Reaction of Tetraethylthiuramdisulfide with Alkali and Its Bearing on Vulcanization Reactions

Klebanski and Fomina have reported on the action of alkali on tetraethylthiuram disulfide (TETD). They suggested the following equation for the reaction: (see PDF for diagram) This equation is based in part on a premise that TETM is one of the reaction products; we feel this premise is incorrect. As partial evidence for their proposed reaction scheme, Klebanski and Fomina claim the isolation of tetraethylthiurammonosulfide (TETM) from the reaction products. They give both the analysis figures and the melting point of the isolated substance. The melting point quoted by them is 64–65°. The melting point of TETM is, however, 28–33°. We have attempted the isolation of the substance reported by Klebanski and Fomina, and have repeated their experiment according to the published instructions. The only water-insoluble material which we were able to isolate, after 8 hours reaction with 2% aqueous sodium hydroxide, was unreacted TETD (73% of the starting material). The material isolated had a melting point of 68.5–70°, mixed melting point with TETD was 68.5–70°, the nitrogen and sulfur content was: %N 9.38, %S 42.82. Recrystallized from ether the substance melted at 70°, and analyzed as: %N 9.48, %S 43.05, mol. wt. 297; TETD requires; %N 9.53, %S 42.93, mol. wt. 296, m. pt. 70°.