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PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
5
pubmed:dateCreated
2002-3-4
pubmed:abstractText
tert-Butyl hydroperoxide (TBHP) efficiently converts a wide variety of sulfides to sulfoxides and sulfones. The method offers the advantage that one product or the other can be obtained in high purity by a modest variation of conditions. The reactions occur smoothly at 25minus sign50 C in chloroform and, to the extent studied, in toluene and methylene chloride. A catalyst is required; the most extensively studied was MeReO(mtp)PPh(3), 1, where mtpH(2) is 2-(mercaptomethyl)thiophenol. Other chelating dithiolate ligands can be used with comparable results. These oxidations were tested for dialkyl, alkylminus signaryl, and diaryl sulfides; thiophenes; and thianthrene. Even the "hard" sulfide, 4,6-dimethyldibenzothiophene (DMDBT) was quantitatively oxidized to the dioxide with TBHP:DMDBT 3.0-3.5 and 0.05-3.8 mol % 1. The mechanism was explored in kinetics studies carried out only for methyl tolyl sulfide. The product buildup curve was complex, with an induction period followed by a rapid growth phase. The kinetic data could be modeled adequately but not perfectly by allowing five rate constants to refine. Their values are consistent with the chemical sense of the mechanism.
pubmed:language
eng
pubmed:journal
pubmed:status
PubMed-not-MEDLINE
pubmed:month
Mar
pubmed:issn
0020-1669
pubmed:author
pubmed:issnType
Print
pubmed:day
11
pubmed:volume
41
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
1272-80
pubmed:dateRevised
2003-11-3
pubmed:year
2002
pubmed:articleTitle
Oxorhenium(V) dithiolates catalyze the oxidation by tert-butyl hydroperoxide of sulfoxides and sulfides, including 4,6-dimethyldibenzothiophene.
pubmed:affiliation
Department of Chemistry, Ames Laboratory, Iowa State University of Science and Technology, Ames, IA 50011, USA.
pubmed:publicationType
Journal Article