膦、胂叶立德的化学与应用(ⅩⅩⅨ)──含全氟烷基胂叶立德水解合成2-吡喃酮衍生物

Chemistry and Applications of Phosphonium and Arsonium Ylides(ⅩⅩⅨ)──Studies on the Hydrolysis of Arsonium Ylides Containing Perfluoroalkyl Group andSynthesis of 2-Pyranone Derivatives

在无水碳酸钾存在下，以无水二氯甲烷作溶剂，室温下将溴化（2－萘甲酰基）甲基三苯基鉮（1）与2－全氟炔酸甲酯（2）反应，高产率地得到加合产物4-（2－萘甲酰基）－2－三苯基胂基－3－全氟烷基－3－丁烯酸甲酯（3）和少量4－（2－萘甲酰基）－4－三苯基胂基－3－全氟烷基－2－丁烯酸甲酯（4）．加合产物3在9：1的甲醇－水溶液中在一定温度下反应，高产率地得到4-全氟烷基－6－（2－萘基）－2－吡喃酮（5）．研究发现硅胶对该反应具有催化作用．提出并讨论了反应机理．

Abstract In the presence of K2CO3, reaction of (2-naphthoyl)methyl arsonium bromide (1) with methyl2-perfluoroalkynoates(2) in methylene chloride at room temperature afforded the adduct methyl4-(2-naphthoyl)-2-triphenylarsoranylidene-3-perfluoroalkyl-3-butenoates(3) as major product and 4-(2-naphthoyl)-4-triphenylarsoranylidene-3-perfluoroalkyl-2-butenoat.es (4) as minor product in high yield.Hydrolysis of compound 3 in V(CH3OH) ∶ V(CH2O) = 9 ∶ 1 methanolic solution at 80 in a sealed tube,4-perfluoroalkyl-6-(2-naphthyl)-2-pyranones(5) was obtained in an excellent yield. The catalytic hydroly-sis of compound 3 with silica gel and the mechanisms for the formation of the products will also be discuss-ed.