2- phenyl methyl sulfide

Dimethyl sulfide Methyl phenyl sulfide 3-(Methylthiolcyclohexene... 

Methyl phenyl sulfide Methyl phenyl sulfoxide Methyl phenyl sulfone... 

Methyl phenyl sulfide, see Thioanisole Methyl phenyl sulfoxide, 46, 78 from methylsulfinyl chloride and benzene with anhydrous alumi num chloride, 46, 80 Methyl vinyl ketone, reaction with 1-morpholino 1 cyclohexene, 45,... 

Sulfoxides such as methyl phenyl sulfoxide 1898 are readily reduced by hexa-methyldisilthiane 601 to give sulfides such as methyl phenyl sulfide 1899 in 90% yield, sulfur, and HMDSO 7 [108-110]. Analogously, the S-oxide of diethylsulfide... 

When a mixture of methyl phenyl sulfide (69a) (1 g, 8.1 mmol), 30% H2O2 (1.84 g, 16.2 mmol), and water (10 ml) was stirred at room temperature for 24 h, rac-lOa was produced (Scheme 11). To the water suspension medium of rac-70a was added 10c (2 g, 4 mmol), and the mixture was stirred for 15 h to give a 1 1 inclusion complex of 10c with (+)-70a. Heating the filtered complex in vacuo gave (+)-70a of 57% ee (0.45 g, 82% yield). From the filtrate left after separation of the inclusion complex, (-)-70a of 54% ee (0.4 g, 73% yield) was obtained by extraction with ether. By the same procedure, optically active 70b-d were also prepared (Table 11). In the case of (+)-70b and (-)-70c,the efficiency of the enantiomeric resolution was very high. 

The oxidation of methyl phenyl sulfide using fresh PWAA gave methyl phenyl sulfone in 97% yield. In the repeated use of recovered catalyst, the yields of sulfone in runs 2 to 5 ranged from 82 to 88%. The activities of recovered catalysts were somewhat reduced. The deactivation may be caused by catalyst pulverization or degradation of the PW12O403- species. While the reusability and stability of the catalyst should be improved, this concept would be useful for the creation of sophisticated solid catalysts. After Ikegami s reports, Neumann and coworkers [140] applied this strategy to the development of alkylated polyethyleneimine/POM synzymes. 

It has been reported that methyl phenyl sulfide acts as a stabilizer phenylthioacetylene did not tend to darken in its presence.5b... 

Steric effects dominate in the oxidation of dialkyl, alkyl phenyl and benzal methyl phenyl sulfides to their sulfoxides by quinolinium fluorochromate (QFC) in aqueous acetic acid. QFC oxidation of phenoxyacetic acids has been smdied. Imidazolium dichromate oxidations of a-hydroxy acids have been smdied. ... 

SCHEME 102. Oxidation of methyl phenyl sulfide 22a by TADOOH 60... 

In 1997, Chmielewski and coworkers investigated the oxidation of methyl phenyl sulfide and methyl p-tolyl sulfide with chiral carbohydrate hydroperoxides, which have been... 

Allylic and benzylic alcohols were oxidized to aldehydes or ketones with BnPhsPHSOs in refluxing CHsCN. The yield increased in the presence of bismuth chloride in a catalytic amount. Selective oxidation of various alcohols under solvent free conditions was also reported Interestingly, benzyl alcohols were oxidized selectively to benzaldehydes in very high yield (95-100%) when reacted with BnPhsPHSOs (1.2 eq.) and AICI3 (1 eq.) in the presence of an equimolar amount of 2-phenethyl alcohol, diphenyl carbinol or methyl phenyl sulfide (equation 72). 

Oxidation of a snlfide to sulfoxide is known to be an electrophilic reaction, in contrast with nncleophUic oxidation of sulfoxide to sulfone. Since 2-nitrobenzenesulfinyl chloride/KOi oxidizes sulfides to sulfoxides selectively, intermediate 48 must be the actual active intermediate. Moreover, in the presence of l,4-diazabicyclo[2.2.2.]octane (DABCO), which is a radical capturing reagent, the oxidation of methyl phenyl sulfide to the sulfoxide was inhibited. In order to further detect the intermediate 48, pure 5,5-dimethyl-l-pyrroUne-l-oxide (DMPO) was used as a trapping reagent and spin adduct was obtained. The ESR spectrum of the DMPO spin adduct was obtained by the reaction of 02 with 2-nitrobenzenesulfinyl chloride (hyperfine coupling constants, aH = 10.0 G and aN = 12.8 G). 

The enantioselective oxidation of prochiral sulfides with DMD has been achieved by using bovine serum albumin (BSA) as the chiral inductor Moderate to good enan-tioselectivities have been reported in the presence of this protein, for which a typical example is shown in equation 22 . As yet, however, no enantioselective oxidation of a prochiral sulfide has been documented by employing an optically active dioxirane. We have tried the enantioselective oxidation of methyl phenyl sulfide with the dioxirane generated from the ketone 7 (Shi s ketone), but an ee value of only ca 5% was obtained. One major hurdle that needs to be overcome with such enantioselective dioxirane oxidations is the suppression of the background oxidation of the sulfide substrate by Caroate, an unavoidable feature of the in-situ mode. 

By the extension of the above-mentioned stereoselective asymmetric addition of alkylithiums to other organolithium reagents such as lithium salts of methyl phenyl sulfide, 2-methylthiazoline, trialkylsilylacetylene, N-nitroso-dimethylamine, and acetonitrile, chiral oxiranes (95) U1), thiiranes (96) nl), acetylenic alcohols (98) 112), and amino alcohols (97) U1) were readily obtained. 

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