A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1936, 16, 28
DOI: 10.15227/orgsyn.016.0028
Submitted by B. B. Corson
Checked by C. R. Noller and J. F. Carson.
1. Procedure
In a 1-l. round-bottomed flask equipped with a reflux condenser and protected by a calcium chloride tube are placed 150 g. (1.1 moles) of phenylacetic acid (Org. Syn. Coll. Vol. I, 1941, 436), 147 g. (1.1 moles) of freshly distilled cinnamic aldehyde, 122 g. of litharge, and 155 cc. of acetic anhydride. The mixture is boiled for five hours (Note 1), poured while still hot into a beaker, and allowed to stand overnight. The semisolid contents are stirred to a mush, filtered with suction in a large Büchner funnel, and pressed dry. The solid is washed on the funnel with two 35-cc. portions of ethyl alcohol, the material being stirred thoroughly before suction is applied. The cake is transferred to a beaker, stirred to a mush with 50 cc. of alcohol, and again filtered with suction. The material is washed with another 50-cc. portion of alcohol in the same manner (Note 2). The product, which is light yellow to tan in color, weighs 62–67 g. (27–29 per cent of the theoretical amount) (Note 3) and melts at 149.5–153.5°.
For purification the material is dissolved in 300 cc. of hot benzene; the solution is boiled three minutes with 5 g. of decolorizing carbon, and filtered hot, with gentle suction, through a warm Büchner funnel. The benzene filtrate is treated with 500 cc. of hot ethyl alcohol, heated to boiling, and then cooled to 10° in an ice bath, with shaking. After the crystals are filtered with suction and pressed thoroughly, 50 cc. of ethyl alcohol is allowed to soak into the cake and suction is applied again. The recrystallized product weighs 52–57 g. (23–25 per cent of the theoretical amount) (Note 4) and melts at 152.5–153.5°. This product is the trans-trans form of the diene.
2. Notes
1. During the first half hour, the flask should be heated gently and shaken several times to facilitate solution of the lead oxide.
2. Thorough washing is essential.
3. About 8 g. of crude hydrocarbon can be recovered from the original mother liquor, but the recovery is tedious and is not recommended.
4. An additional quantity of about 5.5 g. can be obtained by evaporating the mother liquor to 25 cc. and allowing to crystallize.
3. Discussion
The only method of preparative interest is the condensation of phenylacetic acid and cinnamic aldehyde.1 The above procedure follows the method of Kuhn and Winterstein.2 Bistyryl has been obtained also from styrylmagnesium bromide and cupric chloride,3 or azobenzene,4 and by the reduction of β-bromostyrene with hydrazine in the presence of palladium.5
This preparation is referenced from:

References and Notes
  1. Thiele and Schleussner, Ann. 306, 198 (1899).
  2. Kuhn and Winterstein, Helv. Chim. Acta 11, 103 (1928).
  3. Sakellarios and Kyrimis, Ber. 57, 325 (1924); Gilman and Parker, J. Am. Chem. Soc. 46, 2827 (1924).
  4. Gilman and Pickens, ibid. 47, 2410 (1925).
  5. Busch and Weber, J. prakt. Chem. (2) 146, 54 (1936).

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


ethyl alcohol,
alcohol (64-17-5)

Benzene (71-43-2)

acetic anhydride (108-24-7)

decolorizing carbon (7782-42-5)

palladium (7440-05-3)

Phenylacetic acid (103-82-2)

cupric chloride (77447-39-4)

cinnamic aldehyde

hydrazine (302-01-2)

β-bromostyrene (103-64-0)

Azobenzene (103-33-3)

Bistyryl (886-65-7)

styrylmagnesium bromide