Organic Syntheses, CV 1, 494
STYRENE OXIDE
[Oxirane, 2-phenyl-]
Submitted by Harold Hibbert and Pauline Burt.
Checked by Roger Adams and F. E. Kendall.
1. Procedure
To a solution of 42 g. (0.30 mole) of perbenzoic acid (p. 431) in 500 cc. of chloroform is added 30 g. (0.29 mole) of styrene (b.p. 141–143°) (p. 440). The solution is kept at 0° for twenty-four hours and is shaken frequently during the first hour. At the end of twenty-four hours, titration of an aliquot part of the solution shows that only the slight excess of perbenzoic acid remains (Note 1).
The benzoic acid is removed from the chloroform solution by shaking with an excess of 10 per cent sodium hydroxide solution, the alkali is removed by washing with water, and the chloroform solution is dried with anhydrous sodium sulfate. It is then fractionated through an efficient distilling column (p. 130). Removal of the chloroform leaves a practically colorless liquid which distils at 188–192° (uncorr.) (Note 2). The yield is 24–26 g. (69–75 per cent of the theoretical amount).
2. Notes
1. The perbenzoic acid may be analyzed by mixing with an excess of acidified potassium iodide and titrating the liberated iodine with sodium thiosulfate (p. 434).
2. If the styrene oxide is distilled over a free flame some decomposition takes place as indicated by the formation of water. This is not observed if the product is distilled from an oil bath.
3. Discussion
Styrene oxide can be prepared by the action of iodine, water, and mercuric oxide on styrene.1 The procedure described has been published.2
References and Notes
  1. Fourneau and Tiffeneau, Compt. rend. 140, 1596 (1905).
  2. Hibbert and Burt, J. Am. Chem. Soc. 47, 2240 (1925).

Appendix
Compounds Referenced (Chemical Abstracts Registry Number)

sodium hydroxide (1310-73-2)

chloroform (67-66-3)

sodium sulfate (7757-82-6)

potassium iodide (7681-11-0)

sodium thiosulfate (7772-98-7)

Benzoic acid (65-85-0)

mercuric oxide (21908-53-2)

iodine (7553-56-2)

styrene (100-42-5)

Styrene oxide, Oxirane, 2-phenyl- (96-09-3)

Perbenzoic acid (93-59-4)