The Reaction'of Certain Nitriles with Grignard ... - ACS Publications

methane and propionitrile which was isolated as propionic acid, products were l,ldiphenyl-2-butanone, difihenylmaZunic acid and propionitrile. lar man...
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Nov. 20, 1953

REACTION OF CERTAIN NITRILESWITH GRIGNARD REAGENTS

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[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