Phenyl methyl sulphide

Oxidation of dibenzyl and methyl phenyl sulphides by lead tetraacetate in acetic acid was also reported127. 

Recent results. Riddel et al.40 have reported the spectral parameters of some significant sulphur compounds, including some previously unobserved functional groups phenyl isothiocyanate (PhNCS), methyl thiocyanate (MeSCN), thiophenol (PhSH), methyl phenyl sulphide (PhSMe), 2-methylthiazole,... 

The use of a phase-transfer catalyst-aqueous sodium hydroxide system has now been employed in the synthesis of thiophenylcyclopropanes [e.g. (67)] from chloro-methyl phenyl sulphide. In like manner, the addition of chlorofluorocarbene to olefins works well in a two-phase system and has the advantage that olefins with base-... 

Electron Diffraction.—Among completed electron-diffraction studies are ethyl methyl sulphide, chloromethyl methyl sulphide, methyl phenyl sulphide, di-(2-pyridyl) sulphide, sulphones, sulphoxides and sulphones, and trifluoro-methanesulphonyl chloride. A number of precise analyses of gas-phase conformational equilibria have emerged. Methyl ethyl sulphide shows a preference for the gauche conformation rather than for the trans form. ... 

Alkoxy-sulphonlum Salts.— Alkylation of sulphoxides by a trialkyloxonium tetrafluoroborate gives these salts, which are relatively stable to air and moisture. The compounds, which are intermediates in one form of the Pummerer rearrangement, are efficient alkylating agents/ The role of methyl phenyl sulphide as the catalytic electron-carrier in an electrochemical oxidation of alcohols is proposed to involve alkoxysulphonium salt formation, followed by a hydride shift/ The fact that some sulphoxide is also formed in this reaction appears to have encouraged the authors in their proposal PhSMe — 2e PhSMe Ph MeOCHR R Ph (CH2X>CHR R2 - PhSMe + R COR/ However, there are inconsistencies in the adoption of this mechanism, which has been established for dimethyl sulphoxide in the presence of a proton acceptor, particularly since alcohols are readily oxidized in the same electrochemical system in the absence of a... 

Very low asymmetric induction (e.e. 0.3-2.5%) was noted when unsymmetrical sulphides were electrochemically oxidized on an anode modified by treatment with (— )camphoric anhydride or (S)-phenylalanine methyl ester299. Much better results were obtained with the poly(L-valine) coated platinum electrodes300. For example, t-butyl phenyl sulphide was converted to the corresponding sulphoxide with e.e. as high as 93%, when electrode coated with polypyrrole and poly(L-valine) was used. 

Chlorination not accompanied by oxidation occurred on treatment of aliphatic sulphides and phenylated dimethyl sulphide with 3-(dichloroiodo)pyridine in chloroform for example, methyl ethyl sulphide afforded a mixture of the two monochlorinated sulphides (CH2CISCH2CH3 and CH3SCHCICH3) in a ratio of 1 3 [25]. 

In an effort to mimic the proposed cyclization of the germaci tdienyl cation (450) to the cadinane skeleton, Ito et a/.215 have examined the fate of the four hedycaryol phenyl sulphides (451)—(454) on reaction with methyl iodide (cf. Vol. 10, p. 51). In all four cases the products derived (455)—(462) were eudesmane derivatives and this finding has been explained in terms of Hi-induced cycliz-ations, the HI being generated from the initially formed sulphonium salts. De-... 

The scope of the reactions of 5-nitro-3-thienylethyl chloride and acetate with the lithium salt of 2-nitropropane to give (83) (cf. this series, Vol. 2, p. 80) has been investigated. The cyano-group was not found to be sufficiently active, since 4-cyano-2-thienyl-methyl and -ethyl chlorides only gave O-alkylated products by an mechanism. The iSn(AEAE) reaction also occurred between benzenethiolate and 4-nitro-2-thienylmethyl acetate, and a moderate yield of 4-nitro-2-thienylmethyl phenyl sulphide was obtained. 

The thiols formed usually do not survive under the reaction conditions and cyclize to five- and six-membeied rings. Heating of allyl phenyl sulphide (94) in high boiling amines or carboxylic acids yields 2-methyl-2,3-dihydrobenzothiophene (95) and thiachroman (96). The two products are not interconvertible under these conditions. 

This reaction also yields both five and six-membered cyclic products, but has been shown to consist of two parallel processes . Prop-2-ynyl phenyl sulphide (117) on heating initially isomerizes to phenyl allenyl sulphide (118) and both 117 and 118 undergo the thio-Claisen rearrangement to the allenic (119) and acetylenic (120) thiols respectively. Subsequent cyclization yields the final products, 2H-thiachromene (121) and 2-methyl-benzothiophene (122). 

Reactions of Enolates and Enolate Equivalents.—Several papers have appeared on the use of enolates released from silyl enol ethers by Lewis acids. Fleming reports the regiospecific alkylation of either the thermodynamic or the kinetic silyl enol ethers with chloromethyl phenyl sulphide in the presence of titanium(iv) chloride. Oxidative or reductive removal of the sulphur gives a-methylene- or a-methyl-ketones respectively (Scheme 69). ... 

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