3，15-聚{7，11，18，21-四氧杂三螺[5．2．2．5．2．2]二十一烷}化合物的合成及^1H-NMR谱特征

Synthesis and ^1H- NMR Characterization of 3,15- Poly{ 7,11,18, 21- tetraoxa-trispiro [ 5.2.2.5.2.2 ] heneicosane}

本文将4,4’-二环己二酮单缩酮与季戊四醇反应,分别制得化合物3,15-双{8-(1,4-二氧杂螺[4.5]癸烷基)}-7,11,18,21-四氧杂三螺[5.2.2.5.2.2]二十一烷(1)和3,15-聚{7,11,18,21-四氧杂三螺[5.2.2.5.2.2]二十一烷}(2),对其1H-NMR的特征进行了讨论.发现三螺环中(B,C)原季戊四醇中的CH2不裂分,是个单峰;而A、D环上的CH2(H1,H5,H13,H17)受手性轴的影响而裂分成多重峰(如无手性轴的影响应为三峰).表明手性轴对手性的影响主要集中在轴的外侧,对中心影响较小.所获结论对不对称合成中进行手性催化剂和手性固定相的设计具有理论意义.

The compounds of 3,15- bis { 8- （ 1,4 - dioxaspiro [ 4.5 ] decyl） - 7,11,18,21 - tetraoxa- trispiro [ 5.2.2.5.2.2 ] heni- cosane（ 1 ） and 3,15- polyt 7,11,18,21- tetraoxa- trispiro[ 5.2.2.5.2.2 ] henicosane （ 2 ） were synthesized by reaction of di （cyclohexane） - 4,4＇ - dione mono ketal with 2,2- bis （hydroxymethyl） - 1,3- propanediol at the presence of I2 or InBr3. The I HNMR characterization of the compounds were discussed. In the ^1H-NMR spectra, the signals of eight hydrogen atoms of methylene groups（2H^8, 2H^10, 2H^19, 2H^20） in chiral axis-containing compounds 1 and 2 were not split and singlet peak, but the corresponding signal of the hydrogen atoms was four groups of doublets in compound of 3,9- diphenyl-2,4,8,10-tetraoxaspiro[5.5 ] undecane. The signals of hydrogen atoms of methylene groups （H^1, H^5, H^13, H^17） were not split into multiple peak, owing to the influence by chiral axis and adjacent CH2. It was indicated that the effect of chiral axes to chirality is at outboard. The result has a wider significance to design ehiral catalyst and ehiral stationary phase for chiral synthesis.