ACID-CATALYZED HYDROLYSIS OF CIS-1,2-DIMETHOXYETHENE AND TRANS-1,2-DIMETHOXYETHENE IN AQUEOUS-SOLUTION

被引：14

作者：

KRESGE, AJ

LEIBOVITCH, M

机构：

[1] Department of Chemistry, University of Toronto, Toronto, Ontario

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1990年 / 55卷 / 18期

关键词：

D O I：

10.1021/jo00305a018

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Rates of hydrolysis of cis- and frans-l,2-dimethoxyethene were measured in concentrated aqueous perchloric acid solution, and extrapolation of these data to dilute acid gave the catalytic coefficients liff+ = 1.16 X 1CT4 M1s1 for the cis isomer and kw ~ 3.98 X 1CT6 M1s_1 for the trans isomer. These results, plus solvent isotope effects measured in 0.5 M hydrochloric acid (kH+/kD+ = 2.29 for the cis isomer and kH+/kD+ = 2.21 for the trans isomer), indicate that these reactions occur by rate-determining protonation of the substrates on carbon. The reactivities of the two substrates are discussed. © 1990, American Chemical Society. All rights reserved.

引用

收藏

页码：5234 / 5236

页数：3

相关论文

共 15 条

[1] STABILITY AND SOLVATION OF ORGANIC CATIONS [J].

BAGNO, A ;

SCORRANO, G ;

OFERRALL, RAM .

REVIEWS OF CHEMICAL INTERMEDIATES, 1987, 7 (04) :313-352

[2] REACTIVITY OF CYCLIC AND ACYCLIC OLEFINIC HYDROCARBONS IN ACID-CATALYZED HYDRATION [J].

CHWANG, WK ;

NOWLAN, VJ ;

TIDWELL, TT .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (22) :7233-7238

[3] THE EXCESS ACIDITY OF AQUEOUS HCL AND HBR MEDIA - AN IMPROVED METHOD FOR THE CALCULATION OF X-FUNCTIONS AND H0 SCALES [J].

COX, RA ;

YATES, K .

CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1981, 59 (14) :2116-2124

[4]

Hine J., 1975, STRUCTURAL EFFECTS E, P270

[5] STEREOCHEMISTRY OF ADDITIONS OF META-QUINOMETHANE TO OLEFINS AND ACYCLIC DIENES [J].

INGLIN, TA ;

BERSON, JA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1986, 108 (12) :3394-3402

[6] ISOTOPE-EXCHANGE STUDIES WITH DIETHYL ACETALS IN ETHANOL AND THEIR MECHANISTIC IMPLICATIONS TO PROTOLYTIC REACTIONS OF ACETALS AND VINYL ETHERS [J].

KANKAANP.A ;

SALOMAA, P ;

JUHALA, P ;

AALTONEN, R ;

MATTSEN, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (11) :3618-3624

[7]

KEEFFE JR, 1986, TECHNIQUES CHEM 1, V6, P763

[8]

KOPECKY KR, IN PRESS CAN J CHEM

[9] VINYL ETHER HYDROLYSIS .9. ISOTOPE EFFECTS ON PROTON-TRANSFER FROM HYDRONIUM ION [J].

KRESGE, AJ ;

SAGATYS, DS ;

CHEN, HL .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1977, 99 (22) :7228-7233

[10] EXTRAPOLATION FROM CONCENTRATED TO DILUTE AQUEOUS ACIDS [J].

KRESGE, AJ ;

CHEN, HJ ;

CAPEN, GL ;

POWELL, MF .

CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1983, 61 (02) :249-256