It was found that amines were formed efficiently by the photolysis of
O-acyloximes followed by hydrolysis in polystyrene films and the relat
ionship between structures of O-acyloximes and yields of amines were i
nvestigated. O-phenylacetyl acetophenone oxime (PaApO), O-pivaloyl ace
tophenone oxime (PApO), and O-benzoyl acetophenone oxime (BApO) as mon
ofunctional O-acyloximes and O,O'-succinyl diacetophenone oxime (SDApO
) and O,O'-glutaryl diacetophenone oxime (GDApO) as bifunctional O-acy
loximes were examined. The yields of amines for PaApO and SDApO under
N2 were ca. 70%, which was the highest among O-acyloximes examined in
this experiment. On the other hand, the yields for PApO, BApO, and GDA
pO were less than 15% and it was verified that the hydrogen abstractio
n by imino radicals via 6-membered cyclic intermediates resulted in th
e lowering of yields. Although the effect of oxygen under photolysis o
n the yields of amine for PaApO was negligible under 50% conversion of
PaApO, the yield decreased with farther increase in the conversion an
d was 50% at 90% conversion. (C) 1994 John Wiley & Sons, Inc.