• 作者： Liu, Jui-Hsiang; Kuo, Jue-Cheng
• 中文摘要： 本研究由樟腦衍生出一系列之光學活性化合物,更將之設計成光學活性單體ABMA(2-endo-acetoxy-5-endo-bornylmethacrylate)。為探討此光學活性單體之聚合特性,及此光學活性高分子在鏡像面區別反應上之立體區別效應,本研究中先針對光學活性單體(ABMA)之單聚合及與苯乙烯,甲基丙烯酸等單體之共聚合特性行探討,並合成數種光學活性高分子,再針對該些光學活性高分子在立體鏡像面區別反應上之應用行探討。聚合反應及立體區別反應之各項影響因素,如溫度效應,試劑莫耳比及溶劑效應等,在本研究中均有詳細探討。本研究中亦由實驗結果,針對立體鏡像面區別反應之反應機構及可能經由之反應中間體等行合理之推測。
• 英文摘要： Optically active 2-endo-actoxy-5-endo-bornyl methacrylate (ABMA) was prepared from (+)-camphor. The homopolymerization of ABMA and copolymerization of ABMA with achiral methyl methacrylate (MMA) or styrene (St) were carried out with 2,2-azobisisobutyronitrile (AIBN) in benzene. Effects of temperature, solvents and reaction time on the copolymerization were discussed. The monomer reactivity ratios (r/sub 1/, r/sub 2/) for poly(ABMA-co-MMA) and poly(ABMA-co-St), and Q, e values for the chiral ABMA in the copolymerization systems were evaluated by the Fineman-Ross method. It was found that the absolute value of the specific rotation of poly(ABMA-co-MMA) increased with the increase in the ABMA unit content. A small deviation from linearity was observed, which suggests that asymmetry is not introduced into the copolymer main chain. Temperature and solvent effects on the specific rotation of the chiral homopolymer and copolymers were investigated. The results suggest that the chiral polymers synthesized in this investigation did not show a strong preference for a particular helical conformation. Applications of the chiral polymers on the asymmetric addition of n-butyllithium to aldehydes were investigated. The effects of temperature and aldehydes on the enantioface differentiation were also discussed.
• 中文關鍵字： 鏡像面區別; 光學活性高分子; 光學活性; 不對稱合成; 對掌中心; 非對稱碳
• 英文關鍵字： Enantioface Differentiation; Chiral Polymer; Optical Yield; Asymmetric Synthesis; Chiral Center; Asymmetric Carbon