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化学学报
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化学学报 ›› 1991, Vol. 49 ›› Issue (3): 284-289. 上一篇    下一篇

研究论文

膦、胂叶立德的化学与应用 XII. 对硝基苯基亚甲基三苯基膦、胂与2-全氟炔酸甲酯的反应以及(Z)3-全氟烷基 4-对硝基苯基-3-丁烯酸甲酯的立体专一性合成

丁维钰;张平生;浦家齐;张春明;毛世高;王绮文;沈伟   

  1. 上海科技大学;中国科学院上海有机化学研究所
  • 发布日期:1991-03-15

Chemistry and applications of phophonium and arsonium ylides XII. Reaction of p-nitrophenyl methylenetriphenylphosphorane and arsorane with methyl 2-perfluoroalkynoates and stereospecific synthesis of (Z) methyl 3-perfluoroalkyl-4-p-nitrophenyl-3-butenoat

DING WEIYU;ZHANG PINGSHENG;PU JIAQI;ZHANG CHUNMING;MAO SHIGAO;WANG QIWEN;SHEN WEI   

  • Published:1991-03-15

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溴化对硝基苄基三苯基 (1a)、 (1b)在碳酸钾存在下与2-全氟炔酸甲酯(2)在常温下反应, 生成加合物3(当M=As时)或3和4的混合物(当M=P时), 其中3的含量随反应温度升高而增加, 当反应温度为90℃时, 产物全部为3。4c加热时转化为3c。膦加合物3或4在甲醇-水中于封管内150℃加热, 发生P-C键断裂。两者都立体专一性地生成(Z)3-全氟烷基-4-对硝基苯基-3-丁烯酸甲酯(5)。胂加合物3在甲醇-水中回流, 发生As-C键断裂, 生成(Z)-5。对水解机理进行了研究。

关键词: 红外分光光度法, 炔烃, 元素分析, 质谱法, 核磁共振谱法, 溴化物, 硝基苯, 三苯基膦, 甲酯, 三苯基

Reaction of p-nitrobenzylphosphonium or -arsonium bromides with Me 2-perfluoroalkynoates in the presence of K2CO3 gave adducts Ph3P:C(CO2Me)CR:CHC6H4NO2-p (I; R = C3F7, CF3, C2F5) or mixtures of Ph3P:C(CO2Me)CR:CHC6H4CO2-p (II; same R) and Ph3P:C(C6H4NO2-p)CR:CHCO2Me (III; same R). The ratio of II to III was increased with an increase of reaction temperature, the formation of II being favored at higher temperature while at 90? the reaction gave II exclusively. The P-C bond cleavage occurred when II or III were heated in aqueous methanol in sealed tubes at 150? and Me (Z)-3-perfluoroalkyl-4-p-nitrophenyl-3-butenoates (IV) were formed stereospecifically. III could be transformed to II on heating. As-C bond cleavage occurred when I were heated in refluxing aqueous methanol and the same products were formed. The mechanism of hydrolysis was discussed.

Key words: INFRARED SPECTROPHOTOMETRY, ALKYNE, ELEMENTAL ANALYSIS, MASS SPECTROGRAPHY, NMR SPECTROMETRY, BROMIDE, NITROBENZENE, TRIPHENYLPHOSPHINE, METHYL ESTER, TRIPHENYL GROUP

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