8种B环间位取代异黄酮衍生物的核磁共振谱理论研究  

Theoretical Study of Nuclear Magnetic Resonance Spectra of Isoflavone Derivatives with m-substituents on B Ring

作　　者：廖显威[1] 梁晓琴[1] 王莹[1] 邹勤[1] 范志金[2] 

机构地区：[1]四川师范大学化学与生命科学学院,四川成都610066 [2]南开大学元素有机化学国家重点实验室,天津300071

出　　处：《四川师范大学学报（自然科学版）》2002年第6期632-636,共5页Journal of Sichuan Normal University（Natural Science）

基　　金：国家自然科学基金 (2 98740 2 7);南开大学元素有机化学国家重点实验室开放基金资助项目 (第 14期 )

摘　　要：在B3LYP 6 31G 水平下优化了 8种B环间位取代异黄酮衍生物的几何构型 ,在B3LYP 6 311G 水平下计算了该类化合物的核磁共振谱 ,研究结果表明 :对 1A～ 1D而言 ,羟基引入后O(15 )与羟基上的H(19)形成分子内氢键 ,使整个分子形成一个四环的交叉共轭体系 .由于羟基的引入 ,使 βC(5 )、C(6 )的相对化学位移均有较大程度的减小 ,而αC(9)上的化学位移增加幅度最大 .从取代基对NMR的影响来看 ,H(16 )基本不受取代基的影响 ,邻位H(2 4 )、H(2 9)和对位H(2 5 )的NMR数据从 1D～ 1A依此增大 ,间位C(2 3)的NMR数据变化较小 ,即间位碳受取代基的影响也较小 ,对位C(2 1)从 1D～ 1A依次减小 ,邻位C(2 0 )和C(2 6 )的NMR数据变化趋势不明显 .Isoflavone derivatives with m-substituents on B ring have been optimized at B3LYP/6-31G ** level. At B3LYP/6-311G ** level and by GIAO method, NMR spectra of the titled compounds have been studied. The results show that intramolecular hydrogen bonding has been formed in 1A～1D compounds whose bonding distance is 0.166 8 nm. Thus isoflavone derivatives form a four rings cross conjugated system. NMR spectra characteristics of the compounds with 9-hydroxyl substituting hydrogen have been discussed. The chemical shifts of adjacent carbon and adjacent hydrogen decrease owing to the increase of electron cloud density and the strengthening of shielding effect. However, the chemical shift of αC(9) has more increase. In addition, the effect of substituents on chemical shifts has been discussed. The chemical shifts of ortho-and para-hydrogens increase along with substituent groups' ability of donoring electron to benzene. The chemical shift of meta-carbon C(23) has a little change. The chemical shift of para-carbon decreses as substituent groups' ability of donoring electron to benzene increases. The chemical shift of ortho-carbon hasn't distinct change rule.

关 键 词：B环间位取代异黄酮衍生物 核磁共振谱 理论研究 几何构型 化学位移 

分 类 号：O629[理学—有机化学] O621.13[理学—化学]