Org. Synth. 1943, 23, 33
DOI: 10.15227/orgsyn.023.0033
β-ETHOXYPROPIONITRILE
[Propionitrile, β-ethoxy-]
Submitted by George C. Harrison and Harvey Diehl.
Checked by R. L. Shriner and C. H. Tilford.
1. Procedure
In a
3-l. three-necked flask, equipped with a
Hershberg stirrer, a
reflux condenser, and a
dropping funnel, are placed
175 g. (3.6 moles) of sodium cyanide and 125 ml. of distilled water
(Note 1). The mixture is stirred until the
sodium cyanide is dissolved, and then, while vigorous stirring is continued,
535 g. (360 ml., 3.5 moles) of β-ethoxyethyl bromide (p. 370) in
260 ml. of 95% ethanol is added over a period of 15 minutes. The
separatory funnel is replaced by a 360°
thermometer, and the mixture is stirred and gently refluxed for 10 hours.
The mixture is then fractionally distilled until the temperature reaches 140°. The first fraction boiling at 75–95° consists mostly of ethanol and water, and is discarded. The fraction boiling between 95° and 140° contains water and 25–30 g. of β-ethoxypropionitrile. This is extracted twice with 50-ml. 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 ml. 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%).
2. Notes
1.
The reaction should be carried out under the
hood.
2.
Direct distillation without filtration may result in clogging the condenser by
ammonium bromide.
3. Discussion
β-Ethoxypropionitrile has been prepared by the action of
potassium cyanide on
β-ethoxyethyl bromide.
1 The addition of
ethanol to
acrylonitrile with
sodium ethoxide,
2,3 sodium hydroxide,
3 or
benzyltrimethylammonium hydroxide4 is reported to be a superior procedure. The action of
sodium ethoxide on a mixture of
β-hydroxypropionitrile and
ethyl formate,
ethyl benzoate,
ethyl bromide, or
ethyl sulfate also results in the formation of
β-ethoxypropionitrile.
5
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
ethanol (64-17-5)
Benzene (71-43-2)
sodium hydroxide (1310-73-2)
sodium cyanide (143-33-9)
ammonium bromide (12124-97-9)
Ethyl bromide (74-96-4)
potassium cyanide (151-50-8)
sodium ethoxide (141-52-6)
β-hydroxypropionitrile (109-78-4)
ethyl benzoate (93-89-0)
ethyl formate (109-94-4)
ethyl sulfate
acrylonitrile (107-13-1)
β-Ethoxyethyl bromide (592-55-2)
β-Ethoxypropionitrile,
Propionitrile, β-ethoxy- (2141-62-0)
benzyltrimethylammonium hydroxide (100-85-6)
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