作为有机合成中间体,用于构建含三甲基硅基的烯丙基结构单元,在有机化学合成中发挥关键作用。
有机合成中间体
合成路线 1(1. 合成:59376-64-6)
产率:89%
合成条件:Stage #1: With lithium aluminium tetrahydride In tetrahydrofuran at 20℃; for 4 h; Heating / reflux Stage #2: With water; ammonium chloride In tetrahydrofuran
实验步骤:例41;(2E)-3-(三甲基硅烷基)丙-2-烯-1-醇; 在搅拌下,将实施例40中制备的醇(1.54g,12mmol,1当量)在无水THF(12mL)中滴加到LiAlH 4(0.7g,18mmol,1.5当量)在THF(15mL)中的悬浮液中 )在室温下,在氩气下。 然后将混合物回流4小时并用饱和NaHCO 3水溶液淬灭。NH4.Cl. 将其用Et 2 O(3.x.50mL)萃取,并将合并的有机层用盐水洗涤,经MgSO 4干燥并真空除去溶剂,得到产物(1.39g,10.6mmol,89%收率),为无色液体。。 1H NMR(400MHz,CDCl3)δ6.19(1H,m,H-3),5.93(1H,dt,J2-3 = 18.8Hz,J2-4 = 1.45Hz,H-2),4.18(2H,dd) ,J4-3 = 2.72,J4-2 = 1.45,H-4),1.56(1H,s,H-5),0.09(9H,s,H-1); 13C NMR(100MHz,CDCl3)δ144.8(C-3),129.5(C-2),65.5(C-4), - 1.37(C-5); IR(纯,cm -1)3331(b,OH)1622(s,CC)。
参考文献:
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合成路线 2(2. 合成:59376-64-6)
产率:90%
合成条件:With sulfuric acid In hexane; ethyl acetate; toluene
实验步骤:实施例38(E)-3-三甲基甲硅烷基-2-丙烯-1-醇的制备将2g(15.6mmol)3-三甲基甲硅烷基-2-丙炔-1-醇在10ml无水乙醚中的溶液滴加到冰中 - 冷却的双(2-甲氧基乙氧基)铝钠[Red-Al。 在甲苯中的3.4M(7.3ml,25.1mmol)]在10ml无水乙醚中。 然后将反应混合物在室温下进一步搅拌2小时,并倒入冰冷的硫酸(1N)乙醚混合物中。 如果需要,将pH调节至略微碱性,然后除去有机相,并用乙醚进一步萃取水相。 将合并的有机相用硫酸钠干燥,过滤并减压浓缩。 在硅胶柱上快速快速层析残余物,用己烷和乙酸乙酯的8:2混合物洗脱,得到预期的(E)-3-三甲基甲硅烷基-2-丙烯-1-醇,为无色液体(1.8g,90%))。
参考文献:
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