Ketene formation in benzdiyne chemistry: ring cleavage versus Wolff rearrangement.
J Am Chem Soc
; 125(39): 11936-41, 2003 Oct 01.
Article
em En
| MEDLINE
| ID: mdl-14505415
ABSTRACT
In the chemistry toward generating benzdiyne from five benzenetetracarboxylic dianhydride derivatives, ketene formation was exclusively observed in the photolysis of difluorobenzenetetracarboxylic dianhydride in a nitrogen matrix at 13 K. Two ketenes were formed concomitantly with difluorobenzdiyne. These ketenes were identified on the basis of good agreement between the observed and calculated (B3LYP/6-31G level) IR spectra. Neither ketene contained the five-membered-ring moiety as cyclopentadienylideneketene, which is formed by Wolff rearrangement in the benzyne chemistry. The first generated ketene was assigned to a ketene with a cyclopropene moiety, and the second, to a ketene with a butadiyne moiety. The first generated ketene was a major product in the photolysis and was formed by cleavage of the bond connecting the ketene group and the C-F carbon and not the bond connecting the ketene group and the carbene moiety. Thus the structures of these ketenes indicated that a unprecedented ring cleavage, rather than Wolff rearrangement, is the dominant process in the benzdiyne chemistry.
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Base de dados:
MEDLINE
Idioma:
En
Ano de publicação:
2003
Tipo de documento:
Article