Synthesis and Evaluation of Chiral Compounds for Third Nonlinear Optics

手性化合物对左右圆旋转的光具有不同的折射率，因此它们显示与值n_L-n_R成比例的旋光度。当强线偏振光通过手性材料时，会引起偏振面的非线性旋光。这些手性化合物可用作光子学器件。我们对适用于此目的的手性π电子化合物进行了探索性研究，得到了如下结果。（1）通过分子轨道计算，从理论上阐明了手性菁染料的激子耦合机理。（2）研制了樟脑磺酰胺手性探针，用于羧酸的手性拆分和X射线测定。该方法适用于各种手性羧酸。（3）修正了某些手性环蕃化合物的绝对立体化学。（4）通过圆二色光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蕃进行了对映体拆分，并用双氯磺内酰胺/X-射线法确定了其绝对构型。(6)We成功地用手性主客体络合物结晶法拆分了单萜类化合物。（7）用樟脑磺内酰胺/X-射线法测定了双Michael产物的绝对立体结构。（8）建立了手性邻苯二甲酰胺法用于醇类化合物的反相拆分和X射线法测定其绝对构型，并应用于各种醇类化合物的测定。(9)It建立了激子手性方法适用于非环状二苯甲酸酯的绝对构型测定。（10）用X射线衍射法确定了手性[6.6] vespirene化合物的绝对构型。

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.