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8430608 
Journal Article 
Mechanism of the Decomposition of α-Aminothiol Esters 
Searles, S, Jr; Nukina, S 
1965 
Yes 
Journal of the American Chemical Society
ISSN: 0002-7863
EISSN: 1520-5126 
87 
24 
5656-5661 
English 
The question of whether the generally facile thermal decomposition of α-aminomethanethiol esters, forming amides and polythioformaldehyde, proceeds by an intramolecular route, involving a four-membered cyclic intermediate, or by a bimolecular route has been investigated by kinetic studies in various solvents and by a crossover experiment without solvent. The data obtained indicated that both of these mechanisms occur, the bimolecular process being predominant in nitromethane and chloroform solutions and in the neat liquids. In relatively inert solvents, such as n-hexane, acetone, and 1,2-dimethoxyethane, however, a significant amount of the decomposition proceeds by a kinetically first-order process, which seems likely to be the intramolecular path involving a four-membered cyclic intermediate. Other aspects of the reaction are also discussed, including catalysis by tertiary amines and the first-order reaction observed in acetonitrile. © 1965, American Chemical Society. All rights reserved.