PHOTOCHEMISTRY OF CONJUGATED POLYACETYLENES: [2+2] PHOTOCYCLOADDITION OF l‐PHENYL‐l,3,5‐HEXATRIYNES WITH SOME OLEFINS

Abstract— Irradiation of 1‐phenyl‐1,3,5‐hexatriynes with various olefins in methylene chloride yields [2 + 2] type 1:1 photoadducts. The photoreaction proceeds through a triplet excited state and shows site selectivity and regioselectivity. Olefins with electron‐withdrawing substituents, such as dimethyl fumarate, fumaronitrile, acrylonitrile, methyl acrylatc, and styrene, are more reactive than electron‐rich olefins, suggesting that the triplet excited states of 1‐phenyl‐1,3,5‐hexatriynes have a nucleophilic radical character.

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