摘要
文中讨论了(+)-和(-)-9,9′-联菲-10,10′-二甲酸的合成路线设计.选出了最佳的合成路线,其中关键中间体是10-溴-9-菲甲酸.其合成方法是在碱性条件下使9-菲甲酸与溴溴化钾—DMF发生10-位溴代反应,产率很好.研究中也探讨了U11mann反应的条件。合成所得的光学纯的(+)-和(-)-9,9′-联菲-10,10′-二甲酸在碱性和中性条件下均难以消旋,说明它有僵硬的轴不对称结构.
In this article a synthetic design of ( + ) and ( - ) 9,9'-Biphenanthryl-10,10'-dicar-boxylic acid ( 1) was discussed. The best synthetic route was shown in Fig.7. The key intermediate was 10-bromo-9-phenanthroic acid(2), which was prepared by a novel method of ortho-bromination of 9-phenanthroic acid ( 3 ) .Potassium salt of 3 was reacted
with a mixture of bromine and potassium bromide in DMF at -4-8 C to give 2 in
72% yield (Fig.2, route D). The Ullmann reactiou conditions were also studied(Fig.6). Finally, the racemization condition of optically pure 1 was tested. Thus, ( - ) -1 was
separately refluxed in 0.lN KOH at 140. for 10 hours and in nitrobenzene at 210 C for 4 hours.No racemization could be found in both cases. This result confirms that 1 has
rigid and stable axially dissymmetric structure, which is identical with the result of
study by CPK precious molecular model.
基金
中国自然科学基金会资助
