The homologous tert-amino effect: a route to fused 2-benzazepine derivatives

2-Cyano- and 2-carbethoxy-3-[2-(pyrrolidin-1-ylmethyl)phenyl]acrylonitriles were prepared through either amination of appropriate 3-[2-(bromomethyl)phenyl]acrylonitriles with pyrrolidine or condensation of 2-(pyrrolidin-1-ylmethyl)benzaldehyde with malononitrile and ethyl cyanoacetate. These acrylon...

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Veröffentlicht in:Tetrahedron 2011-02, Vol.67 (5), p.1030-1035
Hauptverfasser: Gorulya, Alexander P., Tverdokhlebov, Anton V., Tolmachev, Andrey A., Shishkin, Oleg V., Shishkina, Svetlana V.
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Sprache:eng
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Zusammenfassung:2-Cyano- and 2-carbethoxy-3-[2-(pyrrolidin-1-ylmethyl)phenyl]acrylonitriles were prepared through either amination of appropriate 3-[2-(bromomethyl)phenyl]acrylonitriles with pyrrolidine or condensation of 2-(pyrrolidin-1-ylmethyl)benzaldehyde with malononitrile and ethyl cyanoacetate. These acrylonitrile derivatives were shown to undergo easy mutual interconversion with 1-(pyrrolidin-1-yl)indane-2-carbonitriles driven by solvent polarity. Upon heating at 140–150 °C both acrylonitrile and indane derivatives were found to give 2,3,5,10,11,11 a-hexahydro-1 H-pyrrolo[1,2- b][2]benzazepine-11-carbonitriles. All transformations observed were rationalized in the terms of reactions related to the tert-amino effect. Furthermore, the corresponding piperidin-1-yl and azepan-1-yl analogs of the above acrylonitriles and indanes were obtained similarly. By analogy their heating afforded 1,2,3,4,6,11,12,12 a-octahydropyrido[1,2- b][2]benzazepine-12-carbonitriles and 7,8,9,10,11,11 a, 12,13-octahydro-5 H-azepino[1,2- b][2]benzazepine-12-carbonitriles. [Display omitted]
ISSN:0040-4020
1464-5416
DOI:10.1016/j.tet.2010.11.101