Understanding Kinetic Solvent Effects on Hydrogen Abstraction Reactions from Carbon by the Cumyloxyl Radical

被引：28

作者：

Bietti, Massimo ^{[1
]}

Martella, Roberto ^{[1
]}

Salamone, Michela ^{[1
]}

机构：

[1] Univ Roma Tor Vergata, Dipartimento Sci & Tecnol Chim, I-00133 Rome, Italy

来源：

ORGANIC LETTERS | 2011年 / 13卷 / 22期

关键词：

LOG K-VALUES; BETA-SCISSION; BOND; COMPLEXATION; MECHANISMS; BENZYLOXYL; PHOTOLYSIS; SUBSTRATE; SCALE; RATES;

D O I：

10.1021/ol202561z

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A kinetic study of the hydrogen abstraction reactions from tetrahydrofuran (THF) and cyclohexane (CHX) by the cumyloxyl radical was carried out in different solvents. With THF, a 4.5-fold decrease in rate constant (k(H)) was observed on going from isooctane to 2,2,2-trifluoroethanol. An opposite behavior was observed with CHX, where k(H) increased by a factor 4 on going from isooctane to 2,2,2-trifluoroethanol. The important role of substrate structure and of the solvent hydrogen bond donor ability is discussed.

引用

页码：6110 / 6113

页数：4

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