SOLVENT AND SECONDARY SUBSTRATE ISOTOPE EFFECTS ON THE ACID-CATALYZED KETONIZATION OF ACETOPHENONE ENOL IN AQUEOUS-SOLUTION

被引：5

作者：

ANDRAOS, J

KRESGE, AJ

OBRAZTSOV, PA

机构：

[1] UNIV TORONTO,LASH MILLER CHEM LABS,DEPT CHEM,80 ST GEORGE ST,TORONTO M5S 1A1,ONTARIO,CANADA

[2] ACAD SCI USSR,INST CHEM PHYS,MOSCOW 117977,USSR

来源：

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY | 1992年 / 5卷 / 06期

关键词：

D O I：

10.1002/poc.610050607

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The enol of acetophenone was generated flash photolytically in aqueous solution by photosolvolysis of PhCBr=CH2 and photohydration of PhC=CH and PhC-CD, and rates of its ketonization were measured in dilute perchloric acid solutions in H2O and D2O at 25-degrees-C. The rate constants so obtained provide the solvent isotope effects, k(H)/k(D) = 5.02 +/- 0.08, and the secondary isotope effect for deuterium substitution at the beta-position of the enol double bond, (k(H)/k(D))beta = 0.999 +/- 0.014. Arguments are presented which show that these isotope effects require a stepwise rather than a concerted mechanism for the ketonization reaction.

引用

页码：322 / 326

页数：5