The radical cleavage of the carbon-cobalt bond of 1-phenyl-2-oxocyclopentylmethyl cobaloxime (1) and 1-ethoxycarbonyl-2-oxocyclopentylmethyl cobaloxime (2) gave only 3-phenylcyclohex-2-enone (7) and 3-ethoxycarbonylcyclohex-2-enone (8), respectively, by acyl migration. This rearrangement may be a reasonable mimicry of the ester migration mediated by coenzyme-B12.
Ultraviolet irradiation of 6-methylenetricyclo[3.2.1.02,7]oct-3-en-8-ols (Ia) and (Ib) afforded 3-methylenetetracyclo[3.3.0.0.4,602,8]octan-7-ols (IIa) and (IIb) in fairly good yields. This photorearrangement is considered to be a di-π-methane rearrangement. Oxidation of the photoproducts gave the ketones retaining the carbon skeleton of IIa and IIb
Ultraviolet irradiation of toluene or anisole in the presence of cyclohexene and catalytic amount of BF3-etherate gave cyclohexyltoluene or cyclohexylanisole. Irradiation of β-(1-cyclohexenyl)ethylbenzene (v) under the same reaction conditions afforded octahydrophenanthrene VII.
Photolysis of 2,2-diphenyl-2-hydroxyethyl cobaloxime in the absence of oxygen gave deoxybenzoin, with phenyl rearrangement, and 1,1-diphenylethanol, with hydrogen abstraction, in various solvents. Thermolysis gave the similar results but the formation of 1,1-diphenylethylene becomes a major process.
Photo-solvolysis of 4′-(l-acetoxy)ethylbenzo-15-crown-5 (1) in methanol is depressed by the complex formation of the crown ether moiety with alkali metal ions. This effect is accounted for by the destabilization of excited state of 1 and benzyl cation from 1.
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