CN108440391A - 一种2,4,6-三芳基取代吡啶衍生物的制备方法 - Google Patents

一种2,4,6-三芳基取代吡啶衍生物的制备方法 Download PDF

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CN108440391A
CN108440391A CN201810289048.7A CN201810289048A CN108440391A CN 108440391 A CN108440391 A CN 108440391A CN 201810289048 A CN201810289048 A CN 201810289048A CN 108440391 A CN108440391 A CN 108440391A
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钟为慧
沈磊欣
凌飞
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Zhejiang University of Technology ZJUT
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Abstract

本发明公开了一种2,4,6‑三芳基取代吡啶衍生物的制备方法，其制备方法如下：在溶剂或无溶剂条件下，以芳乙酮类化合物和苄胺衍生物为原料，以三(五氟苯)硼烷为催化剂，在80~160℃和氧气条件下反应6~24小时，得到2,4,6‑三芳基取代吡啶衍生物。本发明的有益效果主要体现在：本发明提供的制备方法中，反应原料易得，催化剂用量可低至千分之五，实验操作简单，可“一锅法”制备目标化合物；底物普适性较好，可构建不同取代基的2,4,6‑三芳基取代吡啶衍生物，有利于进一步的衍生化研究。

Description

一种2,4,6-三芳基取代吡啶衍生物的制备方法
技术领域
本发明属于医药化工中间体合成技术领域，具体涉及一种2,4,6-三芳基取代吡啶衍生物的制备方法。
背景技术
2,4,6-三芳基取代吡啶是一类重要的杂环化合物，在医药、农业、化工、纺染等领域均有应用，尤其是作为制备芳纶的聚酰胺材料的关键中间体PBAPP，其结构式如下：
由于2,4,6-三芳基取代吡啶衍生物具有特殊的材料性能，因此众多学者专注于该类化合物的合成方法研究。最常见的方法为：以芳香醛类化合物、苯乙酮类化合物和醋酸铵为底物，以偏铝酸镁为催化剂，通过微波反应合成2,4,6-三芳基取代的吡啶衍生物(J. Chem. Sci., 2013, 125(5), 1063-1070), 这种方法使用到微波技术，反应比较剧烈，反应条件要求比较高。
第二类方法是以酮类化合物和二苄胺类化合物为底物，以在Cu(OTf)2催化下制得2,4,6-三芳基取代的吡啶衍生物J.Org.Chem., 2013, 78(8), 3774-3782)，该种方法底物普适性较高，但反应时间较长，一般在20小时以上。
第三类方法是以苯甲醛类化合物和烯胺类化合物为底物，在醋酸钯，碘苯，氯化锂，碳酸钠等作用下反应合成2,4,6-三芳基取代的吡啶衍生物（Org. Lett.,2013, 15(2),334-337）。这种方法可以构建不对称的吡啶衍生物，但是需要使用贵金属催化剂，且催化量达10%，无法回收套用。
第四类方法是以氨基酸类化合物和苯乙酮类化合物为底物，在醋酸与碘单质等（Org.Lett.，2016, 18, 24-27）的作用下反应合成2,4,6-三芳基取代的吡啶衍生物。这种方法的反应条件相对温和，但是收率普遍较低，且催化剂的用量高达50%。
因此，开发一种原料易得、操作简单、反应条件温和、选择性高的2,4,6-三芳基取代吡啶衍生物的合成方法极为迫切。
发明内容
针对现有技术中存在的上述问题，本发明的目的在于提供一种原料易得、操作简单、反应条件温和、选择性高的2,4,6-三芳基取代吡啶衍生物的制备方法。
所述的一种2,4,6-三芳基取代吡啶衍生物的制备方法，所述2,4,6-三芳基取代吡啶衍生物的结构式如式（I）所示，其特征在于在溶剂或无溶剂条件下，以如式（Ⅱ）所示的芳乙酮类化合物和如（Ⅲ）所示的苄胺衍生物为原料，以三(五氟苯)硼烷为催化剂，在80~160℃和氧气条件下反应6~24小时，得到如式（I）所示的2,4,6-三芳基取代吡啶衍生物，反应式如下：
结构式I、Ⅱ、Ⅲ中，Ar1为取代苯基和杂芳基；Ar2为取代苯基、杂芳基和二茂铁基；其中，苯环上的取代基选自氢、甲基、甲氧基、氟、氯、溴、硝基、叔丁基、乙酰氧基或三氟甲基；所述杂芳基为噻吩、吡啶或呋喃。
所述的2,4,6-三芳基取代吡啶衍生物的制备方法，其特征在于芳乙酮类化合物、苄胺类化合物、三(五氟苯)硼烷的物质量之比为1: 0.5~1.5: 0.001~0.05，优选为1: 0.8~1.2:0.005~0.01。
所述的2,4,6-三芳基取代吡啶衍生物的制备方法，其特征在于反应温度为110~120℃；反应时间为10~16小时。
所述的2,4,6-三芳基取代吡啶衍生物的制备方法，其特征在于氧气压力为1~5atm。
所述的2,4,6-三芳基取代吡啶衍生物的制备方法，其特征在于溶剂为甲苯、DMSO、1,4-二氧六环。
与现有技术相比，本发明的有益效果主要体现在：本发明提供的制备方法中，反应原料易得，催化剂用量可低至千分之五，实验操作简单，可“一锅法”制备目标化合物；底物普适性较好，可构建不同取代基的2,4,6-三芳基取代吡啶衍生物，有利于进一步的衍生化研究。
具体实施方式
下面结合具体实施例对本发明进行进一步描述，但不仅限于本发明所列出的具体实施例描述的实施方案。
实施例1：2,4,6-三苯基吡啶（a）的制备
将苯乙酮（0.48 g, 4 mmol）、苄胺（0.35 g, 3.2mmol）、三(五氟苯基)硼烷（0.01 g,0.02 mmol）置于耐压管中在氧气氛围(1 atm)下120℃下搅拌反应12小时后，经硅胶柱层析分离，得到白色固体2,4,6-三苯基吡啶（a）0.53 g，收率86%，熔点：134-137℃。
1H NMR (600 MHz, CDCl3, ppm) δ 8.26 (d, J = 7.8 Hz, 4H), 7.94 (s, 2H),7.80 (d, J = 7.2 Hz, 2H), 7.59-7.56 (m, 6H), 7.53-7.48 (m, 3H). 13C NMR (150MHz, CDCl3, ppm) δ 157.5, 150.4, 139.5, 139.0, 129.2, 129.2, 128.8, 127.2,117.3. MS(ESI-MS) 307.1。
实施例2：2,4,6-三苯基吡啶（a）的制备
将苯乙酮（0.48 g, 4 mmol）、苄胺（0.64 g, 6 mmol）、三(五氟苯基)硼烷（0.01 g,0.02 mmol）、0.5 mL DMSO置于耐压管中在氧气氛围(5 atm)下110℃下搅拌反应12小时，反应结束后，用石油醚/乙酸乙酯=30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到白色固体2,4,6-三苯基-吡啶（a）0.40 g，收率：64%，熔点：134-137℃。
实施例3：2,4,6-三苯基吡啶（a）的制备
将苯乙酮（0.48 g, 4 mmol）、苄胺（0.35 g, 3.2 mmol）、三(五氟苯基)硼烷（0.005 g,0.01mmol）置于耐压管中在氧气氛围(1 atm)下120℃下搅拌反应12小时，反应结束后，用石油醚/乙酸乙酯= 30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到白色固体2,4,6-三苯基-吡啶（a）0.50 g，收率：81%，熔点：134-137℃。
实施例4：2,4,6-三苯基吡啶（a）的制备
将苯乙酮（0.48 g, 4 mmol）、苄胺（0.23 g, 2 mmol）、三(五氟苯基)硼烷（0.01g,0.02 mmol）、0.5 mL甲苯置于耐压管中在氧气氛围(1 atm)下120℃下搅拌反应12小时，反应结束后，用石油醚/乙酸乙酯= 30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到白色固体2,4,6-三苯基-吡啶（a）0.37 g，收率：63%，熔点：134-137℃。
实施例5：2,6-二(4，-甲氧基苯基)-4-苯基吡啶（b）的制备
将对甲氧基苯乙酮（0.60 g，4 mmol）、苄胺（0.35 g,3.2 mmol）、三(五氟苯基)硼烷（0.01 g,0.02 mmol）置于耐压管中在氧气氛围(1 atm)中120℃下搅拌反应12小时，反应结束后，用石油醚/乙酸乙酯= 30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到白色固体2,6-二-(4，-甲氧基苯基)-4-苯基吡啶（b）0.60 g，收率：81%，熔点：132-135℃
1H NMR (600 MHz, CDCl3, ppm) δ 8.20 (d, J = 8.4 Hz, 4H), 7.81 (s, 2H),7.77 (d, J = 7.2 Hz, 2H), 7.56 (dd, J =7.2, 7.8 Hz, 2H), 7.50 (dd,J = 7.2,7.2 Hz, 1H), 7.08(d, J = 8.4 Hz, 4H). 13C NMR (150 MHz, CDCl3, ppm) δ 157.4,150.1, 139.3, 139.0, 136.9, 129.5, 129.1, 127.2, 127.1, 116.6, 21.4. MS (ESI-MS) 367.2。
实施例6：4-苯基-2,6-二(二茂铁基)吡啶（c）的制备
将乙酰基二茂铁（0.91 g，4 mmol）、苄胺（0.35 g, 3.2 mmol）、三(五氟苯基)硼烷（0.02 g, 0.04 mmol）置于耐压管中在氧气氛围(1 atm)中120℃下搅拌反应12小时，反应结束后，用石油醚/乙酸乙酯=30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到黄色固体4-苯基-2,6-二(二茂铁基)-吡啶（c）1.04g，收率：86%，熔点：147-150℃。
1H NMR (600 MHz, CDCl3, ppm) δ 7.75 (d, J = 7.2 Hz, 2H), 7.57 (dd, J =7.2, 7.2 Hz, 2H), 7.51 (dd, J = 7.2, 7.2 Hz, 1H), 7.40 (s, 2H), 5.11 (s, 4H),4.47 (s, 4H), 4.14 (s, 10H). 13C NMR (150 MHz, CDCl3, ppm) δ 158.9, 148.3,139.3, 129.0, 128.7, 127.1, 114.9, 85.2, 70.2, 70.1, 67.9. HRMS (ESI-TOF)calcd for C31H25Fe2N [M+H]+: 523.0750; Found: 523.0686。
实施例7：2,6-二(2，-吡啶基)-4-苯基吡啶（d）的制备
将2-乙酰基吡啶（0.48 g, 4 mmol）、苄胺（0.35 g, 3.2 mmol）、三(五氟苯基)硼烷（0.02 g, 0.04 mmol）置于耐压管中在氧气氛围(1 atm)中120℃下搅拌反应12小时，反应结束后，用石油醚/乙酸乙酯=30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到白色固体2,6-二(2，-吡啶基)-4-苯基吡啶（d）0.49 g，收率：81%，熔点: 205-207℃。
1H NMR (600 MHz, CDCl3, ppm) δ 8.77 (s, 2H), 8.76 (d, J = 4.2 Hz, 2H),8.70 (d, J = 7.8 Hz, 2H), 7.94 (d, J = 7.2 Hz, 2H), 7.90-7.87 (m, 2H), 7.53(dd, J = 7.2, 7.8 Hz, 2H), 7.47 (dd, J = 7.8, 7.2 Hz, 1H), 7.37-7.35 (m, 1H).13CNMR (150 MHz, CDCl3, ppm) δ 156.3, 155.9, 150.3, 149.1, 138.5, 136.9,129.0, 128.9, 127.4, 123.8, 121.4, 119.0. MS (ESI-MS) 309.1。
实施例8：2,6-二(4，-硝基苯基)-4-苯基吡啶（e）的制备
将对硝基苯乙酮（0.66 g, 4 mmol）、苄胺（0.35 g, 3.2 mmol）、三(五氟苯基)硼烷（0.01 g, 0.02 mmol）置于耐压管中在氧气氛围(1 atm)下120℃下搅拌反应12小时，反应结束后，用石油醚/乙酸乙酯= 30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到土黄色固体2,6-二(4，-硝基苯基)-4-苯基吡啶（e）0.63g，收率：80%，熔点：310-315℃。
1H NMR (600 MHz, CDCl3, ppm) δ 8.43-8.39 (m, 8H), 8.08 (s, 2H), 7.80(d, J = 8.4 Hz, 2H), 7.61 (dd, J = 7.2, 7.2 Hz, 2H), 7.58-7.56 (m, 1H). 13CNMR (150 MHz, CDCl3, ppm) δ 155.5, 144.8, 137.9, 129.7, 129.4, 128.0, 127.2,124.1, 119.1, 100.0. MS (ESI-MS) 397.1. 。
实施例9：2,4,6-三(4，-甲氧基苯基)吡啶（f）的制备
将对甲氧基苯乙酮（0.60 g，4 mmol）、对甲氧基苄胺（0.35 g, 3.2mmol）、三(五氟苯基)硼烷（0.01 g, 0.02 mmol）置于耐压管中在氧气氛围(1 atm)下120℃下搅拌反应12小时，反应结束后，用石油醚/乙酸乙酯= 30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到白色固体2,4,6-三(4，-甲氧基苯基)吡啶（If）0.56g，收率：71%，熔点：130-133℃。
1H NMR (600 MHz, CDCl3, ppm) δ 8.19 (d, J = 9.0 Hz, 4H), 7.77(s, 2H),7.73 (d, J = 9.0 Hz, 2H), 7.07 (dd, J = 7.2, 8.4 Hz, 6H), 3.91 (s, 9H). 13CNMR (150 MHz, CDCl3, ppm) δ 160.5, 156.9, 149.5, 132.4, 131.6, 128.4, 128.3,115.3, 114.5, 114.0, 55.4, 55.4. MS (ESI-MS) 397.2。
实施例10：2,6-二苯基-(4，-氟苯基)吡啶（Ig）的制备
将苯乙酮（0.48 g, 4 mmol）、对氟苄胺（0.35 g, 3.2 mmol）、三(五氟苯基)硼烷（0.01g, 0.02 mmol）置于耐压管中在氧气氛围(1 atm)下120℃下搅拌反应12小时，反应结束后，用石油醚/乙酸乙酯= 30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到白色固体2，6-(二苯基)-(4’-氟苯基)吡啶（Ig）0.48g，收率：73.8%，熔点：114-116℃。
1H NMR (600 MHz, CDCl3, ppm) δ 8.20 (d, J = 7.8 Hz, 4H), 7.82 (s, 2H),7.72-7.70 (m, 2H), 7.51(dd, J = 7.2, 7.8 Hz, 4H), 7.45 (dd, J = 7.2, 7.8 Hz,1H), 7.21 (dd, J =9.0, 8.4 Hz, 2H). 13C NMR (150 MHz, CDCl3, ppm) δ164.3 (J C-F =246.0 Hz), 157.6, 149.3, 139.3, 135.1, 129.2, 129.0 (J C-F = 9.0 Hz), 128.8,127.2, 117.0, 116.2 (J C-F =22.5 Hz).MS (ESI-MS) 325.1。
实施例11：4-苯并二氧杂环戊烯-2,6-二苯基吡啶（Ih）的制备
将苯乙酮（0.48 g，4 mmol）、胡椒苄胺（0.35 g, 3.2 mmol）、三(五氟苯基)硼烷（0.01g, 0.02 mmol）置于耐压管中在氧气氛围(1 atm)下120℃下搅拌反应12小时，反应结束后，用石油醚/乙酸乙酯= 30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到白色固体4-苯并二氧杂环戊烯-2,6-二苯基吡啶（Ih）0.60g，收率：86%，熔点：141-143℃。
1H NMR (600 MHz, CDCl3, ppm) δ 8.24 (d, J = 7.8 Hz, 4H), 7.85 (s, 2H),7.55 (t, J = 7.8 Hz, 4H),7.48 (dd, J =7.2, 7.2 Hz, 2H), 7.29-7.28 (m, 1H),7.26 (s, 1H), 6.99 (d, J = 8.4 Hz, 1H), 6.08 (s, 2H). 13C NMR (150 MHz, CDCl3,ppm) δ157.5, 149.8, 148.5, 148.5, 139.6, 133.2, 129.1, 128.7, 127.2, 121.1,116.8, 108.9, 107.5, 101.5. MS (ESI-MS) 351.1。
实施例12:2,6-二(4，-氨基苯基) -4-苯基吡啶(PBAPP)的制备
将2,6-二-(4，-硝基苯基)-4-苯基吡啶（e, 1.6 g，4 mmol）、5% Pd/C（0.06g）、48mL无水乙醇置于干燥三口瓶中在氮气氛围(1 atm)下回流3小时，再往反应体系中加入18mL 80%的水合肼，继续回流过夜，反应结束后，用石油醚/乙酸乙酯= 30/1（V/V）混合溶剂作洗脱剂，经硅胶柱层析分离得到淡黄色固体2,6-二(4，-氨基苯基)-4-苯基吡啶（PBAPP）1.32g，收率：95%，熔点：195-196℃。
1H NMR (600 MHz, CDCl3, ppm) δ 8.03 (d, J = 7.8 Hz, 4H), 7.95 (d, J =6.6 Hz, 2H), 7.80 (s, 2H), 7.54 (d, J = 5.4 Hz, 2H), 7.49 (d, J = 6.0 Hz,1H), 6.71 (d, J = 4.2 Hz, 4H), 5.43 (s, 4H). 13C NMR (150 MHz, CDCl3, ppm) δ157.1, 150.3, 149.1, 139.0, 129.5, 128.3, 128.2, 127.5, 127.0, 114.1, 113.2.MS (ESI-MS) 337.2。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员，在不脱离本发明构思的前提下，还可以做出若干改进和润色，这些改进和润色也应视为本发明的保护范围内。

Claims (5)

1.一种2,4,6-三芳基取代吡啶衍生物的制备方法，所述2,4,6-三芳基取代吡啶衍生物的结构式如式（I）所示，其特征在于在溶剂或无溶剂条件下，以如式（Ⅱ）所示的芳乙酮类化合物和如（Ⅲ）所示的苄胺衍生物为原料，以三(五氟苯)硼烷为催化剂，在80~160℃和氧气条件下反应6~24小时，得到如式（I）所示的2,4,6-三芳基取代吡啶衍生物，反应式如下：
结构式I、Ⅱ、Ⅲ中，Ar1为取代苯基和杂芳基；Ar2为取代苯基、杂芳基和二茂铁基；其中，苯环上的取代基选自氢、甲基、甲氧基、氟、氯、溴、硝基、叔丁基、乙酰氧基或三氟甲基；所述杂芳基为噻吩、吡啶或呋喃。
2.根据权利要求1所述的2,4,6-三芳基取代吡啶衍生物的制备方法，其特征在于芳乙酮类化合物、苄胺类化合物、三(五氟苯)硼烷的物质量之比为1: 0.5~1.5: 0.001~0.05，优选为1: 0.8~1.2:0.005~0.01。
3.根据权利要求1所述的2,4,6-三芳基取代吡啶衍生物的制备方法，其特征在于反应温度为110~120℃；反应时间为10~16小时。
4.根据权利要求1所述的2,4,6-三芳基取代吡啶衍生物的制备方法，其特征在于氧气压力为1~5 atm。
5.根据权利要求1所述的2,4,6-三芳基取代吡啶衍生物的制备方法，其特征在于溶剂为甲苯、DMSO、1,4-二氧六环。
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