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新型5-溴嘧啶衍生物的选择性合成

         

摘要

p-Bromophenyl-methoxy triethylene glycol(3) was prepared by esterification of p- tolylsul-fonyl chloride with methoxy triethylene glycol, then condensation with p-bromophenol. Novel 5-bro-mo-2-[p-(methyl triethylene glycol group) phenyl] pyrimidine(la) in yield of 73% was selectively synthesized using Pd(PPh3)4 as a catalyst in toluene under Ar gas by Suzuki-coupling of 5-bromo-2-iodopyrimidine(5) and p-(methyl triethylene glycol group)phenyl-boric acid(4) which was obtained by substitution reaction of 3 with methyl borate, then acidolysis. Novel 5-bromo-2-dodecylpyrimidine (lb) in yield of 82% was selectively synthesized by Suzuki-coupling in "one-pot" from 1-dodecylene and 5 using Pd(dppf)Cl2 as a catalyst in THF. The structures of la and lb were characterized by 1HNMR, 13CNMR and MS.%对甲苯磺酰氯与三甘醇单甲酯完成酯化反应,再与对溴苯酚缩合制得对溴苯基三甘醇单甲醚(3);3与硼酸甲酯完成取代反应、酸解后在Pd( PPh3)4催化下与5-溴-2-碘嘧啶(5)在甲苯中通过Suzuki偶联反应选择性地合成了5-溴-2-对(甲基三甘醇基)苯基嘧啶(1a),收率73%.以1-十二烯和5为主要原料,通过Suzuki偶联反应,一锅法选择性地合成了5-溴-2-十二烷基嘧啶(1b),收率82%.1a和1b未见文献报道,其结构经1H NMR,13C NMR和MS表征.

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