DE4237567A1 - Pesticides - Google Patents

Abstract

The invention relates to the use of partly novel substituted benzimidazoles of general formula (I) where X<1>, X<2>, X<3> and X<4> 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>, X<2>, X<3> and X<4> is different from hydrogen and halogen and in which R<1> is hydrogen, alkyl or possibly substituted aryl, R<2> 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

The invention relates to the use of partially new substituted benzimids zolen as a pesticide.

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

The amount of action or duration of action of these known compounds is dependent yes, especially with certain insects or with low application concentrations not completely satisfactory in all areas of application.

It was found that the partially new substituted benzimidazoles of the gen my 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, cycloalkyloxycarbonyl, for each optionally substituted amino or aminocarbonyl or for each optionally substituted aryl, aryloxy, arylthio, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonyl, aryloxycarbonyl, arylazo or arylthiomethylsulfonyl
however, at least one of the substituents X ¹ , X ² , X ³ and X ^{4 is} different from hydrogen and halogen and
R ^{1 represents} hydrogen, alkyl, cycloalkyl or optionally substituted aryl,
R ² for hydroxy, cyano or for optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, amino, aminocarbonyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, dialkoxyphosphoryl, (hetero) aryl, (hetero) arylcarbonyl, (hetero) Aryloxycarbonyl, (hetero) arylcarbonyloxy or (hetero) arylaminocarbonylaminocarbonyloxy,

have good effectiveness as a pesticide.

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

Surprisingly, the substituted benzene which can be used according to the invention show imidazoles of the general formula (I) have a considerably better insecticidal activity compared to the phosphoric acid esters known from the prior art or  Carbamates, such as the compound O, S-dimethylthiolophosphoric acid amide or the compound N-methyl-O- (2-isopropoxyphenyl) carbamate, which connections that are obviously effective.

The substituted benzimidazoles which can be used according to the invention are those which Formula (I) generally defined. 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 each straight-chain or branched alkyl, alk oxy, alkylthio, alkylsulfinyl or alkylsulfonyl, each with 1 to 8 carbons Substance atoms, for cycloalkyl with 3 to 8 carbon atoms, for each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, halo genalkylsulfinyl, haloalkylsulfonyl each with 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms or for single or multiple, if appropriate, the same or differently substituted and linked 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, and also hydroxycarbonyl , for each straight-chain or branched Al kylcarbonyl or alkoxycarbonyl, each with 1 to 6 carbon atoms in the alkyl part, for cycloalkyloxycarbonyl with 3 to 8 carbon atoms in the cycloalkyl part, or for in each case optionally singly or multiply, identically or differently substituted amino or aminocarbonyl, the amino substituents being suitable in each case:
in each case straight-chain or branched alkyl having 1 to 6 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 halogen atoms, alkoxy alkyl or alkylcarbonyl each having 1 to 6 carbon atoms in the individual alkyl parts or in the aryl part, in each case optionally singly or multiply, identically or differently substituted arylcarbonyl, arylsulfonyl, arylamino carbonyl 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 ;
also for aryl, aryloxy, arylthio, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonyl, aryloxycarbonyl, arylthiomethylsulfonyl or arylazo, each with 6 to 10 carbon atoms in the aryl part, in each case with 6 to 10 carbon atoms, in each case with aryl substituents R ¹ mentioned come into question,
however, 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 stands} for hydrogen, for straight-chain or branched alkyl having 1 to 8 carbon atoms or for phenyl which is monosubstituted or polysubstituted by identical or different substituents, the following being suitable as substituents:
Halogen, cyano, nitro, each straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, halogenoalkylthio, 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 with 1 to 6 carbon atoms in the individual alkyl parts, optionally singly or multiply, identically or differently by halogen and / or straight-chain or branched alkyl with 1 to 6 carbon atoms and / or straight-chain or branched halogen alkyl with 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms substituted, doubly linked dioxyalkylene with 1 to 5 carbon atoms or optionally single or multiple, identical or ve rschie the phenyl substituted 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 to 13 identical or different halogen atoms,
R ² for hydroxy, cyano or for each optionally mono- or polysubstituted, identical or differently substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyl oxy, alkynyloxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or dialkoxyphosphoryl, each with up to 8 carbon atoms in the individual Alkyl or alkenyl or alkynyl parts is available, the following being suitable in each case:
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 also represents in each case optionally substituted once or twice, identically or differently, the substituted amino or aminocarbonyl, the following being suitable as substituents:
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, alkoxy thiocarbonyl or alkylthio-thiocarbonyl each having 1 to 8 carbon atoms in the individual straight-chain or branched alkyl parts, double-linked ring-closed alkanediyloxycarbonyl having 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 being those mentioned in R ¹ ,
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, heteroaryloxycarbonyl, heteroarylcarbonyloxy or heteroarylaminocarbonylaminocarbonyloxy, each optionally mono- or polysubstituted in the same or different ways, each having 2 to 9 carbon atoms and 1 to 5 identical or different heteroatoms - especially nitrogen, oxygen and / or sulfur in the hetero aryl part, the aryl substituents mentioned in R ¹ being suitable as heteroaryl substituents.

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 in each case 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, each for 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 optionally one 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, also for hydroxy carbonyl , for straight-chain or branched alkylc arbonyl or alk oxycarbonyl, each with 1 to 4 carbon atoms in the alkyl part, for cycloalkyl oxycarbonyl with 3 to 7 carbon atoms in the cycloalkyl part, or for in each case monosubstituted or disubstituted, identically or differently substituted amino or aminocarbonyl, the amino substituents in each case being infra:
in each case 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, if appropriate, simply to five times, the same or different substituted arylcarbonyl, arylsulfonyl, arylamino carbonyl or arylmethylsulfonyl each having 6 or 10 carbon atoms in the aryl part, the aryl substituents in each case being those mentioned in R ¹ ;
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,
however, 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 stands} for hydrogen, for straight-chain or branched alkyl having 1 to 6 carbon atoms or for optionally single to triple, identical or differently substituted phenyl, the following being suitable as substituents:
Halogen, cyano, nitro, each straight-chain or branched aryl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 4 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, halogenoalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 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 simply to six times, the same 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, double-linked dioxyalkylene having 1 to 4 carbon atoms or optionally single to five times , phenyl substituted 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,
R ² for hydroxy, cyano or for each optionally mono- to pentuplic, identically or differently substituted by halogen, alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or dialkoxyphosphoryl each having up to 6 carbon atoms in the stands for individual alkyl or alkenyl or alkynyl parts, or for each optionally single 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 is the individual alkyl or alkenyl or alkynyl parts, the following being suitable as substituents:
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 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 following being suitable as substituents:
straight-chain or branched alkyl with 1 to 6 carbon atoms, straight-chain or branched alkenyl with 2 to 6 carbon atoms, cycloalkyl with 3 to 7 carbon atoms, alkoxycarbonyl, alkylthio-carbonyl, alkoxy-thiocarbonyl or alkylthio-thiocarbonyl each with 1 to 6 carbon atoms in each straight-chain or branched alkyl parts, double-linked, ring-closed alkanediyloxycarbonyl having 2 to 5 carbon atoms in the alkanediyl part or in each case optionally single to triple, identically or differently substituted arylalkyl or aryl each having 6 or 10 carbon atoms in the aryl part and optionally 1 to 6 carbon atoms in the ge wheel-chain or branched alkyl part, the aryl substituents in each case being those mentioned in R ¹ ,
R ² also represents aryl, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy or arylaminocarbonylaminocarbonyloxy, each of which has from 6 to 10 carbon atoms in the aryl part and is optionally monosubstituted to fivefold, identical or different, the aryl substituents in each case being those mentioned in R ¹ ,
R ² also for each mono- to pentasubstituted, identically or differently substituted heteroaryl, heteroarylcarbonyl, heteroaryloxycarbonyl, 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 - in the heteroatoms stands, where the aryl substituents mentioned at R ¹ are suitable as heteroaryl substituents.

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

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 each straight-chain or branched alkyl, alkoxy, alkyl thio, alkylsulfinyl or alkylsulfonyl each having 1 to 4 carbon atoms, for cycloalkyl 3, 5 or 6 carbon atoms, each for straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfonyl, 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, double-linked di oxyalkylene having 1 to 3 carbon atoms, also for hydroxycarbonyl, for each straight chain or branched alkylcarbonyl or alkoxycar bonyl each having 1 to 3 carbon atoms in the alkyl part, for cycloalkyloxycar bonyl having 3, 5 or 6 carbon atoms in the cycloalkyl part or for each optionally single or double, identical or differently substituted amino or aminocarbonyl, where in each case infra ge come as amino substituents:
in each case 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 the phenyl part, in each case optionally simply to three times, the same or variously substituted phenylcarbonyl, phenylsulfonyl, phenylaminocarbonyl or phenylmethylsulfonyl, where the phenyl substituents mentioned in R ¹ are possible;
also for phenyl, phenyloxy, phenylthio, phenylsulfinyl, phenylsulfonyl, phenylsulfonyloxy, phenylcarbonyl, phenyloxycarbonyl, phenylthiomethylsulfonyl or phenylazo, each optionally monosubstituted to trisubstituted by identical or different substituents, phenylthiomethylsulfonyl or phenylazo, where the phenyl substituents mentioned in R ¹ are possible
however, at least one of the substituents X ¹ , X ² , X ³ or X ^{4 is} different from hydrogen and halogen, and wherein
R ^{1 stands} for hydrogen, for straight-chain or branched alkyl having 1 to 4 carbon atoms or for optionally single or double, identical or different substituted phenyl, the following being suitable as substituents:
Halogen, cyano, nitro, each straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 3 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy, halogenoalkylthio, 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 with 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 with 1 up to 3 carbon atoms and / or straight-chain or branched haloalkyl with 1 to 3 carbon atoms and 1 to 7 identical or different halogen atoms substituted, doubly linked dioxyalkylene with 1 to 3 carbon atoms or optionally single to triple, identical or different phenyl substituted 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,
R ² for hydroxy, cyano or for each optionally mono- to trisubstituted, identically or differently, halogen-substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or dialkoxyphosphoryl each having up to 4 carbon atoms in the stands for individual alkyl or alkenyl or alkynyl parts, or for each optionally single or double, identical 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 following being suitable as substituents:
straight-chain or branched alkoxy having 1 to 3 carbon atoms or optionally mono- or disubstituted, identically or differently substituted phenyl, the phenyl 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 following being suitable as substituents:
straight-chain or branched alkyl with 1 to 4 carbon atoms, straight-chain or branched alkenyl with 2 to 4 carbon atoms, cycloalkyl with 3 to 6 carbon atoms, alkoxycarbonyl, alkylthio-carbonyl, alkoxy-thiocarbonyl or alkylthio-thiocarbonyl each with 1 to 4 carbon atoms in each 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 the at R ¹ mentioned come into question,
R ² also represents phenyl, phenylcarbonyl, phenyloxycarbonyl, phenylcarbonyloxy or phenylaminocarbonylaminocarbonyloxy, each of which is monosubstituted to trisubstituted in the same or different manner, phenylaminocarbonylaminocarbonyloxy being possible, the phenyl 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 monosubstituted to trisubstituted, identically or differently, in each case with 2 to 9 carbon atoms and 1 to 3 identical or different hetero atoms - in particular nitrogen, oxygen and / or sulfur - in Hete roaryl is available, the heteroaryl substituents in each case being the phenyl substituents mentioned for R ¹ .

The heteroaryl is pyridyl.

In particular, except for the compounds mentioned in the preparation examples the following substituted benzimidazoles of the general formula (I):

(The rest -CHR ¹ R ² is marked with A in the following tables.)

The substituted benzimidazoles of the formula (I) are known in some cases (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 the subject of the invention are substituted benzene imidazoles 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 optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl or cycloalkyl, for optionally substituted, fused dioxyal, for hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, for optionally substituted amino or aminocarbonyl or for optionally substituted aryl, aryloxy, arylthio, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonyl, aryloxyyl stand,
however, at least one of the substituents X ^1-1 , X ^2-1 , X ^3-1 and X ^4-1 for nitro, haloalkyl, haloalkoxy, haloalkyl thio, haloalkylsulfinyl, haloalkylsulfonyl, alkylsulfonyl, for optionally substituted, fused-on dioxyalkylene, for hydroxycarbonyl , Alkylcarbonyl, alkoxycarbonyl, cycloalkyloxy carbonyl, represents in each case optionally substituted amino or amino carbonyl or for each 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 each optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, amino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, dialk oxyphosphoryl, (hetero) aryl, (hetero) arylcarbonyl, (hetero) aryl oxycarbonyl, (hetero) arylcarbonyloxy or (hetero) arylaminocar bonylaminocarbonyloxy.

The known and the not yet known substituted benzimidazoles are obtained of the formulas (I) and (Ia), if one

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),

in which

E stands for a suitable leaving group and
R ¹ and R ^{2 have} the meaning given above,

optionally in the presence of a diluent and optionally in counter were implemented a reaction aid.

For example, 5-nitro-2-cyano-benzimidazole and chloromethyl are used ethyl ether as starting compounds, so the reaction sequence of the manufacturer representation procedure using 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), X ¹ , X ² , X ³ and X ⁴ preferably represent those radicals which have already been mentioned as preferred for these substituents 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 be known methods (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 represents a leaving radical customary in alkylating agents, preferably Ha lied, especially for chlorine, bromine or iodine or for any substi tuiert alkylsulfonyloxy, alkoxysulfonyloxy or arylsulfonyloxy, such as in particular Methanesulfonyloxy, trifluoromethanesulfonyloxy, methoxysulfonyloxy, ethoxysul fonyloxy or p-toluenesulfonyloxy.

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 in analogy on known processes (cf. e.g. DE 20 40 175; DE 21 19 518; Synthesis 1973, 703).

Inert are used as diluents for carrying out the production process organic solvents. These include in particular aliphatic, alicy cical or aromatic, optionally halogenated hydrocarbons, as in for example gasoline, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, Hexane, cyclohexane, dichloromethane, chloroform or carbon tetrachloride; Ether,  such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dime ethyl or diethyl ether; Ketones, such as acetone, butanone or methyl isobutyl ketone; Nitriles such as acetonitrile, propionitrile or benzonitrile; Amides such as N, N-dime thylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or Hexamethylphosphoric triamide; Esters, such as methyl acetate or vinegar acid ethyl ester or bases such as pyridine or organic acids such as formic acid or acetic acid.

The manufacturing process is preferably carried out in the presence of a suitable reac tion aid carried out. As such, all the usual inorganic or organic bases in question. These include, for example, alkaline earth or alkali tall hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen car bonates, such as sodium hydride, sodium amide, lithium diethylamide, natri ummethylate, 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 car bonate or ammonium carbonate, lithium-organic compounds, such as n-butylli thium and tertiary amines, such as trimethylamine, triethylamine, tributylamine, di-iso propyl-ethylamine, tetramethylguanidine, N, N-dimethylaniline, pyridine, piperidine, N- Methylpiperidine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabi cyclonones (DBN) or diazabicycloundecene (DBU).

Alternatively, organic or inorganic come as reaction aids Acids such as sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, perfluoro butanesulfonic acid or strongly acidic ion exchanger, especially if in the used alkylating agents of formula (III) E for a hydroxy, acyloxy or alkoxy radical.

The production process can optionally also be carried out in a two-phase system, such as water / toluene or water / dichloromethane, optionally in the presence of a suitable phase transfer catalyst. Tetrabutylammo bromide, tetrabutylammonium chloride, tributyl-methylphosphonium, tri methyl-C ₁₃ / C ₁₅ trimethyl-C ₁₃ / C tetrabutylammonium iodide, -alkylammoniumchlorid, ₁₅ -alkylammoniumbromid, dibenzyl dimethyl ammonium methyl sulfate, _{dimethyl-C12:} As examples of such catalysts may be mentioned / C ₁₄ -alkyl-benzylammonium chloride, dimethyl-C ₁₂ / C ₁₄ -alkyl-benzylammonium bromide, tetrabutylammonium hydroxide, triethylbenzylammonium chloride, methyltrioctylammonium chloride, trimethylbenzylammonium chloride, 15-crown-5, 18-crown-6 or tris- [2- (2 -methoxyeth oxy) ethyl] amine.

The reaction temperatures can be used when carrying out the manufacturing process can be varied over a wide range. Generally one works at Tempera doors 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. It is however, it is also possible to work under increased or reduced pressure.

To carry out the production process, 1H-benzimidazole is used per mole of the formula (II) generally 1.0 to 5.0 mol, preferably 1.0 to 2.5 mol Alkylating agent of formula (III) and optionally 0.01 to 5.0 mol, preferably two se 1.0 to 3.0 moles of reaction aids.

In a special embodiment, it is also possible to use 1H-benzimidazoles of the formula (II) first in a preceding reaction step with the help of conventional Silylation process, for example with hexamethyldisilazane or trimethylsilylchlo rid, optionally in the presence of a suitable catalyst, such as Sulfuric acid, trifluoroacetic acid, ammonium sulfate, imidazole or saccharin Silylate temperatures between -20 ° C and + 150 ° C and the 1- Trimethylsilylbenzimidazole in a subsequent second stage with alkylly Implementing agents of formula (II) according to the manufacturing process. In this It is advantageous as a catalyst for the alkylation reaction of tin tetrachloride to add (see, for example, Chem. Heterocycl. Comp. USSR 24, 514 [1988]).

He carried out the reaction, working up and isolating the reaction products follows according to known methods (see also the manufacturing examples).  

The end products of the formula (I) are purified using customary processes, for example by column chromatography or by recrystallization.

The characterization takes place with the help of the melting point or with non-crystallizing compounds - especially with regioisomer mixtures - with the help of proton nuclear magnetic resonance spectroscopy ( ¹ H-NMR).

The active compounds are suitable for controlling animal pests, preferably Arthropods and nematodes, especially insects and arachnids, which in the Agriculture, forestry, storage and material protection, and hygiene nesector occur. They are against normally sensitive and resistant species as well as ge against all or individual stages of development.

The pests mentioned above include:

From the order of the Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber;
from the order of the Diplopoda z. B. Blaniulus guttulatus;
from the order of the Chilopoda z. B. Geophilus carpophagus, Scutigera spec .;
from the order of the Symphyla z. B. Scutigerella immaculata;
from the order of the Thysanura z. B. Lepisma saccharina;
from the order of the Collembola z. B. Onychiurus armatus;
from the order of Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leuco phaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta mi gratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria;
from the order of the Dermaptera z. B. Auricular Forficula;
from the order of the Isoptera z. B. Reticulitermes spp .;
from the order of the Anoplura z. B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp .;
from the order of the Mallophaga z. B. Trichodectes spp., Damalinea spp .;
from the order of the Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci;
from the order of Heteroptera z. B. Eurigaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp .;
from the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci, Trialeuro des vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum ave nae, Myzus spp., Phoroponasuli. , Euscelis bi lobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatel lus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp .;
from the order of the Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella ma culipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiisisppppas, Fpp., Phyllocn insula na, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuellonissella, Galline molaellaellaella, Galleria pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana;
from the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysoce phalivest, Oris ., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhyn chus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus sppus, Nidesusium sololuc spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica;
from the order of the Hymenoptera z. B. Dipaon spp., Hoplocampa spp., Lasius spp., Monomorium pharaorus, Vespa spp.,
from the order of the Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chry somyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosox spp., Stom 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 z. B. Xenopsylla cheopis, Ceratophyllus spp .;
from the order of the Arachnida z. B. Scorpio maurus, Latrodectus mactans;
from the order of Acarina z. B. Acarus siro, Argas spp., Ornithodoros spp., Der manyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipice phalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chor spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tet ranychus spp.

The active compounds according to the invention are notable for a high insecticidal action totality.

They can be used with particularly good results in combating plant damage the insects, such as against the tobacco bud caterpillar (Heliothis virescens) as well as for controlling plant-damaging mites, such as against the common spider mite (Tetranychus urticae).

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

Fungicides in crop protection are used to combat plas modiophoromycetes, 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 Pseu doperonospora 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 fuliginea;
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: Drechs lera, 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 good plant tolerance of the active ingredients in the control of plants Concentrations necessary for diseases allow treatment above ground Parts of plants, of seedlings and soil.

The active compounds according to the invention can be used with particularly good success Combating diseases in fruit and vegetable growing, such as against the pathogen of tomato brown rot (Phytophthora infestans) or against the pathogen of apple scab (Venturia inaequalis) or for combating cereal diseases such as against the pathogen of powdery mildew (Erysiphe graminis) or against the causative agent of wheat brown furs (Septoria  nodorum) or against the causative agent of barley mesh spot disease (Pyrenophora teres) can be used.

The active ingredients can depend on their respective physical and / or chemical properties can be converted into the usual formulations, such as Solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, Active ingredient-impregnated natural and synthetic substances, very fine encapsulation in polymeric substances and in coating compositions for seeds, also in formulations with Fuel sets, such as smoking cartridges, cans, spirals and. Ä., and ULV cold and Warm fog formulations.

These formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with diluents, i.e. liquid solvents, are under pressure Liquefied gases and / or solid carriers, optionally with Ver Use of surface-active agents, i.e. emulsifiers and / or dispersants agents and / or foaming agents. In case of using water as Extenders can e.g. B. also organic solvents as auxiliary solvents be used. The following are essentially suitable as liquid solvents: Aro mat, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methyl lene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. Earth Oil fractions, alcohols, such as butanol or glycol, and their ethers and esters, keto ne, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly po lare solvents, such as dimethylformamide and dimethyl sulfoxide, and water; With Liquefied gaseous extenders or carriers are such liquids meant which are gaseous at normal temperature and pressure, e.g. B. aerosol propellants, such as halogenated hydrocarbons and butane, propane, stick fabric and carbon dioxide; as solid carriers are possible: B. natural Rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, Montmo rillonite or diatomaceous earth and synthetic rock powder, such as highly disperse Silica, alumina and silicates; come as solid carriers for granules in question: e.g. B. broken and fractionated natural rocks such as calcite, marble, Pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules made of organic material such as sawdust,  Coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foam Generating funds are possible: B. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkyl aryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydro lysates; Possible dispersants are: B. lignin sulfite and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural, can be used in the formulations and synthetic powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholi pide, such as cephalins and lecithins, and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferro cyan and organic dyes such as alizarin, azo and metal phthalocyanine substances and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, mo lybdenum and tin can be used.

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

The active compounds according to the invention can be in their commercially available formulations and in the use forms prepared from these formulations in a mixture with other active ingredients, such as insecticides, attractants, sterilants, acaricides, Ne maticidal, fungicidal, growth-regulating substances or herbicides are present. Insecticides include, for example, phosphoric acid esters, carbamates, carbon acid esters, chlorinated hydrocarbons, phenylureas, by microorganisms manufactured fabrics u. a.

The active compounds according to the invention can also be used in their commercially available form tion as well as in the use forms prepared from these formulations in Mi with synergists. Synergists are connections through which we kung the active ingredients is increased without the added synergist itself active must be effective.  

The active substance content of the users prepared from the commercially available formulations Forms of application can vary widely. The drug concentration of the An Application forms can be from 0.0000001 to 95 percent by weight of active ingredient, preferably be between 0.0001 and 1 percent by weight.

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

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

When used as fungicides, the active compounds as such, in the form of their Formulations or the use forms prepared from them, such as ready-to-use Solutions, suspensions, wettable powders, pastes, soluble powders, dusts and Granules can be applied. The application is done in the usual way, e.g. B. by pouring, spraying, spraying, scattering, dusting, foaming, loading delete etc. It is also possible to use the active ingredients according to the ultra-low-volume To apply the process or the active ingredient preparation or the active ingredient itself to inject the soil. The seeds of the plants can also be treated.

In the treatment of parts of plants when used as fungicides Active substance concentrations in the application forms in a larger area are varied: They are generally between 1 and 0.0001% by weight preferably between 0.5 and 0.001% by weight.

In seed treatment, when used as fungicides in general Active substance amounts from 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g needed.  

When treating the soil when used as a fungicide active ingredient concentrations from 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02 % By weight required at the site of action.

The manufacture and use of the active compounds according to the invention are based on following examples.

Manufacturing examples example 1

A mixture of 9.0 g (0.03 mol) of 4-bromo-2-cyano-6-trifluoromethyl-1H-benzimide azole (see e.g. EP 239 508), 8.3 g (0.06 mol) potassium carbonate, 4.2 g (0.03 mol) N- Chloromethyl-N-methyl-carbamic acid methyl ester and 105 ml ethyl acetate becomes 4th Heated to reflux for hours. The cooled is worked up Filtered reaction mixture, the filtrate washed with water, ge over sodium sulfate dries and concentrated in vacuo. The residue can be recrystallized from ether / petroleum ether (1:10) and subsequent column chromatography on silica gel (Solvent: dichloromethane) clean.

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 from the melting point 138-141 ° C.  

In a corresponding manner and in accordance with the general information on the manufacture the following substituted benzimidazoles of the general formula (I):

Preparation of the starting compounds Example II-1

900 ml of saturated aqueous ammonia solution are added at 15 ° C to 25 ° C dropwise while stirring a solution of 120 g (0.3 mol) of 4-bromo-2-trichlorme thyl-6-trifluoromethyl-1H-benzimidazole (cf. e.g. EP 239 508) in 300 ml of ethanol and, after the addition has ended, stir at room temperature for one hour. To work up the reaction mixture is brought to pH 1 with 4000 ml of 20 percent hydrochloric acid and extracted three times with 300 ml of dichloromethane each. The united organic Phases are dried with sodium sulfate, concentrated in vacuo and the lead Coloring oil 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-benz are obtained imidazole melting point 130-134 ° C.  

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

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

in the

X represents fluorine or chlorine,

[Specifically, these are chloro (2-fluoro-1-fluoromethyl-thoxy) methane (formula (I), X = fluorine) and chloro (2-chloro-1-fluoromethyl-ethoxy) methane ( Formula (I), X = chlorine).]
are obtainable 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 , alkoxy carbonyl, are 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 substituents X ^1, X ² , X ³ or X ⁴ for haloalkyl with the exception of the chloromethyl radical, haloalkoxy, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, alkylsulfonyl, for optionally substituted condensed dioxyalkylene, for hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, cycloalkyloxycarbonyl, for each given n is substituted amino or aminocarbonyl or are in each case 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 two-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-1-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-benzo- and 1,3-pyridodioxoles of the formula

in the

A for CR ⁴ or N and
X represents hydrogen, fluorine, chlorine or bromine and
R ¹ to R ^{4 may be the} same or different from one another and each is hydrogen, halogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkoxy, halogen C ₁ -C ₆ alkyl, C ₆ -C ₁₀ aryl , CHO, COOH, COCl, CN, OH, NCO, COO-C ₁ -C ₆ alkyl, NO _2, NH _2, NH-C ₁ - C ₆ alkyl, N (C ₁ -C ₆ alkyl) ₂ , SO ₂ Cl, SO ₃ H, SO ₃ Na or SO ₃ K,
where two adjacent radicals from the series R ¹ to R ^{4 can} also jointly represent an optionally substituted -CH = CH-CH = CH bridge,

are obtainable by reacting 1,2-dihydroxybenzenes or 2,3-dihydroxypyri din EN

in the

A and R ¹ to R ^{3 have} the meaning given above, but R ¹ to R ³ do not represent OH, COCl or SO ₂ Cl,

in the presence of a base and a diluent at -20 to + 200 ° C with a Hexafluorobutene of the formula

in the

X ¹ for hydrogen or halogen and
X ^{2 represents} halogen,

or by protecting 1,2-dihydroxybenzenes or 2,3-dihydroxypyridines of the formula

in the

A and R ¹ to R ^{3 have} the meaning given above and
R ⁵ for a protecting group or
R ⁵ together with R ^{1 represent} a -C (CH ₃ ) ₂ -O radical,

first reacted with a hexafluorobutene of the formula

in the

X ¹ for hydrogen or halogen and
X ^{2 represents} halogen,

receives an intermediate of the formula

in the

A and R ¹ to R ³ , R ⁵ and X ^{1 have} the meaning given above,
splits off the protective group R ⁵ from the intermediate product,

the OH compound thus obtainable is reacted with a base and 1,3-benzo- or 1,3-pyrido-dioxoles of the above formula is obtained.  

One can 1,3-benzo- and 1,3-pyrido-dioxoles of the above formula, the one Contain amino group, phosgenate, e.g. B. with phosgene or diphosgene, and so the Convert amino group into an isocyanato group, the isocyanato-1,3- benzo- or -1,3-pyrido-dioxole with a benzimidazole z. B. the formula

in the

R ⁶ , R ⁷ and R ⁸ independently of one another each represent hydrogen, halogen, cyano, nitro, each optionally substituted alkyl, alkoxy, alkylthio, alkyl sulfinyl, alkylsulfonyl or cycloalkyl, for optionally substituted, condensed dioxyalkylene, for hydroxycarbonyl, alkylcarbonyl, , are alkoxycarbonyl, cycloalkyloxycarbonyl for each case optionally substituted amino or aminocarbonyl, or represents in each case optionally substituted aryl, aryloxy, arylthio, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonyl, aryloxy carbonyl, arylazo or arylthiomethylsulphonyl, but where at least one of the substituents R ^6, R ⁷ or R ⁸ for haloalkyl with the exception of the chloromethyl radical, haloalkoxy, haloalkylthio, haloalkylsulfinyl, Ha logenalkylsulfonyl, alkylsulfonyl, for optionally substituted, anodized dioxyalkylene, for hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, cycloalkyloxycarbonyl, for each optionally sub substituted aryl, arylthio, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonyl, aryloxycarbonyl, arylazo or arylthiomethylsulfonyl,
(For production see, for example, Fluorine Chem. 56, 1 (1992) and citations given there),

implement such a urea derivative z. B. get the formula

in which

R ¹ , R ³ , X, R ⁶ , R ⁷ and R ^{8 have} the meaning given above,

and therefrom by alkylation with an alkylating agent e.g. B. the formula

in the

A 'for a suitable leaving group, e.g. B. for halogen, in particular for chlorine, bromine or iodine or for each optionally substituted alkylsulfonyloxy, alkoxysulfonyloxy or arylsulfonyloxy, in particular methanesulfonyloxy, trifluoromethanesulfonyloxy, methoxysulfonyloxy, ethoxysulfonyloxy, p-toluenesulfonyloxy, or an alcohol, alkanoyloxy, alkoxy or alkoxy group, especially an acetoxy or methoxy group,
R ^{9 represents} hydrogen, alkyl, alkoxy or optionally substituted aryl and
R ¹⁰ for hydroxy, cyano or for optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, amino, amino carbonyl, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, dialkoxyphos phonyl, (hetero) aryl, (hetero) arylcarbonyl, ( Hetero) aryloxycarbonyl, (hetero) arylcarbonyloxy or (hetero) arylaminocarbonylaminocarbonyloxy,

receive a corresponding urea derivative in which a nitrogen atom next to R ⁸ with a

is substituted.

The reactions necessary for the production of such urea derivatives (phosgenation, Urea formation from isocyanate and amine, alkylation) can be known Way.

Compounds of the formula

can be obtained by mixing the corresponding isopropanol with formaldehyde and hydrogen chloride at -20 to + 20 ° C.

1,3-benzo- and 1,3-pyridodioxoles, which contain two adjacent amino groups, can with trifluoroacetic acid in the corresponding benzimidazole z. B. the following Formula to be transferred

in the

A, R ¹ and X have the meaning given above.

From these can be obtained by alkylation benzimidazole derivatives, which in Nitrogen atom next to A with a

are substituted.  

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

11 g of pyrocatechol were dissolved in 200 ml of dimethylformamide 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 2a 2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole

110 g of pyrocatechol were dissolved in 1500 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. 1200 ml of the solvent were then distilled off in vacuo and the residue was taken up in 1500 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 3 to 10a

The following examples were carried out analogously to Examples 1 and 2. (See Table 1 for details):  

Table 1

Example 11a 2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl- [1,3] dioxolo [4,5-b-] pyridine

11 g of 2,3-dihydroxypyridine were reacted with 23.5 g of 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene as described in Example 2. After distillation in a high vacuum, the product was obtained in the form of colorless crystals in an amount of 15.5 g (= 50% of theory). The NMR spectra showed the following characteristic absorptions: ¹⁹ F-NMR: -68.5 and -81.6 ppm. ¹ H NMR 4.81 ppm.

Examples 12a 2- (1,1,1,4,4,4-hexafluoro-2-butenoxy) methoxybenzene

260 g of 2-methoxyphenol were dissolved in 1 liter of dimethylformamide (technical quality) and mixed with 220 g of 45% sodium hydroxide solution. Then at 22 ° C with stirring 400 g of 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene were added dropwise. The mixture was stirred for 2 hours 22 ° C after. 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 13a 2- (1,1,1,4,4,4-hexafluoro-2-butenoxy) phenol

286.1 g of 2- (1,1,1,4,4,4-hexafluoro-2-butenoxy) methoxybenzene from Example 12 were dissolved in a mixture of 500 ml of glacial acetic acid and 500 ml of 48% hydrobromic acid and with 5 g Triethylbenzylammoniumchlorid 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 14a 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 13 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 15a 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 16a 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 15 were dissolved in 150 ml of tetrahydrofuran and at room temperature for 4 hours Treated 3 bar hydrogen in the presence of 2 g Pd / C (10%). Subsequently was 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 17a 2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole

11.7 g of 2- (2-chloro-1,1,1,4,4,4-hexafluoro-2-butenoxy) phenol from Example 16 were dissolved in 40 ml of tert-butyl methyl ether and with 40 ml of 1N sodium hydroxide solution transferred. 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 18a 2,2-dimethyl-4- (1,1,1,4,4,4-hexafluoro-2-butenoxy) -1,3-benzodioxole (formula V, R ⁵ together with R ¹ = -C (CH ₃ ) ₂ -O-rest)

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 54.8 g of 2-chloro-1,1,1,4,4,4-hexafluoro-2-butene was added dropwise with stirring at room temperature. 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 19a 1,2-dihydroxy-3- (1,1,1,4,4,4-hexafluoro-2-butenoxy) benzene

65 g of the product from Example 18 were heated to reflux with 200 ml of concentrated aqueous hydrochloric acid for 4 hours with stirring. The mixture was then diluted with 300 ml of water and extracted with methylene chloride. After drying with magnesium sulfate, the solvent was drawn off from the organic phase and 54 g of a 90% pure product were 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 20a 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 19 were dissolved in 300 ml of acetonitrile, and 1.5 g of triethylamine were added at room temperature. After stirring for 2 hours at room temperature, 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 21a 2,2-Dimethyl-4- (3-chloro-1,1,1,4,4,4-hexafluoro-2-butenoxy) -1,3-benzod-ioxol (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 analogously to Example 18 with 47 g of 2,3-dichloro-1,1,1,4,4,4-hexafluoro-2-butene . 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 22a 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 21 were reacted analogously to Example 19 with 50 ml of concentrated hydrochloric acid. 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 23a 2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-4-hydroxy-1,3-benzo-dioxole

15 g of the product from Example 22 were dissolved in 50 ml of acetonitrile and 1 ml of triethylamine was added. After stirring for 15 minutes, the solvent was stripped off 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 24a 5-bromo-2- (2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole

54.4 g of 2- (2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole were dissolved in 300 ml of carbon tetrachloride, and 0.4 g of anhydrous iron (III) chloride was added. Then 32 g of bromine were added dropwise at the reflux temperature and the mixture was stirred until complete conversion (check by gas chromatography). The mixture was then allowed to cool, washed with 10% strength by weight aqueous sodium hydrogen sulfide solution and water, dried with magnesium sulfate and concentrated. The residue was distilled in vacuo. The yield was 58 g (83% of theory), the boiling point 80 ° C at 14 mbar. The characteristic absorptions in the NMR spectra were as follows: ¹⁹ F-NMR: -59.2 and -84.9 ppm. ¹ H NMR: 3.02 ppm.

Example 25a 5-bromo-2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodio-xol

51 g of 2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole from Examples 2 and 17 were dissolved in 300 ml of carbon tetrachloride and mixed with 0.5 g of anhydrous FeCl ₃ . Then 32 g of bromine were added and the mixture was stirred under reflux for 3 hours. After cooling, it was washed with 10% NaHSO ₃ solution, dried with MgSO ₄ and distilled. The yield was 49 g (63% of theory), the boiling point 94-98 ° C at 8 mbar.

Example 26a 5-chloro-6-formyl-2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole

67 g of the aldehyde from Example 5 were dissolved in 150 ml of chloroform. Chlorine gas was introduced at 50-60 ° C until everything was implemented. The crude yield after stripping off the solvent was 73 g (98% of theory). The NMR spectra showed the following characteristic absorptions: ¹⁹ F-NMR: -68.6 and -81.4 ppm. ¹ H NMR: 4.81 ppm.

Example 27a 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 .-% Drops of nitric acid and 40 ml of concentrated sulfuric acid. The approach was Stirred for 1 hour at room temperature, then poured onto ice water, the organi cal phase separated and the aqueous phase extracted with methylene chloride. The combined organic phases were washed with water, dried and dried volatile components freed. 95 g of the product remained (= 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 28a 5-nitro-2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodi-oxol

613 g of 2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole from Example 2 were dissolved in 1.2 l of methylene chloride and at 0 to 10 ° C. to a mixture of 400 ml 65% nitric acid and 400 ml 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 29a 5,6-dinitro-2- (2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole-

317 g of the product from Example 27 were placed in front of them and a while stirring Mixture of 250 ml of 100 wt .-% nitric acid and 350 ml of concentrated Added dropwise sulfuric acid. The mixture was stirred at 55 ° C for 2 hours. Then the mixture was allowed to cool and poured onto ice water. The product came with Extracted methylene chloride, washed neutral with sodium hydrogen carbonate solution, dried and freed of 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 30a 5,6-Dinitro-2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-ben-zodioxole

352 g of 5-nitro-2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodi-oxol from Example 28 were initially charged and with a mixture of 250 ml of 100% strength by weight Nitric acid and 350 ml of concentrated sulfuric acid are added. 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 31a 5-chlorosulfonyl-2- (2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodi-oxol

136 g of 2- (2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole was dissolved in 125 ml of chloroform. 175 g of chlorosulfonic acid were added dropwise at 0 ° C. while stirring and the mixture was stirred at room temperature until the evolution of gas had ended. The mixture was then poured onto 750 g of ice water, the phases were separated and the aqueous phase was extracted with chloroform. The combined organic phases were washed with ice water and sodium hydrogen carbonate solution, dried with magnesium sulfate and freed from volatile constituents on a rotary evaporator. 133 g of product were obtained (= 72% of theory), the melting point was 55 to 57 ° C. ¹⁹ F NMR: -60.8 and -86.5 ppm. ¹ H NMR: 3.13 ppm.

Example 32a 5-cyano-2- (2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole

35 g of the product from Example 24 were dissolved in 75 ml of dimethylformamide and 10.5 g of copper (I) cyanide were added. The mixture was stirred at 160 ° C for 8 hours. The hot mixture was then poured onto 100 ml of ice water and 30 g of 1,2-diaminoethane were added. After stirring for 30 minutes, the organic phase was separated and the aqueous phase extracted with methylene chloride. The combined organic phases were washed with a solution of 30 g of 1,2-diaminoethane in 75 ml of water, dried with magnesium sulfate and distilled under high vacuum. 20.5 g of the product were obtained (= 69% of theory), boiling point 110 ° C. at 0.02 mbar. ¹⁹ F NMR: -58.1 and -84.6 ppm. ¹ H NMR: 3.08 ppm.

Example 33a 5-amino-2- (2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole

57.4 g of the product from Example 27 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 34a 4-amino-2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodi-oxol

84 g of 4-nitro-2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodi-oxol from Example 7 were dissolved in 500 ml of tetrahydrofuran and 5 g of palladium on carbon (5%) hydrogenated for 5 hours at room temperature with 15 to 20 bar of hydrogen. The mixture was then filtered, concentrated and distilled in vacuo. The yield was 31 g (40% of theory), the boiling point 70 ° C at 0.1 mbar. The NMR spectra showed the following characteristic absorptions: ¹⁹ F-NMR: -68.6 and -81.5 ppm. ¹ H NMR: 4.69 ppm.

Example 35a 5-amino-2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodi-oxol

72 g of 5-nitro-2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodi-oxol from Example 28 were dissolved in 500 ml of tetrahydrofuran and 5 g of palladium on carbon (5%) 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 36a 5-isocyanato-2- (2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxo-l

37 g of the product from Example 33 were dissolved in 50 ml of absolute 1,4-dioxane and a solution of 13.5 g of diphosgene in 80 ml of absolute 1,4-dioxane was added. The mixture was then stirred at 110 ° C. (bath temperature) for 6 hours, the solvent was then removed in vacuo and the remaining residue was fractionally distilled in vacuo. 18 g of product (= 44% of theory) with a boiling point of 63 ° C. at 0.1 mbar were obtained. ¹⁹ F NMR: -59.3 and -85.0 ppm. ¹ H NMR: 3.0 ppm.

Example 37a 5,6-diamino-2- (2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole-

339 g of the product from Example 29 were dissolved in 2000 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). ¹⁹F-NMR: -61.2 and -86.6 ppm. ¹ H NMR: 3.02 ppm.

Example 38a 2- (1-chloro-2,2,2-trifluoroethyl) -2- (trifluoromethyl) -5-hydroxy-1,3-ben-zodioxole

50 g of 2- (1-chloro-2,2,2-trifluoroethyl) -2- (trifluoromethyl) -5-formyl-1,3-benzodioxole were dissolved in 500 ml of methylene chloride and 53 g of 70% by weight m-chloroperbenzoic acid added. The mixture was stirred under reflux for 6 hours. The mixture was then cooled and the precipitate which had separated out was filtered off. The filtrate was washed with 5% by weight sodium hydrogen carbonate solution and concentrated on a rotary evaporator. The remaining residue was dissolved in 300 ml of diethyl ether and 100 ml of 1N sodium hydroxide solution were added at room temperature. After the conversion had ended, the phases were separated, the organic phase washed with saturated aqueous ammonium chloride solution, dried with magnesium sulfate and fractionally distilled in vacuo. The yield was 26 g (= 54% of theory), the boiling point 95 ° C at 0.07 mbar. ¹⁹ F NMR: -68.6 and -81.6 ppm. ¹ H NMR: 4.70 ppm.

Example 39a 4-Bromomethyl-2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzodioxole

64 g of 4-methyl-2- (1-chloro-2,2,2-trifluoroethyl) -2-trifluoromethyl-1,3-benzod-ioxol from Example 9 were dissolved in 500 ml of carbon tetrachloride and with 36 g of N-bromo succinimide and 0.5 g of AIBN (azoisobutyronitrile) were added. The mixture was stirred under reflux for 3 hours, then cooled and filtered. The solvent was removed and the residue was distilled in vacuo. The yield was 57 g (71% of theory), the boiling point 80 to 82 ° C at 0.1 mbar. The NMR spectra showed the following characteristic absorptions: ¹ H-NMR: 4.72 ppm.

Example 40a 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 2 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-tetrafluoroethoxy , 1,1,2-trifluoro-2-chloroethylthio or 1,1,2,3,3,3-He xafluoropropylthio, independently
R ² for F, Cl, Br, CN, CH ₃ , OCF ₃ , SO₂-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 described in EP-A 251 013 and EP-A 487 286 Compounds can be obtained by using a benzene derivative of the formula

in the

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
dinitrated, the nitro groups then reduced and thus obtained compounds in which R ¹ and R ^{2 are} in the 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, it is possible, for. B. a nitrobenzene derivative of the formula

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, B. a nitraniline of the formula

in the

R ^{1 has} the meaning given above,

react with a chlorinating or brominating agent, such as a chlorine or Insert the bromine atom in the meta position to the nitro group and then the Reduce nitro group.

If 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. B. COO-C ₁ -C ₆ alkyl, CN, CF ₃ or SO ₂ -C ₁ -C ₆ alkyl and R _{3 is} not hydrogen, z. B. a benzene derivative of the formula

in the

D ^{1 has} the meaning given above and
A represents 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 the NO ₂ group para to D ¹ ), reduce the NO ₂ group to the NH ₂ group, the NH ₂ group e.g. B. acylate with acetic acid or trifluoroacetic acid, mononitrate again (entry of this NO ₂ group in the ortho-position to NHCOR groups with R = z. B. CH ₃ or CF ₃ ), this NO ₂ group to the NH ₂ - Reduce group and if necessary, if you want 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 be converted into 2-trifluoromethylbenzimidazoles of the formula using trifluoroacetic acid

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) aryl carbonyloxy or (hetero) arylaminocarbonylaminocarbonyloxy and
A means a suitable leaving group.

Leaving group 14309 00070 552 001000280000000200012000285911419800040 0002004237567 00004 14190pps 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 6b (Dinitration and Reduction) Example 1b

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 a further 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, 350 g of 96% by weight of pure 1,2-dinitro-4,5-bis (2-chloro-1,1,2-trifluoroethoxy) benzene were obtained (oil, n : 1.4832, GC 99.1%).

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

Example 2b

Analogously 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, n: 1,4852) and the corresponding 4,5-di amino compound (oil, 87% by weight pure).

Example 3b

Analogously to Example 1, 1- (1,1,2-trifluoro-2-chloroethoxy) -2-chlorobenzene was removed speaking 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 4b

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, n: 1.5485) prepared.

Example 5b

Analogously to Example 1, 1-trifluoromethoxy-2-chlorobenzene was converted into the corresponding 4,5- Dinitro compound (melting point 55 to 56 ° C) and the corresponding 4,5-diamino compound (melting point 56-57 ° C).

Example 6b

From 1- (1,1,2,3,3,3-hexafluoropropoxy) -2-chlorobenzene the corresponding 4,5- Dinitroverbindung (oil) and the corresponding 4,5-diamino compound (oil) herge poses.

Examples 7 to 12b Squeeze with ammonia and reduction Example 7b

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

134 g of the nitraniline obtained as described above were dissolved in 800 ml of ethanol dissolves, then 20 ml of water, 10 ml of concentrated aqueous hydrochloric acid and 160 g of iron filings admitted. 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. There were 171 g of 5-chloro-3-trifluoromethyl-1,2-diaminobenzene with a Melting point at 53 ° C.

Example 8b

Analogously to Example 7, 3-nitro-4,6-dichloro-difluorochloromethoxybenzene was initially used 3-nitro-4-amino-6-chloro-difluorochloromethoxybenzene (melting point 73 ° C) and therefrom Obtained 3,4-diamino-6-chloro-difluorochloromethoxybenzene (oil).

Example 9b

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

Example 10b

Analogously to Example 7, 3-cyano-4-chloro-5-nitro-benzotrifluoride was initially used 3-cyan-4-amino-5-nitro-benzotrifluoride (melting point 99 to 100 ° C) and therefrom 3-Cyano-4,5-diamino-benzotrifluoride.

Example 11b

Analogously to Example 7, 3,6-dichloro-5-nitro-benzotrifluoride was first used to produce 3-chloro-5- nitro-6-amino-benzotrifluoride (melting point 53 to 54 ° C) and 3-chloro-5,6- diamino-benzotrifluoride produced.

Example 12b

From 2-bromo-4-fluoro-5-nitro- (1,1,2-trifluoro-2-chloro) ethoxybenzene was initially 2-bromo-4-amino-5-nitro- (1,1,2-trifluoro-2-chloroethoxy) benzene (melting point 90 ° C) and made therefrom 2-bromo-4,5-diamino- (1,1,2-trifluoro-2-chloro) ethoxybenzene.

Example 13b (Halogenation of a nitraniline and reduction)

24 g of finely powdered 2-nitro-4-trifluoromethylmercaptoaniline were dissolved in 50 ml of tri dissolved fluoroacetic acid and metered in 18 g of bromine at 20 ° C. Then it was for 3 hours at 20 ° C and stirred at 40 ° C for a further 30 minutes. The mixture on water given and the product taken up in dichloromethane. It fell after distance of the solvent 31 g of 6-bromo-2-nitro-4-trifluoromethyl-mercapto-aniline.

155 g of the nitraniline thus prepared were dissolved 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 Boiled at reflux, then the mixture was filtered off, the filtrate under reduced pressure Pressure freed from the solvent and umkri the solid crude product from cyclohexane installed. 112 g of 6-bromo-4-trifluoromethyl-mercapto-1,2-diaminobenzene were added obtained a melting point of 60 to 61 ° C.

Example 14b

Analogously to Example 13, 27 g of 2-nitro-4-trifluoromethyl-sulfonylaniline in 100 ml Brominated acetic acid with 18 g bromine.

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

32 g of the nitramine thus prepared were iron shavings in alcohol and aqueous Hydrochloric acid reduced. 24 g of 3-bromo-5-trifluoromethylsulfonyl-phe fell nylene-1,2-diamine, melting point 155-157 ° C.

Example 15b

Analogously to Example 14, 27 g of 2-nitro-4-trifluoromethylsulfonyl-aniline in 100 ml Chlorinated acetic acid with 10 g of chlorine. 29 g of 2-nitro-4-trifluoromethylsulfonyl-6- chlor-aniline on, melting point: 138-139 ° C.

By reduction, 13 g of 3-chloro-5-trifluoromethylsulfonyl-1,2-phenylenediamine (Melting point: 143-145 ° C) obtained.  

Examples 16 to 20b (Nitriding and reduction in 2 stages) Example 16b

263 g of 4- (2,6-dichloro-4-trifluoromethyl) phenoxyacetanilide were dissolved in 1100 ml of Di chloromethane dissolved and submitted at 10 ° C. Then 88 g at this temperature 98% by weight nitric acid added dropwise. It was 1 hour at 10 ° C and 2 more Stirred at 30 ° C for hours. After the addition of 300 ml of water, the Phases separated and the organic phase under reduced pressure Free dichloromethane. 253 g of 2-nitro-4- (2,6-dichloro-4-trifluoromethyl- phenoxy) 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 added and at 25 to 45 ° C in a hydrogenation apparatus with a maximum of 50 bar Hydrogen pressure hydrogenated. After decompression and filtration, the dioxane was added distilled off under a slight vacuum. There remained 65 g of 2-amino-4- (2,6-dichloro-4-trifluoro methyl-phenoxy) -acetanilide with a melting point of 222-223 ° C.

Example 17b

Analogously to Example 16, 3-trifluoromethyl-4-methoxy-acetanilide was first Trifluoromethyl-4-methoxy-6-nitro-acetanilide (melting point 143-144 ° C) and therefrom 3-trifluoromethyl-4-methoxy-6-amino-acetanilide (melting point 164-165 ° C) poses.

Example 18b

Analogously to Example 16, 3-trifluoromethyl-4-fluoro-trifluoromethylacetanilide was added next 3-trifluoromethyl-4-fluoro-6-nitro-trifluoromethylacetanilide (melting point 78 ° C) and therefrom 3-trifluoromethyl-4-fluoro-6-amino-trifluoromethylacetanilide (melting point 92-93 ° C).  

Example 19b

Analogously to Example 16, 3-trifluoromethyl-4-bromo-trifluoromethylacetanilide initially 3-trifluoromethyl-4-bromo-6-nitro-trifluoromethylacetanilide (melting point 110-112 ° C) and therefrom 3-trifluoromethyl-4-bromo-6-amino-trifluoromethylacetanilide (Melting point 63-65 ° C).

Example 20b

Analogously to Example 16, 3-trifluoromethylthio-4-chloro-trifluoromethylacetanilide initially 3-trifluoromethylthio-4-chloro-6-nitro-trifluoromethylacetanilide (melting point 99-100 ° C) and 3-trifluoromethylthio-4-chloro-6-amino-trifluoromethylacetanilide (Melting point 88-90 ° C).

Example 21b

0.2 mol of 3-bromo-5-trifluoromethyl-phenylene-diamine were treated with 150 ml of trifluoroacetic acid acid heated to reflux temperature for 3 hours. To work up was over distilled trifluoroacetic acid and the residue between 100 ml of water and 300 ml of ethyl acetate. The organic phase was separated, one after the other washed with 100 ml of aqueous sodium hydrogen carbonate solution and water, Dried over sodium sulfate and concentrated in vacuo. The residue was by chromatography on silica gel (mobile phase: cyclohexane / ethyl acetate 1: 1) nigt.

4-Bromo-6-trifluoromethyl-2-trifluoromethyl-1H-benzimidazole was obtained from the enamel point 149-151 ° C.

Example 22b

0.03 mol of 4-bromo-6-trifluoromethyl-2-trifluoromethyl-1H-benzimidazole and 0.06 mol Powdered potassium carbonate was in 70 ml of ethyl acetate for 15 minutes Reflux temperature heated, then with 3.9 g (0.04 mol) of chloromethyl methylthioether in 20 ml of ethyl acetate and stirring for a further 4 hours heated to reflux temperature. The cooled down was worked up Reaction mixture washed twice with 40 ml of water, over sodium sulfate  dried, concentrated in vacuo and the residue by chromatography Silica gel (eluent: dichloromethane) cleaned.

1-Methylthiomethyl-4-bromo-6-trifluoromethyl-2-trifluoromethyl-benzimid-a was obtained zol melting point 56-60 ° C.  

Examples of use

In the following application examples, the following were listed Compounds used as reference substances:

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

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 prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified Amount of emulsifier and dilute the concentrate with water to the desired con centering.

Soybean shoots (Glycine max) are dipped into the active ingredient preparation desired concentration and treated with the tobacco bud caterpillar (Heliothis virescens) as long as the leaves are still moist.

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

In this test, e.g. B. the following compounds of the preparation examples superior efficacy over the prior art: 59, 60, 61, 73 and 74.  

Example B Tetranychus test (OP-resistant)

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

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified Amount of emulsifier and dilute the concentrate with water containing emulsifier the desired concentrations.

Bean plants (Phaseolus vulgaris), strongly affected by all stages of development of the ge my spider mite (Tetranychus urticae) are infected in an active ingredient immersion of the desired concentration.

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

In this test, e.g. B. the following connection of the manufacturing examples Effective compared to the state of the 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

Mix in to produce a suitable preparation of active ingredient Part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are sprayed with the Active ingredient preparation to dripping wet. After the spray coating has dried on the plants with an aqueous conidia suspension of the apple scab pathogen (Venturia inaequalis) and then remain in an incubation box for one day bine at 20 ° C and a relative humidity of approx. 100%.

The plants are then grown in a greenhouse at 20 ° C and a relative humidity activity of approx. 70%.

Evaluation is carried out 12 days after the inoculation.

A clear superiority show in this test e.g. B. the connections according to the Manufacturing examples: 8, 9, 13, 74 and 75.

Claims (5)

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, condensed dioxyalkylene, for Hy hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, cycloalkyloxycarbonyl, for each optionally substituted amino or amino carbonyl or for each optionally substituted aryl, aryloxy, arylthio, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonyl, aryloxycarbonyl, arylazo or arylthiomethyl henyl
however, at least one of the substituents X ¹ , X ² , X ³ and X ^{4 is} different from hydrogen and halogen and
R ^{1 represents} hydrogen, alkyl or optionally substituted aryl,
R ² for hydroxy, cyano or for each optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, amino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, dialk oxyphosphoryl, (hetero) aryl, (hetero) arylcarbonyl, (hetero) aryl oxycarbonyl, (hetero) arylcarbonyloxy or (hetero) arylaminocar bonylaminocarbonyloxy is used as a pesticide. 2. Pesticides, characterized by a content of min at least one substituted benzimidazole of the formula (I) according to Claim 1. 3. Process for the production of pesticides, characterized characterized in that substituted benzimidazoles of the formula (I) according to claim 1 mixed with extenders and / or surface-active agents. 4. 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 dioxyal kylene, for hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, cycloalkyloxycarbonyl, for each optionally substituted amino or aminocarbonyl or for each optionally substituted aryl, aryloxy, arylthio, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonylyl, arylcarbonyl, aryl stand nyl,
however, at least one of the substituents X ^1-1 , X ^2-1 , X ^3-1 and X ^4-1 for nitro, haloalkyl, haloalkoxy, haloalkyl thio, haloalkylsulfinyl, haloalkylsulfonyl, alkylsulfonyl, for optionally substituted, fused-on dioxyalkylene, for hydroxycarbonyl , Alkylcarbonyl, alkoxycarbonyl, cycloalkyloxy carbonyl, represents in each case optionally substituted amino or amino carbonyl or for each 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 each optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, amino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, dialk oxyphosphoryl, (hetero) aryl, (hetero) arylcarbonyl, (hetero) aryl oxycarbonyl, (hetero) arylcarbonyloxy or (hetero) arylaminocar bonylaminocarbonyloxy. 5. 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 cycloalkyl , for optionally substituted, fused dioxyal kylene, for hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, cycloalkyloxycarbonyl, for each optionally substituted amino or aminocarbonyl or for each optionally substituted aryl, aryloxy, arylthio, arylsulfinyl, arylsulfonyl, arylsulfonyloxy, arylcarbonylyl, arylcarbonyl, aryl stand nyl,
however, at least one of the substituents X ^1-1 , X ^2-1 , X ^3-1 and X ^4-1 for nitro, haloalkyl, haloalkoxy, haloalkyl thio, haloalkylsulfinyl, haloalkylsulfonyl, alkylsulfonyl, for optionally substituted, fused-on dioxyalkylene, for hydroxycarbonyl , Alkylcarbonyl, alkoxycarbonyl, cycloalkyloxy carbonyl, represents in each case optionally substituted amino or amino carbonyl or for each 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 each optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, amino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, dialk oxyphosphoryl, (hetero) aryl, (hetero) arylcarbonyl, (hetero) aryl oxycarbonyl, (hetero) arylcarbonyloxy or (hetero) arylaminocar bonylaminocarbonyloxy, characterized in that mana) 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), 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.