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有机化学 ›› 2009, Vol. 29 ›› Issue (02): 274-278. 上一篇    下一篇

研究简报

螺环三代树形大分子化合物的合成

魏荣宝* ; 刘 洋; 梁 娅   

  1. (天津理工大学化学化工学院 天津 300191)
  • 收稿日期:2007-10-02 修回日期:2008-07-17 发布日期:2009-02-20
  • 通讯作者: 魏荣宝

Synthesis of Sprio Third Generation Macromolecular Dendrimer

Wei, Rongbao* ; Liu, Yang ; Liang, Ya   

  1. (School of Chemistry & Chemical Engineering, Tianjin University of Technology, Tianjin 300191)
  • Received:2007-10-02 Revised:2008-07-17 Published:2009-02-20
  • Contact: Wei, Rongbao

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以对苯二甲醛单缩醛与季戊四醇反应得到了2,4,8,10-四氧杂-2,9-二(4-二氰基乙烯基苯基)螺[5.5]十一烷(1), 经水解, 再与丙二腈反应, 制备了中间体2,4,8,10-四氧杂-2-(4-二氰基乙烯基苯基)-9-(4-甲酰基苯基)螺[5.5]十一烷(3). 8-(4-氧代环己烷基)-1,4-二氧杂螺[4.5]癸烷经芳构化形成2,6,10-三-(4-氧代环己烷基)-1,2,3,4,5,6,7,8,9,10,11,12-十二氢苯并[l]菲(4), 再与甲醛进行羟醛缩合, 制成了2,6,10-三-(4-羟基-3,3,5,5-四羟甲基环己烷基)-1,2,3,4,5,6,7,8,9,10,11,12-十二氢苯并[l]菲(5), 将5与过量的3反应, 得到了目标树形大分子化合物2,6,10-三-{15-(3,11-二(-4-(3-((9-(4-二氰基乙烯基)苯基)2,4,8,10-四氧杂螺[5.5]十一烷基)))-7-羟基-二螺[5.1.5.3]十六烷基)}-1,2,3,4,5,6,7,8,9,10,11,12-十二氢苯并[l]菲(6), 收率为18.1%. 产品结构经IR, 1H NMR, MS和元素分析进行了表征. 对影响反应的因素进行讨论.

关键词: 丙二腈, 8-(4-氧代环己烷基)-1,4-二氧杂螺[4.5]癸烷, 三代螺环树状化合物, 季戊四醇, 苯二甲醛

3,9-Di(4-(2,2-dicyanovinyl)phenyl)-2,4,8,10-tetraoxaspiro[5.5]-undecane (1) was given by terephthalaldehyde mono-acetal reacting with pentaerythritol under grinding. 3-(4-(2,2-Dicyanovinyl)- phenyl)-9-(4-formylphenyl)-2,4,8,10-tetraoxaspiro[5.5]undecane (3) was obtained through the hydrolysate of compound 1 reacting with malononitrile. The intermediate of 2,6,10-tris(4-oxo-cyclohexyl)-1,2,3,4,5,6, 7,8,9,10,11,12-dodecahydrotriphenylene (4) was prepared by the aromatization of 8-(4-oxocyclohexyl)-1,4- diox-aspiro[4.5]decane in the presence of SOCl2. The sprio third generation macromolecular dendrimer of 2,6,10-tris(4-hydroxy-3,3:5,5-bis((9-(4-(2,2-dicyanovinyl)phenyl)-2,4,8,10-tetraoxaspiro[5.5]-undec-3-yl)
phenylmethylenedi(oxymethyl))cyclohexyl)-1,2,3,4,5,6,7,8,9,10,11,12-dodecahydrotriphenylene (6) was produced in the yield of 18.1% by the reaction of compound 3 with excessive compound 5. The effect pa-rameters were also discussed. The structures of intermediates and target product were determined by IR, 1H NMR and MS techniques.

Key words: pentaerythritol, 8-(4-oxocyclohexyl)-1,4-dioxaspiro[4.5]decane, phthalaldehyde, malononitrile, sprio third generation macromolecular dendrimer