A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1925, 5, 103
DOI: 10.15227/orgsyn.005.0103
Submitted by C. S. Marvel and E. M. McColm.
Checked by H. T. Clarke and E. E. Dreger.
1. Procedure
In a 5-l. round-bottomed flask fitted with a stopper holding a reflux condenser and a separatory funnel are placed 294 g. (6 moles) of sodium cyanide and 300 cc. of water. The flask is heated on a steam bath until most of the sodium cyanide is in solution. This requires two to three hours. A solution of 500 g. (2.47 moles) of trimethylene bromide (Note 1) in 1 l. of 95 per cent alcohol is then added through the separatory funnel over a period of forty to sixty minutes. The mixture is refluxed for thirty to forty hours (Note 2) on a steam bath. Then the solvent is removed, preferably under reduced pressure, using an oil bath.
The residue, consisting of sodium bromide, sodium cyanide, and trimethylene cyanide, is extracted with 300–400 cc. of ethyl acetate, which dissolves the trimethylene cyanide and does not dissolve the inorganic salts. This solution is filtered and the salt washed once with about 100 cc. of ethyl acetate. The ethyl acetate is distilled at ordinary pressure (Note 3) and the residual liquid is distilled under reduced pressure. The yield of trimethylene cyanide boiling at 144–147°/13 mm. or 131–134°/10 mm. is 180–200 g. (77–86 per cent of the theoretical amount).
2. Notes
1. Larger runs seem to give slightly lower yields.
2. The yield is lower if the heating is continued too long, owing to partial hydrolysis of the cyanide.
3. Very little ethyl acetate is lost in this procedure if it is distilled at ordinary pressures. If it is not entirely removed before the pressure is reduced, considerable foaming occurs.
3. Discussion
Trimethylene cyanide can be prepared by the action of potassium cyanide on trimethylene bromide.1
This preparation is referenced from:

References and Notes
  1. Reboul, Compt. rend. 82, 1197 (1876); Henry, ibid. 100, 742 (1885), Bull. soc. chim. (2) 43, 617 (1885); Perkin, J. Chem. Soc. 55, 702 (1889).

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

alcohol (64-17-5)

ethyl acetate (141-78-6)

sodium cyanide (143-33-9)

sodium bromide (7647-15-6)

Trimethylene bromide (109-64-8)

cyanide (57-12-5)

potassium cyanide (151-50-8)

Trimethylene cyanide,
Glutaronitrile (544-13-8)