Nov. 20, 1953
REACTION OF CERTAIN NITRILESWITH GRIGNARD REAGENTS
5587
[CONTRIBUTIONFROM THE COLLEGE O F PHARMACY, UNIVERSITY OF MICHIGAN]
The Reaction'of Certain Nitriles with Grignard Reagents1 BY F. F.
BLICKEAND Eu-PHANGTSA0213 RECEIVED JUNE 12, 1953
It was found that diphenylacetonitrile reacted with ethylmagnesium bromide to form 1,1-diphenyl-2-butanone,diphenylmethane and propionitrile which was isolated as propionic acid, When the reaction mixture was carbonated, the reaction products were l,ldiphenyl-2-butanone, difihenylmaZunic acid and propionitrile. Other Grignard reagents behaved in a similar manner. Reactions between ethylmagnesium bromide and other nitriles were studied.
In a number of instances it has been found that a heptamethylenimin0)-butyronitrile (I), when nitrile reacted with sodium and an a l c o h ~ l , ~ -treated ~ with excess ethylmagnesium bromide, with potassium hydroxidelo or with sodamide"-ls yielded the expected ketone I1 in 46% yield and in such a manner that the cyano group was re- the cleavage product, l,l-diphenyl-2-methyl-3placed by hydrogen. A few examples have also (1-heptamethylenimin0)-propane (111) in 18.7% been reported in which the same type of cleavage yield. The structure of I11 was established by its was produced by a Grignard reagent. Thus tri- synthesis-decyanation of I with sodamide. phenylacetonitrile reacted with benzylmagnesium chloride to produce triphe~~ylmethane'~; dibenzylmalononitrile and phenylmagnesium bromide I I CH( CHs)CHzN
