Ethoxypropionitrile

Submitted by George C. Harrison and Harvey Diehl. Checked by R. L. Shriner amd C. H. Tilford. 

In a 3-1. three-necked flask, equipped with a Hershberg stirrer (Org. Syn. 17, 31 Coll. Vol. 2, 1943, 117), a reflux condenser, and a dropping funnel, are placed 175 g. (3.6 moles) of sodium cyanide 

The mixture is then fractionally distilled until the temperature reaches 140°. The first fraction boiling at 75-95° consists mostly of alcohol and water, and is discarded. The fraction boiling between 95° and 140° contains water and 25-30 g. of /9-ethoxy-propionitrile. This is extracted twice with 50-cc. portions of benzene, and the benzene extracts are added to the cooled residue in the distilling flask. The mixture is filtered (Note 2), the solid material is washed with 75 cc. of benzene, which is added to the filtrate, and the whole is distilled. The fraction boiling at 169-174° is collected it weighs 178-200 g. (52-58 per cent of the theoretical amount). 

Direct distillation without filtration may result in clogging the condenser by ammonium bromide. 

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Phenylethanol lc (1.2 g, 10 mmol) and 3-ethoxypropionitrile 2d (1 g, 10 mmol) were admixed with KSF clay (1.2 g, w/w of alcohol) and subjected to microwave irradiation in a Pyrex test tube for 3 min. Then the reaction mass was cooled to room temperature, charged on a short silica gel column (Merck, 200 mesh) and eluted (ethyl acetate-n-hexane, 2 8) to afford the pure amide as a pale yellow liquid (2.05 g, 93%). 

Ethoxypropionitrile reacted with diethoxymethoxy-ethane and 3-ethoxy-2-methoxymethylenpropionitrile was obtained. 

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