Benzimidazole derivatives

Abstract

Novel benzimidazole derivatives of the formula in which R 1 , R 2 , X 1 ,X 2 , X 3 , X 4 and Y are each as defined in the description, and acid addition salts and metal salt complexes thereof, a process for preparing these compounds and their use as microbicides in crop protection and in the protection of materials.

1 . Benzimidazole derivatives of the formula  
       
         
           
           
               
               
           
         
       
       in which 
 X 1 , X 2 , X 3  and X 4  independently of one another each represent hydrogen, halogen, cyano, nitro, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio, halogenoalkylthio, alkylsulphinyl, halogenoalkylsulphinyl, alkylsulphonyl, halogenoalkylsulphonyl, optionally substituted cycloalkyl, hydroxycarbonyl, alkylcarbonyl, alkoxycarbonyl, cycloalkylcarbonyl, cycloalkoxycarbonyl, represent  
                     
 In which 
 R 3  and R 4  independently of one another each represent hydrogen, alkyl, halogenoalkyl, alkoxyalkyl, alkylcarbonyl, optionally substituted aryl, optionally substituted arylcarbonyl, optionally substituted arylsulphonyl, optionally substituted arylaminocarbonyl or optionally substituted arylmethylsulphonyl or  
 R 3  and R 4  together with the nitrogen atom that they are attached to represent an optionally alkyl-substituted heterocyclic ring which may contain an additional oxygen atom or an alkylimino group,  
 Q represents a direct bond or a carbonyl group,  
 R 5  represents optionally substituted aryl or represents optionally substituted heterocyclyl and  
 Z represents a direct bond, represents CH 2 , O, S, SO, SO 2 , CO or an azo group or  
  represents —CO—O— where the oxygen atom is linked to the aryl or heterocyclyl radical, or  
  represents —SO 2 —O— where the sulphur atom is linked to the aryl or heterocyclyl radical, or  
  represents —S—CH 2 —SO 2 — where the sulphur atom of the thio group is linked to the aryl or heterocyclyl radical, or  
 
 X 2  and X 3  together represent an optionally substituted alkylene chain having 3 or 4 members wherein one or two (non-adjacent) carbon atoms may be replaced by oxygen atoms,  
 R 1  represents cyano or the groupings  
                     
 wherein 
 R 6  represents alkyl, halogenoalkyl or optionally halogen- and/or halogenoalkyl-substituted benzyl,  
 
 R 2  represents optionally substituted heterocyclyl and  
 Y represents a direct bond, represents —CH 2 —, —CH 2 —CH 2 —, —CO—, —SO 2 —, —CO—O— or —SO—O— where in the case of the last two groups the carbon atom or the sulphur atom is linked to the nitrogen atom of the imidazole ring, and acid addition salts and metal salt complexes thereof.  
 
     
     
         2 . Benzimidazole derivatives of the formula (I) according to  claim 1  in which 
 X 1 , X 2 , X 3  and X 4  independently of one another each represent hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, straight-chain or branched alkyl having 1 to 8 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, straight-chain or branched alkoxy having 1 to 8 carbon atoms, straight-chain or branched halogenoalkoxy having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, straight-chain or branched alkylthio having 1 to 8 carbon atoms, straight-chain or branched halogenoalkylthio having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, straight-chain or branched alkylsulphinyl having 1 to 8 carbon atoms, straight-chain or branched halogenoalkylsulphonyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, straight-chain or branched alkylsulphonyl having 1 to 8 carbon atoms, straight-chain or branched halogenoalkylsulphonyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, cycloalkyl having 3 to 6 carbon atoms which is optionally mono- to pentasubstituted by identical or different substituents from the group consisting of halogen and alkyl having 1 to 4 carbon atoms, represent hydroxycarbonyl, alkylcarbonyl having 1 to 6 carbon atoms in the straight-chain or branched alkyl moiety, alkoxycarbonyl having 1 to 6 carbon atoms in the straight-chain or branched alkoxy moiety, cycloalkylcarbonyl having 3 to 6 carbon atoms in the cycloalkyl moiety, cycloalkoxycarbonyl having 3 to 6 carbon atoms in the cycloalkyl moiety, represent  
                     
 R 3  and R 4  independently of one another each represent hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms, straight-chain or branched alkoxyalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, alkylcarbonyl having 1 to 6 carbon atoms in the straight-chain or branched alkyl moiety, aryl having 6 to 10 carbon atoms, arylcarbonyl having 6 to 10 carbon atoms in the aryl moiety, arylsulphonyl having 6 to 10 carbon atoms, arylaminocarbonyl having 6 to 10 carbon atoms in the aryl moiety or represent arylmethylsulphonyl having 6 to 10 carbon atoms in the aryl moiety, it being possible for each of the abovementioned aryl radicals to be mono- to trisubstituted by identical or different substituents from the group consisting of halogen, cyano, nitro, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, alkylsulphinyl having 1 to 4 carbon atoms, alkylsulphonyl having 1 to 4 carbon atoms, halogenoalkylsulphinyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms and halogenoalkylsulphonyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, and  
 R 3  and R 4  together with the nitrogen atom that they are attached to additionally represent a heterocyclic ring having 5 or 6 ring members which is optionally mono- to trisubstituted by alkyl having 1 to 4 carbon atoms and which may contain an additional oxygen atom or a C 1 -C 4 -alkylimino group,  
 Q represents a direct bond or represents a carbonyl group,  
 R 5  represents aryl having 6 to 10 carbon atoms, it being possible for each of these radicals to be mono- to trisubstituted by identical or different substituents from the group consisting of halogen, cyano, nitro, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylthio having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, alkylsulphinyl having 1 to 4 carbon atoms, alkylsulphonyl having 1 to 4 carbon atoms, halogenoalkylsulphinyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms and halogenoalkylsulphonyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, or  
 R 5  represents a saturated or unsaturated heterocyclyl radical having 5 or 6 ring members and 1 to 3 heteroatoms such as nitrogen, oxygen and/or sulphur, it being possible for these radicals to be mono- to trisubstituted by identical or different substituents from the group consisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, alkoxycarbonyl having 1 to 3 carbon atoms in the alkoxy moiety, cycloalkyl having 3 to 6 carbon atoms, cyano and nitro, 
 Z represents a direct bond and also represents CH 2 , O, S, SO, SO 2 , CO or an azo group, or  
  represents —CO—O—, where the oxygen atom is linked to the aryl or heterocyclyl radical, or  
  represents —SO 2 —O—, where the sulphur atom is linked to the aryl or heterocyclyl radical, or  
  represents —S—CH 2 —SO 2 —, where the sulphur atom of the thio group is linked to the aryl or heterocyclyl radical, and furthermore  
 
 X 2  and X 3  together also represent an alkylene chain having 3 or 4 members which is optionally mono- to hexasubstituted by halogen, alkyl having 1 to 4 carbon atoms and/or halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 halogen atoms and in which one or two (non-adjacent) carbon atoms may be replaced by oxygen atoms,  
 R 1  represents cyano or the groupings  
                     
 R 6  represents straight-chain or branched alkyl having 1 to 4 carbon atoms, straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms or represents benzyl which is optionally mono- to trisubstituted by identical or different substituents from the group consisting of halogen and halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms,  
 R 2  represents a saturated or unsaturated, optionally benzo-fused heterocyclyl radical having 5 or 6 ring members and 1 to 3 heteroatoms such as nitrogen, oxygen and/or sulphur, it being possible for these radicals to be mono- to trisubstituted by identical or different substituents from the group consisting of halogen, cyano, nitro, hydroxyl, amino, formyl, carboxy, carbamoyl, thiocarbanoyl, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety, cycloalkyl having 3 to 6 carbon atoms, halogenoalkylsulphinyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, halogenoalkylsulphonyl having 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms, alkylamino having 1 to 4 carbon atoms, hydroxyalkylamino having 1 to 4 carbon atoms, dialkylamino having 1 to 4 carbon atoms in each alkyl group, alkylcarbonyl having 1 to 4 carbon atoms in the alkyl moiety, alkylcarbonylamino having 1 to 4 carbon atoms in the alkyl group, hydroxyiminoalkyl having 1 to 4 carbon atoms in the alkyl moiety, alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, alkylcarbonyloxy having 1 to 4 carbon atoms in the alkyl moiety and halogenoalkylcarbonyloxy having 1 to 4 carbon atoms in the halogenoalkyl group and 1 to 5 identical or different halogen atoms,  
  it being possible for the heterocyclyl radicals to contain oxo groups and  
 Y represents a direct bond, represents CH 2 , CH 2 —CH 2 , CO, SO 2 , —CO—O— or —SO—O—, where in the case of the last two groups the carbon atom or the sulphur atom is linked to the nitrogen atom of the imidazole ring.  
 
     
     
         3 . Process for preparing benzimidazole derivatives of the formula (I) according to  claim 1   and acid addition salts and metal salt complexes thereof, characterized in that cyanobenzimidazoles of the formula                          in which    X 1 , X 2 , X 3  and X 4  are each as defined above     are reacted with halides of the formula   Hal—Y—R 2   (III)   in which    R 2  and Y are each as defined above and    Hal represents chlorine or bromine,    if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, and the resulting benzimidazoles of the formula                          in which    R 2 , Y, X 1 , X 2 , X 3  and X 4  are each as defined above are, if appropriate, either    a) reacted with hydrogen sulphide in the presence of an acid binder and in the presence of a diluent or    b) reacted with a sulphur compound of the formula   H—S—R 6   (IV)   in which 
 R 6  is as defined above  
  in the presence of an acid binder and in the presence of a diluent,  
  and an acid or a metal salt is, if appropriate, added to the resulting compounds of the formula (I).  
   
     
     
         4 . Microbicidal compositions, characterized by a content of at least one benzimidazole derivative of the formula (I) according to  claim 1  or an acid addition salt or metal salt complex of a benzimidazole derivative of the formula (I).  
     
     
         5 . Use of benzimidazole derivatives of the formula (I) according to  claim 1  or of acid addition salts or metal salt complexes thereof as microbicides in crop protection and in the protection of materials.  
     
     
         6 . Process for controlling undesirable microorganisms in crop protection and in the protection of materials, characterized in that benzimidazole derivatives of the formula (I) according to  claim 1  or acid addition salts or metal salt complexes thereof are applied to the microorganisms and/or their habitat.  
     
     
         7 . Process for preparing microbicidal compositions, characterized in that benzimidazole derivatives of the formula (I) according to  claim 1  or acid addition salts or metal salt complexes thereof are mixed with extenders and/or surface active compounds.