PHOTO-INITIATED BASE-FORMATION IN A POLYMER MATRIX

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.