7377-26-6 4-氯甲酰基苯甲酸甲酯

危险性质：非危险化学品

化学合成。

化学合成

合成路线 1（1. 合成：7377-26-6）

产率：73% 合成条件：Stage #1: With potassium hydroxide In methanol; toluene at 65℃; for 3 h; Stage #2: With thionyl chloride In toluene at 67℃; for 3 h; Inert atmosphere 实验步骤：该实施例说明了具有下列结构的4-氯羰基 - 苯甲酸甲酯的制备。在带有机械搅拌器，回流冷凝器，加料漏斗，温度计，水浴和热板的4L釜中，加入438g对苯二甲酸二甲酯（DMT）和2700mL甲苯。将釜加热至约6500℃以溶解所有DMT。溶解后，在45分钟内滴加氢氧化钾溶液（144.54g，在700mL甲醇中）。将反应在65°00搅拌3小时，然后将反应冷却至室温过夜。过滤后收集固体，并在80:00用3750mL甲苯洗涤。再次过滤产物并在110℃的烘箱中干燥。产量为465.9g（95.3％）。在具有机械的2Lthree颈圆底烧瓶中搅拌器，加料漏斗，水浴，温度计，氮气吹扫和热板，加入130.31g前一步骤制备的产物和1000mL甲苯。然后滴加48mL亚硫酰氯。添加完成后，将混合物加热至67°00达3小时。将反应冷却至室温并搅拌过夜。过滤内容物以收集滤液。通过真空除去过量溶剂，得到86.52g产物（收率73％）。 参考文献：

• [1] Patent: WO2015/42561, 2015, A1. Location in patent: Paragraph 0115; 0116; 0117 [2] Patent: WO2015/42563, 2015, A1. Location in patent: Paragraph 0115; 0116; 0117 [3] Canadian Journal of Chemistry, 1974, vol. 52, p. 66 - 79 [4] Journal of Organic Chemistry, 2005, vol. 70, # 7, p. 2763 - 2770 [5] Journal of the American Chemical Society, 1957, vol. 79, p. 96 [6] Journal of Organic Chemistry, 1974, vol. 39, # 23, p. 3384 - 3387 [7] Organic and Biomolecular Chemistry, 2013, vol. 11, # 6, p. 881 - 885 [8] Organic Process Research and Development, 2015, vol. 19, # 3, p. 444 - 448 [9] Patent: US9200142, 2015, B2 [10] Molecules, 2017, vol. 22, # 1, [11] Chemistry - A European Journal, 2018, vol. 24, # 10, p. 2360 - 2364

合成路线 2（2. 合成：7377-26-6）

产率：73% 合成条件：With thionyl chloride In toluene at 67℃; for 3 h; Inert atmosphere 实验步骤：该实施例说明了具有下列结构的4-氯羰基 - 苯甲酸甲酯的制备（0147）（0148）在具有机械搅拌器，回流冷凝器，加料漏斗，温度计，水浴和热板的4L釜中，438g二甲基加入对苯二甲酸酯（DMT）和2700mL甲苯。将釜加热至约65℃以溶解所有DMT。溶解后，在45分钟内滴加氢氧化钾溶液（144.54g，在700mL甲醇中）。将反应在65℃下搅拌3小时，然后将反应冷却至室温过夜。过滤后收集固体，并在80℃下用3750mL甲苯洗涤。再次过滤产物并在110℃的烘箱中干燥。产量为465.9g（95.3％）。 （0149）在具有机械搅拌器，加料漏斗，水浴，温度计，氮气吹扫和热板的2L三颈圆底烧瓶中，加入130.31g前一步骤制备的产物和1000mL甲苯。然后滴加48mL亚硫酰氯。添加完成后，将混合物加热至67℃并保持3小时。将反应冷却至室温并搅拌过夜。过滤内容物以收集滤液。通过真空除去过量溶剂，得到86.52g产物（收率73％）。 参考文献：

• [1] Patent: US9200142, 2015, B2. Location in patent: Page/Page column 34; 35 [2] Patent: US5078907, 1992, A [3] Organic Process Research and Development, 2015, vol. 19, # 3, p. 444 - 448

合成路线 3（3. 合成：7377-26-6）

产率：95% 合成条件：for 15 h; Heating / reflux 实验步骤：4-氯羰基 - 苯甲酸甲酯（2）。 向对苯二甲酸单甲酯的混合物，化合物1（溶液，0.056mol）和SOCl 2（somL）中加入一滴DMF，将混合物在回流下煮沸15升。 真空除去过量的SOCl 2，得到化合物2（0.57g），为白色固体，收率95％。 该化合物无需进一步纯化即可用于下一步。 参考文献：

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