CN113355684B - 一种电催化下多取代异喹啉盐衍生物的制备方法 - Google Patents
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Abstract
本发明公开了属于有机合成技术领域的一种电催化下多取代异喹啉盐衍生物的制备方法。所述方法为：向反应器中，加入取代2‑苯基吡啶，取代二苯基乙炔，六氟磷酸钾，二氯(五甲基环戊二烯基)合铑(III)二聚体。在溶剂中通过电催化促进反应完毕后，使用旋转蒸发仪浓缩得到粗产物，粗产物使用硅胶柱层析分离得到目标产物。本发明提供的一种电催化下多取代异喹啉盐衍生物的合成方法具有科学合理，合成途径绿色环保，条件温和，操作简便，无需外加氧化剂与添加剂，廉价，并且官能团普适性广等特点。其反应方程式如下：
Description
技术领域
本发明属于有机合成技术领域，具体涉及一种电催化下多取代异喹啉盐衍生物的制备方法。
背景技术
含有杂环季铵盐结构的天然产物在自然界中广泛存在，其衍生物具有多种生物活性以及药用价值：如抗菌、消炎，抗肿瘤、抗白血病等多种生物活性；((a)MedRes.Rev.2011,31,821-862.(b)Chem.Biodivers.2008,5,1335-1344(c)Molecules 2008,13,2462-2473.)黄莲素、黄藤素、药根碱、血根碱、等众多的药物分子中也都存在杂环季铵盐结构。((a)Biochem.Pharmacol.1979,28,1081-1084.(b)Phytother.Res.2003,17,834-837(c)Photochem.Photobiol.1989,50,733-738)
异喹啉盐很可能具备含有杂环季铵盐结构化合物的生物活性以及药用价值。鉴于杂环季铵盐衍生物的广泛的生物活性和应用价值，发展一种快速高效地合成多取代异喹啉盐衍生物的新方法具有重要意义。
合成异喹啉盐衍生物的方法有：
2013年，中国科学院兰州化学物理研究所黄汉民课题组报道了铑催化下取代2-苯基吡啶与取代二苯基乙炔分子间环化合成异喹啉盐衍生物。此方法条件苛刻，温度高，反应时间长，需要外加当量的三氟甲磺酸作为添加剂，金属铑催化剂合成步骤繁琐(J.Am.Chem.Soc.2013,135,8850-8853)反应式见式I：
2016年，台湾清华大学郑建鸿课题组报道了钴催化下取代2-苯基吡啶与取代二苯基乙炔分子间环化合成异喹啉盐衍生物。但是此方法添加了金属银作为氧化剂，加入碳酸氢钠作为添加剂，反应时间长，温度高，条件苛刻。(Angew.Chem.2016,128,1876-1880)反应式见式II：
制备异喹啉盐衍生物的上述方法中具有代价高，反应时间长，需要添加其他金属氧化剂，温度高等缺点。
发明内容
为了克服上述现有技术的不足，作为对现有异喹啉盐衍生物合成方法的补充。本发明提供了一种在电催化促进下绿色快速制备多取代异喹啉盐衍生物的方法，此方法条件温和，操作简便，无需外加氧化剂与添加剂，安全绿色廉价，并且官能团普适性广。
一种电催化下多取代异喹啉盐衍生物的制备方法，所述异喹啉盐衍生物具有式III所示的结构：
R1取代基团选自氢、甲基、胡椒基、苯基、叔丁基、溴；R2取代基团选自甲基、氯；R3取代基团选自甲氧基、氯；特征在于，向反应器中，加入取代2-苯基吡啶0.2mmol、取代二苯基乙炔0.24mmol、六氟磷酸钾0.4mmol、二氯(五甲基环戊二烯基)合铑(III)二聚体0.001mmol，在六氟异丙醇∶水＝(3.75mL:1.25mL)中通过电催化促进反应完毕后，使用旋转蒸发仪浓缩得到粗产物，粗产物使用硅胶柱层析分离得到目标产物，其化学过程见反应式IV：
所述的取代2-苯基吡啶、取代二苯基乙炔、六氟磷酸钾、二氯(五甲基环戊二烯基)合铑(III)二聚体的摩尔比值为1：1.2：2：0.005，所述溶剂为六氟异丙醇∶水＝(3.75mL:1.25mL)，在恒流3mA条件下，通过电催化促进反应进行，反应温度35℃，反应时间为3.5h。
本发明的有益效果为：本发明提供的电催化下多取代异喹啉盐衍生物合成方法科学合理，提供了一种合成多取代异喹啉盐衍生物新途径，通过本方法得到了具有多种取代基的异喹啉盐衍生物，其特点为：条件温和，操作简便，无需外加氧化剂与添加剂，安全绿色廉价，并且官能团普适性广。
附图说明
图1为实施例4制备的化合物3da的NMR图谱；
图2为实施例7制备的化合物3ga的NMR图谱；
图3为实施例10制备的化合物3ac的NMR图谱。
具体实施方式
下面结合附图和具体的实施例对本发明进一步详细的说明：
下述实施例中所述试验方法，如无特殊说明，均为常规方法；所述试剂和材料，如无特殊说明，均可从商业途径获得。
实施例1
1)异喹啉盐衍生物3aa的制备
向10mL三口烧瓶中加入2-苯基吡啶1a(0.2mmol,31.0mg)、二苯基乙炔2b(0.24mmol,42.2mg)、六氟磷酸钾(0.4mmol，38.7mg)、二氯(五甲基环戊二烯基)合铑(III)二聚体(0.001mmol，0.6mg)。用橡胶塞将体系密封，阳极采用石墨毡电极(2cm x 1cm x0.5cm)，阴极采用铂电极(1cm x 1cm x 0.25mm)。加入六氟异丙醇：水(3.75mL:1.25mL)。反应于35℃、3mA电流的条件下反应3.5h。反应完毕后，使用旋转蒸发仪除去溶剂得到粗产物，粗产物经柱层析分离(200-300目硅胶)(二氯甲烷/甲醇＝35/1)，使用旋转蒸发仪除去溶剂，得到目标产物无取代异喹啉盐衍生物3aa，其收率为95％。
谱图解析数据3aa:
1H NMR(500MHz,DMSO-d6)δ9.76(d,J＝8.6Hz,1H),9.36(d,J＝8.3Hz,1H),8.79-8.68(m,2H),8.17-8.03(m,3H),7.53-7.42(m,6H),7.38-7.30(m,3H),7.28-7.24(m,2H).13CNMR(125MHz,DMSO-d6)δ143.69,140.44,138.79,137.33,135.84,134.84,134.62,132.52,131.69,131.44,131.29,130.55,130.37,129.80,128.79,128.72,127.28,126.44,125.19,125.09,123.96.
实施例2
用1b代替实例1中的1a,其它条件同实例1,实验结果见表1。
谱图解析数据3ba:
1H NMR(500MHz,DMSO-d6)δ9.67(d,J＝8.6Hz,1H),9.24(d,J＝8.7Hz,1H),8.80-8.52(m,2H),8.03(t,J＝7.0Hz,1H),7.96(d,J＝8.6Hz,1H),7.50-7.38(m,5H),7.35-7.27(m,3H),7.24-7.20(m,3H),2.47(s,3H).13C NMR(125MHz,DMSO-d6)δ145.59,143.61,140.13,138.90,137.01,135.56,134.85,132.93,132.74,131.76,131.44,130.49,130.38,129.75,128.78,128.72,126.49,126.45,124.66,123.69,123.07,22.18.
实施例3
用1c代替实例1中的1a,其它条件同实例1,实验结果见表1。
谱图解析数据3ca:
1H NMR(500MHz,DMSO-d6)δ9.58(d,J＝8.8Hz,1H),8.99(d,J＝9.0Hz,1H),8.58(t,J＝7.9Hz,1H),8.54(d,J＝6.9Hz,1H),7.95(t,J＝7.1Hz,1H),7.83(d,J＝8.9Hz,1H),7.46-7.39(m,5H),7.22-7.18(m,5H),6.01(s,2H).13C NMR(125MHz,DMSO-d6)δ151.65,143.70,143.20,139.98,138.38,136.66,135.56,131.19,131.12,130.84,129.86,129.48,129.08,127.74,127.31,123.57,123.31,122.37,119.24,116.39,113.12,103.07.
实施例4
用1d代替实例1中的1a,其它条件同实例1,实验结果见表1。
谱图解析数据3da:
1H NMR(500MHz,DMSO-d6)δ9.78(d,J＝8.6Hz,1H),9.43(d,J＝8.8Hz,1H),8.79-8.68(m,2H),8.45(d,J＝8.7Hz,1H),8.10(t,J＝6.9Hz,1H),7.63(d,J＝7.4Hz,3H),7.53-7.44(m,8H),7.39-7.34(m,3H),7.32-7.30(m,2H).13C NMR(125MHz,DMSO-d6)δ145.08,143.00,139.95,138.69,137.84,136.80,135.32,134.16,132.61,131.15,130.92,130.08,129.95,129.42,129.31,129.23,128.38,128.35,127.17,126.94,124.58,123.72,123.55.
实施例5
用1e代替实例1中的1a,其它条件同实例1,实验结果见表1。
谱图解析数据3ea:
1H NMR(500MHz,DMSO-d6)δ9.73(d,J＝8.6Hz,1H),9.30(d,J＝8.9Hz,1H),8.79-8.64(m,2H),8.26(d,J＝8.8Hz,1H),8.08(t,J＝6.9Hz,1H),7.54-7.42(m,6H),7.41-7.33(m,3H),7.28(d,J＝6.9Hz,2H),1.26(s,9H).13C NMR(125MHz,DMSO-d6)δ157.19,142.93,139.63,138.27,136.50,135.48,134.33,132.17,131.26,130.94,130.03,129.85,129.29,129.18,128.25,128.22,125.93,124.25,123.31,122.64,122.03,35.31,30.30.
实施例6
用1f代替实例1中的1a,其它条件同实例1,实验结果见表1。
谱图解析数据3fa:
1H NMR(500MHz,DMSO-d6)δ9.75(d,J＝8.6Hz,1H),9.31(d,J＝9.0Hz,1H),8.82-8.73(m,2H),8.38-8.31(m,1H),8.15(t,J＝6.8Hz,1H),7.54(d,J＝1.6Hz,1H),7.51-7.45(m,5H),7.41-7.34(m,3H),7.27(d,J＝6.8Hz,2H).13C NMR(125MHz,DMSO-d6)δ143.46,140.98,140.00,137.64,134.60,134.18,133.91,131.38,131.27,130.68,130.34,129.83,129.11,129.04,128.97,128.76,128.69,125.58,124.17,124.04.
实施例7
用1g代替实例1中的1a,其它条件同实例1,实验结果见表1。
谱图解析数据3ga:
1H NMR(500MHz,DMSO-d6)δ9.68(d,J＝9.0Hz,1H),9.33(d,J＝8.4Hz,1H),8.62(d,J＝8.3Hz,1H),8.46(s,1H),8.11(t,J＝7.6Hz,1H),8.03(t,J＝7.6Hz,1H),7.51-7.42(m,6H),7.37-7.29(m,3H),7.27-7.22(m,2H).13C NMR(125MHz,DMSO-d6)δ141.68,141.41,137.94,135.48,135.17,134.42,133.76,131.73,131.06,130.97,130.76,130.08,129.86,129.27,128.25,128.17,126.73,125.71,124.57,123.00,18.23.
实施例8
用1h代替实例1中的1a,其它条件同实例1,实验结果见表1。
谱图解析数据3ha:
1H NMR(500MHz,DMSO-d6)δ9.81(d,J＝9.5Hz,1H),9.40(d,J＝8.4Hz,1H),8.93(dd,J＝9.4,1.8Hz,1H),8.55(d,J＝1.8Hz,1H),8.17(t,J＝7.6Hz,1H),8.11(t,J＝7.6Hz,1H),7.54-7.45(m,6H),7.39-7.31(m,3H),7.23(d,J＝6.8Hz,2H).13C NMR(125MHz,DMSO-d6)δ142.19,139.77,137.97,136.38,134.66,134.01,133.90,132.10,131.26,130.97,130.49,129.74,129.45,128.39,126.90,126.21,124.86,124.40.
实施例9
用2b代替实例1中的2a,其它条件同实例1,实验结果见表1。
谱图解析数据3ab:
1H NMR(500MHz,DMSO-d6)δ9.75(d,J＝8.5Hz,1H),9.34(d,J＝8.2Hz,1H),8.78(d,J＝6.9Hz,1H),8.69(t,J＝7.7Hz,1H),8.09(t,J＝6.7Hz,2H),8.04(t,J＝7.5Hz,1H),7.51(d,J＝8.1Hz,1H),7.42(d,J＝8.6Hz,2H),7.17(d,J＝8.6Hz,2H),7.04(d,J＝8.7Hz,2H),6.93(d,J＝8.6Hz,2H),3.76(s,3H),3.73(s,3H).13C NMR(125MHz,DMSO-d6)δ160.41,159.15,143.60,140.22,139.01,137.17,135.89,134.42,132.93,132.85,131.61,131.06,127.28,126.99,126.35,125.01,124.94,123.88,123.77,115.27,114.23,55.65,55.50.
实施例10
用2c代替实例1中的2a,其它条件同实例1,实验结果见表1。
谱图解析数据3ac:
1H NMR(500MHz,DMSO-d6)δ9.80(d,J＝8.4Hz,1H),9.40(d,J＝8.3Hz,1H),8.83(d,J＝6.8Hz,1H),8.75(t,J＝7.7Hz,1H),8.16(t,J＝7.6Hz,1H),8.10(q,J＝7.4,6.9Hz,2H),7.61(d,J＝8.5Hz,2H),7.56(d,J＝8.4Hz,2H),7.50(dd,J＝7.8,6.0Hz,3H),7.30(d,J＝8.3Hz,2H).13C NMR(125MHz,DMSO-d6)δ143.73,140.76,137.78,137.71,135.59,134.97,134.77,133.75,133.61,133.44,132.27,132.19,131.51,130.44,130.10,129.08,127.22,126.52,125.32,125.13,123.98。
表1
Claims (2)
1.一种电催化下多取代异喹啉盐衍生物的制备方法，所述异喹啉盐衍生物具有式Ⅰ所示的结构：
R1取代基团选自氢、甲基、胡椒基、苯基、叔丁基、溴；R2取代基团选自甲基、氯；R3取代基团选自甲氧基、氯；其特征在于，向反应器中，加入取代2-苯基吡啶0.2mmol、取代二苯基乙炔0.24mmol、六氟磷酸钾0.4mmol、二氯(五甲基环戊二烯基)合铑(III)二聚体0.001mmol，在六氟异丙醇∶水＝(3.75mL:1.25mL)中通过电催化促进反应完毕后，使用旋转蒸发仪浓缩得到粗产物，粗产物使用硅胶柱层析分离得到目标产物，其化学过程见反应式II：
2.根据权利要求1所述的制备方法，其特征在于：所述的取代2-苯基吡啶、取代二苯基乙炔、六氟磷酸钾、二氯(五甲基环戊二烯基)合铑(III)二聚体的摩尔比值为1：1.2：2：0.005，所述溶剂为六氟异丙醇：水＝3:1(体积比)，石墨毡作阳极，铂片作阴极，在恒流3mA条件下，通过电催化促进反应进行，反应温度35℃，反应时间为3.5h。
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| CN103603007A (zh) * | 2013-11-12 | 2014-02-26 | 北京工业大学 | 2-n-取代苯并噁唑类化合物的电化学催化合成方法 |
| CN110528020A (zh) * | 2019-09-19 | 2019-12-03 | 青岛科技大学 | 一种电催化下异噁唑并异喹啉酮衍生物的制备方法 |
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| CN1333777A (zh) * | 1998-10-14 | 2002-01-30 | 联邦科学和工业研究组织 | 有机硼衍生物及偶联有机化合物的方法 |
| CN103603007A (zh) * | 2013-11-12 | 2014-02-26 | 北京工业大学 | 2-n-取代苯并噁唑类化合物的电化学催化合成方法 |
| CN110528020A (zh) * | 2019-09-19 | 2019-12-03 | 青岛科技大学 | 一种电催化下异噁唑并异喹啉酮衍生物的制备方法 |
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