-thiadiazole,
2 - [[6-Deoxy-4-O- (4-O-methyl-β-D-glycopyranosyl) -α-D-glucopyranosyl] amino] -4- methoxy-1H-pyrrolo [2,3-d] pyrimidine-5-carbonitrile,
2-aminobutane,
2-bromo-2- (bromomethyl) -pentandinitril,
2-chloro-N- (2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl) -3-pyridine carboxamide,
2-chloro-N- (2,6-dimethylphenyl) -N- (isothiocyanatomethyl) acetamide, 2-phenylphenol (OPP),
3,4-dichloro-1- [4- (difluoromethoxy) phenyl] -1H-pyrrole-2,5-dione,
3,5-dichloro-N- [cyano [(1-methyl-2-propynyl) -oxy] -methyl] -benzamide,
3- (1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,
3- [2- (4-chlorophenyl) -5-ethoxy-3-isoxazolidinyl] -pyridine,
4-chloro-2-cyano-N, N-dimethyl-5- (4-methylphenyl) -1H-imidazol-1-sulfonamide,
4-methyl-tetrazolo [1,5-a] quinazolin-5 (4H) -one,
8- (1,1-dimethylethyl) -N-ethyl-N-propyl-1,4-dioxaspiro [4.5] decane-2-methanamine,
8-hydroxyquinoline sulfate,
9H-xanthene-9-carboxylic acid 2 - [(phenylamino) carbonyl] hydrazide,
bis (1-methylethyl) -3-methyl-4 - [(3-methylbenzoyl) oxy] -2,5-thiophene dicarboxylate,
cis-1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) cycloheptanol,
cis-4- [3- [4- (1,1-dimethylpropyl) -phenyl-2-methylpropyl] -2,6-dimethyl-morpholine,
Ethyl - [(4-chlorophenyl) azo] cyanoacetate,
potassium bicarbonate,
Methantetrathiol sodium salt,
Methyl-1- (2,3-dihydro-2,2-dimethyl-1H-inden-1-yl) -1H-imidazole-5-carboxylate,
Methyl-N- (2,6-dimethylphenyl) -N- (5-isoxazolylcarbonyl) -DL-alaninate,
Methyl N- (chloroacetyl) -N- (2,6-dimethylphenyl) -DL-alaninate,
N- (2,3-dichloro-4-hydroxyphenyl) -1-methyl-cyclohexanecarboxamide.
N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-furanyl) acetamide,
N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-thienyl) acetamide,
N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro-benzenesulfonamide,
N- (4-Cyclohexylphenyl) -1,4,5,6-tetrahydro-2-pyrimidinamine,
N- (4-hexylphenyl) -1,4,5,6-tetrahydro-2-pyrimidinamine,
N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) -acetamide,
N- (6-methoxy) -3-pyridinyl) -cyclopropanecarboxamide,
N- [2,2,2-trichloro-1 - [(chloroacetyl) -amino] -ethyl] -benzamide,
N- [3-chloro-4,5-bis- (2-propynyloxy) -phenyl] -N'-methoxy-methanimidamid,
N-formyl-N-hydroxy-DL-alanine-sodium salt,
O, O-diethyl [2- (dipropylamino) -2-oxoethyl] -ethylphosphoramidothioat,
O-methyl-S-phenyl-phenylpropylphosphoramidothioat,
S-Methyl-1,2,3-benzothiadiazole-7-carbothioate,
spiro [2H] -1-benzopyran-2,1 '(3'H) -isobenzofuran] -3'-one, bactericidal bronopol, dichlorophen, nitrapyrin, nickel-dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, Tecloftalam, copper sulfate and other copper preparations. Insecticides / Acaricides / Nematicides Abamectin, Acephate, Acetamiprid, Acrinathrin, Alanycarb, Aldicarb, Aldoxycarb, Alpha-cypermethrin, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azamethiphos, Azinphos M, Azinphos M,
Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Baculoviruses, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfuracarb, Bensultap, Benzoximate, Betacyfluthrin, Bifenazate, Bifenthrin, Bioethanomofufoxin, Bethanomofufoxin, Bethenomethrin Butyl pyridaben
Cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, Chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, Chlovaporthrin, cis-resmethrin, Cispermethrin, Clocythrin, cloethocarb, clofentezine, cyanophos, Cycloprene, cycloprothrin, cyfluthrin , Cyhalothrin, cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlorvos, Diflubenzuron, Dimethoat, Dimethylvinphos, Diofenolan, Disulfoton, Docusat-sodium, Dofenapyn,
Eflusilanate, Emamectin, Empenthrin, Endosulfan, Entomopfthora spp., Eprinomectin, Esfenvalerate, Ethiofencarb, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimfos,
Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate, Fipronil, Fluazuron, Flubrocythrinate, Flucycloxuron, Floxthrinofonate, Fufenzoxinphonate, Fufenoxthhronate, Fufenzenzin, Fufone .
granulosis
Halofenozide, HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene,
Imidacloprid, isazofos, isofenphos, isoxathion, ivermectin,
nucleopolyhedroviruses
Lambda cyhalothrin, lufenuron
Malathion, Mecarbam, Metaldehyde, Methamidophos, Metharhician anisopliae, Metharhician flavoviride, Methidathione, Methiocarb, Methomyl, Methoxyfenozide, Metolcarb, Metoxadiazone, Mevinphos, Milbemectin, Monocrotophos,
Naled, Nitenpyram, Nithiazine, Novaluron
Omethoate, oxamyl, oxydemethone M
Paecilomyces fumosoroseus, Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A, Pirimiphos M, Profenofos, Promecarb, Propoxur, Prothiofos, Prothoat, Pyromhrhridosine, Pymmethrofinos , Pyridathione, pyrimidifen, pyriproxyfen,
quinalphos,
ribavirin
Salithion, Sebufos, Selamectin, Silafluofen, Spinosad, Sulfotep, Sulprofos,
Tau-fluvalinate, tebufenozide, tebufenpyrad, Tebupirimiphos, teflubenzuron, tefluthrin, temephos, Temivinphos, terbufos, tetrachlorvinphos, Thetacypermethrin, thiamethoxam, Thiapronil, Thiatriphos, oxalate hydrogen thiocyclam, thiodicarb, thiofanox, thuringiensin, Tralocythrin, tralomethrin, triarathene, Triazamate, triazophos, Triazuron, trichlophenidine, trichlorfon, triflumuron, trimethacarb,
Vamidothion, Vaniliprole, Verticillium lecanii
YI 5302
Zeta-cypermethrin, zolaprofos
(1R-cis) - [5- (phenylmethyl) -3-furanyl] methyl-3 - [(dihydro-2-oxo-3 (2H) furanylidene) methyl] -2,2-dimethylcyclopropane carboxylate
(3-phenoxyphenyl) methyl-2,2,3,3-tetramethylcyclopropanecarboxylat
1 - [(2-Chloro-5-thiazolyl) methyl] tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2 (1H) - imine
2- (2-Chloro-6-fluorophenyl) -4- [4- (1,1-dimethylethyl) phenyl] -4,5-dihydro-oxazole 2- (acetyloxy) -3-dodecyl-1,4-naphthalenedione
2-chloro-N - [[[4- (1-phenylethoxy) phenyl] amino] carbonyl] -benzamide
2-chloro-N - [[[4- (2,2-dichloro-1,1-difluoroethoxy) phenyl] amino] carbonyl] -benzamide
3-methylphenyl propylcarbamate
4- [4- (4-ethoxyphenyl) -4-methylpentyl] -1-fluoro-2-phenoxy-benzene
4-Chloro-2- (1,1-dimethylethyl) -5 - [[2- (2,6-dimethyl-4-phenoxyphenoxy) ethyl] thio] - 3 (2H) pyridazinone
4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) - pyridazinone
4-chloro-5 - [(6-chloro-3-pyridinyl) methoxy] -2- (3,4-dichlorophenyl) -3 (2H) -pyridazinone
Bacillus thuringiensis strain EG-2348
Benzoic acid [2-benzoyl-1- (1,1-dimethylethyl) hydrazide
Butanoic acid 2,2-dimethyl-3- (2,4-dichlorophenyl) -2-oxo-1-oxaspiro [4.5] dec-3-en-4-yl ester
[3 - [(6-chloro-3-pyridinyl) methyl] -2-thiazolidinylidene] -cyanamide
Dihydro-2- (nitromethylene) -2H-1,3-thiazine-3 (4H) -carboxaldehyde
Ethyl [2 - [[1,6-dihydro-6-oxo-1- (phenylmethyl) -4-pyridazinyl] oxy] ethyl] carbamate
N- (3,4,4-trifluoro-1-oxo-3-butenyl) -glycine
N- (4-chlorophenyl) -3- [4- (difluoromethoxy) phenyl] -4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide
N - [(2-chloro-5-thiazolyl) methyl] -N'-methyl-N "-nitro-guanidine
N-methyl-N '- (1-methyl-2-propenyl) -1,2-hydrazindicarbothioamid
N-methyl-N'-2-propenyl-1,2-hydrazindicarbothioamid
O, O-diethyl [2- (dipropylamino) -2-oxoethyl] -ethylphosphoramidothioat

A mixture with other known active ingredients, such as herbicides or with Fertilizers and growth regulators are possible.

When used as insecticides, the active compounds according to the invention can also be used in their commercial formulations and in those formulations prepared application forms in a mixture with synergists. synergists are compounds by which the action of the active compounds according to the invention is increased without the added synergist itself having to be active.

The active substance content of those prepared from the commercially available formulations Application forms can vary widely. The drug concentration of the Use forms can be from 0.0000001 to 95% by weight of active compound, preferably are between 0.0001 and 1% by weight.

The application takes place in a customary manner adapted to the application forms Wise.

When used against hygiene and storage pests, the Active ingredient through an excellent residual effect on wood and clay as well as through a good alkali stability on limed substrates.

As already mentioned above, according to the invention all plants and their parts can be treated. In a preferred embodiment, go wild occurring or by conventional organic breeding methods, such as crossing or Protoplast fusion obtained plant species and plant varieties and their parts treated. In a further preferred embodiment, transgenes are Plants and plant varieties, if necessary by genetic engineering methods in combination with conventional methods (Genetically Modified Organisms) and their parts. The term "parts" or "parts of." Plants "or" parts of plants "was explained above.

Plants of the commercially available in each case are particularly preferred according to the invention or plant varieties in use.

Depending on the plant species or plant varieties, their location and Growth conditions (soils, climate, growing season, nutrition) can be determined by the Treatment according to the invention also occur via additive ("synergistic") effects. So are, for example, reduced application rates and / or extensions of the Spectrum of activity and / or an enhancement of the effect of the invention usable substances and agents, better plant growth, increased tolerance against high or low temperatures, increased tolerance to drought or against water or soil salt content, increased flowering performance, easier harvesting, Acceleration of ripeness, higher crop yields, higher quality and / or higher Nutritional value of the harvested products, higher shelf life and / or workability of the Harvest products possible that go beyond the expected effects.

Among the preferred transgenic (genetic engineering received) plants or plant varieties include all plants by the genetic engineering modification received genetic material that this Gives plants special beneficial valuable properties ("traits"). Examples for such properties are better plant growth, increased tolerance against high or low temperatures, increased tolerance to drought or against water or soil salt content, increased flowering performance, easier harvesting, Acceleration of ripeness, higher crop yields, higher quality and / or higher Nutritional value of the harvested products, higher shelf life and / or workability of the Harvested products. Further and particularly highlighted examples of such Properties are an increased defense of the plants against animal and microbial Pests, such as against insects, mites, phytopathogenic fungi, bacteria and / or viruses and an increased tolerance of the plants to certain herbicides Agents. The important cultivated plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, rapeseed and Fruit plants (with the fruits apples, pears, citrus fruits and grapes) mentions, especially corn, soybeans, potatoes, cotton and rapeseed be highlighted. The properties are particularly emphasized as "traits" increased defense of the plants against insects by the plants Toxins, especially those caused by the genetic material from Bacillus thuringiensis (e.g. through the genes CryIA (a), CryIA (b), CryIA (c), CryIIA, CryIIIA, CryIIIB2, Cry9c, Cry2Ab, Cry3Bb and CryIF and their combinations) in the Plants are produced (hereinafter "Bt plants"). As properties ("traits") the increased tolerance of the plants are particularly emphasized against certain herbicidal active ingredients, for example imidazolinones, Sulfonylureas, glyphosate or phosphinotricin (e.g. "PAT" gene). The each the genes imparting the desired traits can also be found in Combinations with each other occur in the transgenic plants. As examples of "Bt Plants "are maize, cotton, soy and potato under the trade names YIELD GARD® (e.g. maize, Cotton, soy), KnockOut® (e.g. maize), StarLink® (e.g. maize), Bollgard® (Cotton), Nucotn® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants are maize, cotton and Soybeans known as Roundup Ready® (tolerance against glyphosate e.g. B. corn, cotton, soy), Liberty Link® (tolerance against Phosphinotricin, e.g. Rape), IMI® (tolerance to imidazolinones) and STS® (Tolerance to sulfonylureas e.g. maize). As a herbicide resistant (conventionally grown to herbicide tolerance) plants are also the varieties sold under the name Clearfield® (e.g. maize). Of course, these statements also apply to future developed or future plant varieties with these or in the future developed genetic traits.

The plants listed can be particularly advantageous according to the invention with the Compounds of the general formula (I) or those according to the invention Active ingredient mixtures are treated. The above for the active ingredients or mixtures Preferred ranges given also apply to the treatment of these plants. Plant treatment with those in the present text should be particularly emphasized Specially listed compounds or mixtures.

The active compounds according to the invention act not only against pests from plants, hygiene and stored products, but also in the veterinary sector against animal parasites (ectoparasites) such as tick ticks, leather ticks, mites, running mites, flies (stinging and licking), parasitic fly larvae, lice, hair lice, Featherlings and fleas. These parasites include:
From the order of the Anoplurida z. B. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.
From the order of the Mallophagida and the subordinates Amblycerina and Ischnocerina z. B. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.
From the order Diptera and the subordinates Nematocerina and Brachycerina z. B. Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp ., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp.
From the order of the Siphonapterida z. B. Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
From the order of the Heteropterida z. B. Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
From the order of the Blattarida z. B. Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp.
From the subclass of Acaria (Acarida) and the orders of the Meta and Mesostigmata z. B. Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp. Pneumonyssus spp., Sternostoma spp., Varroa spp.
From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata) z. B. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp. Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., Laminosioptes spp.

For example, they show excellent effectiveness against the Stages of development of ticks such as Amblyomma hebraeum, against parasitic ones Flies such as against Lucilia cuprina, against fleas such as Ctenocephalides felis

The active compounds of the formula (I) according to the invention are also suitable for combating of arthropods, the farm animals, such as. B. cattle, sheep, goats, Horses, pigs, donkeys, camels, buffaloes, rabbits, chickens, turkeys, ducks, geese, Bees, other pets such as B. dogs, cats, house birds, aquarium fish as well as so-called experimental animals, such as. B. hamsters, guinea pigs, rats and Infest mice. By fighting these arthropods, deaths and Reductions in performance (for meat, milk, wool, skins, eggs, honey, etc.) can be reduced, so that by using the active compounds according to the invention more economical and easier animal husbandry is possible.

The active compounds according to the invention are used in the veterinary sector in in a known manner by enteral administration in the form of, for example, tablets, Capsules, watering, drenching, granules, pastes, boluses, the feed-through process, suppositories, by parenteral administration, such as by injections (intramuscular, subcutaneous, intravenous, intraperitoneal, etc.), implants, through nasal Application, by dermal application in the form of, for example, diving or Bathing (dipping), spraying (spray), pouring (pour-on and spot-on), des Washing, powdering and with the help of shaped articles containing active ingredients, such as Collars, ear tags, tail tags, limb straps, holsters, Marking devices etc.

When used for cattle, poultry, pets, etc., you can Active substances of the formula (I) according to the invention as formulations (for example powders, Emulsions, flowable agents), the active ingredients according to the invention in an amount Contain from 1 to 80 wt .-%, directly or after 100 to 10,000 times dilution apply or use it as a chemical bath.

It was also found that the compounds of the invention have a high Show insecticidal activity against insects that destroy technical materials.

The following insects may be mentioned by way of example and preferably, but without limitation:
Beetle like
Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearesces, Lyctus pubis linearis, speculum Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus.
Skin wing like
Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur.
Termites like
Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus.
Bristle tails such as Lepisma saccharina.

In the present context, technical materials include non-living ones Understand materials, such as preferably plastics, adhesives, glues, papers and cardboard, leather, wood, wood processing products and paints.

The one to be protected against insect attack is very particularly preferably Material around wood and wood processing products.

Wood and wood processing products that can be protected by the agent according to the invention or mixtures containing it are to be understood as examples:
Lumber, wooden beams, railway sleepers, bridge parts, jetties, wooden vehicles, boxes, pallets, containers, telephone poles, wooden cladding, wooden windows and doors, plywood, chipboard, carpentry or wooden products that are generally used in house construction or joinery.

The active compounds according to the invention can, as such, in the form of concentrates or general formulations such as powders, granules, solutions, Suspensions, emulsions or pastes can be used.

The formulations mentioned can be prepared in a manner known per se be, e.g. B. by mixing the active ingredients according to the invention with at least a solvent or diluent, emulsifier, dispersing and / or binding agent or fixative, water repellant, optionally desiccant and UV stabilizers and optionally dyes and pigments and others Processing aids.

The insecticidal agents or used to protect wood and wood-based materials Concentrates contain the active ingredient according to the invention in a concentration of 0.0001 to 95% by weight, in particular 0.001 to 60% by weight.

The amount of the agents or concentrates used depends on the type and the Occurrence of insects and depending on the medium. The optimal amount to use can be determined by test series in the application. In general however, it is sufficient 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, of the active ingredient, based on the material to be protected.

An organic chemical is used as the solvent and / or diluent Solvent or solvent mixture and / or an oily or oily heavy volatile organic chemical solvent or solvent mixture and / or a polar organic chemical solvent or solvent mixture and / or Water and optionally an emulsifier and / or wetting agent.

The organic chemical solvents used are preferably oily or oily ones Solvents with an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, used. As such volatile, Water-insoluble, oily and oily solvents become corresponding mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably white spirit, petroleum and / or alkylbenzene used.

Mineral oils with a boiling range of 170 to 220 ° C are advantageous, White spirit with a boiling range of 170 to 220 ° C, spindle oil with a boiling range from 250 to 350 ° C, petroleum or aromatics with a boiling range from 160 to 280 ° C, Turpentine oil and the like.

In a preferred embodiment, liquid aliphatic Hydrocarbons with a boiling range of 180 to 210 ° C or high-boiling mixtures of aromatic and aliphatic hydrocarbons with a boiling range of 180 to 220 ° C and / or spindle oil and / or monochloronaphthalene, preferably α- Monochloronaphthalene.

The organic non-volatile oily or oily solvents with a Evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, can be partly due to slightly or medium-volatile organic chemical Solvents are replaced, provided that the solvent mixture also an evaporation number above 35 and a flash point above 30 ° C, preferably above 45 ° C, and that the insecticide-fungicide mixture in this solvent mixture is soluble or emulsifiable.

According to a preferred embodiment, part of the organic chemical Solvent or solvent mixture or an aliphatic polar organic chemical solvent or solvent mixture replaced. Preferably come aliphatic containing hydroxyl and / or ester and / or ether groups organic chemical solvents such as glycol ether, ester or the like. to use.

As organic-chemical binders in the context of the present Invention known per se and / or used in the water-dilutable organochemical solvents soluble or dispersible or emulsifiable Synthetic resins and / or binding drying oils, in particular binders from or containing an acrylic resin, a vinyl resin, e.g. B. polyvinyl acetate, Polyester resin, polycondensation or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indden Coumarone resin, silicone resin, drying vegetable and / or drying oils and / or physically drying binders based on a natural and / or synthetic resin used.

The synthetic resin used as a binder can be in the form of an emulsion, dispersion or solution. Bitumen or bituminous substances up to 10 wt .-%, are used. In addition, in itself known dyes, pigments, water repellants, odor correctors and Inhibitors or anticorrosive agents and the like are used.

According to the invention, preference is given to at least one organic chemical binder an alkyd resin or modified alkyd resin and / or a drying vegetable Contain oil in the medium or in the concentrate. Are preferred according to the invention Alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight.

The binder mentioned can be wholly or partly by a Fixing agent (mixture) or a plasticizer (mixture) can be replaced. These additions are said to be one Prevent volatilization of the active ingredients as well as crystallization or precipitation. They preferably replace 0.01 to 30% of the binder (based on 100% of the binder used).

The plasticizers come from the chemical classes of phthalic acid esters such as Dibutyl, dioctyl or benzyl butyl phthalate, phosphoric acid esters such as Tributyl phosphate, adipic acid esters such as di (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, oleates such as butyl oleate, glycerol ether or higher molecular weight Glycol ether, glycerol ester and p-toluenesulfonic acid ester.

Fixing agents are chemically based on polyvinyl alkyl ethers such as. B. Polyvinyl methyl ether or ketones such as benzophenone, ethylene benzophenone.

Water is also particularly suitable as a solvent or diluent, optionally in a mixture with one or more of the above-mentioned organic chemical solvents or diluents, emulsifiers and dispersants.

A particularly effective wood protection is achieved through industrial impregnation processes, z. B. vacuum, double vacuum or printing process.

The ready-to-use agents can, if appropriate, still further insecticides and optionally contain one or more fungicides.

The additional mixing partners are preferably those in WO 94/29 268 Insecticides and fungicides mentioned in question. The ones mentioned in this document Connections are an integral part of this application.

Insecticides such as Chlorpyriphos, Phoxim, Silafluofin, Alphamethrin, Cyfluthrin, Cypermethrin, Deltamethrin, Permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, transfluthrin, Thiacloprid, methoxyfenozide and triflumuron, as well as fungicides such as epoxyconazole, Hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, Metconazole, imazalil, dichlorfluanid, tolylfluanid, 3-iodo-2-propynyl butyl carbamate, N-octyl-isothiazolin-3-one and 4,5-dichloro-N-octylisothiazolin-3-one.

At the same time, the compounds according to the invention can protect against fouling objects, in particular hulls, sieves, nets, structures, Quayside and signal systems, which are connected with sea or brackish water come, be used.

Overgrowth by sessile oligochaetes, such as lime tube worms and by mussels and species of the Ledamorpha (barnacles) group, such as various Lepas and Scalpellum species, or by species from the group Balanomorpha (barnacles), such as Balanus or pollicipes species, increases the frictional resistance of ships and subsequently leads through increased energy consumption and moreover through frequent Dry dock stays for a significant increase in operating costs.

In addition to the growth by algae, for example Ectocarpus sp. and Ceramium sp., comes in particular the vegetation by sessile Entomostraken groups, which are summarized under the name Cirripedia (barnacles) special meaning too.

It has now surprisingly been found that the inventive Compounds alone or in combination with other active ingredients, an excellent Have antifouling effect.

By using compounds according to the invention alone or in combination with other active ingredients, can rely on the use of heavy metals such. B. in bis- (trialkyltin) sulfides, tri-n-butyltin laurate, tri-n-butyltin chloride, copper (I) oxide, Triethyltin chloride, tri-n-butyl (2-phenyl-4-chlorophenoxy) tin, tributyltin oxide, Molybdenum disulfide, antimony oxide, polymeric butyl titanate, phenyl (bispyridine) - bismuth chloride, tri-n-butyltin fluoride, manganese ethylene bisthiocarbamate, Zinc dimethyldithiocarbamate, zinc ethylene bisthiocarbamate, zinc and copper salts of 2- Pyridinthiol-1-oxide, bisdimethyldithiocarbamoylzinkethylenististhiocarbamate, Zinc oxide, copper (I) ethylene bisdithiocarbamate, copper thiocyanate, copper naphthenate and Tributyltin halides are omitted or the concentration of these Connections are significantly reduced.

The ready-to-use antifouling paints can also be used if necessary Active ingredients, preferably algicides, fungicides, herbicides, molluscicides or others Contain antifouling ingredients.

Suitable combination partners for the antifouling agents according to the invention are preferably:
Algicides like
2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine, dichlorophene, diuron, endothal, fentin acetate, isoproturon, methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;
Fungicides like
Benzo [b] thiophenecarboxylic acid cyclohexylamide-S, S-dioxide, dichlofluanid, fluorfolpet, 3-iodo-2-propynyl-butylcarbamate, tolylfluanid and azoles such as azaconazole, cyproconazole, epoxyconazole, hexaconazole, metconazole, propiconazole and ticon;
Molluscicides like
Fentin acetate, metaldehyde, methiocarb, niclosamide, thiodicarb and trimethacarb; or conventional antifouling agents such as
4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatrylsulfone, 2- (N, N-dimethylthiocarbamoylthio) -5-nitrothiazyl, potassium, copper, sodium and zinc salts of 2-pyridinthiol-1 -oxide, pyridine-triphenylborane, tetrabutyldistannoxane, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulfide and 2,4,6-trichlorophenylmaleimide.

The antifouling agents used contain the active ingredient according to the invention compounds according to the invention in a concentration of 0.001 to 50% by weight, in particular from 0.01 to 20% by weight.

The antifouling agents according to the invention also contain the usual ones Components such as B. in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.

Antifouling paints contain algicidal, fungicidal, molluscicides and insecticidal active substances according to the invention, in particular binders.

Examples of recognized binders are polyvinyl chloride in one Solvent system, chlorinated rubber in one solvent system, acrylic resins in one Solvent system especially in an aqueous system, Vinyl chloride / vinyl acetate copolymer systems in the form of aqueous dispersions or in the form of organic solvent systems, butadiene / styrene / acrylonitrile rubbers, drying Oils, such as linseed oil, resin esters or modified hard resins in combination with Tar or bitumen, asphalt and epoxy compounds, small amounts Chlorinated rubber, chlorinated polypropylene and vinyl resins.

Paints may also contain inorganic pigments, organic Pigments or dyes, which are preferably insoluble in sea water. Further Paints can contain materials, such as rosin, to be controlled To enable release of the active ingredients. The paintings can also Plasticizers, modifiers influencing the rheological properties, and contain other conventional ingredients. Also in self-polishing antifouling Systems can be the compounds of the invention or those mentioned above Mixtures can be incorporated.

The active compounds according to the invention are also suitable for controlling animal pests, in particular insects, arachnids and mites, which live in closed rooms, such as, for example, apartments, factory halls, offices, vehicle cabins and the like. occur. To control these pests, they can be used alone or in combination with other active ingredients and auxiliaries in household insecticide products. They are effective against sensitive and resistant species and against all stages of development. These pests include:
From the order of the Scorpionidea z. B. Buthus occitanus.
From the order of Acarina z. B. Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides formae.
From the order of the Araneae z. B. Avicularüdae, Araneidae.
From the order of the Opiliones z. B. Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.
From the order of the Isopoda z. B. Oniscus asellus, Porcellio scaber.
From the order of the Diplopoda z. B. Blaniulus guttulatus, Polydesmus spp.
From the order of the Chilopoda z. B. Geophilus spp.
From the order of the Zygentoma z. B. Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus.
From the order of the Blattaria z. B. Blatta orientalies, Blattella germanica, Blattella asahinai, Leucophaea maderae, Panchlora spp., Parcoblatta spp., Periplaneta australasiae, Periplaneta americana, Periplaneta brunnea, Periplaneta fuliginosa, Supella longipalpa.
From the order of the Saltatoria z. B. Acheta domesticus.
From the order of the Dermaptera z. B. Auricular Forficula.
From the order of the Isoptera z. B. Kalotermes spp., Reticulitermes spp.
From the order of Psocoptera z. B. Lepinatus spp., Liposcelis spp.
From the order of the Coleptera z. B. Anthrenus spp., Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius, Sitophilus oryzae, Sitophilus zeamais, Stegobium paniceum.
From the order of the Diptera z. B. Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis. , Stomoxys calcitrans, Tipula paludosa.
From the order of the Lepidoptera z. B. Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
From the order of the Siphonaptera z. B. Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.
From the order of the Hymenoptera z. B. Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
From the order of the Anoplura z. B. Pediculus humanus capitis, Pediculus humanus corporis, Phthirus pubis.
From the order of the Heteroptera z. B. Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.

The application in the field of household insecticides is carried out alone or in Combination with other suitable active ingredients such as phosphoric acid esters, carbamates, Pyrethroids, growth regulators or active ingredients from other known Classes of insecticides.

The application takes place in aerosols, unpressurized sprays, e.g. B. Pump and Atomizer sprays, automatic fog machines, foggers, foams, gels, vaporizer products with evaporator platelets made of cellulose or plastic, liquid evaporators, gel and membrane evaporators, propeller-driven evaporators, energy-free or passive evaporation systems, moth papers, moth bags and Moth angels, as granules or dusts, in lures or bait stations.

The preparation and use of the substances according to the invention can be seen from the following examples. Production Examples Example 1

0.84 g (2.50 mmol) of 5- (2,6-difluorophenyl) -2- (4-bromophenyl) -3,4-dihydro- 2H-pyrrole in toluene (30 ml) and successively mixed with 0.56 g (3.00 mmol) Isobutyl-1-piperazine carboxylate (III-1), 0.2 g (0.50 mmol) palladium (II) acetate, 0.11 g (0.18 mmol) BINAP and 0.98 g (3.00 mmol) cesium carbonate and leaves then stir for 16 h at 90 ° C. After cooling to room temperature, the toluene distilled off. Then 100 ml of water are added and the mixture is extracted twice with 75 ml dichloromethane each, separates the organic phase, dries it over Sodium sulfate, filtered and concentrated. The crude product is by means of chromatography Silica gel (mobile phase: dichloromethane / ethyl acetate 9: 1 → 4: 1) purified.

0.3 g (20.4% of theory) of isobutyl-4- {4- [5- (2,6-difluorophenyl) -3,4-dihydro-2H-pyrrol-2-yl] phenyl} - are obtained. 1-piperazinecarboxylate.
HPLC: Log P (pH 2.3) = 2.52.
1H-NMR (CD3CN): δ = 0.9 (m, 6H), 1.8 (m, 1H), 1.9 (m, 1H), 2.5 (m, 1H), 3.0 (m , 2H), 3.1 (m, 4H), 3.59 (m, 4H), 3.9 (d, 2H), 5.2 (m, 1H), 6.9 (m, 2H), 7 , 1 (m, 2H), 7.3 (m, 2H), 7.45 (m, 1H) ppm.

The following compounds of the formula (I) are obtained analogously to the examples listed above.

Production of foreign substances of the formula (III) Example (III-1)

step 1

To a solution of 1.86 g (10.0 mmol) of tert-butyl-1-piperazine carboxylate in 20 ml Dioxane is added to 1.39 ml of triethylamine and the reaction mixture is cooled to 5 ° C from. Then 1.30 ml (10.00 mmol) of isobutyl chloroformate are added dropwise and the mixture is left stir for 16 h at room temperature. The reaction mixture is mixed with water added, extracted twice with ethyl acetate, the organic phase separated, dried over sodium sulfate, filtered and concentrated.

2.85 g (96.2% of theory) of 1-tert-butyl-4-isobutyl-1,4-piperazine dicarboxylate are obtained.
HPLC: Log P (pH 2.3) = 3.26.
1H-NMR (CD3CN): δ = 0.9 (d, 6H), 1.42 (s, 9H), 1.9 (m, 1H), 3.3-3.4 (m, 8H), 3 .8 (d, 2H) ppm.

Level 2

2.86 g (10.00 mmol) are assumed 1-tert-Butyl-4-isobutyl-1,4-piperazine dicarboxylate in 100 ml dichloromethane. 7.70 ml (100.00 mmol) are added dropwise at 5 ° C. Trifluoroacetic acid and allowed to stir for 5 h at 5-10 ° C. The reaction mixture is concentrated, taken up in dichloromethane and alkaline with 10% sodium hydroxide solution set. The organic phase is separated off, dried over sodium sulfate, filtered and concentrated.

1.3 g (59.3% of theory) of isobutyl-1-piperazinecarboxylate are obtained.
1H-NMR (CD3CN): δ = 0.9 (d, 6H), 1.9 (m, 1H), 2.9 (m, 4H), 3.5 (m, 4H), 3.9 (d , 2H) ppm.

The determination of those in the tables and manufacturing examples above specified logP values are carried out in accordance with EEC Directive 79/831 Annex V.A8 HPLC (High Performance Liquid Chromatography) on a phase reversal column (C 18). Temperature: 43 ° C.

The determination is made in the acidic range at pH 2.3 with 0.1% aqueous Phosphoric acid and acetonitrile as eluents; linear gradient from 10% acetonitrile to 90% acetonitrile (marked with a in the tables).

The determination is made in the neutral range at pH 7.5 with 0.01 molar aqueous Phosphate buffer solution and acetonitrile as eluents; linear gradient of 10% Acetonitrile to 90% acetonitrile (marked with b in the tables).

The calibration is carried out with unbranched alkan-2-ones (with 3 to 16 Carbon atoms) whose logP values are known (determination of the logP values using the Retention times through linear interpolation between two successive Alkanones).

The lambda max values were determined using the UV spectra from 200 nm to 400 nm the maxima of the chromatographic signals determined.

Anwendunusbeispiele Example A Heliothis armigera test

Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate to the desired level with water containing emulsifier Concentration.

Soybean shoots (Glycine max) are dipped into the active ingredient preparation desired concentration and treated with caterpillars of the cotton capsule worm (Heliothis armigera) occupied while the leaves are still moist.

After the desired time, the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.

In this test, e.g. B. the following compounds of the preparation examples have good activity: Table A plant-damaging insects Heliothis armigera test

Example B Phaedon larvae test

Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate to the desired level with water containing emulsifier Concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with larvae of the horseradish leaf beetle (Phaedon cochleariae) occupied while the leaves are still moist.

After the desired time, the kill is determined in%. 100% means that all beetle larvae have been killed; 0% means that no beetle larvae were killed.

In this test, e.g. B. the following compounds of the preparation examples good activity: Table B plant-damaging insects Phaedon larva test

Example C Spodoptera frugiperda test

Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate to the desired level with water containing emulsifier Concentration.

Cabbage leaves (Brassica oleracea) are dipped into the active ingredient preparation the desired concentration and treated with caterpillars of the army worm (Spodoptera frugiperda) occupied while the leaves are still moist.

After the desired time, the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars are killed were.

In this test, e.g. B. the following compounds of the preparation examples have good activity: Table C plant-damaging insects Spodoptera frugiperda test

Example D Tetranychus test (OP-resistant / immersion treatment)

Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 2 parts by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate to the desired level with water containing emulsifier Concentration.

Bean plants (Phaseolus vulgaris), strongly of all stages of the common Spider mite (Tetranychus urticae) are infested in an active ingredient preparation the desired concentration.

After the desired time, the effect is determined in%. 100% means that all spider mites have been killed; 0% means that no spider mites were killed.

In this test, e.g. B. the following compounds of the preparation examples have good activity: Table D mites Tetranychus test (OP-resistant / immersion treatment)

Example E Diabrotica balteata test (larvae in the soil) Limit concentration test / soil insects - treatment of transgenic plants

Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the specified amount of solvent gives the specified Amount of emulsifier and dilute the concentrate with water to the desired level Concentration.

The active ingredient preparation is poured onto the floor. The plays Concentration of the active ingredient in the preparation practically no role, is crucial only the amount of active substance per unit volume of soil, which is in ppm (mg / l) is given. The bottom is filled into 0.25 l pots and left at 20 ° C stand.

Immediately after the preparation, 5 pre-germinated maize kernels of the YIELD variety are added to each pot GUARD (trademark of Monsanto Comp., USA). After 2 days the appropriate test insects are placed in the treated soil. After another 7 The effectiveness of the active ingredient is measured by counting the accumulated days Corn plants determined (1 plant = 20% effect).

Example F Heliothis virescens test (treatment of transgenic plants)

Solvent: 7 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, mix 1 Part by weight of active ingredient with the specified amount of solvent and the specified Amount of emulsifier and dilute the concentrate with water to the desired one Concentration.

Soybean shoots (Glycine max) of the Roundup Ready variety (trademark of Monsanto Comp. USA) are the desired by diving into the active ingredient preparation Treated with concentration and filled with the tobacco bud caterpillar Heliothis virescens, as long as the leaves are still damp.

After the desired time, the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars are killed were.

Example G Blowfly larva test (development-inhibiting effect)

Test animals: Lucilia cuprina larvae
Solvent: dimethyl sulfoxide

20 mg of active ingredient are dissolved in 1 ml of dimethyl sulfoxide. To make one suitable formulation, the active ingredient solution is diluted with water to desired concentration.

About 20 Lucilia cuprina larvae are placed in a test tube, which contains approx. 1 cm ³ horse meat and 0.5 ml of the active ingredient preparation to be tested. The effectiveness of the active substance preparation is determined after 24 and 48 hours. The test tubes are transferred to beakers with a sand-covered bottom. After the specified time, the test tubes are removed and the dolls and flies are counted.

The effect of the drug preparation is based on the number of flies hatched assessed after 1.5 times the development time of an untreated control. there 100% means that no flies hatched; 0% means all flies hatched normally.

In this test, e.g. B. the following compounds of the preparation examples have good action: Table G Blowfly larva test (development-inhibiting action)

Example H Test with Boophilus microplus resistant / SP-resistant Parkhurst strain

Test animals: adult sucked females
Solvent: dimethyl sulfoxide

20 mg of active ingredient are dissolved in 1 ml of dimethyl sulfoxide. To make one suitable formulation, the active ingredient solution is diluted with water to desired concentration.

The test is carried out in 5-fold determination. 1 µl of the solutions is added to the Abdomen injected, the animals transferred into bowls and in an air-conditioned room kept. The effects are checked after 7 days on the laying of fertile eggs. Eggs, whose fertility is not externally visible, are in glass tubes until Larval hatch kept in a climate cabinet. An effect of 100% means that no tick has laid fertile eggs.

In this test, e.g. B. the following compounds of the preparation examples have a good effect: Table H test with Boophilus microplus resistant / SP-resistant Parkhurst strain

Claims (22)

1. Δ ¹ -pyrrolines of the formula (I)


in which
R ¹ , R ² and R ³ independently of one another represent hydrogen, halogen or methyl,
R ^{4 represents} halogen, alkoxy or alkylthio,
m represents 0, 1, 2, 3 or 4, where the substituents R ^{4 are} identical or different if m represents 2, 3 or 4,
R ^{5 represents} alkyl,
n stands for 0, 1, 2, 3 or 4, where the substituents R ^{5 are} identical or different if n stands for 2, 3 or 4,
R ^{6 represents} hydrogen, cyano, formyl, -SOR ⁷ , -SO ₂ R ⁷ , -COR ⁷ , -CO ₂ R ⁷ , -CONR ⁸ R ⁹ , or -C (R ¹⁰ ) = N-OR ¹¹ ,
R ^{7 represents} optionally substituted one or more times, identically or differently, by halogen, alkoxy, alkylthio, haloalkoxy, haloalkylthio, alkylamino and / or dialkylamino;
or represents cycloalkyl, aryl or arylalkyl which is optionally mono- or polysubstituted, identically or differently, by halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and / or haloalkylthio,
R ⁸ and R ^{9 are} independently hydrogen, -SO ₂ R ⁷ ; for alkyl or alkenyl which is optionally mono- or polysubstituted, identically or differently, by halogen, alkylamino, dialkylamino, alkoxy and / or alkylthio;
or in each case optionally mono- or polysubstituted, identically or differently, by halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and / or haloalkylthio, cycloalkyl, cycloalkylalkyl, aryl, arylalkyl, saturated or unsaturated, 5- to 10-membered heterocyclyl or heterocyclylalkyl stand,
R ⁸ and R ⁹ together also represent alkylene which is optionally mono- or polysubstituted, identically or differently, by halogen, cyano, alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and / or haloalkylthio,
R ¹⁰ and R ^{11 are} independently hydrogen, alkyl, alkenyl, haloalkyl or haloalkenyl. 2. Δ ¹ -pyrrolines of formula (I) according to claim 1, in which
R ^{1 represents} hydrogen, fluorine, chlorine, bromine or methyl,
R ² and R ³ independently of one another represent hydrogen, fluorine, chlorine or bromine,
R ^{4 represents} fluorine, chlorine, bromine, C ₁ -C ₆ alkoxy or C ₁ -C ₆ alkylthio,
m represents 0, 1, 2 or 3, where the substituents R ^{4 are} identical or different if m represents 2 or 3,
R ^{5 represents} C ₁ -C ₆ alkyl,
n stands for 0, 1, 2, 3 or 4, where the substituents R ^{5 are} identical or different if n stands for 2, 3 or 4,
R ^{6 represents} hydrogen, cyano, formyl, -SOR ⁷ , -SO ₂ R ⁷ , -COR ⁷ , -CO ₂ R ⁷ , -CONR ⁸ R ⁹ or -C (R ¹⁰ ) = N-OR ¹¹ ,
R ⁷ is optionally mono- or polysubstituted by identical or different halogen, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ haloalkylthio, C ₁ -C ₆ -alkylamino and / or di- (C ₁ - C ₆ alkyl) amino-substituted C ₁ -C ₂₀ alkyl;
or for each optionally optionally up to eight times, identical or different, by halogen, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio substituted C ₃ -C ₆ cycloalkyl, aryl or arylC ₁ -C ₄ alkyl,
R ⁸ and R ^{9 are} independently hydrogen, -SO ₂ R ⁷ ; for in each case optionally up to thirteen times, identically or differently by halogen, C ₁ -C ₆ -alkylamino, di- (C ₁ -C ₆ -alkyl) amino, C ₁ -C ₆ -alkoxy, C ₁ - C ₆ -haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio substituted C ₁ -C ₆ alkyl or C ₂ -C ₆ alkenyl;
or for each optionally one to four times, identical or different, by halogen, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ haloalkoxy, C ₁ -C ₆ alkylthio, C ₁ -C ₆ haloalkylthio substituted C ₃ -C ₇ cycloalkyl, C ₃ -C ₇ cycloalkyl-C ₁ -C ₄ alkyl, aryl, aryl C ₁ -C ₄ alkyl, saturated or unsaturated, 5- to 10-membered heterocyclyl or heterocyclyl-C ₁ -C ₄ -alkyl with 1 to 4 heteroatoms which contain 0 to 4 nitrogen atoms, 0 to 2 non-adjacent oxygen atoms and / or 0 to 2 non-adjacent sulfur atoms ( in particular tetrazolyl, furyl, furfuryl, benzofuryl, tetrahydrofuryl, thienyl, thenyl, benzothienyl, thiolanyl, pyrrolyl, indolyl, pyrrolinyl, pyrrolidinyl, oxazolyl, benzoxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiazolyl, pyridolidyl, pyridine , Piperidinyl, morpholinyl, thiomorpholinyl, triazinyl, triazolyl, quinolinyl or isoquinolinyl) stand,
R ⁸ and R ⁹ also together for optionally single to quadruple, identical or different by halogen, cyano, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ Haloalkoxy, C ₁ -C ₆ -alkylthio, C ₁ -C ₆ -haloalkylthio substituted C ₃ -C ₆ -alkylene,
R ¹⁰ and R ¹¹ independently of one another represent hydrogen, C ₁ -C ₆ alkyl, C ₂ -C ₆ alkenyl, C ₁ -C ₆ haloalkyl or C ₂ -C ₆ haloalkenyl. 3. Δ ¹ -pyrrolines of the formula (I) according to claim 1, in which
R ^{1 represents} fluorine, chlorine or methyl,
R ^{2 represents} hydrogen, fluorine or chlorine, where R ² is bonded in the 6-position of the phenyl ring,
R ^{3 represents} hydrogen,
R ^{4 represents} fluorine, chlorine, bromine, C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkylthio,
m represents 0, 1 or 2, where the substituents R ^{4 are} identical or different if m represents 2,
R ^{5 represents} C ₁ -C ₄ alkyl,
n stands for 0, 1 or 2, where the substituents R ^{5 are} identical or different if n stands for 2,
R ^{6 represents} hydrogen, cyano, formyl, -SOR ⁷ , -SO ₂ R ⁷ , -COR ⁷ , -CO ₂ R ⁷ or -CONR ⁸ R ⁹ ,
R ⁷ is optionally mono- or polysubstituted by identical or different fluorine, chlorine, bromine, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ -haloalkoxy, C ₁ -C ₄ haloalkylthio, Methylamino, ethylamino and / or di (C ₁ -C ₆ alkyl) amino substituted C ₁ -C ₁₀ alkyl; or for each optionally one to four times, the same or different, by fluorine, chlorine, bromine, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ - Haloalkoxy, C ₁ -C ₄ alkylthio and / or C ₁ -C ₄ haloalkylthio substituted cyclopropyl, cyclopentyl, cyclohexyl, phenyl or benzyl,
R ⁸ and R ^{9 are} independently hydrogen, -SO ₂ R ⁷ ; for in each case optionally up to nine times, identical or different by fluorine, chlorine and / or bromine, C ₁ -C ₄ -alkylamino, di- (C ₁ -C ₄ -alkyl) amino, C ₁ - C ₄ -alkoxy, C ₁ -C ₄ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio substituted C ₁ -C ₄ alkyl or C ₂ -C ₆ alkenyl;
or for each optionally single to triple, identical or different by fluorine, chlorine and / or bromine, C ₁ -C ₄ alkyl, cyano, C ₁ - C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C _4- haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio substituted C ₃ -C ₆ cycloalkyl, C ₃ -C ₆ - cycloalkyl-C ₁ -C ₄ alkyl, phenyl, benzyl, phenylethyl, Tetrazolyl, furyl, furfuryl, benzofuryl, tetrahydrofuryl, thienyl, thenyl, benzothienyl, thiolanyl, pyrrolyl, indolyl, pyrrolinyl, pyrrolidinyl, oxazolyl, benzoxazolyl, isoxazolyl, imidazolyl, pyrazolyl, thiazolyl, pyridolidyl, pyridine Piperidinyl, morpholinyl, thiomorpholinyl, triazinyl, triazolyl, quinolinyl or isoquinolinyl,
R ⁸ and R ⁹ furthermore together represent optionally mono- to tetrasubstituted by identical or different fluorine, chlorine, cyano, C ₁ -C ₄ alkyl, C ₁ - C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ - C ₄ -C ₅ haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio substituted C ₄ -C ₅ alkylene. 4. Δ ¹ -pyrrolines of formula (I) according to claim 1, in which
R ^{1 represents} fluorine or chlorine,
R ^{2 represents} hydrogen or fluorine, where R ² is bonded in the 6-position of the phenyl ring,
R ^{3 represents} hydrogen,
R ^{4 represents} fluorine, chlorine, bromine, methoxy, ethoxy, methylthio or ethylthio,
m represents 0 or 1,
R ^{5 represents} methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl or t-butyl,
n stands for 0, 1 or 2, where the substituents R ^{5 are} identical or different if n stands for 2,
R ^{6 represents} hydrogen, -SOR ⁷ , -SO ₂ R ⁷ , -COR ⁷ , -CO ₂ R ⁷ , -CONR ⁸ R ⁹ ,
R ^{7 is} methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, hexyl, -CF ₃ , -CHF ₂ , -CCl ₃ , -CCl ₂ F, methoxymethyl, trifluoromethoxymethyl, methylthiomethyl, trifluoromethylthiomethyl, dimethylaminomethyl, dimethylaminoethyl, diethylaminomethyl, diethylaminoethyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl or benzyl,
R ⁸ and R ^{9 are} independently hydrogen, -SO ₂ CF ₃ ; for methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, hexyl, -CF ₃ , -CH ₂ CF ₃ , - (CF ₂ ) ₃ CF ₃ ;
stand for cyclopropyl, cyclopentyl, cyclohexyl, methoxymethyl, methoxyethyl, or for phenyl or benzyl substituted in each case optionally up to three times, identically or differently by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, trifluoromethoxy,
R ⁸ and R ⁹ also together for - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ - or -CH ₂ -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -CH ₂ - stand. 5. Δ ¹ -pyrrolines of the formula (I) according to claim 1, in which R ¹ and R ² each represent fluorine. 6. Δ ¹ -pyrrolines of the formula (I) according to claim 1, in which R ¹ , R ² and R ³ each represent hydrogen. 7. Δ ¹ -pyrrolines of the formula (I) according to claim 1, in which m represents 0. 8. Δ ¹ -pyrrolines of the formula (I) according to claim 1, in which n is 0 or 1, preferably 0. 9. Δ ¹ -pyrrolines of the formula (I) according to claim 1, in which R ^{6 is} -COR ⁷ , -CO ₂ R ⁷ or -CONR ⁸ R ⁹ , where R ⁷ , R ⁸ and R ^{9 are} those in claim 1 have the meanings given. 10. Compounds of the formula (Ia)


in which
R ^{1 represents} fluorine or chlorine,
R ^{2 represents} hydrogen or fluorine and
R ⁵ , n and R ^{6 have} the meanings given in claim 1. 11. Compounds of formula (Ia) according to claim 10, in which
R ^{1 represents} fluorine or chlorine,
R ^{2 represents} hydrogen or fluorine,
R ^{5 represents} methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl or t-butyl,
n stands for 0, 1 or 2, where the substituents R ^{5 are} identical or different if n stands for 2, and
R ^{6 represents} hydrogen, -SOR ⁷ , -SO ₂ R ⁷ , -COR ⁷ , -CO ₂ R ⁷ , -CONR ⁸ R ⁹ ,
R ^{7 is} methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, hexyl, -CF ₃ , -CHF ₂ , -CCl ₃ , -CCl ₂ F, methoxymethyl, trifluoromethoxymethyl, methylthiomethyl, trifluoromethylthiomethyl, dimethylaminomethyl, dimethylaminoethyl, diethylaminomethyl, diethylaminoethyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl or benzyl,
R ⁸ and R ^{9 are} independently hydrogen, -SO ₂ CF ₃ ; for methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, hexyl, -CF ₃ , -CH ₂ CF ₃ , - (CF ₂ ) ₃ CF ₃ ;
stand for cyclopropyl, cyclopentyl, cyclohexyl, methoxymethyl, methoxyethyl, or for phenyl or benzyl substituted in each case optionally up to three times, identically or differently by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, trifluoromethoxy,
R ⁸ and R ⁹ also together for - (CH ₂ ) ₄ -, - (CH ₂ ) ₅ -, - (CH ₂ ) ₆ - or -CH ₂ -CH (CH ₃ ) -CH ₂ -CH (CH ₃ ) -CH ₂ - stand. 12. Compounds of formula (Ia) according to claim 10, in which
R ^{1 represents} fluorine,
R ^{2 represents} fluorine,
R ^{5 represents} methyl,
n represents 0 or 1,
R ^{6 represents} -COR ⁷ , -CO ₂ R ⁷ or -CONR ⁸ R ⁹ ,
R ^{7 represents} methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, hexyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl or benzyl,
R ⁸ and R ^{9 are} independently hydrogen, -SO ₂ CF ₃ ; for methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, hexyl, -CF ₃ , -CH ₂ CF ₃ , - (CF ₂ ) ₃ CF ₃ ;
stand for cyclopropyl, cyclopentyl, cyclohexyl, methoxymethyl, methoxyethyl, or for phenyl or benzyl substituted in each case optionally up to three times, identically or differently by fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, trifluoromethoxy. 13. Compounds of formula (Ia) according to claim 10, in which R ¹ and R ² each represent fluorine. 14. Compounds of formula (I-a) according to claim 10, in which m is 0. 15. Compounds of formula (I-a) according to claim 10, in which n is 0 or 1, preferably represents 0. 16. Compounds of formula (Ia) according to claim 10, in which R ^{6 is} -COR ⁷ , -CO ₂ R ⁷ or -CONR ⁸ R ⁹ , wherein R ⁷ , R ⁸ and R ^{9 have} the meanings given in claim 1 , 17. (R) -configured compounds of the formula (Ib)


in which
R ¹ , R ² , R ³ , R ⁴ , m, R ⁵ , n and R ^{6 have} the meanings given in Claim 1. 18. A process for the preparation of compounds of formula (I) according to claim 1, characterized in that A) Δ ¹ -pyrrolines of the formula (II)


in which
R ¹ , R ² , R ³ , R ⁴ and m have the meanings given in claim 1,
with piperazine derivatives of the formula (III)


in which
R ⁵ , n and R ^{6 have} the meanings given in claim 1,
in the presence of a catalyst, in the presence of 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl (BINAP), optionally in the presence of a base and optionally in the presence of a diluent. 19. Pesticides, characterized by a content of at least one compound of formula (I) according to claim 1 in addition to extenders and / or surfactants. 20. Use of compounds of formula (I) according to claim 1 for Pest control. 21. A method for controlling pests, characterized in that compounds of formula (I) according to claim 1 on pests and / or their living space. 22. Process for the preparation of pesticides, thereby characterized in that compounds of formula (I) according to claim 1 with Extenders and / or surfactants mixed.