Method of producing pesticides

Abstract

A method of producing a compound of formula and, if appropriate, the E/Z isomers, E/Z isomeric mixtures and/or tautomers thereof, each in free form or in salt form, wherein R 1 is hydrogen or C 1 -C 4 -alkyl; R 2 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl or a radical —CH 2 B; Het is an unsubstituted or substituted heterocyclic radical; and B is phenyl, 3-pyridyl or thiazolyl, which are optionally substituted; characterised in that a compound of formula Q—A—Q  (IIa) wherein A is a direct bond or an organic radical; or of formula wherein U is an organic radical; and in compounds (IIa) and (IIb) Q signifies and R 1 , R 2 and Het are as defined above for formula (I), and optionally the E/Z isomers, E/Z isomeric mixtures and/or tautomers thereof, each in free form or in salt form, is hydrolysed; and a method for producing the compounds of formulae (IIa), (IIb), (IIIa) and (IIIb); are described.

What is claimed is:  
     
         1 . Method of producing a compound of formula  
       
         
           
           
               
               
           
         
       
       and, if appropriate, the E/Z isomers, E/Z isomeric mixtures and/or tautomers thereof, each in free form or in salt form, wherein 
 R 1  is hydrogen or C 1 -C 4 -alkyl;  
 R 2  is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl or a radical —CH 2 B;  
 Het is an aromatic or non-aromatic, monocyclic or bicyclic heterocyclic radical which is unsubstituted or—depending on the substitution possibilities of the ring system—mono- to penta-substituted by substituents selected from the group comprising halogen, C 1 -C 3 -alkyl, C 1 -C 3 -alkoxy, halogen-C 1 -C 3 -alkyl, C 1 -C 3 -halogenalkoxy, cyclopropyl, halogencyclopropyl, C 2 -C 3 -alkenyl, C 2 -C 3 -alkynyl, C 2 -C 3 -halogenalkenyl and C 2 -C 3 -halogenalkynyl, C 1 -C 3 -alkylthio, C 1 -C 3 -halogenalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, halogenallyloxy, halogenallylthio, cyano and nitro; and  
 B is phenyl, 3-pyridyl or thiazolyl, which are optionally substituted by one to three substituents from the group comprising C 1 -C 3 -alkyl, C 1 -C 3 -halogenalkyl, cyclopropyl, halogencyclopropyl, C 2 -C 3 -alkenyl, C 2 -C 3 -alkynyl, C 1 -C 3 -alkoxy, C 2 -C 3 -halogenalkenyl, C 2 -C 3 -halogenalkynyl, C 1 -C 3 -halogenalkoxy, C 1 -C 3 -alkylthio, C 1 -C 3 -halogenalkylthio, allyloxy, propargyloxy, allylthio, propargylthio, halogenallyloxy, halogenallylthio, halogen, cyano and nitro;  
 characterised by hydrolysing a compound of formula  
 Q—A—Q  (IIa)  
 wherein A is a direct bond or an organic radical, or of formula  
                     
 wherein U is an organic radical; and in compounds (IIa) and (Ib)  
 Q signifies  
                     
 wherein R 1 , R 2  and Het are as defined above for formula (I), and optionally the E/Z isomers, E/Z isomeric mixtures and/or tautomers thereof, each in free form or in salt form.  
 
     
     
         2 . Method according to  claim 1  of producing a compound of formula (I) in free form.  
     
     
         3 . Method according to  claim 1  or  2  of producing a compound of formula (I) wherein R. is hydrogen.  
     
     
         4 . Method according to one of  claims 1  to  3  of producing a compound of formula (I), wherein 
 R 2  is hydrogen, C 1 -C 3 -alkyl or cyclopropyl.  
 
     
     
         5 . Method according to one of  claims 1  to  4  of producing a compound of formula (I) from a compound of formula (IIa), wherein 
 A is straight-chained or branched C 2 -C 20 -alkylene, C 2 -C 20 -alkenylene, C 2 -C 20 -alkynylene,  
 C 3 -C 12 -cycloalkylene, arylene or heterocyclylene; whereby the groups C 2 -C 20 -alkylene,  
 C 2 -C 20 -alkenylene, C 2 -C 20 -alkynylene, C 3 -C 12 -cycloalkylene, arylene and heterocyclylene are optionally substituted once or several times, independently of each other, and the groups  
 C 2 -C 20 -alkylene, C 2 -C 20 -alkenylene and C 2 -C 20 -alkynylene are optionally interrupted once or several times, independently of each other, by O, N—H or N—C 1 -C 12 -alkyl, C 3 -C 9 -cycloalkylene, arylene or heterocyclylene; or a group —D 1 -D 2 -D 3 —; wherein  
 D 1  and D 3 , independently of each other, signify optionally substituted C 3 -C 12 -cycloalkylene or arylene and D 2  signifies C 2 -C 20 -alkylene, C 2 -C 20 -alkenylene, C 2 -C 20 -alkynylene, O, N—H or N—C 1 -Cl 2 -alkyl.  
 
     
     
         6 . Method according to one of  claims 1  to  4  of producing a compound of formula (I) from a compound of formula (IIb), wherein 
 U is aryl, heterocyclyl, C 3 -C 12 -cycloalkyl or a group  
                     
 wherein  
 A 1 , A 2  and A 3  independently of one another, have the same significances as given in  claim 5  for A in formula (IIa), and  
 X signifies N or CH.  
 
     
     
         7 . Method according to one of  claims 1  to  6  of producing a compound of formula (I) wherein Het signifies 2-chloropyrid-5-yl, tetrahydrofuran-3-yl, 5-methyl-tetrahydrofuran-3-yl or 2-chlorothiazol-5-yl.  
     
     
         8 . Method according to one of  claims 1  to  7  of producing a compound of formula (I), characterised in that the pH value is less than 6.  
     
     
         9 . Method according to one of  claims 1  to  8  of producing a compound of formula (I), characterised in that it is effected in water, an alcohol or a mixture of water with an alcohol.  
     
     
         10 . Method of producing a compound of formula  
       Q—A—Q  (IIa)  
       wherein A is a direct bond or an organic radical; or of formula  
       
         
           
           
               
               
           
         
       
       wherein U is an organic radical; and in compounds (IIa) and (IIb) 
 Q signifies  
                     
 wherein R 1 , R 2  and Het are as defined in  claim 1  for formula (I), and optionally the E/Z isomers, E/Z isomeric mixtures and/or tautomers thereof, each in free form or in salt form. characterised in that a compound of formula  
 T—A—T  (IIIa)  
 or of formula  
                     
 wherein A and U have the same significance as defined for formulae (IIa) and (IIb);  
 T signifies  
                     
 and R 2  has the same significance as defined in  claim 1  for formula (I); and optionally the E/Z isomers, E/Z isomeric mixtures and/or tautomers thereof, each in free form or in salt form, is reacted when producing a compound of formula (IIa) either with two equivalents, or when producing a compound of formula (IIIb) with three equivalents of a compound of formula  
                     
 wherein R 1  and Het are defined as in  claim 1  for formula (I), and Y is a leaving group.  
 
     
     
         11 . Method of producing a compound of formula (IIa) or (IIIb), as defined in  claim 10 , characterised in that either a compound of formula  
       H 2 N—A—NH 2   (Va)  
       or  
       
         
           
           
               
               
           
         
       
       and optionally the E/Z isomers, E/Z isomeric mixtures and/or tautomers thereof, each in free form or in salt form, wherein A and U have the same significance as defined in  claim 1  for the compounds of formulae (IIa) and (IIb), is reacted when producing a compound of formula (IIIa) either with two equivalents, or when producing a compound of formula (IIIb) with three equivalents of a compound of formula  
       
         
           
           
               
               
           
         
       
       wherein R 2  has the same significance as defined for formula (I), in the presence of an excess of formaldehyde or paraformaldehyde.