Phenyl vinyl sulfide, synthesis

Phenyl vinyl sulfide is prepared from thiophenol and 1,2-dibromoethane according to the procedure described by Paquette and Carr see Org. Synth. 1985, 64, 157. An earlier, three-step synthesis employing 2-chloroethanol instead of 1,2-dibromoethane is available.2... 

Thiiranes react with benzyne in an efficient synthesis of phenyl vinyl sulfides. The reaction is stereospecific, thus producing ds-(phenylthio)stilbene from cis-2,3-diphenylthiirane and trans-(phenylthio)stilbene from fra .v-2,3-diphenylthiirane (Scheme 24) (84TL2679). 

Prior to submission of this manuscript a new, efficient synthesis of phenyl vinyl sulfide was published Brace, N. O. J. Org. Chem. 1993, 58, 4506. 

The usefulness of the cation radical Diels-Alder reaction for natural product synthesis has been illustrated in the synthesis of / -selinene (Scheme 41) [81], which utilizes phenyl vinyl sulfide as a Diels-Alder dienophile and the photosensitized electron transfer method as the preferable method for generating the corresponding cation radical. 

An example of this method is given by the synthesis of brevicomin. The desired a-(phenylthio) ether (7) was made by Diels-Alder addition of phenyl vinyl sulfide and methyl vinyl ketone. Treatment of (7) with lithium l-(dimethylamino)naphthalenide, followed by trapping of the anion with propionaldehyde and ring closure to an acetal during the acidic work-up, afforded a mixture of endo and exo isomers of brevicomin (Scheme 36). 

Scheme 5a. Synthesis of phenyl vinyl sulfide. Solvent. EtOH yield, ca. 50%.

ORGANIC SYNTHESIS PROCEDURES Phenyl Vinyl Sulfide... 

An equimolar amount of 30%-H2O2 added dropwise with stirring to phenyl vinyl sulfide in acetic anhydride, stirring continued 5-6 hrs., and allowed to stand overnight phenyl vinyl sulfoxide. Y 82%. F. e. s. A. V. Sviridova, V. I. Laba, and E. N. Prilezhaeva, Zh. Org. Khim. 7, 2480 (1971) C. A. 76, 72158 with N-chloro-nylon-66 in methanol-benzene or water-dioxane s. Y. Sato, N. Kunieda, and M. Kinoshita, Chem. Lett. 1972, 1023 (Eng) C. A. 77, 164179 with ammonium cerium(IV) nitrate, mostly diaryl sulfoxides, s. T.-L. Ho and C. M. Wong, Synthesis 1972, 561. 

The synthesis of the preceding vinyl amino sulfone offers a very good example of a stereospecific sulfide-directed epoxidation (Scheme 76).Oxidation of optically active sulfide alcohol (12 readily made from epoxycyclopentadiene and resolved) with MCPBA affords the corresponding sulfoxide, which is in equilibrium with the sulfenate ester. Treatment with pyridine hydrobromide and then phenyl disulfide and bromine gives the bromodiol (13), which is simply cyclized to the epoxide with aqueous sodium hydroxide solution (83% overall yield from the sulfoxide). Treatment of the P-epoxy sulfone with DBU followed by in situ silylation with f-butyldiphenylsilyl chloride affords an 86% yield of vinyl sulfone (14). Mesylation of the alcohol moiety followed by immediate treatment with dimethylamine produces the amino vinyl sulfone via a syn Sn2 substitution. ... 

Chloronaphthalene Hydrogen sulfide Tri-m-cresyl phosphate Tri-p-tolyl phosphate EPDM peroxide-cured modifier 1,2-Polybutadiene Vinyl butadiene ephedrine synthesis Ethyl phenyl ketone epilepsy management Boron... 

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