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Synthesis 2008(19): 3071-3080  
DOI: 10.1055/s-2008-1067269
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

A New Synthesis of Bis-Enaminones via Acylation of Ketones

Gunther Buehrdela, Rainer Beckert*a, Eva Petrlikovab, Petra Herzigovab, Vera Klimesovab, Jan Fleischhauera, Helmar Goerlsc
a Institute of Organic and Macromolecular Chemistry, Friedrich Schiller University, Humboldtstr. 10, 07743 Jena, Germany
Fax: +49(3641)948212; e-Mail: c6bera@uni-jena.de;
b Faculty of Pharmacy, Charles University Hradec Kralove, Heyrovskeho 1203, 500 05 Hradec Kralove, Czech Republic
c Institute of Inorganic and Analytical Chemistry, Friedrich Schiller University, August-Bebelstr. 2, 07743 Jena, Germany
Further Information

Publication History

Received 28 May 2008
Publication Date:
05 September 2008 (online)

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Abstract

A short and efficient synthesis for a series of 1,6-diaryl-3,4-diarylaminohexa-2,4-diene-1,6-diones was developed. Based on the acylation-prototropism sequence during the reaction of various aryl methyl ketones with bis-imidoyl chlorides, the products were isolated in good yields. Substituted acetophenones, acetyl­thiophene, 3-acetylpyridine, and acetylferrocene can be integrated into this reaction as ketone component. Similarly, α-tetralone can be transformed with bis-electrophiles into the corresponding bis-enaminones. Treatment of 2-acetylpyridine with N,N′-bis(4-tolyl)ethanebis(imidoyl) dichloride yielded not only the expected bis-enaminone, but also a new quinolizine derivative which was structurally characterized by single crystal X-ray analysis. Analogously, pinacolone and cyclopropyl methyl ketone can readily be converted into bis-enaminones. Monoimidoyl chlorides showed the same reactivity, providing derivatives in high yields.

Key words

acylations - ketones - tautomerism - enaminones - bis-imidoyl­ chlorides

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Derivatives 2 melt under the formation of dark green liquids; at about 260 ˚C formation of a colorless liquid takes place.

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CCDC-688639 (2e) and CCDC-688640 (7) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336 033; or deposit@ccdc.cam.ac.uk).