聚缩醛螺胞二醚的合成及结构表征

Synthesis and Structure Characterization of Poly-acetal-spiro-vic-diether

在 I2 催化剂的作用下, 利用苯甲醛与季戊四醇反应, 制备了聚缩醛螺胞二醚的模型化合物 3,9-二苯基-2,4,8,10-四氧杂螺[5.5]十一烷(1). 在此基础上, 利用 1,3-苯二甲醛与不同摩尔比的季戊四醇合成了化合物 1,3-二(2,6-二氧杂-4,4-二羟甲基环己基)苯(2)和 2,4,8,10-四氧杂-3,9-二(3'-甲酰基苯基)螺[5.5]十一烷(3). 化合物 2 与化合物 3 反应, 制成标题化合物聚缩醛螺胞二醚 4, 收率为 95.4%. 用 FTIR, H NMR 对化合物 1～4 的结构进行了表征. 发现在含有手性轴化合 1物 1, 3, 4 的 H NMR 谱中, 4 个亚甲基中的 8 个氢原子裂分为 4 组双峰, 而不含有手性轴化合物中的 4 个亚甲基中的 8 1个氢原子不裂分, 是个单峰. 这种不同不是由于化合物中刚性环所致, 而是由于有无手性轴造成的.

In the presence of I-2, the model compound 3,9-diphenyl-2,4,8,10-tetraoxa-spiro[5.5]undecane (1) was prepared by the reaction of benzaldehyde with pentaerythritol. The reaction of 1,3-benzodialdehyde with different equivalent of pentaerythritol afforded 1,3-di(2,6-dioxa-4,4-dihydroxymethyl-cyclohexyl)benzene (2) and 2,4,8,10-tetraoxa-3,9-di(3'-formylphenyl)spiro[5.5]undecane (3), respectively. The title compound poly-acetal-spiro-vic-diether (4) was synthesized in 95.4% yield by the reaction of 2 with 3. The structures of compounds 1, 3 and 4 were characterized by FTIR and H-1 NMR. In the H-1 NMR spectra, the signals of eight hydrogen atoms of methylene groups in chiral axis-containing compounds 1, 3 and 4 were split into four groups of the doublets, but the corresponding signal of the hydrogen atoms was a single peak in compounds 5 and 6 un-containing chiral axis. This difference was not due to the presence of rigid cycle but the presence of chiral axis.