GB599178A - Thiolcarbamic esters - Google Patents

Abstract

Thiolcarbamic esters, of the general formula R(NHCOSR1)n, wherein R and R1 represent hydrocarbon radicals, substituted or unsubstituted, the same or different, and n is 1, 2 or 3, are manufactured by treating an alkali or alkaline-earth metal salt of a thiolcarbamic acid R(NHCOSH)n, advantageously in the presence of a solvent, with a substance capable of replacing alkali or alkaline earth metal by an organic radical or radicals, e.g. a substance containing one or more reactive halogen atoms, -SO4 groups (as in dialkyl sulphates) or -SO3 Aryl groups (as in alkyl toluenesulphonates). In examples: (1) sodium phenylthiolcarbamate is stirred with dimethyl or diethyl sulphate in aqueous solution at 0 DEG C. to produce methyl or ethyl phenylthiolcarbamate; (2) sodium cyclohexylthiolcarbamate and dimethyl sulphate similarly yield methyl cyclohexylthiolcarbamate; (3) sodium octadecylthiolcarbamate is heated with dimethyl sulphate in toluene to form methyl octadecylthiolcarbamate; (4) benzyl chloride is stirred with an aqueous solution of disodium hexamethylenebis-(thiolcarbamate) to give dibenzyl hexamethylene-bis-(thiolcarbamate); (5) sodium phenylthiolcarbamate is stirred with ethyl bromide in ethyl alcohol, producing ethyl phenylthiolcarbamate; the ethyl bromide may be replaced by n-propyl, n-butyl or allyl bromide or methallyl chloride; (6) cetyl bromide similarly yields cetyl phenylthiolcarbamate; (7) ethyl chloracetate similarly gives carbethoxymethyl phenylthiolcarbamate; (8) disodium hexamethylene - bis - (thiolcarbamate) and n-propyl bromide similarly yield dipropyl hexamethylene-bis-(thiolcarbamate); the n-propyl bromide may be replaced by ethyl, n-butyl or allyl bromide or methallyl chloride; (9) disodium p : p1-diphenyl-bis-(thiolcarbamate) and allyl bromide similarly give diallyl p : p1-diphenyl-bis-(thiolcarbamate); (10) disodium p : p1 - diphenylmethane - bis - (thiolcarbamate) similarly yields diallyl p : p1-diphenylmethane-bis-(thiolcarbamate); (11) calcium phenylthiolcarbamate is stirred with chloracetamide in aqueous solution to produce carbamylmethyl phenylthiolcarbamate; (12) sodium phenylthiolcarbamate is stirred with methyl or ethyl p-toluenesulphonate in ethyl alcohol at 0-5 DEG C. to form methyl or p ethyl phenylthiolcarbamate; (13) sodium phenylthiolcarbamate is heated with p-chloronitrobenzene to produce p-nitrophenyl phenylthiolcarbamate. Additional starting materials specified are, on the one hand, disodium m - phenylene - bis - (thiolcarbamate) and trisodium 1 : 3 : 5 - triethylbenzene-2 : 4 : 6-tris-(thiolcarbamate), and, on the other hand, ethylene dibromide, trimethylene dibromide, ethylene chlorobromide and p-xylylene dichloride. Alkali and alkaline-earth metal thiolcarbamates are obtainable by treating the corresponding isocyanates with alkali or alkaline-earth metal hydrosulphides. Specification 599,177 is referred to in the Provisional Specification.