Organic Syntheses Procedure

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Org. Synth. 1950, 30, 58

DOI: 10.15227/orgsyn.030.0058

METHANESULFONYL CHLORIDE

Submitted by Peter J. Hearst and C. R. Noller¹.

Checked by R. S. Schreiber, B. D. Aspergren, and R. V. Heinzelmann.

1. Procedure

In a 1-l. three-necked flask fitted with a mechanical stirrer, a reflux condenser, a thermometer, and a separatory funnel (Note 1), and set up in a hood, is placed 152 g. (105 ml., 1.5 moles) of methanesulfonic acid (Note 2). The acid is heated to 95° on a steam bath, and 238 g. (146 ml., 2.0 moles) of thionyl chloride (Note 3) is added over a period of 4 hours. The temperature is kept at 95° throughout the addition and for 3.5 hours after it is completed.

The product is transferred to a modified Claisen flask (Note 4) and distilled under reduced pressure, heat being supplied by an oil bath (Note 5). Most of the thionyl chloride distils at room temperature. The yield of almost colorless product distilling at 64–66°/20 mm. (Note 6) is 122–143 g. (71–83%); n_D23 1.451.

2. Notes

1. The checkers recommend the use of silicone grease on all glass joints.

2. The methanesulfonic acid is a commercial product supplied by the Standard Oil Company of Indiana and reported to be 95% pure and to contain 2% water.

3. Eastman Kodak Company thionyl chloride (b.p. 75–76°) was used without further purification.

4. The checkers used a Claisen head with an attached 10-cm. Vigreux column.

5. A free flame should be avoided, because local superheating causes charring and decomposition. The fumes from the decomposition cause the product (which normally is colorless) to darken. The bath temperature should not exceed 115° at the end of the distillation.

6. The checkers observed a boiling point of 61–62°/18 mm.

3. Discussion

Methanesulfonyl chloride has been prepared by the chlorination of methyl thiocyanate,² S-methylthiourethan,³ sodium methylthiosulfate,⁴ S-methylisothiuronium sulfate⁵ or S-methylisothiuronium p-toluenesulfonate,⁶ and dimethyl disulfide in the presence of water;⁷ from sodium methanesulfonate by the action of phosphorus pentachloride,⁸^,⁹ phosphorus oxychloride,⁹ or benzotrichloride;¹⁰ from methanesulfonic acid by the action of phosphorus pentachloride¹¹ or thionyl chloride;¹² or by the reaction of methylmagnesium iodide with sulfuryl chloride.¹³

References and Notes

Stanford University, Stanford, California.
Johnson and Douglass, J. Am. Chem. Soc., 61, 2548 (1939); Johnson, U. S. pat. 2,174,856 [C. A., 34, 778 (1940)]; Kostova, Zhur. Obshchei Khim. (J. Gen. Chem.), 18, 729 (1948) [C. A., 43, 120 (1949)].
Battegay and Krebs, Compt. rend., 206, 1262 (1938).
Douglass and Johnson, J. Am. Chem. Soc., 60, 1486 (1938).
Johnson and Sprague, J. Am. Chem. Soc., 58, 1348 (1936).
Klamann and Drahowzal, Monatsh., 83, 463 (1952).
Dijkstra and Backer, Rec. trav. chim., 73, 569 (1954).
Billeter, Ber., 38, 2019 (1905); Helferich and Gnüchtel, Ber., 71, 712 (1938).
Dutt, J. Chem. Soc., 125, 1463 (1924).
I. G. Farbenind., A.-G., Ger. pat. 574,836 [C. A., 27, 4543 (1933)].
Carius, Ann., 114, 142 (1860); McGowan, J. prakt. Chem., [2] 30, 281 (1884).
Noller and Hearst, J. Am. Chem. Soc., 70, 3955 (1948).
Cherbuliez and Schnauder, Helv. Chim. Acta, 6, 256 (1923).

Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)

S-methylisothiuronium sulfate

S-methylisothiuronium p-toluenesulfonate

phosphorus pentachloride (10026-13-8)

thionyl chloride (7719-09-7)

Phosphorus Oxychloride (21295-50-1)

sulfuryl chloride (7791-25-5)

benzotrichloride (98-07-7)

methylmagnesium iodide (917-64-6)

methyl thiocyanate (556-64-9)

Methanesulfonyl chloride (124-63-0)

methanesulfonic acid (75-75-2)

S-methylthiourethan

sodium methylthiosulfate

dimethyl disulfide (624-92-0)

sodium methanesulfonate (2386-57-4)

Notes

References/EndNotes

Article Compounds

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