Direct observation of α-oxo ketenes from the photolysis of α-diazo β-diketones

Leung-Toung R. and Wentrup C. (1992) Direct observation of α-oxo ketenes from the photolysis of α-diazo β-diketones. Journal of Organic Chemistry, 57 18: 4850-4858. doi:10.1021/jo00044a019


Author Leung-Toung R.
Wentrup C.
Title Direct observation of α-oxo ketenes from the photolysis of α-diazo β-diketones
Journal name Journal of Organic Chemistry   Check publisher's open access policy
ISSN 0022-3263
Publication date 1992-01-01
Year available 1992
Sub-type Article (original research)
DOI 10.1021/jo00044a019
Open Access Status Not yet assessed
Volume 57
Issue 18
Start page 4850
End page 4858
Total pages 9
Place of publication WASHINGTON
Publisher AMER CHEMICAL SOC
Language eng
Subject 1605 Policy and Administration
Abstract Monitoring by IR spectroscopy of the broad-band irradiation of the symmetrically substituted 2-diazocyclohexane-1,3-dione (11), 3-diazopentane-2,4-dione (19), and 4-diazo-2,2,6,6-tetramethylheptane-3,5-dione (24) in Ar matrices at 12 K showed the formation of 2-carbonylcyclopentanone (s-Z-12), acetyl(methyl)ketene (s-E-20), and tert-butyl(pivaloyl)ketene (s-E-25), respectively, in less than 10 min. On increasing the photolysis time to >3 h, the α-oxo ketenes 12, 20, and 25 decarbonylated to the corresponding oxocarbenes which underwent Wolff rearrangement to carbonylcyclobutane (15), dimethylketene (23), and di-tert-butylketene (28), respectively. The reaction of 2-carbonylcyclopentanone (12) with CH3OH was monitored by IR spectroscopy. Thus, it was found that the reaction started at ca. 100 K and was essentially complete at 140 K, involving the initial formation of the enol form (9) of methyl 2-oxocyclopentanecarboxylate.
Keyword Ring Cyclic Alkynes
Aqueous-Solution
Abinitio
Acid
C3O
1,3-Dioxin-4-Ones
Rearrangement
Spectroscopy
Ketocarbenes
Spectrometry
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Article (original research)
Collection: Scopus Import - Archived
 
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