化学合成。
化学合成
合成路线 1（1. 合成：21988-87-4）
产率：99%
合成条件：at 95℃; for 12 h; Inert atmosphere
实验步骤：在N 2下，在N 2下加入均三甲苯（0.7ml，5mmol），然后加入乙酸（2.6ml）和HBr的AcOH溶液（33％wt溶液）（3.5ml）。 然后加入对甲醛（570mg，18.8mmol，3.7当量）。 将溶液在95℃下搅拌。 3小时后，固体开始生长。 将混合物再搅拌9小时，然后将混合物冷却至室温。 将混合物撞到冰上后，过滤固体并干燥。 将固体从CH 2 Cl 2中重结晶：P.E。 得到所需的溴甲基化产物，为白色针状物（1.99g，5mmol，99％）。 1H NMR（500MHz，氯仿-d）8 4.61（s，6H），2.50（s，9H）。 130 NMR（126MHZ，CDCl3）δ137.84,133.18,29.93,15.38。
参考文献：
- [1] Journal of Organic Chemistry, 1993, vol. 58, # 5, p. 1262 - 1263 [2] Patent: WO2018/106112, 2018, A1. Location in patent: Page/Page column 70 [3] Synthesis, 1994, # 11, p. 1132 - 1132 [4] Organic Letters, 2009, vol. 11, # 11, p. 2229 - 2232 [5] Tetrahedron Letters, 2013, vol. 54, # 8, p. 771 - 774 [6] CrystEngComm, 2016, vol. 18, # 15, p. 2735 - 2741 [7] Synlett, 2016, vol. 27, # 2, p. 294 - 300 [8] Organic and Biomolecular Chemistry, 2018, vol. 16, # 45, p. 8769 - 8782 [9] European Journal of Organic Chemistry, 2010, # 33, p. 6359 - 6365 [10] European Journal of Organic Chemistry, 2015, vol. 2015, # 9, p. 2012 - 2022 [11] Synlett, 2016, vol. 27, # 1, p. 141 - 145 [12] Journal of Materials Chemistry A, 2015, vol. 3, # 6, p. 3051 - 3058 [13] RSC Advances, 2014, vol. 4, # 106, p. 61884 - 61890 [14] Molecules, 2018, vol. 23, # 1, [15] Patent: WO2007/64227, 2007, A1. Location in patent: Page/Page column 58 [16] Tetrahedron, 1998, vol. 54, # 5-6, p. 949 - 968 [17] Dyes and Pigments, 2012, vol. 92, # 1, p. 696 - 704 [18] Arkivoc, 2012, vol. 2012, # 8, p. 187 - 197 [19] Inorganic Chemistry, 2013, vol. 52, # 3, p. 1161 - 1163 [20] Dalton Transactions, 2011, vol. 40, # 34, p. 8630 - 8642 [21] Journal of Chemical Crystallography, 2012, vol. 42, # 2, p. 165 - 172 [22] Journal of the Chemical Society, Chemical Communications, 1988, # 16, p. 1081 - 1083 [23] Organic and Biomolecular Chemistry, 2013, vol. 11, # 38, p. 6569 - 6579 [24] Synthesis, 1999, # 6, p. 993 - 998 [25] Collection of Czechoslovak Chemical Communications, 1976, vol. 41, p. 1777 - 1790 [26] Tetrahedron Letters, 2001, vol. 42, # 33, p. 5777 - 5779 [27] Journal of the American Chemical Society, 2002, vol. 124, # 49, p. 14510 - 14511 [28] Tetrahedron Letters, 2004, vol. 45, # 4, p. 723 - 727 [29] Journal of Molecular Structure, 2012, vol. 1019, p. 174 - 182 [30] Photochemical and Photobiological Sciences, 2013, vol. 12, # 2, p. 330 - 338 [31] RSC Advances, 2016, vol. 6, # 23, p. 19612 - 19619 [32] Journal of Chemical Sciences, 2015, vol. 127, # 2, p. 337 - 342
