Anodic oxidation of substituted [4-hydroxy-3-coumarinyl]-phenylthiomethanes in acetonitrile. Evidence for a cationic intermediate in carbon–sulfur bond fragmentation

The anodic oxidation of substituted [4-hydroxy-3-coumarinyl]-phenylthiomethanes, 1a– 1c, in acetonitrile is shown to correspond to a one electron process. The radical cation produced undergoes carbon–sulfur bond fragmentation through loss of a phenylthio radical to give a cation which is trapped by...

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Bibliographic Details
Published in:Electrochimica acta 1998-01, Vol.43 (12), p.1773-1778
Main Authors: Tabakovic, Ibro, Gaon, Igor, Distefano, Mark D.
Format: Article
Language:English
Subjects:
Chemistry
cyclic voltammetry
Electrochemistry
Exact sciences and technology
General and physical chemistry
geranyl [4-hydroxy-3-coumarinyl]-phenylthiomethane
Kinetics and mechanism of reactions
preparative anodic oxidation
reaction mechanism
substituted [4-hydroxy-3-coumarinyl]-phenylthiomethanes
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Summary:The anodic oxidation of substituted [4-hydroxy-3-coumarinyl]-phenylthiomethanes, 1a– 1c, in acetonitrile is shown to correspond to a one electron process. The radical cation produced undergoes carbon–sulfur bond fragmentation through loss of a phenylthio radical to give a cation which is trapped by Ritter reaction with acetonitrile to yield the final products 2a– 2c in 64–82% yield. In the case of geranyl [4-hydroxy-3-coumarinyl]-phenylthiomethane, 1d, the intermediate allylic cation is attacked intramolecularly by a hydroxy nucleophile followed by loss of a proton, to give 2d in 40% yield.
ISSN:0013-4686
1873-3859
DOI:10.1016/S0013-4686(97)00318-6