5956. Methanethiol

Nomenclature

CAS number: 74-93-1
Methyl mercaptan; mercaptomethane; thiomethyl alcohol; methyl sulfhydrate.
CH4S; mol wt 48.11.
C 24.97%, H 8.38%, S 66.65%.
CH3SH.

Description and references

Occurs in “sour” gas of W. Texas, in coal tar, and in petroleum distillates. Isolated from roots of Raphanus sativus. Produced in the intestinal tract by the action of anaerobic bacteria on albumin. Evolved from Penicillium brevicaule bread cultures containing disulfides. Prepn from sodium methyl sulfate and KHS: Klason, Ber. 20, 3409 (1887); Arndt, ibid. 54, 2236 (1921); catalytically from methanol and hydrogen sulfide: Kramer, Reid, J. Am. Chem. Soc. 43, 880 (1921); from methyl chloride and sodium hydrosulfide: Scott et al., Ind. Eng. Chem. 47, 876 (1955). Review of occurrence, preparation, properties and reactions: E. E. Reid, Organic Chemistry of Bivalent Sulfur vol. I (Chemical Publishing Co., New York, 1958) pp 15-261; of toxicology and human exposure: Toxicological Profile for Methyl Mercaptan (PB93-110799, 1992) 92 pp.

Properties

Flammable gas; odor of rotten cabbage. mp 123°. bp760 5.95°; d420 0.8665; d425 0.9600. Critical temp 196.8°. Critical pressure 71.4 atm. Heat capacity (solid at 14.97-146.57 K): 0.773-17.47 cal/deg/mole; (liquid at 154.16-271.06 K): 21.27-21.13 cal/deg/mole, Russell et al., J. Am. Chem. Soc. 64, 165 (1942). Azeotrope with isobutane (14.9% methanethiol) bp 13.00°. Soly in water at 20°: 23.30 g/l. Forms a cryst hydrate.

Derivative

Sodium salt heminonahydrate.
CH3SNa.4H2O; mol wt 151.16.
C 7.95%, H 8.00%, S 21.21%, Na 15.21%, O 47.63%.

Properties

Needles. Freely sol in water, methanol. Practically insol in ether.

Derivative

Copper salt.
CH3SCu; mol wt 110.65.
C 10.85%, H 2.73%, S 28.98%, Cu 57.43%.

Properties

Pale yellow crystals. Practically insol in water, ethanol, ether, benzene.

Caution

Potential symptoms of overexposure to methanethiol are irritation of eyes, skin and respiratory system; narcosis; cyanosis; convulsions; direct contact with liquid may cause frostbite. See NIOSH Pocket Guide to Chemical Hazards (DHHS/NIOSH 97-140, 1997) p 214.

Use

Intermediate in manuf of jet fuels, pesticides, fungicides, plastics; synthesis of methionine.