Photoreactions of cisoid 1,4-diphenyl-1,3-butadienes. Direct irradiation in solution and in low temperature organic glass.

The photoreactions of 1,4-diphenyl-1,3-butadienes (DPB) fused with a bicyclo[2.2.1]heptano ring under direct irradiation were examined in solution at room temperature and in organic glass at liquid nitrogen temperature. Photocyclization yielding a phenylnaphthalene compound was shown to be preceded by facile E,E to E,Z photoisomerization. The reverse E,Z to E,E isomerization took place with equal ease in low temperature organic glass and in solution at room temperature. The pattern of reaction at low temperature is consistent with the involvement of the Hula-twist mechanism. However, complexity in conformational population, suggested by ab initio calculated data, made the experimental evidence less clear-cut than in previously reported examples of HT.