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Promotional effect of ionic liquids in electrophilic fluorination of methylated uracils

机译:离子液体在甲基化尿嘧啶电泳中的促进作用

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A novel efficient protocol has been developed for fluorination of methylated uracils involving a stoichiometric amount of ionic liquid (IL) in alcohols. The fluorination of 6-methyluracil and 1,3,6-trimethyluracil has been carried out using the electrophilic fluorinating reagent Selectfluor? (F-TEDA-BF _(4) ) in MeOH and EtOH solvents with the formation of 5-fluoro-6-methyluracil, 5-fluoro-1,3,6-trimethyluracil as well as α-fluoromethoxy- and α-fluoroethoxy ethers of difluorodihydrouracils as the main products. The use of a stoichiometric amount of ionic liquid as an additive results in acceleration of the reaction. It has been found that the effect of the anion of the IL on the rate of the reaction is more pronounced compared to that of the cation, the effectiveness of the anions decreasing in the following order: [HSO _(4) ~(?) ] > [OTf ~(?) ] ~ [NTf _(2) ~(?) ] > [BF _(4) ~(?) ] > [PF _(6) ~(?) ]. The influence of metal carbonates on the yields of fluorouracils has also been evaluated.
机译:已经开发了一种新的高效方案,用于氟化甲基化尿嘧啶,涉及醇中的化学计量量的离子液体(IL)。使用亲电子氟化试剂选择氟荧光剂进行了6-甲基脲和1,3,6-三甲基脲酸的氟化脲? (F-Teda-BF _(4))在MeOH和EtOH溶剂中,形成5氟-6-甲基脲,5氟-1,3,6-三甲基脲以及α-氟甲氧基和α-氟乙氧基Difluorodihydracils作为主要产品的醚。使用化学计量的离子液体作为添加剂导致加速反应。已经发现,与阳离子相比,IL对反应速率对反应速率的影响,阴离子的有效性按以下顺序减少:[HSO_(4)〜(?) ]> [otf〜(?)]〜[ntf _(2)〜(?)]> [bf _(4)〜(?)]> [pf _(6)〜(?)]。还评估了金属碳酸盐对氟尿嘧啶产率的影响。

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