Study on Synthesis of Functional Materials Having a Chiral Molecule as a Component

以手性分子为组分的功能材料的合成研究

• 批准号: 06555276
• 负责人: NOHIRA Hiroyuki
• 金额: $ 9.28万
• 依托单位: Saitama University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06555276/
• 关键词: Chiral; Optical Resolution; Asymmetric Synthesis; Liquid Crystal; Fluorine; Photochromic; Spiropyran; Ferroelectric; 強誘電性液晶; ホトクロミック

We have mainly studied on optical resolutions with crystallization methods which are classified as preferential crystallizations and diastereomeric crystallizations. Using a preferential crystallization method, the salt of p-toluenesulfonic acid and 3-methyl-2-phenyl-1-butylamine which was useful for an optical resolution of ibuprofen was resolved. Analogously, the salt of 1-aminoindan or 1-aminotetralin and phenylacetic acid was successfully resolved. It was also clarified that 2-oxo-4,5-diphenyl-1,3-oxazolidine derived from erythro-2-amino-1,2-diphenylethanol was resolved with the preferential crystallization method. Concerning the diastereomeric crystallization methods, we developed 2-aryl-3-methylbutylamines and erythro-2-amino-1,2-diphenylethanol series as basic optical resolving agents. Thus, their preparation methods and utilities were established. On the other hand, 2-phenylpropanesulfonic acid and 2- (p-isobutylphenyl) propanesulfonic acid were derived from 2-phenylpropanoic a … More cid or 2- (p-isobutylphenyl) propanoic acid.In this way the strong acidic chiral sulfonic acids were successfully developed. Using these optical resolving agents, alpha-amino-epsilon-caprolactam, proline, pipecolic acid, tert-leucine, tryptophan, dihydrojasmonic acid, jasminlactone, tuberolactone, delta-decalactone and chroman-2-carboxylic acid were effectively resolved.New ferroelectric liquid crystals (FLCs) derived from optically active fluorinated alkanol were synthesized, and a relationship between rotational viscosity and the fluorinated position of FLCs was clarified. Using optically active 1,1,1-trifluoro-2-alkanols resolved by trans-2- (benzamido) cyclohexane carboxylic acid, many FLCs and antiferroelectric liquid crystals were synthesized. Novel FLCs having a semi-perfluorinated terminal chain were synthesized, and a relationship between fluorination extent and mesophases properties was elucidated. Many liquid crystals derived from newly designed optically active compound, 4,4,4-trifluoro-3- (4-methoxyphenyl) butanoic acid, were synthesized. Thus, novel AFLCs without any carbonyl moiety in the molecule were found. Some chiral nematic materials having fluorinated asymmetric frame were synthesized, and a relationship between their structures and a helical twisting power were evaluated.An optically active spiropyran with trans-2- (benzamido) cyclohexane carboxylate moiety was synthesized, and its photochromic properties were analyzed by X-ray structural analysis and NMR spectroscopy. Some novel spiropyran metal complexes were synthesized, and their molecular structures were determined by X-ray analysis. Less

我们主要研究了优先结晶法和非对映体结晶法在光学拆分中的应用。采用优先结晶法拆分了布洛芬的光学拆分所需的对甲苯磺酸-3-甲基-2-苯基-1-丁胺盐。类似地，1-氨基茚满或1-氨基四氢化萘和苯乙酸的盐被成功地拆分。还阐明了用优先结晶法拆分由邻氨基-1，2-二苯基乙醇衍生的2-氧代-4，5-二苯基-1，3-恶唑烷。对于非对映体的结晶方法，我们开发了2-芳基-3-甲基丁胺和邻位-2-氨基-1，2-二苯基乙醇系列作为基本的光学拆分剂。从而确立了它们的制备方法和用途。另一方面，2-苯基丙磺酸和2-（对异丁基苯基）丙磺酸是由2-苯基丙酸衍生的。 ...更多信息 cid或2-（对异丁基苯基）丙酸，从而成功地合成了强酸性手性磺酸。利用这些光学拆分剂，对α-氨基-ε-己内酰胺、脯氨酸、哌啶酸、叔亮氨酸、色氨酸、二氢茉莉酸、茉莉内酯、tuberolactone、δ-癸内酯和色满-2-羧酸进行了有效拆分，合成了光学活性氟代烷醇衍生的新型铁电液晶，并研究了旋转粘度与氟代位置的关系。利用反式-2-（苯甲酰氨基）环己烷羧酸拆分光学活性的1，1，1-三氟-2-烷醇，合成了多种FLC和反铁电液晶。合成了具有半全氟末端链的新型FLC，并阐明了中间相性质与取代度之间的关系。合成了一系列新设计的光学活性化合物4，4，4-三氟-3-（4-甲氧基苯基）丁酸衍生物液晶。合成了几种含氟不对称骨架的手性光致变色材料，并研究了它们的结构与螺旋扭曲力的关系;合成了一种含反式-2-（苯甲酰氨基）环己烷羧酸酯结构的旋光螺吡喃，并通过X-射线结构分析和核磁共振谱对其光致变色性能进行了研究。合成了几种新型螺吡喃金属配合物，并通过X-射线衍射分析确定了它们的分子结构。少

项目成果

Yoshio Aoki: "New Antiferroelectric Liquid Crystals witha Trifluoromethyl Group at the Chiral Center" Liquid Crystals.

Yoshio Aoki：“手性中心具有三氟甲基的新型反铁电液晶”液晶。

Yoshio Aoki: "Synthesis and Properties of Optically Active α-trifluoromethylbenzyl Derivatives for Ferroelectric Liquid Crystals" Liquid Crystals. 18. 197-205 (1995)

Yoshio Aoki：“铁电液晶光学活性 α-三氟甲基苄基衍生物的合成和性能” 液晶 18. 197-205 (1995)

Y.Aoki: "Novel antiferroelectric liquid crystals with a trifluoromethyl group at the chiral center" Ferroelectrics. 178. 213-220 (1996)

Y.Aoki：“手性中心具有三氟甲基的新型反铁电液晶”铁电体。

H.Liu: "Effects of fluorination extent and direction of ester group in semiperfluorinated phenyl benzoate FLCs on mesomorphic properties" Liquid Crystals. 22. 217-222 (1997)

H.Liu：“半全氟苯甲酸苯酯FLC中酯基的氟化程度和方向对介晶性质的影响”液晶。

H.Liu: "Synthesis and mesomorphic properties of fluorinated liquid crystals obtained from optically active 2-fluoro-octanol" Liquid Crystals. 20. 581-586 (1996)

H.Liu：“从光学活性2-氟辛醇获得的氟化液晶的合成和介晶性质”液晶。