螺环三代树形大分子化合物的合成

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.

Synthesis of Sprio Third Generation Macromolecular Dendrimer

3,9-Di(4-(2,2-dicyanovinyl)phenyl)-2,4,8,10-tetraoxaspiro5.5]-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-tetraoxaspiro5.5]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-aspiro4.5]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-tetraoxaspiro5.5]-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.