Excited carbonyl formation in the combination and disproportionation of free radicals
作者:
J. R. De La Fuente U.,
E. A. Lissi G.,
期刊:
Journal of Bioluminescence and Chemiluminescence
(WILEY Available online 1992)
卷期:
Volume 7,
issue 1
页码: 27-35
ISSN:0884-3996
年代: 1992
DOI:10.1002/bio.1170070105
出版商: John Wiley&Sons, Ltd.
关键词: Chemiluminescence;benzil;free‐radical;recombination;carbonyl
数据来源: WILEY
摘要:
AbstractThe pyrolyisis of di‐tert‐butyl peroxyoxalate in the presence of para‐substituted benzaldehydes produces almost quantitatively the corresponding p,p′‐disubstituted benzils. The formation of these products is accompanied by chemiluminescence arising from excited triplets. From the quantum yield of excited triplet generation and the rate constants for the triplet photocleavage it is possible to obtain the change in Gibbs free energy associated with triplet formation. The values obtained are −5.6, −5.7 and −8.1 kcal/mol for benzil,p,p′‐dimethylbenzil andp,p′‐dimethoxybenzil, respectively.The pyrolysis of di‐tert‐butyl peroxyoxalate in the presence of isopropanol or benzoin leads to the formation of acetone and benzil. These products are generated in disproportionation processes involving the α‐hydroxy radical produced by hydrogen abstraction. The luminescence observed in these reactions constitutes the first experimental indication of excited species generation in the disproportionation
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