DE102004013528A1 - New aza-heterocyclic spiro-cyclopropyl compounds, useful as pesticides, e.g. insecticides, acaricides, nematocides, ectoparasiticides and antifouling agents - Google Patents

Abstract

Spiro-cyclopropyl substituted 2-(cyanoimino, nitroimino or nitromethylene)-1-aza-cycloalkane derivatives (I) are new. Heterocyclic spiro-cyclopropyl compounds of formula (I) are new. A1>, A2>direct bond, CH2 or CH2CH2; A3>O, S or NR2>; R2>H or 1-6C alkyl (optionally substituted by CN, halo, OT, ST, SOT or SO2T); or 2-6C alkenyl or 2-6C alkynyl (both optionally substituted by halo); R1>H or T; Y1>N-CN, N-NO2 or CH-NH2; Y2>6-10C aryl or heterocyclyl (containing up to 9C, 1-5 N and/or one O or S), both optionally substituted by NO2, CN, halo, T', OT', ST', SOT' or SO2T'; T : 1-4C alkyl; T' : T or 1-4C haloalkyl. Independent claims are included for: (A) the preparation of (I); and (B) new spiro-cyclopropane and cyclopropane derivative intermediates of formulae (II) and (IV). [Image] [Image] ACTIVITY : Insecticide, Acaricide; Nematocide; Parasiticide; Antifouling; Herbicide; Fungicide; Antibacterial. 1-((2-Chloro-pyridin-5-yl)-methyl)-4-(spiro-cyclopropyl)-imidazolidin-2-ylidene-nitroamine (Ia) at an application rate of 500 g/ha gave 100% mortality of all stages of Myzus persicae on Chinese cabbage leaves in 5 days. MECHANISM OF ACTION : None given in the source material.

Description

The present application relates to novel heterocyclic spirocyclopropyl compounds, Process for their preparation and their use for controlling animal pests, especially of arthropods, especially insects.

Various Cyclopropyl compounds are already as insecticidal compounds become known (see EP-811 593 A1). These connections have However, due to various disadvantages as crop protection or pesticide no special meaning attained.

in welcher
A¹ für eine Einfachbindung, für Methylen oder für Dimethylen steht,
A² für eine Einfachbindung, für Methylen oder für Dimethylen steht,
A³ für O (Sauerstoff), S (Schwefel) oder die Gruppierung N-R² steht, wobei R² für Wasserstoff für gegebenenfalls durch Cyano, Halogen, C₁-C₄-Alkoxy, C₁-C₄-Alkylthio, C₁-C₄-Alkylsulfinyl oder C₁-C₁-Alkylsulfonyl substituiertes Alkyl mit 1 bis 6 Kohlenstoffatomen, oder für jeweils gegebenenfalls durch Halogen substituiertes Alkenyl oder Alkinyl mit jeweils 2 bis 6 Kohlenstoffatomen steht,
R¹ für Wasserstoff oder Alkyl mit 1 bis 4 Kohlenstoffatomen steht,
Y¹ für Cyanoimino (N-CN), Nitroimino (N-NO₂) oder Nitromethylen (CH-NO₂) steht, und
Y² für jeweils gegebenenfalls durch Nitro, Cyano, Halogen, C₁-C₄-Alkyl, C₁-C₄-Halogenalkyl, C₁-C₄-Alkoxy, C₁-C₄-Halogenalkoxy, C₁-C₄-Alkylthio, C₁-C₄-Halogenalkylthio, C₁-C₄-Alkylsulfinyl, C₁-C₄-Halogenalkylsulfinyl, C₁-C₄-Alkylsulfonyl oder C₁-C₄-Halogenalkylsulfonyl substituiertes Aryl mit 6 oder 10 Kohlenstoffatomen oder Heterocyclyl mit bis zu 9 Kohlenstoffatomen, 1 bis 5 Stickstoffatomen und/oder einem Sauerstoff- oder Schwefelatom steht.New heterocyclic spirocyclopropyl compounds of the formula (I) have now been found,

in which
A ^{1 represents} a single bond, methylene or dimethylene,
A ^{2 is} a single bond, methylene or dimethylene,
A ^{3 is} O (oxygen), S (sulfur) or the group NR ² , where R ^{2 is} hydrogen, optionally substituted by cyano, halogen, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylthio, C ₁ - C ₄ alkylsulfinyl or C ₁ -C ₁ -alkylsulfonyl-substituted alkyl having 1 to 6 carbon atoms, or represents in each case optionally halogen-substituted alkenyl or alkynyl having in each case 2 to 6 carbon atoms,
R ^{1 is} hydrogen or alkyl of 1 to 4 carbon atoms,
Y ^{1 is} cyanoimino (N-CN), nitroimino (N-NO ₂ ) or nitromethylene (CH-NO ₂ ), and
Y ^{2 is} in each case optionally nitro, cyano, halogen, 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, C ₁ -C ₄ -haloalkylthio, C ₁ -C ₄ -alkylsulfinyl, C ₁ -C ₄ -haloalkylsulfinyl, C ₁ -C ₄ -alkylsulfonyl or C ₁ -C ₄ -haloalkylsulfonyl-substituted aryl having 6 or 10 carbon atoms or heterocyclyl with up to 9 carbon atoms, 1 to 5 nitrogen atoms and / or an oxygen or sulfur atom.

• (a) Spirocyclopropylverbindungen der Formel (II)
  
  in welcher A¹, A², A³ und Y¹ die oben angebenene Bedeutung haben, mit Verbindungen der Formel (III)
  
  in welcher R¹ und Y² die oben angebenene Bedeutung haben und X für eine Abgangsgruppe aus der Reihe Halogen, Methylsulfonyloxy, Trifluormethylsulfonyloxy steht, gegebenenfalls in Gegenwart eines oder mehrerer Reaktionshilfsmittel und gegebenenfalls in Gegenwart eines oder mehrerer Verdünnungsmittel umsetzt, oder wenn man
• (b) Cyclopropanderivate der Formel (IV)
  
  in welcher A¹, A², A³, R¹ und Y² die oben angebenene Bedeutung haben, mit Verbindungen der Formel (V)
  
  in welcher Y¹ die oben angebenene Bedeutung hat und X¹ und X² gleich oder verschieden sind und für eine Abgangsgruppe aus der Reihe Amino, Methoxy, Ethoxy, Phenoxy, Nitro-phenoxy, Methylthio, Ethylthio, Methylsulfinyl, Ethylsulfinyl, Methylsulfonyl, Ethylsulfonyl stehen, gegebenenfalls in Gegenwart eines oder mehrerer Reaktionshilfsmittel und gegebenenfalls in Gegenwart eines oder mehrerer Verdünnungsmittel umsetzt.

It has furthermore been found that the compounds of the formula (I) are obtained when

• (a) Spirocyclopropyl compounds of the formula (II)
  
  in which A ¹ , A ² , A ³ and Y ^{1 have} the abovementioned meaning, with compounds of the formula (III)
  
  in which R ¹ and Y ^{2 have} the abovementioned meaning and X is a leaving group selected from the group consisting of halogen, methylsulfonyloxy, trifluoromethylsulfonyloxy, if appropriate in the presence of one or more reaction auxiliaries and if appropriate in the presence of one or more diluents, or if
• (b) Cyclopropane derivatives of the formula (IV)
  
  in which A ¹ , A ² , A ³ , R ¹ and Y ^{2 have} the abovementioned meaning, with compounds of the formula (V)
  
  in which Y ^{1 has} the abovementioned meaning and X ¹ and X ^{2 are} identical or different and represent a leaving group from the series amino, methoxy, ethoxy, phenoxy, nitrophenoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl , if appropriate in the presence of one or more reaction auxiliaries and if appropriate in the presence of one or more diluents.

Finally became found that the new compounds of the formula (I) strongly biological Possess properties and especially for controlling animal pests, in particular of insects, arachnids and nematodes present in the Agriculture, forestry, storage and materials protection, and on the hygiene sector are suitable.

The Compounds of the invention are generally defined by the formula (I).

preferred Substituents or ranges of the formulas mentioned in the above and below listed Remains are explained below.

A ¹ is preferably a single bond, methylene or dimethylene.

A ² preferably represents a single bond, methylene or dimethylene, with the proviso that A ¹ and A ² are different in each individual case.

A ³ is preferably O (oxygen), S (sulfur) or the group NR ² , where R ^{2 is} hydrogen, in each case optionally by cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-propoxy, methylthio , Ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s- , n- or neo-pentyl, or is in each case optionally substituted by fluorine, chlorine or bromine substituted ethenyl, propenyl, butenyl, pentenyl, ethynyl, propynyl, butynyl or pentynyl.

R ¹ is preferably hydrogen, methyl, ethyl, n- or i-propyl.

Y ¹ is preferably cyanoimino (N-CN) or nitroimino (N-NO ₂ ).

Y ² is preferably in each case optionally nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, Fluorodichloromethyl, chlorodifluoromethyl, fluoroethyl, chloroethyl, difluoroethyl, dichloroethyl, chlorofluoroethyl, triorethyl, trichloroethyl, chlorodifluoroethyl, fluorodichloroethyl, tetrafluoroethyl, pentafluoroethyl, fluoropropyl, chloropropyl, difluoropropyl, dichloropropyl, chlorofluoropropyl, trifluoropropyl, trichloropropyl, tetrafluoropropyl, pentafluoropropyl, perfluoropropyl, methoxy, ethoxy, n- or i-propoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, fluoroethoxy, chloroethoxy, difluoroethoxy, dichloroethoxy, trifluoroethoxy, tetrafluoroethoxy, pentafluoroethoxy, fluoropropoxy, chloropropoxy, difluoropropoxy, dichloropropoxy, chlorofluoropropoxy, trifluoropropoxy, tetrafluoropropoxy, pentafluoropropoxy or perfluoropropoxy substituted phenyl, furyl , Tetrahydrofuryl, thienyl, pyr rolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, oxadiazolyl, thiadiazolyl, triazolyl, pyridinyl, pyrimidinyl, pyridazinyl or pyrazinyl.

A ¹ particularly preferably represents a single bond or methylene.

A ² particularly preferably represents a single bond or methylene, with the proviso that A ¹ and A ² are different in each individual case.

A ³ particularly preferably represents O (oxygen), S (sulfur) or the grouping NR ² , where R ^{2 is} hydrogen, in each case optionally by cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-propoxy, Methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl-substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, or in each case optionally by fluorine, chlorine or bromine substituted propenyl, butenyl, propynyl or butynyl.

R ¹ particularly preferably represents hydrogen, methyl or ethyl.

Y ¹ is particularly preferably cyanoimino.

Y ² particularly preferably represents in each case optionally nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, fluorodichloromethyl, chlorodifluoromethyl, fluoroethyl, chloroethyl, difluoroethyl, dichloroethyl, Chlorofluoroethyl, trifluoroethyl, trichloroethyl, chlorodifluoroethyl, fluorodichloroethyl, tetrafluoroethyl, pentafluoroethyl, methoxy, ethoxy, n- or i-propoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, fluoroethoxy, chloroethoxy, difluoroethoxy, dichloroethoxy, trifluoroethoxy, tetrafluoroethoxy, pentafluoroethoxy, fluoropropoxy, Phenyl, furyl, tetrahydrofuryl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyridazinyl or pyrazinyl.

A ³ very particularly preferably represents S (sulfur) or the group NR ² , where R ^{2 is} hydrogen.

R ¹ very particularly preferably represents hydrogen.

Y ² very particularly preferably represents in each case optionally substituted by nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, methoxy or ethoxy-substituted thiazolyl or pyridinyl.

A very particularly preferred group are those compounds of the formula (I) in which
A ^{1 represents} a single bond,
A ^{2 is} methylene,
A ³ S (sulfur) or the group NR ² , wherein R ^{2 is} hydrogen, each optionally substituted by cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i Propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl-substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, or represents in each case optionally substituted by fluorine, chlorine or bromine propenyl, butenyl, propynyl or butynyl stands,
R ^{1 is} hydrogen or methyl,
Y ^{1 is} cyanoimino (N-CN) or nitroimino (N-NO ₂ ), and
Y ^{2 is} in each case optionally nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, fluorodichloromethyl, chlorodifluoromethyl, fluoroethyl, chloroethyl, difluoroethyl, dichloroethyl, chlorofluoroethyl, trifluoroethyl , Trichloroethyl, chlorodifluoroethyl, fluorodichloroethyl, tetrafluoroethyl, pentafluoroethyl, methoxy, ethoxy, n- or i-propoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, fluoroethoxy, chloroethoxy, difluoroethoxy, dichloroethoxy, trifluoroethoxy, tetrafluoroethoxy, pentafluoroethoxy, fluoropropoxy, difluoropropoxy, dichloropropoxy, Chlorofluoropropoxy, trifluoropropoxy, tetrafluoropropoxy, pentafluoropropoxy or perfluoropropoxy-substituted furyl, tetrahydrofuryl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyridazinyl or pyrazinyl.

Another particularly preferred group are those compounds of formula (I) in which
A ^{1 is} methylene,
A ^{2 stands} for a single bond,
A ^{3 is} the group NR ² , where R ^{2 is} hydrogen, in each case optionally by cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, Ethylsulfinyl, methylsulfonyl or ethylsulfonyl-substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, or for in each case optionally substituted by fluorine, chlorine or bromine substituted propenyl, butenyl, propynyl or butynyl stands,
R ^{1 is} hydrogen or methyl,
Y ^{1 is} cyanoimino (N-CN) or nitroimino (N-NO ₂ ), and
Y ^{2 is} in each case optionally nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, fluorodichloromethyl, chlorodifluoromethyl, fluoroethyl, chloroethyl, difluoroethyl, dichloroethyl, chlorofluoroethyl, trifluoroethyl , Trichloroethyl, chlorodifluoroethyl, fluorodichloroethyl, tetrafluoroethyl, pentafluoroethyl, methoxy, ethoxy, n- or i-propoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, fluoroethoxy, chloroethoxy, difluoroethoxy, dichloroethoxy, trifluoroethoxy, tetrafluoroethoxy, pentafluoroethoxy, fluoropropoxy, difluoropropoxy, dichloropropoxy, Chlorofluoropropoxy, trifluoropropoxy, tetrafluoropropoxy, pentafluoropropoxy or perfluoropropoxy-substituted furyl, tetrahydrofuryl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, pyridinyl, pyrimidinyl, pyridazinyl or pyrazinyl.

In the case of the very particularly preferred groups, the compounds of the formula (I) in which
A ³ S (sulfur) or the group NR ² , where R ^{2 is} hydrogen or methyl,
R ^{1 is} hydrogen,
Y ^{1 is} cyanoimino (N-CN) or nitroimino (N-NO ₂ ), and
Y ^{2 is} tetrahydrofuran-3-yl, 2-chloro-thiazol-5-yl or 2-chloro-pyridin-5-yl.

The listed above general or preferred radical definitions or Explanations apply to the end products and for the starting and intermediate products accordingly. These remainder definitions can between each other, including between the respective preferred areas, be combined.

According to the invention preferred are the compounds of formula (I) in which a combination of the mentioned above as being preferred Meanings exist.

Particularly according to the invention preference is given to the compounds of the formula (I) in which a combination the meanings listed above as being particularly preferred.

Very particular according to the invention preference is given to the compounds of the formula (I) in which a combination the meanings listed above as very particularly preferred is present.

In those listed above and below Residual definitions are hydrocarbon radicals, such as alkyl - also in Compound with heteroatoms as in alkoxy - as far as possible in each case straight-chain or branched.

If, for example, 6-thia-4-azaspiro [2.4] hept-5-ylidene cyanamide and 2-chloro-5-chloromethyl-1,3-thiazole are used as starting materials, the course of the process (a) according to the invention can be characterized by the following reaction scheme is given:

If, for example, [1- (aminomethyl) -cyclopropyl] [(6-chloro-pyridin-3-yl) -methyl] -amine and nitroguanidine are used as starting materials, the course of process (b) according to the invention can be represented by the following reaction scheme :

The in process (a) for the preparation of the compounds of general formula (I) as starting materials to be used substituted spirocyclopropyl compounds are represented by the formula (II) generally defined. In the general formula (II), A ¹ , A ² , A ³ , R ¹ and Y ¹ preferably have those meanings which have already been mentioned above in connection with the description of the compounds of general formula (I) according to the invention as being preferred, particularly preferred or complete particularly preferred for A ¹ , A ² , A ³ , R ¹ and Y ^{1 have been} specified.

The Starting materials of the general formula (II) are not yet known from Literature known; they are also the subject of new substances present application.

in welcher
A¹, A² und A³ die oben angebenene Bedeutung haben,
– oder gegebenenfalls auch Säureaddukte dieser Verbindungen, wie z.B. die Hydrochloride –
mit Verbindungen der Formel (V)

in welcher
Y¹ die oben angebenene Bedeutung hat und
X¹ und X² gleich oder verschieden sind und jeweils für eine Abgangsgruppe aus der Reihe Amino, Methoxy, Ethoxy, Phenoxy, Nitro-phenoxy, Methylthio, Ethylthio, Methylsulfinyl, Ethylsulfinyl, Methylsulfonyl, Ethylsulfonyl stehen,
gegebenenfalls in Gegenwart eines oder mehrerer Reaktionshilfsmittel, wie z.B. Kaliumcarbonat oder Kaliumhydroxid, und gegebenenfalls in Gegenwart eines oder mehrerer Verdünnungsmittel, wie z.B. Ethanol, Methanol, Acetonitril und/oder Wasser, bei Temperaturen zwischen 0°C und 120°C umsetzt (vgl. die Herstellungsbeispiele).The novel spirocyclopropyl compounds of the formula (II) are obtained when cyclopropane derivatives of the formula (VI)

in which
A ¹ , A ² and A ^{3 have} the meaning given above,
- or optionally also acid adducts of these compounds, such as the hydrochlorides -
with compounds of the formula (V)

in which
Y ^{1 has} the meaning given above and
X ¹ and X ^{2 are} identical or different and each represent a leaving group from the series amino, methoxy, ethoxy, phenoxy, nitrophenoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl,
optionally in the presence of one or more reaction auxiliaries, such as potassium carbonate or potassium hydroxide, and optionally in the presence of one or more diluents, such as ethanol, methanol, acetonitrile and / or water, at temperatures between 0 ° C and 120 ° C (see Preparation Examples).

The needed as precursors Cyclopropane derivatives of the formula (VI) are known and / or can according to processes which are known per se (compare J. Org. Chem. 57 (1992), 6071-6075; loc. cit. 67 (2002), 3965-3968; see. also the production examples).

durch Umsetzung mit Methansulfonsäurechlorid in Gegenwart eines Säureakzeptors, wie z.B. Triethylamin bei Temperaturen zwischen 0°C und 50°C, anschließende Umsetzung des Mesylierungsproduktes mit Thiolessigsäure in Gegenwart eines Verdünnungsmittels, wie z.B. Acetonitril, bei Temperaturen zwischen 10°C und 100°C, und anschließende Abspaltung der Boc-Schutzgruppe durch Umsetzung mit einer starken Säure, wie z.B. Salzsäure, bei Temperaturen zwischen 10°C und 50°C erhalten werden.Compounds of the formula (VI) in which A ^{1 is} a single bond, A ^{2 is} methylene and A ^{3 is} S (sulfur) can be prepared, for example, from tert-butyl 1-hydroxymethyl-cyclopropylcarbamate (cf. Heterocycl Chem 25 (1988), 1769-1772, J. Org. Chem. 67 (2002), 3965-3968) of the formula (VII)

by reaction with methanesulfonyl chloride in the presence of an acid acceptor, such as triethylamine at temperatures between 0 ° C and 50 ° C, then reacting the Mesylierungsproduktes with thiolacetic acid in the presence of a diluent, such as acetonitrile, at temperatures between 10 ° C and 100 ° C, and subsequent cleavage of the Boc protective group by reaction with a strong acid, such as hydrochloric acid, be obtained at temperatures between 10 ° C and 50 ° C.

The in process (a) for the preparation of the compounds of general formula (I) as starting materials to be used compounds are generally defined by the formula (III). In the general formula (III), R ¹ and Y ² preferably have those meanings which have already been mentioned above in the context of in connection with the description of the compounds of the general formula (I) according to the invention have been given as preferred, particularly preferred or very particularly preferred for R ¹ and Y ² ; X is preferably fluorine, chlorine, bromine, iodine, methylsulfonyloxy or trifluoromethylsulfonyloxy, in particular chlorine or bromine.

The Starting materials of the general formula (III) are known and / or can are prepared by processes known per se (see J. Heterocycl. Chem. 16 (1979), 333-337; EP-260560; EP-260,485; EP-373,463; EP-373464; EP-649,845; EP-685,477; EP-780,384; WO 97/23469).

The in process (b) for the preparation of the compounds of general formula (I) as starting materials to be used cyclopropane derivatives are generally defined by the formula (IV). In the general formula (IV), A ¹ , A ² , A ³ and Y ¹ preferably have those meanings which have already been mentioned above in connection with the description of the compounds of the general formula (I) according to the invention as being preferred, particularly preferred or very particularly preferred A ¹ , A ² , A ³ and Y ^{1 have been} indicated.

The Starting materials of the general formula (IV) are not yet known from Literature known; they are also the subject of new substances present application.

in welcher
A¹, A² und A³ die oben angebenene Bedeutung haben,
– oder gegebenenfalls auch Säureaddukte dieser Verbindungen, wie z.B. die Hydrochloride –
mit Verbindungen der Formel (III)

in welcher
R¹, X und Y² die oben angebenene Bedeutung haben,
gegebenenfalls in Gegenwart eines oder mehrerer Reaktionshilfsmittel, wie z.B. Kaliumcarbonat oder Triethylamin, und gegebenenfalls in Gegenwart eines oder mehrerer Verdünnungsmittel, wie z.B. Methyl-isobutylketon, Acetonitril oder N,N-Dimethyl-formamid, bei Temperaturen zwischen 0°C und 150°C umsetzt.The novel cyclopropane derivatives of the formula (IV) are obtained when cyclopropane derivatives of the formula (VI)

in which
A ¹ , A ² and A ^{3 have} the meaning given above,
- or optionally also acid adducts of these compounds, such as the hydrochlorides -
with compounds of the formula (III)

in which
R ¹ , X and Y ^{2 have} the meaning given above,
optionally in the presence of one or more reaction auxiliaries, such as potassium carbonate or triethylamine, and optionally in the presence of one or more diluents, such as methyl isobutyl ketone, acetonitrile or N, N-dimethyl-formamide, at temperatures between 0 ° C and 150 ° C. ,

durch Umsetzung mit Stickstoffwasserstoffsäure (HN₃) in Gegenwart eines Reaktionshilfsmittels, wie Triphenylphosphin, und in Gegenwart eines Verdünnungsmittels, wie Tetrahydrofuran, bei Temperaturen zwischen –80°C und +20°C, anschließende Abspaltung der Boc-Schutzgruppe durch Umsetzung mit einer starken Säure, wie z.B. Salzsäure, bei Temperaturen zwischen 10°C und 50°C, anschließende Umsetzung mit einer Verbindung der Formel (III) in Gegenwart eines Reaktionshilfsmittels, wie z.B. Kaliumcarbonat, und gegebenenfalls in Gegenwart eines Verdünnungsmittels, wie z.B. Acetonitril, bei Temperaturen zwischen 10°C und 100°C, und anschließende Umsetzung mit Triphenylphoshin in Gegenwart eines Verdünnungsmittels, wie z.B. Tetrahydrofuran, bei Temperaturen zwischen 10°C und 100°C erhalten werden.Cyclopropane derivatives of the formula (IV) can also be obtained, for example, from tert-butyl 1-hydroxymethyl-cyclopropylcarbamate (compare J. Heterocycl Chem 25 (1988), 1769-1772, J. Org. Chem. , 3965-3968) of the formula (VII)

by reaction with hydrazoic acid (HN ₃ ) in the presence of a reaction auxiliary, such as triphenylphosphine, and in the presence of a diluent, such as tetrahydrofuran, at temperatures between -80 ° C and + 20 ° C, followed by cleavage of the Boc protective group by reaction with a strong acid , such as hydrochloric acid, at temperatures between 10 ° C and 50 ° C, followed by reaction with a compound of formula (III) in the presence of a reaction auxiliary, such as potassium carbonate, and optionally in the presence of a diluent, such as acetonitrile, at temperatures between 10 ° C and 100 ° C, and subsequent reaction with triphenylphosphine in the presence of a diluent, such as tetra hydrofuran, at temperatures between 10 ° C and 100 ° C.

The The sequence of the reaction steps can also be changed here, i. the first Step-generated azido compound can react with triphenylphosphine directly be converted into the corresponding amino compound, which by subsequent reaction with a compound of formula (III) and subsequent cleavage of Boc protective group are also converted into a compound of formula (IV) can.

The in process (b) for the preparation of the compounds of general formula (I) as starting materials to be used compounds are generally defined by the formula (V). In the general formula (V), Y ¹ preferably has those meanings which have already been mentioned above in connection with the description of the compounds of the general formula (I) according to the invention as being preferred, particularly preferred or very particularly preferred for Y ¹ ; X ¹ and X ² are preferably amino, methoxy, phenoxy, methylthio or methylsulfonyl, in particular amino.

The Starting materials of the general formula (V) are known and / or can be prepared according to known methods.

The inventive method (a) and (b) for the preparation of the compounds of the general formula (I) are preferably prepared using one or more reaction auxiliaries carried out. As a reaction aid for the methods of the invention generally come the usual inorganic or organic bases or acid acceptors into consideration. These include preferably alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides, such as For example, sodium, potassium or Calcium acetate, lithium, sodium, potassium or calcium amide, sodium, Potassium, cesium or calcium carbonate, sodium, potassium or calcium bicarbonate, Lithium, sodium, potassium or calcium hydride, lithium, sodium, Potassium or calcium hydroxide, sodium or potassium methoxide, -ethanolate, -n- or -i-propanolate, n-, -i-, -s- or -t-butanolate; also basic organic nitrogen compounds, such as Trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N, N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, 2-methyl, 3-methyl, 4-methyl, 2,4-dimethyl, 2,6-dimethyl, 3,4-dimethyl and 3,5-dimethyl-pyridine, 5-ethyl-2-methylpyridine, 4-dimethylaminopyridine, N-methyl-piperidine, 1,4-diazabicyclo [2,2,2] octane (DABCO), 1,5-diazabicyclo [4,3,0] -non-5-ene (DBN), or 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU).

The inventive method (a) and (b) for the preparation of the compounds of the general formula (I) are preferably prepared using one or more diluents carried out. As a diluent to carry out the inventive method (a) and (b) are especially inert organic solvents into consideration. For this belong in particular aliphatic, alicyclic or aromatic, if appropriate halogenated hydrocarbons, such as gasoline, benzene, Toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, Dichloromethane, chloroform, carbon tetrachloride; Ethers, such as diethyl ether, Diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones, such as acetone, butanone or methyl isobutyl ketone; Nitriles, such as acetonitrile, propionitrile or butyronitrile; amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate, Sulfoxides, such as dimethyl sulfoxide, alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, whose Mixtures with water or pure water.

The Reaction temperatures can during execution the inventive method (a) and (b) in a wider range be varied. In general, one works at temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 120 ° C.

The inventive method (a) and (b) are generally carried out under normal pressure. It but it is also possible the methods of the invention under increased or reduced pressure - in general between 0.1 bar and 10 bar - perform.

To carry out the processes (a) and (b) according to the invention, the starting materials are generally employed in approximately equimolar amounts. However, it is also possible to use one of the components in a larger excess. The reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary and the reaction mixture is generally stirred for several hours at the required temperature. The work-up is carried out according to customary Me carried out methods (see the preparation examples).

The active compounds are suitable for good plant tolerance, favorable toxicity to warm-blooded animals and good environmental compatibility for the protection of plants and plant organs, for increasing crop yields, improving the quality of the crop and for controlling animal pests, in particular insects, arachnids and nematodes used in agriculture, in agriculture Forestry, gardens and recreational facilities, materials and supplies, and the hygiene sector. They can preferably be used as crop protection agents. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The above mentioned pests include:
From the order of Isopoda, for example, Oniscus asellus, Armadillidium vulgare, Porcellio scaber.
From the order of Diplopoda eg Blaniulus guttulatus.
From the order of Chilopoda eg Geophilus carpophagus, Scutigera spp ..
From the order of Symphyla eg Scutigerella immaculata.
From the order of Thysanura eg Lepisma saccharina.
From the order of the Collembola eg Onychiurus armatus.
From the order of the Orthoptera eg Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca gregaria.
From the order Blattaria orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica.
From the order of the Dermaptera eg Forficula auricularia.
From the order of the Isoptera eg Reticulitermes spp ..
From the order of Phthiraptera, for example, Pediculus humanus corporis, Haematopinus spp., Linognathus spp., Trichodectes spp., Damalinia spp.
From the order of Thysanoptera eg Hercinothrips femoralis, Thrips tabaci, Thrips palmi, Frankliniella accidentalis.
From the order of Heteroptera eg Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
From the order of Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus spp. Phorodon humuli, Rhopalosiphum 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 Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella xylostella, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp , Earias insulana, Heliothis spp., Mamestra brassicae, Panolis flammea, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella , Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae.
From the order Coleoptera eg Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp. , Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica, Lissorhoptrus oryzophilus.
From the order of Hymenoptera eg Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
From the order of Diptera eg Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp , Stomoxys spp., 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 Siphonaptera eg Xenopsylla cheopis, Ceratophyllus spp ..
From the class Arachnida eg Scorpio maurus, Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp ., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Hemitarsonemus spp., Brevipalpus spp.

To the plant parasite Nematodes belong e.g. 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 the invention of the formula (I) are characterized in particular by strong action against beetle larvae (e.g., Phaedon chochleariae), butterfly caterpillars (e.g., Spodoptera frugiperda) and aphids (e.g., Myzus persicae).

The Compounds of the invention can optionally in certain concentrations or application rates also as herbicides and microbicides, for example as fungicides, Antifungals and bactericides are used. They can be optionally also as intermediates or precursors for the synthesis of other active ingredients deploy.

According to the invention, all Plants and parts of plants are treated. Among plants are here understood all plants and plant populations, as desired and undesirable Wild plants or crops (including naturally occurring crops). Crops can Be plants by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or Combinations of these methods can be obtained, including transgenic ones Plants and including protected by plant variety rights or non-protectable plant varieties. Under plant parts are all above ground and underground Parts and organs of plants, such as shoot, leaf, flower and root By way of example, leaves, needles, stems, stems, flowers, fruiting bodies, fruits and Seeds as well as roots, tubers and rhizomes. To the plant parts belongs also harvested material as well as vegetative and generative propagation material, For example, cuttings, tubers, rhizomes, offshoots and seeds.

The Treatment according to the invention the plants and plant parts with the active ingredients are made directly or by affecting their environment, habitat or storage space the usual Treatment methods, e.g. by dipping, spraying, evaporating, misting, Spreading, spreading, injecting and propagating material, in particular in seeds, further by single or multi-layer wrapping.

The Active ingredients can in the usual Formulations are transferred, like solutions, Emulsions, wettable powders, suspensions, powders, dusts, Pastes, soluble Powders, granules, suspension-emulsion concentrates, drug-impregnated Natural and synthetic substances as well as ultrafine encapsulations in polymers Substances.

These Formulations are prepared in a known manner, e.g. by Mixing the active ingredients with extenders, ie liquid solvents and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents.

in the Traps of using water as diluent may be e.g. also organic solvents as auxiliary solvent be used. As liquid solvent are essentially in question: aromatics, such as xylene, toluene, or Alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic Hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. 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, as well as water.

Suitable solid carriers are:
For example, ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic minerals, such as finely divided silica, alumina and silicates, as solid carriers for granules in question: eg broken and fractionated natural rocks such Calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: for example lignin-sulphite liquors and methylcellulose.

It can in the formulations adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-shaped Polymers such as gum arabic, polyvinyl alcohol, Polyvinyl acetate, as well as natural Phospholipids such as cephalins and lecithins and synthetic phospholipids. Other additives can mineral and vegetable oils be.

It can Dyes such as inorganic pigments, e.g. 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 are used.

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

Of the active ingredient according to the invention can in its commercial Formulations and in those prepared from these formulations Forms of use mixed with other active substances, such as insecticides, attractants, Sterilizers, bactericides, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. To the Count insecticides for example, phosphoric acid esters, Carbamates, carboxylic esters, chlorinated hydrocarbons, phenylureas, by microorganisms Fabrics u.a.

Especially favorable Mixing partners are e.g. the following:

fungicides:

2-phenylphenol; 8-hydroxyquinoline sulfate; Acibenzolar-S-methyl; aldimorph; amidoflumet; Ampropylfos; Ampropylfos-potassium; andoprim; anilazine; azaconazole; azoxystrobin; benalaxyl; Benodanil; benomyl; Benthiavalicarb-isopropyl; Benzamacril; Benzamacril-isobutyl; bilanafos; binapacryl; biphenyl; bitertanol; Blasticidin-S; bromuconazole; Bupirimate; Buthiobate; butylamine; Calcium polysulfides; capsimycin; captafol; captan; carbendazim; carboxin; carpropamid; carvones; chinomethionat; Chlobenthiazone; Chlorfenazole; chloroneb; chlorothalonil; chlozolinate; Clozylacon; cyazofamid; cyflufenamid; cymoxanil; Cypro conazole; cyprodinil; cyprofuram; Dagger G; debacarb; dichlofluanid; dichlone; dichlorophen; diclocymet; Diclomezine; dicloran; diethofencarb; Difenoconazole; diflumetorim; dimethirimol; dimethomorph; dimoxystrobin; diniconazole; Diniconazole-M; dinocap; diphenylamines; Dipyrithione; Ditalimfos; dithianon; dodine; Drazoxolon; edifenphos; epoxiconazole; ethaboxam; ethirimol; etridiazole; famoxadone; fenamidone; Fenapanil; fenarimol; Fenbuconazole; fenfuram; fenhexamid; Fenitropan; fenoxanil; fenpiclonil; fenpropidin; fenpropimorph; ferbam; fluazinam; Flubenzimine; fludioxonil; flumetover; flumorph; fluoromides; fluoxastrobin; fluquinconazole; flurprimidol; flusilazole; flusulfamide; flutolanil; flutriafol; folpet; Fosetyl-Al; Fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; Furcarbanil; Furmecyclox; guazatine; Hexachlorobenzene; hexaconazole; hymexazol; imazalil; Imibenconazole; Iminoctadine triacetate; Iminoctadine tris (albesilate); iodocarb; ipconazole; iprobenfos; iprodione; iprovalicarb; Irumamycin; isoprothiolane; Isovaledione; kasugamycin; Kresoxim-methyl; mancozeb; maneb; Meferimzone; mepanipyrim; mepronil; metalaxyl; Metalaxyl-M; metconazole; methasulfocarb; Methfuroxam; metiram; metominostrobin; Metsulfovax; mildiomycin; myclobutanil; myclozoline; natamycin; nicobifen; nitrothal; Noviflumuron; nuarimol; ofurace; orysastrobin; oxadixyl; Oxolinic acid; Oxpoconazole; oxycarboxin; Oxyfenthiin; paclobutrazol; Pefurazoate; penconazole; pencycuron; phosdiphen; phthalides; picoxystrobin; piperalin; Polyoxins; Polyoxorim; Probenazole; prochloraz; procymidone; propamocarb; Propanosine-sodium; propiconazole; propineb; proquinazid; prothioconazole; pyraclostrobin; Pyrazohos; pyrifenox; pyrimethanil; pyroquilon; Pyroxyfur; Pynolnitrine; Quinconazole; quinoxyfen; quintozene; Simeconazole; spiroxamine; Sulfur; tebuconazole; tecloftalam; Tecnazene; Tetcyclacis; tetraconazole; thiabendazole; Thicyofen; Thifluzamide; Thiophanate-methyl; thiram; Tioxymid; Tolclofos-methyl; tolylfluanid; triadimefon; triadimenol; Triazbutil; triazoxide; Tricyclamide; Tricyclazole; tridemorph; trifloxystrobin; triflumizole; triforine; triticonazole; Uniconazole; Validamycin A; vinclozolin; Zineb; ziram; zoxamide; (2S) -N- [2- [4 - [[3- (4-chlorophenyl) -2-propynyl] oxy] -3-methoxyphenyl] ethyl] -3-methyl-2 - [(methylsulfonyl) amino] -butanamide ; 1- (1-naphthalenyl) -1H-pynole-2,5-dione; 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyridine; 2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide; 2-chloro-N- (2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl) -3-pyridinecarboxamides; 3,4,5-trichloro-2,6-pyridinedicarbonitrile; Actinovate; cis-1- (4-chlorophenyl) -2- (1H-1,2,4-triazole-1-yl) cycloheptanol; methyl 1- (2,3-dihydro-2,2-dimethyl-1H-inden-1-yl) -1H-imidazole-5-carboxylate; monopotassium carbonate; N- (6-methoxy-3-pyridinyl) -cyclopropanecarboxamide; N-butyl-8- (1,1-dimethylethyl) -1-oxaspiro [4.5] decan-3-amine; Sodium tetrathiocarbonate;
and copper salts and preparations, such as Bordeaux mixture; Copper hydroxide; Copper naphthenates; Copper oxychloride; Copper sulfate; Cufraneb; Cuprous oxides; mancopper; Oxinecopper.

bactericides:

bronopol, Dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, Octhilinone, furancarboxylic acid, Oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides:

Abamectin, ABG-9008, acephate, acequinocyl, acetamiprid, acetoprole, acrinathrin, AKD-1022, AKD-3059, AKD-3088, alanycarb, aldicarb, aldoxycarb, allethrin, alpha-cypermethrin (alphamethrin), amidoflumet, aminocarb, amitraz, avermectin , AZ-60541, azadirachtin, azamethiphos, azinphos-methyl, azinphos-ethyl, azocyclotin,
Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Bacillus thuringiensis strain EG-2348, Bacillus thuringiensis strain GC-91, Bacillus thuringiensis strain NCTC-11821, Baculoviruses, Beauveria bassiana, Beauveria tenella, Benclothiaz, Bendiocarb, Benfuracarb, Bensultap, Benzoximate , Beta-Cyfluthrin, Beta-Cypermethrin, Bifenazate, Bifenthrin, Binapacryl, Bioallethrin, Bioallethrin-S-cyclopentyl-isomer, Bioethanomethrin, Biopermethrin, Bioresmethrin, Bistrifluron, BPMC, Brofenprox, Bromophos-ethyl, Bromopropylate, Bromfenvinfos (-methyl), BTG -504, BTG-505, Bufencarb, Buprofezin, Butathiofos, Butocarboxim, Butoxycarboxim, Butylpyridaben,
Cadusafos, camphechlor, carbaryl, carbofuran, carbophenothione, carbosulfan, cartap, CGA-50439, quinomethionate, chlordane, chlordimeform, chloethocarb, chloroethoxyfos, chlorfenapyr, chlorfenvinphos, chlorofluorazuron, chlormephos, chlorobenzilates, chloropicrin, chlorproxyfen, chlorpyrifos-methyl, chlorpyrifos (-ethyl ), Chlovaporthrin, chromafenozide, cis-cypermethrin, cis-resmethrin, cis-permethrin, clocythrin, cloethocarb, clofentezine, clothianidin, clothiazoben, codlemone, coumaphos, cyanofenphos, cyanophos, cycloprene, cycloprothrin, cydia pomonella, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin , Cyphenothrin (1R-trans-isomer), Cyromazine,
DDT, deltamethrin, demeton-S-methyl, demeton-S-methyl sulphone, diafenthiuron, dialifos, diazinon, dichlorofenthione, dichlorvos, dicofol, dicrotophos, dicyclanil, diflubenzuron, dimefluthrin, dimethoates, dimethylvinphos, dinobutone, dinocap, dinotefuran, diofenolane, disulfonyl, Docusate-sodium, Dofenapine, DOWCO-439,
Eflusilanate, Emamectin, Emamectin benzoate, Empenthrin (1R isomer), Endosulfan, Entomopthora spp., EPN, Esfenvalerate, Ethiofencarb, Ethiprole, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimfos,
Famphur, Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenfluthrin, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fensulfothion, Fenthion, Fentrifanil, Fenvalerate, Fipronil, Flonicamide, Fluacrypyrim, Fluazuron, Flubenzimines, Flubrocythrinates, Flucycloxuron , Flucythrinate, Flufenerim, Flufenoxuron, Flufenprox, Flumethrin, Flupyrazofos, Flutenzine (Flufenzine), Fluvalinate, Fonofos, Formetanate, Formothion, Fosmethilane, Fosthiazate, Fubfenprox (Fluproxyfen), Furathiocarb,
Gamma-cyhalothrin, gamma-HCH, gossyplure, grandlure, granulosis viruses,
Halfenprox, Halofenozide, HCH, HCN-801, Heptenophos, Hexaflumuron, Hexythiazox, Hydramethylnone, Hydroprene,
IKA-2002, Imidacloprid, Imiprothrin, Indoxacarb, Iodofenphos, Iprobenfos, Isazofos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,
Japonilure,
Kadethrin, nuclear poly-derviruses, kinoprene,
Lambda-Cyhalothrin, Lindane, Lufenuron,
Malathion, mecarbam, mesulfenfos, metaldehyde, metam-sodium, methacrifos, methamidophos, metharhizium anisopliae, metharhizium flavoviride, methidathion, methiocarb, methomyl, methoprene, methoxychlor, methoxyfenozide, metofluthrin, metolcarb, metoxadiazone, mevinphos, milbemectin, milbemycin, MKI-245, MON-45700, monocrotophos, moxidectin, MTI-800,
Naled, NC-104, NC-170, NC-184, NC-194, NC-196, Niclosamide, Nicotine, Nitenpyram, Nithiazine, NNI-0001, NNI-0101, NNI-0250, NNI-9768, Novaluron, Noviflumuron,
OK-5101, OK-5201, OK-9601, OK-9602, OK-9701, OK-9802, Omethoate, Oxamyl, Oxydemetonemethyl,
Paecilomyces fumosoroseus, parathion-methyl, parathion (-ethyl), permethrin (cis-, trans-), petroleum, PH-6045, phenothrin (1R-trans isomer), phenthoates, phorates, phosalones, phosmet, phosphamidone, phosphocarb, phoxim, Piperonyl butoxide, Pirimicarb, Pirimiphos-methyl, Pirimiphos-ethyl, Potassium oleate, Prallethrin, Profenofos, Profuthrin, Promecarb, Propaphos, Propargite, Propetamphos, Propoxur, Prothiofos, Prothoate, Protrifenbute, Pymetrozine, Pyraclofos, Pyresmethrin, Pyrethrum, Pyridaben, Pyridalyl, Pyridapenthione, Pyridathione, Pyrimidifen, Pyriproxyfen,
quinalphos,
Resmethrin, RH-5849, Ribavirin, RU-12457, RU-15525,
S-421, S-1833, Salithion, Sebufos, SI-0009, Silafluofen, Spinosad, Spirodiclofen, Spiromesifen, Sulfluramid, Sulfotep, Sulprofos, SZI-121,
Tau Fluvalinate, Tebufenozide, Tebufenpyrad, Tebupirimfos, Teflubenzuron, Tefluthrin, Temephos, Temivinphos, Terbam, Terbufos, Tetrachlorvinphos, Tetradifon, Tetramethrin, Tetramethrin (1R-isomer), Tetrasul, Theta-Cypermethrin, Thiacloprid, Thiamethoxam, Thiapronil, Thiatriphos, Thiocyclam hydrogen oxalate, thiodicarb, thiofanox, thiometone, thiosultap-sodium, thuringiensin, tolfenpyrad, tralocythrin, tralomethrin, transfluthrin, triarathene, triazamates, triazophos, triazuron, trichlophenidines, trichlorfone, trichloroermatitis, triflumuron, trimethacarb,
Vamidothion, Vaniliprole, Verbutin, Verticillium lecanii,
WL-108477, WL-40027,
YI-5201, YI-5301, YI-5302,
XMC, xylylcarb,
ZA-3274, zeta-cypermethrin, zolaprofos, ZXI-8901,
the compound 3-methyl-phenyl-propylcarbamate (Tsumacide Z),
the compound 3- (5-chloro-3-pyridinyl) -8- (2,2,2-trifluoroethyl) -8-azabicyclo [3.2.1] octane-3-carbonitrile (CAS Reg. No. 185982-80 -3) and the corresponding 3-endo isomer (CAS Reg. No. 185984-60-5) (see WO-96/37494, WO-98/25923),
and preparations containing insecticidal plant extracts, nematodes, fungi or viruses.

Also a mixture with other known active substances, such as herbicides, fertilizers, Growth regulators, safeners or semiochemicals is possible.

The active ingredients according to the invention can also when used as insecticides in their commercial Formulations and in those prepared from these formulations Application forms in mixture with synergists are present. synergists are compounds that increase the effect of the active ingredients without the added synergist itself must be active.

The active ingredients according to the invention can also when used as insecticides in their commercial Formulations and in those prepared from these formulations Application forms in mixtures with inhibitors are present, the one Degradation of the active substance after application in the environment of the plant, on the surface of plant parts or in plant tissues.

Of the Active substance content prepared from the commercial formulations Application forms can vary widely. The drug concentration the application forms may range from 0.0000001 up to 95% by weight of active ingredient, preferably between 0.0001 and 1 wt .-%.

The Application is done in a custom forms adapted to the applications Wise.

at the application against hygiene and storage pests is characterized by the active ingredient by an excellent residual effect on wood and clay as well by a good alkali stability on limed Documents out.

As already mentioned above, can According to the invention, all plants and their parts are treated. In a preferred embodiment are wild or by conventional biological breeding methods, such as crossing or protoplast fusion obtained plant species and Treated plant varieties and their parts. In a further preferred embodiment are transgenic plants and plant varieties produced by genetic engineering Methods if necessary in combination with conventional methods were obtained (Genetic Modified Organisms) and treated their parts. The term "parts" or "parts of plants" or "plant parts" has been explained above.

Especially plants according to the invention are preferred the respective commercial or plant varieties in use. Among plant varieties one understands plants with new characteristics ("Traits"), which by both conventional breeding, by mutagenesis or by recombinant DNA techniques are. This can Be varieties, biotypes and genotypes.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also give rise to superadditive ("synergistic") effects. Thus, for example, reduced application rates and / or extensions of the spectrum of action and / or enhancement of the effect of the substances and agents usable according to the invention, better plant growth, increased tolerance to high or low temperatures, he increased tolerance to dryness or to water or soil salt content, increased flowering, easier harvest, 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 possible, beyond the actual expected effects.

The preferred plants or plant varieties to be treated according to the invention to be treated include all plants which, as a result of the genetic engineering modification, obtained genetic material which gives these plants particularly advantageous valuable properties ("traits"). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased tolerance to dryness or to bottoms salt, increased flowering, 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 emphasized examples of such properties are an increased defense of the plants against animal and microbial pests, as against insects, mites, phytopathogenic fungi, bacteria and / or viruses as well as an increased tolerance of the plants against certain herbicidal active substances. Examples of transgenic plants include the important crops such as cereals (wheat, rice), corn, soybean, potato, cotton, tobacco, oilseed rape and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with corn, soybean, potato , Cotton, tobacco and oilseed rape. Traits which are particularly emphasized are the increased defense of the plants against insects, arachnids, nematodes and snails by toxins which are formed in the plants, in particular those which are produced by the genetic material from Bacillus thuringiensis (for example by the genes CryIA (a) , CryIA (b), CryIA (c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF and their combinations) in the plants (hereinafter "Bt plants"). Traits also highlight the increased resistance of plants to fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits which are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (eg "PAT" gene). The genes which confer the desired properties ("traits") can also occur in combinations with one another in the transgenic plants. Examples of "Bt plants" are maize varieties, cotton varieties, soya bean varieties and potato varieties may be mentioned, under the trade names YIELD GARD ^® (for example maize, cotton, soya beans), KnockOut ^® (for example maize), StarLink ^® (for example maize), Bollgard ^® ( cotton), NuCOTN ^® (cotton) and NewLeaf ^® (potato). Examples of herbicide-tolerant plants are maize varieties, cotton varieties and soybean varieties may be mentioned, under the trade names Roundup Ready ^® (tolerance to glyphosate, for example maize, cotton, soya bean), Liberty Link ^® (tolerance to phosphinotricin, for example oilseed rape), IMI ^® (tolerance against imidazolinone) and ^STS® (tolerance to sulfonylureas eg corn). Herbicide-resistant (conventionally grown on herbicide tolerance) plants are also the varieties marketed under the name Clearfield ^® (eg corn) mentioned. Of course, these statements also apply to future or future marketed plant varieties with these or future developed genetic traits.

The listed Plants can particularly advantageous according to the invention with the compounds of the general Formula I or the active substance mixtures according to the invention be treated. The specified in the active ingredients or mixtures above Preferential ranges also apply to the treatment of these plants. Particularly emphasized is the Plant treatment with the compounds specifically listed herein or mixtures.

The active compounds of the invention act not only against plant, hygiene and storage pests, but also in the veterinary sector against animal parasites (ectoparasites) such as ticks, leather ticks, mange mites, mites, flies (stinging and licking), parasitic fly larvae, lice, hair pieces, Featherlings and fleas. These parasites include:
From the order of the Anoplurida eg Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.
From the order of Mallophagida and the suborders Amblycerina and Ischnocerina eg Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.
From the order Diptera and the suborders Nematocerina and Brachycerina eg 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., Cal liphora 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 siphon adapter eg Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
From the order of Heteropterida eg Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
From the order Blattarida eg Blatta orientalis, Periplaneta americana, Blattela germanica, Supella spp ..
From the subclass of Acari (Acarina) and the orders of meta and mesostigmata eg 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 Actinedida (Prostigmata) and Acaridida (Astigmata) eg 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.

The active ingredients according to the invention of the formula (I) are also suitable for controlling arthropods, the agricultural livestock, such as Cattle, sheep, goats, Horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, Ducks, geese, Bees, other pets such as e.g. Dogs, cats, caged birds, aquarium fish and so-called experimental animals, e.g. Hamster, guinea pig, Rats and mice affected. By fighting These arthropods are said to be deaths and reductions in performance (in the case of meat, milk, wool, hides, eggs, Honey, etc.) are reduced, so that through the use of the active compounds of the invention a more economical and easier animal husbandry is possible.

The Application of the active compounds according to the invention happens in the veterinary sector in a known manner by enteral administration in the form of, for example Tablets, capsules, potions, Drenchen, granules, pastes, boluses, the feed-through process, of suppositories, by parenteral administration, such as by injections (Intramuscular, subcutaneously, intravenously, intraperitoneal, etc.), implants, by nasal application dermal application in the form of, for example, diving or bathing (Dipping), spraying (spray), infusing (Pour-on and spot-on), washing, powdering and with help of active substance-containing moldings, like collars, Ear tags, tail tags, limb bands, halters, marking devices etc.

at the application for Livestock, poultry, Pets etc. can be the active ingredients of the formula (I) as formulations (For example, powders, emulsions, flowable agents) containing the active ingredients in an amount of 1 to 80 wt .-%, directly or after 100 up to 10 000-fold dilution apply or use as a chemical bath.

It was also found that the Compounds of the invention show a high insecticidal activity against insects, the technical Destroy materials.

By way of example and preferably without limiting however, the following insects are mentioned:
Beetles such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec. Tryptodendron spee. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus;
Hymenoptera such as Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur;
Termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus;
Bristle tails like Lepisma saccharina.

Under technical materials are non-living in the present context Materials, such as preferably plastics, adhesives, Glues, papers and cartons, leather, wood, woodworking products and paints.

All it is particularly preferable for the insect infestation protected Material around wood and woodworking products.

By wood and woodworking products, which can be protected by the composition according to the invention or mixtures containing it, is to be understood by way of example:
Timber, wooden beams, railway sleepers, bridge parts, boat jetties, wooden vehicles, crates, pallets, containers, telephone poles, wooden cladding, wooden windows and doors, plywood, chipboard, carpentry or wood products, which are generally used in home construction or joinery.

The Active ingredients can as such, in the form of concentrates or general Formulations such as powders, granules, solutions, suspensions, emulsions or pastes are applied.

The mentioned formulations in a manner known per se, e.g. by mixing the active ingredients with at least one solvent or diluent, Emulsifier, dispersing and / or binding or fixing agent, water repellent, optionally siccative and UV stabilizers and optionally Dyes and pigments and other processing aids.

The insecticides used for the protection of wood and wood-based materials Agents or concentrates contain the active ingredient according to the invention in a concentration of 0.0001 to 95 wt .-%, in particular 0.001 to 60% by weight.

The Amount of funds used or concentrates is of the type and depending on the occurrence of the insects and on the medium. The optimal application rate can be determined in each case by test series become. In general, however, it is sufficiently from 0.0001 to 20% by weight, preferably 0.001 to 10 wt .-%, of the active ingredient, based on the to be protected Material to use.

When solvent and / or diluents serves an organic-chemical solvent or solvent mixture and / or an oily one 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.

When organic-chemical solvents are preferably oily or oil-like solvent with an evaporation number over 35 and a flash point above 30 ° C, preferably above 45 ° C used. As such low-volatility, water-insoluble, oily and oily solvent become appropriate mineral oils or their aromatic fractions or mineral oil-containing solvent mixtures, preferably White spirit, petroleum and / or alkylbenzene used.

Advantageous get mineral oils with a boiling range of 170 to 220 ° C, white spirit with a boiling range from 170 to 220 ° C, spindle oil with a boiling range of 250 to 350 ° C, petroleum or aromatics from Boiling range of 160 to 280 ° C, turpentine and the like. For use.

In a preferred embodiment become liquid aliphatic hydrocarbons having 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 locker oil and / or Monochloronaphthalene, preferably α-monochloronaphthalene.

The organic low volatility oily or oily solvent with an evaporation number over 35 and a flash point above 30 ° C, preferably above 45 ° C, can partially by light or medium volatile organic-chemical solvents be replaced, with the proviso that this Solvent mixture also an evaporation number over 35 and a flash point above 30 ° C, preferably above 45 ° C, having and that Insecticide-fungicide mixture in this solvent mixture soluble or is emulsifiable.

To a preferred embodiment becomes part of the organic chemical solvent or solvent mixture or an aliphatic polar organic chemical solvent or solvent mixture replaced. Preferably, hydroxyl and / or ester and / or Ether group-containing aliphatic organic-chemical solvents such as glycol ethers, esters or the like. For use.

In the context of the present invention, organic-chemical binders are the water-dilutable and / or soluble or dispersible or emulsifiable synthetic resins and / or binding drying oils used in the organic-chemical solvents used, in particular binders consisting of or containing an acrylate resin, a vinyl resin, eg polyvinyl acetate, polyester resin, polycondens sations- or polyaddition resin, polyurethane resin, alkyd resin or modified alkyd resin, phenolic resin, hydrocarbon resin such as indene-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 Resin used as a binder may be in the form of an emulsion, Dispersion or solution, be used. Bitumen or bituminous substances can also be used as binders up to 10% by weight. In addition, known dyes, Pigments, water repellents, scents and inhibitors or corrosion inhibitors and the like. Be used.

Prefers is according to the invention as organic-chemical binder at least one alkyd resin or modified alkyd resin and / or a drying vegetable oil on average or in the concentrate. Preferred according to the invention Alkyd resins with an oil content of more than 45% by weight, preferably 50 to 68% by weight.

The mentioned Binder may be wholly or partly by a fixative (mixture) or a plasticizer (mixture) are replaced. These additives should a volatilization prevent the active ingredients and crystallization or precipitation. Preferably, they replace 0.01 to 30% of the binder (based on 100% of the binder used).

The Plasticizers come from the chemical classes of phthalates such as dibutyl, dioctyl or Benzylbutylphthalat, phosphoric acid esters such as tributyl phosphate, adipic acid ester such as di (2-ethylhexyl) adipate, stearates such as butyl stearate or amyl stearate, Oleates such as butyl oleate, glycerol ethers or higher molecular weight glycol ethers, Glycerol ester and p-toluenesulfonic acid ester.

fixative are chemically based on polyvinyl alkyl ethers such as e.g. polyvinyl methyl or ketones such as benzophenone, ethylene benzophenone.

When solvent or diluent In particular, water is also suitable, if appropriate as a mixture with one or more of the above organic chemical solvent or diluents, Emulsifiers and dispersants.

One particularly effective wood protection is achieved by large-scale impregnation e.g. Vacuum, double vacuum or printing process achieved.

The ready to use means optionally further insecticides and optionally also contain one or more fungicides.

When additional Zumischpartner preferably come in WO 94/29 268 mentioned Insecticides and fungicides in question. The ones mentioned in this document Links are more explicit Component of the present application.

Very particularly preferred admixing partners may be insecticides such as chlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25, flufenoxuron, hexaflumuron, transfluthrin, thiacloprid, methoxyfenozide, triflumuron, clothianidin, spinosad, tefluthrin,
and fungicides such as epoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole, cyproconazole, metconazole, imazalil, dichlorofluid, tolylfluanid, 3-iodo-2-propynylbutylcarbamate, N-octylisothiazolin-3-one and 4,5-dichloro-N-octylisothiazoline -3-on, his.

at the same time can the compounds of the invention for protection against the growth of objects, in particular hulls, sieves, Nets, structures, wharves and signal systems connected with sea or brackish water are used.

growth by sessile Oligochaeten, like Kalkröhrenwürmer as well as by shells and Species of the group Ledamorpha (barnacles), like different lepas and scalpel species, or by species of the group Balanomorpha (barnacles), like Balanus or Pollicipes species, increases the frictional resistance of Ships and guides increased in consequence by Energy consumption and above Beyond frequent Dry dock stays at a significant increase in operating costs.

In addition to the vegetation by algae, for example Ectocarpus sp. and Ceramium sp., comes in particular the vegetation by sessile Entomostraken groups, which under the name Cirripedia (tendrils crayfish) are of particular importance.

It was now surprisingly found that the Compounds of the invention alone or in combination with other active ingredients, a superb Antifouling (antifouling) effect exhibit.

By Use of compounds of the invention alone or in combination with other active ingredients, can be applied to the Use of heavy metals such as e.g. 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 bis-thiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bis-thiocarbamate, Zinc and copper salts of 2-pyridinethiol-1-oxide, Bisdimethyldithiocarbamoylzinc ethylene bisthiocarbamate, zinc oxide, Copper (I) ethylene-bisdithiocarbamate, Copper thiocyanate, copper naphthenate and Tributylzinnhalogeniden omitted or significantly reduce the concentration of these compounds become.

The ready-to-use antifouling paints may possibly have others Active ingredients, preferably algicides, fungicides, herbicides, molluscicides or other antifouling agents.

Suitable combination partners for the antifouling agents according to the invention are preferably:
Algicides such as 2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine, dichlorophene, diuron, endothal, fentin acetate, isoproturon, methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;
Fungicides such as benzo [b] thiophenecarboxylic cyclohexylamide S, S-dioxide, dichlofluanid, fluoro-folpet, 3-iodo-2-propynyl-butylcarbamate, tolylfluanid and azoles such as azaconazoles, cyproconazoles, epoxyconazoles, hexaconazoles, metconazoles, propiconazoles and tebuconazoles;
Molluscicides such as fentin acetate, metaldehyde, methiocarb, niclosamide, thiodicarb and trimethacarb, Fe-chelates,
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-pyridinethiol-1-oxide, pyridine-triphenylborane, tetrabutyldistannoxane, 2,3,5,6-tetrachloro-4- (methylsulfonyl) -pyridine, 2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram disulfide and 2,4,6- Trichlorphenylmaleinimid.

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

The Antifouling agent according to the invention also contain the usual Ingredients such as e.g. in Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, Antifouling Marine Coatings, Noyes, Park Ridge, 1973.

Antifouling paints contained in addition to the algicides, fungicides, molluscicides and insecticides according to the invention Active ingredients, in particular binders.

Examples for recognized Binders are polyvinyl chloride in a solvent system, chlorinated rubber in a solvent system, Acrylic resins in a 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 Bitumens, asphalt and epoxy compounds, small amounts of chlorinated rubber, chlorinated polypropylene and vinyl resins.

Possibly Paint also contains inorganic pigments, organic Pigments or dyes which are preferably insoluble in seawater. Furthermore, can Coating materials, such as rosin, contain a controlled Allow release of the active ingredients. The paintings can also Plasticizers, modifiers which influence the rheological properties as well as other conventional ones Contain ingredients. Also in self-polishing antifouling systems can the compounds of the invention or the above mixtures are incorporated.

The active compounds are also suitable for controlling animal pests, in particular insects, arachnids and mites, which are used in enclosed spaces, such as, for example, apartments, factory halls, offices, vehicle cabins and the like. occurrence. They can be used to control these pests, alone or in combination with other active ingredients and adjuvants 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 Scorpionidea eg Buthus occitanus.
From the order of the Acarina eg Argas persicus, Argas reflexus, Bryobia ssp., Dermanyssus gallinae, Glyciphagus domesticus, Ornithodorus moubat, Rhipicephalus sanguineus, Trombicula alfreddugesi, Neutrombicula autumnalis, Dermatophagoides pteronissimus, Dermatophagoides forinae.
From the order of the Araneae eg Aviculariidae, Araneidae.
From the order of the Opiliones eg Pseudoscorpiones chelifer, Pseudoscorpiones cheiridium, Opiliones phalangium.
From the order of the Isopoda eg Oniscus asellus, Porcellio scaber.
From the order of the Diplopoda eg Blaniulus guttulatus, Polydesmus spp ..
From the order of Chilopoda eg Geophilus spp ..
From the order of Zygentoma eg Ctenolepisma spp., Lepisma saccharina, Lepismodes inquilinus.
From the order of the Blattaria eg 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 Saltatoria eg Acheta domesticus.
From the order of the Dermaptera eg Forficula auricularia.
From the order of the Isoptera eg Kalotermes spp., Reticulitermes spp.
From the order of Psocoptera eg Lepinatus spp., Liposcelis spp.
From the order of Coleoptera, for example, 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 Diptera eg Aedes aegypti, Aedes albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus, Culex pipiens, Culex tarsalis, Drosophila spp., Fannia canicularis, Musca domestica, Phlebotomus spp., Sarcophaga carnaria , Simulium spp., Stomoxys calcitrans, Tipula paludosa.
From the order of Lepidoptera eg Achroia grisella, Galleria mellonella, Plodia interpunctella, Tinea cloacella, Tinea pellionella, Tineola bisselliella.
From the order of the Siphonaptera, for example, Ctenocephalides canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans, Xenopsylla cheopis.
From the order of the Hymenoptera, for example, Camponotus herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus, Monomorium pharaonis, Paravespula spp., Tetramorium caespitum.
From the order of Anoplura eg Pediculus humanus capitis, Pediculus humanus corporis, Phthirus pubis.
From the order of Heteroptera eg Cimex hemipterus, Cimex lectularius, Rhodinus prolixus, Triatoma infestans.

The Application in the field of household insecticides takes place alone or in combination with other suitable active substances, such as phosphoric esters, Carbamates, pyrethroids, neonicotinoids, growth regulators or agents from other known classes of insecticides.

The Application is in aerosols, non-pressurized sprays, e.g. Pump and atomizer sprays, Fog machines, foggers, foams, Gels, evaporator products with evaporator plates 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 gels, as granules or dusts, in straw baits or Bait stations.

Preparation Examples:

Example 1 + 2

1 - [(2'-chloro-pyridin-5'-yl) methyl] -4- (spirocyclopropyl) imidazolidin-2-ylidene-nitro amine

1 - [(2'-chloro-pyridin-5'-yl) methyl] -5- (spirocyclopropyl) imidazolidin-2-ylidene-nitro amine

To a mixture of 64 mg (0.41 mmol) of 4- (spirocyclopropyl) -imidazolidin-2-ylidene-nitroamine and 66 mg (0.41 mmol) of 2-chloro-5-chloromethyl-pyridine (COMP) in 2 200 ml (1.43 mmol) of potassium carbonate are added to acetonitrile and the mixture is heated Reaction mixture at 70 ° C for 24 hours. Then you leave cool to room temperature, filtered from undissolved Residue off, washes 3 times with 5 ml of acetonitrile and the filtrate is concentrated. The obtained Crude product is purified by column chromatography on 10 g of flash silica gel column [Pillar 2 × 20 cm, methanol / methylene chloride 1:20, Rf = 0.30].

64 mg (56% of theory) of a (1: 1) mixture of 1 - [(2'-chloro-pyridin-5'-yl) -methyl] -4- (spirocyclopropyl) -imidazolidin-2-ylidene are obtained -nitroamine and 1 - [(2'-chloro-pyridin-5'-yl) -methyl] -5- (spirocyclopropyl) -imidazolidin-2-ylidene-nitroamine in the form of a light yellow oil which can be separated by chromatography.
IR (film): ν = 3090 (Ar-H), 3050 (cPr-H), 2980, 2950 (CH ₂ ), 1563, 1544, 1461 (CH ₂ ), 1446, 1282 (NNO ₂ ), 1241, 1107 , 1025, 952, 817 (Ar-H), 784 (Ar-H), 752 (Ar-H) cm ^-1 .
1 - ((2'-chloro-pyridin-5'-yl) methyl] -4- (spirocyclopropyl) imidazolidin-2-ylidene-nitro amine:
¹ H-NMR (300 MHz, CDCl ₃ , additional NOESY): δ = 0.82-0.88 (m, 2H, cPr-H); 1.10-1.16 (m, 2H, cPr-H); 3.52 (s, 2H, 4-H); 4.28 (m, 2H, NCH ₂ ); 7.34-7.37 (d, ³ J = 8.2 Hz, 1H, 3'-H); 7.69-7.73 (dd, ⁴ J = 2.5 Hz, ³ J = 8.2 Hz, 1H, 4'-H); 8.03 (br s, 1H, NH); 8.30-8.31 (d, ⁴ J = 2.5 Hz, 1H, 6'-H) ppm.
¹³ C-NMR (75.5 MHz, CDCl ₃ , additional CH correlation HMQC): δ = 12.36 (2C, cPr-C); 42.32 (C-5); 45.20 (C-4); 52.03 (NCH ₂ ); 124.77 (C-5 '); 131.44 (C-3 '); 139.05 (C-4 '); 149,22 (C-2 '); 151.58 (C-6 '); 161.31 (C-2) ppm.
1 - [(2'-chloro-pyridin-5'-yl) methyl] -5- (spirocyclopropyl) imidazolidin-2-ylidene-nitro amine:
¹ H-NMR (300 MHz, CDCl ₃ , additional NOESY): δ = 0.70-0.76 (m, 2H, cPr-H); 1.03-1.08 (m, 2H, cPr-H); 3.87 (s, 2H, 4-H); 4.28 (m, 2H, NCH ₂ ); 7.29-7.32 (d, ³ J = 8.2 Hz, 1H, 3'-H); 7.62-7.66 (dd, ⁴ J = 2.6 Hz, 3J = 8.2 Hz, 1H, 4'-H); 8.22-8.23 (d, 47 = 2.6 Hz, 1H, 6'-H, 8.30 (br s, 1H, NH) ppm.
¹³ C-NMR (75.5 MHz, CDCl ₃ , additional CH correlation HMQC): δ = 8.55 (2C, cPr-C); 38.89 (C-5); 39.83 (C-4); 49.97 (NCH ₂ ); 124.49 (C-5 '); 129.69 (C-3 '); 137.95 (C-4 '); 147.98 (C-2 '); 151.03 (C-6 '); 151.03 (C-6 '; 160.36 (C-2) ppm.
MS (EI, 70 eV); m / z (%): 283/281 (14/14) [M ⁺ ], 237/235 (19/50) [M ⁺ -NO ₂ ]; 128/126 (32/100) [CH ₂ (C ₅ H ₃ NCl) ⁺ ].
C ₁₁ H ₁₂ ClN ₅ O ₂ : calc. 281.0680; gef. 281.0680 (MS)

Analogous to Production Example 1 + 2 and according to the general description the production process according to the invention can for example, the compounds listed in Table 1 below of the formula (I).

Table 1: Examples of the compounds of the formula (I)

Starting materials of the formula (II):

Example (II-1)

4- (spiro cyclopropyl) imidazolidine-2-ylidene-nitro amine

In a 50 ml flask, 2.0 g (36 mmol) of potassium hydroxide were dissolved in 5.0 ml of water and treated with 2.3 g (22 mmol) of nitroguanidine. To this mixture was added a solution of 2.7 g (17 mmol) of 1- (aminomethyl) -cyclopropylamine dihydrochloride in 10 ml of water and stirred at 70 ° C. for 24 hours. The mixture was allowed to cool to room temperature, filtered from the insoluble solid, washed with water (2 x 5 mL), and the solvent removed. The residue was extracted with dichloromethane (3 × 20 ml), concentrated again, and then purified by column chromatography on 20 g of silica (column: 2.5 × 20 cm, dichloromethane, Rf = 0.70). In this case, it was possible to obtain 0.923 g (35% of theory) of 4- (spirocyclopropyl) -imidazolidin-2-ylidene-nitroamine in the form of a colorless solid (mp: 118 ° C.).
IR (pill): ν = 2966 (CH ₂ ), 1588, 1554, 1476 (CH ₂ ), 1364, 1295 (NNO ₂ ), 1198, 1100, 1070, 985 cm ^-1 .
¹ H-NMR (250 MHz, CDCl _3): δ = 0.70 to 0.75 (m, 2H, cPr-H); 0.92-0.97 (m, 2H, cPr-H); 3.60 (s, 2H, CH ₂ ); 8.44 (br s, 1H, NCH); 8.70 (br s, 1H, NH) ppm.
¹³ C-NMR (62.9 MHz MHz, CDCl ₃ , add. DEPT): δ = 12.26 (-, 2C, cPr-C); 37.42 (C _quart , C-4); 46.52 (-, C-5) ppm.
MS (EI, 70 eV); m / z (%): 156 (18) [M ⁺ ], 110 (27) [M ⁺ - NO ₂ ], 94 (25) [M ⁺ - NO ₂ - NH ₂ ], 55 (100) [HNC ( = N) NH ⁺ ].
C ₅ H ₈ N ₄ O ₂ : calc. 156.0647; gef. 156.0647 (MS).

Starting materials of the formula (VI):

Example (VI-1)

1- (aminomethyl) cyclopropylamine dihydrochloride

In a 100 ml two-necked flask, 500 mg (470 μmol, corresponding to 3 mol% with respect to the number of benzyl groups) of palladium on activated carbon (oxidic form, Merck-Schuchardt, Art. 807104) in 25 ml of methanol / dichloromethane (DCM) (10: 1) and stirred to saturation for 2 hours under a hydrogen atmosphere. Then, a solution of 1.35 g (3.4 mmol) of N, N-dibenzyl-1 - [(N ', N'-dibenzylaminomethyl) -cyclopropyl] -amine in 10 ml of methanol / dichloromethane (DCM) (10 1) and the mixture stirred at room temperature for 10 hours. The reaction mixture was then filtered through Celite, 10 ml of 5M ethereal HCl added and the solvent removed. In this case, 602 mg (yield> 95%) of the expected product could be obtained as dihydrochloride, according to the ¹ H-NMR spectrum, small traces (<5%) of impurity were included. The hydrochloride was used without further purification for subsequent reactions.
IR (pill): ν = 3384 (NH ₂ ), 3050 (cPr-H), 2950 (CH ₂ ), 1658, 1632, 1454 (CH ₂ ), 1214, 1198, 974 cm ^-1 .
¹ H-NMR (250 MHz, CD ₃ OD): δ = 1.07 (m, 4H, cPr-H); 3.21 (s, 2H, CH ₂ ) ppm.
¹³ C-NMR (62.9 MHz, CD ₃ OD, additional DEPT): δ = 11.46 (-, 2C, cPr-C); 33.83 (C _quart , C-1); 45.61 (-, C-1 ') ppm.
MS (EI, 70 eV); m / z (%): 106 (34) [M ⁺ + HCl - NH ₂ ], 86 (90) [M ⁺ ], 69 (100), 58 (67) [M ⁺ + 2H - CH ₂ NH ₂ ].

Precursors to (VI-1):

(A) N, N-Dibenzyl-1 - [(N ', N'-dibenzylaminomethyl) -cyclopropyl] -amine

6.4 g (15 mmol) of N, N-dibenzylaminoacetic acid N ', N'-dibenzylamide were dissolved in 20 ml of tetrahydrofuran and admixed with 4.3 ml (18 mmol) of methyl titanium triisopropoxide. Subsequently, 11 ml (33 mmol) of a 3.0 M solution of ethylmagnesium bromide were added and the mixture was stirred overnight at room temperature. After hydrolysis and extractive work-up, the resulting mixture was chromatographed on 250 g of silica (column: 4.5 × 40 cm, DCM, Rf = 0.60) to give 3.14 g (47% of theory) of the N, N -dibenzyl-1 - [(N ', N'-dibenzylaminomethyl) -cyclopropyl] -amine as a colorless solid (mp: 135 ° C).
IR (pill): ν = 3083 (Ar-H); 3028 (cPr-H); 2935 (CH ₂ ); 2800, 1493, 1452 (CH ₂ ); 1363, 1212, 1123, 1023, 746 (Ph-H); 698 (Ph-H).
¹ H-NMR (250 MHz, CDCl _3): δ = 0.31-.36 (m, 2H, cPr-H); 0.42-0.45 (m, 2H, cPr-H); 2.63 (s, 2H, CH ₂ ); 3.60 (s, 4H, NBn ₂ ); 3.82 (s, 4H, NBn ₂ ), 7.05-7.51 (m, 20H, Ph-H) ppm.
¹³ C-NMR (62.9 MHz, _CDCl3, Additional DEPT.): Δ = 14.06 (-, 2C, cPr-C); 40.35 (C _quart , C-1); 56.66 (-, 2C, CH ₂ Ph); 57.01 (-, CH ₂ ); 59.60 (-, 2C, CH ₂ Ph); 126.35 (+, Ph-C); 127.02 (+, Ph-C); 128.30 (+, Ph-C); 128.78 (+, Ph-C); 129.17 (+, Ph-C); 139.69 (C " _quart , 2C, Ph-C); 140.96 (C " _quart , 2C, Ph-C) ppm.
MS (DCI, NH ₃₎ m / z (%): 447 (100) [M ⁺ H +]; 357 (32) [M ⁺ + H - Bn]; 265 (5) [M ⁺ + H - 2 Bn]; 196 (9) [NBn ₂ ⁺ ].

(B) N, N-dibenzylaminoacetic acid N ', N'-dibenzylamide

A solution of 77 ml (400 mmol) of dibenzylamine in 180 ml of dichloromethane (DCM) was cooled in an ice bath to 5 ° C (internal thermometer and mechanical stirrer used). Subsequently, a solution of 8.7 ml (100 mmol) of bromoacetic acid bromide in 50 ml of DCM was added dropwise such that the temperature did not rise above 10 ° C. (duration about 2 hours). The reaction mixture was stirred at room temperature overnight and then filtered from the solid, washed with DCM (3 x 50 mL) and concentrated in vacuo. The residue was taken up again with 250 ml of water and 250 ml of DCM, the aqueous phase extracted with DCM (3 × 50 ml), washed with 50 ml of saturated sodium chloride solution and concentrated after drying over magnesium sulfate. The highly viscous residue was purified by column chromatography on 500 g of silica (column: 10 × 40 cm, DCM, Rf = 0.25). This gave 39.9 g (92% of theory) of N, N-dibenzylaminoacetic acid N ', N'-dibenzyl-amide as a colorless solid (mp: 187 ° C).
IR (pill): ν = 3085 (Ar-H); 3062, 3028, 2921 (CH ₂ ); 2835, 2803, 2720, 1702, 1651 (C = O); 1604 (CON), 1495, 1452 (CH ₂ ); 1363, 1206, 1077, 1028, 989, 967, 747 (Ph-H); 699 (Ph-H) cm ^-1 . ¹ H-NMR (250 MHz, CDCl ₃ ): δ = 3.35 (s, 2H, COCH ₂ ); 3.77 (s, 4H, NCH ₂ Ph); 4.33, 4.57 (s, 4H, CONHBn ₂ ); 7.17-7.33 (m, 20H, Ph-H) ppm.
¹³ C-NMR (62.9 MHz, CDCl ₃ , add. DEPT): δ = 47.72, 49.14 (-, CON (CH ₂ Ph) ₂ ); 55.48 (-, CH2); 58.83 (-, 2C, N (CH ₂ Ph) ₂ ); 126.35 (+, Ph-C), 127.13 (+, Ph-C), 127.18 (+, Ph-C), 127.33 (+, Ph-C), 128.17 (+, Ph-C), 128.24 (+, Ph-C), 128.55 (+, Ph-C), 128.59 (+, Ph-C), 129.19 (+, Ph-C); 136.46 (C " _quart , Ph-C); 137.22 (C _quart , Ph-C); 138.51 (C " _quart , 2C, Ph-C); 171.16 (C _quart , CO) ppm.
MS (EI, 70 eV); m / z (%): 434 (1) [M ⁺ ], 343 (72) [M ⁺ - Bn], 210 (79) [M ⁺ - CONBn ₂ ], 91 (100) [Bn ⁺ ]

Application examples:

Example A

• Myzus test (spray treatment) Solvent: 78 parts by weight of acetone 1.5 parts by weight of dimethylformamide emulsifier: 0.5 part by weight of alkylaryl polyglycol ether

to Preparation of a suitable preparation of active ingredient 1 part by weight of active compound is mixed with the stated amounts solvent and emulsifier and diluted concentrate with emulsifier-containing water to the desired concentration.

Discs of Chinese cabbage (Brassica pekinensis) from all stages of the Green Peach aphid (Myzus persicae) are infested with a drug preparation the desired Concentration sprayed.

To the desired Time the effect is determined in%. 100% means that all aphids killed were; 0% means that no aphids have been killed.

at show this test e.g. the compounds of the preparation examples 1, 2, 3, 4, 8 and 10 are effective.

Table A Plant Harmful Insects Myzus Test (Spray Treatment)

Example B

• Phaedon test (spray treatment) Solvent: 78 parts by weight of acetone 1.5 parts by weight of dimethylformamide emulsifier: 0.5 part by weight of alkylaryl polyglycol ether

to Preparation of a suitable preparation of active ingredient 1 part by weight of active compound is mixed with the stated amounts solvent and emulsifier and diluted concentrate with emulsifier-containing water to the desired concentration.

Discs of Chinese cabbage (Brassica pekinensis) with an active ingredient preparation of desired concentration sprayed and after drying with larvae of horseradish beetle (Phaedon cochleariae).

To the desired Time the effect is determined in%. 100% means that all beetle larvae killed were; 0% means that no beetle larvae have been killed.

at show this test e.g. the compounds of the preparation examples 1, 4 and 7 good activity.

Table B Plant Harmful Insects Phaedon Test (Spray Treatment)

Example C

• Spodoptera frugiperda test (spray treatment) Solvent: 78 parts by weight of acetone 1.5 parts by weight of dimethylformamide emulsifier: 0.5 part by weight of alkylaryl polyglycol ether

to Preparation of a suitable preparation of active ingredient 1 part by weight of active compound is mixed with the stated amounts solvent and emulsifier and diluted concentrate with emulsifier-containing water to the desired concentration.

Discs of maize leaves (Zea mays) are with an active ingredient preparation of the desired Concentration sprayed and after drying with caterpillars of the armyworm (Spodoptera frugiperda) occupied.

To the desired Time the effect is determined in%. 100% means that all Caterpillars killed were; 0% means that no caterpillar has been killed.

at show this test e.g. the compounds of the preparation examples 1, 3 and 4 good activity.

Table C Plant Harmful Insects Spodoptera frugiperda test (spray treatment)

Claims (11)

Compounds of the formula (I)

in which A ^{1 represents} a single bond, methylene or dimethylene, A ^{2 represents} a single bond, methylene or dimethylene, A ^{3 represents} O (oxygen), S (sulfur) or the group NR ² , wherein R ² is hydrogen, optionally substituted by cyano, halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl or C ₁ -C ₄ alkylsulfonyl-substituted alkyl having 1 to 6 carbon atoms, or in each case optionally halogen-substituted alkenyl or alkynyl having in each case 2 to 6 carbon atoms, R ^{1 is} hydrogen or alkyl having 1 to 4 carbon atoms, Y ^{1 is} cyanoimino (N-CN), nitroimino (N-NO ₂ ) or nitromethylene ( CH-NO ₂ ), and Y ^{2 is} in each case optionally substituted by nitro, cyano, halogen, 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, C ₁ -C ₄ haloalkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ haloalkylsulfinyl, C ₁ -C ₄ -Alkylsulfony 1 or C ₁ -C ₄ -haloalkylsulfonyl-substituted aryl having 6 or 10 carbon atoms or heterocyclyl having up to 9 carbon atoms, 1 to 5 nitrogen atoms and / or an oxygen or sulfur atom. Process for the preparation of compounds of the formula (I) according to Claim 1, characterized in that (a) compounds of the formula (II)

in which A ¹ , A ² , A ³ and Y ^{1 have} the meaning given in claim 1, with compounds of the formula (III)

in which R ¹ and Y ^{2 have} the meaning given in claim 1 and X is a leaving group selected from halogen, methylsulfonyloxy, trifluoromethylsulfonyloxy, if appropriate in the presence of one or more reaction auxiliaries and if appropriate in the presence of one or more diluents, or b) compounds of the formula (IV)

in which A ¹ , A ² , A ³ , R ¹ and Y ^{2 have} the meaning given in claim 1, with compounds of the formula (V)

in which Y ^{1 has} the meaning given in claim 1 and X ¹ and X ^{2 are} identical or different and represent a leaving group from the series amino, methoxy, ethoxy, phenoxy, nitrophenoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, Ethylsulfonyl, optionally in the presence of one or more reaction auxiliaries and if appropriate in the presence of one or more diluents. Compounds of formula (I) according to claim 1, characterized in that A ^{1 represents} a single bond, methylene or dimethylene, A ^{2 represents} a single bond, methylene or dimethylene and A ¹ and A ² are different in each individual case, A ^{3 is} O, S or the group NR ² , where R ^{2 is} hydrogen, in each case optionally by cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i Propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-, i-, s-, n- or neo-pentyl or is in each case optionally substituted by fluorine, chlorine or bromine substituted ethenyl, propenyl, butenyl, pentenyl, ethynyl, propynyl, butynyl or pentynyl, R ^{1 is} hydrogen, methyl, ethyl, n- or i-propyl, Y ^{1 is} cyanoimino (N-CN) or nitroimino (N-NO ₂ ), and Y ^{2 is} in each case optionally substituted by nitro, cyano, Fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, fluorodichloromethyl, chlorodifluoromethyl, fluoroethyl, chloroethyl, difluoroethyl, dichloroethyl, Chlorofluoroethyl, trifluoroethyl, trichloroethyl, chlorodifluoroethyl, fluorodichloroethyl, tetrafluoroethyl, pentafluoroethyl, fluoropropyl, chloropropyl, difluoropropyl, dichloropropyl, chlorofluoropropyl, trifluoropropyl, trichloropropyl, tetrafluoropropyl, pentafluoropropyl, perfluoropropyl, methoxy, ethoxy, n- or i-propoxy, fluoromethoxy, difluoromethoxy, Phenyl, furyl, tetrahydrofuryl Thiazolyl, isothiazolyl, pyrazolyl, Oxadiazolyl, thiadiazolyl, triazolyl, pyridinyl, pyrimidinyl, pyridazinyl or pyrazinyl. Compounds of the formula (I) according to Claim 1, characterized in that A ^{1 is} a single bond or methylene, A ^{2 is} a single bond or methylene and A ¹ and A ² are different in each individual case, A ^{3 is} O, S or the group NR ² , where R ^{2 is} hydrogen, in each case optionally by cyano, fluorine, chlorine, bromine, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, Ethylsulfinyl, methylsulfonyl or ethylsulfonyl-substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, or represents in each case optionally substituted by fluorine, chlorine or bromine substituted propenyl, butenyl, propynyl or butynyl. R ^{1 is} hydrogen, methyl or ethyl, Y ^{1 is} cyanoimino, and Y ^{2 is} in each case optionally nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, difluoromethyl, dichloromethyl, trifluoromethyl, Trichloromethyl, fluorodichloromethyl, chlorodifluoromethyl, fluoroethyl, chloroethyl, difluoroethyl, dichloroethyl, chlorofluoroethyl, trifluoroethyl, trichloroethyl, chlorodifluoroethyl, fluorodichloroethyl, tetrafluoroethyl, pentafluoroethyl, methoxy, ethoxy, n- or i-propoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, fluoroethoxy, chloroethoxy , Difluoroethoxy, dichloroethoxy, trifluoroethoxy, tetrafluoroethoxy, pentafluoroethoxy, fluoropropoxy, difluoropropoxy, dichloropropoxy, chlorofluoropropoxy, trifluoropropoxy, tetrafluoropropoxy, pentafluoropropoxy or perfluoropropoxy-substituted phenyl, furyl, tetrahydrofuryl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, pyridinyl, pyrimidinyl , Pyridazinyl or pyrazinyl. Compounds of the formula (I) according to Claim 1, characterized in that A ^{3 is} S (sulfur) or the grouping NR ² , where R ^{2 is} hydrogen, R ^{1 is} hydrogen, and Y ^{2 is} in each case optionally nitro, Cyano, fluoro, chloro, bromo, methyl, ethyl, methoxy or ethoxy substituted thiazolyl or pyridinyl. Compounds of the formula (II)

in which A ¹ , A ² , A ³ and Y ^{1 have} the meanings given in claim 1. Compounds of the formula (IV)

in which A ¹ , A ² , A ³ , R ¹ and Y ^{2 have} the meanings given in claim 1. Pesticides, characterized by the content of at least one compound of the formula (I) according to claim 1. Use of compounds of the formula (I) according to claim 1 to combat of pests. Method for controlling pests, characterized in that compounds of the formula (I) according to claim 1 or agent according to claim 8 on pests and / or their habitat. Process for the preparation of pesticides, characterized that compounds of the formula (I) according to claim 1 with extenders and / or surface-active Mixtures mixed.