Asymmetric radical polymerization and copolymerization of N‐(1‐phenyldibenzosuberyl)methacrylamide and its derivative leading to optically active helical polymers
Asymmetric radical polymerization and copolymerization of N‐(1‐phenyldibenzosuberyl)methacrylamide and its derivative leading to optically active helical polymers
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DOI：
10.1002/pola.21902
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发表时间：
2007-04
期刊：
影响因子：
--
通讯作者：
A. Azam;M. Kamigaito;Y. Okamoto
中科院分区：
文献类型：
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作者：
A. Azam;M. Kamigaito;Y. Okamoto
合成了N-（1-苯基二苯并环己基）甲基丙烯酰胺（PDBSMAM）及其衍生物N-[（4-丁基苯基）二苯并环己基]甲基丙烯酰胺（BuPDBSMAM），并在（+）-和（-）-薄荷醇存在下于不同温度下进行聚合。的聚合物的立构规整度估计为近100%全同立构从1H NMR光谱中衍生的D2 SO 4的聚甲基丙烯酰胺。聚（PDBSMAM）不溶于常用的有机溶剂，其固态圆二色性光谱与光学活性的聚（1-苯基二苯并环庚基甲基丙烯酸酯）（聚（PDBSMA））的圆二色性光谱相似，具有普遍的单手螺旋性，表明聚（PDBSMAM）也具有相似的螺旋性。Poly（BuPDBSMAM）具有光学活性，可溶于THF和氯仿。其光学活性远高于聚[N-（三苯基甲基）甲基丙烯酰胺]，表明在聚（BuPDBSMAM）上可以更有效地诱导单手螺旋。BuPDBSMAM与少量光学活性N-[（R）-（+）-1-（1-萘基）乙基]甲基丙烯酰胺的共聚反应，特别是在（-）-薄荷醇存在下，产生了具有高光学活性的聚合物。也可以有效地诱导占主导地位的螺旋度。详细研究了所得聚合物的手性光学性质。还评估了聚合物的手性识别。© 2007 Wiley Periodicals，Inc.聚合物科学杂志A部分：聚合物化学45：1304-1315，2007
N-(1-Phenyldibenzosuberyl)methacrylamide (PDBSMAM) and its derivative N-[(4-butylphenyl)dibenzosuberyl]methacrylamide (BuPDBSMAM) were synthesized and polymerized in the presence of (+)- and (−)-menthols at different temperatures. The tacticity of the polymers was estimated to be nearly 100% isotactic from the 1H NMR spectra of polymethacrylamides derived in D2SO4. Poly(PDBSMAM) was not soluble in the common organic solvents, and its circular dichroism spectrum in the solid state was similar to that of the optically active poly(1-phenyldibenzosuberyl methacrylate) (poly(PDBSMA)) with a prevailing one-handed helicity, indicating that the poly(PDBSMAM) also has a similar helicity. Poly(BuPDBSMAM) was optically active and soluble in THF and chloroform. Its optical activity was much higher than that of the poly[N-(triphenylmethayl)methacrylamide], suggesting that one-handed helicity may be more efficiently induced on the poly(BuPDBSMAM). The copolymerization of BuPDBSMAM with a small amount of optically active N-[(R)-(+)-1-(1-naphthyl)ethyl]methacrylamide, particularly in the presence of (−)-menthol, produced a polymer with a high optical activity. The prevailing helicity may also be efficiently induced. The chiroptical properties of the obtained polymers were studied in detail. The chiral recognition by the polymers was also evaluated. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1304–1315, 2007