Diphenyl disulfide, oxidation to methyl

Diphenylcyclopropenone, 47, 62 Dii henyldiacetylene, 45, 39 Diphenyl disulfide, oxidation to methyl benzenesulfinate, 46, 62 1,1-Diphenylethylene, reaction with N,or diphenylmtrone, 46,129 N,N -Diphi iiyli tiiyleni diamine, condensation with triethyl orthoformate, 47, 14... 

Diphenylcyclopropane, 48, 75 Diphenylcyclopropenone, 47, 62 Diphenyldiacetylene, 46,39 Diphenyl disulfide, oxidation to methyl... 

In the photochemical one-electron oxidation of aromatic sulfides, dimer radical cations were formed in rapid equilibrium with monomeric radical cation (59). The complex formation of a- and tt-types has been shown to be sensitive to the steric and electronic influence of substituent. For the case of jo-(methylthio)anisole the formation of TT-type dimer was shown to be reduced due to steric hindrance of two methyl groups. No formation of dimer radical cation was observed for jo-(methoxy)thioanisole and diphenyl disulfide where the corresponding monomer radical cations are stabilized by the delocalization of positive charge on the sulfur atom. Density-functional calculations supported the experimental results. The intramolecular formation of similar radical... 

Plant. In plants, fonofos is oxidized to the phosphonothioate (Hartley and Kidd, 1987). Oat plants were grown in two soils treated with [ C]fonofos. Most of the residues remained bound to the soil. Less than 2% of the applied [ C]fonofos was recovered from the oat leaves. Metabolites identified in both soils and leaves were methyl phenyl sulfone, 2-, 3- and 4-hydroyxymethyl phenyl sulfone, thiophenol, diphenyl disulfide, and fonofos oxon (Fuhremann and Lichtenstein, 1980 Lichtenstein et al., 1982). 

The reactivity of 120 is much less than that of either a normal alkene or a dithioacetal. Attempts to hydrogenolyze (see Section IV,3) or reduce 120 with Raney nickel, to hydrolyze the dithioacetal (see Section IV,1) with mercury(II) chloride (even in the presence of an overwhelming excess of the reagent), and to ozonize the double bond at —78°, produce only the starting material an analytical sample was prepared by extended treatment of the crude product with a concentrated, aqueous, alkaline solution of potassium permanganate at the reflux temperature.20 Acetolysis, ozonolysis, or brominolysis of 120 at room temperature affords diphenyl disulfide, and extended oxidation with hydrogen peroxide in acetone, with peroxypropionic acid, and with peroxyacetic acid, produces benzene-sulfonic acid, methyl phenyl sulfone, and an uncharacterized explosive, respectively the products occur as intractable mixtures, and the yields are invariably low. 

Oxidation, of diphenyl disulfide to methyl benzenesulfinate with lead tetraacetate in methanol, 46,62... 

Pyrolysis of sulfoxides provides a convenient method for introducing unsaturation at the position a- to carbonyl compounds. Formation of the enolate and reaction with dimethyl (or diphenyl) disulfide gives the a-methylthio (or phenylthio) derivative. Oxidation with a suitable oxidant, such as mCPBA or NaI04, gives the sulfoxide, which eliminates sulfenic acid on heating to give the a,(3-unsaturated carbonyl compound. For example, the methyl ester of a pheromone of queen honey bees was synthesized from methyl 9-oxodecanoate after initial protection of the ketone as the acetal (2.24). The -isomer usually predominates in reactions... 

Thiocyanogen [(SCN)2, 5°C, 4h, 40% yield] selectively oxidizes an 5-triphe-nylmethyl thioether to the disulfide (RSSR) in the presence of an 5-diphenyl-methyl thioether. ... 

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