Diphenyl Sulfoxide Derivatives

Predominant formation of the C-benzylated product can be understood by considering the soft carbon nucleophile attacking the benzyl carbon of the oxosulfonium trilluoromethane sulfonate, with diphenyl sulfoxide acting as a soft leaving group. The reaction also proceeds smoothly with various other substituted benzyl alcohols with moderate to good yields. Sodium enolates derived from esters, a-cyano esters, a-aromatic and aliphatic ketones can also be benzylated with consistent high yields. 

Yeom, H.-S., Shin, S. (2013). Au(I)-catalyzed intramolecular oxidative cyclopropanation of 1,6-enynes derived from propiolamides with diphenyl sulfoxide. Organic Biomolec-ular Chemistry, 11, 1089-1092. 

The photochemical behavior of a number of substituted derivatives of thiochroman-4-one 1-oxides has been examined by Still and coworkers192-194. These authors also report that rearrangement to cyclic sulfenates, with subsequent reaction by homolysis of the S—O bond, appears to be a particularly favorable process. For example, ultraviolet irradiation of a solution of 8-methylthiochroman-4-one 1-oxide (133) in benzene for 24h afforded a single crystalline product which was assigned the disulfide structure 134 (equation 54). More recently, Kobayashi and Mutai195 have also suggested a sulfoxide-sulfenate rearrangement for the photochemical conversion of 2,5-diphenyl-l,4-dithiin 1-oxide (135) to the 1,3-dithiole derivatives 136 and 137 (equation 55). 

The C—S bond lengths vary upon changing carbon valence states. However, the sulfones and sulfoxides show less sensitivity to these changes than the analogous sulfides . These effects can be illustrated by considering the C—S bond lengths (A) in analogous dimethyl and diphenyl derivatives ... 

Diphenylurea Crystallization. 1,3-hfsphenylurea (13) is the parent compound of a large family of derivatives, most of which do not cocrystallize with guest molecules (Etter et al. 1990). Even when put into solution with strong hydrogen bond acceptors, e.g., dimethyl sulfoxide (DMSO), triphenylphosphineoxide (TPPO) and tetrahydrofuran (THF), most diphenyl ureas crystallize with other molecules of the same kind in a connectivity pattern viewed as is shown below (14), instead of forming cocrystals (e.g., 15). 

Cycloalkane ring-fused 2,4-diaminopyrido[2,3-, pyrimidine 580 was obtained by direct treatment of sulfone 579 with guanidine carbonate in boiling diphenyl ether. Sulfoxide 579 was prepared by perbenzoic acid oxidation of the methylthio derivative <1994T199>. 

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