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非对映体过剩率

非对映体过剩率(Diastereoisomer excess, 缩写为d.e.),通常用来表征两个以上掌性中心分子时的光学纯度。[1]

化合物含有2个掌性碳原子,在GCHPLC测定的时候,采用掌性管柱,可以得到4个同分异构体峰,可以利用峰面积直接求de值及ee值(对映体过量百分数)。

非对映体过量产生于核磁共振技术以前。当时人们无法测量非对映体的绝对含量,于是就用非对映体过量来表示光学纯度。而现在人们可以做到测量非对映体的绝对含量,所以有人建议逐渐废除非对映体过量这个概念。[2]

计算方式

某个拥有两个掌性中心的分子,有四种掌性结构:(R,R)、(R,S)、(S,S)、(S,R),将其中两个非对映体做比较(如: (R,R)和(R,S),令为D1和D2)。则两个非对映体之间就有含量比值。其计算公式为:

如果D1占80%,D2占20%,则dr值(非对映体比例,Diastereomeric Ratio[3])为4:1,de值为 (80%-20%)/(80%+20%) = 60%

需注意,

  • D1和D2加起来需为100%
  • 不能把(R,R)和(S,S)、(S,R)和(R,S)作分组,因为它们互为对映体
  • 此公式仅能使用两个非对映体,超过两个则不适用

注释

  1. ^ Chemistry (IUPAC), The International Union of Pure and Applied. IUPAC - diastereoisomer excess (D01675). goldbook.iupac.org. [2022-03-01]. (原始内容存档于2022-03-01). 
  2. ^ Gawley, Robert E. Do the Terms “% ee” and “% de” Make Sense as Expressions of Stereoisomer Composition or Stereoselectivity?. The Journal of Organic Chemistry. 2006-03, 71 (6): 2411–2416 [2022-03-01]. ISSN 0022-3263. PMC 2536600可免费查阅. PMID 16526791. doi:10.1021/jo052554w. (原始内容存档于2019-06-10) (英语). 
  3. ^ Chemistry (IUPAC), The International Union of Pure and Applied. IUPAC - diastereomeric ratio (D01681). goldbook.iupac.org. [2022-03-01]. (原始内容存档于2022-03-01). 


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非对映体过剩率
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