Reactive intermediates in the photochemistry of 4-diazo-2-pyrazolin-5-ones

Photolysis of 4-diazo-2-pyrazolin-5-ones in methanol gives a mixture of stereoisomeric methyl 3-aryl-(or alkyl-)azo-2-alkenoates. A study of the absorption spectra of the species generated upon steady-state photolyses in glasses at 77 K, in solution at 296 K, and by laser and lamp flash photolysis e...

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Bibliographic Details
Published in:Canadian journal of chemistry 1984-11, Vol.62 (11), p.2456-2463
Main Authors: Umrigar, Pesi, Griffin, Gary W, Ege, Seyhan N, Adams, Alan D, Das, Paritosh K
Format: Article
Language:English
Subjects:
Chemistry
Exact sciences and technology
General and physical chemistry
Photochemistry
Physical chemistry of induced reactions (with radiations, particles and ultrasonics)
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Summary:Photolysis of 4-diazo-2-pyrazolin-5-ones in methanol gives a mixture of stereoisomeric methyl 3-aryl-(or alkyl-)azo-2-alkenoates. A study of the absorption spectra of the species generated upon steady-state photolyses in glasses at 77 K, in solution at 296 K, and by laser and lamp flash photolysis experiments suggests that a long-lived heterocyclic intermediate that we formulate as a carbene or its valence isomer, as well as a ketene generated by ring opening, are precursors to the esters.
ISSN:0008-4042
1480-3291
DOI:10.1139/v84-423