Synthesis of dimethyl 3-perfluoroalkyl-4-(3-oxo-2-triphenyl-phosphoranylidenbutanylidene)-pent-2-enedioate and its cyclization  

作　　者：Ding, WY Cao, WG Yao, Y Zhu, ZM 

机构地区：[1]SHANGHAI UNIV SCI & TECHNOL,DEPT CHEM,SHANGHAI 201800,PEOPLES R CHINA

出　　处：《Chinese Journal of Chemistry》1995年第5期468-474,共7页中国化学（英文版）

基　　金：Project supported by the National Natural Science Foundation of China.

摘　　要：The title compounds 5a-5c were prepared via the reaction of methyl 2-perfluoroalkynoates (4) with methyl 5-oxo-4-(triphenylphosphoranylidene)hex-2-enoate (3), which was obtained from the reaction of methyl propynate (2) with acetylmethylenetriphenylphosphorane (1) at -5-0 degrees C. Intramolecular elimination of Ph(3)PO took place when compound 5 was heated in aqueous methanol at 115-120 degrees C in sealed tube, yielding dimethyl 2-trifluoromethyl-4-methylisophthalate (6a) from 5a and methyl 5-acetyl-4-hydroxy-2-heptafluoropropanylbenzoate (6b) from 5b, respectively. The structures of compounds 5, 6a and 6b were confirmed by IR, MS, H-1 NMR, F-19 NMR and C-13 NMR spectroscopy and elemental analyses. Rection mechanisms for the formation of compounds 5, 6a and 6b were proposed.The title compounds 5a-5c were prepared via the reaction of methyl 2-perfluoroalkynoates (4) with methyl 5-oxo-4-(triphenylphosphoranylidene)hex-2-enoate (3), which was obtained from the reaction of methyl propynate (2) with acetylmethylenetriphenylphosphorane (1) at -5-0 degrees C. Intramolecular elimination of Ph(3)PO took place when compound 5 was heated in aqueous methanol at 115-120 degrees C in sealed tube, yielding dimethyl 2-trifluoromethyl-4-methylisophthalate (6a) from 5a and methyl 5-acetyl-4-hydroxy-2-heptafluoropropanylbenzoate (6b) from 5b, respectively. The structures of compounds 5, 6a and 6b were confirmed by IR, MS, H-1 NMR, F-19 NMR and C-13 NMR spectroscopy and elemental analyses. Rection mechanisms for the formation of compounds 5, 6a and 6b were proposed.

关 键 词：PHOSPHORANE polysubstituted arene intramolecular cyclization 

分 类 号：O625[理学—有机化学]