Addition of hydrogen cyanide derivatives

The usual procedure36 is to add a slight excess of a secondary amine to an ethereal solution of ethylmagnesium bromide (50% excess relative to the nitrile) and, when evolution of ethane ceases, to heat the mixture under reflux for about 20 min before adding an ethereal solution of the nitrile the whole is then boiled under reflux for 2-3 h, then decomposed with ice. In many cases this method is superior to the Pinner synthesis of amidines from imidoyl esters. 

Hydroxylamines add appreciably more easily than amines to nitriles they yield amide oximes,38 RC(=NOH)NH2. 

Benzamide oxime,39 for example, is obtained merely by warming an aqueous-alcoholic solution of equivalent amounts of hydroxylamine hydrochloride, benzonitrile, and sodium carbonate for several hours at 60-80°. 

Amidrazones, RC(NH2)=NNH2 or RC(=NH)—NHNH2, are formed in good yield by adding sodium hydrazide to nitriles and including hydrolysis in the working up.40 

For the addition of compounds containing amine groups to cyanic esters see Martin.41 

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