三苯胺及其衍生物具有较好的给电子性、较低的离子化电位、较好的溶解性与无定形成膜性、较强的荧光性能与光稳定性，因此在有机电致发光二极管（OLEDs）、有机太阳能电池、场效应晶体管、双光子荧光材料等领域应用广泛；4-甲酰基三苯胺中由于甲酰基活性极高，可以发生很多化学反应，在合成上述系列功能材料的过程中扮演着举足轻重的作用。
有机电致发光二极管（OLEDs）；有机太阳能电池；场效应晶体管；双光子荧光材料；化学合成；材料科学
合成路线 1（1. 合成：4181-05-9）
- 步骤: 在0℃下将磷酰氯（24mL，315mmol）滴加到DMF（30mL）中，并在该温度下搅拌混合物1小时。然后加入三苯胺（10g，40mmol），并将反应混合物在100℃下搅拌6小时。当反应完成时，将混合物冷却至室温，倒入冰水中，用5％NaOH水溶液中和至pH7。用乙酸乙酯萃取溶液。用无水硫酸镁干燥有机层，并通过真空蒸发浓缩。使用石油和二氯甲烷的混合物（体积比2：1）作为洗脱液，通过柱色谱法纯化粗产物，得到所需化合物，为对羟基苯甲酸酯固体（5.76g），产率为52.74％。
- 条件: at 100℃; for 6 h; 0℃搅拌1小时
- 收率: 52.74%
- 参考文献: [1] Inorganic Chemistry, 2017, vol. 56, # 5, p. 2409 - 2416 [2] Dyes and Pigments, 2014, vol. 100, # 1, p. 127 - 134 [3] Patent: US6603020, 2003, B1 [4] Patent: EP771809, 1997, A1 [5] Patent: EP1087006, 2001, A1 [6] Patent: EP1591836, 2005, A1 [7] Chemistry - A European Journal, 2013, vol. 19, # 29, p. 9629 - 9638
合成路线 2（2. 合成：4181-05-9）
- 步骤: 将一部分2.16g（29.5mmol）N，N-二甲基甲酰胺滴加到一部分三氯氧化磷（4.52g，29.5mmol）中。将反应混合物在0℃下搅拌30分钟。将混合物加入到三苯胺（0.48g，1.97mmol）的10mL二氯乙烷溶液中。然后将反应混合物在90℃下搅拌12小时。将一部分100mL水加入到反应混合物中，用50mL二氯甲烷（MC）萃取三次。将合并的有机层用碳酸氢钠（10wt％）洗涤，然后用无水硫酸镁（MgSO 4）干燥。使用旋转蒸发器除去溶剂。白色晶体的产量为0.49g（92.7％）。熔点135.6 oC。 1H-NMR（400MHz，CDCl3）9.80（s，1H），7.69-7.66（d，J = 11.36Hz，2H），7.35-7.31（t，J = 7.68Hz，4H），7.18-7.15（m，6H），7.03-7.01（d，J = 8.8Hz，3H），13C-NMR（100MHz，CDCl3）190.29,153.23,146.05,131.21,129.65,129.01,126.21,125.02,119.25。计算值：C 19 H 13 NO 2：C，79.43; H，4.56; N，4.88; O，11.14。实测值：C，79.82; H，4.51; N，4.782。
- 条件: Stage #1: at 0℃; for 0.50 h; Stage #2: at 90℃; for 12 h
- 收率: 92.7%
- 参考文献: [1] Chemistry - An Asian Journal, 2015, vol. 10, # 1, p. 252 - 262 [2] Organic Letters, 2010, vol. 12, # 22, p. 5192 - 5195 [3] Molecular Crystals and Liquid Crystals, 2010, vol. 532, p. 55 - 64 [4] Journal of Materials Chemistry C, 2014, vol. 2, # 4, p. 651 - 659 [5] Chemical Communications, 2014, vol. 50, # 20, p. 2569 - 2571 [6] Synlett, 1997, vol. 1997, # 11, p. 1275 - 1276 [7] Synlett, 1997, vol. 1997, # 11, p. 1275 - 1276 [8] New Journal of Chemistry, 2016, vol. 40, # 10, p. 8371 - 8381 [9] Bulletin of the Korean Chemical Society, 2014, vol. 35, # 2, p. 569 - 574 [10] Australian Journal of Chemistry, 2015, vol. 68, # 10, p. 1485 - 1491 [11] Patent: CN104341439, 2016, B. Location in patent: Paragraph 0032; 0033 [12] Patent: CN105061256, 2018, B. Location in patent: Paragraph 0063; 0067-0069 [13] Journal of Organic Chemistry, 2010, vol. 75, # 21, p. 7273 - 7278 [14] Tetrahedron Letters, 2002, vol. 43, # 19, p. 3521 - 3524 [15] Chemistry Letters, 2008, vol. 37, # 6, p. 570 - 571 [16] Patent: US2009/43109, 2009, A1. Location in patent: Page/Page column sheet 5; 11; sheet 7; 13 [17] New Journal of Chemistry, 2009, vol. 33, # 10, p. 2120 - 2127 [18] Macromolecules, 2013, vol. 46, # 12, p. 4754 - 4763 [19] Journal of Medicinal Chemistry, 2013, vol. 56, # 21, p. 8484 - 8496 [20] New Journal of Chemistry, 2016, vol. 40, # 10, p. 8837 - 8845 [21] Crystal Growth and Design, 2017, vol. 17, # 1, p. 146 - 155 [22] New Journal of Chemistry, 2013, vol. 37, # 8, p. 2440 - 2447 [23] Tetrahedron Letters, 2018, vol. 59, # 37, p. 3416 - 3422 [24] Tetrahedron Letters, 2011, vol. 52, # 42, p. 5467 - 5470 [25] European Journal of Organic Chemistry, 2012, # 31, p. 6127 - 6131,5 [26] European Journal of Organic Chemistry, 2012, # 31, p. 6127 - 6131 [27] Journal of Photochemistry and Photobiology A: Chemistry, 2015, vol. 299, p. 194 - 202 [28] Patent: CN108034277, 2018, A. Location in patent: Paragraph 0028 [29] Chemical Papers, 2015, vol. 70, # 2, p. 218 - 230 [30] Chemistry - A European Journal, 2010, vol. 16, # 44, p. 13127 - 13138 [31] Chemistry of Materials, 2011, vol. 23, # 3, p. 862 - 873 [32] Dyes and Pigments, 2016, vol. 128, p. 209 - 214 [33] Journal of Materials Chemistry, 2000, vol. 10, # 12, p. 2698 - 2703 [34] Journal of Organic Chemistry, 2003, vol. 68, # 3, p. 839 - 853 [35] Chemistry - A European Journal, 2010, vol. 16, # 21, p. 6193 - 6202 [36] Journal of Organic Chemistry, 2010, vol. 75, # 9, p. 3053 - 3068 [37] Chemical Communications, 2013, vol. 49, # 100, p. 11785 - 11787 [38] Journal of Materials Chemistry C, 2014, vol. 2, # 28, p. 5709 - 5716 [39] New Journal of Chemistry, 2014, vol. 38, # 12, p. 5736 - 5746 [40] Physical Chemistry Chemical Physics, 2016, vol. 18, # 40, p. 28052 - 28060 [41] CrystEngComm, 2017, vol. 19, # 43, p. 6489 - 6497 [42] New Journal of Chemistry, 2018, vol. 42, # 23, p. 18979 - 18990 [43] Tetrahedron Letters, 2011, vol. 52, # 30, p. 3879 - 3882 [44] Journal of Fluorescence, 2010, vol. 20, # 6, p. 1255 - 1265 [45] Dyes and Pigments, 2012, vol. 94, # 1, p. 143 - 149 [46] Organic and Biomolecular Chemistry, 2014, vol. 12, # 32, p. 6128 - 6133 [47] Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 2014, vol. 121, p. 355 - 362 [48] Tetrahedron, 2014, vol. 70, # 25, p. 3909 - 3914 [49] RSC Advances, 2017, vol. 7, # 15, p. 8832 - 8842 [50] Patent: CN104262404, 2017, B. Location in patent: Paragraph 0045; 0046 [51] Patent: US6376695, 2002, B1 [52] Organic Process Research and Development, 2012, vol. 16, # 5, p. 934 - 938 [53] Australian Journal of Chemistry, 2010, vol. 63, # 4, p. 712 - 718 [54] Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry, 2012, vol. 42, # 2, p. 196 - 204 [55] Tetrahedron, 2014, vol. 70, # 21, p. 3390 - 3399 [56] Journal of Materials Chemistry C, 2014, vol. 2, # 44, p. 9523 - 9535 [57] RSC Advances, 2015, vol. 5, # 106, p. 87157 - 87167 [58] RSC Advances, 2017, vol. 7, # 48, p. 30229 - 30241 [59] Chemical Communications, 2014, vol. 50, # 40, p. 5258 - 5260 [60] Chemical Communications, 2015, vol. 51, # 18, p. 3915 - 3918 [61] Journal of Photochemistry and Photobiology A: Chemistry, 2013, vol. 272, p. 58 - 64 [62] RSC Advances, 2014, vol. 4, # 65, p. 34332 - 34342 [63] New Journal of Chemistry, 2015, vol. 39, # 12, p. 9700 - 9713 [64] Bioorganic and Medicinal Chemistry Letters, 2016, vol. 26, # 15, p. 3770 - 3773 [65] Bioorganic and Medicinal Chemistry Letters, 2018, vol. 28, # 5, p. 926 - 929 [66] Dyes and Pigments, 2017, vol. 137, p. 256 - 264 [67] Patent: CN108676000, 2018, A. Location in patent: Paragraph 0163; 0166; 0168; 0169 [68] New Journal of Chemistry, 2017, vol. 41, # 4, p. 1637 - 1644 [69] New Journal of Chemistry, 2017, vol. 41, # 21, p. 12375 - 12379 [70] Patent: CN105670608, 2017, B. Location in patent: Paragraph 0038-0039 [71] Patent: CN108409642, 2018, A. Location in patent: Paragraph 0035; 0041; 0042; 0063 [72] Asian Journal of Chemistry, 2010, vol. 22, # 5, p. 3929 - 3935 [73] Dyes and Pigments, 2011, vol. 88, # 3, p. 358 - 365 [74] Chinese Journal of Chemistry, 2013, vol. 31, # 4, p. 456 - 464 [75] Patent: CN106631998, 2017, A. Location in patent: Paragraph 0069; 0070 [76] Tetrahedron, 2011, vol. 67, # 22, p. 4110 - 4117 [77] Tetrahedron Letters, 2018, vol. 59, # 29, p. 2788 - 2792 [78] Bulletin of the Korean Chemical Society, 2016, vol. 37, # 11, p. 1812 - 1819 [79] Journal of Nanoscience and Nanotechnology, 2010, vol. 10, # 11, p. 7730 - 7734 [80] Journal of Materials Chemistry, 2011, vol. 21, # 11, p. 3768 - 3774 [81] Journal of Nanoscience and Nanotechnology, 2012, vol. 12, # 5, p. 4403 - 4408 [82] European Journal of Organic Chemistry, 2011, # 25, p. 4773 - 4787 [83] Journal of Inclusion Phenomena and Macrocyclic Chemistry, 2011, vol. 70, # 1-2, p. 97 - 107 [84] RSC Advances, 2016, vol. 6, # 51, p. 45475 - 45481 [85] Patent: US2558285, 1947, [86] Journal of Organic Chemistry, 1965, vol. 30, p. 3714,3716 [87] Journal of Physical Chemistry B, 1999, vol. 103, # 49, p. 10741 - 10745 [88] Spectrochimica Acta - Part A Molecular and Biomolecular Spectroscopy, 2001, vol. 57, # 3, p. 419 - 422 [89] Molecular Crystals and Liquid Crystals Science and Technology Section A: Molecular Crystals and Liquid Crystals, 2002, vol. 377, p. 329 - 332 [90] Tetrahedron, 2003, vol. 59, # 25, p. 4673 - 4685 [91] Tetrahedron Letters, 2006, vol. 47, # 27, p. 4715 - 4719 [92] Tetrahedron Letters, 2004, vol. 45, # 33, p. 6361 - 6363 [93] Chemical Physics Letters, 2007, vol. 435, # 1-3, p. 54 - 58 [94] Patent: EP771806, 1997, A1 [95] Patent: US2009/118521, 2009, A1. Location in patent: Page/Page column 10-11; sheet 9; sheet 12 [96] Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy, 2010, vol. 77, # 1, p. 292 - 296 [97] Chinese Journal of Chemistry, 2010, vol. 28, # 6, p. 950 - 960 [98] Journal of Polymer Science, Part A: Polymer Chemistry, 2010, vol. 48, # 1, p. 82 - 90 [99] Dyes and Pigments, 2011, vol. 88, # 1, p. 57 - 64 [100] Organic Letters, 2011, vol. 13, # 4, p. 556 - 559 [101] Chemistry Letters, 2010, vol. 39, # 6, p. 582 - 583 [102] Dyes and Pigments, 2011, vol. 88, # 3, p. 301 - 306 [103] Macromolecules, 2010, vol. 43, # 13, p. 5544 - 5553 [104] Journal of Fluorescence, 2011, vol. 21, # 2, p. 545 - 554 [105] Journal of Organic Chemistry, 2011, vol. 76, # 21, p. 8726 - 8736 [106] Journal of Fluorescence, 2011, vol. 21, # 1, p. 149 - 159 [107] Dyes and Pigments, 2012, vol. 95, # 3, p. 743 - 750,8
合成路线 3（3. 合成：4181-05-9）
- 步骤: （1）在冰浴中加入纯化的DMF（N，N-二甲基甲酰胺）（5.85g，80mmol）于100mL圆底烧瓶中，边搅拌边滴加POCl3溶液（15.33g，100mmol），滴加约0.5h后，形成白浆; 升温至55℃，加入三苯胺（2.45g，10mmol），TLC进行微量反应，1h后反应液变为深红色，将反应液倒入大量冰水中，加入碳酸钠溶液调节将pH值调至8以获得大量黄色沉淀物，抽滤，得到粗产物，为浅黄色粗产物，得到硅胶柱色谱纯化（洗脱液：石油醚/乙酸乙酯丙烯酸酯= 25/1（V / V））得到2.59g式1化合物1，化合物1，收率为95％。
- 条件: Stage #1: for 0.50 h; Cooling with ice; Stage #2: at 55℃; for 1 h
- 收率: 95%
- 参考文献: [1] Patent: CN103709070, 2016, B. Location in patent: Paragraph 0045
