Isolation of Epimers in the Synthesis of Vinylcyclopropane Bearing Two Alanine Moieties and Their Radical Ring-Opening Polymerization
Isolation of Epimers in the Synthesis of Vinylcyclopropane Bearing Two Alanine Moieties and Their Radical Ring-Opening Polymerization
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带两个丙氨酸的乙烯基环丙烷合成中差向异构体的分离及其自由基开环聚合
DOI：
10.1021/acs.macromol.6b02778
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发表时间：
2017
期刊：
影响因子：
5.5
通讯作者：
T. Endo
中科院分区：
文献类型：
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作者：
Naoya Takahashi;A. Sudo;T. Endo
通过1，1-二羧基-2-乙烯基环丙烷与L-丙氨酸甲酯缩合，合成了一种新的带有两个酰胺基的手性乙烯基环丙烷衍生物1。将由此制备的乙烯基环丙烷分离成两种差向异构体，即RSS-1和SSS-1。差向异构体和差向异构体混合物都经历自由基开环聚合（RROP），其中聚合物的数均分子量（Mns）取决于1的构型;即，SSS-1的RROP得到相应的聚合物，其Mn高于通过RSS-1的RROP得到的聚合物。这种聚合行为的差异成功地与两种差向异构体之间的分子间和分子内氢键的方式的差异相关联，这一点通过SSS-1的聚合是由分子间氢键辅助的来阐明。除了溶液中的RROP之外，研究了SSS-1在其固态下的RROP，发现其高效地提供相应的聚合物。
By condensing 1,1-dicarboxy-2-vinylcyclopropane with l-alanine methyl ester, a new chiral vinylcyclopropane derivative bearing two amide moieties 1 was synthesized. The vinylcyclopropane thus prepared was separated into two epimers, namely, RSS-1 and SSS-1. Both the epimers and an epimeric mixture underwent radical ring-opening polymerization (RROP), where the number-average molecular weights (Mns) of the polymers depended on the configuration of 1; i.e., the RROP of SSS-1 gave the corresponding polymer, of which Mn was higher than the polymer obtained by the RROP of RSS-1. This difference in polymerization behaviors was correlated successfully with the difference in manners of intermolecular and intramolecular hydrogen bonds between the two epimers, which were clarified by the polymerization of SSS-1 was assisted by intermolecular hydrogen bonds. Besides the RROP in solution, the RROP of SSS-1 in its solid state was investigated to find that it afforded the corresponding polymer highly efficiently.
N-羧基氨基酸酐反应性的重新检验 1. 氨基酸 NCA 在乙腈中和在己烷中的固态聚合
DOI：
--
发表时间：
2006
期刊：
Macromolecular Symposia 242
影响因子：
--
作者：
Hitoshi Kanazawa;Aya Inada;Nobukazu Kawana
通讯作者：
Nobukazu Kawana