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
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
收藏
页码:2037 / 2038
页数:2
相关论文
共 20 条
[11]   BASE-CATALYZED HYDROLYSIS OF N-ACYLPYRROLES - MEASURABLE ACIDITY OF A STEADY-STATE TETRAHEDRAL INTERMEDIATE [J].
MENGER, FM ;
DONOHUE, JA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (02) :432-437
[12]   AROMATIC SUBSTITUTION .31. FRIEDEL-CRAFTS SULFONYLATION OF BENZENE AND TOLUENE WITH ALKYLSULFONYL AND ARYLSULFONYL HALIDES AND ANHYDRIDES [J].
OLAH, GA ;
KOBAYASH.S ;
NISHIMUR.J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (02) :564-569
[13]  
Page M. I., 1992, CHEM BETA LACTAMS, P79
[14]   THE MECHANISMS OF REACTIONS OF BETA-LACTAM ANTIBIOTICS [J].
PAGE, MI .
ADVANCES IN PHYSICAL ORGANIC CHEMISTRY, 1987, 23 :165-270
[15]   THE ENERGETICS OF INTRAMOLECULAR REACTIONS AND ENZYME CATALYSIS [J].
PAGE, MI .
PHILOSOPHICAL TRANSACTIONS OF THE ROYAL SOCIETY OF LONDON SERIES B-BIOLOGICAL SCIENCES, 1991, 332 (1263) :149-156
[16]   THE CHEMICAL-REACTIVITY OF PENICILLINS AND OTHER BETA-LACTAM ANTIBIOTICS [J].
PROCTOR, P ;
GENSMANTEL, NP ;
PAGE, MI .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1982, (09) :1185-1192
[17]   NUCLEOPHILIC SUBSTITUTION AT TETRACOORINATE HEXAVALENT SULFUR . REACTION OF (-)-MENTHYL PHENYLMETHANESULFONATE WITH P-TOLYLMAGNESIUM BROMIDE [J].
SABOL, MA ;
ANDERSEN, KK .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1969, 91 (13) :3603-&
[18]  
THATCHER GRJ, 1989, ADV PHYS ORG CHEM, V25, P99
[19]  
WEBSTER P, 1990, J CHEM SOC P2, P805
[20]   ENERGETICS OF CARBONYL ADDITION AND ELIMINATION - KINETIC MANIFESTATIONS OF ACYL SUBSTITUENT EFFECTS IN ANILIDE HYDROLYSIS [J].
YOUNG, JK ;
PAZHANISAMY, S ;
SCHOWEN, RL .
JOURNAL OF ORGANIC CHEMISTRY, 1984, 49 (22) :4148-4152