螺环三代树形大分子化合物的合成

Synthesis of Sprio Third Generation Macromolecular Dendrimer

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,1HNMR,MS和元素分析进行了表征.对影响反应的因素进行讨论.

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 SOC12. 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 parameters were also discussed. The structures of intermediates and target product were determined by IR, ^1H NMR and MS techniques.