論文

査読有り
2009年5月

3,4-Dihydro-3H-pyrrol-2-imines as Conformationally Restrained 1,3-Diazabutadienes: Synthesis, Structural Properties and Protonation

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
  • Simon Janich
  • ,
  • Roland Froehlich
  • ,
  • Andrea Wilken
  • ,
  • Jan von Zamory
  • ,
  • Atsushi Wakamiya
  • ,
  • Shigehiro Yamaguchi
  • ,
  • Ernst-Ulrich Wuerthwein

2009
13
開始ページ
2077
終了ページ
2087
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1002/ejoc.200900045
出版者・発行元
WILEY-V C H VERLAG GMBH

5-Aryl-3,3,4,4-tetramethyl-3,4 -dihydro-3H-pyrrol-2-imines, conformationally restrained 1,3-diazabuta-1,3-diene derivatives, were, easily prepared by treating aryllithium species with 2,2,3,3-tetramthylsuccinonitrile (1). Trapping the reaction intermediate with chlorotrimethylsilane gave N-silylaled compounds 2a-e, whereas aqueous workup gave N-H derivatives 3a,b. Pyrenyl-substituted compound 3b was characterised by X-ray diffraction studies, revealing the presence of both intermolecular aromatic face-to-face contacts and the formation of homodimers by twotold H-bonding. N-Silylated derivatives 2a-d were used successfully as nucleophilic components in palladium-catalysed C-N bond-forming reactions to obtain N-arylated compounds 5b-h,j,k,m and 7a-d. The UV spectra of compounds 5 and 7 exhibit long wavelength absorptions up to 462 nm for 7d, thus indicating extended pi-pi* conjugation. Dihydropyrrolimine-based compounds with larger conjugated aryl substituents in the 5-position react. with Bronsted and Lewis acids displaying a significant colour change that could be used to estimate. the pK(1), of 3a to a value of -4.5. Derivatives 2c,e and 3a,b, which are not N-arylated, are fluorescent with a Stokes shift of 107 nm (6034 cm(-1)) for 3a. ((c) Wiley-VCH Verlag GmbH & Co, KGaA, 69451 Weinheim, Germany, 2009)

リンク情報
DOI
https://doi.org/10.1002/ejoc.200900045
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000265858600008&DestApp=WOS_CPL
ID情報
  • DOI : 10.1002/ejoc.200900045
  • ISSN : 1434-193X
  • eISSN : 1099-0690
  • Web of Science ID : WOS:000265858600008

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