3,5-二羟基-4-碘苯甲酸甲酯为羧酸酯类有机物,可用作有机中间体。可由3,5-二羟基苯甲酸为原料先碘代制备3,5-二羟基-4-碘-苯甲酸,然后酯化得到。
有机中间体
路线1:
- 步骤:向含有3,5-二羟基苯甲酸甲酯(4-1)(5.0g,30mmol)的甲醇(70mL)和NaHCO₃(70mL,1M)的小瓶中通过注射泵(12mL/min)在0℃下加入碘(7.4g,29.3mmol)的碘化钾水溶液(10mL,3.8M)。1小时后,用HCl(37%)将反应骤冷至pH2,然后温热至室温。将反应浓缩至干,并从甲醇-水中重结晶。分离出最终产物3,5-二羟基-4-碘苯甲酸甲酯(4-2),为黄色晶体(4.4g,14.8mmol,49%收率)。
- 条件:With hydrogenchloride; iodine; sodium hydrogencarbonate In methanol; 0℃;1小时;
- 收率:49%
- 参考文献:[1] Organic Letters, 2016, vol. 18, # 3, p. 360 - 363 [2] Organic Process Research and Development, 2010, vol. 14, # 1, p. 180 - 187 [3] European Journal of Organic Chemistry, 2012, # 1, p. 188 - 192 [4] Patent: US2015/50659, 2015, A1. Location in patent: Page/Page column [5] Patent: US2016/237279, 2016, A1. Location in patent: Paragraph 0281-0282 [6] Patent: US9957291, 2018, B2. Location in patent: Page/Page column 295-296 [7] Angewandte Chemie - International Edition, 2012, vol. 51, # 30, p. 7567 - 7571 [8] Patent: US2017/321268, 2017, A1. Location in patent: Paragraph 0228
路线2:
- 步骤:将3,5-二羟基-4-碘-苯甲酸(810g; 2.89mol)溶解在甲醇(3,800ml)中,同时搅拌并用氩气充气,小心地加入硫酸(57.5ml)并将混合物加热至60℃。在该温度下3小时后,再次加入硫酸(12ml)并继续搅拌45分钟。除去加热浴后,小心地加入水(5,000ml),将混合物冷却至0℃。然后抽出沉淀出的晶体,用冰水(2×500ml)洗涤并干燥。在高真空下。
- 条件:at 60℃; for 3.75 h;
- 收率:90%
- 参考文献:[1] Patent: US6821980, 2004, B1. Location in patent: Page column 21