Trimethylsulfonium chloride

Epoxidation of aldehydes and ketones is the most profound utility of the Corey-Chaykovsky reaction. As noted in section 1.1.1, for an a,P-unsaturated carbonyl compound, 1 adds preferentially to the olefin to provide the cyclopropane derivative. On the other hand, the more reactive 2 generally undergoes the methylene transfer to the carbonyl, giving rise to the corresponding epoxide. For instance, treatment of P-ionone (26) with 2, derived from trimethylsulfonium chloride and NaOH in the presence of a phase-transfer catalyst Et4BnNCl, gave rise to vinyl epoxide 27 exclusively. ... 

Trifluoromethanesulfonic acid, Acyl chlorides, Aromatic hydrocarbons, 0375 Trimethylsulfonium chloride, 1303 Trimethylsulfoxonium bromide, 1299 Uronium nitrate, 0494... 

Trichlorophenol, 2107 Trifluoromethyl perchlorate, 0321 Trifluoromethylsulfm trifluoride, 0363 Trimethyl orthoformate, 1708 Trimethylsulfonium chloride, 1303... 

Dimethylsulfonium methylide. The reagent can be generated conveniently by reaction of NaOH with trimethylsulfonium chloride rather than NaH, required for generation from trimethylsulfonium iodide, the usual precursor.1 An added advantage is that the chloride can be prepared readily by reaction of dimethyl sulfide with methyl chloroformate in 73% yield.2... 

Trimethylsilylprop-2-enyl trifluoromethanesulfonate, 2843 3-Trimethylsilyl-2-propyn-1 -ol, 2489b iV-Trimethylsilyl-iV-trimethylsilyloxyacetoacetamide, 3369 Trimethylstibine, see Trimethylantimony, 1316 Trimethylsulfonium chloride, 1299 Trimethylsulfoxonium bromide, 1295 Trimethylthallium, 1317 f 2,4,6-Trimethyltrioxane, 2509 Trinitroacetonitrile, 1005... 

Trifluoromethyl hypofluorite, Lithium, 0352 2,4,6-Trimethylpyrilium perchlorate, 2987 Trimethylsulfonium chloride, 1299 Trimethylsulfoxonium bromide, 1295 Urea hydrogen peroxidate, 0475... 

Trichlorophenol, 2100 Trifluoromethyl perchlorate, 0320 Trifluoromethylsulfur trifluoride, 0362 Trimethyl orthoformate, 1702 Trimethylsulfonium chloride, 1299... 

Wagner et al. (22) isolated Pseudomonas MS which grew on trimethylsul-phonium salts as a sole source of carbon and energy, with the evolution of DMS. A partially purified enzyme preparation catalyzed the transfer of a methyl group from trimethylsulfonium chloride to tetrahydrofolate. Neither S-aaenosyl-methionine nor DMSP functioned in the methyl transfer reaction. The methyltransferase was devoid of vitamin B12, had a molecular weight of about 100,(JOO with a pH optimum of 7.8. 

This rate enhancement appears to be due to n complexing in the transition state, such as in Fig. 17. In the solvolysis of trimethylsulfonium chloride, where 7t complexing is impossible, the rate is higher with hydroxide, as expected. This fact lends support to the complexing interpretation. 

Finally, very recent work from our laboratory (Ref. 48) has focused on the use of phase transfer catalysis for the preparation of reactive polystyrene resins with vinyl or oxirane pendant groups (Scheme 7) by reaction of V with aqueous formaldehyde in the presence of sodium hydroxide and tetrabutyl ammonium hydroxide, or by reaction of aldehyde resin VII with trimethylsulfonium chloride under similar conditions. Success of the latter reaction hinges on the use of trimethylsulfonium chloride rather than the corresponding iodide. When the iodide is used the reaction is... 

In an ice bath, 20 ml. of 50% sodium hydroxide was slowly added into 50 ml.of methylene chloride solution containing the polymer, 0.25 g. of benzyltriethyl ammonium chloride and 0.83 g. of trimethylsulfonium chloride. After the complete addition, the solution mixture was brought to room temperature and continued stirring for 12 hrs. The resulting polymer was then collected and washed with water, methanol and ether. After drying at 70 under reduced pressure, the product was characterized and determined for the epoxide content by the modified iodometric method. 

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