Synthesis and application of novel optically active maleimide polymers with thermostability

新型热稳定性光学活性马来酰亚胺聚合物的合成及应用

• 批准号: 08651054
• 负责人: OISHI Tsutomu
• 金额: $ 1.47万
• 依托单位: YAMAGUCHI UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08651054/
• 关键词: Optically active polymer; N-Substituted Maleimide; Radical Polmerization; Asymmetric Anionic Polymerization; Monomer Reactivity Ratios; Q and e Values; Asymmetric Induction; Cirular Dichoism; 不斉アニオン重合

New types of maleimides having methylbenzyl, L-menthyl and amino-acid residual group were synthesized and homopolymerized and copolymerized with stirene and methyl methacrylate. Optical activity of the polymers and copolymers were investigated by circular dichroism and specific rotation measurements. Asymmetric induction took place to the main chain of the polymer and copolymer. Asymmetric anionic polymerizations of optically inactive N-substituted maleimide (N-substituent : cyclohexyl, phenyl) were performed with organometal - chiral ligands to obtain the optically active polymers having + 117 to -155 deg.of specific rotation, which were the highest in the values resported previously. The optical activity of the polymers was attributed to the different content between (S,S) and (R,R) absolute configuration by the threo-diisotactic structures in the main chain. It is considered that the (+) -polymer has more (S,S) absolute configuration than (R,R) and the (-) -polymer has more (R,R) absolute configuration than (S,S), judging from the exciton chirality method and the model compounds. The asymmetric polymerizations of the maleimides having bulky group in the N-substituents such as triphenylmethyl, diphenylmethyl and fluorenyl were also carried out with organometal-chiral ligand to give optically active polymers. The polymers were applied for optical resolution reagents because the polymers have relatively higher specific rotation.

合成了含有甲基苄基、L-薄荷基和氨基酸残基的新型马来酰亚胺，并分别与苯乙烯、甲基丙烯酸甲酯进行了均聚和共聚反应。通过圆二色性和比旋光度测定研究了聚合物和共聚物的旋光活性。聚合物和共聚物的主链发生不对称诱导。用有机金属-手性配体进行旋光惰性N-取代马来酰亚胺（N-取代基：环己基、苯基）的不对称阴离子聚合，以获得具有+117至-155 °比旋光度的旋光聚合物，其在先前报道的值中是最高的。聚合物的旋光性归因于主链上苏式双等规结构导致的（S，S）和（R，R）绝对构型含量的不同。根据激子手性方法和模型化合物的性质，认为（+）-聚合物具有比（R，R）多的（S，S）绝对构型，（-）-聚合物具有比（S，S）多的（R，R）绝对构型。此外，还研究了N-取代基上含有三苯甲基、二苯甲基和芴基等大体积基团的马来酰亚胺与有机手性配体的不对称聚合反应，得到了光学活性高分子。由于聚合物具有较高的比旋光度，因此被用作光学拆分试剂。

项目成果

Tsutomu Oishi: "Synthesis and polymerization of maleimide containing an L-methyl group" Polymer. 38・6. 1461-1469 (1997)

大石勉：“含有L-甲基的马来酰亚胺的合成和聚合”聚合物38・6（1997）。

Kenjiro Onimura: "Asymmetric polymerization of N-substituted maleimides with organolithium - bisoxazolines complex" Polymer Bulletin. 39. 437-444 (1997)

Kenjiro Onimura：“N-取代马来酰亚胺与有机锂-双恶唑啉复合物的不对称聚合”聚合物通报。

Tsutomu Oishi: "Synthesis and polymerization of N-substituted malemides based on L-alanine ester" Polymer. (印刷中). (1998)

Tsutomu Oishi：“基于 L-丙氨酸酯的 N-取代马来酰亚胺的合成和聚合”聚合物（正在出版）。

Tsutomu Oishi, Tetsuji Kawamoto and Hiromori Tsutsumi: "Synthesis and polymerization of optically active itaconamate bearing an (R) -alpha-methylbenzyl group" Polymer. 37 (24). 5513-5520 (1996)

Tsutomu Oishi、Tetsuji Kawamoto 和 Hiromori Tsutsumi：“带有 (R)-α-甲基苄基的光学活性衣康酸酯的合成和聚合”聚合物。

Tsutomu Oishi, Kenso Kagawa and Haruo Nagata: "Synthesis and polymerization of maleimide containing an L-methyl group" Polymer. 38 (6). 1461-1469 (1997)

Tsutomu Oishi、Kenso Kakawa 和 Haruo Nagata：“含 L-甲基的马来酰亚胺的合成和聚合”聚合物。