The importance of conformation in the reactivity of radical cations.
Date
1992
Authors
Perrott, Allyson L.
Journal Title
Journal ISSN
Volume Title
Publisher
Dalhousie University
Abstract
Description
The photosensitized (electron transfer) bond cleavage of radical cations has been investigated. In previous studies, the feasibility of the bond cleavage was thought to depend solely on the bond dissociation energy of the radical cation. However, this simple hypothesis led to several incorrect predictions. In this thesis, the hypothesis has been extended to include several conformational criteria. The most stable conformers of neutral molecules have been calculated with molecular mechanics; these calculations have been used to rationalize previous results and to predict the reactivity of new compounds.
In Chapter I, photosensitized (electron transfer) carbon-carbon bond cleavage of $\beta$-phenyl ethers is considered. The ethers studied are 2-methoxy-1-phenylpropane (11), 2-methoxy-1-phenylindane (13 cis and trans), 1-methoxy-2-phenylcyclopentane (15 cis and trans), 1-methoxy-2-phenylcyclohexane (18 cis and trans), 6-phenyl-1,4-dioxaspiro (4.5) decane (19), 2-methoxy-3-phenylbutane (27, both diastereomers) and 2-methyl-3-phenyltetrahydropyran (28 cis and trans).
In Chapter II, the feasibility of deprotonation (C-H bond cleavage) of the radical cations of 1-methyl-2-phenylcyclopentane (39 cis and trans) and 1-methyl-2-phenylcyclohexane (40 cis and trans) is investigated.
Thesis (Ph.D.)--Dalhousie University (Canada), 1992.
In Chapter I, photosensitized (electron transfer) carbon-carbon bond cleavage of $\beta$-phenyl ethers is considered. The ethers studied are 2-methoxy-1-phenylpropane (11), 2-methoxy-1-phenylindane (13 cis and trans), 1-methoxy-2-phenylcyclopentane (15 cis and trans), 1-methoxy-2-phenylcyclohexane (18 cis and trans), 6-phenyl-1,4-dioxaspiro (4.5) decane (19), 2-methoxy-3-phenylbutane (27, both diastereomers) and 2-methyl-3-phenyltetrahydropyran (28 cis and trans).
In Chapter II, the feasibility of deprotonation (C-H bond cleavage) of the radical cations of 1-methyl-2-phenylcyclopentane (39 cis and trans) and 1-methyl-2-phenylcyclohexane (40 cis and trans) is investigated.
Thesis (Ph.D.)--Dalhousie University (Canada), 1992.
Keywords
Chemistry, Organic.