化学合成。
化学合成
合成路线 1(1. 合成:68470-59-7)
产率:70%
合成条件:With carbon tetrabromide; triphenylphosphine In dichloromethane at 0℃; for 0.50 h;
实验步骤:A.在0℃向搅拌的(6-甲基吡啶-2-基)甲醇(640mg,5.2mmol)和四溴化碳(2.77g,8.35mmol)的二氯甲烷(12mL)溶液中加入PPh 3(0.4gx 4, 6.1毫摩尔),间隔2分钟。 继续反应总共30分钟。 然后将混合物用Flashmaster直接用10%EtOAc的己烷溶液纯化,得到2-(溴甲基)-6-甲基吡啶,为结晶固体(675mg,70%)。
参考文献:
- [1] Journal of the American Chemical Society, 1994, vol. 116, # 18, p. 8410 - 8411 [2] Patent: WO2008/110793, 2008, A1. Location in patent: Page/Page column 112 [3] Patent: WO2008/125839, 2008, A2. Location in patent: Page/Page column 44 [4] Tetrahedron Letters, 2001, vol. 42, # 32, p. 5393 - 5395 [5] Canadian Journal of Chemistry, 2002, vol. 80, # 8, p. 973 - 982 [6] Patent: WO2012/49161, 2012, A1. Location in patent: Page/Page column 29-30 [7] Patent: US2013/203802, 2013, A1. Location in patent: Paragraph 0246; 0247 [8] Journal of the Chemical Society, 1958, p. 3594,3601 [9] Tetrahedron Asymmetry, 2009, vol. 20, # 14, p. 1672 - 1682 [10] Patent: WO2011/79076, 2011, A1. Location in patent: Page/Page column 81; 119 [11] Chemistry - A European Journal, 2015, vol. 21, # 19, p. 7053 - 7056 [12] Patent: WO2006/117754, 2006, A1. Location in patent: Page/Page column 44
合成路线 2(2. 合成:68470-59-7)
产率:68%
合成条件:With N-Bromosuccinimide; 2,2'-azobis(isobutyronitrile) In tetrachloromethane for 7 h; Reflux
:向250mL烧瓶中依次加入2,6-二甲基吡啶(5mL,43mmol),NBS(N-溴代琥珀酰亚胺)(7.65g,43mmol)和CCl 4(75mL),并将混合物在回流下加热。 向上述回流溶液中加入AIBN(偶氮二异丁腈)(0.125g /次,每1h加1次,加7次),滤出反应物,除去白色琥珀酰亚胺沉淀,汽提滤液,除去溶剂。 得到褐色油状物,通过柱色谱法使用CH 2 Cl 2作为洗脱液分离为粉红色油状物(5.4g,68%)。
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