主要用于化学合成领域,具体应用场景未在提供数据中详细说明。
化学合成
合成路线 1(1. 合成:78137-76-5)
- 步骤:向苯胺或酚(0.7mmol)的混合物中加入溴化剂(1)(0.72g,0.7mmol)的二氯甲烷(30ml)-甲醇(15ml)溶液,室温搅拌至橙色溶液脱色,TLC监测(洗脱液:正己烷/乙酸乙酯,7:3),反应完成后蒸发溶剂,乙醚(10ml)加入残余物,滗析上清液,乙醚(3×10ml)洗涤不溶性残余物,合并萃取物用硫酸镁干燥,真空蒸发,硅胶快速柱色谱(正己烷/乙酸乙酯,7:3)纯化。
- 条件:With 1,2-ethanediylbis(triphenylphosphonium) ditribromide In methanol; dichloromethane at 20℃; for 0.08 h;
- 产率:85%
- 参考文献:[1] Tetrahedron Letters, 2009, vol. 50, #9, p.1007-1009 [2] Synthetic Communications, 2010, vol.40, #5, p.647-653 [3] Journal of the Iranian Chemical Society, 2016, vol.13, #11, p.2019-2028 [4] Journal of the Chemical Society, 1930, p.928,933 [5] Patent: US6143208, 2000, A
合成路线 2(2. 合成:78137-76-5)
- 步骤:Stage #1: 在-78℃下,1小时内将三溴化硼(250mmol)的二氯甲烷(200mL)溶液逐滴加入到硝基溴(100mmol)的二氯甲烷(250mL)溶液中,温热至室温并保持30小时;Stage #2: 冷却至0℃,用水(300mL)淬灭,水层用乙酸乙酯(2×300mL)萃取,合并有机层用饱和碳酸氢钠(2×300mL)洗涤,干燥(硫酸镁)并浓缩。
- 条件:Stage #1: With boron tribromide In dichloromethane at -78 - 20℃; for 31 h; Stage #2: With water In dichloromethane at 0℃;
- 产率:87%
- 参考文献:[1] Patent: US2007/78147, 2007, A1. Location in patent: Page/Page column 68 [2] Patent: WO2007/56582, 2007, A1. Location in patent: Page/Page column 77-78 [3] Tetrahedron Letters, 2011, vol.52, #26, p.3376-3378 [4] Patent: WO2012/73146, 2012, A1. Location in patent: Page/Page column 24-25 [5] Tetrahedron Letters, 1996, vol.37, #40, p.7189-7192 [6] Bioorganic and Medicinal Chemistry, 2003, vol.11, #4, p.521-528 [7] Patent: WO2014/210255, 2014, A1. Location in patent: Page/Page column 264 [8] Patent: US2002/165275, 2002, A1
合成路线 3(3. 合成:78137-76-5)
- 步骤:(1)重氮化反应:12g3-氨基-4-硝基苯酚溶于64g40wt%氢溴酸,冷却至0-10℃,加入36g20wt%亚硝酸钠水溶液,保温反应1h;(2)溴化反应:1.2g溴化亚铜溶于27g40wt%氢溴酸,温度升至40-45℃后,逐滴加入步骤(1)反应溶液,加毕保温反应1h,冷却至20-25℃,沉淀固体,滤出产物,少量水洗涤并干燥。
- 条件:Stage #1: With hydrogen bromide; sodium nitrite In water at 0 - 10℃; for 1 h; Stage #2: at 40 - 45℃; for 1 h;
- 产率:13.1g(含量95%)
- 参考文献:[1] Journal of the Chemical Society, 1930, p.928,933 [2] Chemische Berichte, 1909, vol.42, p.2192 [3] Patent: CN102060717, 2017, B. Location in patent: Paragraph 0007; 0016-0018
合成路线 4(4. 合成:78137-76-5)
- 步骤:在氩气保护下,1-溴-4-甲氧基-2-硝基苯(170g,0.73mol)溶于二氯甲烷(1.5L),冷却至-78℃,三溴化硼(176mL,1.86mol)溶于预冷二氯甲烷(1.6L,0℃),2小时内缓慢加入反应体系,移除冷却浴,升温至室温搅拌48小时,加入冷水(2.0L,冰/水浴)淬灭,分液,水层用EtOAc(2.0L)萃取,合并有机层用饱和碳酸氢钠(2×1.2L)和盐水(1L)洗涤,干燥浓缩,残余物悬浮二氯甲烷(320mL)浆化过夜,过滤,固体溶于2.0M氢氧化钠水溶液(500mL),二氯甲烷(500mL)萃取,合并水层用1.0M HCl(790mL)酸化至pH2,过滤沉淀,40℃真空干燥18小时。
- 条件:With boron tribromide In dichloromethane at -78 - 20℃; for 48 h;淬灭后冷水(2.0L,冰/水浴); 萃取条件:EtOAc(2×300mL); 洗涤:饱和碳酸氢钠(2×300mL)、盐水(1L); 酸化:1.0M HCl(790mL)至pH2;
- 产率:125.5g(0.5757mol,收率79%)
- 参考文献:[1] Patent: US2007/78147, 2007, A1. Location in patent: Page/Page column 68 [2] Patent: WO2007/56582, 2007, A1. Location in patent: Page/Page column 77-78 [3] Tetrahedron Letters, 2011, vol.52, #26, p.3376-3378 [4] Patent: WO2012/73146, 2012, A1. Location in patent: Page/Page column 24-25 [5] Tetrahedron Letters, 1996, vol.37, #40, p.7189-7192