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
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- 巻
- 2009
- 号
- 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
- ID情報
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- DOI : 10.1002/ejoc.200900045
- ISSN : 1434-193X
- eISSN : 1099-0690
- Web of Science ID : WOS:000265858600008