DIRECT MEASUREMENTS OF THE RATES OF 1,3-SIGMATROPIC AND 1,5-SIGMATROPIC HYDROGEN SHIFTS IN THE PHOTO-FRIES REARRANGEMENTS OF PHENYL ACETATE

被引：23

作者：

ARAI, T ^{[1
]}

TOBITA, S ^{[1
]}

SHIZUKA, H ^{[1
]}

机构：

[1] GUNMA UNIV,DEPT CHEM,KIRYU,GUNMA 376,JAPAN

来源：

CHEMICAL PHYSICS LETTERS | 1994年 / 223卷 / 5-6期

关键词：

D O I：

10.1016/0009-2614(94)80006-5

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The rate constants for the 1,3- and 1,5-sigmatropic hydrogen shifts of the photo-Fries rearranged intermediates of phenyl acetate produced by laser flash photolysis at 266 nm were directly measured in several solvents. The rate constant for the 1,3-hydrogen shift (3.6 s-1) was faster than that for the 1,5-shift (6.5 x 10(-2) s-1) in the ground state in methylcyclohexane at 293 K, contrary to the expectation by the Woodward-Hoffmann rule. In protic solvents, ethanol and methanol, a remarkable increase in the rate constants (approximately 10(5) s-1) was observed. A tentative mechanism including the role of the non-bonding electrons of the intermediates is discussed.

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页码：521 / 526

页数：6

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