synthesis and intramolecular [4+2] cycloaddition reactions of 4-pyridazinecarbonitriles with alkyne side chains合成和分子内[4 + 2]环加成反应的反应4-pyridazinecarbonitriles炔烃与侧链.pdfVIP

Molecules 1998, 3, 10 – 15 molecules ISSN 1420-3049 Synthesis and Intramolecular [4+2] Cycloaddition Reactions of 4-Pyridazinecarbonitriles with Alkyne Side Chains Günther Fülep and Norbert Haider* Institute of Pharmaceutical Chemistry, University of Vienna, A-1090 Vienna, Austria FAX +43 1 31336 771 (nhaider@merian.pch.univie.ac.at) Dedicated to Professor Gottfried Heinisch on the occasion of his 60th birthday Received: 15 October 1997 / Accepted: 19 November 1997 / Published: 25 January 1998 Abstract: The preparation of a series of new 3-(alkynyl-X)-substituted 4-pyridazinecarbonitriles 2-5 (X = O, NH) is described. The compounds are shown to undergo thermally induced intramolecular Diels-Alder reactions with inverse electron demand, affording the fused benzonitriles 6-8. Incorporation of a 1,2-phenyl- ene unit into the side chain, as in the case of compounds 10 and 13, results in a more favorable conformation of the dienophilic substructure and thus to a pronounced acceleration of the [4+2] cycloaddition reaction. Keywords: [4+2] Cycloaddition, inverse-electron-demand Diels-Alder reaction, 4-pyridazinecarbonitriles. Introduction diazadienes with either flexible or rigid acetylenic sub- structures as the side-chain dienophiles. The intramolecular variant of the inverse-electron- demand Diels-Alder reaction of -deficient N-hetero- Results and Discussion aromatics such as tetrazines, triazines, diazines and even pyridines has been shown to