0-Methyl benzenesulfenate

Methyl benzenesulfinate has been prepared by the three-stage process of reduction of benzenesulfonyl chloride to benzenesulfinic add, conversion of the acid to benzenesulfinyl chloride, and esterification of the chloride with methanol. 7 It has been prepared also by ozonolysis of methyl benzenesulfenate.4 The present procedure is based on one reported by Field, Hoelzel, and Locke.6... 

Pentamethoxyphosphorane, PfOCHj),. Mol. wt. 186.15, b.p. 37°. The material can be prepared in about 55% yield by reaction of trimethyl phosphite with methyl benzenesulfenate (which is converted during the reaction into diphenyl disulfide). It is stable to 80°. It reacts with acids to form methyl esters (methyl benzoate, 90% yield). It converts phenols into methyl ethers (anisole, 90% 2,4-dimethylanisole, 77% thioanisole, 87%). ... 

The reaction of tri-O-benzoylgalactal with methyl benzenesulfenate in the presence of trimethyl-silyl triflate and molecular sieves at —15 °C for 30 minutes gives a 68 20 12 mixture of products. 

Methyl benzenesulfenate activated by Lewis acids, such as trimethylsilyl triflate or boron tri-fluoride-diethyl ether complex, induces arenealkene cyclization, presumably via an episulfonium... 

Methyl benzenesulfenate has been reported [244] to be cleaved to thiophenol and methanol at —0.5 V (SCE) in aqueous buffer at pH 7 methyl 2-nitrobenzenesulfenate in DMF is reductively cleaved similarly [245]. 

Treatment of a-dichloromethyl phenyl sulfoxide with lithium diisopropylamide in THF gave monolithiated derivative 122, which upon further treatment with aldehyde afforded the )S-hydroxy-a-dichlorosulfoxide 123. Thermolysis of 123 gave dichloroketone 124, by extruding benzenesulfenic acid as shown below . Similarly, in the reaction of lithio-a-fluoromethyl phenyl sulfoxide and aldehyde, fluoromethyl ketone 126 was obtained, after thermolysis of the hydroxy intermediate 125. Diethylphosphorylmethyl methyl sulfoxide was shown by Miko/ajczyk and coworkers to be lithiated with n-BuLi to intermediate 127, which upon treatment with carbonyl compounds afforded the corresponding a, -unsaturated sulfoxides 128 in good yields. 

Phenol annelation.1 Methyl vinyl ketone (and substituted vinyl ketones) undergo Robinson annelation with the j8-keto sulfoxide (1) to afford the 5,6,7,8-tetrahydro-2-naphthol (2) with loss of benzenesulfenic acid. Sodium methoxide is used as base, and the reaction proceeds at 0 -> 25°. 

VSO can be used to form block copolymers with PS followed by VSO elimination to form EA-PS block copolymers [73,89,90]. th monomers can be polymerized anionical the s ene was initiated first and end-capped with 1,1-diphenyl ethylene (DPE). Vfith the addition of a few drops of DPE to the living styr solution, the styryl carbanions were converted to diphenyl methyl car-banions [91], which were bull, less reactive, and less nucleophilic than the styryl carbanions, thus minimizing any side reactions. The VSO monomer was then added to the DPE-capped styryl chains to generate a PS/PVSO copolymer. The resulting precursor copolymer had PDIs that were as low as 1.09. To thermally eliminate the benzenesulfenic acid moieties from the PVSO block, the copolymer was heated from room temperature to 80° C at l°C/min and then held at 80°C for 1 h [90]. It was then heated to 150°C at I°C/min to get the maximum amoimt of elimination (87-92%). Whereas the PS/PVSO precursor copolymer was soluble in many solvents, the PS/PA copolymer was soluble only when the PA content was less than 50 mol%. th 78 mol% PA content the conductivity of the copolymer was 8 x 10 S/cm after iodine doping. 

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