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化学学报
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化学学报 ›› 1987, Vol. 45 ›› Issue (1): 47-51. 上一篇    下一篇

研究论文

第五、六族元素的有机化合物在有机合成中应用的研究 XXXIII: 氰基亚甲基三苯基膦、胂与2-全氟炔酸甲酯的反应以及3-全氟烷基-4-氰基-3-丁烯酸甲酯的立体选择性合成

丁维钰;浦家齐;张平生   

  1. 上海科学技术大学化学系
  • 发布日期:1987-01-15

Studies on the application of elemento-organic compounds of the fifth and sixth groups in organic syntheses XXXIII: Reactions of cyanomethylenetriphenylphosphorane and arsorane with methyl perfluoro-2-alkynoates and stereoselective synthesis of methyl 3-p

DING WEIYU;PU JIAQI;ZHANG PINGSHENG   

  • Published:1987-01-15

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469

被引次数

5

氰基亚甲基三苯基胂(1)与2-全氟炔酸甲酯(2)反应,生成加合产物2-三苯胂基-3-全氟烷基-4-氰基丁烯-3-酸甲酯(3)通过3的水解,立体选择性地合成了3-全氟烷基-4-氰基-3-丁烯酸甲酸甲酯[5(Z),6(E)],Z:E约为95:5.氰基亚甲基三苯基膦(7)与2亦可反应,生成加合产物2-三苯基膦叉-3-全氟烷基-4-氰基丁烯-3-酸甲酯的顺式和反式异构体(8)和(9).总产率在90%左右.8与9的比例受反应介质极性的影响,若溶剂极性增大,则有利于8的生成.

关键词: 甲叉, 羧酸酯, 羧酸酯, 有机化合物, 氰基, 氰基, 三苯基膦, 三苯基, 有机合成, 立体选择性

Addition of Ph3As+ CH-CN with RCYCCO2Me (R = CF3, C2F5, n-C3F7) followed by hydrolysis of the adducts gave NCCH:CRCH2CO2Me (Z/E = 95/5). Similar reaction of Ph3P:CHCN with RCYCCO2Me gave adducts Ph3P:C(CO2Me)CR:CHCN and their Z/E ratio was influenced by the polarity of the solvents.

Key words: METHYLENE, CARBOXYLIC ACID ESTER, CARBOXYLIC ACID ESTER, ORGANIC COMPOUNDS, CYANO GROUP, CYANO GROUP, TRIPHENYLPHOSPHINE, TRIPHENYL GROUP, ORGANIC SYNTHESIS, STEREOSELECTIVITY

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