Transient spectroscopy and kinetics of the reactions of mesocyclic diamines with tert-butoxyl and with ketone triplets. Effects of ring conformation

Absolute rate constants for the reactions of tert-butoxyl and triplet benzophenone, with a series of di-tert-amines have been obtained via laser flash photolysis. These diamines have in common the feature that the nitrogen centers are in the backbone of an aliphatic eight-membered ring at positions...

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Bibliographic Details
Published in:Canadian journal of chemistry 1984-07, Vol.62 (7), p.1339-1343
Main Authors: Scaiano, J. C, Stewart, Laura C, Livant, P, Majors, A. W
Format: Article
Language:English
Subjects:
Chemistry
Exact sciences and technology
Free radicals chemistry
Organic chemistry
Reactivity and mechanisms
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Summary:Absolute rate constants for the reactions of tert-butoxyl and triplet benzophenone, with a series of di-tert-amines have been obtained via laser flash photolysis. These diamines have in common the feature that the nitrogen centers are in the backbone of an aliphatic eight-membered ring at positions 1 and 5. A modest rate enhancement is observed, particularly for 1 in its H-abstraction reaction with tert-butoxyl, which may be explained by the operation of a stereoelectronic effect. From the absorption maxima of the radical cations of these diamines (produced quenching acetophenone triplets), information concerning the conformations of the eight-membered rings may be inferred. It is concluded that these radical-cations are stabilized by relatively strong through-space bonding interactions between the two nitrogen centers.
ISSN:0008-4042
1480-3291
DOI:10.1139/v84-226