CN108586334A - 一种无过渡金属催化的2-卤代吡啶化合物的制备方法 - Google Patents
一种无过渡金属催化的2-卤代吡啶化合物的制备方法 Download PDFInfo
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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
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- 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
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
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Abstract
本发明提供了一种无过渡金属催化的2‑卤代吡啶化合物的制备方法。2‑卤代吡啶化合物是许多药物和生物活性分子的重要组成部分，在有机合成及药物化学等领域有着重要的应用，具有广阔的市场前景。本项目涉及一种无过渡金属催化的2‑卤代吡啶化合物的制备方法，该方法以吡啶‑2‑甲酸及其衍生物和NaF、KF、CsF、TBAF、NaCl、KCl、CsCl、TBAC、NCS、NaBr、KBr、CsBr、Br2、TBAB、NBS、NaI、KI、CsI、I2、NIS为原料，在碱及促进剂的存在下，在温和的条件下合成2‑卤代吡啶化合物。该发明专利的方法具有步骤简单、原料易得、反应条件温和等优点。本发明具有较大的使用价值和社会经济效益。
Description
技术领域
本发明涉及医药化工中间体的制备方法，涉及一种2-卤代吡啶化合物的制备方法。
背景技术
2-卤代吡啶化合物不但是医药、农药、染料、功能材料、香料和天然产物等重要结构组成部分，而且也是有机合成重要的中间体。制备2-卤代吡啶化合物的方法有很多种，最经典方法有两种，一是利用2-羟基吡啶与POCl3、CBr4的反应，但反应条件比较苛刻，需要较高的反应温度，使该反应受到一定限制[J.Org. Chem.,2011,76,4149-4153；TetrahedronLetters.,2012,53,647-677]。二是以吡啶氮氧化物为原料与Cl3CCN、POBr3为卤源，但此方法选择性差，使得此类反应应用性差[Tetrahedron.,2016,72,4604-4607；Eur.J.Org.Chem.,2016, 1606-1611]。
相比于以往使用羟基吡啶、吡啶氮氧化物或溴代吡啶为原料来合成氯代吡啶，使用廉价、稳定易存储且更为绿色的吡啶-2-甲酸衍生物为原料更具优势。有关于过渡金属催化羧酸脱羧卤代反应有很多，但或多或少都存在着一定的缺陷[J.Am.Chem.Soc.2012,134,4258-4263；J.Org.Chem.,2016,81,2794.J.Am. Chem.Soc.2017,134,11527-11536]，如：使用贵金属催化剂钯、银等或有毒的汞催化剂，反应温度过高，底物范围狭窄，仅适用于芳基羧酸等。并且有关于吡啶羧酸的脱羧卤代还无人报道，因此开发一种无过渡金属催化体系来实现吡啶 -2-甲酸衍生物的脱羧氯代反应具有重要意义和潜在的应用价值。
发明内容
本发明的目的是提供一种步骤简单、原料易得的合成2-卤代吡啶化合物的新方法。该方法条件温和，没有过渡金属参与，经济又环保。
本发明的技术方案：
一种无过渡金属催化的2-卤代吡啶化合物的制备方法，步骤如下：
以吡啶-2-甲酸及其衍生物和卤源为原料，在促进剂和碱的存在下，构建一系列含C-X键的2-卤代吡啶化合物，反应式如下：
式中：R选自氢、烷基、苯基、氟、氯、溴、碘、甲氧基、硝基、萘环、三氟甲基和酯基中的一种。
在上述制备方法的反应中，所用的促进剂为tBuOCl、TBHP、DTBP、AIBN 中的一种或两种以上混合，其加入量为吡啶-2-甲酸及其衍生物的100～300 mol％。
在上述制备方法的反应中，所用的卤源为NaF、KF、CsF、TBAF、NaCl、 KCl、CsCl、TBAC、NCS、NaBr、KBr、CsBr、Br2、TBAB、NBS、NaI、KI、CsI、I2、NIS中的一种或两种以上混合，其加入量为吡啶-2-甲酸及其衍生物的 100～300mol％。
在上述制备方法的反应中，所用的碱为碳酸钾、碳酸钠、碳酸铯、碳酸氢钠、氢氧化钠、磷酸钾、三乙胺中的一种或两种以上混合，其加入量为吡啶-2- 甲酸及其衍生物的10～200mol％。
在上述制备方法的反应中，所述有机溶剂为CH2Cl2、CH2Br2、CHCl3、CCl4、 CH2I2、THF、CHCl3、CCl4、CH3CN、acetone、1,4-dioxane、toluene、benzene、 DMF、DMSO、DMA、EtOH中的一种或两种以上混合，吡啶-2-甲酸及其衍生物在有机溶剂中的摩尔浓度为0.01mmol/mL～2mmol/mL。
在上述制备方法的反应中，反应温度为25～150℃；反应时间为2～20h。
本发明的有益效果：2-卤代吡啶化合物是许多药物和生物活性分子的重要组成部分，在有机合成及药物化学等领域有着重要的应用，具有广阔的市场前景。本发明的合成方法，该方法具有步骤简单、条件温和、原料易得等优点。本发明具有较大的使用价值和社会经济效益。
附图说明
图1为化合物2a的1H-NMR谱图。
图2为化合物2a的13C-NMR谱图。
图3为化合物2b的1H-NMR谱图。
图4为化合物2b的13C-NMR谱图。
图5为化合物2c的1H-NMR谱图。
图6为化合物2c的13C-NMR谱图。
图7为化合物2d的1H-NMR谱图。
图8为化合物2d的13C-NMR谱图。
图9为化合物2e的1H-NMR谱图。
图10为化合物2e的13C-NMR谱图。
图11为化合物2f的1H-NMR谱图。
图12为化合物2f的13C-NMR谱图。
图13为化合物2g的1H-NMR谱图。
图14为化合物2g的13C-NMR谱图。
图15为化合物2h的1H-NMR谱图。
图16为化合物2h的13C-NMR谱图。
图17为化合物2i的1H-NMR谱图。
图18为化合物2i的13C-NMR谱图。
图19为化合物2j的1H-NMR谱图。
图20为化合物2j的13C-NMR谱图。
具体实施方式
下面结合实施例子进一步说明本发明以及本发明方法进行的方式。这些实施例子仅是为了进一步阐述本发明而非本发明的保护范围仅限于此。
实施例1：2-chloroquinoline(2a)的合成
称取喹啉-2-甲酸(51.9mg,0.3mmol)、碳酸钠(16.0mg,0.15mmol)，NaCl (26.3mg,0.45mmol)、次氯酸叔丁酯(102μL,0.9mmol)到25mL的Schlenk反应瓶中，然后加入CH2Cl2(2mL)置于60℃油浴中反应5h。反应结束后，减压除去溶剂，使用石油醚/乙酸乙酯作为洗脱剂，硅胶柱分离，2-氯喹啉的收率为 82％。
1H NMR(400MHz,CDCl3):δ8.06(d,J＝8.6Hz,1H),8.00(d,J＝8.5Hz,1H), 7.78(d,J＝8.1Hz,1H),7.75–7.67(m,1H),7.53(t,J＝7.5Hz,1H),7.34(d,J＝8.6 Hz,1H)；13C NMR(100MHz,CDCl3):δ150.6,147.9,138.9,130.6,128.6,127.6, 127.0,126.8,122.3.
实施例2：2-chloropyridine(2b)的合成
称取吡啶-2-甲酸(36.9mg,0.3mmol)、碳酸钾(4.2mg,0.03mmol)，NCS (60.1mg,0.45mmol)、次氯酸叔丁酯(68μL,0.6mmol)到25mL的Schlenk反应瓶中，然后加入CH2Cl2(2mL)置于150℃油浴中反应10h。反应结束后，减压除去溶剂，使用石油醚/乙酸乙酯作为洗脱剂，硅胶柱分离，2-氯吡啶的收率为68％。
1H NMR(400MHz,CDCl3):δ8.40(dd,J＝4.8,1.8Hz,1H),7.66(td,J＝7.7,2.0 Hz,1H),7.34(d,J＝8.0Hz,1H),7.23(ddd,J＝7.3,4.9,0.7Hz,1H)；13C NMR(100 MHz,CDCl3):δ151.61,149.81,138.69,124.47,122.23.
实施例3：2-chloro-3-phenylpyridine(2c)的合成
称取3-苯基吡啶-2-甲酸(56.7mg,0.3mmol)、碳酸钠(32.0mg,0.3mmol)，NaCl(26.3mg,0.45mmol)、TBHP(102μL,0.9mmol)到25mL的Schlenk反应瓶中，然后加入THF(2mL)置于80℃油浴中反应20h。反应结束后，减压除去溶剂，使用石油醚/乙酸乙酯作为洗脱剂，硅胶柱分离，2-氯吡啶的收率为91％。1H NMR(400MHz,CDCl3):δ8.38(s,1H),7.80–7.57(m,1H),7.44(d,J＝5.7Hz, 5H),7.29(dd,J＝11.4,6.6Hz,1H)；13C NMR(100MHz,CDCl3):δ149.7,148.4, 139.7,137.5,137.0,129.3,128.4,122.6.
实施例4：2-chloro-3-methylpyridine(2d)的合成
称取3-甲基吡啶-2-甲酸(56.7mg,0.3mmol)、氢氧化钠(16.0mg,0.15 mmol)，TBAC(26.3mg,0.45mmol)、DTBP(165μL,0.9mmol)到25mL的 Schlenk反应瓶中，然后加入CH3CN(0.5mL)置于50℃油浴中反应20h。反应结束后，减压除去溶剂，使用石油醚/乙酸乙酯作为洗脱剂，硅胶柱分离，2-氯 -3-甲基吡啶的收率为70％。
1H NMR(400MHz,CDCl3):δ8.54(d,J＝5.8Hz,1H),7.98-7.96(m,2H),7.52(s, 1H),7.47-7.37(m,3H),7.04(d,J＝5.8Hz,1H),2.38(s,3H)；13C NMR(100MHz, CDCl3):δ157.4,149.4,147.8,139.5,128.8,128.8,126.9,123.1,121.5,21.2.
实施例5：2,3-dichloropyridine(2e)的合成
称取3-氯吡啶-2-甲酸(47.3mg,0.3mmol)、碳酸氢钠(50.4mg,0.6mmol)， NaCl(52.7mg,0.9mmol)、次氯酸叔丁酯(102μL,0.9mmol)到25mL的Schlenk 反应瓶中，然后加入CH2Cl2(10mL)置于30℃油浴中反应20h。反应结束后，减压除去溶剂，使用石油醚/乙酸乙酯作为洗脱剂，硅胶柱分离，2,3-二氯吡啶的收率为50％。
1H NMR(400MHz,CDCl3):δ8.51(s,1H),7.97(d,J＝7.2Hz,2H),7.61(d,J＝ 8.0Hz,1H),7.53-7.42(m,3H),7.40-7.35(m,1H),2.34(s,3H)；13C NMR(100 MHz,CDCl3):δ154.8,150.1,139.4,137.3,131.6,128.7,128.6,126.7,120.0,18.2.
实施例6：2-chloro-3-(trifluoromethyl)pyridine的合成
称取3-氯吡啶-2-甲酸(57.3mg,0.3mmol)、三乙胺(30.1mg,0.3mmol)， NaCl(35.1mg,0.6mmol)、AIBN(147.8,0.9mmol)到25mL的Schlenk反应瓶中，然后加入DMF(0.2mL)置于25℃油浴中反应20h。反应结束后，减压除去溶剂，使用石油醚/乙酸乙酯作为洗脱剂，硅胶柱分离，3-三氟甲基-2-氯吡啶的收率为65％。
1H NMR(400MHz,CDCl3):δ8.59(d,J＝4.5Hz,1H),8.04(d,J＝7.6Hz,1H), 7.39(dd,J＝7.7,5.0Hz,1H)；13C NMR(100MHz,CDCl3):δ152.4,136.6,136.6, 123.5,122.0,120.8.
实施例7：2-chloro-3-nitropyridine(2g)的合成
称取3-硝基吡啶-2-甲酸(50.4mg,0.3mmol)、碳酸钠(64.0mg,0.6mmol)， NaCl(17.6mg,0.3mmol)、次氯酸叔丁酯(32μL,0.3mmol)到25mL的Schlenk 反应瓶中，然后加入CH2Cl2(3mL)置于25℃油浴中反应20h。反应结束后，减压除去溶剂，使用石油醚/乙酸乙酯作为洗脱剂，硅胶柱分离，2-氯-3-硝基吡啶的收率为58％。
1H NMR(400MHz,CDCl3):δ8.64(dd,J＝4.7,1.6Hz,1H),8.24(dd,J＝8.0,1.6 Hz,1H),7.48(dd,J＝8.0,4.7Hz,1H)；13C NMR(100MHz,CDCl3):δ152.4,148.9, 143.6,134.2,122.9.
实施例8：2-chloro-4-methylpyridine(2h)的合成
称取4-甲基-2-吡啶甲酸(50.4mg,0.3mmol)、碳酸钠(64.0mg,0.6mmol)， NaCl(17.6mg,0.3mmol)、次氯酸叔丁酯(32μL,0.3mmol)到25mL的Schlenk 反应瓶中，然后加入toluene(5mL)置于80℃油浴中反应20h。反应结束后，减压除去溶剂，使用石油醚/乙酸乙酯作为洗脱剂，硅胶柱分离，4-甲基-2-氯吡啶的收率为71％。
1H NMR(400MHz,CDCl3):δ8.24(d,J＝5.1Hz,1H),7.16(s,1H),7.03(d,J＝5.0 Hz,1H),2.35(s,3H)；13C NMR(100MHz,CDCl3):δ151.5,150.4,149.3,124.9, 20.8.
实施例9：methyl 6-chloronicotinate(2g)的合成
称取5-甲脂基吡啶-2-甲酸(54.3mg,0.3mmol)、碳酸钠(64.0mg,0.6mmol)， NaCl(17.6mg,0.3mmol)、次氯酸叔丁酯(32μL,0.3mmol)到25mL的Schlenk 反应瓶中，然后加入CH2Cl2(1mL)置于100℃油浴中反应20h。反应结束后，减压除去溶剂，使用石油醚/乙酸乙酯作为洗脱剂，硅胶柱分离，2-氯-3-硝基吡啶的收率为30％。
1H NMR(400MHz,CDCl3):δ9.00(d,J＝2.2Hz,1H),8.25(dd,J＝8.3,2.4Hz, 1H),7.42(d,J＝8.3Hz,1H)；13C NMR(100MHz,CDCl3):δ164.9,155.7,151.2, 139.6,125.0,124.2,52.6.
实施例10：2-bromoquinoline(2j)的合成
称取喹啉-2-甲酸(51.9mg,0.3mmol)、碳酸钠(64.0mg,0.6mmol)，NaBr(17.6 mg,0.3mmol)、次氯酸叔丁酯(32μL,0.3mmol)到25mL的Schlenk反应瓶中，然后加入CH2Br2(2mL)置于60℃油浴中反应20h。反应结束后，减压除去溶剂，使用石油醚/乙酸乙酯作为洗脱剂，硅胶柱分离，2-溴喹啉的收率为75％。1H NMR(400MHz,CDCl3):δ8.03(d,J＝8.4Hz,1H),7.97(d,J＝8.4Hz,1H), 7.74–7.70(m,1H),7.58–7.54(m,1H),7.50(d,J＝8.8Hz,1H)；13C NMR(100MHz, CDCl3):δ148.6,141.8,138.4,130.5,128.7,127.7,127.1,127.0,125.8。
Claims (10)
1.一种无过渡金属催化的2-卤代吡啶化合物的制备方法，其特征在于，以吡啶-2-甲酸及其衍生物和卤源为原料，在促进剂和碱的存在下，构建一系列含C-X键的2-卤代吡啶化合物，反应式如下：
式中：R选自氢、烷基、苯基、氟、氯、溴、碘、甲氧基、硝基、萘环、三氟甲基和酯基中的一种。
2.根据权利要求1所述的制备方法，其特征在于，所述的卤源为NaF、KF、CsF、TBAF、NaCl、KCl、CsCl、TBAC、NCS、NaBr、KBr、CsBr、Br2、TBAB、NBS、NaI、KI、CsI、I2、NIS中的一种或两种以上混合，其加入量为吡啶-2-甲酸及其衍生物的100～300mol％。
3.根据权利要求1或2所述的制备方法，其特征在于，所述的碱为碳酸钾、碳酸钠、碳酸铯、碳酸氢钠、氢氧化钠、磷酸钾、三乙胺中的一种或两种以上混合，其加入量为吡啶-2-甲酸及其衍生物的10～200mol％。
4.根据权利要求3所述的制备方法，其特征在于，所述的促进剂为tBuOCl、TBHP、DTBP、AIBN中的一种或两种以上混合，其加入量为吡啶-2-甲酸及其衍生物的100～300mol％。
5.根据权利要求1、2或4所述的制备方法，其特征在于，所述的有机溶剂为CH2Cl2、CH2Br2、CHCl3、CCl4、CH2I2、THF、CHCl3、CCl4、CH3CN、acetone、1,4-dioxane、toluene、benzene、DMF、DMSO、DMA、EtOH中的一种或两种以上混合，吡啶-2-甲酸及其衍生物在有机溶剂中的摩尔浓度为0.01mmol/mL～2mmol/mL。
6.根据权利要求3所述的制备方法，其特征在于，所述的有机溶剂为CH2Cl2、CH2Br2、CHCl3、CCl4、CH2I2、THF、CHCl3、CCl4、CH3CN、acetone、1,4-dioxane、toluene、benzene、DMF、DMSO、DMA、EtOH中的一种或两种以上混合，吡啶-2-甲酸及其衍生物在有机溶剂中的摩尔浓度为0.01mmol/mL～2mmol/mL。
7.根据权利要求1、2、4或6所述的制备方法，其特征在于，反应温度为25～150℃。
8.根据权利要求3所述的制备方法，其特征在于，反应温度为25～150℃。
9.根据权利要求5所述的制备方法，其特征在于，反应温度为25～150℃。
10.根据权利要求1、2、4、6、8或9所述的合成方法，其特征在于，反应时间为2～20h。
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| CN109836376A (zh) * | 2019-04-10 | 2019-06-04 | 江苏汉阔生物有限公司 | 一种以2，3-吡啶二羧酸为原料制备2-氯代烟酸的方法 |
| CN113717099A (zh) * | 2021-08-03 | 2021-11-30 | 四川大学 | 一种含氮杂环化合物溴代反应的方法及应用 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109836376A (zh) * | 2019-04-10 | 2019-06-04 | 江苏汉阔生物有限公司 | 一种以2，3-吡啶二羧酸为原料制备2-氯代烟酸的方法 |
| CN109836376B (zh) * | 2019-04-10 | 2022-03-22 | 江苏汉阔生物有限公司 | 一种以2，3-吡啶二羧酸为原料制备2-氯代烟酸的方法 |
| CN113717099A (zh) * | 2021-08-03 | 2021-11-30 | 四川大学 | 一种含氮杂环化合物溴代反应的方法及应用 |
| CN113717099B (zh) * | 2021-08-03 | 2023-06-27 | 四川大学 | 一种含氮杂环化合物溴代反应的方法及应用 |
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