3d-orbital resonance in divalent sulphide—X

Autor:	Shigeru Oae, K. Uneyama, Waichiro Tagaki, I. Minamida
Rok vydání:	1968
Předmět:	chemistry.chemical_classification Decarboxylation Aryl Organic Chemistry Inorganic chemistry chemistry.chemical_element Biochemistry Medicinal chemistry Oxygen Divalent chemistry.chemical_compound chemistry Drug Discovery Resonance effect
Zdroj:	Tetrahedron. 24:5283-5291
ISSN:	0040-4020
DOI:	10.1016/s0040-4020(01)96324-0
Popis:	Several α-mercaptoacetic and related acids were synthesized and the rates of the amine-catalysed decarboxylation were measured. In the carbanion-forming reaction, the α-mercapto group exhibits a dramatic rate-enhancement, due to the 3d-orbital resonance effect of the divalent sulphide group. For example, the rate of the decarboxylation of diphenylmercaptoacetic acid was 8·8 × 103 fold greater than that of the oxygen analog, diphenoxyacetic acid; while the substitution of one phenylmercapto group at α-position of phenylmercaptoacetic acid was found to accelerate the rate by 1·7 × 103. These results can be correlated with those of the base-catalysed HD exchange reactions of various sulphides previously reported1 and explained on the basis of 3d orbital resonance involving the S atom in divalent sulphides.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::e5212fcbe4263435db6524ad2620dbb1 https://doi.org/10.1016/s0040-4020(01)96324-0 Zobrazit plný text záznamu