WO1994011352A1

WO1994011352A1 - 2-cyano-substituted benzimidazoles, their production and their use as pesticides

Info

Publication number: WO1994011352A1
Application number: PCT/EP1993/002945
Authority: WO
Inventors: Winfried Lunkenheimer; Christoph Erdelen; Ulrike Wachendorff-Neumann; Heinz-Wilhelm Dehne; Ulrich Görgens
Original assignee: Bayer Aktiengesellschaft
Priority date: 1992-11-06
Filing date: 1993-10-25
Publication date: 1994-05-26
Also published as: DE4237567A1; AU5370794A

Abstract

The invention relates to the use of partly novel substituted benzimidazoles of general formula (I) where X?1, X2, X3 and X4¿ are mutually independently hydrogen, halogen, cyano, nitro, possibly substituted alkyl, alkoxy, alkylthio, alkylsulphinyl, alkylsulphonyl or cycloalkyl, possibly substituted condensed dioxyalkylene, hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, cycloalkyloxycarbonyl, possibly substituted amino or aminocarbonyl or possibly substituted aryl, aryloxy, arylthio, arylsulphinyl, arylsulphonyl, arylsulphonyloxy, arylcarbonyl, aryloxycarbonyl, arylazo or arylthiomethyl sulphonyl, in which at least one of the substituents X?1, X2, X3 and X4¿ is different from hydrogen and halogen and in which R1 is hydrogen, alkyl or possibly substituted aryl, R2 is hydroxy, cyano or possibly substituted alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkinyloxy, alkylthio, amino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, dialkoxyphosphoryl, (hetero)aryl, (hetero)arylcarbonyl, (hetero)aryloxycarbonyl, (hetero)arylcarbonyloxy or (hetero)arylaminocarbonyl aminocarbonyloxy, as pesticides, and novel substituted benzimidazoles and their production.

Description

2-cyano-substituted benzimi dazoles, their manufacture and their use as pesticides

The invention relates to the use of partially new substituted benzimidazoles as pesticides.

It is known that certain phosphoric acid esters or carbamates such as the compound O, S-dimethyl-thiolophosphoric acid amide or the compound N-methyl-O- (2-isopropoxyphenyl) carbamate have insecticidal properties (cf., for example, DE 12 10 835 or DE 11 08 202).

However, the level of action or duration of action of these previously known compounds is not entirely satisfactory in all areas of application, in particular in the case of certain insects or at low application concentrations.

It was found that the partially new substituted benzimidazoles of the general formula (I)

in which

X ¹ , X ² , X ³ and X ⁴ independently of one another each for hydrogen, halogen, cyano, nitro, for each optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or cycloalkyl, for optionally substituted, fused-on dioxyalkylene, for hydroxycarbonyl, alkylcarbonyl , Alkoxycarbonyl, cycloalkyloxycar bonyl represent each case optionally substituted amino or aminocarbonyl, or represents in each case optionally substituted aryl, aryloxy, Aryltlύo, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonyl, aryloxycarbonyl, arylazo or arylthiomethylsulphonyl, but where at least one of the substituents X ^1, X ^2, X ³ and X ^{4 is} different from hydrogen and halogen and where

R ^{1 represents} hydrogen, alkyl, cycloalkyl or optionally substituted aryl, R ^{2 represents} hydroxy, cyano or optionally substituted in each case

Alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, amino, aminocarbonyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, dialkoxyphosphoryl, (hetero) aryl, (hetero) - arylcarbonyl, (hetero) aryloxycarbonyl, (hetero) arylcarbonooxy or (hetero) Arylaminocarbonylaminocarbonyloxy stands, have good effectiveness as a pesticide.

Depending on the type and number of the substituents, the compounds of the formula (I) can optionally be present as geometric and / or optical isomers or regioisomers or their isomer mixtures in different compositions. Both the use of the pure isomers and that of the isomer mixtures are claimed according to the invention.

Surprisingly, the substituted benzimidazoles of the general formula (I) which can be used according to the invention have a considerably better insecticidal activity compared to the phosphoric acid esters or carbamates known from the prior art, such as, for example, the compound O, S-dimethyl-thiolophosphoric acid amide or the compound N- Methyl-O- (2-isopropoxyphenyl) carbamate, which are effective compounds. Formula (I) provides a general definition of the substituted benzimidazoles which can be used according to the invention. Compounds of formula (I) are preferred in which

X ¹ , X ² , X ³ and X ⁴ independently of one another each for hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, for straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 8 carbon atoms, for cycloalkyl with 3 to 8 carbon atoms, for each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl each with 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms or for optionally single or multiple, identical or different by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms substituted, doubly linked dioxyalkylene having 1 to 5 carbon atoms, are also for

Hydroxycarbonyl, for each straight-chain or branched alkylcarbonyl or alkoxycarbonyl each having 1 to 6 carbon atoms in the alkyl part, for cycloalkyloxycarbonyl having 3 to 8 carbon atoms in the cycloalkyl part or for each optionally mono- or polysubstituted, identical or differently substituted amino or aminocarbonyl, with amino substituents in question in each case come: in each case straight-chain or branched alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 6 carbon atoms and 1 to 13 halogen atoms, alkoxyalkyl or alkylcarbonyl each having 1 to 6 carbon atoms in the individual alkyl parts or in the aryl part in each case, if appropriate, once or several times, identically or differently substituted arylcarbonyl, arylsulfonyl, arylaminocarbonyl or arylmethylsulfonyl each having 6 to 10 carbon atoms in the aryl part, the aryl substituents in each case being those mentioned in R ¹ ; moreover for aryl, aryloxy, arylthio, arylsulfinyl, arylsulfo which are mono- or polysubstituted in the aryl part, in each case mono- or polysubstituted in the same or different ways nyl, arylsulfonyloxy, arylcarbonyl, aryloxycarbonyl, arylthiomethylsulfonyl or arylazo each having 6 to 10 carbon atoms in the aryl part, the aryl substituents in each case being those mentioned in R ¹ , but at least one of the substituents X ¹ , X ² , X ³ and X ^{4 is} different from hydrogen and halogen and wherein

R ^{1 represents} hydrogen, straight-chain or branched alkyl having 1 to 8 carbon atoms or phenyl which may be mono- or polysubstituted by identical or different substituents, the following being suitable as substituents: halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy,

Alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, each straight-chain or branched alkoxyalkyl, alkoxyalkoxy, alkanoyl,

Alkoxycarbonyl or alkoximinoalkyl, each having 1 to 6 carbon atoms in the individual alkyl parts, optionally one or more times, identically or differently, by halogen and / or straight-chain or branched alkyl having 1 to 6 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 6 carbon atoms and 1 up to 13 identical or different halogen atoms substituted, doubly linked dioxyalkylene with 1 to 5 carbon atoms or optionally single or multiple, identical or different by halogen and / or straight-chain or branched alkyl with 1 to 6 carbon atoms and / or straight-chain or branched halogenoalkyl with 1 to 6 Carbon atoms and 1 to 13 identical or different halogen atoms substituted phenyl,

R ² for hydroxy, cyano or for each optionally mono- or polysubstituted, identical or differently substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or dialkoxyphosphoryl each having up to 8 carbon atoms in the individual NEN is alkyl or alkenyl or alkynyl parts, the following being suitable as substituents:

Halogen, straight-chain or branched alkoxy having 1 to 8 carbon atoms or optionally mono- or polysubstituted, identically or differently substituted aryl having 6 to 10 carbon atoms, the aryl substituents mentioned in R ^{1 being} suitable,

R ² furthermore represents amino or aminocarbonyl which may be mono- or disubstituted in the same way or differently, the substituents being suitable: straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched alkenyl having 2 to 8 carbon atoms, cycloalkyl having 3 to 8 Carbon atoms, alkoxycarbonyl, alkylthio-carbonyl, alkoxythiocarbonyl or alkylthio-thiocarbonyl each with 1 to 8 carbon atoms in the individual straight-chain or branched alkyl parts, doubly linked, ring-closed alkanediyloxycarbonyl with 2 to 6 carbon atoms in the

Alkanediyl part or in each case optionally mono- or polysubstituted, identically or differently substituted arylalkyl or aryl each having 6 to 10 carbon atoms in the aryl part and optionally 1 to 6 carbon atoms in the straight-chain or branched alkyl part, the aryl substituents in each case those mentioned in R ^{1 being} suitable,

R ² also represents aryl, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy or arylaminocarbonylaminocarbonyloxy, each of which is mono- or polysubstituted by identical or different substituents, each having 6 to 10 carbon atoms in the aryl part, the aryl substituents in each case being those mentioned in R ¹ ,

R ² also for heteroaryl, heteroarylcarbonyl, heteroaryloxycarbonyl, heteroarylcarbonyloxy or heteroarylaminocarbonylaminocarbonyloxy, each of which is optionally mono- or polysubstituted by identical or different substituents, each having 2 to 9 carbon atoms and 1 to 5 identical or different heteroatoms - in particular nitrogen, oxygen and / or sulfur - im Hetero- aryl part, the heteroaryl substituents in each case being the aryl substituents mentioned for R ¹ .

Compounds of the formula (I) in which

X ¹ , X ² , X ³ and X ⁴ independently of one another each for hydrogen, fluorine, chlorine, bromine, cyano, nitro, for each straight-chain or branched alkyl, alkoxy,

Alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms, for cycloalkyl having 3 to 7 carbon atoms, for each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl each having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms or for double-linked dioxyalkylene optionally substituted up to six times, identically or differently, by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms 1 to 4 carbon atoms are also hydroxycarbonyl, each straight-chain or branched alkylcarbonyl or alkoxycarbonyl each having 1 to 4 carbon atoms in the alkyl part, cycloalkyloxycarbonyl having 3 to 7 carbon atoms in the cycloalkyl part or for each optionally mono- or disubstituted, identically or differently substituted amino or aminocarbonyl, the amino substituents in each case being suitable: straight-chain or branched alkyl having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms. Alkoxyalkyl or alkylcarbonyl, each having 1 to 4 carbon atoms in the individual alkyl parts or in the aryl part, in each case optionally up to five times, the same or differently substituted arylcarbonyl, arylsulfonyl, arylaminocarbonyl or arylmethylsulfonyl each having 6 or 10 carbon atoms in the aryl part, the aryl substituents in each case being those in R ¹ mentioned in question; in addition, each aryl, aryloxy, arylthio, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonyl, aryloxycarbonyl, arylthiomethylsulfonyl or arylazo, each having 6 or 10 carbon atoms in the aryl part, in each case having 6 or 10 carbon atoms in the aryl part, in each case with aryl substituents ¹ mentioned are suitable, but at least one of the substituents X ¹ , X ² , X ³ and X ^{4 is} different from hydrogen and halogen and is for hydrogen, for straight-chain or branched alkyl having 1 to 6 carbon atoms or for optionally simply to phenyl which is substituted three times, identically or differently, the following being suitable as substituents:

Halogen, cyano, nitro, each straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 4 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 4

4 carbon atoms and 1 to 9 identical or different halogen atoms, each straight-chain or branched alkoxyalkyl, alkoxyalkoxy, alkanoyl, alkoxycarbonyl or alkoximinoalkyl, each with 1 to 4 carbon atoms in the individual alkyl parts, optionally single to six times, identical or different, by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms substituted, doubly linked dioxyalkylene having 1 to 4 carbon atoms or optionally single to five times, identical or different, by halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms substituted by phenyl, R ² for hydroxy, cyano or for each optionally mono- to pentasubstituted, identical or different by halogen-substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or dialkoxyphosphoryl, each with up to 6 carbon atoms in each Alkyl or alkenyl or alkynyl parts, or represents in each case optionally mono- to trisubstituted, identically or differently substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or dialkoxyphosphoryl each having up to 6 carbon atoms in each Alkyl or alkenyl or alkynyl parts, the substituents in each case being suitable: straight-chain or branched alkoxy having 1 to 6 carbon atoms or optionally mono- to trisubstituted, identically or differently substituted aryl having 6 or 10 carbon atoms, the aryl substituents being those mentioned in R ¹ come, R ² also represents in each case optionally mono- or disubstituted, identical or differently substituted amino or aminocarbonyl, the following being suitable as substituents: straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkenyl having 2 to 6 carbon atoms, cycloalkyl having 3 up to 7 carbon atoms, alkoxycarbonyl, alkylthio-carbonyl, alkoxythiocarbonyl or alkylthio-thiocarbonyl, each with 1 to 6 carbon atoms in the individual straight-chain or branched alkyl parts, double-linked, ring-closed alkanediyloxycarbonyl with 2 to 5 carbon atoms in the alkanediyl part or in each case, if appropriate, simply to triple, identical or differently substituted arylalkyl or aryl, each with 6 or 10 carbon atoms in the aryl part and optionally 1 to 6 carbon atoms in the straight-chain or branched alkyl part, the aryl substituents in each case being those mentioned in R ¹ ,

R ² also for aryl, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy which are each mono- to pentasubstituted or substituted in the same way or differently or arylaminocarbonylaminocarbonyloxy, each having 6 or 10 carbon atoms in the aryl part, the aryl substituents in each case being those mentioned in R ¹ ,

R ² also for heteroaryl, heteroarylcarbonyl, heteroaryloxycarbonyl which are each mono- to pentasubstituted by identical or different substituents,

Heteroarylcarbonyloxy or heteroarylaminocarbonylaminocarbonyloxy each having 2 to 9 carbon atoms and 1 to 4 identical or different heteroatoms - in particular nitrogen, oxygen and / or sulfur - is in the heteroaryl part, the heteroaryl substituents mentioned in R ¹ being suitable in each case.

Phenyl or naphthyl may be mentioned as aryl radicals, and pyridyl may be mentioned as heteroaryl radicals.

Compounds of the formula (I) in which

X ¹ , X ² , X ³ and X ⁴ independently of one another each for hydrogen, chlorine, bromine, cyano, nitro, for straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 4 carbon atoms, for cycloalkyl having 3 , 5 or 6 carbon atoms, each for straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl each having 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms or for optionally up to four times, identical or different, by halogen and / or straight-chain or branched alkyl having 1 to 3 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms, substituted, doubly linked dioxyalkylene having 1 to 3 carbon atoms, and also hydroxycarbonyl, for each straight-chain or branched alkylcarbonyl or he alkoxycarbonyl each having 1 to 3 carbon atoms in the alkyl part, for cycloalkyloxycarbonyl having 3, 5 or 6 carbon atoms in the cycloalkyl part or for in each case optionally mono- or disubstituted, identically or differently substituted Amino or aminocarbonyl, the amino substituents in each case being suitable: straight-chain or branched alkyl having 1 to 3 carbon atoms, haloalkyl having 1 to 3 carbon atoms and 1 to 7 halogen atoms, alkoxyalkyl or alkylcarbonyl each having 1 to 3 carbon atoms in the individual alkyl parts or in Phenyl part in each case optionally monosubstituted to trisubstituted, identically or differently, phenylcarbonyl, phenylsulfonyl, phenylaminocarbonyl or phenylmethylsulfonyl, the phenyl substituents in each case being those mentioned in R ¹ ; also for phenyl, phenyloxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonyloxy, phenylcarbonyl, phenyloxycarbonyl, phenylthiomethylsulfonyl or phenylazo, each of which is monosubstituted to trisubstituted by identical or different substituents, optionally substituted in the phenyl part, phenylthiomethylsulfonyl or phenylazo being possible, but the phenyl substituents mentioned are suitable in each case, but R ¹ at least one of the substituents X ¹ , X ² , X ³ or X ^{4 is} different from hydrogen and halogen and is hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms or phenyl which is mono- or disubstituted, identically or differently, where the following are suitable as substituents: halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy,

Alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 3 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms, each straight-chain or branched alkoxyalkyl, alkoxyalkoxy, alkanoyl,

Alkoxycarbonyl or alkoximinoalkyl each having 1 to 3 carbon atoms in the individual alkyl parts, optionally one to four times, identically or differently, by halogen and / or straight-chain or branched alkyl having 1 to 3 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 3 carbon atoms and 1 up to 7 identical or different halo Genetically atom-substituted, double-linked dioxyalkylene with 1 to 3 carbon atoms or optionally single to triple, identical or different, by halogen and / or straight-chain or branched alkyl having 1 to 3 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 3 carbon atoms and 1 to 7 phenyl substituted by the same or different halogen atoms,

R ² for hydroxy, cyano or for each optionally mono- to trisubstituted, identically or differently, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or dialkoxyphosphoryl each having up to 4 carbon atoms in represents the individual alkyl or alkenyl or alkynyl parts, or represents in each case optionally mono- or disubstituted, identically or differently substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or dialkoxyphosphoryl each having up to 4 carbon atoms in is the individual alkyl or alkenyl or alkynyl parts, the substituents in each case being suitable: straight-chain or branched alkoxy having 1 to 3 carbon atoms or optionally mono- or disubstituted, identically or differently substituted phenyl, where the phenyl substituents mentioned in R ¹ are suitable, R ² also f r is optionally mono- or disubstituted, identically or differently substituted amino or aminocarbonyl, the following being suitable as substituents: straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched alkenyl having 2 to 4 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, alkoxycarbonyl , Alkylthio-carbonyl, alkoxythiocarbonyl or alkylthio-thiocarbonyl each having 1 to 4 carbon atoms in the individual straight-chain or branched alkyl parts, double-linked, ring-closed alkanediyloxycarbonyl having 2 to 4 carbon atoms in the alkanediyl part or in each case optionally mono- or disubstituted, identically or differently substituted, phenylalkyl or phenyl with optionally 1 to 3 Carbon atoms in the straight-chain or branched alkyl part, the phenyl substituents in each case being those mentioned in R ¹ ,

R ² furthermore represents phenyl, phenylcarbonyl, phenyloxycarbonyl, phenylcarbonyloxy or phenylaminocarbonylaminocarbonyloxy which may be monosubstituted to trisubstituted by identical or different substituents, the phenyl substituents in each case being those mentioned in R ¹ ,

R ² also represents in each case monosubstituted to trisubstituted, identically or differently, heteroaryl, heteroarylcarbonyl, heteroaryloxycarbonyl, heteroarylcarbonyloxy or heteroarylaminocarbonylaminocarbonyloxy, each having 2 to 9 carbon atoms and 1 to 3 identical or different heteroatoms - in particular nitrogen, oxygen and / or sulfur - in the hetero atom , the heteroaryl substituents in each case being the phenyl substituents mentioned for R ¹ ,

The heteroaryl is pyridyl. In addition to the compounds mentioned in the preparation examples, the following substituted benzimidazoles of the general formula (I) may be mentioned individually:

(l)

Some of the substituted benzimidazoles of the formula (I) are known (cf., for example, DE 20 47 369; DE 20 14 293; EP 448 206; J. Chem. Soc. C, 1967, 2536-2540).

Not yet known and also a subject of the invention are substituted benzimidazoles of the formula (Ia)

in which

X ^{1 -1} , X ^2-2 , X ^3-1 and X ^4-1 independently of one another each for hydrogen, halogen, cyano, nitro, for each optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or cycloalkyl, for optionally substituted , condensed dioxyalkylene, for hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, cycloalkyloxycarbonyl, for optionally substituted amino or aminocarbonyl or for optionally substituted aryl, aryloxy, arylthio, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonyl, aryloxycarbonylthyl, aryl, at least one, are aryl, aryloxycarbonylthyl, aryl, at least one, the substituents X ^1-1 , X ^2-1 , X ^3-1 and X ^4-1 for nitro, haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, alkylsulfonyl, for optionally substituted, fused-on dioxyalkylene, for hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, Cycloalkyloxycarbonyl, each optionally substituted ized amino or ami nocarbonyl or for optionally substituted aryl, arylthio, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonyl, aryloxycarbonyl, arylazo or arylthiomethylsulfonyl and where

R ^{1 represents} hydrogen, alkyl or optionally substituted aryl,

R ² for hydroxy, cyano or for optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, amino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, dialkoxyphosphoryl, (hetero) aryl, (hetero) arylcarbonyl, (hetero) aryloxycarbonyl, (Hetero) arylcarbonyloxy or (hetero) arylaminocarbonylaminocarbonyloxy.

The known and the as yet unknown substituted benzimidazoles of the formulas (I) and (Ia) are obtained if a) 1H-benzimidazoles of the formula (II),

in which

X ¹ , X ² , X ³ and X ^{4 have} the meaning given above, with alkylating agents of the formula (III),

(lll)

in which

E stands for a suitable leaving group and

R ¹ and R ^{2 have} the meaning given above, if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary.

If, for example, 5-nitro-2-cyano-benzimidazole and chloromethyl ethyl ether are used as starting compounds, the reaction sequence of the production process can be represented by the following formula:

Formula (II) provides a general definition of the 1H-benzimidazoles required as starting materials for carrying out the production process. In this formula (II) ste hen X ¹ , X ² , X ³ and X ⁴ preferably for those radicals which have already been mentioned as preferred for this substituent in connection with the description of the compounds of the formula (I) which can be used according to the invention.

The 1H-benzimidazoles of the formula (II) are known or can be obtained in analogy to known processes (see, for example, J. Amer. Chem. Soc. 75, 2192 [1953]; US 3,576,818)

Formula (III) provides a general definition of the alkylating agents which are furthermore required as starting products for carrying out the production process. In this formula (III), R ¹ and R ² preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) which can be used according to the invention.

E stands for a leaving radical customary in alkylating agents, preferably for halogen, in particular for chlorine, bromine or iodine or for optionally substituted alkylsulfonyloxy, alkoxysulfonyloxy or arylsulfonyloxy, such as in particular methanesulfonyloxy, trifluoromethanesulfonyloxy, methoxysulfonyloxy, ethoxysulfonyloxy or p-toluenesulfonyl.

E also stands for an alcohol, alkanoyloxy or alkoxy group, such as a hydroxy, acetoxy or methoxy group, in particular if compounds of the formula (I) in which R ^{1 is} different from hydrogen are prepared using the process according to the invention should. The compounds of the formula (III) are generally known or can be obtained analogously to known processes (cf., for example, DE 20 40 175; DE 21 19 518; Synthesis 1973, 703).

Inert organic solvents are suitable as diluents for carrying out the production process. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform or 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 benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformaniiide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate or bases such as pyridine or organic acids such as formic acid or acetic acid.

The production process is preferably carried out in the presence of a suitable reaction auxiliary. All conventional inorganic or organic bases are suitable as such. These include, for example, alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as sodium hydride, sodium amide, lithium diethylamide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide , Ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate, lithium-organic compounds such as n-butyllithium and tertiary amines such as trimethylamine, triethylamine, tributylamine, di-isopropylethylamine, tetramethylguanidine , N-dimethylaniline, pyridine, piperidine, N-methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

Alternatively, organic or inorganic acids, such as, for example, sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, perfluorobutanesulfonic acid or strongly acidic ion exchangers, are also suitable as reaction auxiliaries, especially if the alkylating agents of the formula (III) E used are hydroxyl, acyloxy or alkoxy.

The production process can optionally also be carried out in a two-phase system, such as water / toluene or water / dichloromethane, if appropriate in the presence of a suitable phase transfer catalyst. Trimethyl-C ₁₃ / C ₁₅ tetrabutylammonium iodide, tetrabutylammonium bromide, tetrabutylammonium chloride, tributyl-methylphosphonium, -alkylammoniumchlorid, trimethyl-C ₁₃ / C ₁₅ -alkylammoniumbromid, Dib enzyl-dimethyl-ammonπ immethylsulfat, dimethyl-C _12: As examples of such catalysts may be mentioned / C ₁₄ alkyl benzyl ammonium chloride, dimethyl C ₁₂ / C ₁₄ alkyl benzyl ammonium bromide, tetrabutyl ammonium hydroxide, triethylbenzylammonium chloride, methyltrioctylammonium chloride, trimethylbenzylammonium chloride, 15-crown-5, 18-crown-6 or tris- [2- (2-methoxyethoxy) ethyl] amine.

The reaction temperatures can be varied within a substantial range when carrying out the production process. In general, temperatures between -70 ° C and + 200 ° C, preferably at temperatures between 0 ° C and 130 ° C.

The manufacturing process is usually carried out under normal pressure. However, it is also possible to work under increased or reduced pressure. To carry out the preparation process, 1.0 to 5.0 mol, preferably 1.0 to 2.5 mol, of alkylating agent of the formula (III) and, if appropriate, 0.01 to 0.1 mol are generally employed per mol of 1H-benzimidazole of the formula (II) 5.0 moles, preferably 1.0 to 3.0 moles of reaction auxiliary.

In a special embodiment, it is also possible to first of all use the 1H-benzimidazoles of the formula (II) in a preceding reaction step using customary silylation processes, for example using hexamethyldisilazane or trimethylsilylchloride, optionally in the presence of a suitable catalyst, such as sulfuric acid, trifluoroacetic acid, ammonium sulfate, imidazole or To silylate saccharin at temperatures between -20 ° C and + 150 ° C and to implement the 1-trimethylsilylbenzimidazoles thus obtainable in a subsequent second step with alkylating agents of the formula (II) according to the preparation process. In this case it is advantageous to add tin tetrachloride as a catalyst for the alkylation reaction (cf. e.g. Chem. Heterocycl. Comp. USSR 24, 514 [1988]).

The reaction is carried out, worked up and isolated by known processes (see also the preparation examples).

The end products of the formula (I) are purified using customary methods, for example by column chromatography or by recrystallization. The characterization takes place with the help of the melting point or with non-crystallizing compounds - in particular with regioisomer mixtures - with the help of proton nuclear magnetic resonance spectroscopy ( ¹ H-NMR).

The active substances are suitable for combating animal damage, preferably arthropods and nematodes, in particular insects and arachnids, which occur in agriculture, in forests, in the protection of stored goods and materials and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development.

The pests mentioned above include: From the order of the Isopoda e.g. Oniscus asellus, Armadillidium vulgare, Porcellio scaber;

from the order of the Diplopoda e.g. Blaniulus guttulatus;

from the order of the Chilopoda e.g. Geophilus carpophagus, Scutigera spec;

from the order of the Symphyla e.g. Scutigerella immaculata;

from the order of the Thysanura e.g. Lepisma saccharina;

from the order of the Collembola e.g. Onychiurus armatus;

from the order of the Orthoptera e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria;

from the order of the Dermaptera e.g. Auricular forficula;

from the order of the Isoptera e.g. Reticulitermes spp .;

from the order of the anoplura e.g. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp .;

from the order of the Mallophaga e.g. Trichodectes spp., Damalinea spp .;

from the order of the Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci;

from the order of the Heteroptera, for example Eurigaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp .; from the order of the Homoptera, for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum ave nae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens .; Aonidiella aurocla spp, Psidiotoc. from the order of the Lepidoptera, for example Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Agristella sppber, Bucculisellapp ., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuellellaiellaellaellaiellaellaiellaellaiellaellaiellaellaellaiellaellaellaiellaellaiellaellaiellaellaiellaellaellaiellaellaiellaellaiellaellaiellaellaiellaellaiellaellaiellaellae , Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fümiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana; from the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscehdes obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodivusisisam. , Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus holpp., Ptinus holpp. Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica;

From the order of the Hymenoptera, for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp .; from the order of the Diptera, for example Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca ., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa; from the order of the Siphonaptera, for example Xenopsylla cheopis. Ceratophyllus spp .;

from the order of the Arachnida e.g. Scorpio maurus, Latrodectus mactans;

from the order of the Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,. Chori ., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp ..

The active compounds according to the invention are notable for high insecticidal activity. They can be used with particularly good success for controlling plant-damaging insects, for example against the tobacco bud caterpillar (Heliothis virescens), and for combating plant-damaging mites, for example for the common spider mite (Tetranychus urticae).

In addition, the active compounds according to the invention have a strong fungicidal action and can be used practically to combat unwanted microorganisms. The active ingredients are also suitable for use as fungicides.

Fungicidal agents in crop protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes. Some pathogens of fungal diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubense;

Plasmopara species, such as, for example, Plasmopara viticola;

Peronospora species, such as, for example, Peronospora pisi or Peronospora brassicae; Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca Fülliginea; Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or Pyrenophora graminea

(Conidial form: Drechslera, synonym: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus (conidial form: Drechslera, synonym: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea;

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens;

Alternaria species, such as, for example, Alternaria brassicae;

Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides. The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases allows treatment above ground

Parts of plants, of seedlings and soil.

The active compounds according to the invention can be used with particularly good results to combat diseases in fruit and vegetable cultivation, such as, for example, against the pathogen causing tomato brown rot (Phytophthora infestans) or against the pathogen of apple scab (Venturia inaequalis) or for combating cereal diseases, such as against Pathogen of the powdery mildew (Erysiphe graminis) or against the pathogen of brown-furred wheat (Septoria nodorum) or against the pathogen of barley mesh spot disease (Pyrenophora teres).

Depending on their respective physical and / or chemical properties, the active compounds can be converted into the customary formulations, such as Solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active ingredient-impregnated natural and synthetic substances, fine encapsulation in polymeric substances and in coating compositions for seeds, furthermore in formulations with fuel sets, such as smoking cartridges, cans, spirals etc. , as well as ULV cold and warm fog formulations.

These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol, and the like Ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide; Solid carrier materials are suitable: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates; Solid carriers for granules are possible: for example broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; Suitable emulsifying and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydro lysates; The following may be used as dispersants: for example lignin sulfite waste liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

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 tin can be used.

The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with other active compounds, such as insecticides, attractants, sterilants, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. Insecticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, etc.

The active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms prepared from these formulations in a mixture with synergists. Synergists are compounds through which the action of the active ingredients is increased without the added synergist itself having to be active.

The active substance content of the use forms prepared from the commercially available formulations can vary within wide ranges. The active ingredient concentration of the use forms can be from 0.0000001 to 95 percent by weight of active ingredient, preferably between 0.0001 and 1 percent by weight. The application takes place in a customary manner adapted to the application forms.

When used as fungicides, the active compounds according to the invention can also be present in the formulations in a mixture with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, and also in mixtures with fertilizers and growth regulators.

When used as fungicides, the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the usual way, e.g. by pouring, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume process or to inject the active ingredient preparation or the active ingredient into the soil itself. The seeds of the plants can also be treated. In the treatment of parts of plants, when used as fungicides, the active compound concentrations in the use forms can be varied within a substantial range: they are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.

In the case of seed treatment, when used as fungicides, amounts of active compound of 0.001 to 50 g per kg of seed, preferably 0.01 to 10 g, are generally required.

In the treatment of the soil, when used as fungicides, active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the site of action. The preparation and use of the active compounds according to the invention can be seen from the examples below. Manufacturing examples:

Example 1:

A mixture of 9.0 g (0.03 mol) of 4-bromo-2-cyano-6-trifluoromethyl-1H-benzimidazole (see, for example, EP 239 508), 8.3 g (0.06 mol) of potassium carbonate , 4.2 g (0.03 mol) of N-chloromethyl-N-methyl-carbamic acid methyl ester and 105 ml of ethyl acetate is heated to the reflux temperature for 4 hours. For working up, the cooled reaction mixture is filtered, the filtrate is washed with water, dried over sodium sulfate and concentrated in vacuo. The residue can be purified by recrystallization from ether / petroleum ether (1:10) and subsequent column chromatography on silica gel (mobile phase: dichloromethane).

6.0 g (51% of theory) of N- (4-bromo-2-cyano-6-trifluoromethyl-1H-benzimidazol-1-yl-methyl) -N-methyl-carbamic acid methyl ester of melting point 138-141 ° are obtained C.

The following substituted benzimidazoles of the general formula (I) are obtained in a corresponding manner and in accordance with the general information on the preparation:

*) The ¹ H-NMR spectra were recorded in deuterochloroform (CDCI ₃ ) or hexadeutero-dimethyl sulfoxide (DMSO-dö) with tetramethylsilane (TMS) as the internal standard. The chemical shift of the N-CH ₂ -N group is given as the d-value in ppm.

Preparation of the starting compounds:

Example II-1:

A solution of 120 g (0.3 mol) of 4-bromo-2-trichloromethyl-6-trifluoromethyl-1H-benzimidazole (cf., for example, EP.) Is added dropwise to 900 ml of saturated aqueous ammonia solution at 15 ° C. to 25 ° C. while stirring 239 508) in 300 ml of ethanol and, after the addition has ended, stir for one hour at room temperature. For working up, the reaction mixture is brought to pH 1 with 4,000 ml of 20% hydrochloric acid and extracted three times with 300 ml of dichloromethane each time. The combined organic phases are dried with sodium sulfate, concentrated in vacuo and the remaining oil is purified by chromatography on silica gel (mobile phase: cyclohexane / ethyl acetate 2: 1) and crystallization from petroleum ether.

49.1 g (55% of theory) of 4-bromo-2-cyano-6-trifluoromethyl-1H-benzimidazole with a melting point of 130-134 ° C. are obtained.

The following substituted 1H-benzimidazoles of the general formula (II) are obtained in a corresponding manner:

Chloro (2-halogen-1-fluoromethyl-ethoxy) methane of the formula

in the

X stands for fluorine or chlorine, [in particular it is chloro (2-fluoro-1-fluoromethyl-ethoxy) methane (formula (I), X = fluorine) and chloro (2-chloro-1- fluoromethyl-ethoxy) methane (formula (I), X = chlorine).] can be obtained by reacting halogenated isopropanols of the formula

in the

X represents fluorine or chlorine, at -20 to + 20 ° C with formaldehyde and hydrogen chloride.

They are used to prepare substituted benzimidazoles of the formula

in the X represents fluorine or chlorine and

X ¹ , X ² , X ³ and X ⁴ independently of one another each for hydrogen, halogen, cyano, nitro, for each optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or cycloalkyl, for optionally substituted, fused-on dioxyalkylene, for hydroxycarbonyl, alkylcarbonyl , Alkoxycarbonyl, cycloalkyl oxycarbonyl, for in each case optionally substituted amino or aminocarbonyl or for in each case optionally substituted aryl, aryloxy, arylthio, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonyl, aryloxycarbonyl, arylazo or arylthiomethylsulfonyl, where X is at least one, but at least one of the substituents ² , but at least one of the substituents X is ¹ , but at least one of the substituents X is ¹ , but at least one of the substituents X is ¹ , but at least one of the substituents X is ¹ , but at least one of the substituents X denotes ¹ , , X ³ or X ⁴ for haloalkyl with

Exception of the chloromethyl radical, haloalkoxy, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, alkylsulfonyl, for optionally substituted condensed dioxyalkylene, for hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, cycloalkyloxycarbonyl, for each optionally substituted amino or aminocarbonyl or for each optionally substituted aryl,

Arylthio, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonyl, aryloxycarbonyl, arylazo or arylthiomethylsulfonyl, from benzimidazoles of the formula

example

192 g of 1,3-difluoro-2-propanol were mixed with 66 g of paraformaldehyde (finely powdered). A vigorous hydrogen chloride gas stream was then introduced at -10 ° C. with stirring until a clear 2-phase mixture had formed. The organic phase was then separated off, dried with calcium chloride and fractionally distilled in vacuo. With a boiling point of 50 to 54 ° C at 20 mbar, 183 g (60% of theory) of chloro (2-fluoro-l-fluoromethyl-ethoxy) methane were obtained. The characteristic absorptions in the NMR spectra were as follows:

¹ H NMR: 5.6 ppm and 4.55 ppm. ¹⁹ F NMR: -233 ppm.

Fluorinated 1,3-benzodioxoles of the formula

in the

X represents hydrogen, fluorine, chlorine or bromine and R ¹ and R ^{4 can be the} same or different from one another and each hydrogen, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogen-C ₁ -C ₆ alkyl, C ₆ -C ₁₀ aryl, COOH, CN, NCO, COO-C ₁ -C ₆ - alkyl, NH-C ₁ -C ₆ alkyl, N (C ₁ -C ₆ alkyl) _2, mean,

R ² and R ^{3 represent} NO ₂ or NH ₂ , can be obtained by reacting 1,2-dihydroxybenzenes or 2,3-dihydroxypyridines

in the

R ¹ to R ^{4 have} the meaning given above, in the presence of a base and a diluent at -20 to + 200 ° C with a hexafluorobutene of the formula

cis-trans

in the

X ¹ for hydrogen or halogen and

X ^{2 represents} halogen,

or by protecting 1,2-dihydroxybenzenes of the formula provided with a protective group

in the

R ¹ to R ^{4 have} the meaning given above and

R ⁵ for a protective group or

R ⁵ together with R ^{1 represent} a -C (CH ₃ ) ₂ -O radical,

first reacted with a hexafluorobutene of the formula

cis-trans

in the

X ¹ for hydrogen or halogen and X ^{2 represents} halogen, thus obtaining an intermediate of the formula

in which R ¹ to R ⁴ , R ⁵ and X ^{1 have} the meaning given above, splitting off the protective group R ⁵ from the intermediate, reacting the OH compound thus obtainable with a base and thus 1,3-benzo-dioxoles of the above formula receives.

1,3-Benzo-dioxoles, which contain two adjacent amino groups, can in a known manner by reaction with trichloroacetimidomethyl ester and then with ammonia in the corresponding benzimidazole e.g. the following formula

in which R ¹ , R ⁴ and X have the meaning given above. From these can be obtained by alkylation benzimidazole derivatives which are in the nitrogen atom with a

-Rest are substituted.

Examples

Example 1 a

2- (2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3benzodioxole

11 g of pyrocatechol were dissolved in 200 ml of dimethylfomamide and 18 g of 45% strength by weight aqueous sodium hydroxide solution were added. 20 g of 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene were added dropwise to the mixture at 75 ° C. The mixture was stirred at 75 ° C for 30 minutes. The mixture was then poured onto 500 ml of ice water and extracted with diethyl ether. The organic phase was washed with water, dried with magnesium sulfate and concentrated. The product was finally distilled in a high vacuum. The yield was 15 g (= 56%), the boiling point was 60 ° C. at 10 mbar. The NMR spectra showed the following characteristic absorptions: ¹⁹ F-NMR: -59.0 and -84.6 ppm. ¹ H NMR: 3.02 ppm.

Example 2 a

2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole 110 g of pyrocatechol were dissolved in 1,500 ml of acetonitrile and 200 g of triethylamine were added. 235 g of 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene were added dropwise to the mixture at 75 ° C. The mixture was stirred at 75 ° C for 2 hours. 1,200 ml of the solvent were then distilled off in vacuo and the residue was taken up in 1,500 ml of water. The product was extracted with diethyl ether, the organic phase was washed twice with 10% strength by weight aqueous sodium hydroxide solution and once with water. After drying with magnesium sulfate, the mixture was concentrated and fractionally distilled in vacuo. The yield was 258 g (= 84% of theory). The boiling point at 63 ° C was 12 mbar. The NMR spectra showed the following characteristic absorptions: ¹⁹ F-NMR: -66.8 and -79.7 ppm. ¹ H NMR: 4.71 ppm. Examples 3a

2- (1,1,1,4,4,4-hexafluoro-2-butenoxy) methoxybenzene

260 g of 2-methoxyphenol were dissolved in 1 1 of dimethylformamide (technical quality) and mixed with 220 g of 45% sodium hydroxide solution. Then 400 g of 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene were added dropwise at 22 ° C. with stirring. The mixture was stirred at 22 ° C for 2 hours. Then 1.5 l of ice water were added and the mixture was extracted with methylene chloride.

The combined organic phases were washed twice with 10% sodium hydroxide solution and once with saturated NaCl solution, dried with MgSO ₄ and distilled. The yield was 329 g (58% of theory), the boiling point 68-70 ° C at 12 mbar. The NMR spectra showed the following characteristic absorptions: ¹⁹ F-NMR: -57.6 and -67.9 ppm. ¹ H NMR: 5.92 ppm.

Example 4a

2- (1,1,1,4,4,4-hexafluoro-2-butenoxy) phenol 286.1 g 2- (1,1,1,4,4,4-hexafluoro-2-butenoxy) methoxybenzene from Example 3a were dissolved in a mixture of 500 ml of glacial acetic acid and 500 ml of 48% hydrobromic acid, and 5 g of triethylbenzylammonium chloride were added. The mixture was stirred at a bath temperature of 150.degree. C. until a complete conversion was reached according to the gas chromatographic control. Then allowed to cool and mixed with 2 kg of ice water. The aqueous phase was extracted thoroughly with CH ₂ Cl ₂ . After drying with MgSO ₄ , the solvent was removed and the residue was distilled in vacuo. The yield was 200 g (50% of theory), the boiling point was 80 ° C. at 16 mbar. The NMR spectra showed the following characteristic absorptions: ¹⁹ F-NMR: -59.6 and -69.6 ppm. ¹ H NMR: 6.1 ppm. Example 5a 2- (2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole

200 g of 2- (1, 1, 1,4,4,4-hexafluoro-2-butenoxy) phenol from Example 4a were dissolved in 400 ml of acetonitrile and 5 g of triethylamine were added. The mixture was stirred at 70 ° C for 4 h. Then it was distilled in vacuo. The yield was 162 g (81% of theory), the boiling point 60 ° C at 10 mbar. The NMR spectra showed the following characteristic absorptions: ¹⁹ F-NMR: -59.0 and -84.6 ppm. ¹ H NMR: 3.02 ppm.

Example 6a 2- (2-chloro-1,1,1,4,4,4-hexafluoro-2-butenoxy) -1-benzyloxybenzene

20 g of 2-benzyloxyphenol were dissolved in 100 ml of dimethylformamide and 9 g of 45% sodium hydroxide solution were added. Then 23 g of 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene were added dropwise at room temperature. After the exothermic reaction had subsided, the mixture was stirred at room temperature for 1 hour, added to water and extracted with tert-butyl methyl ether. After drying with MgSO ₄ , the solvent was removed. The yield was 29 g (74% of theory). The NMR spectra showed the following characteristic absorptions: ¹⁹ F-NMR: -59.5; -60.5; -61.7 and -62.8 ppm.

Example 7a 2- (2-chloro-1,1,1,4,4,4-hexafluoro-2-butenoxy) phenol

24.4 g of 2- (2-chloro-1,1, 1,4,4,4-hexafluoro-2-butenoxy) -1-benzyloxybenzene from Example 6a were dissolved in 150 ml of tetrahydrofuran and at room temperature for 4 hours at 3 bar Treated hydrogen in the presence of 2 g Pd / C (10%). The mixture was then filtered, concentrated and distilled in vacuo. The yield was 13.2 g (69% of theory), the boiling point 56 ° C. at 0.15 mbar. Example 8a

2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole

1 1.7 g of 2- (2-chloro-1, 1,1,4,4,4-hexafluoro-2-butenoxy) phenol from Example 7a were tert in 40 ml. -Butylmethylether dissolved and mixed with 40 ml ln sodium hydroxide solution. After stirring for 30 minutes at room temperature, the organic phase was separated, dried with MgSO ₄ and distilled. The yield was 10 g (88% of theory), the boiling point 63 ° C at 12 mbar. The NMR spectra showed the following characteristic absorptions: ¹⁹ F-NMR: -66.8 and -79.7 ppm. ¹ H NMR: 4.71 ppm.

Example 9a 2,2-Dimethyl-4- (1,1,4,4,4-hexafluoro-2-butenoxy) -1,3-benzodioxole (Formula V, R ⁵ together with R ¹ = -C (CH ₃ ) ₂ -O-residue)

46 g of 2,2-dimethyl-4-hydroxy-1,3-benzodioxole (formula IV, R ⁵ together with R ³ = -C (CH ₃ ) ₂ -O radical) were dissolved in 200 ml of N-methylpyrrolidone and with 31 g of 40% by weight aqueous sodium hydroxide solution were added. Then, with stirring at room temperature, 54.8 g of 2-chloro-1, 1,1,4,4,4-hexafluoro-2-butene was added dropwise. After stirring for 1 hour, the mixture was poured onto water and extracted with tert-butyl methyl ether. The organic phase was washed with 10% strength by weight aqueous sodium hydroxide solution, dried with magnesium sulfate and the volatile components were removed on a rotary evaporator. There remained 73.8 g (= 80% of theory) of a 95% pure product according to gas chromatography. The characteristic absorptions in the NMR spectra were: ¹⁹ F-NMR: -58.1 and -68.5 ppm. ¹ H NMR: 6.73, 6.55, 6.03 and 1.70 ppm.

Example 10a

1,2-Dihydroxy-3- (1,1,1,4,4,4-hexafluoro-2-butenoxy) -benzene 65 g of the product from Example 9a were boiled with 200 ml of concentrated aqueous hydrochloric acid for 4 hours with stirring heated at reflux. The mixture was then diluted with 300 ml of water and extracted with methylene chloride. After drying with magnesium sulfate, the organic Phase the solvent is stripped off and 54 g of a 90% pure product are obtained. Recrystallization from cyclohexane gave colorless crystals with a melting point of 105 ° C. The characteristic absorptions in the NMR spectra were as follows: ¹⁹ F-NMR -57.7 and -67.7 ppm. ¹ H NMR: 6.77, 6.50, 6.21 and 5.42 ppm.

Example 1 1a

2- (2,2,2-trifluoroethyl) -2- (trifluoromethyl) -4-hydroxy-1,3-benzodioxole (formula (I), R ¹ = OH, X = H, A = CH, R ² and R ³ = H).

43.5 g of the product from Example 10a were dissolved in 300 ml of acetonitrile and 1.5 g of triethylamine were added at room temperature. After stirring at room temperature for 2 hours, the solvent was stripped off and the residue was distilled in vacuo. The yield was 17 g (= 39% of theory), the boiling point 85 ° C. at 0.15 mbar, the melting point 65 ° C. The characteristic absorptions in the NMR spectra were as follows: ¹⁹ F-NMR: -59.0 and -84.5 ppm. ¹ H NMR: 6.80, 6.55, 6.2 and 3.01 ppm.

Example 12a

2,2-dimethyl-4- (3-chloro-1,1,1,4,4,4-hexafluoro-2-butenoxy) -1,3-benzodioxole (formula (V), R ¹ and R ⁵ together - C (CH ₃ ) ₂ -O-, X ¹ = Cl, R ² + R ³ = H, A = CH).

33.2 g of 2,2-dimethyl-4-hydroxy-1,3-benzodioxole were reacted with 47 g of 2,3-dichloro-1, 1,1,4,4,4-hexafluoro-2-butene analogously to Example 9a . The product obtained was distilled in vacuo and a 1: 1 molar mixture of cis / trans isomers was obtained. The yield was 51 g (= 70% of theory), the boiling point 70 ° C at 0.15 mbar. The characteristic absorptions in the NMR spectra were as follows: ¹⁹ F-NMR: -60.0, -61.6, -62.2 and 63.4 ppm. ¹ H NMR: 6.79, 6.65 to 6.48 and 1.7 ppm. Example 13a

1,2-Dihydroxy-3- (3-chloro-1,1,1,4,4,4-hexafluoro-2-butenoxy) benzene (formula (V), R ¹ = OH, R ² + R ³ = H, A = CH, R ⁵ = H, X ¹ = Cl)

18 g of the product from Example 12a were reacted with 50 ml of concentrated hydrochloric acid analogously to Example 10a. 15.7 g of a 97% pure product were obtained. The product was a 1: 1 molar mixture of the cis / trans isomers. The characteristic absorptions in the NMR spectra were as follows: ¹⁹ F-NMR: -60.2, -61.3, -62.2 and -63.3 ppm. ¹ H NMR: 6.80, 6.45 and 6.25 ppm.

Example 14a 2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-4-hydroxy-1,3-benzodioxole

15 g of the product from Example 13a were dissolved in 50 ml of acetonitrile and 1 ml of triethylamine was added. After stirring for 15 minutes, the solvent was removed and the residue was distilled in vacuo. For purification, the product was taken up in diethyl ether and filtered through silica. After the diethyl ether had been stripped off, 10.5 g of the product remained (= 70% of theory). The melting point was 139 to 141 ° C. The characteristic absorptions in the NMR spectra were as follows: ¹⁹ F-NMR: -66.6 and -79.3 ppm. ¹ H NMR: 8.4, 6.76, 6.60, 6.50 and 4.70 ppm.

Example 15a 5-Nitro-2- (2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole

A solution of 54.4 g of 2- (2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole in 75 ml of methylene chloride was at 10 ° C to a mixture of 40 ml of 65 wt .-% nitric acid and 40 ml of concentrated sulfuric acid. The mixture was stirred at room temperature for 1 hour, then poured onto ice water, the organic phase was separated off and the aqueous phase was extracted with methylene chloride. The combined organic phases were washed with water, dried and freed from volatile constituents. There remained 95 g of the product (= 86% of theory) with a melting point of 87 to 88 ° C. The NMR spectra showed the following characteristic absorptions: ¹⁹ F-NMR: -59.0 and -69.4 ppm. ¹ H NMR: 3.10 ppm.

Example 16a

5-nitro-2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole 613 g of 2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl - 1,3-benzodioxol from Example 2a were dissolved in 1.2 1 methylene chloride and at 0 to 10 ° C to a mixture of 400 ml of 65% nitric acid and 400 ml of conc. Dropped sulfuric acid. The mixture was subsequently stirred at room temperature for 2 hours. Then it was carefully added to 2 l of ice water and extracted with methylene chloride. The combined organic phases were washed twice with water, dried and concentrated. The yield was 652 g (93% of theory). The NMR spectra showed the following characteristic absorptions: ¹⁹ F-NMR: -66.4 and -79.2 ppm. ¹ H NMR: 4.81 ppm.

Example 17a

5,6-Dinitro-2- (2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole 317 g of the product from Example 15a were initially introduced and, with stirring, a mixture of 250 ml of 100% by weight nitric acid and 350 ml of concentrated sulfuric acid added dropwise. The mixture was stirred at 55 ° C for 2 hours. Then the batch was allowed to cool and poured onto ice water. The product was extracted with methylene chloride, washed neutral with sodium hydrogen carbonate solution, dried and freed from volatile constituents on a rotary evaporator. The yield was 339 g (= 94% of theory), the melting point 101 to 103 ° C.

The NMR spectra showed the following characteristic absorptions: ¹⁹ F-NMR: -60.9 and -86.5 ppm. ¹ H NMR: 3.18 ppm. Example 18a

5,6-Dιnitro-2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole

352 g of 5-nitro-2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole from Example 16a were initially charged and with a mixture of 250 ml of 100% strength by weight nitric acid and 350 ml of concentrated sulfuric acid. The mixture was stirred at 60 ° C for 2 hours. After cooling, it was poured onto ice water and extracted with methylene chloride. After washing with sodium bicarbonate solution and drying, the mixture was evaporated. The yield was 392 g (91% of theory), the melting point 125 ° C. The NMR spectra showed the following characteristic absorptions: ¹⁹ F-NMR: -68.5 and -81.0 ppm. ¹ H NMR: 4.86 ppm.

Example 19a

5-amino-2- (2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole

57.4 g of the product from Example 15a were dissolved in 400 ml of tetrahydrofuran and hydrogenated with hydrogen in the presence of 4 g of catalyst (palladium on carbon, 10% by weight) for 5 hours at 30 ° C. at 50 bar. The mixture was then filtered off, the solvent was removed and the residue was distilled under high vacuum. 37 g of product (= 63% of theory) with a boiling point of 83 ° C. at 0.07 mbar were obtained. ¹⁹ F NMR: -59.0 and -84.6 ppm. ¹ H NMR: 2.98 ppm.

Example 20a 5-Amino-2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole

72 g of 5-nitro-2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole from Example 16a were dissolved in 500 ml of tetrahydrofuran and 5 g of palladium on carbon (5% ig) hydrogenated for 5 hours at room temperature with 15 to 20 bar of hydrogen. It was then filtered and the solvent removed in vacuo. The yield was 60 g (93% of theory), the boiling point 80 to 82 ° C at 0.1 mbar. The NMR spectra showed the following characteristic absorptions: ¹⁹ F-NMR: -66.5 and -79.4 ppm. ¹ H NMR: 4.68 ppm. Example 21a 5,6-Diamino-2- (2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole

339 g of the product from Example 17a were dissolved in 2,000 ml of tetrahydrofuran and 20 g of catalyst (palladium on carbon, 5% by weight) were added. At 25 to 30 bar, the mixture was hydrogenated with hydrogen at room temperature for 13 hours. The mixture was then filtered off and the solvent was removed in vacuo. A solid remained. The yield was 274 g (= 96% of theory). ¹⁹ F NMR: -61.2 and -86.6 ppm. ¹ H NMR: 3.02 ppm.

Example 22a 2- (2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole

306.5 g of 2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole from Example 2a were dissolved in 500 ml of THF and mixed with 101 g of triethylamine and 30 g of palladium on carbon ( 5 wt .-%) added. The mixture was then hydrogenated with 110 bar of hydrogen at 110 ° C. for 48 h. The mixture was then filtered, the solvent was stripped off and the residue was fractionated in vacuo. The yield was 126 g (46% of theory), the boiling point was 60 ° C. at 10 mbar. The NMR spectra showed the following characteristic absorption: ¹⁹ F-NMR: -59.0 and -84.6 ppm. ¹ H NMR: 3.02 ppm.

Fluoroalkyl (en) group-containing o-phenylenediamines of the formula

in the

R ¹ for CF ₃ , OCF ₃ , SCF ₃ , SO ₂ -C ₁ -C ₆ alkyl, which can be straight-chain or branched and can be completely or partially substituted by fluorine, N (CF ₃ ) ₂ , a phenyl or phenoxy radical CF ₃ or CN in the 4-position and optionally further substituents, 1,1,2,3,3,3-hexafluoropropoxy, 1,1,2-trifluoro-2-chloroethoxy, 1,1,2,2-tetra1luoroethoxy , 1,1,2-trifluoro-2-chloroethylthio or 1,1,2,3,3,3-hexafluoropropylthio, regardless of which R ^{2 is} F, Cl, Br, CN, CH ₃ , OCF ₃ , SO ₂ -C ₁ -C ₆ alkyl, which can be straight-chain or branched and can be completely or partially substituted by fluorine, COO-C ₁ - C ₆ alkyl, COOC ₆ H ₅ , 1,1,2,2-tetrafluoroethoxy, 1,1, 2,3,3,3-hexafluoropropoxy or 1,1,2-trifluoro-2-chloroethoxy and

R ^{3 represents} hydrogen, COCH ₃ or COCF ₃ , where R ¹ and R ² together can represent an -O-CFCl-CFCl-O radical, with the exception of those in EP-A 251 013 and EP-A 487 Compounds described 286 can be obtained by using a benzene derivative of the formula

in D ¹ for CF ₃ O, CF ₃ S, CHF ₂ CF ₂ O, CHFCl-CF ₂ O, CF ₃ CHFCF ₂ O, CF ₃ CF ₂ O, CF ₃ CF ₂ CF ₂ O, CF ₃ CF ₂ S or CF ₃ CHFCF ₂ O and D ² for CF ₃ O, CF ₃ S, CHF ₂ CF ₂ O, CHFCl-CF ₂ O, CF ₃ CHF-CF ₂ O, CF ₃ CF ₂ O, CF ₃ CF ₂ CF ₂ O, CF ₃ CF ₂ S , CF ₃ CHFCF ₂ O, fluorine, chlorine, bromine, C ₁ -C ₆ alkyl or C ₁ -C ₆ alkoxy is dinitrated, the nitro groups are then reduced and thus compounds are obtained in which R ¹ and R ^{2 are} in 4- and 5-position to the amino groups and have the meaning of D ¹ and D ² .

If compounds are to be prepared in which R ^{1 has} the meaning given above and is in the 4-position to the amino groups and R ^{2 is} Cl or Br in the 5-position to the amino groups, a nitrobenzene derivative of the formula can be used, for example

in the

R ^{1 has} the meaning given in the formula and Hal represents fluorine, chlorine or bromine, react with ammonia, so replace the Hal group with an amino group and reduce the nitraniline thus obtained.

If compounds are to be prepared in which R ^{1 has} the meaning given above and is in the 4-position to the amino groups, R ^{2 is} chlorine or bromine in the 6-position to the amino groups and R ^{3 is} hydrogen, a nitraniline can be used, for example of the formula

in the

R ^{1 has} the meaning given above. react with a chlorinating or brominating agent, so insert a chlorine or bromine atom in the meta position to the nitro group and then reduce the nitro group.

Compounds are to be prepared in which R ^{1 is} a donor group in the 4-position to the two amino groups, R ^{2 is} an acceptor group, for example COO-C ₁ -C ₆ -alkyl, CN, CF ₃ or SO ₂ -C ₁ -C _{6 represents} alkyl and R3 is not hydrogen, for example, a benzene derivative of the formula

in the

D ^{1 has} the meaning given above and

A is CF ₃ , SO ₂ -C ₁ -C ₆ -alkyl, which can be straight-chain or branched and can be completely or partially substituted by fluorine, COO-C ₁ -C ₆ -alkyl or CN, mononitrate (entry of NO ₂ - Group in para position to D ¹ ), reduce the NO ₂ group to the NH ₂ group, acylate the NH ₂ group with acetic acid or trifluoroacetic acid, for example, mononitrate again (entry of this NO ₂ group into ortho-posi- tion to NHCOR groups with R = for example CH ₃ or CF ₃ ), reduce this NO ₂ group to the NH ₂ group and, if one wishes to produce a compound of the above formula with R ³ = hydrogen, split off the acyl group by saponification .

The fluoroalkyl (en) group-containing o-phenylenediamines in which R ^{3 is} hydrogen can first with trichloroacetimidomethyl ester and subsequent reaction with ammonia to 2-cyanobenzimidazoles of the following formula

implemented and then further with compounds of the formula

are implemented, wherein R ¹ and R ² assume the above scope, R ^{4 represents} hydrogen, alkyl, alkoxy or optionally substituted aryl,

R ⁵ for hydroxy, cyano or for optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, amino, aminocarbonyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, dialkoxyphosphonyl, (hetero) aryl, (hetero) arylcarbonyl, (hetero) Aryloxycarbonyl, (hetero) arylcarbonyloxy or (hetero) arylaminocarbonylaminocarbonyloxy and

A means a suitable leaving group.

Leaving groups are known to the person skilled in the art and are, for example, halogen, alkyl (alkoxy, aryl) sulfonyloxy, hydroxy or alkoxy.

Examples

Examples 1 to 6 b (Dinitration and Reduction)

Example 1 b

320 g of 1,2-bis (2-chloro-1,1,2-trifluoroethoxy) benzene were added dropwise to 500 g of a mixed acid containing 33% by weight of HNO ₃ and 67% by weight of H ₂ SO ₄ . After one hour at 40 ° C., 250 ml of 20% by weight oleum were added dropwise. The mixture was then heated to 80 ° C and stirred for 15 hours. Then a further 120 ml of 20% by weight oleum and 250 g of the above-mentioned mixed acid were added dropwise. After 6 hours at 80 to 82 ° C was cooled and poured onto ice. The organic phase was separated and washed with water. After azeotropic drying with

1,2-dichloroethane was 350 g of 96% by weight of pure 1,2-dinitro-4,5-bis- (2-chloro-1,1,2-

_n .

trifluoroethoxy) benzene obtained (oil, D 1.4832, GC 99.1%)

350 g of this dinitro compound were added dropwise to a mixture of 1.5 l of ethanol, 50 ml of water, 30 ml of concentrated aqueous hydrochloric acid and 470 g of iron filings and the mixture was heated under reflux for a total of 15 hours. The cooled solution was then filtered off, concentrated and the residue was recrystallized from cyclohexane. 216 g of 1,2-diamino-4,5-bis (2-chloro-1,1,2-trifluoroethoxy) benzene with a melting point of 58 to 60 ° C. were obtained.

Example 2 b Analogous to Example 1, the ent was obtained from 1,2-bis (1,1,2,3,3,3-hexafluoropropoxy) benzene

speaking 4,5-dinitro compound (oil, D 1,4852) and the corresponding 4,5-diamino compound (oil, 87 wt .-% pure).

Example 3 b

Analogously to Example 1, 1- (1,1,2-trifluoro-2-chloroethoxy) -2-chlorobenzene was converted into the corresponding 4,5-dinitro compound (melting point 56 to 57 ° C) and the corresponding 4,5-diamino compound ( Melting point 67 to 68 ° C) prepared. Example 4 b

Analogously to Example 1, 1-trifluoromethoxy-2-bromobenzene was converted into the corresponding 4,5-

Dinitro compound (melting point 73 to 75 ° C) and the corresponding 4,5-

Diamino compound (oil, 98 wt .-% pure, D 1.5485) prepared. Example 5 b

Analogously to Example 1, the corresponding 4,5-dinitro compound (melting point 55 to 56 ° C.) and the corresponding 4,5-diamino compound (melting point 56-57 ° C.) were prepared from 1-trifluoromethoxy-2-chlorobenzene.

Example 6 b The corresponding 4,5-dinitro compound (oil) and the corresponding 4,5-diamino compound (oil) were prepared from 1- (1,1,2,3,3,3-hexafluoropropoxy) -2-chlorobenzene .

Examples 7 to 12 b

Squeezing with ammonia and reduction Example 7 b

260 g of 3-nitro-2,5-dichlorobenzotrifluoride, 130 ml of water and 10 g of tetraethylammonium chloride were placed in an autoclave and 120 ml of liquid ammonia were injected. The mixture was then heated to 130 ° C. and stirred at this temperature for 10 hours. After cooling, the mixture was filtered off, the separated precipitate was washed with water and dried. 194 g of 2-amino-3-nitro-5-chloro-benzotrifluoride with a melting point of 67 ° C. were obtained.

134 g of the nitraniline obtained as described above were dissolved in 800 ml of ethanol, then 20 ml of water, 10 ml of concentrated aqueous hydrochloric acid and 160 g of iron filings were added. The mixture was refluxed for 15 hours, then cooled, suction filtered, the filter residue washed with dichloromethane and then the organic phases under reduced pressure from the solvent exempted. 171 g of 5-chloro-3-trifluoromethyl-1,2-diaminobenzene with a melting point of 53 ° C. were obtained.

Example 8 b

Analogously to Example 7, 3-nitro-4-amino-6-chloro-difluorochloromethoxybenzene (melting point 73 ° C.) and then 3,4-diamino-6-chloro-difluorochloromethoxybenzene ( Oil).

Example 9 b

Analogously to Example 7, 3-bromo-5-nitro-6-chlorobenzotrifluoride was first used to make 3-bromo-5-nitro-6-amino-benzotrifluoride (melting point 80 to 82 ° C.) and 3-bromo-5,6-diamino- benzotrifluoride (melting point 52 to 54 ° C).

Example 10 b

Analogously to Example 7, 3-cyano-4-chloro-5-nitro-benzotrifluoride was first converted into 3-cyano-4-amino-5-nitro-benzotrifluoride (melting point 99 to 100 ° C.) and from it 3-cyano-4,5- diamino-benzotrifluoride produced. Example 11 b

Analogously to Example 7, 3-chloro-5-nitro-6-amino-benzotrifluoride (melting point 53 to 54 ° C.) and then 3-chloro-5,6-diamino- manufactured benzotrifluoride.

Example 12b 2-Bromo-4-fluoro-5-nitro- (1,1,2-trifluoro-2-chloro) ethoxybenzene was first used to give 2-bromo-4-amino-5-nitro- (1,1, 2-trifluoro-2-chloro-ethoxy) -benzene (melting point 90 ° C) and from it 2-bromo-4,5-diamino- (1,1,2-, rifluoro-2-chloro) -ethoxybenzene. Example 13 b

(Halogenation of a nitraniline and reduction)

24 g of finely powdered 2-nitro-4-trifluoromethylmercaptoaniline were dissolved in 50 ml of trifluoroacetic acid and 18 g of bromine were metered in at 20 ° C. The mixture was then stirred at 20 ° C. for 3 hours and at 40 ° C. for a further 30 minutes. The mixture was poured into water and the product was taken up in dichloromethane. After removal of the solvent, 31 g of 6-bromo-2-nitro-4-trifluoromethyl-mercapto-aniline were obtained.

155 g of the nitraniline thus prepared were refluxed in 700 ml of ethanol with 15 ml of water, 10 ml of concentrated aqueous hydrochloric acid and 70 g of iron shavings for 15 hours, then the mixture was filtered off, the filtrate was freed from the solvent under reduced pressure and the solid Crude product recrystallized from cyclohexane. 112 g of 6-bromo-4-trifluoromethyl-mercapto-1,2-diaminobenzene with a melting point of 60 to 61 ° C. were obtained.

Example 14b Analogously to Example 13, 27 g of 2-nitro-4-trifluoromethylsulfonylaniline in 100 ml of acetic acid were brominated with 18 g of bromine.

After working up, 32 g of 2-nitro-6-bromo-4-trifluoromethylsulfonyl-anialine were obtained. Melting point 147 ° C.

32 g of the nitramine thus produced was reduced with iron filings in alcohol and aqueous hydrochloric acid. 24 g of 3-bromo-5-trifluoromethylsulfonyl-phenylene-1,2-diamine were obtained, melting point 155 ° -157 ° C.

Example 15 b

Analogously to Example 14, 27 g of 2-nitro-4-trifluoromethylsulfonyl-aniline in 100 ml of acetic acid were chlorinated with 10 g of chlorine. 29 g of 2-nitro-4-trifluoromethylsulfonyl-6-chlororaniline were obtained, melting point: 138-139 ° C. 13 g of 3-chloro-5-trifluoromethylsulfonyl-1,2-phenylenediamine (melting point: 143-145 ° C.) were obtained by reduction.

Examples 16 to 20 b

(Nitration and reduction in 2 stages) Example 16 b

263 g of 4- (2,6-dichloro-4-trifluoromethyl) phenoxyacetanilide were dissolved in 1 100 ml of dichloromethane and placed at 10 ° C. Then 88 g of 98% strength by weight nitric acid were added dropwise at this temperature. The mixture was stirred at 10 ° C. for 1 hour and at 30 ° C. for a further 2 hours. After the addition of 300 ml of water, the phases were separated and the organic phase was freed from dichloromethane under reduced pressure. There remained 253 g of 2-nitro-4- (2,6-dichloro-4-trifluoromethylphenoxy) acetanilide with a melting point of 138-140 ° C.

91 g of the acetanilide thus prepared were dissolved in 800 ml of dioxane, 10 g of Raney nickel were added and the mixture was hydrogenated at 25 to 45 ° C. in a hydrogenation apparatus with a maximum hydrogen pressure of 50 bar. After decompression and filtration, the dioxane was distilled off under a slight vacuum. There remained 65 g of 2-amino-4- (2,6-dichloro-4-trifluoromethyl-phenoxy) acetanilide with a melting point of 222-223 ° C.

Example 17 b

Analogously to Example 16, 3-trifluoromethyl-4-methoxy-acetanilide was initially 3-trifluoromethyl-4-methoxy-6-nitro-acetanilide (melting point 143-144 ° C.) and from it 3-trifluoromethyl-4-methoxy-6-amino -acetanilide (melting point 164-165 ° C).

Example 18 b

Analogously to Example 16, 3-trifluoromethyl-4-fluoro-trifluoromethylacetanilide was first converted to 3-trifluoromethyl-4-fluoro-6-nitro-trifluoromethylacetanilide (melting point 78 ° C.) and from it 3-trifluoromethyl-4-fluoro-6-amino-trifluoromethylacetanilide ( Melting point 92-93 ° C). Example 19 b

Analogously to Example 16, 3-trifluoromethyl-4-bromo-trifluoromethylacetanilide was first converted into 3-trifluoromethyl-4-bromo-6-nitro-trifluoromethylacetanilide (melting point 110-112 ° C.) and from it 3-trifluoromethyl-4-bromo-6-amino- trifluoromethylacetanilide (melting point 63 - 65 ° C).

Example 20 b

Analogously to Example 16, 3-trifluoromethylthio-4-chloro-trifluoromethylacetanilide was first converted to 3-trifluoromethylthio-4-chloro-6-nitro-trifluoromethylacetanilide (melting point 99-100 ° C.) and from it 3-trifluoromethylthio-4-chloro-6-amino- trifluoromethylacetanilide (melting point 88 - 90 ° C).

Examples of use:

In the following application examples, the compounds listed below were used as comparison substances:

N-methyl-O- (2-isoρropoxyphenyl) carbamate (see e.g. DE 11 08 202)

(B)

O, S-dimethyl-thiolophosphoric acid amide (see, for example, DE 12 10 835)

Example A:

Heliothis virescens test

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

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted with water to the desired concentration. Soybean shoots (Glycine max) are treated by dipping into the active ingredient preparation of the desired concentration and populated with the tobacco bud caterpillar (Heliothis virescens) while the leaves are still moist.

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

In this test, for example, the following compounds of the preparation examples show superior activity over the prior art: 59, 60, 61, 73 and 74.

Example B

Tetranychus test (OP-resistant)

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier, and the concentrate is diluted to the desired concentrations with water containing emulsifier. Bean plants (Phaseolus vulgaris), which are heavily infested with all stages of development of the common spider mite (Tetranychus urticae), are immersed in an active ingredient preparation of the desired concentration.

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

In this test, for example, the following compound of the preparation examples shows superior activity compared to the prior art: 13.

Example C

Venturia test (apple) / protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkyl aryl polyglycol ether To produce a suitable preparation of active compound, one part by weight of active compound is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test for protective efficacy, young plants are sprayed with the preparation of active compound until they are dripping. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the apple scab pathogen (Venturia inaequalis) and then remain in an incubation cabin at 20 ° C. and a relative air humidity of approx. 100% for one day.

The plants are then placed in a greenhouse at 20 ° C. and a relative humidity of approx. 70%. Evaluation is carried out 12 days after the inoculation.

In this test, for example, the compounds according to the preparation examples: 8, 9, 13, 74 and 75 show a clear superiority.

Claims

1. Use of substituted benzimidazoles of the general formula (I)

in which X ¹ , X ² , X ³ and X ⁴ independently of one another each represent hydrogen, halogen, cyano, nitro, each optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or cycloalkyl, for optionally substituted, fused-on dioxyalkylene, for hydroxycarbonyl ,,,, are alkylcarbonyl alkoxycarbonyl cycloalkyloxycarbonyl for each case optionally substituted amino or aminocarbonyl, or represents in each case optionally substituted aryl, aryloxy, arylthio, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonyl, aryloxycarbonyl, arylazo or arylthiomethylsulphonyl, but where at least one of the Substituentenχl, X ^2, X ³ and X ^{4 are} different from hydrogen and halogen and where

R ^{1 represents} hydrogen, alkyl or optionally substituted aryl,

R ² for hydroxy, cyano or for optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio,

Amino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, dialkoxyphosphoryl, (hetero) aryl, (hetero) arylcarbonyl, (hetero) aryl oxycarbonyl, (hetero) arylcarbonyloxy or (hetero) arylaminocarbonylaminocarbonyloxy is used as a pesticide.

Pesticides, characterized in that they contain at least one substituted benzimidazole of the formula (I) according to Claim 1.

Process for the preparation of pesticides, characterized in that substituted benzimidazoles of the formula (I) according to Claim 1 are mixed with extenders and / or surface-active agents.

Substituted benzimidazoles of the formula (Ia)

in which

X ^{1 -1} , X ^2-1 , X ^{3- 1} and X ^4-1 independently of one another each for hydrogen, halogen, cyano, nitro, for each optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or cycloalkyl, for optionally substituted , fused-on dioxyalkylene, for hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, cycloalkyloxycarbonyl, for optionally substituted amino or aminocarbonyl or for optionally substituted aryl, aryloxy, arylthio, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonyl, aryloxycarbonylthylyl, aryla, however, at least one of the substituents X ^{1 - 1} , X ^{2- 1} , X ^{3- 1} and X ^{4- 1} for nitro, haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, alkylsulfonyl, for optionally substituted, condensed dioxyalkylene, for Hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, cycloalkyloxycarbonyl, for in each case optionally substituted amino or aminocarbonyl or for in each case optionally substituted aryl, arylthio, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonyl, aryloxycarbonyl, arylazo or arylthiomethylsulfonyl and where

R ^{1 represents} hydrogen, alkyl or optionally substituted aryl,

Process for the preparation of the substituted benzimidazoles of the formula (Ia),

in which

X ^{1 - 1} , X ^{2- 1} , X ^3-1 and X ^4-1 independently of one another each for hydrogen, halogen, cyano, nitro, for each optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or Cyc loalkyl, for optionally substituted, fused-on dioxyalkylene, for hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, cycloalkyloxycarbonyl, for optionally substituted amino or aminocarbonyl or for optionally substituted aryl, aryloxy, arylthio, arylsulfinyl, arylsulfonyl, arylsulfonyloxy,

Arylcarbonyl, aryloxycarbonyl, arylazo or arylthiomethylsulfonyl, but at least one of the substituents X ^{1 - 1} , X ^{2- 1} , X ^{3- 1} and X ^{4- 1 represents} nitro, haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, alkylsulfonyl , for optionally substituted, fused-on dioxyalkylene, for hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, cycloalkyloxycarbonyl, for in each case optionally substituted amino or aminocarbonyl or for in each case optionally substituted aryl, arylthio, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonyl, arylzoylsulfonyl, aryloxy-aryloxy-aryloxy, in which

R ^{1 represents} hydrogen, alkyl or optionally substituted aryl,

Amino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, dialkoxyphosphoryl, (hetero) aryl, (hetero) arylcarbonyl, (hetero) aryloxycarbonyl, (hetero) arylcarbonyloxy or (hetero) arylaminocarbonylaminocarbonyloxy, characterized in that one a) 1H-benzimidazoles of the formula (II),

in which

(|||)

in which

E stands for a suitable leaving group and