Electro-organic reactions. Part 24. Preparative and mechanistic aspects of the anodic oxidation of dithioacetals and 1,3-dithianes

Autor:	Paulo R. Schumacher, Vera L. Pardini, Pedro D. Machion, Quentin N. Porter, Hans Viertler, James H. P. Utley
Rok vydání:	1984
Předmět:	chemistry.chemical_classification Reaction mechanism chemistry.chemical_compound Ketone Organic reaction chemistry Radical ion Polymer chemistry Substituent Organic chemistry Aldehyde Bond cleavage Alkyl
Zdroj:	Journal of the Chemical Society, Perkin Transactions 1. :973
ISSN:	1364-5463 0300-922X
DOI:	10.1039/p19840000973
Popis:	Anodic oxidation of the title compounds is a convenient and efficient method for deprotection, i.e. for the regeneration of carbonyl compounds.A detailed investigation of the sulphur-containing products confirmed that the initial, 2 F mol–1, products are disulphides which, in aqueous acetonitrile, are oxidised further to alkyl alkanethiosulphinates and the corresponding thiosulphonates. In some cases alkyl polysulphides and N-alkylacetamides are important products. Unsymmetrical dithioacetals are oxidised anodically to the three possible disulphides, i.e. cross-coupling occurs. Unsymmetrical disulphides are similarly oxidised to a complex mixture of symmetrical and Unsymmetrical thiosulphinates and thiosulphonates.These results, combined with those of cyclic voltammetric and coulometric experiments, suggest a mechanism in which the key step is carbon–sulphur bond cleavage in the initially formed radical cation. The direction of the cleavage is determined by understandable substituent effects.
Databáze:	OpenAIRE
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