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有机化学
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有机化学 ›› 2009, Vol. 29 ›› Issue (9): 1423-1428. 上一篇    下一篇

研究论文

新型萘并氧杂并喹啉酮和萘并吖啶二酮的合成及其荧光性质的研究

高文涛* 张朝花 李 阳 姜 云   

  1. (渤海大学超精细化学品研究所辽宁省应用化学重点试验室 锦州 121000)
  • 收稿日期:2009-04-02 修回日期:2009-07-20 发布日期:2009-12-30
  • 通讯作者: 高文涛

Effective Preparation and Fluorescent Properties of Novel Naphthooxepinoquinolinones and Naphthoacridinediones

Gao, Wentao* Zhang, Chaohua Li, Yang Jiang, Yun   

  1. (Liaoning Key Laboratory of Applied Chemistry, Institute of Superfine Chemicals, Bohai University, Jinzhou 121000)
  • Received:2009-04-02 Revised:2009-07-20 Published:2009-12-30
  • Contact: Gao, Wentao

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以2-溴甲基-3-喹啉甲酸乙酯(1)为底物, 分别与α-萘酚和β-萘酚“一锅法”高产率合成了2-(α-萘氧甲基)-3-喹啉甲酸(2a)和2-(β-萘氧甲基)-3-喹啉甲酸(2b). 化合物2a, 2b用Eaton试剂(五氧化二磷-甲基磺酸)作为环化试剂, 发生分子内Friedel-Crafts酰基化反应得到两种新型闭环产物: 萘并[2’,1’,6,7]氧杂并[3,4-b]喹啉-7(14H)-酮(3a)和萘并[1’,2’,6,7]氧杂并[3,4-b]喹啉-15(8H)-酮(3b). 化合物3a, 3b在氢氧化钾的乙醇-水溶液中经1,2-Wittig重排和空气氧化生成萘并[2,1-b]吖啶-7,14-二酮(4a)和萘并[1,2-b]吖啶-7,14-二酮(4b). 所合成新化合物2a～4a, 2b～4b的结构通过 IR, UV, 1H NMR, MS和元素分析进行了确认. 测定了化合物2a～4a, 2b～4b在三氯甲烷中的紫外光谱和化合物3a, 4a和3b, 4b的固体荧光光谱, 2a～4a, 2b～4b在三氯甲烷中的最大吸收峰分别位于280, 261, 312, 273, 256和313 nm; 3a, 4a和3b, 4b在固态状态下的最大发射波长分别为350, 300, 274和330 nm.

关键词: 一锅法, 荧光, Eaton 试剂, 萘并氧杂并喹啉酮, 萘并吖啶二酮, 1,2-Wittig重排

Naphtho[2’,1’,6,7]oxepino[3,4-b]quinolin-7(14H)-one (3a) and naphtho[1’,2’,6,7]oxepino[3,4-
b]quinolin-15(8H)-one (3b) were synthesized by the intramolecular Friedel-Crafts acylation reactions of 2-[(naphthalen-1-yloxy)methyl]quinoline-3-carboxylic acid (2a) and 2-[(naphthalen-2-yloxy)methyl]-
quinoline-3-carboxylic acid (2b) under the treatment of Eaton’s reagent (P2O5-MeSO3). Compounds 2a and 2b were prepared by a one-pot method of ethyl 2-(bromomethyl)quinoline-3-carboxylate (1) with α-naphthol and β-naphthol, respectively. The synthesized compounds 3a and 3b could be further treated with potassium hydroxide in 60% (V/V) ethanol-water solution to undergo 1,2-Wittig rearrangement and atmospheric oxida-tion reactions to afford naphtho[2,1-b] acridine-7,14-dione (4a) and naphtho[1,2-b]acridine-7,14-dione (4b). The structures of 2a～4a and 2b～4b were confirmed by IR, UV, 1H NMR, MS techniques and elemental analysis. The UV-vis spectra of 2a～4a and 2b～4b measured in trichloromethane showed that the maxi-mum absorption peaks were at 280, 261, 312, 273, 256 and 313 nm, respectively. The fluorescence emission spectra of 3a, 4a and 3b, 4b in the solid state showed that the maximum emission wavelengths were at 350, 300, 274 and 330 nm, respectively.

Key words: Eaton’s reagent, naphthooxepinoquinolinone, naphthoacridinedione, 1,2-Wittig rearrangment, fluorescence, one-pot