Patent GB-1429457-A (GB)
Title: Derivatives of 2-mercapto-4,5-dichlorothiazole processes for their preparation and their use as herbicides
IPC: C07D277/20
Filed: 1974-08-30
Abstract: 1429457 2 - Mercapto - 4,5 - dichloro - thiazole derivatives BAYER AG 30 Aug 1974 [1 Sept 1973] 38006/74 Heading C2C Carbonic acid derivatives of 2-mercapto-4,5- dichlorothiazole of the general formula in which X is oxygen or sulphur, Y is a radical -OR, -SR or R is alkyl with 1 to 12 carbon atoms, alkenyl with 2 to 12 carbon atoms or alkynyl with 3 to 12 carbon atoms (each of the aforesaid radicals optionally being substituted by one or more substituents selected from halogen, alkoxy, aryloxy, alkylmercapto and arylmercapto), aralkyl with 1 or 2 aryl radicals on the alkyl moiety and 1 to 4 carbon atoms in the alkyl moiety (the aryl moiety optionally being substituted by one or more substituents selected from halogen, alkyl, halogenoalkyl, nitro, alkoxy, alkylmercapto and nitrile), cycloalkyl with 4 to 8 carbon atoms (the ring being optionally substituted by alkyl and/or containing a fused ring), or aryl (optionally being substituted by one or more substituents selected from halogen, alkyl, halogenoalkyl, nitro, alkoxy, alkylmercapto, dialkylamino, carbalkoxy, N,N-dialkylcarbamoyl and nitrile); and R<SP>1</SP> and R<SP>2</SP>, which may be identical or different, are each hydrogen, alkyl with 1 to 12 carbon atoms (optionally being substituted by one or more substituents selected from alkoxy, hydroxyl, alkylmercapto, aryloxy, arylmercapto, nitrile, carbalkoxy and N,N-dialkylcarbamoyl), alkenyl with 2 to 5 carbon atoms, alkynyl with 3 to 12 carbon atoms, cycloalkyl with 3 to 8 carbon atoms, aralkyl with 1 or 2 aryl radicals on the alkyl moiety and 1 to 4 carbon atoms in the alkyl moiety (the aryl moiety optionally being substituted by one or more substituents selected from alkyl, alkoxy, alkylmercapto, halogen, halogenoalkyl, nitro and dialkylamino) or aryl (optionally being substituted by one or more substituents selected from halogen, alkyl, halogenoalkyl, alkoxy, alkylmercapto and nitro); or R<SP>1</SP> and R<SP>2</SP> conjointly with the adjoining nitrogen atom form a threemembered to seven-membered ring in which one or two carbon atoms can be replaced by oxygen, sulphur or nitrogen; or X and Y conjointly form a triply bonded nitrogen atom, are prepared by either (a) reacting 2-mercapto-4,5- dichlorothiazole with a compound in which Hal is Cl or Br and Y<SP>1</SP> is -OR, -SR, -NR<SP>1</SP>R<SP>2</SP> or -O-(CH 2 ) 4 OC = Cl, in the presence of an acid-binding agent or in the form of a metal salt and in the presence of a diluent; or (b) by reacting a compound of general formula with an alcohol, phenol, mercaptan, thiophenol or amine of formula H-Y in the presence of an acid-binding agent and a diluent. Amongst the examples the compounds thiocarbonic acid O- methyl 4,5-dichloro-thiazolyl-(2)-ester, N,N-dimethylthiocarbamic acid S-4,5-dichlorothiazolyl ester and Z-thiocyanato-4,5-dichlorothiazole are prepared. 2 - Mercapto - 4,5 - dichlorothiazole is prepared by addition of NaHS to trichloro-thiazole in dioxane. Thiocarbonic acid S-4,5-dichlorothiazolyl ester chloride is obtained by the reaction of the Na salt of Z-mercapto-4,5-dichlorothiazole with COCl 2  in toluene. Herbicidal compositions comprise as active ingredient a compound of Formula I in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.