CN103664747A - 一种杂环联苯类化合物的制备方法 - Google Patents

一种杂环联苯类化合物的制备方法 Download PDF

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CN103664747A
CN103664747A CN201310684378.3A CN201310684378A CN103664747A CN 103664747 A CN103664747 A CN 103664747A CN 201310684378 A CN201310684378 A CN 201310684378A CN 103664747 A CN103664747 A CN 103664747A
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汤娜娜
刘雷芳
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Dezhou University
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    • C07D213/00—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
    • 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
    • C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
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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
    • C07D213/06—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/16—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 containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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    • C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
    • C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
    • C07D215/04—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to the ring carbon atoms
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Abstract

本发明公开了一种杂环联苯类化合物的制备方法。它是将0.5mmol的溴代杂环芳烃，0.6mmol的芳基三氟硼酸钾，1mmol的碱，1-2mol％的醋酸钯于反应器中，加入3mL水和3g聚乙二醇，在80℃-100℃下搅拌4-15h小时，用乙醚萃取，旋干溶剂后，分离即得产品。本发明的优点：1)选择水和聚乙二醇作为反应介质，无有机溶剂参与，对环境无污染，为绿色反应体系；2)该方法不需要任何配体或惰性气体的保护，在空气中能很好的进行；3)该反应在温和的条件下进行，反应时间短，反应产率高，经过简单的乙醚萃取就能达到产物和反应体系的分离；4)该方法可以允许多种溴代杂环芳烃参与反应。

Description

一种杂环联苯类化合物的制备方法
技术领域
本发明涉及一种杂环联苯类化合物的制备方法。
背景技术
杂环联苯类化合物是药物分子中常见的结构单元，通常具有一些特殊的生物活性。因此对于杂环联苯类化合物的构建一直是金属有机化学研究的重点内容。其中，通过溴代杂环芳烃与有机硼酸的Suzuki偶联反应成为制备该类化合物的重要方法之一。然而，研究发现，有机硼酸具有明显的缺点：1)常以二聚或三聚硼酸酯的形式存在，导致有机硼酸难以纯化和难以定量；2)易于发生自身偶联反应，因此反应中常需要过量的有机硼酸的参与；3)对一些常规的合成条件敏感，不适合存在于底物结构的修饰中。
芳基三氟硼酸钾是有机硼试剂的一种，研究发现，该类物质能够克服有机硼酸以上缺点，逐渐成为有机硼酸的理想替代物。然而通过溴代杂环芳烃与芳基三氟硼酸钾的Suzuki反应来制备杂环联苯类化合物的方法却较少，尤其是以水作为介质的绿色合成方法。
2003年，Molander研究小组首次报道了Pd(OAc)2/K2CO3/H2O中溴代杂环芳烃与芳基三氟硼酸钾的反应，为合成杂环联苯类化合物提供了一种绿色合成方法(Molander,G.A.，Biolatto，B.J.Org.Chem.，2003，68，4302-4314.)。然而，该方法却对溴代杂环芳烃有特殊的结构要求，该底物中必须含有-COOH。2008年，Nájera小组也发展了一种纯水中合成杂环联苯类化合物的方法，然而在该反应体系却需要TBAB和配体的参与，限制了该方法在实际中的应用(Alacid，E.，Nájera，C.Org.Lett.，2008，10，5011-5014.)。尽管文献中也有水/有机溶剂体系中也有杂环联苯类化合物合成的报道，然而，这些催化体系中一些特殊条件的使用也限制了这些方法的进一步应用(Molander，G.A.，Rivero，M.R.Org.Lett.，2002，4，107-109.Molander，G.A.，Beaumard，F.Org.Lett.，2010，12，4022-4025.Chow,W.K.，So，C.M.，Lau，C.P.，Kwong，F.Y.J.Org.Chem.，2010，75，5109-5112.)。
发明内容
本发明的目的是提供一种杂环联苯类化合物的制备方法。
它是将0.5mmol的溴代杂环芳烃，0.6mmol的芳基三氟硼酸钾，1mmol的碱，1-2mol％的醋酸钯于反应器中，加入3mL水和3g聚乙二醇，在80℃-100℃下搅拌4-15h小时，用乙醚萃取，旋干溶剂后，分离即得产品。
本发明的优点：
1)选择水和聚乙二醇作为反应介质，无有机溶剂参与，对环境无污染，为绿色反应体系；
2)该方法不需要任何配体或惰性气体的保护，在空气中能很好的进行；
3)该反应在温和的条件下进行，反应时间短，反应产率高，经过简单的乙醚萃取就能达到产物和反应体系的分离；
4)该方法可以允许多种溴代杂环芳烃参与反应。
具体实施方式
本发明采用水和聚乙二醇作为反应溶剂，在碱作用和醋酸钯的存在下，无需配体和惰性气体的保护，溴代杂环芳烃和芳基三氟硼酸钾发生交叉偶联反应，得到各种不同的杂环芳基-芳基联苯类化合物。反应基本的方程式为：
Figure BSA0000098996540000021
其中，溴代杂环芳烃为2-溴吡啶、3-溴吡啶、5-溴嘧啶、2-溴吡嗪、3-溴喹啉、4-溴异喹啉、3-溴噻吩、2-溴噻吩。聚乙二醇为聚乙二醇400、聚乙二醇600、聚乙二醇1000、聚乙二醇2000、聚乙二醇4000或聚乙二醇6000。芳基三氟硼酸钾为苯基三氟硼酸钾。碱为碳酸钾、碳酸钠、磷酸钾、氢氧化钾或氢氧化钠。反应温度为80℃-100℃，反应时间为4-15小时。醋酸钯的用量为1-2mol％。
以下实施例将有助于理解本发明，但不限于本发明的内容：
实施例1
称取0.5mmol的2-溴吡啶，0.6mmol的PhBF3K，1mmol的碳酸钠，1mol％的醋酸钯于25mL的小烧瓶中，加入3mL水和3g聚乙二醇2000，在80℃下搅拌4h。反应结束后，用4×10mL的乙醚萃取。旋干溶剂后，用石油醚/乙酸乙酯进行柱分离可以得到分析纯的样品，产率为75％。
Figure BSA0000098996540000022
1H NMR(400MHz，DMSO)δ8.66(m，1H)，8.02-8.15(m，2H)，7.91-8.00(m，1H)，7.86(m，1H)，7.46-7.54(m，2H)，7.43(m，1H).MS(EI)：m/e(％)155(100)，127(19)，77(22)，63(5)，51(14).
实施例2
称取0.5mmol的3-溴吡啶，0.6mmol的PhBF3K，1mmol的碳酸钠，1mol％的醋酸钯于25mL的小烧瓶中，加入3mL水和3g聚乙二醇2000，在80℃下搅拌8h。反应结束后，用4×10mL的乙醚萃取。旋干溶剂后，用石油醚/乙酸乙酯进行柱分离可以得到分析纯的样品，产率为87％。
Figure BSA0000098996540000031
1H NMR(400MHz，DMSO)δ8.90(d，J＝2.0Hz，1H)，8.58(m，1H)，8.00-8.15(m，1H)，7.73(m，2H)，7.46-7.55(m，3H)，7.36-7.46(m，1H).MS(EI)：m/e(％)155(100)，127(15)，102(11)，76(10).
实施例3
称取0.5mmol的3-溴喹啉，0.6mmol的PhBF3K，1mmol的碳酸钠，1mol％的醋酸钯于25mL的小烧瓶中，加入3mL水和3g聚乙二醇2000，在80℃下搅拌4h。反应结束后，用4×10mL的乙醚萃取。旋干溶剂后，用石油醚/乙酸乙酯进行柱分离可以得到分析纯的样品，产率为96％。
Figure BSA0000098996540000032
1H NMR(300MHz，CDCl3)δ9.20(d，J＝3.0Hz，1H)，8.31(d，J＝1.9Hz，1H)，8.16(d，J＝8.4Hz，1H)，7.89(d，J＝7.5Hz，1H)，7.74(m，3H)，7.48-7.65(m，3H)，7.38-7.48(m，1H).MS(EI)：m/e(％)205(100)，176(12)，151(8)，102(15)，88(13)，76(28)，51(5).
实施例4
称取0.5mmol的4-溴异喹啉，0.6mmol的PhBF3K，1mmol的碳酸钠，1mol％的醋酸钯于25mL的小烧瓶中，加入3mL水和3g聚乙二醇2000，在100℃下搅拌15h。反应结束后，用4×10mL的乙醚萃取。旋干溶剂后，用石油醚/乙酸乙酯进行柱分离可以得到分析纯的样品，产率为70％。
Figure BSA0000098996540000033
1H NMR(400MHz，CDCl3)δ9.26(s，1H)，8.49(s，1H)，8.03(d，J＝7.6Hz，1H)，7.92(d，J＝8.2Hz，1H)，7.57-7.72(m，2H)，7.40-7.58(m，5H).MS(EI)：m/e(％)205(100)，176(20)，151(9)，102(23)，88(21)，76(15).
实施例5
称取0.5mmol的2-溴噻吩，0.6mmol的PhBF3K，1mmol的碳酸钠，1mol％的醋酸钯于25mL的小烧瓶中，加入3mL水和3g聚乙二醇2000，在80℃下搅拌4h。反应结束后，用4×10mL的乙醚萃取。旋干溶剂后，用石油醚/乙酸乙酯进行柱分离可以得到分析纯的样品，产率为85％。
Figure BSA0000098996540000041
1H NMR(400MHz，CDCl3)δ7.61-7.65(m，2H)，7.38(t，J＝7.6Hz，2H)，7.23-7.33(m，3H)，7.08(m，1H).MS(EI)：m/e(％)160(100)，128(14)，115(42)，63(6)，39(6).

Claims (7)

1.一种杂环联苯类化合物的制备方法，其特征在于：它是将0.5mmol的溴代杂环芳烃，0.6mmol的芳基三氟硼酸钾，1mmol的碱，1-2mol％的醋酸钯于反应器中，加入3mL水和3g聚乙二醇，在80℃-100℃下搅拌4-15h小时，用乙醚萃取，旋干溶剂后，分离即得产品。
2.根据权利要求1所述的一种杂环联苯类化合物的制备方法，其特征在于：所述的溴代杂环芳烃为2-溴吡啶、3-溴吡啶、5-溴嘧啶、2-溴吡嗪、3-溴喹啉、4-溴异喹啉、3-溴噻吩、2-溴噻吩。
3.根据权利要求1所述的一种杂环联苯类化合物的制备方法，其特征在于：所述的芳基三氟硼酸钾为苯基三氟硼酸钾。
4.根据权利要求1所述的一种杂环联苯类化合物的制备方法，其特征在于：所述的聚乙二醇为聚乙二醇400、聚乙二醇600、聚乙二醇1000、聚乙二醇2000、聚乙二醇4000或聚乙二醇6000。
5.根据权利要求1所述的一种杂环联苯类化合物的制备方法，其特征在于：所述的碱为碳酸钾、碳酸钠、磷酸钾、氢氧化钾或氢氧化钠。
6.根据权利要求1所述的一种杂环联苯类化合物的制备方法，其特征在于：所述的反应温度为80℃，反应时间为4小时。
7.根据权利要求1所述的一种杂环联苯类化合物的制备方法，其特征在于：所述的醋酸钯的用量为1-2mol％。
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CN110359097A (zh) * 2019-07-08 2019-10-22 上海药明康德新药开发有限公司 DNA编码化合物库构建中通过Suzuki偶联反应得到On-DNA芳烃化合物的方法
CN110359097B (zh) * 2019-07-08 2022-09-20 上海药明康德新药开发有限公司 DNA编码化合物库构建中通过Suzuki偶联反应得到On-DNA芳烃化合物的方法

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