Synthesis and Intramolecular Pericyclization of 1-Azulenyl Thioketones
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- 作者：Shunji Ito ; Tetsuo Okujima ; Shigeru Kikuchi ; Taku Shoji ; Noboru Morita ; Toyonobu Asao ; Tadaaki Ikoma ; Shozo Tero-Kubota ; Jun Kawakami ; Akio Tajiri
- 刊名：Journal of Organic Chemistry
- 出版年：2008
- 出版时间：March 21, 2008
- 年：2008
- 卷：73
- 期：6
- 页码：2256 - 2263
- 全文大小：152K
- 年卷期：v.73,no.6(March 21, 2008)
- ISSN：1520-6904
文摘
Several azulene-substituted thioketones, 1-thiobenzoylazulene (1a) and di(1-azulenyl) thioketone (2a)and their derivatives (1b and 2b-d) with alkyl substituents on each azulene ring, were prepared andtheir intramolecular pericyclization reaction was examined. The thioketones with a 3-alkyl substituenton each azulene ring exhibited the presumed pericyclization reaction under thermal and acid-catalyzedconditions, although the cases of the 1-azulenyl thioketones without the 3-alkyl substituents afforded acomplex mixture under similar conditions. The intramolecular reaction following the intramolecularhydrogen transfer afforded the products 13b, 14b, and 14c. The products 13b and 14b were convertedinto the corresponding cations 18+ and 19+, which have structural similarity with that of the phenalenylcation. These cations exhibited the expected two-step reduction waves upon CV, although the ESR analysisrevealed that the neutral radical state did not have the presumed high stability.