化学合成。
化学合成
合成路线 1(1. 合成:931-33-9)
产率:73%
合成条件:at 50℃; for 2 h;
实验步骤:一般步骤:在圆底烧瓶中,将底物(1mmol)和HBr水溶液(48%)(1mL)在DMSO(1mL)中混合。 将混合物在相应温度下搅拌1-4小时。 冷却至室温后,用NaOH水溶液(4M)将反应调节至pH 7-8。 然后将混合物用EtOAc洗涤两次,将合并的有机萃取物干燥,过滤并减压浓缩,得到溴化产物。
参考文献:
- [1] Organic Letters, 2015, vol. 17, # 8, p. 1822 - 1825 [2] Journal of Medicinal Chemistry, 2015, vol. 58, # 18, p. 7286 - 7309 [3] Journal of Chemical Research, 2014, vol. 38, # 10, p. 593 - 596 [4] Patent: WO2017/20944, 2017, A1. Location in patent: Page/Page column 32 [5] Journal of Organic Chemistry, 2006, vol. 71, # 11, p. 4092 - 4102 [6] Patent: WO2007/64842, 2007, A2. Location in patent: Page/Page column 89-91; 104 [7] Patent: WO2014/202528, 2014, A1. Location in patent: Page/Page column 78 [8] European Journal of Medicinal Chemistry, 2016, vol. 113, p. 102 - 133 [9] Tetrahedron, 2016, vol. 72, # 19, p. 2456 - 2463 [10] Journal of Organic Chemistry, 2017, vol. 82, # 18, p. 9350 - 9359 [11] Chemistry of Heterocyclic Compounds (New York, NY, United States), 1986, vol. 22, # 7, p. 806 - 807 [12] Khimiya Geterotsiklicheskikh Soedinenii, 1986, vol. 22, # 7, p. 998 - 999 [13] European Journal of Medicinal Chemistry, 2018, vol. 152, p. 235 - 252
合成路线 2
产率:75%
合成条件:With 1,3-dibromo-5,5-dimethylimidazolidine-2,4-dione In tetrahydrofuran at -78℃; for 5 h;
实验步骤:一般步骤:在-78℃下,在10分钟内向搅拌的55(2.0g,13.42mmol)的THF(100mL)溶液中分批加入DBDMH(1.90g,6.71mmol)。 然后将反应混合物搅拌5小时,同时将其温热至室温。 用5%KHSO 4水溶液淬灭反应,并用乙酸乙酯(3×75mL)萃取。 将合并的有机层用盐水洗涤,并经无水Na 2 SO 4干燥。 减压蒸发溶剂,将产物在硅胶上进行色谱分离,用乙酸乙酯/己烷作为洗脱液,得到纯产物56(2.48g,82%)。 1 H NMR(CDCl 3,400MHz)δ10.60(br s,1H),9.41(s,1H),2.83(m,2H),2.42(m,2H),1.77(m,4H); 13C NMR(CDCl 3,100MHz)δ175.7,134.7,128.9,122.7,110.5,22.8,22.6,21.3,21.0; HRMS(ESI)计算值C 9 H 11 BrNO(M + H)+ 228.0019,实测值228.0031
参考文献: