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
收藏
页码：6110 / 6113
页数：4
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