4-溴-3-甲基苯酚为酚类衍生物,可用作医药中间体。
医药中间体
合成路线 1(1. 合成:14472-14-1)
产率:96%
合成条件:With o-xylylene bis(triethylammonium tribromide) In acetonitrile at 20℃; for 0.08 h;
实验步骤:通用方法:向芳族化合物(1mmol)在乙腈(5mL)中的磁性溶液中加入OXBTEATB(0.233g,0.5mmol)并在室温下搅拌适当的时间(表1)。 通过TLC监测反应(洗脱液:正己烷/乙酸乙酯:5/1)。 过滤OXBTEAB后,将反应混合物转移到分液漏斗中,用水(15mL)和二氯甲烷(20mL)萃取。 将有机层用无水Na 2 SO 4干燥,并将溶剂在旋转蒸发器中浓缩。将粗产物通过硅胶柱纯化,使用正己烷和乙酸乙酯的混合物作为洗脱剂。 为了再生试剂,用液体溴处理白色固体。 所有产物结构都通过熔点或1HNMR光谱与文献[29a-29e]中报道的光谱进行比较来确认。
参考文献:
- [1] Letters in Organic Chemistry, 2018, vol. 15, # 8, p. 682 - 687 [2] Bulletin of the Chemical Society of Japan, 1987, vol. 60, # 11, p. 4187 - 4189 [3] Journal of Organic Chemistry, 2005, vol. 70, # 11, p. 4267 - 4271 [4] Synlett, 2011, # 15, p. 2265 - 2269 [5] Journal of Chemical Research - Part S, 2003, # 9, p. 597 - 598 [6] Green Chemistry, 2010, vol. 12, # 12, p. 2124 - 2126 [7] Synthetic Communications, 2010, vol. 40, # 6, p. 868 - 876 [8] Organic Letters, 2015, vol. 17, # 12, p. 2886 - 2889 [9] Chinese Journal of Chemistry, 2010, vol. 28, # 11, p. 2221 - 2225 [10] Monatshefte fur Chemie, 2013, vol. 144, # 2, p. 179 - 181 [11] Journal of the Chilean Chemical Society, 2011, vol. 56, # 4, p. 863 - 865 [12] Synthesis, 2005, # 7, p. 1103 - 1108 [13] Tetrahedron, 2010, vol. 66, # 34, p. 6928 - 6935 [14] Organic Preparations and Procedures International, 1997, vol. 29, # 6, p. 715 - 719 [15] Synthetic Communications, 2010, vol. 40, # 21, p. 3226 - 3232 [16] Oriental Journal of Chemistry, 2011, vol. 27, # 2, p. 429 - 434 [17] Synthetic Communications, 2011, vol. 41, # 1, p. 147 - 155 [18] Australian Journal of Chemistry, 2015, vol. 68, # 3, p. 513 - 517 [19] Chinese Chemical Letters, 2012, vol. 23, # 4, p. 387 - 390 [20] Journal fuer Praktische Chemie - Practical Applications and Applied Chemistry (Germany), 1999, vol. 341, # 1, p. 59 - 61 [21] Journal of the Iranian Chemical Society, 2012, vol. 9, # 3, p. 321 - 326 [22] Journal of Heterocyclic Chemistry, 1983, vol. 20, # 1, p. 149 - 153 [23] Angewandte Chemie - International Edition, 2016, vol. 55, # 13, p. 4361 - 4366 [24] Angew. Chem., 2016, vol. 128, # 13, p. 4434 - 4439,6 [25] Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry, 2016, vol. 46, # 6, p. 832 - 837 [26] Asian Journal of Chemistry, 2018, vol. 30, # 8, p. 1892 - 1896 [27] Chemistry - A European Journal, 2013, vol. 19, # 26, p. 8447 - 8456 [28] Journal of the Chemical Society, Chemical Communications, 1980, # 3, p. 110 - 111 [29] Patent: US6632963, 2003, B1. Location in patent: Page/Page column 20 [30] Journal of Chemical Research, Miniprint, 1989, # 11, p. 2713 - 2739 [31] Journal of the Chemical Society, 1937, p. 510,512 [32] Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1931, vol. 193, p. 292 [33] Zhurnal Obshchei Khimii, 1932, vol. 2, p. 472,475 [34] Chem. Zentralbl., 1933, vol. 104, # I, p. 604 [35] Journal of the Chemical Society, 1936, p. 319,321 [36] Journal fuer Praktische Chemie (Leipzig), 1915, vol. <2> 91, p. 380 [37] Zhurnal Russkago Fiziko-Khimicheskago Obshchestva, 1928, vol. 60, p. 161 [38] Chem. Zentralbl., 1928, vol. 99, # II, p. 767 [39] Journal of Organic Chemistry, 1979, vol. 44, p. 4733 - 4735 [40] Bulletin of the Chemical Society of Japan, 1975, vol. 48, p. 2127 - 2133 [41] Recueil des Travaux Chimiques des Pays-Bas, 1978, vol. 97, p. 223 - 248 [42] Russian Journal of Organic Chemistry, 1993, vol. 29, # 11.2, p. 1868 - 1870 [43] Zhurnal Organicheskoi Khimii, 1993, vol. 29, # 11, p. 2251 - 2254 [44] Tetrahedron Letters, 2006, vol. 47, # 49, p. 8693 - 8697 [45] Tetrahedron Letters, 2008, vol. 49, # 1, p. 189 - 194 [46] Synthesis (Germany), 2013, vol. 45, # 11, p. 1497 - 1504