Photoreactions of benzonitrile with cyclic enol ethers

Upon irradiation, cyclic enol ethers such as 1-methoxy-cyclopentene (4) mainly add across the cyano group of benzonitrile (1), under formation of 2-azabutadienes of an imidoester type. This is in agreement with the so-called Δ G-correlation which was reported earlier (ref. 5 and 6). 4-Phenyloxazole (9) is formed from 1 and 1,3-dioxole (5) probably by a similar photochemical process followed by electrocyclic ring opening and hydrolysis. The low yield of the latter photoreaction and the almost exergonic electron transfer between 5 and 1 may point to back electron transfer as the main energy wasting process. From 1 and 2,3-dihydrido-furan (2) only the ortho cycloadduct 6 has been isolated in low yields.