Synthesis and Secondary Structure of cis-Stereoregular Poly(N-propargylcarbamates) Having Various Side Chains
Synthesis and Secondary Structure of cis-Stereoregular Poly(N-propargylcarbamates) Having Various Side Chains
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具有不同侧链的顺式有规聚(N-炔丙基氨基甲酸酯)的合成和二级结构
DOI：
10.1021/ma0502248
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发表时间：
2005
期刊：
影响因子：
5.5
通讯作者：
T. Masuda
中科院分区：
文献类型：
--
作者：
F. Sanda;Shino Nishiura;M. Shiotsuki;T. Masuda
通过相应单体[1: (S)-CH⋮CCH2NHCOOCH(CH3)CH2CH3;的聚合合成顺式立构规整聚(N-炔丙基氨基甲酸酯)[poly(1)−poly(6)]； 2: (S)-CH⋮CCH2NHCOOCH2CH(CH3)CH2CH3; 3: (S)-CH⋮CCH2NHCOOCH2CH2CH(CH3)CH2CH3; 4: (S)-CH⋮CCH2NHCOOCH2CH2CH2CH(CH3)CH2CH3; 5: (S)-CH⋮CCH2NHCOOCH(CH3)CH2CH2CH2CH2CH3; 6: (S)-CH⋮CCH2NHCOOCH(CH3)Ph]与铑催化剂。 Poly(2)−poly(6) 具有通过分子内氢键稳定的螺旋结构。他们随着温度和极性溶剂的添加改变了构象。考察了手性中心和主链与苯基之间的距离的影响。 1H NMR和CD光谱分析表明，手性中心与主链之间的距离越近，螺旋越稳定，聚合物刚性越强，即poly(5)>poly(2)>poly(3)>poly(4)。当手性中心与主链之间的距离相同时，不含苯基的聚合物[poly(5)]比不含苯基的聚合物刚性更大...
cis-Stereoregular poly(N-propargylcarbamates) [poly(1)−poly(6)] were synthesized by the polymerization of the corresponding monomers [1: (S)-CH⋮CCH2NHCOOCH(CH3)CH2CH3; 2: (S)-CH⋮CCH2NHCOOCH2CH(CH3)CH2CH3; 3: (S)-CH⋮CCH2NHCOOCH2CH2CH(CH3)CH2CH3; 4: (S)-CH⋮CCH2NHCOOCH2CH2CH2CH(CH3)CH2CH3; 5: (S)-CH⋮CCH2NHCOOCH(CH3)CH2CH2CH2CH2CH3; 6: (S)-CH⋮CCH2NHCOOCH(CH3)Ph] with a rhodium catalyst. Poly(2)−poly(6) took helical structure stabilized by intramolecular hydrogen bonding. They changed the conformation with temperature and addition of a polar solvent. Effects of the distance between the chiral center and main chain and the phenyl group were examined. 1H NMR and CD spectroscopic analyses revealed that the closer the distance between the chiral center and main chain, the more stable the helix and the rigid the polymer, i.e., poly(5) > poly(2) > poly(3) > poly(4). When the distance between the chiral center and main chain was the same, the polymer without phenyl groups [poly(5)] was more rigid than the one w...