A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1928, 8, 102
DOI: 10.15227/orgsyn.008.0102
[Oxirane, 2-phenyl-]
Submitted by Harold Hibbert and Pauline Burt.
Checked by Roger Adams and F. E. Kendall.
1. Procedure

Caution! Reactions and subsequent operations involving peracids and peroxy compounds should be run behind a safety shield. For relatively fast reactions, the rate of addition of the peroxy compound should be slow enough so that it reacts rapidly and no significant unreacted excess is allowed to build up. The reaction mixture should be stirred efficiently while the peroxy compound is being added, and cooling should generally be provided since many reactions of peroxy compounds are exothermic. New or unfamiliar reactions, particularly those run at elevated temperatures, should be run first on a small scale. Reaction products should never be recovered from the final reaction mixture by distillation until all residual active oxygen compounds (including unreacted peroxy compounds) have been destroyed. Decomposition of active oxygen compounds may be accomplished by the procedure described in Korach, M.; Nielsen, D. R.; Rideout, W. H. Org. Synth. 1962, 42, 50 (Org. Synth. 1973, Coll. Vol. 5, 414). [Note added January 2011].

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).

Chemical Abstracts Nomenclature (Collective Index Number);
(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)