2-苄氧基乙酸乙酯在医药和农药领域有应用,具体用途未详细说明。
医药; 农药
合成路线 1(1. 合成:32122-09-1)
产率:77.5%
合成条件:Stage #1: With sodium hydride In toluene at 0 - 20℃; for 3.50 h; Stage #2: at 0℃; for 1.50 h;
实验步骤:在0℃下向氢化钠(60%,1.428g,35.71mmol)的无水甲苯(50ml)悬浮液中滴加苄基氯(3.000g,27.47mmol)。 加入醇后,将who在室温下搅拌3.5小时。 将混合物再次冷却至0℃并加入溴乙酸乙酯(4.493g,26.09mmol),并在0℃下继续搅拌90分钟。 加入50ml水后,将混合物用6M氢氯酸溶液中和至pH7。用乙酸乙酯(5×20mL)萃取分离产物。 用硫酸钠干燥有机层并浓缩。 得到4.136g油形式的title产物(产率77.5%).MS-ESI:(m / z)计算值C11H14O3Na [M + Na] +:217.21,实测值217.1。
参考文献:
- [1] Patent: WO2014/16789, 2014, A1. Location in patent: Page/Page column 29 [2] Patent: US5942515, 1999, A [3] Patent: WO2016/157091, 2016, A1. Location in patent: Page/Page column 20-21 [4] Tetrahedron, 2009, vol. 65, # 34, p. 6925 - 6931 [5] European Journal of Medicinal Chemistry, 2017, vol. 138, p. 630 - 643 [6] Patent: EP2634180, 2013, A1. Location in patent: Paragraph 0077 [7] Patent: WO2017/189866, 2017, A1. Location in patent: Paragraph 0259 [8] Patent: WO2011/109267, 2011, A1. Location in patent: Page/Page column 48-49 [9] Patent: WO2003/105766, 2003, A2. Location in patent: Page 46-47 [10] Medicinal Chemistry Research, 2004, vol. 13, # 8-9, p. 660 - 676 [11] Patent: EP2330098, 2011, A1. Location in patent: Page/Page column 28 [12] Patent: US2011/319458, 2011, A1. Location in patent: Page/Page column 18-19 [13] Journal of Natural Products, 2015, vol. 78, # 8, p. 1859 - 1867 [14] Patent: WO2015/116460, 2015, A1. Location in patent: Page/Page column 33
合成路线 2(2. 合成:32122-09-1)
产率:73%
合成条件:With tetra-(n-butyl)ammonium iodide; sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; for 12.50 h; Inert atmosphere
实验步骤:化合物24的合成在氮气氛下,向羟基乙酸乙酯23(99.6g,0.96mol)的THF(1.5L)溶液中加入NaH(42g,I .Omol:60%的矿物油)。 分数为°C。 将混合物在0℃下搅拌30分钟,加入四丁基碘化铵(35.3g,0.1Mol)和苄基溴(163.6g,0.96mol)。 将混合物温热至室温并在该温度下搅拌12小时。 将反应混合物用水稀释并用乙酸乙酯萃取。 用MgSO 4干燥有机层,高真空蒸发溶剂,蒸馏粗产物(121℃/ 4mBar),得到化合物24(135.5g,收率:73%)。 1H-NMR(CDC):δ= 7.41-7.22(m,5H),4.65(s,2H),4.27(q,2H),4.11(s,2H),1.25(t,3H)。
参考文献:
- [1] Patent: WO2012/10633, 2012, A1. Location in patent: Page/Page column 61-62 [2] Patent: WO2013/104561, 2013, A1. Location in patent: Page/Page column 54; 55 [3] Tetrahedron Asymmetry, 1998, vol. 9, # 17, p. 3081 - 3094 [4] Patent: WO2014/43068, 2014, A1. Location in patent: Page/Page column 167; 168 [5] Patent: WO2012/136834, 2012, A1. Location in patent: Page/Page column 11 [6] Patent: US2014/45849, 2014, A1. Location in patent: Paragraph 0051; 0052; 0053 [7] Journal of Medicinal Chemistry, 2016, vol. 59, # 17, p. 7936 - 7949 [8] Patent: WO2009/106539, 2009, A1. Location in patent: Page/Page column 29-30
合成路线 3(3. 合成:32122-09-1)
产率:90%
合成条件:Inert atmosphere; Reflux
实验步骤:步骤1将催化量的浓硫酸加入到化合物10a(33.2g,0.2mol)的乙醇(300mL)溶液中。 将反应加热至回流过夜。 浓缩溶剂,将所得残余物溶于乙酸乙酯中,然后用饱和碳酸氢钠水溶液洗涤。 收集有机相并用无水硫酸钠干燥。 浓缩溶剂,得到化合物10b(35g,收率90%)。
参考文献:
- [1] Patent: EP2754659, 2014, A1. Location in patent: Paragraph 0168-0170 [2] Patent: US2014/378488, 2014, A1. Location in patent: Paragraph 0380; 0381; 0382 [3] Journal of Medicinal Chemistry, 2013, vol. 56, # 2, p. 437 - 450 [4] Scientia Sinica (English Edition), 1957, vol. 6, p. 279,289 [5] Huaxue Xuebao, 1956, vol. 22, p. 542