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Effect of sulfuric acid on reactions of peroxymonosulfate ion with sulfides and thiol esters
Author(s) -
Bunton Clifford A.,
Kumar Anurag
Publication year - 1998
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/(sici)1099-1395(1998110)11:11<803::aid-poc70>3.0.co;2-a
Subject(s) - chemistry , thiol , sulfonate , sulfuric acid , solvent , aqueous solution , inorganic chemistry , catalysis , reaction rate constant , ion , medicinal chemistry , organic chemistry , kinetics , physics , quantum mechanics , sodium
Peroxymonosulfate ion, HSO 5 −, as Oxone in aqueous H 2 SO 4 , oxidizes sulfides [MeSC 6 H 4 X( p ), X = Me, H, NO 2 ] to sulfoxides and converts aryl thiobenzoates [PhCOSC 6 H 4 X( p ), X = Me, H] and thiol phosphorus(V) esters [Ph 2 POSPh, (EtO) 2 POSPh, Ph 2 POSEt, Ph(EtO)POSEt] into the acids and sulfonate ions. Second‐order rate constants increase with increasing concentration of H 2 SO 4 (10–53 wt%), owing to the high polarity of the medium rather than to acid catalysis. The rate increases fit the Grunwald–Winstein equation based on Y OTs solvent parameters derived from rate effects on S N 1 solvolyses. © 1998 John Wiley & Sons, Ltd.