膦、胂叶立德的化学与应用——ⅩⅩⅥ.含全氟烷基胂叶立德的合成及水解反应研究  

Chemistry and Applications of Phosphonium and Arsonium Ylides XXVI. Synthesis of Arsonium Ylides Containing Perfluoroalkyl Group and Study on Their Hydrolysis

作　　者：曹卫国[1] 丁维钰[1] 刘仁德[1] 黄涛宏 

机构地区：[1]上海大学化学化工学院,上海201800

出　　处：《化学学报》1999年第11期1270-1276,共7页Acta Chimica Sinica

基　　金：国家自然科学基金(29772021);上海市教委基金;中国科学院上海有机化学研究所金属有机开放实验室基金资助项目

摘　　要：报道溴化（α－呋喃酮甲酰基）甲基三苯基胂（１）在无水碳酸钾存在下，以无水二氯甲烷作溶剂，保持０～５℃下与２－全氟炔酸甲酯（２）反应，高产率地得到加合产物４－（α－呋喃甲酰基）－２－三苯基胂基－３－全氟烷基－３－丁烯酸甲酯（３）。加合产物３在Ｖ（甲醇）：Ｖ（水）＝９：１溶液中分别于室温、回流和封管１２０℃三种条例下反应。In the presence of K2CO3, reaction of (α - furoyl)methyl - arsoniumbromide(1) with methyl2- perfluoroalkynoates(2) in methylene chloride at 0 - 5℃ afforded the adduct-methyl 4 - (α -furoyl) - 2 - triphenylarsoranylidene - 3 - perfluoroalkyl - 3 - butenoates(3) in high yield. Hydrolysis of 3 in V(CH3OH): V(H2O) = 9:1 methanolic solution at room temperature, 70℃ and 120℃ in a sealed tube respectively, 4 - perfluoroalkyl - 6 - (α - furyl) - 2 - pyranones(4) and methyl 4 - (α - furoyl) -3 - perfluoroalkyl - 3 - butenoates (5) were obtained in excellent yield. Compounds 4 and 5 could be separated by column chromatography. 5 is a mixture of Z - and E- isomers which couldn't be separated by column chromatography, but the ratio of Z - and E - isomers could be estimated by 1H NMR. The catalytic hydrolysis of compound 3 with silica gel and the mechanisms for the formation of products are also discussed in this paper.

关 键 词：胂叶立德 全氟烷基 呋喃基 吡喃酮 丁烯酸甲酯 

分 类 号：O626.11[理学—有机化学] O626.31[理学—化学]