An Abnormal Hydrolysis of -Nitro-,-Disubstituted Butyric Acid Derivatives

J . C. L1;ESTFAIIL

3428

[CONTRIBUTION F R O M

THE

so

Vol.

B. I?. GOODRICII RESEARCH CENTER]

An Abnormal Hydrolysis of r-Nitro-r,r-Disubstituted Butyric Acid Derivatives BY J. C. ~ V E S T P A I ~ L RECEIVED J A N U A R Y 17, 1958 Refluxing y-nitro-r, y-disubstituted butyric acid derivatives with concentratcd hydrochloric acid was shoivn to produce r,y-disubstituted-y-butyrolactones.Five examples and a plausible mechanism of this unusual reaction are given.

In two recent papers a series of compounds prepared from active hydrogen compounds and low molecular weight polyvinylidene cyanide were reported. The structures of these compounds were established by hydrolysis and identification of the acids produced and by infrared spectroscopy. For the compounds derived from 2-nitropropane and froin nitroethane, and assigned structures I and IT, the hydrolyses proceeded abnormally. The hydrolysis of I and I1 will be discussed in this paper.

CHARTI CHz-CHz CH1CHZCOOR I I I CHaMgI 1 C=O O=C CHzCHzCOOR

-

CH, NO2

CHz-CHz

v

CHa

I

o=c

OzSCCHzCH (CN),

0

I1

VI

H'

Hydrolysis of I by refluxing with hydrochloric acid gave a neutral, nitrogen-free hydrolysis product which was shown to be y-isocaprolactone (111). Refluxing the cyanoethylation product of

I

O=C

CH3

1

aq. HCI

OzSCCHzCH(CS)2 II

-+

OZSCCH2CHzCOOH I CHI V

CH3

1

I

CHz

I

I1

+

--f

02NCCHzCH2CN

I

\ /c