Gupta O D, Kirchmeier R L, Shreeve J M
Department of Chemistry, University of Idaho, Moscow, Idaho 83844-2343.
Inorg Chem. 2000 Jan 10;39(1):117-20. doi: 10.1021/ic9911567.
A series of pyrimidine methyl and polyfluoroalkyl ethers were synthesized from the reactions of trifluoroamine oxide (1) with several 5-substituted uracils in the presence of tetrabutylammonium hydroxide and methanol, 2,2,2-trifluoroethanol (6), or 1H,1H-pentafluoropropanol (7). With 5-(trifluoromethyl)uracil (2), the new ethers formed were 5-fluoro-5-(trifluoromethyl)-6-methoxypyrimidine-2,4-dione (8), 5-fluoro-5-(trifluoromethyl)-6-(trifluoroethoxy)pyrimidine-2,4-dione (9), and 5-fluoro-5-(trifluoromethyl)-6-(1H,1H- pentafluoropropoxy)pyrimidine-2,4-dione (10). With 5-chlorouracil (3), the new ethers 5-chloro-5-fluoro-6-methoxypyrimidine-2,4-dione (11), 5-chloro-5-fluoro-6-(trifluoroethoxy)pyrimidine-2,4-dione (12), and 5-chloro-5-fluoro-6-(1H,1H-pentafluoropropoxy)pyrimidine-2,4-dione (13) were obtained. With 5-fluorouracil (4), the new ethers 5,5-difluoro-6-methoxypyrimidine-2,4-dione (14), 5,5-difluoro-6-(trifluoroethoxy)pyrimidine-2,4-dione (15) and 5,5 difluoro-6-(1H,1H-pentafluoropropoxy)pyrimidine-2,4-dione (16) were found. By reaction of 5-nitrouracil (5), the new ethers 5-nitro-5-fluoro-6 methoxypyrimidine-2,4-dione (17), 5-nitro-5-fluoro-6-(trifluoroethoxy)pyrimidine-2,4-dione (18), and 5-nitro-5-fluoro-6-(1H,1H-pentafluoropropoxy)pyrimidine-2,4-dione (19) were obtained. Each of the new compounds was characterized by using IR, 19F and 1H NMR, and mass spectroscopy, and elemental analysis. A single-crystal X-ray diffraction study of 8 was helpful in confirming compound structure.
在氢氧化四丁基铵和甲醇、2,2,2-三氟乙醇（6）或1H,1H-五氟丙醇（7）存在的条件下，三氟氧化胺（1）与几种5-取代尿嘧啶反应，合成了一系列嘧啶甲基和多氟烷基醚。对于5-（三氟甲基）尿嘧啶（2），生成的新醚为5-氟-5-（三氟甲基）-6-甲氧基嘧啶-2,4-二酮（8）、5-氟-5-（三氟甲基）-6-（三氟乙氧基）嘧啶-2,4-二酮（9）和5-氟-5-（三氟甲基）-6-（1H,1H-五氟丙氧基）嘧啶-2,4-二酮（10）。对于5-氯尿嘧啶（3），得到了新醚5-氯-5-氟-6-甲氧基嘧啶-2,4-二酮（11）、5-氯-5-氟-6-（三氟乙氧基）嘧啶-2,4-二酮（12）和5-氯-5-氟-6-（1H,1H-五氟丙氧基）嘧啶-2,4-二酮（13）。对于5-氟尿嘧啶（4），发现了新醚5,5-二氟-6-甲氧基嘧啶-2,4-二酮（14）、5,5-二氟-6-（三氟乙氧基）嘧啶-2,4-二酮（15）和5,5-二氟-6-（1H,1H-五氟丙氧基）嘧啶-2,4-二酮（16）。通过5-硝基尿嘧啶（5）的反应，得到了新醚5-硝基-5-氟-6-甲氧基嘧啶-2,4-二酮（17）、5-硝基-5-氟-6-（三氟乙氧基）嘧啶-2,4-二酮（18）和5-硝基-5-氟-6-（1H,1H-五氟丙氧基）嘧啶-2,4-二酮（19）。每种新化合物都通过红外光谱、19F和1H核磁共振以及质谱和元素分析进行了表征。对8进行的单晶X射线衍射研究有助于确认化合物结构。
