Synthesis and Evaluation of Chiral Compounds for Third Nonlinear Optics

第三非线性光学手性化合物的合成与评价

基本信息

批准号：
05554017
负责人：
HARADA Nobuyuki
金额：
$ 3.52万
依托单位：
TOHOKU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Developmental Scientific Research (B)
财政年份：
1993
资助国家：
日本
起止时间：
1993 至 1995
项目状态：
已结题

项目摘要

Chiral compounds have different refractive indices for left and right circularly rotated lights, and hence they show optical rotation proportional to the value n_L-n_R. When a intense linearly polarized light travels through a chiral material, it induces nonlinear optical rotation of the polarization plane. These chiral compounds can be used as photonics device. We have made exploatory studies of chiral pi-electron compounds suitable for such purpose and got the results described below.(1)The exciton coupling mechanism of chiral cyanin dye was theoretically clarified by the MO calculation.(2)The chiral probe of camphoresultamuseful for enantioresolution of carboxylic acids and X-ray determination of their absolute stereochemistry was developed. The method was applied to various chiral carboxylic acids.(3)The absolute stereochemistry of some chiral cyclophane compounds previously determined was revised.(4)The absolute configuration of a cage molecule was determined by the theoretical calculation of CD spectra.(5)The chiral cyclophane with a side chain containing oxygen atoms was enantioresolved and its absolute configuration was determined by the camphorsultam/X-ray method.(6)We succeeded in enantioresolution of monoterpenes by the chiral host-guest complex crystallization method.(7)The absolute stereostructure of double Michael product was determined by the camphoresultam/X-ray method.(8)The chiral phthalic acid amide method useful for anantioresolution of alcohols and determination of their absolute configuration by the X-ray method was developed and applied to various alcohols.(9)It was established that the exciton chirality method was applicable to acyclic dibenzoates to determine their absolute configuration.(10)The absolute configuration of unique chiral [6.6] vespirene compounds were determined by the X-ray method.

手性化合物对于左右旋光具有不同的折射率，因此它们表现出与n_L-n_R值成比例的旋光度。当强线偏振光穿过手性材料时，会引起偏振面的非线性旋光。这些手性化合物可用作光子器件。我们对适合此目的的手性π电子化合物进行了探索性研究，并得到了如下结果：(1)通过MO计算从理论上阐明了手性花青染料的激子耦合机理。(2)樟脑结果的手性探针可用于开发了羧酸的对映体拆分和其绝对立体化学的 X 射线测定。该方法适用于多种手性羧酸。(3)对之前确定的部分手性环芳化合物的绝对立体化学进行了修订。(4)通过CD谱的理论计算确定了笼型分子的绝对构型。(5)对侧链含氧原子的手性环芳烷进行对映拆分，并采用樟脑磺内酰胺/X射线法测定了其绝对构型。(6)成功实现了手性单萜的对映拆分。主客体络合结晶法。(7)采用樟脑磺内酰胺/X射线法测定双Michael产物的绝对立体结构。(8)手性邻苯二甲酰胺法可用于醇的拆分并测定其绝对构型。开发了X射线方法并应用于各种醇。(9)确定了激子手性方法适用于无环二苯甲酸酯测定其绝对构型。(10)独特的绝对构型手性[6.6]vespirene化合物通过X射线法测定。