立体异构体的机械重新配置
Kelly M Wiggins1, Todd W Hudnall, Qilong Shen
1Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, Texas 78712, USA.
Journal of the American Chemical Society
|February 20, 2010
概括
高分子量聚甲基烯酸衍生物在超声波下经历显著的种族化,与低分子量对应物不同. 这一发现突出了分子重量.
科学领域:
- 聚合物化学 聚合物化学
- 立体化学是一种立体化学.
- 状聚合物 状聚合物
背景情况:
- 嵌合体聚合物在不对称合成和嵌合体识别中至关重要.
- 在聚合物合成和加工过程中控制立体化学是必不可少的.
- 迪托普基启动器使得能够合成精确定义的性聚合物.
研究的目的:
- 为了研究不同分子重量的聚甲烯酸的种族化行为.
- 确定分子质量对性聚合物的立体化学稳定性的影响.
- 探索超声波作为一种方法来诱导在性聚合物中的种族化.
主要方法:
- 聚甲基烯酸盐的合成,使用二氧化基启动剂 ((R) -或 (S) -1,1'-二甲基-2,2'-二甲基烯酸)).
- 聚合物分子重量和立体化学的表征.
- 在0°C下对聚合物溶液进行超声波检测,并通过循环二元化分析拉塞米化.
主要成果:
- 高分子量聚甲烯酸 (MN) >25kDa) 经过24小时的超声波,呈现出>95%的种族化.
- 在相同的条件下,低分子量衍生品没有显著的种族化.
- 对照实验排除了热性种族化作为导致因素.
结论:
- 分子重量显著影响了在超声波下聚甲酸的立体化学稳定性.
- 超声波可以是一个有效的方法来诱导高分子量性聚合物的racemization.
- 这些发现对性聚合物的加工和应用具有重要意义,其中立体化学完整性至关重要.
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