GB542641A - Manufacture of organic sulphur compounds - Google Patents

Abstract

542,641. Mercapto-substituted esters. DU PONT DE NEMOURS & CO., E. I., BURKE, W. J., and PETERS, F. T. May 17, 1940, No. 8834. [Class 2 (iii)] Organic sulphur containing compounds containing mercapto and carboxylic ester groups are prepared by re-acting with hydrogen sulphide a monomeric ester of an α#-unsaturated monocarboxylic acid containing at least four carbon atoms preferably in the presence of a .basic catalyst such as an amine. The reaction is preferably carried out in a closed vessel under pressure. Temperatures used range from 25‹ C.-95‹ C. depending on whether or not a catalyst is present. It is possible however to use temperatures up to as much as 300‹ C. Catalysts mentioned include basic organic compounds in general such as butylamine, diethylamine, ethanolamine, morpholine, aniline, triethylamine, cyclohexylamine, phenyl hydrazine, tetramethylammonium hydroxide, sodium acetate, sodium methylate, as well as the inorganic basic compounds sodium hydroxide, sodium carbonate, calcium oxide and ammonia. The compounds of the invention have the general formula : where R 4 is the radical of an organic hydroxyl compound, i.e. an alcohol or phenol minus at least one of its hydroxyl groups and X is the number of the missing hydroxyl groups R 1' R 2 , and R 3 may be hydrogen, or substituted or unsubstituted, saturated or unsaturated aliphatic, aromatic. alicyclic or heterocyclic organic radicals,. excluding the case where all R 1 , R 2 and R 3 are hydrogen. The radical R 4 may be saturated or unsaturated monovalent or polyvalent, aliphatic, aromatic, alicyclic or heterocyclic. The preferred form is monovalent aliphatic, and examples mentioned include the radicals of methanol, cyclohexanol, benzyl alcohol, ethoxyethanol, dodecanol-1, betachloroethanol, sec-butanol, phenol, naphthol, furfuryl alcohol, glycol, glycerol, xylenol. In examples (1) methyl-α-methacrylate and hydrogen sulphide are mixed in a closed bomb cooled in an acetone-solid carbon dioxide bath and then slowly heated to 200‹ C. to give methyl- 2-methyl-3-mercaptopropionate. (2) Methyl-α- methacrylate and hydrogen were mixed in the presence of piperidine and re-acted under the conditions of example (1) to give a similar product. (3) n-Butyl-α-methacrylate and hydrogen sulphide are re-acted as in example (2) to give a mixture of n-butyl-α-methacrylate and butyl-2-methyl-3-mercaptopropionate. (4) A mixture of monohydric alcohols obtained by hydrogenation of coconut oil, or oil acids and hydrogen sulphide are re-acted as in example (2) to give a mixture which is fractionally distilled-the fraction b.p. 130-156‹ C. is the " coconut alcohols " esters of 2-methyl-3- mercaptopropionic acid. The compounds of the present invention are useful as petroleum chemicals, pesticides, and agents for controlling the emulsion polymerization of chloroprene.