无溶剂法合成4,6,10,12,16,18,22,24-八羟基-2,8,14,20-四-{(联三-(3-苯基-2,4,8,10-四氧杂螺[5.5]十一烷基))-(4-(2-(4,6,10,12,16,18,22,24-八羟基)杯[4]芳基)苯基)}杯[4]芳烃螺环树形大分子化合物

Solvent-free Synthesis of 4,6,10,12,16,18,22,24-Octa-hydroxy-2,8,14,20-tetra{(tri-(3-phenyl-2,4,8,10-tetraoxaspiro[5.5]undecyl))-(4-(2-(4,6,10,12,16,18,22,24-octa-hydroxy)Calix[4]resorcinarenyl)phenyl)} calix[4]resorcinarene Spiro macromolecular Dendrimer

以对苯二甲醛、丙二腈为原料,合成对苯二甲醛单缩醛,再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,经水解,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).用乙酸酐保护的对苯二甲醛单缩醛与间苯二酚反应,制备了杯[4]芳烯中间体(6).将化合物6与过量的化合物3反应,得到中间体7,经水解后与过量的化合物6反应,得到了4,6,10,12,16,18,22,24-八羟基-2,8,14,20-四-{(联三-(3-苯基-2,4,8,10-四氧杂螺[5.5]十一烷基))-(4-(2-(4,6,10,12,16,18,22,24-八羟基)杯[4]芳基)苯基)}杯[4]芳烃螺环树形大分子化合物(9).总收率为12·7%.产物结构用IR,1H NMR,13C NMR,MS和元素分析进行了表征,对影响反应的因素进行了讨论.

The terephthalaldehydes mono-acetal was prepared by the reaction of terephthalaldehyde and malononitrile. The 2- （ 4-dicyano-vinyl-phenyl ） -9- （ 4-formylphenyl ） -2,4,8,10-tetraxaspiro [ 5.5 ] undecanes （ 3 ） were given through terephthalaldehydes mono-acetal reacting with pentaerythritol and then the hydrolysis occurred in the presence of InBr3. The calix [ 4 ] resorcinarenes 6 was prepared by using terephthalaldehydes mono-acetal and resorcinol as the material. Through compound 6 reacting with compound 3, calix [ 4 ] resorcinarene macromolecular dendrimer of 4,6,10,12,16,18,22,24-octahydroxy-2,8,14,20 -tetra { （ tri （ 3 -phenyl-2, 4,8,10-tetraoxaspiro [ 5.5 ] undecyl ） ） - （ 4- （ 2 - （ 4,6,10,12,16,18,22,24-octahydroxy ） calix [ 4 ] resorcinarenyl）phenyl） } calix[4]resorcinarene （9） was produced. The product was characterized by IR, ^1H NMR, ^13C NMR, MS and elemental analysis. The effect factors on the reactions were discussed.