Halogen-substituted phenoxyphenylamidines and the use thereof as fungicides

Abstract

The present invention relates to halogen-substituted phenoxyphenylamidines of the general formula (I), to a process for their preparation, to the use of the amidines according to the invention for controlling unwanted microorganisms and also to an agrochemical formulation for this purpose, comprising the halogen-substituted phenoxyphenylamidines according to the invention. Furthermore, the invention relates to a method for controlling unwanted microorganisms by applying the compounds according to the invention to the microorganisms and/or their habitat.

1 . A process for preparing the phenoxyphenylamidine of formula (I) 
       
         
           
           
               
               
           
         
         wherein 
         R 1  is selected from the group consisting of halogen and halomethyl; 
         R 2  is methyl; 
         R 3  is halogen; 
         and/or a salt, N-oxide, metal complex and/or a stereoisomer thereof, 
       
       which method comprises comprising at least one of the following:
 (a) reacting a nitrobenzene derivative of formula (III) with a phenol derivative of formula (II) according to the reaction scheme below: 
 
       
         
           
           
               
               
           
         
         (b) reacting a nitrophenol derivative of formula (V) with a phenyl derivative of formula (IV) according to the reaction scheme below: 
       
       
         
           
           
               
               
           
         
         (c) reacting an aniline of formula (VII) with a phenol (II) according to the reaction scheme below: 
       
       
         
           
           
               
               
           
         
         (d) reacting an aminophenol of formula (XII) with a phenyl derivative of formula (IV) according to the reaction scheme below: 
       
       
         
           
           
               
               
           
         
         (e) reducing a nitrophenoxy ether of formula (VI) to an aminophenyl ether of formula (VIII) according to the reaction scheme below: 
       
       
         
           
           
               
               
           
         
         (f) reacting the aminophenyl ether of the formula (VIII) with 
         (i) an aminoacetal of formula (XIII) or 
         (ii) with an N-ethyl-N-methylformamide of formula (XIV) or 
         (iv) with an N-methylethanamine of formula (XV) in the presence of an ortho ester of formula (XVI) 
       
       according to the reaction scheme below: 
       
         
           
           
               
               
           
         
         (g) reacting an aminophenol of formula (XII) with 
         (i) an aminoacetal of formula (XIII) or 
         (ii) with an N-ethyl-N-methylformamide of formula (XIV) or 
         (iv) with an N-methylethanamine of formula (XV) in the presence of an ortho ester of formula (XVI) 
         according to the reaction scheme below: 
       
       
         
           
           
               
               
           
         
         (h) reacting the aniline of the formula (VII) with 
         (i) aminoacetal of the formula (XIII) or 
         (ii) with N-ethyl-N-methylformamide of the formula (XIV) or 
         (iii) with N-methylethanamine of the formula (XV) in the presence of an ortho ester of the formula (XVI) according to the reaction scheme below: 
       
       
         
           
           
               
               
           
         
         (i) reacting an amidine of formula (XI) with the phenol derivative of the formula (II) according to the reaction scheme below: 
       
       
         
           
           
               
               
           
         
       
       and/or
 (j) reacting the amidine of the formula (X) with the phenyl derivative of the formula (IV) according to the reaction scheme below: 
 
       
         
           
           
               
               
           
         
         wherein in the above schemes 
         Z is a leaving group; 
         R 6  and R 7  independently of one another are selected from the group consisting of C 1-12 -alkyl, C 2-12 -alkenyl, C 2-12 -alkynyl, C 5-18 -aryl, and C 7-19 -arylalkyl groups and together with the atoms to which they are attached may form a five-, six- or seven-membered ring; 
         R 8  to R 10  independently of one another are selected from the group consisting of C 1-12 -alkyl, C 2-12 -alkenyl, C 2-12 -alkynyl, C 5-18 -aryl, C 7-19 -arylalkyl, and C 7-19 -alkylaryl groups and in each case R 8  with R 9 , R 9  with R 10  or R 8  with R 10  together with the atoms to which they are attached and optionally together with further carbon, nitrogen, oxygen or sulfur atoms may form a five-, six- or seven-membered ring. 
       
     
     
         2 . The process of  claim 1 , wherein
 R 1  is selected from the group consisting of fluoro, chloro, bromo, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, and trifluoromethyl;   R 2  is methyl; and   R 3  is selected from the group consisting of bromo, chloro and fluoro.   
     
     
         3 . The process of  claim 1 , wherein
 R 1  is selected from the group consisting of chloro, bromo, difluoromethyl, and trifluoromethyl;   R 2  is methyl; and   R 3  is fluoro or chloro.   
     
     
         4 . The process of  claim 1 , wherein
 R 1  is chloro,   R 2  is methyl; and   R 3  is fluoro.   
     
     
         5 . The process of  claim 1 , wherein the phenoxyphenylamidine is selected from the group consisting of N′-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylimidoformamide, N′-[2-(difluoromethyl)-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylimidoformamide, N′-[2-bromo-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylimidoformamide, N′-[2-bromo-4-(2-chlorophenoxy)-5-methylphenyl]-N-ethyl-N-methylimidoformamide, N′-[2-chloro-4-(2-chlorophenoxy)-5-methylphenyl]-N-ethyl-N-methylimidoformamide, N′-[2-chloro-4-(2-iodophenoxy)-5-methylphenyl]-N-ethyl-N-methylimidoformamide, and N′-[2-bromo-4-(2-bromophenoxy)-5-methylphenyl]-N-ethyl-N-methylimidoformamide. 
     
     
         6 . A nitrophenyl ether of formula (VI) 
       
         
           
           
               
               
           
         
         wherein 
         R 1  is selected from the group consisting of halogen and halomethyl; 
         R 2  is methyl; 
         R 3  is halogen. 
       
     
     
         7 . The nitrophenyl ether of  claim 6 , wherein
 R 1  is selected from the group consisting of fluoro, chloro, bromo, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, and trifluoromethyl;   R 2  is methyl; and   R 3  is selected from the group consisting of bromo, chloro and fluoro.   
     
     
         8 . The nitrophenyl ether of  claim 6 , wherein
 R 1  is selected from the group consisting of chloro, bromo, difluoromethyl, and trifluoromethyl;   R 2  is methyl; and   R 3  is fluoro or chloro.   
     
     
         9 . The nitrophenyl ether of  claim 6 , wherein
 R 1  is chloro,   R 2  is methyl; and   R 3  is fluoro.   
     
     
         10 . An aminophenyl ether of formula (VIII) 
       
         
           
           
               
               
           
         
       
       wherein
 R 1  is selected from the group consisting of halogen and halomethyl; 
 R 2  is methyl; 
 R 3  is halogen. 
 
     
     
         11 . The aminophenyl ether ether of  claim 10 , wherein
 R 1  is selected from the group consisting of fluoro, chloro, bromo, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, and trifluoromethyl;   R 2  is methyl; and   R 3  is selected from the group consisting of bromo, chloro and fluoro.   
     
     
         12 . The aminophenylether of  claim 10 , wherein
 R 1  is selected from the group consisting of chloro, bromo, difluoromethyl, and trifluoromethyl;   R 2  is methyl; and   R 3  is fluoro or chloro.   
     
     
         13 . The aminophenylether of  claim 10 , wherein
 R 1  is chloro,   R 2  is methyl; and   R 3  is fluoro.