Reaction of diethyl 2,2-difluoro-3-（a-methylbenzyl）imino-4,4,4-trifluoropropanephosphonate （3） with triethylamine afforded a mixture of normal [1,3]-proton shift reaction product 5 and its HF-eliminated compound 6...Reaction of diethyl 2,2-difluoro-3-（a-methylbenzyl）imino-4,4,4-trifluoropropanephosphonate （3） with triethylamine afforded a mixture of normal [1,3]-proton shift reaction product 5 and its HF-eliminated compound 6Z in 1 ： 1 ratio. Upon hydrolysis, this reaction mixture gave solely 1,3,3,3-tetrafluoro-2-dioxypropanephosphonate （9）. Reaction of 3 with DBU provided only 6, in which the ratio of E/Z forms was dependent on the reaction conditions. Aqueous hydrolysis of 6 led to 9. Catalytic hydrogenation and hydrogenolysis of 6 gave geometric isomers of 11 as expected. The reaction mechanism involved was discussed.展开更多
基金Project supported by the National Natural Science Foundation of China （Nos. 20272075. 20372076）. Dedicated to Professor Xikui Jiang on the occasion of his 80th birthday.
文摘Reaction of diethyl 2,2-difluoro-3-（a-methylbenzyl）imino-4,4,4-trifluoropropanephosphonate （3） with triethylamine afforded a mixture of normal [1,3]-proton shift reaction product 5 and its HF-eliminated compound 6Z in 1 ： 1 ratio. Upon hydrolysis, this reaction mixture gave solely 1,3,3,3-tetrafluoro-2-dioxypropanephosphonate （9）. Reaction of 3 with DBU provided only 6, in which the ratio of E/Z forms was dependent on the reaction conditions. Aqueous hydrolysis of 6 led to 9. Catalytic hydrogenation and hydrogenolysis of 6 gave geometric isomers of 11 as expected. The reaction mechanism involved was discussed.
