N-新戊酰基对氯苯胺作为中间体或活性成分,在医药和农药领域有重要应用,具体用途需参考相关专利及文献。
医药; 农药
合成路线 1(1. 合成:65854-91-3)
产率:99.7%
合成条件:With sodium hydrogencarbonate In water; ethyl acetate at 15 - 20℃; for 2 h;
实验步骤:参考实施例2将N-新戊酰基 - 对氯苯胺CAB(113kg,886mol),城市用水(565L)和碳酸氢钠(89.3kg,1.2当量)加入到乙酸乙酯(1695L)和新戊酰氯(112kg)中 在15℃或更低温度下向其中滴加1.05当量),并将溶液在约25℃下搅拌2小时。 分离各层后,用市政水(848L×2)洗涤有机层,并在减压下浓缩至约600L。 向其中加入乙基环己烷(848L),并在减压下再次浓缩至约600L。 将残余物冷却至约5℃,搅拌至成熟1小时。 过滤收集沉淀的晶体,减压干燥,得到标题化合物(187kg,收率99.7%)。
参考文献:
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合成路线 2(2. 合成:65854-91-3)
产率:97%
合成条件:With sodium hydroxide In water
实验步骤:实施例1 N-(4-氯苯基)-2,2-二甲基丙酰胺的制备将4-氯苯胺(52.7kg,413mol)溶于叔丁基甲基醚(180kg),30%氢氧化钠水溶液(61.6)的混合物中 然后将冷却至15℃,向所得浆液中加入三甲基乙酰氯(52.2kg,448mol),保持温度低于40℃。搅拌30分钟后,向所得浆液中加入1kg,463mol)和水(24.2kg)。 在30℃下,将浆料冷却至-10℃并保持2小时。 过滤收集产物,用90/10水/甲醇(175kg)溶液洗涤,然后真空干燥,得到85kg(产率97%)标题化合物,为结晶固体:mp 152-153℃。 1 H NMR(300MHz,CDCl 3)δ7.48(d,J = 9Hz,2H)7.28(d,J = 9Hz,2H); 13 C NMR(75MHz,CDCl 3)d 176.7,136.6,129.1,128.9,121.4,39.6,27.6。
参考文献:
- [1] Patent: US5925789, 1999, A [2] Patent: US5932726, 1999, A [3] Patent: US6028237, 2000, A [4] Patent: US6673372, 2004, B1
合成路线 3(3. 合成:65854-91-3)
产率:82.2%
合成条件:With 1,3-bis(1-adamantyl)imidazolium tetrafluoroborate; N-chloro-succinimide; camphor-10-sulfonic acid In 1,4-dioxane at 25℃; for 24 h;
实验步骤:一般步骤:将乙酰苯胺(0.2mmol),NCS(0.26mmol),D-CSA(0.1mmol)和1,3-二(1-金刚烷基)咪唑鎓四氟硼酸盐(0.01mmol)在二恶烷(1mL)中的混合物搅拌均匀。 在空气气氛下室温(25℃)保持24小时。 GC-MS监测反应。 当乙酰苯胺完全消耗时,将反应混合物用饱和的水溶液淬灭。 NaHCO 3(4mL)。 将得到的混合物用EtOAc(4mL×3)萃取。 用纯水(4ml×3)洗涤有机层。 将合并的有机层用无水Na 2 SO 4干燥,过滤,减压除去溶剂,得到粗产物。 通过硅胶快速柱色谱法进行纯化。
参考文献:
- [1] Synlett, 2015, vol. 26, # 20, p. 2831 - 2834