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

• 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
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-05554017/
• 关键词: Chiral Compounds; Third Nonlinearity; Optical Activity; Enantioresolution; Absolute Structure; Chiral Pigments; Ternaphthalenes; X-Ray Analysis

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.

手性化合物的左右圆形旋转灯具有不同的折射率，因此它们显示出与值N_L-N_R成正比的光学旋转。当强烈的线性极化光通过手性材料传播时，它会诱导极化平面的非线性光学旋转。这些手性化合物可用作光子设备。我们已经对适合此目的的手性pi电子化合物进行了剥削性研究，并得到了下面描述的结果。（1）理论上通过MO计算阐明了手性氰染料的激子耦合机制。（2）camphorsultamuse的手性质量用于弹药型和X-ray酸的启示式陈述。 （3）对先前确定的某些手性环烷化合物的绝对立体化学的绝对立体化学进行了修订。 （6）我们通过手性宿主 - 宿主 - 最佳复杂的结晶方法成功地对单烯烯进行了解决。 （9）已经确定，激子手性方法适用于无环二苯甲酸酯以确定其绝对构型。（10）通过X射线方法确定了独特的手性[6.6] vispirens的绝对构型。

项目成果

N. Harada: "Absolute Stereochemistry of 1- (9-Phenanthryl) -2-naphthoic Acid as Determined by CD and X-Ray Methods." Tetrahedron : Asymmetry. 4. 1789-1792 (1993)

N. Harada：“通过 CD 和 X 射线方法测定 1-(9-菲基)-2-萘酸的绝对立体化学。”

N.Harada: "Synthesis and Absolute Stereochemistry of(+)-Adociaquinones A and B" Tetrahedron:Asymmetry. 6. 375-376 (1995)

N.Harada：“( )-Adociaquinones A 和 B 的合成和绝对立体化学”四面体：不对称性。

N.Harada: "Revision of the Absolute Configurations of [8]Paracyclophane-10-carboxylic and 15-Methyl[10]paracyclophane-12-carboxylic Acids." Journal of the American Chenical Society. 115. 7547-7548 (1993)

N.Harada：“[8]对环芳烷-10-羧酸和 15-甲基[10]对环芳烷-12-羧酸的绝对构型的修订。”

N. Harada: "A CD Method for Determination of the Absolute Stereochemistry of Acyclic Glycols. 2. Application of the CD Exciton Chirality Method to Acyclic 1, 2-Dibenzoates Systems." Enantiomer. 1(in press). (1996)

N. Harada：“用于测定无环二醇绝对立体化学的 CD 方法。2. CD 激子手性方法在无环 1, 2-二苯甲酸酯体系中的应用。”

N.Berova, D.Gargiulo, F.Derguini, K.Nakanishi, and N.Harada: "Unique UV-VIS Absorption Circular Dichroic Exciton-Split Spectra of a and Chiral Biscyanine Dye : Origin and Nature." Journal of the American Chemical Society. 115. 4769-4775 (1993)

N.Berova、D.Gargiulo、F.Derguini、K.Nakanishi 和 N.Harada：“a 和手性双氰染料的独特 UV-VIS 吸收圆二色性激子分裂光谱：起源和性质。”