CN103755631B - 吡啶衍生物的直接芳香化工艺 - Google Patents

吡啶衍生物的直接芳香化工艺 Download PDF

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CN103755631B
CN103755631B CN201410006894.5A CN201410006894A CN103755631B CN 103755631 B CN103755631 B CN 103755631B CN 201410006894 A CN201410006894 A CN 201410006894A CN 103755631 B CN103755631 B CN 103755631B
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黄一波
李东升
管丹
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CHANGZHOU XIAOGUO INFORMATION SERVICES Co.,Ltd.
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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Abstract

本发明涉及芳香类吡啶衍生物的制备工艺技术领域，具体涉及一种吡啶衍生物的直接芳香化工艺，该工艺流程如下：在烧瓶中依次加入吡啶衍生物、芳硼酸、亚铁盐、三氟乙酸物料，将上述混合物在室温下搅拌均匀，加入过二硫酸盐继续搅拌，反应结束后，将所得产物过滤、萃取、浓缩、分离，即得到吡啶的芳香化衍生物。本发明采用亚铁盐作为催化剂，过二硫酸盐作为氧化剂，利用过二硫酸根氧化亚铁离子反应过程中促使芳硼酸产生芳基自由基，芳基自由基加成到吡啶衍生物中，从而获得相应产物，生产成本较低、反应收率较高，适宜推广使用。

Description

吡啶衍生物的直接芳香化工艺
技术领域
本发明涉及芳香类吡啶衍生物的制备工艺技术领域，具体涉及一种吡啶衍生物的直接芳香化工艺。
背景技术
吡啶衍生物的传统芳香化过程主要有两种，一种是使用RMgX或RLi有机金属试剂，与有机卤化物（C-Y）反应制备芳香化产物，另一种是使用Pd,Rh,Ru等过渡金属的配合物作为催化剂，促进芳基卤与芳硼酸的Suzuki偶联反应。后来，人们又发现了Ag盐与过二硫酸盐组成催化氧化体系，其可促进蒽醌与缺电子吡啶的直接芳香化过程。但是，这些报道的方法需使用昂贵的金属试剂或者有机金属试剂，且一些金属试剂对空气和水蒸气敏感，限制了上述芳香化过程的实际推广应用。
发明内容
本发明所要解决的技术问题是：针对现有技术中的吡啶衍生物的芳香化过程存在的使用昂贵的金属试剂或者有机金属试剂的问题，提供一种生产成本较低、反应收率较高的吡啶衍生物的芳香化过程。
本发明解决其技术问题所采用的技术方案是：一种吡啶衍生物的直接芳香化工艺，其工艺流程如下：
在烧瓶中依次加入吡啶衍生物、芳硼酸、二氯甲烷、水、亚铁盐、三氟乙酸，将上述混合物在室温下搅拌均匀，加入过二硫酸盐，在22-28℃的室温下继续搅拌24-48h；
反应结束后，将所得产物过滤，残渣用二氯甲烷洗涤2-3次；合并二氯甲烷溶液后，再用5%碳酸氢钠水溶液洗涤两次；用无水硫酸镁干燥二氯甲烷溶液，抽滤，取滤液，经旋转蒸发除去二氯甲烷，得到粗品。粗品经硅胶柱（填充200-300目硅胶）柱层析分离，以正己烷：乙酸乙酯体积比为（95：5）到（85：15）的混合溶剂洗脱，即可得到吡啶的芳香化衍生物。
所述吡啶衍生物、芳硼酸、亚铁盐、三氟乙酸和过二硫酸盐的摩尔比为1.0：（1.0～3.0）：（1.0～3.0）：（0.05～0.2）：（1.0～3.0）。
进一步，所述吡啶衍生物为4-氰基吡啶、4-乙酰基吡啶、4-氟吡啶、4-三氟甲基吡啶或异烟酸乙酯；芳硼酸为苯硼酸；所述亚铁盐为硫化亚铁、草酸亚铁、氯化亚铁、硫酸亚铁中的一种、两种或多种的混合物；过二硫酸盐为过二硫酸钾或过二硫酸铵。
有益效果：本发明采用亚铁盐作为催化剂，过二硫酸盐作为氧化剂，利用过二硫酸根氧化亚铁离子反应过程中促使芳硼酸产生芳基自由基，芳基自由基加成到吡啶衍生物中，从而获得相应产物，不使用昂贵的金属试剂或者有机金属试剂，生产成本较低、反应收率较高，适宜推广使用。
具体实施方式
下面结合具体实施例对本发明做进一步说明。
实施例一
4-氰基吡啶的芳香化
在50mL三口烧瓶中，加入4-氰基吡啶4mmol(0.42g)，苯硼酸4.4mmol(0.54g)，二氯甲烷10mL，水10mL，亚铁盐草酸亚铁0.4mmol，三氟乙酸4mmol(0.46g；306μL)，在室温(25℃)搅拌下，加入过二硫酸钾12mmol(3.24g),在室温(25℃)下，继续搅拌24h。
反应结束后，将所得产物过滤，残渣用少量二氯甲烷洗涤2-3次（每次约使用5mL）；合并二氯甲烷溶液后，再用5%碳酸氢钠水溶液洗涤两次；用2g无水硫酸镁干燥二氯甲烷溶液，抽滤，取滤液，所得滤液经旋转蒸发除去二氯甲烷，得到粗品。粗品经普通硅胶柱(含200目-300目硅胶)柱层析分离，以正己烷：乙酸乙酯体积比为85：15的混合溶剂洗脱，即可得到2-苯基-4-氰基吡啶0.54g(收率为75.0%)，3-苯基-4-氰基吡啶0.11g(收率达到15.2%)。
2-苯基-4-氰基吡啶表征数据：1HNMR(400MHz,CDCl3),δ=8.87(d,J=4.8Hz,1H),8.01(d,J=6.3Hz,1H),7.95(s,1H),7.52(J=5.6Hz,1H),7.50(s,2H),7.45(d,J=5.0,1H);13CNMR(100MHz,CDCl3)δ=158.8,150.6,137.3,130.2,129.1,127.0,123.2,122.1,121.2,116.7；
3-苯基-4-氰基吡啶表征数据：1HNMR(400MHz,CDCl3),δ=8.86(s,1H),8.75(J=5.0Hz,1H),7.63(d,J=5.0Hz,1H),7.60-7.52(m,5H);13CNMR(100MHz,CDCl3)δ=151.0,148.7,135.1,134.4,129.6,129.2,128.8,126.1,118.9,116.3。
实施例二
4-氰基吡啶的芳香化
在50mL三口烧瓶中，加入4-氰基吡啶4mmol(0.42g)，苯硼酸4.4mmol(0.54g)，二氯甲烷10mL，水10mL，硫化亚铁0.4mmol，三氟乙酸4mmol(0.46g；306μL)。在室温(25℃)搅拌下，加入过二硫酸铵（2.74g）,在室温(25℃)下，继续搅拌48h。
反应结束后，将所得产物过滤，残渣用少量二氯甲烷洗涤2-3次（每次约使用5mL）；合并二氯甲烷溶液后，再用5%碳酸氢钠水溶液洗涤两次；用2g无水硫酸镁干燥二氯甲烷溶液，抽滤取滤液，滤液经旋转蒸发除去二氯甲烷，得到粗品。粗品经普通硅胶柱(含200目-300目硅胶)柱层析分离，以正己烷：乙酸乙酯体积比为85：15的混合溶剂洗脱，即可得到2-苯基-4-氰基吡啶收率为78.5%，3-苯基-4-氰基吡啶收率为14.3%。2-苯基-4-氰基吡啶和3-苯基-4-氰基吡啶的表征数据同上。
实施例三
4-乙酰基吡啶的芳香化
在50mL三口烧瓶中，加入4-乙酰基吡啶4mmol(0.48g)，苯硼酸4.4mmol(0.54g)，二氯甲烷10mL，水10mL，草酸亚铁0.4mmol，三氟乙酸4mmol(0.46g；306μL)。在室温(25℃)搅拌下，加入过二硫酸钾12mmol(3.24g)，在此温度下，继续搅拌24h。
反应结束后，将所得产物过滤，残渣用少量二氯甲烷洗涤2-3次（每次约使用5mL）；合并所得二氯甲烷溶液后，再用5%碳酸氢钠水溶液洗涤两次；再用2g无水硫酸镁干燥二氯甲烷溶液，抽滤取滤液，滤液经旋转蒸发除去二氯甲烷，得到粗产品。粗产品经普通硅胶柱(含200-300目硅胶)柱层析分离，以正己烷：乙酸乙酯体积比为85：15的混合溶剂洗脱，即可得到4-乙酰基吡啶的芳香化产物2-苯基-4-乙酰基吡啶和3-苯基-4-乙酰基吡啶，2-苯基-4-乙酰基吡啶0.69g，收率为88.2%；3-苯基-4-乙酰基吡啶的收率低于10%。
2-苯基-4-乙酰基吡啶表征数据：1HNMR(400MHz,CDCl3),δ=9.04(d,J=4.8Hz,1H),8.53(s,1H),8.22(d,J=5.6Hz,2H),7.70(d,J=5.0,1H),7.28-7.53(m,3H),2.52(m,3H);13CNMR(100MHz,CDCl3)δ=164.3,157.4,149.3,142.6,137.5,137.9,126.2,125.0,120.2,118.8,117.0,21.5.
3-苯基-4-乙酰基吡啶表征数据：1HNMR(400MHz,CDCl3),δ=8.80(d,J=9.6Hz,1H),8.11(s,1H),7.98(d,J=6.0Hz,1H),7.60(d,J=4.0Hz,2H),7.39-7.46(m,3H),2.54(m,3H);13CNMR(100MHz,CDCl3)δ=157.8,149.6,142.9,137.9,136.1,123.2,122.1,121.2,118.6,117.1,21.8.
实施例四
4-乙酰基吡啶的芳香化
在50mL三口烧瓶中，加入4-乙酰基吡啶4mmol(0.48g)，苯硼酸4.4mmol(0.54g)，二氯甲烷10mL，水10mL，硫化亚铁0.4mmol，三氟乙酸4mmol(0.46g；306μL)。在室温(25℃)搅拌下，加入过二硫酸铵（2.74g），在此温度下，继续搅拌48h。
反应结束后，将所得产物过滤，残渣用少量二氯甲烷洗涤2-3次（每次约使用5mL）；合并所得二氯甲烷溶液后，再用5%碳酸氢钠水溶液洗涤两次；再用2g无水硫酸镁干燥二氯甲烷溶液，抽滤取滤液，滤液经旋转蒸发除去二氯甲烷，得到粗产品。粗产品经普通硅胶柱(含200-300目硅胶)柱层析分离，以正己烷：乙酸乙酯体积比为85：15的混合溶剂洗脱，即可得到4-乙酰基吡啶的芳香化产物2-苯基-4-乙酰基吡啶和3-苯基-4-乙酰基吡啶，2-苯基-4-乙酰基吡啶收率为80.3%；3-苯基-4-乙酰基吡啶的收率为12.4%。2-苯基-4-乙酰基吡啶和3-苯基-4-乙酰基吡啶的表征数据同上。
实施例五
异烟酸乙酯的芳香化
在50mL三口烧瓶中，加入异烟酸乙酯4mmol(0.60g)，苯硼酸4.4mmol(0.54g)，二氯甲烷10mL，水10mL，草酸亚铁0.4mmol，三氟乙酸4mmol(0.46g；306μL)；在室温(25℃)搅拌下，加入过二硫酸钾12mmol(3.24g)。在此温度下，继续搅拌24h。
反应结束后，将所得产物过滤，残渣用少量二氯甲烷洗涤2-3次（每次约使用5mL）。合并所得二氯甲烷层溶液后，再用5%碳酸氢钠水溶液洗涤两次；再用2g无水硫酸镁干燥二氯甲烷溶液，抽滤取滤液，滤液经旋转蒸发除去二氯甲烷，得到粗品；粗产品经普通硅胶柱(含200-300目硅胶)柱层析分离，以正己烷：乙酸乙酯体积比为85：15的混合溶剂洗脱，即可得到芳香化产物，2-苯基异烟酸乙酯0.65g，收率为71.4%；3-苯基异烟酸乙酯0.18g，收率为19.7%。
2-苯基-异烟酸乙酯表征数据：1HNMR(400MHz,CDCl3),δ=8.85(d,J=5.0Hz,1H),8.31(s,1H),8.07(J=8.0Hz,2H),7.80(d,J=5.0Hz,1H),7.45-7.54(m,3H),4.44-4.82(m,2H),1.44-1.46(m,3H);13CNMR(100MHz,CDCl3)δ=164.3,157.4,149.3,137.5,128.4,127.9,126.2,125.0,120.2,118.8,60.9,13.3。
3-苯基-异烟酸乙酯表征数据：1HNMR(400MHz,CDCl3),δ=8.61(d,J=5.0Hz,1H),7.57(d,J=5.0Hz,1H),7.33-7.36(m,3H),7.32-7.33(m,2H),4.04-4.08(m,2H),0.93-0.96(m,3H);13CNMR(100MHz,CDCl3)δ=165.9,149.7,147.3,137.8,136.1,135.4,127.5,127.2,121.8,60.8,13.2。
实施例六
异烟酸乙酯的芳香化
在50mL三口烧瓶中，加入异烟酸乙酯4mmol(0.60g)，苯硼酸4.4mmol(0.54g)，二氯甲烷10mL，水10mL，硫化亚铁0.4mmol，三氟乙酸4mmol(0.46g；306μL)；在室温(25℃)搅拌下，加入过二硫酸铵（2.74g）。在此温度下，继续搅拌48h。
反应结束后，将所得产物过滤，残渣用少量二氯甲烷洗涤2-3次（每次约使用5mL）。合并所得二氯甲烷层溶液后，再用5%碳酸氢钠水溶液洗涤两次；再用2g无水硫酸镁干燥二氯甲烷溶液，抽滤取滤液，滤液经旋转蒸发除去二氯甲烷，得到粗品；粗产品经普通硅胶柱(含200-300目硅胶)柱层析分离，以正己烷：乙酸乙酯体积比为85：15的混合溶剂洗脱，即可得到芳香化产物，2-苯基-异烟酸乙酯，收率为70.5%；3-苯基异烟酸乙酯，收率为20.4%。2-苯基-异烟酸乙酯和3-苯基异烟酸乙酯测试数据同上。

Claims (1)

1.一种4-乙酰基吡啶的芳香化工艺，其特征是：该工艺流程如下：
在烧瓶中加入4-乙酰基吡啶4mmol，苯硼酸4.4mmol，二氯甲烷10mL，水10mL，草酸亚铁0.4mmol，三氟乙酸4mmol，室温下搅拌，加入过二硫酸钾12mmol，继续搅拌24h；反应结束后，将所得产物过滤，残渣用少量二氯甲烷洗涤2-3次；合并所得二氯甲烷溶液后，再用5％碳酸氢钠水溶液洗涤两次；再用2g无水硫酸镁干燥二氯甲烷溶液，抽滤取滤液，滤液经旋转蒸发除去二氯甲烷，得到粗产品；
所述粗产品经含200-300目硅胶的普通硅胶柱柱层析分离，以正己烷：乙酸乙酯体积比为85：15的混合溶剂洗脱，即可得到4-乙酰基吡啶的芳香化产物2-苯基-4-乙酰基吡啶和3-苯基-4-乙酰基吡啶。
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