Benzophenone-Sensitized Photolysis of N,N-Dibenzyl-O-acylhydroxylamines. Mechanism of the Imine-Forming Radical Elimination Reaction.

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概要

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• Title hydroxylamines (<B>1</B>) undergo benzophenone-sensitized photolysis to give <I>N</I>-benzylidenebenzylamine (<B>2</B>), <I>p</I>-substituted benzoic acids (<B>3</B>), and monosubstituted benzenes (<B>4</B>) derived from decarboxylation of <I>p</I>-substituted benzoyloxyl radicals. Analysis of the linear Stern–Volmer plots, both for the sensitized photolysis of <B>1</B> and for the phosphorescence quenching of benzophenone by <B>1</B>, demonstrates the participation of triplet <B>1</B> in this photolysis. The logarithm of the ratio (<I>k</I><SUB>r</SUB>⁄<I>k</I><SUB>d</SUB>), where <I>k</I><SUB>t</SUB> is the rate constant for homolytic cleavage of the N–O bond in triplet <B>1</B> and <I>k</I><SUB>d</SUB> is that for its deactivation, used as a measure of the triplet-state reactivities of <B>1</B>, exhibited a good Hammett-type relationship against the substituent constant (σ) with a slope (ρ) of −0.75. This indicates the exclusive occurrence of homolysis of the N–O bond in the first excited triplet state of <B>1</B>. Thus the decomposition of <B>1</B> activated by triplet benzophenone is classified as an imine-forming radical elimination. The results of deuterium isotope and micellar effects on the sensitized photolysis suggest that the "out-of-cage" products <B>4</B> are obtained by decarboxylation and subsequent hydrogen abstraction of <I>p</I>-substituted benzoyloxyl radicals which escaped from the triplet cage in competition with spin inversion to the singlet cage. In this singlet cage, hydrogen abstraction giving <B>2</B> and <B>3</B> and recombination affording the starting <B>1</B> were found to take place exclusively.

• 公益社団法人 日本化学会の論文

著者

• Sakurai Tadamitsu

  Department Of Applied Chemistry Faculty Of Engineering Kanagawa University

• Inoue Hiroyasu

  Department Of Applied Chemistry Faculty Of Technology Kanagawa University

• Mizuno Hisashi

  Department of Applied Chemistry, Faculty of Technology, Kanagawa University

• Kubota Tsuneari

  Department of Applied Chemistry, Faculty of Technology, Kanagawa University

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