Magnetic field effects on photochemical reaction——III. Mechanistic study of the photodecarboxylation

来源 :Chinese Journal of Chemistry | 被引量 : 0次 | 上传用户:zhengwei2
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Photolysis of benzyl phenylacetate (ACO_2A), benzyl p-methylphenylacetate (BCO_2A) and1-naphthyl phenylacetate (ACO_2Np) in homogeneous and micellar solutions results in products typicalof radical coupling reactions and loss of carbon dioxide. The cage effects upon direct photolysis ofthese esters in acetonitrile are significantly greater than zero and those in SDS or HDTBr micellarsolutions are even greater. In the triplet sensitization reaction of ACO_2 Np in micellar solutions thecage effects are smaller than those obtained upon direct irradiation. However, the application of a0.05 or 0.2 T external magnetic field in the photolysis in micellar solutions decreases the cage effectsdramatically. All these results suggest that the photoextrusions of carbon dioxide from these estersproceed via radical intermediates, and upon direct photolysis the reactive states for the cleavage re-action involve both singlet and triplet excited states. Phenolysis of benzyl phenylacetate (ACO_2A), benzyl p-methylphenylacetate (BCO_2A) and 1-naphthyl phenylacetate (ACO_2Np) in homogeneous and micellar solutions results in products typical of radical coupling reactions and loss of carbon dioxide. The cage effects upon direct photolysis of these esters in acetonitrile are the greater than than and those in SDS or HDTBr micellarsolutions are even greater. However, the application of a0.05 or 0.2 T external all these results suggest that the photoextrusions of carbon dioxide from these estersproceed via radical intermediates, and upon direct photolysis the reactive states for the cleavage re-action with both singlet and triplet excited states .
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