The syntheses and photoreactions of haloarenes, in which the aryl and haloaryl moieties are tethered by a simple alkyl group, were studied. For 2-benzyl-1-halobenzene, in which two aryl moieties were connected by methylene group, photoreduced product, diphenylmethane, was obtained along with the minor formation of the photocyclized product, fluorene, in acetonitrile solvent. For 1-halo-2-phenethylbenzene, in which two aryl moieties were connected by ethylene group, photocyclized products, 9,10-dihydrophenanthrene and phenanthrene, were obtained along with the minor formation of photoreduced product, bibenzyl, in acetonitrile solvent. The photoreaction selectivities in several solvent systems were studied: In cyclohexane, 2-benzyl-1-chlorobenzene was photoreduced more effective than 2-benzyl-1-bromobenzene; In the presence of NaOH, 1-halo-2-phenethylbenzenes gave 9,10-dihydrophenanthrene and, in the presence of toluene, they gave phenanthrene. A radical reaction mechanism is proposed for the explanation of the reactions. This study shows that the photoreaction of haloarene, in which haloaryl and aryl moieties are tethered by ethylene group, can be used for ring formation of 9,10-dihydrophenanthrene otherwise difficultly accessible.
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