Oxidation of Methyl (Methylthio)methyl Sulfoxide

Abstract

Oxidation of methyl (methylthio)methyl sulfoxide (2) with hydrogen peroxide in acetic acid or methanol produced bis(methylsulfinyl)methane in high yield. Similar results were obtained in oxidation of 2 with ozone, sodium metaperiodate, and m-chloroperbenzoic acid. In contrast, methyl (methylthio)methyl sulfone (4) was exclusively formed when oxidation of 2 with hydrogen peroxide was carried out in methanol in the presence of sodium hydroxide. Furthermore, we established a convenient and efficient method of preparing 4 by oxidation of 2 with potassium permanganate.

Oxygen transfer reactions. 2. A comparison of the reactions of ruthenium tetroxide, chromyl chloride, and permanganate with thianthrene 5-oxide

“…This result is consistent with the work of Ogura et al (19) who found that methyl (methy1thio)methyl Results sulfoxide, 1, was oxidized by permanganate to methyl (methThe products were analyzed by HPLC. Chromatograms were y1thio)methyl sulfone, 2, in 97% yield.…”

Conformationally Constrained Oxides of 1,3‐Dithiane: Synthesis and NMR Spectroscopic Investigations

“…The reaction outcome of the oxidation of the equatorial sulfoxide 13 was strongly dependent on the oxidant used. It has already been noted by Ogura et al25,28 for related compounds that nucleophilic oxidants like permanganate attack the sulfur of the more electrophilic sulfoxide and not the sulfide in the molecule. Accordingly, when we exposed sulfoxide 13 to potassium permanganate we obtained the sulfone 14 in an excellent 86 % yield (entry 6).…”

“…The best results for the preparation of sulfoxide 13 were achieved with sodium periodate25 or a hydrogen peroxide/urea complex (UHP) in the presence of acetic acid,26 which gave sulfoxide 13 in yields of 74 and 70 %, respectively (Table 1, entries 1 and 2). A minor product was the axial sulfoxide 12 (<10 %), which could not be separated after purification of the crude material.…”

“…We considered it likely that a 2‐fluorenylidene‐substituted 1,3‐dithiane 46 (which was prepared by Peterson olefination starting with dithiane 21 ) could not be oxidised at the equatorial positions of the sulfur atoms because this would lead to considerable steric hindrance and therefore we expected instead an axial oxidation. In fact, oxidation of fluorenylidene‐dithiane 46 with m ‐chloroperbenzoic acid25 led to symmetrical disulfoxide 47 (proven by MS and NMR spectroscopy) in which it could not be decided whether its sulfoxide groups were diaxial or diequatorial (Scheme ). Reaction with hydroxide led to the elimination of fluorenone, but unfortunately a dithiane derivative could neither be identified in the crude mixture nor be isolated.…”

Reações de α-sulfonil carbânions: alquilação e sulfenilação de alguns α-sulfonil tioésteres. Descarboxilação alquilativa dos ácidos α-fenilsulfonil-α-fenilpropanóicos racêmico e opticamente ativo

“…Ftue: ácido periódico, obteve-se, após mna hora de reação, mna mistura não identificada de produtos. Em mna outra tentativa, empregando-se mna mistura de ácido acético glacial e solução de peróxido de hidrogêni0 161 30 % e, variando as quantidades e a ordem de adição de reagentes, obtiveram-se, em todos os casos, misturas de sulfonil e sulfmil ácidos correspondentes, ao lado do reagente de partida e, em alguns casos, produtos provenientes da descarboxilação destes compostos. Tentou-se também C:…”