A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1934, 14, 36
DOI: 10.15227/orgsyn.014.0036
[Phenyl sulfide]
Submitted by W. W. Hartman, L. A. Smith, and J. B. Dickey.
Checked by Reynold C. Fuson and S. H. Babcock.
1. Procedure
In a 5-l. three-necked, round-bottomed flask, fitted with a mechanical stirrer, dropping funnel, and a condenser connected to an apparatus for removing hydrogen chloride, are placed 858 g. (980 cc., 11 moles) of dry benzene (Note 1) and 464 g. (3.48 moles) of aluminum chloride. The reaction mixture is cooled in an ice bath to 10°, and then 405.1 g. (3 moles) of commercial sulfur chloride in 390 g. (450 cc., 5 moles) of benzene is added, with stirring, over a period of one hour, the temperature being kept at about 10°. The reaction begins at once as evidenced by the evolution of hydrogen chloride and the separation of a yellow viscous aluminum chloride complex. When all the sulfur chloride has been added, the reaction mixture is removed from the ice bath, stirred at room temperature for two hours, and then heated at 30° until practically no hydrogen chloride is evolved (one hour). The mixture is then poured on 1 kg. of cracked ice, and, when hydrolysis is complete, the benzene layer is separated from the water layer by means of a separatory funnel. The benzene is distilled on a steam bath, and the resulting dark-colored oil is cooled to 0° and filtered through a Büchner funnel to remove the sulfur which separates. The residue is dissolved in 500 cc. of commercial methyl alcohol, and the solution is cooled to 0°. Stirring is continued for three hours, and the precipitated sulfur is removed as before. The alcohol is removed on a steam bath, and the residue is distilled from a 1-l. modified Claisen flask with a water-cooled side-arm receiver. After a small amount of low-boiling product passes over, there is obtained 470–490 g. (Note 2) of a yellow liquid boiling at 155–170°/18 mm. The material thus obtained is heated for one hour on a steam bath, with stirring, with 70 g. of zinc dust and 200 g. of 40 per cent sodium hydroxide solution (Note 3). The diphenyl sulfide is then separated from the sodium hydroxide, washed with two 500-cc. portions of water, dried over anhydrous sodium sulfate, and distilled. The yield of colorless diphenyl sulfide boiling at 162–163°/18 mm. is 450–464 g. (81–83 per cent of the theoretical amount).
2. Notes
1. The benzene can be dried by distilling on a steam bath until the distillate is no longer milky. About 15 per cent of the benzene is distilled.
2. On distillation of the residue in the distillation flask a fraction boiling at 170–200°/18 mm. is obtained. Crystallization of this material from methyl alcohol yields 8–10 g. of thianthrene, melting at 155–156°.
3. It is necessary to treat the diphenyl sulfide as described in order to obtain a colorless product.
3. Discussion
Diphenyl sulfide can best be prepared by treating benzene and aluminum chloride with sulfur chloride,1 sulfur dichloride,2 or sulfur.3 In addition to diphenyl sulfide, traces of thiophenol and varying amounts of thianthrene are found.

References and Notes
  1. Böeseken, Rec. trav. chim. 24, 209 (1905); Böeseken and Waterman, ibid. 29, 319 (1910); Böeseken and Koning, ibid. 30, 116 (1911); Genvresse, Bull. soc. chim. (3) 15, 409 (1896); Hartman, Smith, and Dickey, Ind. Eng. Chem. 24, 1317 (1932).
  2. Böeseken, Rec. trav. chim. 24, 217 (1905); Böeseken and Koning, ibid. 30, 116 (1911).
  3. Friedel and Crafts, Ann. chim. phys. (6) 14, 437 (1888); Böeseken, Rec. trav. chim. 24, 17, 219 (1905); Dougherty and Hammond, J. Am. Chem. Soc. 57, 117 (1935).

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

hydrogen chloride (7647-01-0)

Benzene (71-43-2)

methyl alcohol (67-56-1)

sodium hydroxide (1310-73-2)

sodium sulfate (7757-82-6)

sulfur (7704-34-9)

aluminum chloride (3495-54-3)

zinc (7440-66-6)

sulfur chloride

Thiophenol (108-98-5)

Diphenyl sulfide,
Phenyl sulfide (139-66-2)

thianthrene (92-85-3)

sulfur dichloride (10545-99-0)