High-pressure mechanistic delineation based on activation volumes

被引：36

作者：

Jenner, G ^{[1
]}

机构：

[1] Univ Strasbourg, Inst Chim, UMR 7509, Lab Piezochim Organ, F-67008 Strasbourg, France

来源：

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY | 2002年 / 15卷 / 01期

关键词：

mechanism; kinetics; pressure; activation volume;

D O I：

10.1002/poc.458

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

High-pressure kinetics is a useful tool for the determination and the assessment of mechanisms in organic chemistry. The volume of activation DeltaV* deduced from these kinetic measurements is an indicator of the position of the transition state. In addition, if accurately determined, DeltaV* permits the detection of fine mechanistic effects such as alteration of mechanism according to substrates within the same reaction type, operation of secondary orbital interactions in Diels-Alder cycloadditions, angular hydrogen transfer in ene reactions, etc. Copyright (C) 2001 John Wiley Sons, Ltd.

引用

页码：1 / 13

页数：13

共 36 条

[1] MECHANISM OF THE (O --- H --- O) HYDROGEN TRANSFER IN ENE REACTIONS [J].

BENSALEM, R ;

JENNER, G .

TETRAHEDRON LETTERS, 1986, 27 (14) :1575-1576

[2] ACTIVATION VOLUME AS A MEASURE OF E2-E1CB CHARACTER IN ELIMINATION-REACTIONS [J].

BROWER, KR ;

MUHSIN, M ;

BROWER, HE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1976, 98 (03) :779-782

[3] PERTURBATION OF THE DEGENERATE, CONCERTED COPE REARRANGEMENT BY 2 PHENYL GROUPS IN ACTIVE POSITIONS OF (E)-1,4-DIPHENYLHEXA-1,5-DIENE - ACCELERATION BY HIGH-PRESSURE AS CRITERION OF CYCLIC TRANSITION-STATES [J].

DOERING, WVE ;

BIRLADEANU, L ;

SARMA, K ;

TELES, JH ;

KLARNER, FG ;

GEHRKE, JS .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (10) :4289-4297

[4]

DRIJACA A, 1998, CHEM REV, V98, P2169

[5] THE ROLES OF CHANGES IN BONDING VS PACKING FRACTION IN THE PRESSURE-INDUCED ACCELERATION OF THE DIELS-ALDER REACTION [J].

FIRESTONE, RA ;

SMITH, GM .

CHEMISCHE BERICHTE, 1989, 122 (06) :1089-1094

[6] Volume of concert and heavy atom effects in Diels-Alder reaction mechanisms [J].

Firestone, RA .

TETRAHEDRON, 1996, 52 (46) :14459-14468

[7] Reply to "Comment on phantom activation volumes" [J].

Firestone, RA ;

Swiss, KA .

JOURNAL OF PHYSICAL CHEMISTRY A, 2001, 105 (13) :3430-3432

[8] DESULFINATION OF ALLYLIC SULFINIC ACIDS - CHARACTERIZATION OF A RETRO-ENE TRANSITION-STATE [J].

HISCOCK, SD ;

ISAACS, NS ;

KING, MD ;

SUE, RE ;

WHITE, RH ;

YOUNG, DJ .

JOURNAL OF ORGANIC CHEMISTRY, 1995, 60 (22) :7166-7169

[9] THE VOLUME PROFILE FOR A CHELETROPIC REACTION [J].

ISAACS, NS ;

LAILA, A .

JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 1994, 7 (04) :178-180

[10] EVIDENCE FROM ACTIVATION VOLUMES FOR AN ELIMINATIVE MECHANISM IN THE HYDROLYSIS OF 2,4-DINITROPHENYL 4-HYDROXYBENZOATE [J].

ISAACS, NS ;

NAJEM, T .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1984, (20) :1361-1362

← 1 2 3 4 →