3-甲氧基-4-硝基苯甲醛作为中间体或原料,广泛应用于医药和农药领域的有机合成反应中,具体用途需结合具体应用场景确定。
医药; 农药
合成路线 1(1. 合成:80410-57-7)
产率:100%
合成条件:With dipyridinium dichromate In dichloromethane at 20℃; for 17 h;
实验步骤:将(3-甲氧基-4-硝基苯基)甲醇(43)(1.4mmol)和重铬酸吡啶鎓(2.3mmol)在无水DCM(38mL)中的分散体在室温下搅拌17小时,并加入硅藻土和二氧化硅的混合物。。 过滤分散体并用DCM(3×10mL)洗涤。 真空蒸发所得溶液的溶剂,得到棕色残余物(1.3mmol,定量收率)。 1H NMR(400MHz,CDCl3)δ10.05(s,1H),7.92(d,J = 8.1Hz,1H),7.60(d,J = 1.3Hz,1H),7.54(dd,J = 8.1,1.5Hz) ,1H),4.03(s,3H)。
参考文献:
- [1] Patent: EP2853565, 2015, A1. Location in patent: Paragraph 0220 [2] Bioorganic and Medicinal Chemistry, 2000, vol. 8, # 10, p. 2417 - 2425 [3] Angewandte Chemie - International Edition, 2018, vol. 57, # 24, p. 7040 - 7045 [4] Angew. Chem., 2018, vol. 130, # 24, p. 7158 - 7163,6 [5] Patent: EP3290419, 2018, A1. Location in patent: Paragraph 0176; 0177 [6] Patent: WO2012/151561, 2012, A1. Location in patent: Page/Page column 71 [7] Patent: WO2013/169401, 2013, A1. Location in patent: Page/Page column 84 [8] Journal of Fluorine Chemistry, 2007, vol. 128, # 12, p. 1461 - 1468
合成路线 2(2. 合成:80410-57-7)
产率:98%
合成条件:With potassium carbonate In N,N-dimethyl-formamide at 20℃; for 4 h;
实验步骤:向3-羟基-4-硝基苯甲醛(2.000g,11.98mmol)的DMF(24ml)溶液中加入K 2 CO 3(1.687g,12.22mmol)和碘甲烷(1.52ml,24.44mmol)。 将反应混合物在室温下静置4小时。 将混合物用水稀释并用EtOAc萃取两次。 合并的有机物用饱和NaHCO 3溶液(3次),水,饱和NaCl 3溶液洗涤,用MgSO 4干燥,过滤并蒸发,得到中间体ha(2.137g,98%)。 1 H NMR(500MHz,CDCl 3)10.06(s,1H),7.93(d,J = 8.1Hz,1H),7.60(s,1H),7.54(dd,J = 8.1,1.4Hz,1H), 4.04(s,3H)。
参考文献:
- [1] ACS Medicinal Chemistry Letters, 2017, vol. 8, # 10, p. 1002 - 1006 [2] Patent: WO2016/124747, 2016, A1. Location in patent: Page/Page column 62; 63 [3] Patent: US2018/202388, 2018, A1 [4] Patent: EP2123637, 2009, A1. Location in patent: Page/Page column 19 [5] Organic and Biomolecular Chemistry, 2014, vol. 12, # 30, p. 5629 - 5633 [6] Patent: WO2015/120390, 2015, A1. Location in patent: Page/Page column 91; 128; 129 [7] Patent: WO2009/98283, 2009, A1. Location in patent: Page/Page column 100 [8] Patent: WO2010/136438, 2010, A1. Location in patent: Page/Page column 30 [9] Patent: US2010/324021, 2010, A1. Location in patent: Page/Page column 11; 12 [10] Patent: WO2013/41458, 2013, A1. Location in patent: Page/Page column 63 [11] Patent: WO2013/87744, 2013, A1. Location in patent: Page/Page column 23 [12] Patent: WO2013/66740, 2013, A1. Location in patent: Page/Page column 18
合成路线 3(3. 合成:80410-57-7)
产率:49%
合成条件:at -10 - 20℃; for 2 h;
实验步骤:在-10℃下将硝酸(0.46mL,11.0mmol)和硫酸(0.59mL,11.1mmol)缓慢加入到3-甲氧基苯甲醛(1a)(0.5g,3.7mmol)中并搅拌1小时。 在室温下再搅拌1小时。 将冰水加入反应混合物中并将所得沉淀物过滤在滤纸中并用水洗涤。 将过滤的沉淀物溶解在乙酸乙酯中,使用硫酸镁除去水,并将滤液减压浓缩。 将残渣用硅胶柱色谱法(己烷:乙酸乙酯= 10:1)精制,得到黄色粉末状的1b化合物(收率49%):
参考文献:
- [1] Organic and Biomolecular Chemistry, 2015, vol. 13, # 37, p. 9564 - 9569 [2] Patent: KR2017/17173, 2017, A. Location in patent: Paragraph 0042; 0043