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Reaction of di‐ tert ‐butylnitroxide radicals
Author(s) -
Lissi E. A.,
Rubio M. A.,
Araya D.,
Zanocco G.
Publication year - 1980
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550121106
Subject(s) - chemistry , radical , photochemistry , triphenylmethane , ether , ethanethiol , medicinal chemistry , bond cleavage , activation energy , hydrogen peroxide , kinetics , peroxide , phenol , thiophenol , homolysis , organic chemistry , catalysis , physics , quantum mechanics
Di‐ tert ‐butylnitroxide (DTBN) is the simplest of the stable nitroxide radicals and is only consumed at temperatures higher than 90°C or in the presence of very reactive substrates. The pyrolysis of DTBN in solution gives, at least at low conversion, 2‐methyl‐2‐nitrosopropane and di‐ tert ‐butylnitroxide‐ tert ‐butyl ether. The reaction involves, as the rate‐limiting step, the cleavage of the CN bond. This reaction takes place with an activation energy of 33 kcal/mol. DTBN is stable in the presence of styrene, aldehydes, hydrogen peroxide, α‐methyl‐ N ‐ethyl nitrone, phenol, and triphenylmethane. On the other hand, it reacts readily with diethylhydroxylamine, ascorbid acid, ethanethiol, and hexanethiol. For the two former compounds the reaction involves a hydrogen transfer as the rate‐determining step, and the reaction proceeds, a low conversion, with simple second‐order kinetics. The reaction with the thiols is complex and shows a clear inductiontime.