On the reaction of bis(phosphothioyl)disul‐fanes with hydroxamic acids,part I: Ionic versus radical reaction pathways

Among sodium N‐alkyl‐4‐chlorobenzo‐hydroxamates treated with bis(phosphothioyl)disul‐fanes >P(S)SSP(S)< (where >P(S) is phosphorothioyl, phosphonothioyl, and phosphinothioyl), only the N‐methyl one yields quantitatively the respective O‐phosphothioyl derivatives exhibiting complete inversion of configuration at phosphorus in a reaction whose products are inert toward dithiophosphate arising in the reaction. For branched N‐alkyl benzohydroxamates, products of a SET process predominated. The mechanism of the title reaction is discussed. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:271–282, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20423