A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1934, 14, 18
DOI: 10.15227/orgsyn.014.0018
[Sulfide, β-chloroethyl methyl]
Submitted by W. R. Kirner and Wallace Windus.
Checked by H. T. Clarke and S. Gurin.
1. Procedure
In a 1-l. three-necked flask are mixed 150 g. (1.63 moles) of β-hydroxyethyl methyl sulfide (p. 345) (Note 1) and 200 g. of dry chloroform (Note 2). The flask is placed on a steam bath and is fitted with a dropping funnel, a mechanical stirrer, and a condenser. The condenser is fitted with a trap to remove the vapors of hydrogen chloride and sulfur dioxide. A solution of 204 g. (1.7 moles) (Note 3) of thionyl chloride in 135 cc. of dry chloroform is added dropwise to the β-hydroxyethyl methyl sulfide over a period of about two hours (Note 4). The reaction mixture is stirred vigorously during this addition and for about four hours after the addition is complete. The chloroform is distilled on the steam bath and the residue is distilled under reduced pressure. The yield is 135–153 g. (75–85 per cent of the theoretical amount) of a product boiling at 55–56°/30 mm. (Note 5).
2. Notes
1. Quantities of material seven times as large as the above may be used without decreasing the percentage yield of the product.
2. The chloroform is dried by distillation, and the fraction boiling at 60–61° is used.
3. The thionyl chloride is redistilled, and the fraction boiling over a two-degree range is employed.
4. The reaction mixture is heated once when about half the thionyl chloride has been added in order to keep the chloroform refluxing gently. Heating after the complete addition of the thionyl chloride is undesirable.
5. β-Chloroethyl methyl sulfide is a vesicant and must be handled with care. It boils at 140° under atmospheric pressure.
3. Discussion
The above method is essentially that described in the literature.1
This preparation is referenced from:

References and Notes
  1. Kirner, J. Am. Chem. Soc. 50, 2452 (1928).

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

hydrogen chloride (7647-01-0)

thionyl chloride (7719-09-7)

chloroform (67-66-3)

sulfur dioxide (7446-09-5)

β-Chloroethyl methyl sulfide,
Sulfide, β-chloroethyl methyl (542-81-4)

β-Hydroxyethyl methyl sulfide (5271-38-5)