Helix-Sense-Selective Radical Polymerization of Methacrylamides

甲基丙烯酰胺的螺旋选择性自由基聚合

基本信息

批准号：
14350485
负责人：
OKAMOTO Yoshio
金额：
$ 7.94万
依托单位：
Nagoya University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2003
项目状态：
已结题

项目摘要

In this study, the radical polymerization of N-(triphenylmethyl)methacrylamide (TrMAM) and N-[di(4-butylphenyl)phenylmethyl]-methacrylamide (DBuTrMAM) was carried out in order to attain the helix-sense-selective polymerization leading to optically active polymers. The radical polymerization of TrMAM and DBuTrMAM proceeded in an isotactic-specific manner, and the ^1H NMR spectra of the obtained polymers in D_2SO_4 indicated that the obtained polymers were almost 100% isotactic polymers, which may produce an equimolar mixture of left-and right-handed helices. The poly(DBuTrMAM)s prepared in chiral menthols were optically active, and the polymerization in (+)-menthol and (-)-menthol produced the polymers having the negative and positive specific rotation, respectively. In the circular dichroism (CD) spectra of the poly(DBuTrMAM)s synthesized in menthols at 0℃, the peak patterns suggested that the polymer having an excess single-handed helicity was produced. Although poly(TrMAM)s were insoluble in common organic solvents, the analogous CD patterns were observed in Nujol in for the poly(TrMAM)s obtained in menthols. Triphenylmethyl methacrylate is easily solvolyzed in 10 minutes in methanol-chloroform at 35℃, but TrMAM was quite stable for the solvolysis for a week. Thus, the optically active poly(TrMAM) must afford a much stable chiral stationary phase against alcoholic solvents.

在这项研究中，进行N-（三苯基甲基）甲基丙烯酰胺（TRMAM）和N- [DI（4-丁基苯基）苯基甲基] - 甲基丙烯酰胺（DBUTRMAM）的根治性聚合，以实现螺旋 - 义相关的聚合型，以实现呼吸势能聚合的聚合。 TRMAM和DBUTRMAM的根部聚合以同型特异性方式进行，并且在D_2SO_4中获得的聚合物的 ^1H NMR光谱表明，所获得的聚合物几乎是100％的同骨聚合物，可能会产生左右右手螺旋的等效混合物。在手性薄荷醇中制备的聚（dbutrmam）是光学活跃的，并且（+） - 薄荷醇和（ - ） - 薄荷醇的聚合分别产生了具有负和阳性特异性旋转的聚合物。在薄荷醇在0℃中合成的聚（Dbutrmam）S的圆形二色性（CD）光谱中，峰模式表明产生了具有过量单手螺旋性的聚合物。尽管聚（TRMAM）S不溶于常见有机溶液，但在Nujol中观察到类似的CD模式，用于在精神病中获得的聚（TRMAM）。甲基丙烯酸甲酯在10分钟内很容易在35℃的甲醇 - 氯仿中溶解，但TRMAM对于溶剂分解非常稳定。这就是光学活性聚（TRMAM）必须针对酒精溶液提供非常稳定的手性固定相。