KINETICS OF ADDITION OF BENZENESULUFINIC ACID TO P-BENZOQUINONE

被引：24

作者：

OGATA, Y

SAWAKI, Y

ISONO, M

机构：

[1] Department of Applied Chemistry, Faculty of Engineering, Nagoya University, Chikusa-ku, Nagoya

来源：

TETRAHEDRON | 1969年 / 25卷 / 13期

关键词：

D O I：

10.1016/0040-4020(69)80013-X

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Addition of benzenesulfinic acid to p-benzoquinone-h4 and -d4 has been studied kinetically in aqueous solutions by means of UV spectrophotometry. Reactions at pH's below 5·7 give 2,5-dihydroxydiphenyl sulfone (II) and follow the kinetics of ν = k [quinone] [sulfinic acid]. The reactions at pH's below ca. 3·1 are subject to general acid catalysis and no kinetic isotope effect is observed, while the reactions at pH's ca. 4·0-5·7 are catalyzed by general base and exhibit increasing ratios of kH/kD from 1·15 to 1·87 with increasing pH. A mechanism is postulated which includes nucleophilic addition of the sulfinate ion followed by deprotonation of the adduct. The rate-determining stop shifts from addition to deprotonation with increasing pH. A similar mechanism may be applied to the reaction of p-benzoquinone with thiosulfate.1. © 1969.

引用

页码：2715 / &

共 13 条

[1]

ACHMOTOWICZ O, 1963, ZH OBSHCH KHIM, V33, P2111

[2]

ACHMOTOWICZ O, 1962, ZH OBSHCH KHIM, V32, P944

[3] DARSTELLUNG VON ALPHA-OXY-SULFONEN UND ALPHA-AMINO-SULFONEN SOWIE VON SULFINSAUREN SALZEN ORGANISCHER BASEN .1. UBER POLYMERISATIONEN UND POLYMERISATIONSKATALYSATOREN [J].