화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Journal of Industrial and Engineering Chemistry, Vol.4, No.2, 127-134, June, 1998
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Unexpected Formation of 1,2-Dithiolan-3-one by Oxidation of 3-Acetylthio-2-methylpropanoic Acid with Thionyl Chloride [1]
Hee Bong Lee, and Young Gyu Kim
  • School of Chemical Engineering, Seoul National University, Seoul 151-742, Korea
An unexpected oxidation reaction of 3-acetylthio-2-methylpropanoic acid (3) with thionyl chloride occurred to give 4-methyl-1,2-dithiolan-3-one (4) and 4-methyl-1,2-dithiolen-3-one (5) in the course of the synthesis of α-methyl- β-propiothiolactone (1). Their structures were characterized extensively with the spectroscopic means. It was proposed that 5 was derived from 4 based on the literature precedents. In an effort to explain the formation of 4 and 5, two stable intermediates, disulfide dicarboxylate 8 and trisulfide dicarboxylate 9, were isolated from the reaction mixture and identified with full spectroscopic data. The structural assignments and their interconnections were secured by independent syntheses and interconversions between them. Further evidence was provided by transformation of disulfide dicarboxylic acid 11 into 4 via disulfide diacid dichloride 12 and its carbonate 13. The oxidation reaction of a thioester or thiol group with thionyl chloride seemed unknown and it was proposed that chlorothiosulfite 18 or 19 be the initial intermediate in the oxidation reaction, compared with its known oxygen analog, chlorosulfite and the literature precedents. Thus, thiol 10 was oxidized much faster to give the same sulfide mixture as one obtained with thioester 3.
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