4151-69-3Relevant articles and documents
Electro-organic Reactions. Part 24. Preparative and Mechanistic Aspects of the Anodic Oxidation of Dithioacetals and 1,3-Dithianes
Porter, Quentin N.,Utley, James H. P.,Machion, Pedro D.,Pardini, Vera L.,Schumacher, Paolo R.,Viertler, Hans
, p. 973 - 979 (2007/10/02)
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 sulphur-containing products confirmed that the initial, 2 F mol-1, products are disulphides which, in aqueous acetonitrile, are oxidised further to alkyl alkane thiosulphinates 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 in carbon-sulphur bond cleavage in the initially formed radical cation.The direction of the cleavage is determined by understandable substituent effects.
Reaction of thiyl radicals. XIII. Photochemically induced exchange reactions of liquid alkyl disulfides
Gupta, Dinesh,Knight, Arthur R.
, p. 1350 - 1354 (2007/10/02)
The liquid phase photolysis of some 35 liquid alkyl disulfide mixtures has been studied.The corresponding unsymmetrical disulfide is the only significant product of the reaction and the system attains a photo-equilibrium state at longer exposure times.Product formation is completely eliminated by the addition of nitric oxide.Quantum yields have been redetermined for the methyl disulfide- ethyl disulfide system using four different light sources.Initial rates have been measured for each of the 35 combinations and have been shown to be a function of total molecular weight of the disulfide mixture and to be strongly influenced by steric factors.These effects are most pronounced for mixtures wherein the exchange reaction between thiyl radical and a symmetrical disulfide is important as indicated by quantum yields above unity.Combinations of isodisulfides give rise to anomalously high rates.
