Absolute Rate Constants for the Addition of the 1‐(tert‐Butoxy)carbonylethyl Radical onto Cyclic Alkenes in Solution期刊界 All Journals 搜尽天下杂志传播学术成果专业期刊搜索期刊信息化学术搜索

Absolute Rate Constants for the Addition of the 1‐(tert‐Butoxy)carbonylethyl Radical onto Cyclic Alkenes in Solution

Authors:	Hanns Fischer Bernhard Knühl Sylvain R. A. Marque

Affiliation:	1. Institute of Physical Chemistry, University of Zurich, Winterthurerstrasse 190, CH-8057 Zurich;2. Université de Provence, case 542, Avenue Escadrille Normandie – Niemen, F-13397 Marseille, Cedex 20

Abstract:	Absolute rate constants are reported for the addition of the 1‐[(tert‐butoxy)carbonyl]ethyl (= 2‐(1,1‐dimethylethoxy)‐1‐methyl‐2‐oxoethyl) radical ^.CHMeCO₂(t‐Bu) to several cyclic and monosubstituted alkenes in MeCN as obtained by time‐resolved electron paramagnetic resonance (EPR). The activation energies for the addition of this alkyl radical are mainly governed by the addition enthalpy but are also substantially lowered by the ambiphilic effect and by relief of cyclic strain.

Keywords:	Radical addition Rate constants Alkenes, cyclic EPR Spectroscopy