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溴化对硝基苄基三苯基鏻(1a)、鉮(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.
P-Nitrobenzyltriphenylphosphonium bromide (1a) and (1b) are reacted with methyl 2-perfluoroalkynoate (2) in the presence of potassium carbonate at normal temperature to form adduct 3 (when M = As) or a mixture of 3 and 4 (when M = P), where the content of 3 increases with increasing reaction temperature, when the reaction temperature is 90 ° C, the product is all 3.4c and converts to 3c when heated. Compound 3 or 4 was heated in a sealed tube at 150 ° C in methanol-water to cleave P-C bonds, both of which generated the (Z) 3-perfluoroalkyl-4-p- nitrophenyl- 3-butenoate (5). Arsine adduct 3 was refluxed in methanol-water and the As-C bond was cleaved to form (Z) -5. The hydrolysis mechanism was studied.