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Facile generation of dialkylaminyl radicals from N-hydroxypyridine-2-thione carbamates. Application in kinetic studies of small ring cycloalkylaminyl radical ring openings

✍ Scribed by Martin Newcomb; Park Seung-Un; Jere Kaplan; Donald J. Marquardt


Book ID
104233352
Publisher
Elsevier Science
Year
1985
Tongue
French
Weight
251 KB
Volume
26
Category
Article
ISSN
0040-4039

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✦ Synopsis


The preparation of N-hydroxypyridine-2-thione carbamates and the formation of dialkylaminyl radicals from these species are described, and the application of this methodology in kinetic studies of aminyl radical rearrangements is demonstrated.

We have used aminyl radical rearrangements as probe reactions to detect the formation of aminyl radicals, and by inference electron transfer processes, in reactions of lithium dialkylamides with various organic oxidants.' Although we could confirm qualitatively that aminyl radical rearrangements would be expected in our probe substrates by generating the aminyl radicals from tetrazenes, 3 this method was poorly suited for kinetic studies, and the