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Concerted Wolff rearrangement in two simple acyclic diazocarbonyl compounds.
- Source :
-
The journal of physical chemistry. A [J Phys Chem A] 2010 Dec 23; Vol. 114 (50), pp. 13065-8. Date of Electronic Publication: 2010 Nov 30. - Publication Year :
- 2010
-
Abstract
- The photochemistry of two simple acyclic diazo carbonyl compounds, azibenzil and diazoacetone, were studied using the tools of ultrafast time-resolved spectroscopy. In the former case, UV-vis detection allows observation of an absorption band of singlet benzoylphenylcarbene, decaying with a 740 ± 150 ps time-constant in acetonitrile. IR detection shows that the ketene product of Wolff rearrangement (∼2100 cm(-1)) is formed by two parallel pathways: a stepwise mechanism with carbene intermediacy with a slow rise time-constant of 660 ± 100 ps, and directly in the diazo excited state as confirmed by the immediate formation of an IR band of a nascent hot ketene species. Photolysis (270 nm) of diazoacetone in chloroform leads mainly to the ketene species through a concerted process, consistent with the predominance of the syn conformation in the diazoacetone electronic ground state and a zero quantum yield of the internal conversion process.
Details
- Language :
- English
- ISSN :
- 1520-5215
- Volume :
- 114
- Issue :
- 50
- Database :
- MEDLINE
- Journal :
- The journal of physical chemistry. A
- Publication Type :
- Academic Journal
- Accession number :
- 21117638
- Full Text :
- https://doi.org/10.1021/jp108690n