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Studies on Asymmetric Synthesis, Structure, and Function of Optically Active Poly(methacrylamide) Derivatives

光学活性聚甲基丙烯酰胺衍生物的不对称合成、结构与功能研究

基本信息

批准号：
17550116
负责人：
OKAMOTO Yoshio
金额：
$ 2.43万
依托单位：
Nagoya University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2005
资助国家：
日本
起止时间：
2005 至 2006
项目状态：
已结题

项目摘要

1. The radical polymerization of the methacrylamides having a bulky side group, such as N-[(4-butyl)triphenylmethyl]methacrylamide (BuTrMAM) and N-[(4-butylphenyl)dibenzosuberyl]methacrylamide (BuPDBSMAM), in the presence of (+)-menthol or (-)-menthol was carried out in order to attain the helix-sense-selective polymerization leading to the optically active polymers. The tacticity of the polymers was estimated to be nearly 100% isotactic from the ^1H NMR spectra of the polymers in D_2SO_<4->. The circular dichroism (CD) spectra of the polymers suggested that the polymers have a helical conformation with an excess right-or left-handed helicity. The radical copolymerization of BuTrMAM with an optically active comonomer, such as N-[(R)-(+)-1-(1-naphthyl)ethyl]methacrylamide ((+)-NEMAM), was also carried out. The optical activity of the copolymers significantly depended on the comonomer contents. When (+)-NEMAM content was low in the copolymer, the (+)-NEMAM units effectively induced the one-handed helicity consisting of BuTrMAM monomeric sequences.2. BuTrMAM was polymerized with the chiral anionic initiator systems consisting of n-Bu_4ZnLi_2 and halogeno sugars, such as 2,3,4,6-tetra-0-acetyl-α-D-galactopyranosyl bromide. The ^1H NMR spectra in D_2SO_4 suggested that the polymers were highly isotactic, and the initiating chain end of polymers has a sugar residue. The obtained polymers exhibited an optical activity, and the halogeno sugars affected the specific rotations and Cotton effect in the CD spectra. These results indicate that the polymers prepared by the n-Bu_4ZnLi_2/halogeno sugars initiator systems have a helical conformation with an excess right- or left-handed helicity.

1.在（+）-薄荷醇或（-）-薄荷醇存在下，进行了具有大体积侧基的甲基丙烯酰胺如N-[（4-丁基）三苯基甲基]甲基丙烯酰胺（BuTrMAM）和N-[（4-丁基苯基）二苯并环己基]甲基丙烯酰胺（BuPDBSMAM）的自由基聚合，以获得导致光学活性聚合物的螺旋选择性聚合。聚合物在D_2SO_2中的^1HNMR谱表明，聚合物的立构规整度接近100%<4->。聚合物的圆二色性（CD）光谱表明，聚合物具有螺旋构象与过量的右手或左手螺旋。还进行了BuTrMAM与光学活性共聚单体如N-[（R）-（+）-1-（1-萘基）乙基]甲基丙烯酰胺（（+）-NEMAM）的自由基共聚合。共聚物的旋光性显著依赖于共聚单体的含量。当共聚物中（+）-NEMAM含量较低时，（+）-NEMAM单元有效地诱导了由BuTrMAM单体序列组成的单手螺旋.以n-Bu_4 ZnLi_2和卤代糖（如2，3，4，6-四-O-乙酰基-α-D-吡喃半乳糖基溴）组成的手性阴离子引发剂体系引发BuTrMAM聚合。在D_2SO_4介质中的~ 1H NMR谱表明，聚合物为高度全同立构的聚合物，且聚合物的起始链端有一个糖残基。所得聚合物具有旋光性，卤代糖影响CD光谱中的比旋光度和Cotton效应。这些结果表明，由n-Bu_4 ZnLi_2/卤代糖引发体系制备的聚合物具有过量的右旋或左旋螺旋度的螺旋构象。