A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1952, 32, 39
DOI: 10.15227/orgsyn.032.0039
Submitted by Eugene E. van Tamelen1
Checked by Charles C. Price and Paul F. Kirk.
1. Procedure
Ninety-eight grams (1 mole) of cyclohexene oxide (Note 1) is divided into two approximately equal portions; one portion is added to a solution of 121 g. (1.25 moles) of potassium thiocyanate in 100 ml. of water and 75 ml. of 95% ethanol. After standing for 3–4 hours (Note 2) the clear solution is transferred to a 1-l. flask equipped with a mechanical stirrer. The second portion of oxide is added, and the resulting solution is stirred vigorously for 36 hours at room temperature. The supernatant layer and the aqueous phase are then decanted from the precipitated potassium cyanate into a 1-l. separatory funnel. The potassium cyanate is rinsed with 50 ml. of ether, which is subsequently added to the separatory funnel and used to extract the cyclohexene sulfide. The ether extract is washed twice with 50-ml. portions of saturated sodium chloride solution and then dried over anhydrous sodium sulfate. The excess ether is removed on the steam bath, and the residual liquid is distilled under reduced pressure through an 18-in. Vigreux column while the distillate is being cooled in ice. The main fraction boils at 71.5–73.5°/21 mm. (69–71°/19 mm.) (Note 3); n25D 1.5306–1.5311. A fore-run, boiling up to 71.5°/21 mm., yields more of the product on redistillation. The total yield of cyclohexene sulfide is 81.5–83.5 g. (71–73%).
2. Notes
1. The cyclohexene oxide (b.p. 129–134°) was prepared from 2-chlorocyclohexanol.2
2. During this time a temperature rise of about 5° occurs.
3. Cyclohexene sulfide can be stored at about 5° in a closed container for at least a month without apparent decomposition.
3. Discussion
Cyclohexene sulfide has been prepared by the action of thiourea, potassium thiocyanate, or ammonium thiocyanate on cyclohexene oxide,3 by the hydrolysis of S-(trans-2-hydroxycyclohexyl)thiuronium sulfate in sodium carbonate solution,4 and by the alkaline hydrolysis of 2-mercaptocyclohexyl acetate or 2-acetylmercaptocyclohexyl acetate.5.
The method described above is a modification of that of Snyder, Stewart, and Ziegler.6

References and Notes
  1. University of Wisconsin, Madison, Wisconsin.
  2. Org. Syntheses Coll. Vol. 1, 185 (1941).
  3. Culvenor, Davies, and Pausacker, J. Chem. Soc., 1946, 1050.
  4. Bordwell and Andersen, J. Am. Chem. Soc., 75, 4959 (1953).
  5. Harding, Miles, and Owen, Chem. & Ind. (London), 1951, 887.
  6. Snyder, Stewart, and Ziegler, J. Am. Chem. Soc., 69, 2672 (1947).

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

ethanol (64-17-5)

ether (60-29-7)

ammonium thiocyanate (1762-95-4)

sodium chloride (7647-14-5)

sodium carbonate (497-19-8)

sodium sulfate (7757-82-6)

2-Chlorocyclohexanol (1561-86-0)

Cyclohexene oxide (286-20-4)

potassium thiocyanate (333-20-0)

potassium cyanate (590-28-3)

thiourea (62-56-6)

Cyclohexene sulfide,
7-Thiabicyclo[4.1.0]heptane (286-28-2)

2-mercaptocyclohexyl acetate

2-acetylmercaptocyclohexyl acetate

S-(trans-2-hydroxycyclohexyl)thiuronium sulfate