有机化学 ›› 2000, Vol. 20 ›› Issue (5): 836-839. 上一篇    

研究论文

不对称受阻酚型杯芳烃的合成

涂海燕;袁立华;蒋建康;黄枢;田宝芝;冯文   

  1. 四川大学化学学院;四川大学原子核科学技术研究所.成都(610064);四川大学 教育部辐射物理与技术重点实验室
  • 发布日期:2000-10-25

Synthesis of unsymmetrically hindered phenol-substituted calixarenes

Tu Haiyan;Yuan Lihua;Jiang Jiankang;Huang Shu;Tian Baozhi;Feng Wen   

  1. Sichuan Univ., Inst of Nuclear Sci and Tech.Chengdu(610064)
  • Published:2000-10-25

以对叔丁基苯酚和甲醛水溶液为原料,经过环化缩聚、脱叔丁基、氯甲基化三步反应,最后与2-甲基-6-叔丁基苯酚进行亲核取代反应,合成了不对称酚型杯[n]芳烃4a(n=4)和4b(n=6),表征了它们的结构,并确认了4a中杯环为锥体构象。

关键词: 不对称, 锥型体, 构象, 受阻酚, 杯芳烃, 结构表征

Clixarene, as a class of special cyclic hindered phenols, have displayed good performance in polymer stabilization towards light, heat, oxygen and radiation. In the present paper, two new calixarene derivatives----unsymmetrically hindered phenol-substituted calix[n] arene 4a(n=4) and were 4b(n=6) were synthesized with p-tert- butylphenol and aqueous formaldehyde as starting materials via cyclic condensation, de-tert-butylation, chloromethyllation, and nucleophilic substitution with 2-tert-bytyl-6-methylphenol. Their structures were established by IR, MS, UV, and ^1H NMR spectra oscopy, and elemental analysis 4a was assigned to be in the cone conformation. Introduction of unsymmetrical structure into the calixarene results in decrease in melting point to ca. 100℃. This is advantageous to the polymer processing and provides a new way to design calixarene stabilizers. Preliminary results of the antioxidant activities show that unsymmetrically hindered phenols-substituted calix[n]arenes exhibit a higher stoichiometric factor (4.8) compared to calixarene with symmetrical phenol stricture (4.2) and a much higher factor to small phenol compound such as 2-tert-bytyl-6-methylphenol(1.4) and 2, 6-di-tert-butyl-6-methyl phenol(2.0).

Key words: ASYMMETRY, CONES, CONFORMATION, HINDERED PHENOL, CALIXARENE, STRUCTURE CHARACTERISTICS

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