Gas-phase H/D exchange between arenium ions and selected bases. The site of protonation of simple aromatics

被引：19

作者：

Chiavarino, B ^{[1
]}

Crestoni, ME ^{[1
]}

Di Rienzo, B ^{[1
]}

Fornarini, S ^{[1
]}

机构：

[1] Univ Roma La Sapienza, Dipartimento Studi Chim & Tecnol Sostanze Biol At, I-00185 Rome, Italy

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 1998年 / 120卷 / 42期

关键词：

D O I：

10.1021/ja981488v

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

H/D exchange between arenium ions bearing various substituents (Y = Et, Me(2)CH, CF(3), CF(3)CO, NO(2), Me(3)Si) on a perdeuterated ring and bases having at least one H atom at the active site are described. A radiolytic technique operating at atmospheric pressure and allowing the recovery of neutral end products was used. The exchange depends on features of both the base (structure, proton affinity) and the arenium ion. The elementary step for back proton transfer from the protonated base to the neutral arene has been studied by NMR analysis of the H distribution within YC(6)D(4)H. The protonation was found to involve the most basic ring positions: ortho/para for alkyl substituents (Y = Et, Me(2)CH) and ortho/meta for electron-withdrawing substituents (Y = CF(3), CF(3)CO, NO(2)).

引用

页码：10856 / 10862

页数：7

共 71 条

[21] BRONSTED VERSUS LEWIS ACID REACTIVITY OF GASEOUS CATIONS (C2H5+, I-C3H7+, HCO+) TOWARD ARENES [J].

CERICHELLI, G ;

CRESTONI, ME ;

FORNARINI, S .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (06) :2002-2009

[22] MECHANISTIC STUDY OF HYDROGEN-DEUTERIUM EXCHANGE BETWEEN [M-1]- IONS OF CHLORINATED BENZENES AND D2O OR ND3 [J].

CHAN, S ;

ENKE, CG .

JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY, 1994, 5 (04) :282-291

[23] LONG-LIVED IPSO-SILYLATED P-TOLUENIUM IONS - EVIDENCE FROM A KINETIC ISOTOPE EFFECT [J].

CRESTONI, ME ;

FORNARINI, S .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1994, 33 (10) :1094-1096

[24] Cluster chemical ionization and deuterium exchange mass spectrometry in supersonic molecular beams [J].

Dagan, S ;

Amirav, A .

JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY, 1996, 7 (06) :550-558

[25]

DELEPINE M, 1895, B SOC CHIM FR, V13, P1044

[26] GAS-PHASE REACTIONS OF ORGANIC-ANIONS AS STUDIED BY THE FLOWING AFTERGLOW TECHNIQUE [J].

DEPUY, CH ;

BIERBAUM, VM .

ACCOUNTS OF CHEMICAL RESEARCH, 1981, 14 (05) :146-153

[27]

DEPUY CH, 1987, STRUCTURE REACTIVITY

[28] GAS-PHASE H-D EXCHANGE-REACTIONS OF PROTONATED AMINO-ACIDS AND PEPTIDES WITH ND3 [J].

DOOKERAN, NN ;

HARRISON, AG .

JOURNAL OF MASS SPECTROMETRY, 1995, 30 (05) :666-674

[29] REACTIVE COLLISIONS IN QUADRUPOLE CELLS .3. H/D EXCHANGE-REACTIONS OF PROTONATED AROMATIC-AMINES WITH ND(3) [J].

DOOKERAN, NN ;

HARRISON, AG .

JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY, 1995, 6 (01) :19-26

[30] A theoretical study of the additivity of proton affinities in aromatics: Polysubstituted benzenes [J].

EckertMaksic, M ;

Klessinger, M ;

Maksic, ZB .

CHEMISTRY-A EUROPEAN JOURNAL, 1996, 2 (10) :1251-1257

← 1 2 3 4 5 6 7 8 →