2-碘二苯醚用作有机中间体;可由苯酚和1-氟-2-硝基苯为原料经多步反应制备。
化学合成
路线1:
- 步骤:冰浴冷却中间体Bn-2(1eq.)与PTSA·H₂O(3eq.)在乙腈(1.3M)中的混合物至5℃,逐滴加入NaNO₂(2eq.,溶于水),5℃反应1h;加入KI(2eq.,溶于水)处理重氮盐,反应完成后用EtOAc萃取,有机层经Na₂SO₃洗涤、Na₂SO₄干燥,减压浓缩后硅胶柱色谱纯化得产物。
- 条件:水/乙腈混合溶剂,5℃,1h;
- 收率:78.2%
- 参考文献:[1] Chemistry - A European Journal, 2014, vol.20, #39, p.12553-12558;[2] Journal of the Indian Chemical Society, 2013, vol.90, #10, p.1537-1555;[3] Chemistry - A European Journal, 2012, vol.18, #11, p.3286-3291;[4] Patent: US2018/155312, 2018, A1;[5] Journal of the American Chemical Society, 2015, vol.137, #11, p.3775-3778;[6] Macromolecules, 2010, vol.43, #24, p.10355-10365;[7] European Journal of Organic Chemistry, 2006, #20, p.4676-4684;[8] Patent: KR2015/130206, 2015, A;[9] Patent: KR2016/13678, 2016, A;[10] Patent: KR2017/86011, 2017, A;[11] Patent: CN107207454, 2017, A;[12] Patent: US2017/342318, 2017, A1;[13] Journal of the Chemical Society, 1932, p.281,282;[14] Journal of the Chemical Society, 1931, p.137,144;[15] Angewandte Chemie - International Edition, 2015, vol.54, #35, p.10317-10323;[16] Angew. Chem., 2015, vol.127, p.10457-10461,5;[17] Organic and Biomolecular Chemistry, 2018, vol.16, #42, p.7861-7870
路线2:
- 步骤:向4-mL螺旋盖小瓶中加入Cs₂CO₃(1.0mmol,325mg)、Cu₂O(0.005mmol,0.7mg)、1H-咪唑-4-羧酸(0.01mmol,1.1mg)和乙腈(0.25mL),密封搅拌后注入碘代芳烃(0.5mmol)和苯酚(0.6mmol),80℃搅拌24h;反应后用CH₂Cl₂稀释,经硅藻土垫过滤,真空浓缩后柱色谱分离(己烷/乙酸乙酯洗脱)得产物。
- 条件:乙腈溶剂,80℃,24h;
- 收率:42%
- 参考文献:[1] Tetrahedron Letters, 2012, vol.53, #1, p.71-75