CN110156668B - 一种合成4-多氟烷基-2,6-二芳基取代吡啶化合物的方法 - Google Patents

一种合成4-多氟烷基-2,6-二芳基取代吡啶化合物的方法 Download PDF

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CN110156668B
CN110156668B CN201910602006.9A CN201910602006A CN110156668B CN 110156668 B CN110156668 B CN 110156668B CN 201910602006 A CN201910602006 A CN 201910602006A CN 110156668 B CN110156668 B CN 110156668B
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翁志强
王增
游晨辉
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Abstract

本发明公开了一种合成4‑多氟烷基‑2,6‑二芳基取代吡啶化合物的方法，以N‑（1‑苯基乙烯基）乙酰胺作为底物，多氟烷基羧酸酐作为多氟烷基源，在不添加任何催化剂的条件下，制得4‑多氟烷基‑2,6‑二芳基取代吡啶化合物。该合成方法具有操作简便、原料廉价易得、产物多样化等优点。

Description

一种合成4-多氟烷基-2,6-二芳基取代吡啶化合物的方法
技术领域
本发明属于有机氟的化学合成技术领域，具体涉及一种合成4-多氟烷基-2,6-二芳基取代吡啶化合物的方法。
背景技术
吡啶衍生物是一类重要的杂环化合物，广泛存在于天然产物和具有生物活性的分子中，以及应用于合成农药、医药、先进材料等中间体，因此合成吡啶衍生物具有重要的实际应用价值。将含氟基团引入到吡啶分子中，能极大地改变吡啶分子的理化、以及生物性质，增强脂溶性、提高生物利用度等。许多的药物、农药分子含有4-多氟烷基取代吡啶片段。目前文献报道合成该分子片段的方法主要是通过氟-氯交换间接法，或对吡啶底物直接多氟烷基化反应，以及多氟烷基砌块法，但都存在使用昂贵的、不易制备的试剂、反应条件极端、步骤繁琐、适用范围窄、区域选择性低等缺点。本发明提供一种利用廉价易得的多氟烷基羧酸酐与烯酰胺，经串联反应合成4-多氟烷基-2,6-二芳基取代吡啶化合物的方法。
发明内容
本发明的目的在于提供一种合成4-多氟烷基-2,6-二芳基取代吡啶化合物的方法，该合成方法具有操作简便、原料廉价易得、产物多样化等优点。
为实现上述目的，本发明采用如下技术方案：
一种4-多氟烷基-2,6-二芳基取代吡啶化合物的合成方法，其是以N-（1-苯基乙烯基）乙酰胺作为底物，多氟烷基羧酸酐作为多氟烷基源，在不添加任何催化剂的条件下，经串联反应，得到4-多氟烷基-2,6-二芳基取代吡啶化合物；其反应式为：
Figure DEST_PATH_IMAGE001
，RF为CF3、CF2H、CF2Cl、C2F5或CF2CF2CF3。
其中，所述N-（1-苯基乙烯基）乙酰胺底物为下述式1-式20中的任意一种：
Figure 340267DEST_PATH_IMAGE002
。
所述4-三氟甲基-2,6-二芳基取代吡啶化合物为下述式1-式24中的任意一种：
Figure DEST_PATH_IMAGE003
。
所述4-二氟甲基-2,6-二芳基取代吡啶化合物为下述式1-式20中的任意一种：
Figure 880577DEST_PATH_IMAGE004
。
所述其他的4-多氟烷基-2,6-二芳基取代吡啶化合物为下述式1-式7中的任意一种：
Figure 597997DEST_PATH_IMAGE005
。
所述4-多氟烷基-2,6-二芳基取代吡啶化合物合成方法的具体步骤如下：在氮气气氛中，N-（1-苯基乙烯基）乙酰胺，多氟烷基羧酸酐混合物置于装有磁力搅拌子的反应器中，加入溶剂，在 60 -100℃ 下反应1-24 h,将反应混合物用乙酸乙酯稀释，用饱和NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，通过硅胶柱纯化，得到所述4-多氟烷基-2,6-二芳基取代吡啶化合物。
所述溶剂为乙腈、1,2-二氯乙烷、或甲苯中的任意一种，优选为1,2-二氯乙烷。
所用N-（1-苯基乙烯基）乙酰胺，多氟烷基羧酸酐、溶剂的摩尔比为(0.2-1):(0.3-1.5):(13-65)。
本发明的有益效果在于：
本发明以简单易得的N-（1-苯基乙烯基）乙酰胺，多氟烷基羧酸酐为原料，在无金属催化下，经串联反应合成4-多氟烷基-2,6-二芳基取代吡啶化合物，官能团的适应性较好，且其操作简便，原料廉价易得、产物多样化等优点。
附图说明
图1为实施例1制得的2,6-二苯基-4-（三氟甲基）吡啶的单晶结构图。
具体实施方式
为了使本发明所述的内容更加便于理解，下面结合具体实施方式对本发明所述的技术方案做进一步的说明，但是本发明不仅限于此。
实施例1
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-苯基乙烯基）乙酰胺，1.5 mmol 的三氟乙酸酐，最后加入5 mL的溶剂，于80℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以正戊烷和乙酸乙酯为洗脱剂，通过硅胶柱层析分离得到2,6-二苯基-4-（三氟甲基）吡啶 (分离产率65%)。1H NMR (400 MHz, CDCl3) δ 8.23 (d, J = 7.4 Hz, 4H), 7.93(s, 2H), 7.65 – 7.46 (m, 4H). 19F NMR (376 MHz, CDCl3) δ -64.6 (s, 3F). 13C NMR(101 MHz, CDCl3) δ 158.2 (s), 140.0 (q, J = 33.4 Hz), 138.2 (s), 129.9 (s),128.9 (s), 127.2 (s), 123.3 (q, J = 273.3 Hz), 114.0 (q, J = 3.5 Hz). GC-MSm/z 299 (M+).
实施例2
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-（邻甲苯基）乙烯基）乙酰胺，1.5 mmol 的三氟乙酸酐，最后加入5 mL的溶剂，于80℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以正戊烷和乙酸乙酯为洗脱剂，通过硅胶柱层析分离得到2,6-二邻甲苯基-4-（三氟甲基）吡啶 (分离产率72%)。1H NMR (400 MHz, CDCl3) δ 7.65 (s, 2H), 7.52 (d,J = 6.9 Hz, 2H), 7.43 – 7.31 (m, 6H), 2.49 (s, 6H). 19F NMR (376 MHz, CDCl3) δ-64.5 (s, 3F). 13C NMR (101 MHz, CDCl3) δ 160.9 (s), 139.3 (s), 138.9 (q, J =33.5 Hz), 136.0 (s), 131.0 (s), 129.9 (s), 129.0 (s), 126.1 (s), 123.1 (q, J= 273.4 Hz), 117.6 (q, J = 3.6 Hz), 20.6 (s). GC-MS m/z 327 (M+).
实施例3
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-（间甲苯基）乙烯基）乙酰胺，1.5 mmol 的三氟乙酸酐，最后加入5 mL的溶剂，于60℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以正戊烷和乙酸乙酯为洗脱剂，通过硅胶柱层析分离得到2,6-二间甲苯基-4-（三氟甲基）吡啶 (分离产率71%)。1H NMR (400 MHz, CDCl3) δ 8.00 (d, J = 10.3 Hz,4H), 7.89 (s, 2H), 7.46 (t, J = 7.2 Hz, 2H), 7.34 (d, J = 7.3 Hz, 2H), 2.53(s, 6H). 19F NMR (376 MHz, CDCl3) δ -64.6 (s, 3F). 13C NMR (101 MHz, CDCl3) δ158.5 (s), 139.9 (q, J = 33.5 Hz), 138.6 (s), 138.3 (s), 130.6 (s), 128.8(s), 127.8 (s), 124.4 (s), 123.3 (q, J = 273.2 Hz), 114.1 (q, J = 3.6 Hz),21.6 (s). GC-MS m/z 327 (M+).
实施例4
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-（对甲苯基）乙烯基）乙酰胺，1.5 mmol 的三氟乙酸酐，最后加入5 mL的溶剂，于60℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以正戊烷和乙酸乙酯为洗脱剂，通过硅胶柱层析分离得到2,6-二对甲苯基-4-（三氟甲基）吡啶 (分离产率73%)。1H NMR (400 MHz, CDCl3) δ 8.12 (d, J = 7.7 Hz,4H), 7.87 (s, 2H), 7.38 (d, J = 7.8 Hz, 4H), 2.49 (s, 6H). 19F NMR (376 MHz,CDCl3) δ -64.6 (s, 3F). 13C NMR (101 MHz, CDCl3) δ 158.1 (s), 139.9 (s), 139.9(q, J = 33.2 Hz), 135.6 (s), 129.6 (s), 127.0 (s), 123.4 (q, J = 273.3 Hz),113.4 (q, J = 3.6 Hz), 21.7 (s). GC-MS m/z 327 (M+).
实施例5
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-（4-乙基苯基）乙烯基）乙酰胺，1.5 mmol 的三氟乙酸酐，最后加入5 mL的溶剂，于80℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以正戊烷和乙酸乙酯为洗脱剂，通过硅胶柱层析分离得到2,6-双（4-乙基苯基）-4-（三氟甲基）吡啶 (分离产率74%)。1H NMR (400 MHz, CDCl3) δ 8.14 (d, J =7.4 Hz, 4H), 7.87 (s, 2H), 7.40 (d, J = 7.4 Hz, 4H), 2.90 – 2.66 (m, 4H),1.35 (t, J = 6.8 Hz, 6H). 19F NMR (376 MHz, CDCl3) δ -64.6 (s, 3F). 13C NMR(101 MHz, CDCl3) δ 158.2 (s), 146.3 (s), 139.9 (q, J = 33.2 Hz), 135.9 (s),128.4 (s), 127.1 (s), 123.3 (q, J = 273.2 Hz), 28.8 (s), 15.5 (s). GC-MS m/z355 (M+).
实施例6
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-（2,4-二甲基苯基）乙烯基）乙酰胺，1.5 mmol 的三氟乙酸酐，最后加入5 mL的溶剂，于80℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以正戊烷和乙酸乙酯为洗脱剂，通过硅胶柱层析分离得到2,6-双（2,4-二甲基苯基）-4-（三氟甲基）吡啶 (分离产率84%)。1H NMR (400 MHz, CDCl3) δ 7.63(s, 2H), 7.46 (d, J = 7.6 Hz, 2H), 7.18 (d, J = 8.7 Hz, 4H), 2.50 (s, 6H),2.44 (s, 6H). 19F NMR (376 MHz, CDCl3) δ -64.50(s, 3F). 13C NMR (101 MHz,CDCl3) δ 160.8 (s), 138.8 (s), 138.7 (q, J = 33.4 Hz), 136.7 (s), 135.9 (s),131.8 (s), 129.9 (s), 126.8 (s), 123.2 (q, J = 273.3 Hz), 117.2 (q, J = 3.6Hz), 21.2 (s), 20.6 (s). GC-MS m/z 355 (M+).
实施例7
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-（4-甲氧基苯基）乙烯基）乙酰胺，1.5 mmol 的三氟乙酸酐，最后加入5 mL的溶剂，于60℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以正戊烷和乙酸乙酯为洗脱剂，通过硅胶柱层析分离得到2,6-双（4-甲氧基苯基）-4-（三氟甲基）吡啶 (分离产率80%)。1H NMR (400 MHz, CDCl3) δ 8.16 (d, J= 7.4 Hz, 4H), 7.77 (s, 2H), 7.06 (d, J = 7.4 Hz, 4H), 3.91 (s, 6H). 19F NMR(376 MHz, CDCl3) δ -64.7 (s, 3F). 13C NMR (101 MHz, CDCl3) δ 161.1 (s), 157.6(s), 139.8 (q, J = 33.1 Hz), 131.0 (s), 128.5 (s), 123.4 (q, J = 273.3 Hz),114.2 (s), 112.4 (q, J = 3.5 Hz), 55.4 (s). GC-MS m/z 359 (M+).
实施例8
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-（4-甲硫基苯基）乙烯基）乙酰胺，1.5 mmol 的三氟乙酸酐，最后加入5 mL的溶剂，于60℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以正戊烷和乙酸乙酯为洗脱剂，通过硅胶柱层析分离得到2,6-双（4-甲硫基苯基）-4-（三氟甲基）吡啶 (分离产率80%)。1H NMR (400 MHz, CDCl3) δ 8.11 (d, J= 6.8 Hz, 4H), 7.82 (s, 2H), 7.39 (d, J = 6.8 Hz, 4H), 2.58 (d, J = 1.6 Hz,6H). 19F NMR (376 MHz, CDCl3) δ -64.7 (s, 3F). 13C NMR (101 MHz, CDCl3) δ 157.5(s), 141.2 (s), 140.0 (q, J = 33.3 Hz), 134.7 (s), 127.4 (s), 126.3 (s),123.2 (q, J = 273.5 Hz), 113.27 (q, J = 3.6 Hz), 15.39 (s). GC-MS m/z 391 (M+).
实施例9
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-（2-氟苯基）乙烯基）乙酰胺，1.5 mmol 的三氟乙酸酐，最后加入5 mL的溶剂，于80℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以正戊烷和乙酸乙酯为洗脱剂，通过硅胶柱层析分离得到2,6-双（2-氟苯基）-4-（三氟甲基）吡啶 (分离产率51%)。1H NMR (400 MHz, CDCl3) δ 8.23 (t, J = 7.7 Hz,2H), 8.06 (s, 2H), 7.47 (dd, J = 12.9, 6.6 Hz, 2H), 7.34 (t, J = 7.4 Hz, 2H),7.24 (dd, J = 11.1, 8.6 Hz, 2H). 19F NMR (376 MHz, CDCl3) δ -64.6 (s), -116.3– -116.6 (m). 13C NMR (101 MHz, CDCl3) δ 160.8 (d, J = 250.8 Hz), 154.2 (d, J= 2.4 Hz), 139.4 (q, J = 33.5 Hz), 131.3 (d, J = 8.7 Hz), 131.2 (d, J = 2.6Hz), 126.2 (d, J = 10.9 Hz), 124.7 (d, J = 3.5 Hz), 123.1(q, J = 273.5 Hz),118.6 (dq, J = 11.0, 3.5 Hz), 116.4 (d, J = 23.0 Hz). GC-MS m/z 335 (M+).
实施例10
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-（3-氟苯基）乙烯基）乙酰胺，1.5 mmol 的三氟乙酸酐，最后加入5 mL的溶剂，于80℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以正戊烷和乙酸乙酯为洗脱剂，通过硅胶柱层析分离得到2,6-双（3-氟苯基）-4-（三氟甲基）吡啶 (分离产率50%)。1H NMR (400 MHz, CDCl3) δ 7.92 (d, J = 8.2 Hz,4H), 7.88 (s, 2H), 7.51 (dd, J = 14.1, 7.6 Hz, 2H), 7.26 – 7.13 (m, 2H). 19FNMR (376 MHz, CDCl3) δ -64.70 (s, 3F), -112.16 – -112.27 (m, 1F). 13C NMR (101MHz, CDCl3) δ 163.4 (d, J = 246.1 Hz), 156.9 (d, J = 2.7 Hz), 140.4 (q, J =33.7 Hz), 140.1 (d, J = 7.6 Hz), 130.5 (d, J = 8.1 Hz), 123.0 (q, J = 273.5Hz), 122.6 (d, J = 2.9 Hz), 116.9 (d, J = 21.4 Hz), 114.6 (q, J = 3.6 Hz),114.1 (d, J = 23.1 Hz). GC-MS m/z 335 (M+).
实施例11
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-（4-氟苯基）乙烯基）乙酰胺，1.5 mmol 的三氟乙酸酐，最后加入5 mL的溶剂，于80℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以正戊烷和乙酸乙酯为洗脱剂，通过硅胶柱层析分离得到2,6-双（4-氟苯基）-4-（三氟甲基）吡啶 (分离产率65%)。1H NMR (400 MHz, CDCl3) δ 8.37 – 7.96 (m, 4H),7.84 (s, 2H), 7.24 (t, J = 7.9 Hz, 4H). 19F NMR (376 MHz, CDCl3) δ -64.7 (s,3F), -111.3 – -111.4 (m, 1F). 13C NMR (101 MHz, CDCl3) δ 164.1 (d, J = 250.1Hz), 157.2 (s), 140.3 (q, J = 33.5 Hz), 134.2 (d, J = 3.1 Hz), 129.0 (d, J =8.5 Hz), 123.1 (q, J = 273.4 Hz), 115.9 (d, J = 21.7 Hz), 113.6 (q, J = 3.5Hz). GC-MS m/z 335 (M+).
实施例12
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-（2-氯苯基）乙烯基）乙酰胺，1.5 mmol 的三氟乙酸酐，最后加入5 mL的溶剂，于60℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以正戊烷和乙酸乙酯为洗脱剂，通过硅胶柱层析分离得到2,6-双（2-氯苯基）-4-（三氟甲基）吡啶 (分离产率42%)。 1H NMR (400 MHz, CDCl3) δ 7.96 (s, 2H), 7.76(d, J = 6.1 Hz, 2H), 7.56 (d, J = 6.1 Hz, 2H), 7.43 (d, J = 3.7 Hz, 4H). 19FNMR (376 MHz, CDCl3) δ -64.5 (s, 3F). 13C NMR (101 MHz, CDCl3) δ 157.9 (s),138.4 (q, J =33.6 Hz), 137.9 (s), 132.3 (s), 131.8 (s), 130.3 (s), 130.3 (s),127.2 (s), 122.9 (q, J = 273.5 Hz), 119.1 (q, J = 3.4 Hz). GC-MS m/z 367 (M+).
实施例13
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-（4-氯苯基）乙烯基）乙酰胺，1.5 mmol 的三氟乙酸酐，最后加入5 mL的溶剂，于60℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以正戊烷和乙酸乙酯为洗脱剂，通过硅胶柱层析分离得到2,6-双（4-氯苯基）-4-（三氟甲基）吡啶 (分离产率62%)。 1H NMR (400 MHz, CDCl3) δ 8.09 (d, J = 8.0 Hz,4H), 7.84 (s, 2H), 7.50 (d, J = 8.0 Hz, 4H). 19F NMR (376 MHz, CDCl3) δ -64.7(s, 3F). 13C NMR (101 MHz, CDCl3) δ 157.0 (s), 140.3 (q, J = 33.6 Hz), 136.3(s), 136.2 (s), 129.1 (s), 128.3 (s), 123.0 (q, J = 273.5 Hz), 114.0 (q, J =3.5 Hz). GC-MS m/z 367 (M+).
实施例14
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-（3-溴苯基）乙烯基）乙酰胺，1.5 mmol 的三氟乙酸酐，最后加入5 mL的溶剂，于60℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以正戊烷和乙酸乙酯为洗脱剂，通过硅胶柱层析分离得到2,6-双（3-溴苯基）-4-（三氟甲基）吡啶 (分离产率55%)。1H NMR (400 MHz, CDCl3) δ 8.29 (s, 2H), 8.07(d, J = 7.8 Hz, 2H), 7.86 (s, 2H), 7.63 (d, J = 7.9 Hz, 2H), 7.41 (t, J = 7.8Hz, 2H). 19F NMR (376 MHz, CDCl3) δ -64.60 (s, 3F). 13C NMR (101 MHz, CDCl3) δ156.8 (s), 140.4 (q, J = 33.8 Hz), 139.8 (s), 133.0 (s), 130.5 (s), 130.1(s), 125.7 (s), 123.3 (s), 122.9 (q, J = 273.5 Hz), 114.7 (q, J = 3.5 Hz).GC-MS m/z 455 (M+).
实施例15
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-苯基乙烯基）乙酰胺，1.5 mmol 的二氟乙酸酐，最后加入5 mL的溶剂，于100℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以正戊烷和乙酸乙酯为洗脱剂，通过硅胶柱层析分离得到4-（二氟甲基）-2,6-二苯基吡啶 (分离产率40%)。1H NMR (400 MHz, CDCl3) δ 8.21 (d, J = 7.5 Hz, 4H),7.82 (s, 2H), 7.54 (dt, J = 14.1, 7.6 Hz, 6H), 6.78 (t, J = 55.9 Hz, 1H). 19FNMR (376 MHz, CDCl3) δ -115.3 (d, J = 55.9 Hz, 2F). 13C NMR (101 MHz, CDCl3) δ157.9 (s), 143.9 (t, J = 23.0 Hz), 138.6 (s), 129.6 (s), 128.9(s), 127.1 (s),114.8 (t, J = 5.9 Hz), 113.4 (t, J = 241.0 Hz). GC-MS m/z 281 (M+).
实施例16
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-（邻甲苯基）乙烯基）乙酰胺，1.5 mmol 的二氟乙酸酐，最后加入5 mL的溶剂，于100 ℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以正戊烷和乙酸乙酯为洗脱剂，通过硅胶柱层析分离得到4-（二氟甲基）-2,6-二邻甲苯基吡啶 (分离产率56%)。1H NMR (400 MHz, CDCl3) δ 7.54 (s, 2H), 7.51(d, J = 7.4 Hz, 2H), 7.41 – 7.30 (m, 6H), 6.78 (t, J = 55.8 Hz, 1H), 2.49 (s,6H). 19F NMR (376 MHz, CDCl3) δ -115.2 (d, J = 55.8 Hz, 2F). 13C NMR (101 MHz,CDCl3) δ 160.6 (s), 142.8 (t, J = 23.1 Hz), 139.8 (s), 135.9 (s), 130.9 (s),129.9 (s), 128.7 (s), 126.0 (s), 118.2 (t, J = 5.8 Hz), 113.3 (t, J = 241.0Hz), 20.6 (s). GC-MS m/z 309 (M+).
实施例17
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-（对甲苯基）乙烯基）乙酰胺，1.5 mmol 的二氟乙酸酐，最后加入5 mL的溶剂，于100 ℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以正戊烷和乙酸乙酯为洗脱剂，通过硅胶柱层析分离得到4-（二氟甲基）-2,6-二对甲苯基吡啶 (分离产率47%)。1H NMR (400 MHz, CDCl3) δ 8.10 (d, J = 7.3 Hz,4H), 7.76 (s, 2H), 7.35 (d, J = 7.3 Hz, 4H), 6.76 (t, J = 56.4 Hz, 1H), 2.47(s, 6H). 19F NMR (376 MHz, CDCl3) δ -115.3 (d, J = 55.9 Hz). 13C NMR (101 MHz,CDCl3) δ 157.7 (s), 143.7 (t, J = 22.9 Hz), 139.7 (s), 135.9 (s, 2F), 129.6(s), 127.1 (s), 114.2 (t, J = 5.9 Hz), 113.5 (t, J = 240.9 Hz), 21.4 (s). GC-MS m/z 309 (M+).
实施例18
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-（4-乙基苯基）乙烯基）乙酰胺，1.5 mmol 的二氟乙酸酐，最后加入5 mL的溶剂，于100 ℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以正戊烷和乙酸乙酯为洗脱剂，通过硅胶柱层析分离得到4-（二氟甲基）-2,6-双（4-乙基苯基）吡啶 (分离产率50%)。1H NMR (400 MHz, CDCl3) δ 8.14 (d, J= 7.6 Hz, 4H), 7.77 (s, 2H), 7.39 (d, J = 7.5 Hz, 4H), 6.76 (t, J = 55.9 Hz,1H), 2.78 (q, J = 7.1 Hz, 4H), 1.35 (t, J = 7.3 Hz, 6H). 19F NMR (376 MHz,CDCl3) δ -115.2 (d, J = 56.0 Hz, 2F). 13C NMR (101 MHz, CDCl3) δ 157.8 (s),146.0 (s), 143.7 (t, J = 22.9 Hz), 136.2 (s), 128.4 (s), 127.1 (s), 114.1 (t,J = 5.9 Hz), 113.6 (t, J = 240.9 Hz), 28.8 (s), 15.5 (s). GC-MS m/z 337 (M+).
实施例19
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-苯基乙烯基）乙酰胺，1.5 mmol 的氯二氟乙酸酐，最后加入5 mL的溶剂，于60℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以正戊烷和乙酸乙酯为洗脱剂，通过硅胶柱层析分离得到4-（氯二氟甲基）-2,6-二苯基吡啶 (分离产率70%). 1H NMR (400 MHz, CDCl3) δ 8.23 (d, J = 7.3 Hz, 4H),7.93 (s, 2H), 7.56 (dt, J = 13.4, 7.2 Hz, 6H). 19F NMR (376 MHz, CDCl3) δ -51.9 (s, 2F). 13C NMR (101 MHz, CDCl3) δ 158.2 (s), 145.6 (t, J = 27.6 Hz),138.3 (s), 129.8 (s), 128.9 (s), 127.2 (s), 125.4 (t, J = 290.3 Hz), 113.4(t, J = 4.5 Hz). GC-MS m/z 315 (M+).
实施例20
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-（2-甲基苯基）乙烯基）乙酰胺，1.5 mmol 的氯二氟乙酸酐，最后加入5 mL的溶剂，于60 ℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以石油醚为洗脱剂，通过硅胶柱层析分离得到4-（氯二氟甲基）-2,6-二邻甲苯基吡啶 (分离产率52%). 1H NMR (400 MHz, CDCl3) δ 7.67 (s, 2H), 7.55 (d, J= 7.2 Hz, 2H), 7.46 – 7.32 (m, 6H), 2.52 (s, 6H). 19F NMR (376 MHz, CDCl3) δ -51.7 (s, 3F). 13C NMR (101 MHz, CDCl3) δ 160.9 (s), 144.4 (t, J = 27.7 Hz),139.5 (s), 136.0 (s), 131.0 (s), 129.9 (s), 128.9 (s), 126.1 (s), 125.3 (t, J= 290.2 Hz), 20.6 (s). GC-MS m/z 343 (M+).
实施例21
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-（2-甲基苯基）乙烯基）乙酰胺，1.5 mmol 的五氟丙酸酐，最后加入5 mL的溶剂，于120 ℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以正戊烷和乙酸乙酯为洗脱剂，通过硅胶柱层析分离得到4-（五氟乙基）-2,6-二邻甲苯基吡啶 (分离产率22%). 1H NMR (400 MHz, CDCl3) δ 7.62 (s, 2H),7.53 (d, J = 7.2 Hz, 2H), 7.42 – 7.32 (m, 6H), 2.48 (s, 6H). 19F NMR (376 MHz,CDCl3) δ -84.4 (s, 3F), -116.7 (s, 2F). 13C NMR (101 MHz, CDCl3) δ 160.7 (s),139.30 (s), 137.4 (t, J = 24.6 Hz), 135.9 (s), 131.0 (s), 129.9 (s), 129.0(s), 126.1 (s), 118.9 (qt, J = 286.5, 38.1 Hz), 118.7 (t, J = 5.8 Hz), 112.5(tq, J = 256.5, 38.4 Hz), 20.51 (s). GC-MS m/z 377 (M+).
实施例22
氮气保护气氛下，在一个置有聚四氟乙烯磁力搅拌子的25 mL反应管中，加入1.0mmol 的N-（1-（4-氟苯基）乙烯基）乙酰胺，1.5 mmol 的七氟丁酸酐，最后加入5 mL的溶剂，于100 ℃油浴条件下在密闭体系中搅拌反应24 h后冷却至室温，将反应混合物用乙酸乙酯稀释，用饱和 NaHCO3 溶液和饱和食盐水洗涤，有机相用无水 MgSO4 干燥，过滤并通过旋转蒸发除去溶剂，以正戊烷和乙酸乙酯为洗脱剂，通过硅胶柱层析分离得到2,6-双（4-氟苯基）-4-（全氟丙基）吡啶 (分离产率14%). 1H NMR (400 MHz, CDCl3) δ 8.18 (dd, J =7.3, 5.9 Hz, 4H), 7.81 (s, 2H), 7.25 (t, J = 8.3 Hz, 4H). 19F NMR (376 MHz,CDCl3) δ -79.9 (t, J = 9.8 Hz，3F), -111.2 – -111.3 (m, 1F), -113.8 (qd, J =9.3, 3.2 Hz, 2F), -126.2 (s, 3F). 13C NMR (101 MHz, CDCl3) δ 164.11 (d, J =250.2 Hz), 157.08 (s), 138.93 (t, J = 24.7 Hz), 134.18 (d, J = 3.1 Hz),129.09 (d, J = 8.5 Hz), 118.1 (qt, J = 288.6, 34.4 Hz), 116.0 (d, J = 21.7Hz), 115.4 (tt, J = 255.3, 30.7 Hz), 115.1 (t, J = 6.0 Hz). 108.8 (tq, J =264.7, 37.8 Hz). GC-MS m/z 435 (M+).
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。

Claims (5)

1.一种合成4-多氟烷基-2,6-二芳基取代吡啶化合物的方法，其特征在于：N-(1-苯基乙烯基)乙酰胺作为底物，多氟烷基羧酸酐作为多氟烷基源，在不添加任何催化剂的条件下，一步合成4-多氟烷基-2,6-二芳基取代吡啶化合物，结构式为：
Figure FDA0003518144970000021
Figure FDA0003518144970000031
Figure FDA0003518144970000041
Figure FDA0003518144970000042
中的任一种。
2.根据权利要求1所述的方法，其特征在于：N-(1-苯基乙烯基)乙酰胺为下述式1-式20中的任意一种：
Figure FDA0003518144970000051
3.根据权利要求1所述的方法，其特征在于：具体合成步骤如下：在氮气气氛中，N-(1-苯基乙烯基)乙酰胺和多氟烷基羧酸酐混合，边磁力搅拌边加入溶剂，60-100℃反应1-24h，用乙酸乙酯稀释，依次用饱和NaHCO3溶液和饱和食盐水洗涤，有机相用无水MgSO4干燥，过滤，旋蒸除去溶剂，纯化，得到4-多氟烷基-2,6-二芳基取代吡啶化合物。
4.根据权利要求3所述的方法，其特征在于：所述溶剂为乙腈、1,2-二氯乙烷、甲苯中的任意一种。
5.根据权利要求3所述的方法，其特征在于：N-(1-苯基乙烯基)乙酰胺，多氟烷基羧酸酐、溶剂的摩尔比为(0.2-1):(0.3-1.5):(13-65)。
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