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化学学报
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化学学报 ›› 2010, Vol. 68 ›› Issue (07): 703-706. 上一篇    下一篇

研究论文

缩氨基(硫)脲席夫碱化合物的自发对称性破缺研究

林丽榕*,1，胡望霞1，马杰1，章慧1，黄荣彬1，郑兰荪1,2   

  1. (1厦门大学化学化工学院化学系 厦门 361005)
    (2厦门大学固体表面国家重点实验室 厦门 361005)
  • 投稿日期:2009-08-10 修回日期:2009-10-25 发布日期:2010-04-14
  • 通讯作者: 林丽榕 E-mail:linlr@xmu.edu.cn
  • 基金资助:

    厦门大学科技创新项目（K70025和20061027）、国家重点基础研究发展计划（2007CB815301）和国家基金创新研究群体项目（20721001）

Spontaneous Chiral Symmetry Breaking of (Thio)semicarbazide Compounds

Lin Lirong*,1 Hu Wangxia1 Ma Jie1 Zhang Hui1 Huang Rongbin1 Zheng Lansun1,2   

  1. (1 Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005)
    (2 State Key Laboratory for Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen 361005)
  • Received:2009-08-10 Revised:2009-10-25 Published:2010-04-14

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1306

被引次数

14

制备了4-苯基-1-(吡啶-2-亚甲基)氨基脲(PPMSC)和4-苯基-1-(吡啶-2-亚甲基)氨基硫脲(PPMTC). 用元素分析、MS、1H NMR、UV吸收光谱、X射线单晶衍射和固体CD光谱等对其进行了表征. 晶体结构数据显示PPMSC属于Sohncke P212121空间群, 单个分子之间通过氢键形成一个一维螺旋链状结构, 沿a轴形成左手螺旋结构. 固体CD光谱和重结晶实验证明, PPMSC手性晶体的形成是结晶诱导的绝对不对称合成. PPMTC的固体CD光谱和重结晶实验具有与PPMSC类似现象.

关键词: 4-苯基-1-(吡啶-2-亚甲基)氨基脲, 4-苯基-1(吡啶-2-亚甲基)氨基硫脲, 手性对称性破缺, 绝对不对称合成, 手性晶体, 固体CD光谱

Two (thio)semicarbazide compounds, 4-phenyl-1-(pyrid-2-ylmethylene)semicarbazide (PPMSC) and 4-phenyl-1-(pyrid-2-ylmethylene)thiosemicarbazide (PPMTC), were prepared and characterized by elemental analysis, MS, IR, 1H NMR, UV absorption spectra, solid-state circular dichroism (CD) spectra, and X-ray single-crystal diffraction. The X-ray crystallographic data indicated that PPMSC crystallized in a space group of Sohncke P212121, PPMSC molecules formed the left-handed helix running along the crystallographic axis a via the intermolecular hydrogen bondings. The solid-state CD spectra and repeated recrystallization revealed that the formation of chiral PPMSC crystals could be regarded as crystallization- induced asymmetric synthesis. Although the crystal structure of PPMTC has not been obtained, PPMTC has the similar properties with PPMSC.

Key words: 4-phenyl-1-(pyrid-2-ylmethylene)semicarbazide, 4-phenyl-1-(pyrid-2-ylmethylene)thio- semicarbazide, chiral symmetry breaking, absolute asymmetric synthesis, chiral crystal, solid-state circular dichroism spectroscopy