6,6'-二溴-1,1'-联-2-萘酚的偶联合成与手性拆分——对一个有机化学综合实验的改进与发展

Coupling Synthesis and Chiral Splitting of 6,6’-Dibromo-1,1’-Bi-2-Naphthol:Improvement and Development of a Comprehensive Organic Chemistry Experiment

6,6'-二溴-1,1'-联-2-萘酚是1,1'-联-2-萘酚(BINOL)的衍生物,两者同为典型的轴手性有机物分子,这类分子的合成与拆分研究对于本科生深入认识和理解轴手性类化合物具有重要意义,本实验考虑到(±)-BINOL及其衍生物的价格较为高昂,不适合开展大批量合成和拆分的教学实验,因此采用了微波合成的方式实现6,6'-二溴-1,1'-联-2-萘酚的偶联合成。除此之外,本实验还开发了拆分剂N-苄基氯化辛可尼丁的微波合成方法,并用合成的N-苄基氯化辛可尼丁直接对6,6'-二溴-1,1'-联-2-萘酚进行化学拆分。本实验通过引入微波合成、改良合成反应用溶剂以及回收拆分剂等方式使实验更加符合绿色化学的宗旨。在教学效果上,本实验涉及的操作较多,有助于考查学生的综合实验水平,更富教学价值,具有强的实践意义。

6,6'-Dibromo-1,1'-bi-2-naphthol is a derivative of 1,1'-bi-2-naphthol(BINOL),both of which are archetypal axially chiral organic molecules.The study of the synthesis and separation of such molecules is crucial for undergraduates to deepen their understanding of axially chiral compounds.Considering the high cost of(±)-BINOL and its derivatives,which hinders extensive synthesis and separation experiments for educational purposes,this study employs microwave-assisted synthesis for the coupling of 6,6'-ibromo-1,1'-bi-2-naphthol.In addition,we have developed a microwave synthesis method for the chiral separating agent,N-benzylcinchonidine chloride,and used it directly for the chemical separation of 6,6'-dibromo-1,1'-bi-2-naphthol.By introducing microwave-assisted synthesis,optimizing the solvents for the synthetic reactions,and recycling the separating agent,this experiment aligns more closely with the principles of green chemistry.Pedagogically,the experiment involves multiple operations,serving as a comprehensive test of students’experimental skills and offering significant educational value.