Process for the preparation of 2-chloro-5-chloromethyl-thiazole

Abstract

The invention relates to a process for the preparation of 2-chloro-5-chloromethyl-thiazole, which is employed as intermediate in the preparation of compounds having a pesticidal action, which process comprises reacting a compound of formula (II), in free form or in salt form, (III), (IV), (V) or (VI) with a chlorinating agent, where R and M + are as defined in claim 1 ; to the compounds of the formulae (III) and (IV), which are used in this process as intermediates; and to the use of, and a process for the preparation of, the compounds of the formulae (III) and (IV).

1 . A process for preparing the compound of the formula 
       
         
           
           
               
               
           
         
       
       which comprises
 a) reacting a compound of the formula 
 
       
         
           
           
               
               
           
         
       
       In the presence of absence of a free-radical catalyst, with a chlorinating agent,
 Or 
 b1) first reacting the compound of the formula II or the compound 2-mercapto-5-methyl-thiazole, in each case in free form or in salt form, with a chlorinating agent and 
 b2) subjecting the compound of the formula III, which is obtainable in this way, to further reaction, with or without isolating it, with a chlorinating agent in accordance with variant a), wherein compound of formula II is 
 
       
         
           
           
               
               
           
         
         or 
         c1) first subjecting a salt of the formula 
       
       
         
           
           
               
               
           
         
       
       in which M +  is an alkali metal ion, one equivalent of an alkaline earth metal ion or is a nonalkylated ammonium ion or an ammonium ion which is alkylated with from one to four identical or different alkyl radicals, and is preferably a potassium ion or, in particular, a sodium ion, to treatment with a base
 (c2) subjecting the compound of the formula II thus obtainable, in free form or in salt form, with or without isolating it, to further reaction with a chlorinating agent in accordance with variant b1)/b2), 
 or 
 d1) first reacting the compound of the formula 
 
       
         
           
           
               
               
           
         
       
       with carbon disulfide, in the presence or absence of a base, and
 d2) further reacting the compound of the formula II thus obtainable, in free form or in salt form, with or without isolating it, with a chlorinating agent in accordance with variant b1)/b2). 
 
     
     
         2 . The process according to  claim 1 , wherein the chlorinating agent is selected from the group consisting of elemental chlorine, Javelle water, N-chlorosuccinimide, phosphorus trichloride, phosphorus pentachloride, sulfuryl chloride, thionyl chloride and mixtures of two or more of these compounds. 
     
     
         3 . The process according to  claim 2 , wherein the chlorinating agent is N-chlorosuccinimide. 
     
     
         4 . The process according to  claim 3 , wherein the solvent is selected from the group consisting of water, strong organic carboxylic acids, aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, and mixtures of these solvents. 
     
     
         5 . The process according to  claim 1 , wherein the solvent is selected from the group consisting of water, formic acid, acetic acid, propionic acid, benzene, toluene, xylene, mesitylene, tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene and tetrachloroethene, and mixtures of these solvents. 
     
     
         6 . The process according to  claim 5 , wherein the solvent is selected from the group consisting of water, formic acid, acetic acid, dichloromethane, trichloromethane, tetrachloromethane and dichloroethane, and mixtures of these solvents. 
     
     
         7 . The process according to  claim 6 , wherein the solvent is tetrachloromethane. 
     
     
         8 . The process according to  claim 1 , wherein the reaction is carried out at from +20° C. to +80° C. 
     
     
         9 . The process according to  claim 1 , wherein the reaction period is from 1 to 120 hours. 
     
     
         10 . The process according to  claim 9 , wherein the reaction period is from 48 to 96 hours. 
     
     
         11 . The process according to  claim 1  for preparing the compound of the formula 
       
         
           
           
               
               
           
         
       
       which comprises first reacting the compound 2-mercapto-5-methyl-thiazole, in free form or in salt form, with a chlorinating agent and further reacting the compound thus obtainable of the formula 
       
         
           
           
               
               
           
         
       
       with or without isolating it, with a chlorinating agent in accordance with variant a) as defined in  claim 1 . 
     
     
         12 . The process according to  claim 1  for preparing the compound of the formula 
       
         
           
           
               
               
           
         
       
       which comprises first subjecting a salt of the formula 
       
         
           
           
               
               
           
         
       
       in which M +  is as defined in  claim 1 , to treatment with a base and further reacting the compound thus obtainable of the formula 
       
         
           
           
               
               
           
         
       
       in free form or in salt form, with or without isolating it, with a chlorinating agent in according with variant b1)/b2) as defined in  claim 1 . 
     
     
         13 . The process according to  claim 1  for preparing the compound of the formula 
       
         
           
           
               
               
           
         
       
       which comprises first reacting the compound of the formula 
       
         
           
           
               
               
           
         
       
       with carbon disulfide, in the presence or absence of a base, and further reacting the compound thus obtainable of the formula 
       
         
           
           
               
               
           
         
       
       in tree form or in salt form, with or without isolating it, with a chlorinating agent in accordance with variant b1)/b2) as defined in  claim 1 .