Mechanistic pathways of aromatic nucleophilic substitution in conventional solvents and ionic liquids

被引：42

作者：

Gazitua, Marcela ^{[1
]}

Tapia, Ricardo A. ^{[2
]}

Contreras, Renato ^{[3
]}

Campodonico, Paola R. ^{[1
]}

机构：

[1] Clin Alemana Univ Desarrollo, Fac Med, Ctr Quim Med, Santiago 7710162, Chile

[2] Pontificia Univ Catolica Chile, Fac Quim, Santiago 7820436, Chile

[3] Univ Chile, Fac Ciencias, Dept Quim, Santiago, Chile

来源：

NEW JOURNAL OF CHEMISTRY | 2014年 / 38卷 / 06期

关键词：

SECONDARY-AMINES; ARYL AZIDES; SOLVATION; BENZENESULFONATES; REGIOSELECTIVITY; KINETICS; 1-FLUORO-2,4-DINITROBENZENE; RATIONALIZATION; AMINOLYSIS;

D O I：

10.1039/c4nj00130c

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Solvation effects on the reaction mechanism of the title reactions have been kinetically evaluated in 21 conventional solvents and 17 ionic liquids. Solvent polarity affects the catalyzed and non-catalyzed SNAr pathways differently. The ambiphilic character of water and formamide, which act as a hydrogen bond donor/acceptor, induces nucleophilic activation at the nitrogen center of the nucleophile. The ionic liquid EMIMDCN appears to be the best solvent for the SNAr route probably due to the high polarizability of the dicyanamide anion.

引用

页码：2611 / 2618

页数：8

共 50 条

[31] THE DIMER MECHANISM IN AROMATIC NUCLEOPHILIC-SUBSTITUTION BY AMINES IN APROTIC-SOLVENTS
NUDELMAN, NS
JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, 1989, 2 (01) : 1 - 14
[32] Nucleophilic Aromatic Substitution (SNAr) and Related Reactions of Porphyrinoids: Mechanistic and Regiochemical Aspects
Sample, Harry C.
Senge, Mathias O.
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2021, 2021 (01) : 7 - 42
[33] Solvation effects of organic reactions in ionic liquids, deep eutectic solvents, and conventional solvents
Dey, Ranjan
FRONTIERS IN CHEMISTRY, 2023, 11
[34] NUCLEOPHILIC AROMATIC SUBSTITUTION WITH ETHYLENEDIAMINE
LAMM, B
ACTA CHEMICA SCANDINAVICA, 1965, 19 (06): : 1492 - &
[35] STUDIES IN NUCLEOPHILIC AROMATIC SUBSTITUTION
LAMM, B
SVENSK KEMISK TIDSKRIFT, 1966, 78 (10): : 583 - &
[36] Electrochemically promoted nucleophilic aromatic substitution in room temperature ionic liquids-an environmentally benign way to functionalize nitroaromatic compounds
Cruz, Hugo
Gallardo, Iluminada
Guirado, Gonzalo
GREEN CHEMISTRY, 2011, 13 (09) : 2531 - 2542
[37] Facile aromatic nucleophilic substitution (SNAr) reactions in ionic liquids: an electrophile-nucleophile dual activation by [Omim]Br for the reaction
Zhang, Xiao
Lu, Guo-ping
Cai, Chun
GREEN CHEMISTRY, 2016, 18 (20) : 5580 - 5585
[38] NUCLEOPHILIC AROMATIC SUBSTITUTION REACTIONS
ROSS, SD
PROGRESS IN PHYSICAL ORGANIC CHEMISTRY, 1963, 1 : 31 - 74
[39] THE SOLVENT IN AROMATIC NUCLEOPHILIC SUBSTITUTION
MILLER, J
CHEMISTRY & INDUSTRY, 1953, (02) : 40 - 40
[40] Nucleophilic aromatic substitution with dialkoxycarbenes
Ross, JP
Couture, P
Warkentin, J
CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1997, 75 (10): : 1331 - 1335

← 1 2 3 4 5 →