Rates of decarboxylation of acyloxy radicals formed in the photocleavage of substituted 1-naphthylmethyl alkanoates

Autor:	J. W. Hilborn, James A. Pincock
Rok vydání:	1991
Předmět:	Decarboxylation Chemistry Radical Photodissociation General Chemistry Ion pairs Biochemistry Medicinal chemistry Catalysis Homolysis Electron transfer Colloid and Surface Chemistry Bond cleavage Excited singlet
Zdroj:	Journal of the American Chemical Society. 113:2683-2686
ISSN:	1520-5126 0002-7863
DOI:	10.1021/ja00007a049
Popis:	Rates of decarboxylation (k CO2 R ) have been estimated for the acyloxy radicals formed in the photolysis of substituted 1-naphthylmethyl alkanoates. These rates are based on a proposed mechanism involving initial carbon-oxygen homolytic bond cleavage from the excited singlet state. The products are formed by two competing pathways: electron transfer in the radical pair to give an ion pair and decarboxylation. Measured product yields along with an estimate of the electron-transfer rate (k ET ) allow calculation of k CO2 R as a function of R. The values obtained are the following (R, k (10 9 s −1 )): CH 3
Databáze:	OpenAIRE
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