A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1935, 15, 85
DOI: 10.15227/orgsyn.015.0085
Submitted by J. S. Buck and W. S. Ide.
Checked by John R. Johnson and E. Amstutz.
1. Procedure
In a 1-l. round-bottomed flask, 83 g. (0.5 mole) of veratraldehyde (p. 619) is dissolved in 200 cc. of warm 95 per cent alcohol, and a warm solution of 42 g. (0.6 mole) of hydroxylamine hydrochloride (Org. Syn. Coll. Vol. I, 1941, 318) in 50 cc. of water is added. The two solutions are mixed thoroughly, and a solution of 30 g. (0.75 mole) of sodium hydroxide in 40 cc. of water is introduced. After the mixture has stood for two and one-half hours at room temperature, 250 g. of crushed ice is added and the solution is saturated with carbon dioxide. This causes the separation of the aldoxime as an oil which solidifies on standing overnight in an ice chest (Note 1). The crystalline oxime is filtered with suction, washed thoroughly with water, and allowed to dry in the air. The yield of oxime is 88–89 g. (97–98 per cent of the theoretical amount).
The veratraldoxime is placed with 100 g. of acetic anhydride (94–96 per cent) in a 300-cc. round-bottomed flask provided with a ground-glass air condenser (Note 2), and heated cautiously. A vigorous reaction takes place, and when this occurs the flame is removed. After the reaction has subsided the solution is boiled gently for twenty minutes and then poured carefully, with stirring, into 300 cc. of cold water. The stirring is continued, and on cooling the nitrile separates in small, almost colorless crystals, which are filtered and dried in the air. The veratronitrile thus obtained is quite pure; it weighs 57–62 g. (70–76 per cent of the theoretical amount, based upon the veratraldehyde), and melts at 66–67°.
2. Notes
1. Occasionally the oxime does not solidify after standing overnight. If this happens it is advisable to separate the oily layer, treat with crushed ice, and induce crystallization by scratching. If a seed crystal of the oxime is available no difficulty is experienced.
2. If a cork or rubber stopper is used the product is likely to be colored.
3. Discussion
Veratronitrile has been obtained from 4-aminoveratrole by diazotization and treatment with cuprous cyanide,1 and by heating veratrylglyoxylic acid with hydroxylamine.2 The general method employed above has been used for the preparation of a variety of substituted aromatic nitriles.3
This preparation is referenced from:

References and Notes
  1. Moureu, Bull. soc. chim. (3) 15, 650 (1896).
  2. Garelli, Gazz. chim. ital. 20, 700 (1890).
  3. Marcus, Ber. 24, 3650 (1891); Pschorr, Ann. 391, 33 (1912).

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

alcohol (64-17-5)

acetic anhydride (108-24-7)

sodium hydroxide (1310-73-2)

Cuprous Cyanide (544-92-3)

carbon dioxide (124-38-9)

Hydroxylamine hydrochloride (5470-11-1)

hydroxylamine (7803-49-8)

4-Aminoveratrole (6315-89-5)

Veratronitrile (2024-83-1)

Veratraldehyde (120-14-9)

veratrylglyoxylic acid (2460-33-5)