Thermolysis of a Tertiary Alkoxyamine. Recombination and Disproportionation of α-Phenethyl/Diethyl Nitroxyl Radical Pairs

Autor:	Shaoming Duan, Paul S. Engel, Graciela B. Arhancet
Rok vydání:	1997
Předmět:	chemistry.chemical_classification Radical Organic Chemistry Nitroxyl Disproportionation Photochemistry Medicinal chemistry Ethylbenzene Styrene Nitrone chemistry.chemical_compound Reaction rate constant Diethylhydroxylamine chemistry
Zdroj:	The Journal of Organic Chemistry. 62:3537-3541
ISSN:	1520-6904 0022-3263
Popis:	Alkoxyamine 3 undergoes thermolysis only on heating to over 150 °C, ΔH⧧ = 34.3 ± 1.6 kcal/mol and ΔS⧧ = 0.8 ± 3.7 eu. The initially formed nitroxyl (6) and α-phenethyl radicals (5) mainly disproportionate to styrene plus diethylhydroxylamine (2) but they also recombine to starting material and undergo a new reaction, disproportionation to ethylbenzene plus nitrone (12). The latter reacts with the styrene product to yield oxazolidines 8 and 9. The competition between attack of 5, generated from azo-α-phenylethane (1), on 2 versus styrene allowed us to calculate a rate constant at 120 °C of 5 × 103 M-1 s-1 for H• transfer from diethylhydroxylamine to 5.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_________::91e46e15d5710f650850a2df9c6b4a92 https://doi.org/10.1021/jo961852d Zobrazit plný text záznamu