| Aryliminopropadienone-C-Amidoketenimine- Amidinoketene-2-Aminoquinolone Cascades and the Ynamine-Isocyanate Reaction. | |
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MedLine Citation:
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PMID: 11674488 Owner: NLM Status: Publisher |
Abstract/OtherAbstract:
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Imidoylketenes 11 and oxoketenimines 12 are generated by flash vacuum thermolysis of Meldrum's acid derivatives 9, pyrrolediones 17 and 18, and triazole 19 and are observed by IR spectroscopy. Ketenimine-3-carboxylic acid esters 12a are isolable at room temperature. Ketenes 11 and ketenimines 12 undergo rapid interconversion in the gas phase, and the ketenes cyclize to 4-quinolones 13. When using an amine leaving group in Meldrum's acid derivatives 9c, the major reaction products are aryliminopropadienones, ArN=C=C=C=O (15). The latter react with 1 equiv of nucleophile to produce ketenimines 12 and with 2 equiv to afford malonic acid imide derivatives 16. N-Arylketenimine-C-carboxamides 12c cyclize to quinolones 13c via the transient amidinoketenes 11c at temperatures of 25-40 degrees C. This implies rapid interconversion of ketenes and ketenimines by a 1,3-shift of the dimethylamino group, even at room temperature. This interconversion explains previously poorly understood outcomes of the ynamine-isocyanate reaction. The solvent dependence of the tautomerism of 4-quinolones/4-quinolinols is discussed. Rotational barriers of NMe(2) groups in amidoketenimines 12c and malonioc amides and amidines 16 (24) are reported. |
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Authors:
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Curt Wentrup; V. V. Ramana Rao; Wilhelm Frank; Belinda E. Fulloon; Daniel W. J. Moloney; Thomas Mosandl |
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Publication Detail:
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Type: JOURNAL ARTICLE |
Journal Detail:
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Title: The Journal of organic chemistry Volume: 64 ISSN: 1520-6904 ISO Abbreviation: J. Org. Chem. Publication Date: 1999 May |
Date Detail:
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Created Date: 2001-Oct-24 Completed Date: - Revised Date: - |
Medline Journal Info:
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Nlm Unique ID: 2985193R Medline TA: J Org Chem Country: - |
Other Details:
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Languages: ENG Pagination: 3608-3619 Citation Subset: - |
Affiliation:
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Chemistry Department, The University of Queensland, Brisbane, Queensland 4072, Australia. |
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From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
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