Oxoketene-oxoketene, imidoylketene-imidoylketene and oxoketenimine-imidoylketene rearrangements. 1,3-shifts of phenyl groups

George, L., Netsch, K. P., Penn, G., Kollenz, G. and Wentrup, C. (2006) Oxoketene-oxoketene, imidoylketene-imidoylketene and oxoketenimine-imidoylketene rearrangements. 1,3-shifts of phenyl groups. Organic & Biomolecular Chemistry, 4 3: 558-564. doi:10.1039/b515917b


Author George, L.
Netsch, K. P.
Penn, G.
Kollenz, G.
Wentrup, C.
Title Oxoketene-oxoketene, imidoylketene-imidoylketene and oxoketenimine-imidoylketene rearrangements. 1,3-shifts of phenyl groups
Journal name Organic & Biomolecular Chemistry   Check publisher's open access policy
ISSN 1477-0520
Publication date 2006
Sub-type Article (original research)
DOI 10.1039/b515917b
Open Access Status Not Open Access
Volume 4
Issue 3
Start page 558
End page 564
Total pages 7
Place of publication Cambridge, United Kingdom
Publisher Royal Society of Chemistry
Collection year 2006
Language eng
Abstract Dibenzoylketene 5 undergoes degenerate 1,3-shifts of the phenyl group between acyl and ketene carbon atoms, thus interconverting it with 6 and 7. This 1,3-shift takes place in the gas phase under flash vacuum thermolysis (FVT) conditions, but not in solution at 110-145 degrees C. Imidoyl(benzoyl)ketene 13 undergoes degenerate 1,3-shift of the phenyl group on FVT, thus interconverting it with 14, but the ketenimine isomer 15 is not formed, and none of these shifts take place in the solid state at 250 degrees C. Imidoyl(p-toluoyl)ketene 21 undergoes a 1,3-p-tolyl shift, interconverting it with ketene 22 but not with ketenimine 23. The imidoyl(p-toluoyl)ketene rotamer 25 cyclizes to 4-toluoyloxyquinoline 28 and 4-quinolone 29. The cyclization of imidoyl(benzoyl)ketene 13 to 4-benzoyloxyquinoline 18, and of 25 to 28 involves 1,3-C-to-O shifts of benzoyl (toluoyl) groups. Calculations of the transition states for the transformations at the B3LYP/6-31G** level of theory are in agreement with the observed reaction preferences.
Keyword Chemistry, Organic
Cyclic Oxalyl Compounds
Ketene-ketenimine Rearrangements
Heterocyclic-compounds
Ab-initio
Pseudopericyclic Reactions
1,3-migration
Cyclization
Products
Interconversion
Conformations
Q-Index Code C1

Document type: Journal Article
Sub-type: Article (original research)
Collections: 2007 Higher Education Research Data Collection
School of Chemistry and Molecular Biosciences
 
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Created: Wed, 15 Aug 2007, 09:04:20 EST