Evidence for a trigonal bipyramidal intermediate during nucleophilic substitution at a sulfonyl centre and for a sulfonylium cation in the acid catalysed reaction

被引：6

作者：

Baxter, NJ ^{[1
]}

Laws, AP ^{[1
]}

Rigoreau, L ^{[1
]}

Page, MI ^{[1
]}

机构：

[1] UNIV HUDDERSFIELD, DEPT CHEM & BIOL SCI, HUDDERSFIELD HD1 3DH, W YORKSHIRE, ENGLAND

来源：

CHEMICAL COMMUNICATIONS | 1997年 / 21期

基金：

英国医学研究理事会;

关键词：

D O I：

10.1039/a705416e

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The rate of alkaline hydrolysis of a substituted beta-sultam shows a dominant term second-order in hydroxide ion, clearly indicating the reversible formation of a monoanionic trigonal bipyramidal intermediate; substituent effects and kinetic parameters for the acid catalysed hydrolysis are indicative of the formation of a sulfonylium ion intermediate.

引用

页码：2037 / 2038

页数：2

共 20 条

[1] The hydrolytic reactivity of beta-sultams [J].

Baxter, NJ ;

Laws, AP ;

Rigoreau, L ;

Page, MI .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1996, (11) :2245-2246

[2] HYDROLYSIS OF AMIDES .3. DILUTE ACID HYDROLYSIS OF AMIDES OF TYPE R-CH2-CONH2 [J].

BOLTON, PD ;

JACKSON, GL .

AUSTRALIAN JOURNAL OF CHEMISTRY, 1969, 22 (03) :527-&

[3] RECENT PERSPECTIVES CONCERNING THE MECHANISM OF H3O+-PROMOTED AND OH--PROMOTED AMIDE HYDROLYSIS [J].

BROWN, RS ;

BENNET, AJ ;

SLEBOCKATILK, H .

ACCOUNTS OF CHEMICAL RESEARCH, 1992, 25 (11) :481-488

[4]

Bruylants A., 1960, REC CHEM PROGR, V21, P213

[5]

Buglass A. J., 1991, CHEM SULFONIC ACIDS

[6] HYDROLYSIS OF FORMANILIDES IN ALKALINE SOLUTIONS [J].

DEWOLFE, RH ;

NEWCOMB, RC .

JOURNAL OF ORGANIC CHEMISTRY, 1971, 36 (25) :3870-&

[7] HYDROLYSIS OF ANILIDES .4. HYDROXYLAMINOLYSIS HYDRAZINOLYSIS AND GENERAL ACID-CATALYSED ALKALINE HYDROLYSIS OF TRIFLUOROACETANILIDE [J].

ERIKSSON, SO .

ACTA CHEMICA SCANDINAVICA, 1968, 22 (03) :892-&

[8] SULFONYL TRANSFER-REACTIONS [J].

GORDON, IM ;

MASKILL, H ;

RUASSE, MF .

CHEMICAL SOCIETY REVIEWS, 1989, 18 (02) :123-151

[9] CHEMISTRY SULFOXIDES AND RELATED COMPOUNDS .33. STEREOCHEMISTRY OF SUBSTITUTION AT TETRACOORDINATE HEXAVALENT SULFUR - NUCLEOPHILIC REACTIONS AT SULFUR IN SULFONIMIDOYL COMPOUNDS [J].

JONSSON, EU ;

JOHNSON, CR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1971, 93 (20) :5308-&

[10]

KICE JL, 1980, ADV PHYS ORG CHEM, V17, P65

← 1 2 →