37945-60-1Relevant academic research and scientific papers
Formation of Elusive vic-Disulfoxides and OS-Sulfenyl Sulfinates during the m-Chloroperoxybenzoic Acid (MCPBA) Oxidation of Alkyl Aryl Disulfides and Their Regioisomeric Sulfinothioic Acid S-Esters
Freeman, Fillmore,Angeletakis, Christos N.
, p. 793 - 798 (2007/10/02)
The initial step in the 1 equiv m-chloroperoxybenzonic acid (MCPBA) oxidation of 2,2-dimethylpropyl phenyl disulfide (10) and phenyl phenylmethyl disulfide (14) occurs predominantly at the sulfur atom bonded to the alkyl group to give S-phenyl 2,2-dimethylpropanesulfinothioate (5) and S-phenyl phenylmethanesulfinothioate (6), respectively.The 2 equiv MCPBA oxidation of disulfide 10 gives S-phenyl 2,2-dimethylpropanesulfonothioate (23) as the major product.The 1 equiv MCPBA oxidation of thiosulfinates 5 and 6 and S-2,2-dimethylpropyl benzenesulfinothioate (9) ultimately gives thiosulfonate 23, S-phenyl phenylmethanesulfonothioate (17), and thiosulfonate 23, respectively, as the major products.Thus, peroxidation of regioisomeric S-alkyl and S-aryl sulfinothioates 5 and 9 occurs predominantly at the sunfenyl sulfur atom to give diastereomeric vic-disulfoxides (α-disulfoxides) which may undergo cycloelimination to sulfines and sulfenic acids, dissociate to sulfinyl radicals, and rearrange intramoleculary to OS-sulfenyl silfinates and/or to sulfonothioic acid S-esters.OS-Sulfenyl sulfinates may isomerize to sulfonothioic acid S-esters or dissociate to sulfinyl radicals and/or to thiyl and sulfonyl radicals.The sulfinyl radicals may combine to form vic-disulfoxides and/or OS-sulfenyl sulfinates while the thiyl and sulfonyl radicals may lead to sulfonothioic acid S-esters.
Intermediates in the Peroxy Acid Oxidation of Phenyl Phenylmethanethiosulfinate
Freeman, Fillmore,Angeletakis, Christos N.
, p. 3991 - 3996 (2007/10/02)
The m-chloroperoxybenzoic acid (MCPBA) oxidation of phenyl phenylmethanethiosulfinate (9) in CDCl3 has been studied.Low-temperature 1H NMR and 13C NMR spectra show that phenyl phenylmethanethiosulfonate (7), phenylmethanesulfonic acid (26), and phenylmethanesulfinic acid (27) are formed during the early stages of oxidation.Although 7 may be formed via direct attack of MCPBA at the sulfinyl sulfur atom of 9, the presence of 7, 26, and 27 is also explicable in terms of formation and rearrangement of metastable α-disulfoxide (13) and sulfenyl sulfinate (14) intermediates.
