Dynamics of the Wolff Rearrangement: spectroscopic evidence of oxirene intermediate

Journal Article · Wed Sep 16 00:00:00 EDT 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00253a069· OSTI ID:5890663

Tanigaki, K; Ebbesen, T W

The Wolff rearrangement, involving the decomposition of an ..cap alpha..-diazoketone to yield a ketene, is of great interest and importance in chemistry. Although it has been studied for many years by various techniques, the dynamics of this reaction from excitation of a diazoketone to the formation of the final product(s) have eluded direct observation. Only the last intermediate ketene has been observed to react with solvents to yield stable products. Ketene is postulated to be formed from other precursors, ketocarbene and/or oxirene. Ketocarbenes were finally detected by Chapman and his co-workers, very recently, in solid matrices at 15 K by using strained diazoketones. Here the authors report the direct observation of the dynamics of the Wolff rearrangement for an unstrained diazoketone in water at 298 K. The precursor to ketene is observed and assigned to be an oxirine, an important chemical species that had yet be unambiguously detected. Both spectral and dynamic features are presented.

• Research Organization: NEC Corp., Kawasaki, Japan
• OSTI ID: 5890663
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:19; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
AZO COMPOUNDS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
DATA
DECOMPOSITION
EXPERIMENTAL DATA
HYDROGEN COMPOUNDS
INFORMATION
KETENES
KETONES
MEDIUM TEMPERATURE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXYGEN COMPOUNDS
REACTION INTERMEDIATES
SYNTHESIS
WATER