2,4-二硝基苯基羟胺是有机合成中优良的胺化剂,可用于各类含仲氮及负碳离子化合物的胺化反应。
有机合成
路线1:
- 步骤:制备化合物1-2(2-(2,4-硝基苯氧基)异吲哚啉-1,3-二酮)17.74g(53.88mmol),将肼一水合物溶于二氯甲烷(350mL),加入反应混合物,搅拌4小时。反应完成后倒入0N搅拌的1N HCl中,过滤所得固体,用MeCN洗涤,滤液用MC和有机层萃取,得到所需化合物1-2 10.50g(98%),用MgSO₄干燥。
- 条件:With hydrazine hydrate In dichloromethane at 0℃; for 4 h;
- 产率:98%
- 参考文献:[1] Patent: KR101551895, 2015, B1. Location in patent: Paragraph 0171-0172; 0180-0181 [2] Patent: KR2015/74833, 2015, A. Location in patent: Paragraph 0134-0135; 0138-0139; 0191; 0194-0195 [3] Patent: KR2015/74793, 2015, A. Location in patent: Paragraph 0093-0094; 0097-0098 [4] Organic Letters, 2017, vol. 19, # 8, p. 1994 - 1997 [5] Patent: WO2009/146358, 2009, A1. Location in patent: Page/Page column 87-88 [6] Patent: WO2009/38385, 2009, A2. Location in patent: Page/Page column 11 [7] Patent: US2010/256133, 2010, A1. Location in patent: Page/Page column 9 [8] Journal of Organic Chemistry, 2003, vol. 68, # 18, p. 7119 - 7122 [9] Patent: WO2011/79804, 2011, A1. Location in patent: Page/Page column 43 [10] Patent: WO2012/116217, 2012, A1. Location in patent: Page/Page column 102 [11] Patent: US2012/245178, 2012, A1. Location in patent: Page/Page column 27 [12] Journal of the American Chemical Society, 2012, vol. 134, # 44, p. 18253 - 18256 [13] Angewandte Chemie - International Edition, 2017, vol. 56, # 9, p. 2454 - 2458 [14] Angew. Chem., 2017, vol. 129, # 9, p. 2494 - 2498,5
路线2:
- 步骤:将35g水、35g(0.50mol)盐酸羟胺加入500ml四口烧瓶,室温搅拌溶解后加入44.4g(0.60mol)乙酸甲酯,恒温25℃,滴加30%液体碱120g(0.90mol),加入时间1h,25℃反应1h后升温至50℃,滴加1:1的2,4-二硝基氯苯甲酸乙酯溶液121.5g(0.30mol),加入时间2h,50℃反应2h后降温至25℃,过滤,滤饼用1:1的5%液体烧碱洗涤,再次过滤;在四个烧瓶中加入500毫升固体,加入36.6g水、36.6g(0.30mol)31%盐酸,升温至60℃,冷却至25℃后反应2小时,过滤,固体用5倍重量甲醇回流重结晶,50℃真空干燥得到37.1g产物。
- 条件:With hydrogenchloride In water at 25 - 60℃; for 2 h;
- 产率:62.1%
- 参考文献:[1] Patent: CN104529815, 2016, B. Location in patent: Paragraph 0034; 0035; 0036