Methoxymethyl sulfides

Methoxymethyl sulfides undergo oxidative cleavage on treatment with NBS in methanol, generating methyl sulfinates (8 examples, 53-98%). ... 

Ethers, esters, amides and imidazolidines containing an epithio group are said to be effective in enhancing the antiwear and extreme pressure peiformance of lubricants. Other uses of thiiranes are as follows fuel gas odorant (2-methylthiirane), improvement of antistatic and wetting properties of fibers and films [poly(ethyleneglycol) ethers of 2-hydroxymethyl thiirane], inhibition of alkene metathesis (2-methylthiirane), stabilizers for poly(thiirane) (halogen adducts of thiiranes), enhancement of respiration of tobacco leaves (thiirane), tobacco additives to reduce nicotine and to reduce phenol levels in smoke [2-(methoxymethyl)thiirane], stabilizers for trichloroethylene and 1,1,1-trichloroethane (2-methylthiirane, 2-hydroxymethylthiirane) and stabilizers for organic compounds (0,0-dialkyldithiophosphate esters of 2-mercaptomethylthiirane). The product of the reaction of aniline with thiirane is reported to be useful in the flotation of zinc sulfide. 

The carbenoid displacement reaction (see Section 1.4.5.2.1.4.) of the optically active acetoxy sulfide derivative 19 (or the corresponding methoxymethyl ether) with diazomalonate in the presence of a catalytic amount of rhodium acetate in refluxing benzene affords the tram-alkylation productl22. 

Another example of asymmetric induction in the transfer of chirality from tricoordinate sulfur to the nitrogen atom was reported by Kobayashi (157), who found that methylation of benzylethylani-line with (+)-methoxymethyl-p-tolylsulfonium salt 113 yields (-)-benzylethylmethylphenylammoniumtetrafluoroborate 268. A similar asymmetric methylation reaction was observed with benzyl ethyl sulfide. Chiral ammonium 268 and sulfonium salts 112 were formed... 

Chlor-ethoxy)-4-methyl- E2, 380 2-(2-Chlor-ethoxy)- -2-sulfid XII/2, 650 2-(2-Chlor-etliyl)-4-methyl- -2-oxid E2, 380 2-Chlor-4-methoxymethyl- -2-sulfid XII/2, 610,... 

Ethoxy-4-methoxymethyl- -2-sulfid XII/2, 631 4-Ethoxvmethyl-2-hydroxy- -2-oxid XII/2, 310 2-Ethoxy-4-mcthyl- -2-sulfid XlI/2, 631, 647, 650 4-Ethoxymethyl-2-vinyloxy- -2-oxid XII/2, 310 2-Ethoxy- -2-oxid XII/2, 345fi E2, 506 2-Ethoxy- -2-sulfid XII/2, 646 4-Ethyl-2-fiuor- E2, 334 2-Fluor- E2, 153, 334, 520, 675... 

Similarly, 56 reacts with sodium methoxide to give small quantities of the methoxymethyl analog of 56. In the same way, treatment of dichloro(2,2-dimethyl-3-buten-l-yl methyl sulfide)palladium(II) with CH2N2 gives the expected chloromethyl complex and a cyclopropanation product. 

Amines (S)-1 -Amino-2-methoxymethyl-1 -pyrrolidine. Azidomethyl phenyl sulfide. Bis(methoxycarbonyl)sulfur diimide. N,N-Bis(trimethylsilyl)rnethoxymethylamine. 

CSH10CIN 4-chloro-N,N-dimethyl aniline 698-69-1 504.15 44.283 1,2 13941 C8H10OS methoxymethyl phenyl sulfide 13865-50-4 453.82" 39.465 2... 

Treatment of 2-(phenylthio)alkanols (217), obtainable from methoxymethyl phenyl sulfide and ketones, with thionyl chloride affords the aldehydes (218) with rearrangement in high yields (Scheme 51). The cyclization of (218) to thiophenes (219) can be simply performed by stirring a solution of (218) with 2 equiv. of triethyloxonium tetrafluoroborate in dichloromethane. Although, in cases of R = Me, = Ph and R = Me, R = Ph, the formation of isomeric mixtures was expected, the reaction led to the predominant formation of the isomer (219) <85S434>. 

In an analogous approach, the effect of imidazole was also observed by Inoue et al. [114]. When alkyl aryl sulfides were oxidized with a novel iron porphyrin catalyst (52) (0.2 mol% equiv), the reaction proceeded enantioselectively under appropriate conditions. Iodosobenzene was used as oxidant in dichloromethane at -43°C. The turnover number increases to 142, and an ee of 73% was obtained in the presence of a 100 to 600 molar ratio of imidazole to catalyst for the synthesis of (5)-methoxymethyl phenyl sulfoxide. In the absence of imidazole, the enantioselectivity disappeared, giving the racemic sulfoxide. 

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