Veratronitrile

Veratronitrile, Dissolve 83 g. of veratraldehyde in 200 ml. of warm rectified spirit in a 1 litre bolt-head flask, and add a warm solution of 42 g. of hydroxylamine hydrochloride in 50 ml. of water. Mix thoroughly and run in a solution of 30 g. of sodium hydroxide in 40 ml. of water. Allow the mixture to stand for 2-5 hours, add 250 g. of crushed ice, and saturate the solution with carbon dioxide. The aldoxime separates as an oil allow the mixture to stand for 12-24 hours in an ice chest or refrigerator when the oil will sohdify. Filter off the crystalline aldoxime at the pump, wash well with cold water, and dry in the air upon filter paper. The yield of veratraldoxime is 88 g. 

Into a 250 ml. Pyrex round-bottomed flask, provided with a ground-in glass air condenser, place 88 g. of veratraldoxime and 100 g. (92 -5 ml.) of redistilled acetic anhydride. Heat cautiously. Immediately the vigorous reaction commences, remove the flame. When the reaction 

Aromatic nitriles are generally liquids or low melting point solids, and usually have characteristic odours. They give no ammonia with aqueous sodium hydroxide solution in the cold, are hydrolysed by boiling aqueous alkali but more slowly than primary amides  

When distilled with soda lime (Section IV.175), nitriles yield some ammonia, but pass over, in part, unchanged. They are identified by the b.p. and by hydrolysis to, and characterisation of, the corresponding 

Hydrolysis may be effected with 10-20 per cent, sodium hydroxide solution (see TolunitrUe and Benzonitrile in Section IV,66) or with 10 per cent, methyl alcoholic sodium hydroxide. For difficult cases, e.g., OL-Naphthonitrile (Section IV.163), a mixture of 50 per cent, sulphuric acid and glacial acetic acid may be used. In alkaline hydrolysis the boiling is continued until no more ammonia is evolved. In acid hydrolysis 2-3 hours boiling is usually sufficient the reaction product is poured into water, and the organic acid is separated from any unchanged nitrile or from amide by means of sodium carbonate solution. The resulting acid is identified as detailed in Section IV,175. 

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Kon, 109 Perkin, 108 n-Valeraldehyde, 322 n-Valeric acid, 354, 355,357,359,487 iso-Valeric acid, 354, 355 n-Valeronitrile, 408 Vanadium pentoxide catalyst, 463 Vapour pressure, 1, 2 of mixtures, 6-11 Veratraldehyde, 803, 804 Veratronitrile, 803, 804 Veronal, 1002, 1003 Vibro mixer, 65 Vinylacetio acid, 463, 465... 

The indirect conversion of an aromatic aldehyde into the corresponding nitrile by dehydration of an oxime is illustrated by the synthesis of veratronitrile (Expt 6.170). The dehydrating agent is acetic anhydride which probably effects an initial acetylation of the oximino group followed by the elimination of acetic acid. 

Continue the stirring and cool in ice. Filter off the almost colourless crystals of veratronitrile and dry in the air. The resulting nitrile (60 g, 73.5% overall) is quite pure and melts at 67 °C. 

Veratronitrile has been obtained from 4-aminoveratrole by diazotization and treatment with cuprous cyanide1 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... 

Crude veratric aldehyde, obtained as described in the preceding paragraph, gives a 90 per cent yield of the oxime (m.p. 89-90 ) and an overall yield of 68-70 per cent of veratronitrile (m.p. 65-66 ). The nitrile thus produced is satisfactory for conversion to veratric amide and 4-aminoveratrole (p. 4) without further purification. 

In 1952, Ritter and Murphy reported cases of intramolecular Ritter behavior resulting in formation of dihydroisoquinolines from reactions of methyleugenol with nitriles such as veratronitrile (equation 30). Such reactions involve nucleophilic attack by the aromatic ring on the nitrilium ion and are enhanced by... 

Nitriles. Veratronitrile is prepared by heating a mixture of the oxime with acetic anhydride cautiously until a vigorous reaction is over, refluxing for 20 min., and then CH=NOH C =N... 

John R. Johnson and H. B. Stevenson, private communication. Veratronitrile (15, 85) ... 

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