(1; R = p-MeC6H4SO2)

[13150-75-9]  · C9H13NO2S2  · S,S-Dimethyl-N-(p-toluenesulfonyl)sulfilimine  · (MW 231.37) (2; R = 2,4-(NO2)2C6H3)

[37873-98-6]  · C8H9N3O4S  · S,S-Dimethyl-N-(2,4-dinitrophenyl)sulfilimine  · (MW 243.27)

(reagents for a-S,S-dimethylsulfuranylation of active methylene compounds,2 and ortho-methylation of phenols;3,4 (1) is a methylene transfer agent which converts carbonyl compounds into epoxides5)

Alternate Names: (1) DMTS; (2) DMDNS.

Physical Data: (1) mp 154-155 °C; (2) mp 175-176 °C (dec).

Solubility: insol H2O; sol ethyl and methyl alcohols, acetone, chloroform, and other common polar organic solvents.

Form Supplied in: (1) white solid; (2) orange solid.

Preparative Methods: (1) is conveniently prepared by adding a slight excess of Dimethyl Sulfide to an aqueous solution of Chloramine-T, and collecting the deposited crystals by filtration and recrystallization from ethanol.1 The yield of white crystalline solid is >95% based on chloramine T.

For preparation of (2), Phosphorus(V) Oxide (60 mmol) is added with stirring to 25 mL of DMF at 0 °C. After 30 min, Dimethyl Sulfoxide (60 mmol) is added. After stirring for 1 h, 20 mmol of 2,4-dinitroaniline in 25 mL of DMF is added dropwise at 0 °C with continued stirring. After 3 h, 180 mmol of Triethylamine is added at 0-5 °C, and stirring is continued for 3 h. The deposited crystals are collected by filtration and recrystallized from THF. The yield of orange crystalline material is 96% based on 2,4-dinitroaniline.2,3

Handling, Storage, and Precautions: stable at rt in a sealed bottle, but storage at lower temperature is recommended for (2). Use in a fume hood.

Reagent (2) reacts with p-toluenesulfonamide (at 90 °C for 7 h in DMF) to give (1) (58%), in an ylide exchange reaction.

Reactions of (1) and (2) with active methylene compounds in DMF give the corresponding sulfuranes (eq 1). Reagent (2), which is more basic than (1), gives higher yields of sulfuranes. Furthermore, the yields of the ylide exchange reactions depend on the pKa value of the active methylene compounds, as shown in Table 1. The lower the pKa value, the higher the yield of sulfurane.2,3

Reactions of (1) and (2) with phenols give o-methylthiomethylated phenols (eq 2).3,4 Mixtures of the phenols and 0.5 equiv of (1) or (2) are heated without solvent at 120-130 °C for 3-7 h. 2-Methylthiomethylphenols are obtained from 2- and 4-methyl, 2,5- and 3,5-dimethyl-, 2,3,5-trimethyl-, and 2-methoxyphenols in 55-95% yield (Table 2). In some case, significant amounts of bis(methylthiomethyl) products are also formed. The yields using (2) are higher than those using (1).

Like S,S-Dimethyl-N-(p-toluenesulfonyl)sulfoximine6 and (dimethylamino)dimethyloxosulfonium tetrafluoroborate,7 the N-tosylsulfilimine (1) reacts as a methylene transfer reagent, converting aldehydes and ketones to epoxides (eq 3). Thus (1) is heated at 80-90 °C for 0.5 h in DMSO in the presence of Sodium Hydride, and the resulting anion is allowed to react with carbonyl compounds to give 1-mono- and 1,1-disubstituted oxiranes in 46-56% yields.5

Related Reagents.

N,S-Dimethyl-S-phenylsulfoximine; Dimethylsulfonium Methylide; Dimethylsulfoxonium Methylide; S,S-Dimethyl-N-(p-toluenesulfonyl)sulfoximine; S,S-Diphenylsulfilimine.

1. Mann, F. G.; Pope, W. J. JCS 1922, 121, 1052.
2. Yamamoto, T.; Harigaya, Y.; Okawara, M. CL 1972, 1009.
3. Yamamoto, T.; Harigaya, Y.; Okawara, M. T 1978, 34, 3097.
4. Yamamoto, T.; Okawara, M. BCJ 1978, 51, 2443.
5. Tamura, Y.; Matsushima, H.; Ikeda, M.; Sumoto, K. S 1976, 35.
6. Johnson, C. R.; Katekar, G. F. JACS 1970, 92, 5753.
7. Johnson, C. R.; Rogers, P. E. JOC 1973, 38, 1793.

Tamotsu Yamamoto

Kanto Gakuin University, Yokohoma, Japan

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