CN112209916B - 一种钌配合物、制备方法和催化用途 - Google Patents

一种钌配合物、制备方法和催化用途 Download PDF

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CN112209916B
CN112209916B CN202011146293.6A CN202011146293A CN112209916B CN 112209916 B CN112209916 B CN 112209916B CN 202011146293 A CN202011146293 A CN 202011146293A CN 112209916 B CN112209916 B CN 112209916B
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郝志强
林进
霍帅聪
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Hebei Normal University
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Abstract

本发明公开了一种钌配合物、制备方法和催化用途，该钌配合物为首次报道。本发明研究发现，该钌配合物具有催化合成喹唑啉及其衍生物或催化合成喹啉及其衍生物的活性。本发明提供的钌配合物在催化合成喹唑啉及其衍生物或喹啉及其衍生物时，具有反应条件较为温和、底物范围广、催化产物收率较高、官能团容忍性好的优点，显著优于现有技术。

Description

一种钌配合物、制备方法和催化用途
技术领域
本发明属于化学领域，涉及新化合物及其制备方法和应用，具体涉及一种钌配合物、制备方法和催化用途。
背景技术
芳香族N-杂环是许多天然产物、生物学相关化合物和药物中的核心结构，这些N-杂环的人工合成方法是目前科研工作者关注的热门领域。但合成N-杂环衍生物的常规方法通常使用昂贵或有毒的试剂，反应条件苛刻，收率低。因此，非常需要开发绿色、高效且温和的合成方法来构建含氮杂环。
近年来，无受体脱氢偶联构建N-杂环化合物受到了广泛关注，在该合成方法中，H2和 H2O是仅有的副产物，符合绿色化学的要求。近来，基于Ni、Ir、Ru、Fe和Mn等的过渡金属配合物被用于催化该类反应，该类偶联反应具有绿色环保、原子经济性高等特点。
基于Ni、Mn等廉价过渡金属的催化剂在该类反应中表现了不错的催化活性，但Ni、Mn 等廉价过渡金属的催化剂在反应过程中存在催化剂用量大，反应时间长等问题。相对而言，钌(Ru)作为一种多价态的稀有金属，与铂族元素铂(Pt)、钯(Pd)相比，价格相对便宜，因而受到了科研工作者的重视。此外，由于钌4d75s1核外电子排布特点，在不同的化合物中常常会呈现不同的价态，因而钌基催化剂在有机合成主要表现为氧化脱氢和还原加氢两大反应类型, 在C-H活化、不对称合成、烯醇异构化等方面中有着重要的用途。近年来，基于钌配合物催化醇类化合物脱氢的C-N偶联、C-C偶联等反应成为了科研工作者研究讨论的热点话题之一。
2014年，Jiang等报道了以Ru3(CO)12/Xantphos为催化剂(Org.Lett.2014,16,6028-6031)，合成喹唑啉及其衍生物方法。但该反应在底物苯腈类化合物的芳环上带有Me、OMe等供电子基团时产率明显下降，且催化产物整体产率较低。
2017年Yu等人报道的一类Pincer-Ru配合物(Organometallics,2017,36,24,4936-4942)。在t-BuOK的作用下，该类钌配合对脂肪及芳香二级醇表现出了良好的催化活性，目标化合物的产率较高。但该催化剂使用的是价格较高且对空气敏感的含膦配体，且当催化底物取代基变化时，对产率影响较大。
2019年Srimani课题组报道了一类NNS型三齿Mn配合物(Org.Lett.2019,21,3223-3227)，该类配合物催化合成喹唑啉时需要在140℃下进行，反应时间通常在30h以上，且催化产物的产率较低。
总之，现有技术在催化合成N-杂环化合物时常具有反应时间长，反应温度高，产率低，底物范围小等缺陷。
由此可见，现有技术在催化合成喹唑啉及其衍生物方面尚存在明显不足。
发明内容
本发明的目的在于克服现有技术的不足，提供一种钌配合物、制备方法和催化用途。
本发明上述目的通过如下技术方案实现：
一种钌配合物，其化学结构如下式所示：
Figure BDA0002739835360000021
一种所述配合物1a的制备方法，合成路线如下：
Figure BDA0002739835360000022
进一步地，化合物L1H的合成路线如下：
Figure BDA0002739835360000023
一种所述配合物1b的制备方法，合成路线如下：
Figure BDA0002739835360000024
进一步地，化合物L2H的合成路线如下：
Figure BDA0002739835360000031
一种所述配合物1c的制备方法，合成路线如下：
Figure BDA0002739835360000032
进一步地，化合物L3H的合成路线如下：
Figure BDA0002739835360000033
一种所述配合物1d的制备方法，合成路线如下：
Figure BDA0002739835360000034
进一步地，化合物L4H的合成路线如下：
Figure BDA0002739835360000035
上述钌配合物用作催化合成喹唑啉及其衍生物的催化剂的用途，或用作催化合成喹啉及其衍生物的催化剂的用途。
有益效果：
本发明提供的钌配合物在催化合成喹唑啉及其衍生物或喹啉及其衍生物时，具有反应条件较为温和、底物范围广、催化产物收率较高、官能团容忍性好的优点。以钌配合物1a催化喹唑啉及其衍生物为例，与现有技术的效果对比如表1和表2所示。
表1
Figure BDA0002739835360000041
表2
Figure BDA0002739835360000051
Figure BDA0002739835360000061
具体实施方式
下面结合实施例具体介绍本发明实质性内容，但并不以此限定本发明的保护范围。
以下实施例中，所用的化学试剂均为市售的化学纯或者分析纯。使用标准的Schlenk和真空管线技术，在干燥和纯化的氮气气氛下进行所有操作。在使用前，所有溶剂均在N2氛下适当的干燥剂中进行干燥处理。RuCl3·xH2O和其他试剂购自商业供应商，未经进一步纯化即可使用。1H和13C NMR光谱在Zhongke-Niujin Quantum-I 400MHz光谱仪上表征。高分辨质谱(HR-MS)使用Agilent 6210ESI-TOF质谱仪，液相质谱AB SCIEX 3200QTRAP液相色谱质谱联用仪。红外光谱在Thermo Fisher iS 50光谱仪上用KBr片表征。X射线衍射研究是在带有石墨单色Mo-K+辐射
Figure BDA0002739835360000063
的Bruker SMART 1000CCD衍射仪上进行的。所有非氢原子均经过各向异性精制。将氢原子与主体碳原子的位移因子一起引入计算位置。使用 SHELXTL对所有晶体结构进行求解，改进和几何计算。CIF格式的X射线晶体学文件可从剑桥晶体学数据中心获得。
实施例1：钌配合物的合成和结构确证
2-(6-(1H-吡唑-1-基)吡啶-2-基)丙-2-醇(L1H)的合成
Figure BDA0002739835360000062
在100mL反应容器中装入6-BrPyC(CH3)2OH(1.08g,5.0mmol)，吡唑(0.34g,5.0mmol), CuI(0.19g,1mmol),K2CO3(2.48g,15mmol)和DMSO(40mL)在N2气氛下。将混合物在 110℃下搅拌6h。冷却至室温后，加入10mL盐水，并将所得溶液用二氯甲烷(3×15mL)萃取。合并的有机相用无水Na2SO4干燥并过滤。真空除去溶剂后，将残余物通过Al2O3柱色谱法纯化(石油醚和乙酸乙酯作为洗脱剂)，得到L1H，为黄色油状物(0.86g,85％)。1H NMR(400MHz,DMSO-d6):δ7.87(t,J＝7.9Hz,1H),7.63(d,J＝8.1Hz,1H),7.53(d,J＝7.7Hz,1H),6.07(s,1H),5.31(s,1H),2.59(s,3H),2.18(s,3H),1.46(s,6H).13C NMR(101MHz,DMSO-d6):δ167.33,152.11,149.10,140.98,139.60,115.93,112.72,109.47,72.91,31.03,15.19, 13.87.ESI-MS m/z:204.1[M+H]+.
1-(6-(1H-吡唑-1-基)吡啶-2-基)-1-苯基乙-1-醇(L2H)的合成
Figure BDA0002739835360000071
在100mL反应容器中装入6-BrPyCCH3C6H5OH(1.39g,5.0mmol)，吡唑(0.34g,5.0mmol), CuI(0.19g,1mmol),K2CO3(2.48g,15mmol)和DMSO(40mL)在N2气氛下。将混合物在 110℃下搅拌6h。冷却至室温后，加入10mL盐水，并将所得溶液用二氯甲烷(3×15mL)萃取。合并的有机相用无水Na2SO4干燥并过滤。真空除去溶剂后，将残余物通过Al2O3柱色谱法纯化(石油醚和乙酸乙酯作为洗脱剂)，得到L2H，为黄色油状物(1.09g,82％)。1H NMR(400MHz,DMSO-d6):δ8.73(d,J＝2.5Hz,1H),7.91(t,J＝7.9Hz,1H),7.80(d,J＝0.9Hz,1H),7.73 (d,J＝7.5Hz,1H),7.59(d,J＝10.7Hz,3H),7.28(t,J＝7.7Hz,2H),7.16(t,J＝7.3Hz,1H),6.62 –6.49(m,1H),6.06(s,1H),1.96(s,3H).13C NMR(101MHz,DMSO-d6):δ166.42,149.87, 148.45,142.46,140.28,128.23,127.60,126.80,125.87,118.06,109.68,108.52,75.93,29.82. ESI-MS m/z:266.1[M+H]+.
(6-(1H-吡唑-1-基)吡啶-2-基)二苯基甲醇(L3H)的合成
Figure BDA0002739835360000072
在100mL反应容器中装入6-BrPyC(C6H5)2OH(1.70g,5.0mmol)，吡唑(0.34g,5.0mmol), CuI(0.19g,1mmol),K2CO3(2.48g,15mmol)和DMSO(40mL)在N2气氛下。将混合物在 110℃下搅拌6h。冷却至室温后，加入10mL盐水，并将所得溶液用二氯甲烷(3×15mL)萃取。合并的有机相用无水Na2SO4干燥并过滤。真空除去溶剂后，将残余物通过Al2O3柱色谱法纯化(石油醚和乙酸乙酯作为洗脱剂)，得到L3H，为白色固体(1.36g,83％)。1H NMR(400MHz,DMSO-d6):δ8.49(d,J＝3.0Hz,1H),7.98(t,J＝7.9Hz,1H),7.85–7.67(m,2H),7.49(d,J＝7.7Hz,1H),7.41-7.16(m,10H),6.70(s,1H),6.55–6.34(m,1H).13C NMR(101MHz, DMSO-d6):δ164.44,149.76,147.28,142.56,140.38,128.33,127.98,127.54,127.30,119.79,110.12,108.59,81.20.ESI-MS m/z:328.1[M+H]+.
2-(6-(3,5-二甲基-1H-吡唑-1-基)吡啶-2-基)丙-2-醇(L4H)的合成
Figure BDA0002739835360000073
在100mL反应容器中装入6-BrPyC(CH3)2OH(1.08g,5.0mmol),3，5-二甲基吡唑(1.16g, 5.0mmol),CuI(0.19g,1mmol),K2CO3(2.48g,15mmol)和DMSO(40mL)在N2气氛下。将混合物在110℃下搅拌12h。冷却至室温后，加入10mL盐水，并将所得溶液用二氯甲烷(3×15mL)萃取。合并的有机相用无水Na2SO4干燥并过滤。真空除去溶剂后，将残余物通过Al2O3柱色谱法纯化(石油醚和乙酸乙酯作为洗脱剂)，得到L4H，为黄色油状物(0.82g,71％)。1HNMR(400MHz,DMSO-d6):δ7.87(t,J＝7.9Hz,1H),7.63(d,J＝8.1Hz,1H),7.53(d,J＝7.7Hz,1H),6.07(s,1H),5.31(s,1H),2.59(s,3H),2.18(s,3H),1.46(s,6H).13C NMR(101MHz,DMSO-d6):δ167.3,152.1,149.1,141.0,139.6,115.9,112.7,109.5,72.9,31.0,15.2,13.9.MS (ESI,positiveions):m/z 232.1.
配合物1a的制备：
Figure BDA0002739835360000081
在氮气气氛下，将RuCl3·xH2O(0.26g,1.0mmol),Et3N(0.11g,1.0mmol)和配体L1H(0.41 g,2.0mmol)在乙醇(30mL)中的混合物回流3h。冷却至室温后，将混合物在减压下冷凝。粗产物通过Al2O3柱色谱法纯化(石油醚：乙醇8∶1,v/v)，得到1a，为橙色固体(0.451g,83.2％产率)。用CH2Cl2溶液培养出1a晶体并用X-射线单晶衍射测定其结构。HR-MS(ESI-TOF): 计算值C22H24ClN6O2Ru,[M-Cl]+506.0999，实测值506.0993.IR(KBr disk,cm-1):3409(m), 3063(w),2970(w),1606(m),1570(m),1480(s),1401(m),1377(w),1352(m),1294(w),1188 (m),1133(w),965(m),866(m),808(w).
配合物1b的制备：
Figure BDA0002739835360000082
在氮气气氛下，将RuCl3·xH2O(0.26g,1.0mmol),Et3N(0.11g,1.0mmol)和配体L2H(0.530g,2.0mmol)在乙醇(30mL)中的混合物回流3h。冷却至室温后，将混合物在减压下冷凝。粗产物通过Al2O3柱色谱法纯化(石油醚：乙醇8∶1,v/v)，得到1b，为橙色固体(0.57g,85.1％收率)。HR-MS(ESI-TOF):计算值C32H28ClN6O2Ru,[M-Cl]+630.1312,实测值630.1319.IR(KBrdisk,cm-1):3398(m),3058(w),2924(w),1607(w),1569(m),1471(s),1446(w),1401(m),1349(m),1291(w),1041(m),886(m),799(m),773(w),743(m).
配合物1c的制备：
Figure BDA0002739835360000091
在氮气气氛下，将RuCl3·xH2O(0.26g,1.0mmol),Et3N(0.11g,1.0mmol)和配体L3H(0.654g,2.0mmol)在乙醇(30mL)中的混合物回流3h。冷却至室温后，将混合物在减压下冷凝。粗产物通过Al2O3柱色谱法纯化(石油醚：乙醇8∶1,v/v)，得到1c，为橙色固体(0.67g,84.5％收率)。用CH2Cl2溶液培养出1c晶体并用X-射线单晶衍射测定其结构。HR-MS (ESI-TOF):计算值C42H32ClN6O2Ru,[M-Cl]+754.1625,实测值754.1633.IR(KBrdisk,cm-1): 3389(m),3057(w),1602(w),1569(m),1475(s),1444(m),1400(m),1349(m),1292(w),1056 (m),985(m),796(m),766(m),742(m).
配合物1d的制备：
Figure BDA0002739835360000092
在氮气气氛下，将RuCl3·xH2O(0.26g,1.0mmol),Et3N(0.11g,1.0mmol)和配体L4H(0.462g,2.0mmol)在乙醇(30mL)中的混合物回流3h。冷却至室温后，将混合物在减压下冷凝。粗产物通过Al2O3柱色谱法纯化(石油醚：乙醇8∶1,v/v)，得到1d，为橙色固体(0.48g,80％收率)。用CH2Cl2溶液培养出1d晶体并用X-射线单晶衍射测定其结构。HR-MS(ESI-TOF):计算值C26H32ClN6O2Ru,[M-Cl]+562.1625,实测值562.1615.IR(KBr disk,cm-1):3405(m),3065 (w),2961(w),1600(m),1560(m),1471(s),1420(m),1387(w),1357(w),1297(w),1197(m), 1111(m),993(w),877(m),789(m).
实施例2：钌配合物用作催化剂催化合成喹唑啉及其衍生物
以实施例1中合成的配合物1a为例，研究其对喹唑啉及其衍生物的催化性能，催化反应通式及反应产物如下：
Figure BDA0002739835360000101
(1)化合物6a的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.20mg,1.00mmol)，苯甲腈5a(103.12mg,1.00 mmol)，配合物1a(10.80mg,0.02mmol)和KOtBu(112.00mg,1.00mmol)。在氮气氛下，加入 4mL的叔戊醇并在95℃下搅拌24h。冷却至室温后，添加10mL水，并将混合物用EtOAc (3×10mL)萃取。合并的有机层在减压下浓缩。然后将残余物通过快速柱色谱法(石油醚：乙酸乙酯50∶1,v/v)纯化，得到白色固体6a(169.00mg,82％)。1H NMR(400MHz,CDCl3):δ 9.45(s,1H),8.63(d,J＝6.4Hz,2H),8.08(d,J＝9.0Hz,1H),7.88(t,J＝8.2Hz,2H),7.61–7.48 (m,4H).13C NMR(101MHz,CDCl3):δ161.08,160.51,150.80,138.09,134.11,130.64, 128.67(2C),128.63,127.27,127.13,123.63.
(2)化合物6b的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.20mg,1.00mmol)，4-甲基苯甲腈5b(117.15mg, 1.00mmol)，配合物1a(10.80mg,0.02mmol)和KOtBu(112.00mg,1.00mmol)。在氮气氛下，加入4mL的叔戊醇并在95℃下搅拌24h。冷却至室温后，添加10mL水，并将混合物用 EtOAc(3×10mL)萃取。合并的有机层在减压下浓缩。然后将残余物通过快速柱色谱法(石油醚：乙酸乙酯50∶1,v/v)纯化，得到白色固体6b(178.28mg,81％)。1H NMR(400MHz,CDCl3):δ9.45(s,1H),8.51(d,J＝8.2Hz,2H),8.08(d,J＝8.4Hz,1H),7.94–7.87(m,2H),7.60 (t,J＝7.5Hz,1H),7.35(d,J＝8.0Hz,2H),2.45(s,3H).13C NMR(101MHz,CDCl3):δ161.18, 160.47,150.83,140.93,135.32,134.09,129.45,128.58(2C),127.15,127.08,123.56,21.54.
(3)化合物6c的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.20mg,1.00mmol)，3-甲基苯甲腈(5c)(117.15mg, 1.00mmol)，配合物1a(10.80mg,0.02mmol)和KOtBu(112.00mg,1.00mmol)。在氮气氛下，加入4mL的叔戊醇并在95℃下搅拌24h。冷却至室温后，添加10mL水，并将混合物用 EtOAc(3×10mL)萃取。合并的有机层在减压下浓缩。然后将残余物通过快速柱色谱法(石油醚：乙酸乙酯50∶1,v/v)纯化，得到白色固体6c(171.69mg,78％)。1H NMR(400MHz,CDCl3): δ9.45(s,1H),8.43(d,J＝9.3Hz,2H),8.09(d,J＝8.6Hz,1H),7.89(t,J＝7.9Hz,2H),7.58(t,J ＝7.5Hz,1H),7.44(t,J＝7.6Hz,1H),7.33(d,J＝7.5Hz,1H),2.50(s,3H).13C NMR(101MHz, CDCl3):δ161.25,160.47,150.81,138.31,138.01,134.12,131.48,129.18,128.65,128.63,127.23, 127.15,125.86,123.62,21.59.
(4)化合物6d的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.20mg,1.00mmol)，2-甲基苯甲腈5d(117.15mg, 1.00mmol)，配合物1a(10.80mg,0.02mmol)和KOtBu(112.00mg,1.00mmol)。在氮气氛下，加入4mL的叔戊醇并在95℃下搅拌24h。冷却至室温后，添加10mL水，并将混合物用 EtOAc(3×10mL)萃取。合并的有机层在减压下浓缩。然后将残余物通过快速柱色谱法(石油醚：乙酸乙酯50∶1,v/v)纯化，得到黄色固体6d(158.47mg,72％)。1H NMR(400MHz,CDCl3): δ9.51(s,1H),8.10(d,J＝8.5Hz,1H),7.99–7.88(m,3H),7.66(t,J＝8.0Hz,1H),7.41–7.31 (m,3H),2.61(s,3H).13C NMR(101MHz,CDCl3):δ164.08,160.11,150.43,138.61,137.41, 134.15,131.32,130.66,129.33,128.62,127.56,127.09,126.00,122.95,21.05.
(5)化合物6e的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.20mg,1.00mmol)，4-甲氧基基苯甲腈5e(133.15 mg,1.00mmol)，配合物1a(10.80mg,0.02mmol)和KOtBu(112.00mg,1.00mmol)。在氮气氛下，加入4mL的叔戊醇并在95℃下搅拌24h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10mL)萃取。合并的有机层在减压下浓缩。然后将残余物通过快速柱色谱法(石油醚：乙酸乙酯50∶1,v/v)纯化，得到白色固体6e(193.60mg,82％)。1H NMR(400MHz,CDCl3):δ9.42(s,1H),8.58(d,J＝8.9Hz,2H),8.05(d,J＝8.4Hz,1H),7.88(t,J＝8.6Hz,2H), 7.57(t,J＝7.5Hz,1H),7.05(d,J＝8.9Hz,2H),3.90(s,3H).13C NMR(101MHz,CDCl3):δ 161.90,160.88,160.44,150.84,134.08,130.71,130.26,128.42,127.16,126.83,123.35,114.02, 55.42.
(6)化合物6f的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.20mg,1.00mmol)，4-氯苯甲腈5f(137.57mg, 1.00mmol)，配合物1a(10.80mg,0.02mmol)和KOtBu(112.00mg,1.00mmol)。在氮气氛下，加入4mL的叔戊醇并在95℃下搅拌24h。冷却至室温后，添加10mL水，并将混合物用 EtOAc(3×10mL)萃取。合并的有机层在减压下浓缩。然后将残余物通过快速柱色谱法(石油醚：乙酸乙酯50∶1,v/v)纯化，得到白色固体6f(192.04mg,80％)。1H NMR(400MHz,CDCl3): δ9.44(s,1H),8.57(d,J＝8.6Hz,2H),8.07(d,J＝9.0Hz,1H),7.98–7.31(m,2H),7.62(t,J＝ 7.5Hz,1H),7.50(d,J＝8.6Hz,2H).13C NMR(101MHz,CDCl3):δ160.55,160.07,150.72, 136.87,136.55,134.28,129.94,128.85,128.63,127.49,127.18,123.65.
(7)化合物6g的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.20mg,1.00mmol)，3-氯苯甲腈5g(137.57mg, 1.00mmol)，配合物1a(10.80mg,0.02mmol)和KOtBu(112.00mg,1.00mmol)。在氮气氛下，加入4mL的叔戊醇并在95℃下搅拌24h。冷却至室温后，添加10mL水，并将混合物用 EtOAc(3×10mL)萃取。合并的有机层在减压下浓缩。然后将残余物通过快速柱色谱法(石油醚：乙酸乙酯50∶1,v/v)纯化，得到白色固体6g(177.63mg,74％)。1H NMR(400MHz,CDCl3): δ9.46(s,1H),8.64(s,1H),8.51–8.55(m,1.6Hz,1H),8.09(d,J＝8.6Hz,1H),7.92(t,J＝7.8 Hz,2H),7.63(t,J＝7.5Hz,1H),7.51–7.39(m,2H).13C NMR(101MHz,CDCl3):δ160.58, 159.74,150.70,139.90,134.82,134.33,130.57,129.87,128.72,128.70,127.67,127.17,126.68, 123.80.
(8)化合物6h的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.20mg,1.00mmol)，2-氯苯甲腈5h(137.12mg, 1.00mmol)，配合物1a(10.80mg,0.02mmol)和KOtBu(112.00mg,1.00mmol)。在氮气氛下，加入4mL的叔戊醇并在95℃下搅拌24h。冷却至室温后，添加10mL水，并将混合物用 EtOAc(3×10mL)萃取。合并的有机层在减压下浓缩。然后将残余物通过快速柱色谱法(石油醚：乙酸乙酯50∶1,v/v)纯化，得到黄色固体6h(158.43mg,66％)。1H NMR(400MHz,CDCl3): δ9.52(s,1H),8.13(d,J＝8.5Hz,1H),8.01–7.91(m,2H),7.86–7.78(m,1H),7.69(t,J＝7.5 Hz,1H),7.57–7.50(m,1H),7.45–7.36(m,2H).13C NMR(101MHz,CDCl3):δ162.10,160.37, 150.48,138.41,134.53,133.05,131.94,130.68,130.46,128.77,128.20,127.28,127.02,123.41.
(9)化合物6i的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.20mg,1.00mmol)，4-溴苯甲腈5i(182.02mg, 1.00mmol)，配合物1a(10.80mg,0.02mmol)和KOtBu(112.00mg,1.00mmol)。在氮气氛下，加入4mL的叔戊醇并在95℃下搅拌24h。冷却至室温后，添加10mL水，并将混合物用 EtOAc(3×10mL)萃取。合并的有机层在减压下浓缩。然后将残余物通过快速柱色谱法(石油醚：乙酸乙酯50∶1,v/v)纯化，得到白色固体6i(221.52mg,78％)。1H NMR(400MHz,CDCl3): δ9.42(s,1H),8.49(d,J＝8.6Hz,2H),8.05(d,J＝8.9Hz,1H),7.95–7.85(m,2H),7.70–7.56 (m,3H).13C NMR(101MHz,CDCl3):δ160.53,160.10,150.69,136.99,134.28,131.81,130.19, 128.64,127.50,127.17,125.44,123.67.
(10)化合物6j的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.20mg,1.00mmol)，3-溴苯甲腈5j(182.02mg, 1.00mmol)，配合物1a(10.80mg,0.02mmol)和KOtBu(112.00mg,1.00mmol)。在氮气氛下，加入4mL的叔戊醇并在95℃下搅拌24h。冷却至室温后，添加10mL水，并将混合物用 EtOAc(3×10mL)萃取。合并的有机层在减压下浓缩。然后将残余物通过快速柱色谱法(石油醚：乙酸乙酯50∶1,v/v)纯化，得到白色固体6j(213.00mg,75％)。1H NMR(400MHz,CDCl3): δ9.43(s,1H),8.78(s,1H),8.55(d,J＝7.8Hz,1H),8.07(d,J＝8.9Hz,1H),7.95–7.85(m,2H), 7.61(t,J＝7.2Hz,2H),7.39(t,J＝7.9Hz,1H).13C NMR(101MHz,CDCl3):δ160.56,159.56, 150.66,140.11,134.32,133.48,131.61,130.14,128.70,127.67,127.16,127.13,123.77,122.96.
(11)化合物6k的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.20mg,1.00mmol)，4-硝基苯甲腈5k(148.12mg, 1.00mmol)，配合物1a(10.80mg,0.02mmol)和KOtBu(112.00mg,1.00mmol)。在氮气氛下，加入4mL的叔戊醇并在95℃下搅拌24h。冷却至室温后，添加10mL水，并将混合物用 EtOAc(3×10mL)萃取。合并的有机层在减压下浓缩。然后将残余物通过快速柱色谱法(石油醚：乙酸乙酯50∶1,v/v)纯化，得到黄色固体6k(95.41mg,38％)。1H NMR(400MHz,CDCl3): δ9.87(s,1H),8.36(d,J＝8.7Hz,2H),7.88(d,J＝8.7Hz,2H),7.48(d,J＝7.8Hz,1H),7.31(t,J ＝8.4Hz,2H),6.75(t,J＝7.4Hz,1H),6.65(d,J＝8.3Hz,1H).13C NMR(101MHz,CDCl3):δ 160.73,158.82,150.63,149.22,143.85,134.62,130.92,129.41,128.88,128.34,127.23,123.77.
(12)化合物6l的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.20mg,1.00mmol)，2-氰基噻吩5l(109.14mg, 1.00mmol)，配合物1a(10.80mg,0.02mmol)和KOtBu(112.00mg,1.00mmol)。在氮气氛下，加入4mL的叔戊醇并在95℃下搅拌24h。冷却至室温后，添加10mL水，并将混合物用 EtOAc(3×10mL)萃取。合并的有机层在减压下浓缩。然后将残余物通过快速柱色谱法(石油醚：乙酸乙酯50∶1,v/v)纯化，得到黄色固体6l(161.15mg,76％)。1H NMR(400MHz,CDCl3): δ9.34(s,1H),8.18–8.13(m,1H),8.00(d,J＝8.9Hz,1H),7.90–7.82(m,2H),7.59–7.48(m, 2H),7.15–7.21(m,1H).13C NMR(101MHz,CDCl3):δ160.55,157.88,150.63,143.87,134.37, 129.98,129.28,128.41,128.20,127.29,127.01,123.39.
(13)化合物6m的催化合成
将反应容器中加入2-氨基-3-甲基苯甲醇2a(137.18mg,1.00mmol)，苯甲腈5a(103.12mg, 1.00mmol)，配合物1a(10.80mg,0.02mmol)和KOtBu(112.00mg,1.00mmol)。在氮气氛下，加入4mL的叔戊醇并在95℃下搅拌24h。冷却至室温后，添加10mL水，并将混合物用 EtOAc(3×10mL)萃取。合并的有机层在减压下浓缩。然后将残余物通过快速柱色谱法(石油醚：乙酸乙酯50∶1,v/v)纯化，得到白色固体6p(176.08mg,80％)。1H NMR(400MHz,CDCl3):δ9.40(s,1H),8.69(d,J＝6.6Hz,2H),7.72(m,J＝7.3,2.5Hz,2H),7.60–7.42(m,4H), 2.86(s,3H).13C NMR(101MHz,CDCl3):δ160.55,159.94,149.74,138.42,137.15,133.86, 130.49,128.61,128.57,126.93,124.82,123.53,16.96.
(14)化合物6n的催化合成
将反应容器中加入2-氨基-3-甲基苯甲醇2a(137.18mg,1.00mmol)，4-甲氧基苯甲腈5a (133.15mg,1.00mmol)，配合物1a(10.80mg,0.02mmol)和KOtBu(112.00mg,1.00mmol)。在氮气氛下，加入4mL的叔戊醇并在95℃下搅拌24h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10mL)萃取。合并的有机层在减压下浓缩。然后将残余物通过快速柱色谱法(石油醚：乙酸乙酯50∶1,v/v)纯化，得到白色固体6n(210.09mg,84％)。1H NMR(400MHz, CDCl3):δ9.31(s,1H),8.59(d,J＝9.0Hz,2H),7.64(d,J＝7.2Hz,2H),7.38(t,J＝7.5Hz,1H), 7.01(d,J＝8.9Hz,2H),3.86(s,3H),2.79(s,3H).13C NMR(101MHz,CDCl3):δ161.75,160.43, 159.75,149.77,136.84,133.75,131.16,130.15,126.42,124.81,123.18,113.93,55.39,16.94.
(15)化合物6o的催化合成
将反应容器中加入2-氨基-5-氯苯甲醇2a(157.60mg,1.00mmol)，苯甲腈5a(103.12mg, 1.00mmol)，配合物1a(10.80mg,0.02mmol)和KOtBu(112.00mg,1.00mmol)。在氮气氛下，加入4mL的叔戊醇并在95℃下搅拌24h。冷却至室温后，添加10mL水，并将混合物用 EtOAc(3×10mL)萃取。合并的有机层在减压下浓缩。然后将残余物通过快速柱色谱法(石油醚：乙酸乙酯50∶1,v/v)纯化，得到白色固体6o(175.23mg,73％)。1H NMR(400MHz,CDCl3):δ9.38(s,1H),8.55–8.64(m,2H),8.02(d,J＝9.0Hz,1H),7.88(s,1H),7.81(d,J＝9.0 Hz,1H),7.57–7.47(m,3H).13C NMR(101MHz,CDCl3):δ161.32,159.53,149.28,137.63,135.10,132.81,130.92,130.43,128.73,128.63,125.85,124.02.
(16)化合物6p的催化合成
将反应容器中加入2-氨基-5-溴苯甲醇2a(202.04mg,1.00mmol)，苯甲腈5a(103.12mg, 1.00mmol)，配合物1a(10.80mg,0.02mmol)和KOtBu(112.00mg,1.00mmol)。在氮气氛下，加入4mL的叔戊醇并在95℃下搅拌24h。冷却至室温后，添加10mL水，并将混合物用 EtOAc(3×10mL)萃取。合并的有机层在减压下浓缩。然后将残余物通过快速柱色谱法(石油醚：乙酸乙酯50∶1,v/v)纯化，得到白色固体6p(198.79mg,70％)。1H NMR(400MHz,CDCl3):δ9.37(s,1H),8.64–8.54(m,2H),8.06(s,1H),7.94(d,J＝1.2Hz,2H),7.59–7.47(m, 3H).13C NMR(101MHz,CDCl3):δ161.35,159.41,149.46,137.62,130.94,130.49,129.25, 128.73(2C),128.65,124.50,120.76.
配合物1b、1c、1d对上述喹唑啉及其衍生物也具有较优异的催化性能，化合物6a的催化合成为例，四种配合物的对比如下。
Figure BDA0002739835360000151
Figure BDA0002739835360000152
aReaction conditions:2a(1.0mmol),5a(2.0mmol),KOtBu(1.0mmol),tamylalcohol(4.0 mL),0.1MPa N2.bIsolsted yields.
实施例3：钌配合物用作催化剂催化合成喹啉及其衍生物
以实施例1中合成的配合物1a为例，研究其对喹啉及其衍生物的催化性能，催化反应通式及反应产物如下：
Figure BDA0002739835360000161
(1)化合物4a的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.2mg,1.0mmol)，苯乙酮3a(120.2mg,1.0mmol)，配合物1a(10.8mg,0.02mmol)和KHMDS(1mL,1.0mmol)。在氮气气氛下，加入2mL 甲苯并在110℃下加热12h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10mL) 萃取。合并的有机相在减压下浓缩。然后将残余物通过快速柱色谱纯化(石油醚：乙酸乙酯 100∶1,v/v)，得到白色固体4a(191mg,93％)。1H NMR(400MHz,CDCl3):δ8.27–8.14(m, 4H),7.87(d,J＝8.5Hz,1H),7.82(d,J＝8.1Hz,1H),7.79–7.71(m,1H),7.59–7.45(m,4H).13C NMR(101MHz,CDCl3):δ157.4,148.3,139.7,136.9,129.7,129.4,129.0,128.9,127.6,127.5,127.2,126.4,119.1
(2)化合物4b的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.2mg,1.0mmol)，4-甲基苯乙酮3b(134.1mg,1.0 mmol)，配合物1a(10.8mg,0.02mmol)和KHMDS(1mL,1.0mmol)。在氮气气氛下，加入2mL 甲苯并在110℃下加热12h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10mL) 萃取。合并的有机相在减压下浓缩。然后将残余物通过快速柱色谱纯化(石油醚：乙酸乙酯 100∶1,v/v)，得到白色固体4b(206mg,94％)。1H NMR(400MHz,CDCl3):δ9.24-8.14(m, 2H),8.11(d,J＝8.1Hz,2H),7.85(d,J＝8.6Hz,1H),7.80(d,J＝8.1Hz,1H),7.74(t,J＝7.7Hz, 1H),7.52(t,J＝7.5Hz,1H),7.36(d,J＝8.0Hz,2H),2.46(s,3H).13C NMR(101MHz,CDCl3):δ 157.3,148.3,139.4,136.9,136.7,129.7,129.6,129.6,127.5,127.1,126.2,126.0,118.9,21.4.
(3)化合物4c的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.2mg,1.0mmol)，4-甲氧基苯乙酮3c(150.1mg, 1.0mmol)，配合物1a(10.8mg,0.02mmol)和KHMDS(1mL,1.0mmol)。在氮气气氛下，加入2mL甲苯并在110℃下加热12h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10 mL)萃取。合并的有机相在减压下浓缩。然后将残余物通过快速柱色谱纯化(石油醚：乙酸乙酯100∶1,v/v)，得到白色固体4c(214mg,91％)。1H NMR(400MHz,CDCl3):δ8.18(d,J＝ 8.4Hz,2H),8.15(d,J＝8.9Hz,2H),7.87–7.77(m,2H),7.71(t,J＝8.3Hz,1H),7.50(t,J＝7.0 Hz,1H),7.05(d,J＝8.9Hz,2H),3.89(s,3H).13C NMR(101MHz,CDCl3):δ157.6,148.2,139.6, 138.6,136.8,130.2,129.7,128.8,128.3,127.5,126.3,124.8,119.2,21.7.
(4)化合物4d的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.2mg,1.0mmol)，4-氯苯乙酮3d(154.0mg,1.0 mmol)，配合物1a(10.8mg,0.02mmol)和KHMDS(1mL,1.0mmol)。在氮气气氛下，加入2mL甲苯并在110℃下加热12h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10mL) 萃取。合并的有机相在减压下浓缩。然后将残余物通过快速柱色谱纯化(石油醚：乙酸乙酯100∶1,v/v)，得到白色固体4d(208mg,87％)。1H NMR(400MHz,CDCl3):δ8.18(d,J＝7.1 Hz,1H),8.15(s,1H),8.10(d,J＝8.6Hz,2H),7.78(t,J＝8.1Hz,2H),7.76–7.67(m,1H),7.57–7.50(m,1H),7.48(d,J＝8.6Hz,2H).13C NMR(101MHz,CDCl3):δ155.9,148.2,138.8,137.0,135.6,129.8,129.8,129.1,128.9,127.5,127.2,126.4,118.5.
(5)化合物4e的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.2mg,1.0mmol)，4-溴苯乙酮3e(198.0mg,1.0 mmol)，配合物1a(10.8mg,0.02mmol)和KHMDS(1mL,1.0mmol)。在氮气气氛下，加入2mL甲苯并在110℃下加热12h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10mL) 萃取。合并的有机相在减压下浓缩。然后将残余物通过快速柱色谱纯化(石油醚：乙酸乙酯100∶1,v/v)，得到白色固体4e(241mg,85％)。1H NMR(400MHz,CDCl3):δ8.21(d,J＝5.9 Hz,1H),8.17(d,J＝7.8Hz,1H),8.05(d,J＝8.5Hz,2H),7.82(d,J＝3.3Hz,1H),7.80(d,J＝3.8Hz,1H),7.74(t,J＝7.7Hz,1H),7.64(d,J＝8.5Hz,2H),7.53(t,J＝7.1Hz,1H).13C NMR(101MHz,CDCl3):δ156.0,148.2,138.4,137.02,132.09,129.9,129.7,129.1,127.5,127.2,126.5, 124.0,118.5.
(6)化合物4f的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.2mg,1.0mmol)，3-甲基苯乙酮3f(134.1mg,1.0 mmol)，配合物1a(10.8mg,0.02mmol)和KHMDS(1mL,1.0mmol)。在氮气气氛下，加入2mL 甲苯并在110℃下加热12h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10mL) 萃取。合并的有机相在减压下浓缩。然后将残余物通过快速柱色谱纯化(石油醚：乙酸乙酯 100∶1,v/v)，得到白色固体4f(197mg,90％)。1H NMR(400MHz,CDCl3):δ8.23(d,J＝8.5 Hz,2H),8.17(d,J＝8.6Hz,2H),8.05(s,2H),7.96(d,J＝7.7Hz,2H),7.85(d,J＝8.6Hz,2H), 7.81(d,J＝8.1Hz,2H),7.75(t,J＝7.7Hz,2H),7.52(t,J＝7.5Hz,2H),7.44(t,J＝7.6Hz,2H), 7.31(d,J＝7.5Hz,2H),2.51(s,6H).13C NMR(101MHz,CDCl3):δ157.6,148.3,139.7,138.6, 136.8,130.2,129.8,129.7,128.8,128.4,127.5,127.2,126.3,124.8,119.2,21.7.
(7)化合物4g的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.2mg,1.0mmol)，3-甲氧基苯乙酮3g(150.1mg, 1.0mmol)，配合物1a(10.8mg,0.02mmol)和KHMDS(1mL,1.0mmol)。在氮气气氛下，加入2mL甲苯并在110℃下加热12h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10 mL)萃取。合并的有机相在减压下浓缩。然后将残余物通过快速柱色谱纯化(石油醚：乙酸乙酯100∶1,v/v)，得到黄色油状物4g(209mg,89％)。1H NMR(400MHz,CDCl3):δ8.25–8.17 (m,2H),8.03(s,1H),7.94(d,J＝7.7Hz,1H),7.87(d,J＝8.6Hz,1H),7.82(d,J＝8.1Hz,1H), 7.74(t,J＝7.7Hz,1H),7.53(t,J＝7.5Hz,1H),7.43(t,J＝7.6Hz,1H),7.30(d,J＝7.5Hz,1H), 2.49(s,3H).13C NMR(101MHz,CDCl3):δ160.2,157.1,148.2,141.2,136.8,129.8,129.8,129.7, 127.5,127.3,126.7,120.1,119.1,115.4,112.8,55.5.
(8)化合物4h的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.2mg,1.0mmol)，3-氯苯乙酮3h(154.0mg,1.0 mmol)，配合物1a(10.8mg,0.02mmol)和KHMDS(1mL,1.0mmol)。在氮气气氛下，加入2mL甲苯并在110℃下加热12h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10mL) 萃取。合并的有机相在减压下浓缩。然后将残余物通过快速柱色谱纯化(石油醚：乙酸乙酯100∶1,v/v)，得到白色固体4h(194mg,81％)。1H NMR(400MHz,CDCl3):δ8.23–8.14(m, 3H),8.06–7.96(m,1H),7.78(d,J＝8.5Hz,2H),7.74(t,J＝7.7Hz,1H),7.56–7.50(m,1H),7.47–7.40(m,2H).13C NMR(101MHz,CDCl3):δ155.7,148.2,141.4,137.0,135.0,130.1,130.0, 129.9,129.4,127.7,127.6,127.4,126.6,125.6,118.6
(9)化合物4i的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.2mg,1.0mmol)，2-甲基苯乙酮3i(134.1mg,1.0 mmol)，配合物1a(10.8mg,0.02mmol)和KHMDS(1mL,1.0mmol)。在氮气气氛下，加入2mL 甲苯并在110℃下加热12h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10mL) 萃取。合并的有机相在减压下浓缩。然后将残余物通过快速柱色谱纯化(石油醚：乙酸乙酯 100∶1,v/v)，得到白色固体4i(184mg,84％)。1H NMR(400MHz,CDCl3):δ8.21(d,J＝8.4 Hz,2H),7.86(d,J＝8.0Hz,1H),7.76(t,J＝7.6Hz,1H),7.60–7.49(m,3H),7.35(s,3H),2.45(s, 3H).13C NMR(101MHz,CDCl3):δ160.3,147.9,140.7,136.2,136.0,130.9,130.8,129.7,128.6, 127.56,126.5,126.4,126.1,122.5,122.4,20.5.
(10)化合物4j的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.2mg,1.0mmol)，2-氯苯乙酮3j(154.0mg,1.0 mmol)，配合物1a(10.8mg,0.02mmol)和KHMDS(1mL,1.0mmol)。在氮气气氛下，加入2mL甲苯并在110℃下加热12h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10mL) 萃取。合并的有机相在减压下浓缩。然后将残余物通过快速柱色谱纯化(石油醚：乙酸乙酯100∶1,v/v)，得到白色固体4j(177mg,74％)。1H NMR(400MHz,CDCl3):δ8.21(d,J＝5.3 Hz,1H),8.19(d,J＝5.2Hz,1H),7.86(d,J＝8.1Hz,1H),7.79–7.67(m,3H),7.57(t,J＝7.2Hz,1H),7.51(d,J＝9.1Hz,1H),7.45–7.34(m,2H).13C NMR(101MHz,CDCl3):δ157.4,148.1,139.66,135.7,132.4,131.8,131.7,130.0,129.7,127.6,127.1,126.9,126.7,122.8,122.8.
(11)化合物4k的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.2mg,1.0mmol)，2-萘乙酮3k(170.1mg,1.0 mmol)，配合物1a(10.8mg,0.02mmol)和KHMDS(1mL,1.0mmol)。在氮气气氛下，加入2mL甲苯并在110℃下加热12h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10mL) 萃取。合并的有机相在减压下浓缩。然后将残余物通过快速柱色谱纯化(石油醚：乙酸乙酯100∶1,v/v)，得到白色固体4k(217mg,85％)。1H NMR(400MHz,CDCl3):δ8.63(s,1H),8.42 –8.34(m,1H),8.26(d,J＝8.5Hz,2H),8.09–7.97(m,3H),7.94–7.88(m,1H),7.85(d,J＝8.2Hz,1H),7.80–7.71(m,1H),7.61–7.49(m,3H).13C NMR(101MHz,CDCl3):δ157.1,148.3,136.9,136.9,133.9,133.5,129.8,129.7,128.9,128.6,127.8,127.5,127.2,127.1,126.8,126.4, 125.1,119.2.
(12)化合物4l的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.2mg,1.0mmol)，3-乙酰基吡啶3l(121.1mg,1.0 mmol)，配合物1a(10.8mg,0.02mmol)和KHMDS(1mL,1.0mmol)。在氮气气氛下，加入2mL 甲苯并在110℃下加热12h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10mL) 萃取。合并的有机相在减压下浓缩。然后将残余物通过快速柱色谱纯化(石油醚：乙酸乙酯 100∶1,v/v)，得到棕色固体4l(169mg,82％)。1H NMR(400MHz,CDCl3):δ9.33(d,J＝1.8 Hz,1H),8.71–8.61(m,1H),8.48–8.41(m,1H),8.17(d,J＝8.6Hz,1H),8.13(d,J＝8.5Hz, 1H),7.80(s,1H),7.77(d,J＝7.1Hz,1H),7.74–7.67(m,1H).13C NMR(101MHz,CDCl3):δ 154.5,150.1,148.9,148.3,137.1,135.0,134.8,130.9,129.7,127.6,127.3,126.7,123.6,118.4.
(13)化合物4m的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.2mg,1.0mmol)，2-乙酰基噻吩3m(126.0mg,1.0 mmol)，配合物1a(10.8mg,0.02mmol)和KHMDS(1mL,1.0mmol)。在氮气气氛下，加入2mL 甲苯并在110℃下加热12h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10mL) 萃取。合并的有机相在减压下浓缩。然后将残余物通过快速柱色谱纯化(石油醚：乙酸乙酯 100∶1,v/v)，得到白色固体4m(179mg,85％)。1H NMR(400MHz,CDCl3):δ8.14(d,J＝7.4 Hz,1H),8.09(d,J＝8.7Hz,1H),7.78(d,J＝7.7Hz,1H),7.75(d,J＝6.4Hz,1H),7.72(d,J＝3.6 Hz,1H),7.71–7.66(m,1H),7.51–7.41(m,2H),7.18–7.13(m,1H).13C NMR(101MHz, CDCl3):δ152.3,148.1,145.4,136.7,129.9,129.3,128.5,128.2,127.6,127.2,126.2,126.0,117.7
(14)化合物4n的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.2mg,1.0mmol)，环庚酮3n(112.1mg,1.0mmol)，配合物1a(10.8mg,0.02mmol)和KHMDS(1mL,1.0mmol)。在氮气气氛下，加入2mL 甲苯并在110℃下加热12h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10mL) 萃取。合并的有机相在减压下浓缩。然后将残余物通过快速柱色谱纯化(石油醚：乙酸乙酯 100∶1,v/v)，得到白色固体4n(167mg,85％)。1H NMR(400MHz,CDCl3):δ7.99(d,J＝8.4 Hz,1H),7.79(s,1H),7.69(d,J＝8.1Hz,1H),7.61(t,J＝7.0Hz,1H),7.44(t,J＝7.5Hz,1H), 3.29–3.13(m,2H),2.99–2.85(m,2H),1.94-1.85(m,2H),1.84–1.67(m,4H).13C NMR(101 MHz,CDCl3):δ164.7,146.2,136.5,134.6,128.5,128.4,127.4,126.8,125.8,40.1,35.5,32.3,28.9, 27.1.
(15)化合物4o的催化合成
将反应容器中加入2-氨基苯甲醇2a(123.2mg,1.0mmol)，苯并环己酮3o(146.1mg,1.0 mmol)，配合物1a(10.8mg,0.02mmol)和KHMDS(1mL,1.0mmol)。在氮气气氛下，加入2mL甲苯并在110℃下加热12h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10mL) 萃取。合并的有机相在减压下浓缩。然后将残余物通过快速柱色谱纯化(石油醚：乙酸乙酯100∶1,v/v)，得到白色固体4o(199mg,86％)。1H NMR(400MHz,CDCl3):δ8.64(d,J＝7.7 Hz,1H),8.19(d,J＝8.4Hz,1H),7.88(s,1H),7.73(d,J＝8.1Hz,1H),7.68(t,J＝7.7Hz,1H),7.51–7.48(m,1H),7.47–7.44(m,1H),7.40(t,J＝7.4Hz,1H),7.29(d,J＝7.4Hz,1H),3.14–3.06(m,2H),3.04–2.96(m,2H).13C NMR(101MHz,CDCl3):δ153.4,147.6,139.5,134.7,133.8, 130.6,129.8,129.4,128.8,128.7,128.0,127.9,127.1,126.2,126.0,28.8,28.4.
(16)化合物4p的催化合成
将反应容器中加入2-氨基-5-氯苯甲醇2p(123.2mg,1.0mmol)，苯乙酮3a(157.0mg,1.0 mmol)，配合物1a(10.8mg,0.02mmol)和KHMDS(1mL,1.0mmol)。在氮气气氛下，加入2mL 甲苯并在110℃下加热12h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10mL) 萃取。合并的有机相在减压下浓缩。然后将残余物通过快速柱色谱纯化(石油醚：乙酸乙酯 100∶1,v/v)，得到白色固体4p(203mg,85％)。1H NMR(400MHz,CDCl3):δ8.15(d,J＝7.0 Hz,2H),8.10(d,J＝9.0Hz,1H),8.07(d,J＝8.8Hz,1H),7.85(d,J＝8.6Hz,1H),7.76(t,J＝5.7 Hz,1H),7.70–7.61(m,1H),7.54(t,J＝7.2Hz,2H),7.49(d,J＝7.0Hz,1H).13CNMR(101MHz, CDCl3):δ157.5,146.6,139.2,135.9,131.9,131.3,130.6,129.6,129.0,127.7,127.5,126.2,119.8
(17)化合物4q的催化合成
将反应容器中加入2-氨基-5-溴苯甲醇2q(201.0mg,1.0mmol)，苯乙酮3a(120.2mg,1.0 mmol)，配合物1a(10.8mg,0.02mmol)和KHMDS(1mL,1.0mmol)。在氮气气氛下，加入2mL 甲苯并在110℃下加热12h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10mL) 萃取。合并的有机相在减压下浓缩。然后将残余物通过快速柱色谱纯化(石油醚：乙酸乙酯 100∶1,v/v)，得到白色固体4q(226mg,80％)。1H NMR(400MHz,CDCl3):δ8.26–8.11(m, 3H),8.09–8.01(m,1H),7.94(d,J＝2.1Hz,1H),7.84(d,J＝8.7Hz,1H),7.81–7.73(m,1H), 7.57–7.46(m,3H).13C NMR(101MHz,CDCl3):δ157.6,146.8,139.2,136.9,135.8,133.1,131.5, 129.5,129.0,128.2,127.6,119.8,119.1.
(18)化合物4r的催化合成
将反应容器中加入2-氨基-3,5-二溴苯甲醇2r(279.9mg,1.0mmol)，苯乙酮3a(120.2mg, 1.0mmol)，配合物1a(10.8mg,0.02mmol)和KHMDS(1mL,1.0mmol)。在氮气气氛下，加入2mL甲苯并在110℃下加热12h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10 mL)萃取。合并的有机相在减压下浓缩。然后将残余物通过快速柱色谱纯化(石油醚：乙酸乙酯100∶1,v/v)，得到白色固体4r(264mg,73％)。1H NMR(400MHz,CDCl3):δ8.26(d,J＝6.8 Hz,2H),8.11(s,1H),8.00(d,J＝8.6Hz,1H),7.90–7.82(m,2H),7.56–7.47(m,3H).13CNMR (101MHz,CDCl3):δ157.6,143.8,138.4,136.2,135.8,131.4,129.5,129.3,128.8,127.5,126.5, 119.9,119.3.
(19)化合物4s的催化合成
将反应容器中加入2-氨基-3-甲基苯甲醇2s(137.1mg,1.0mmol)，苯乙酮3a(120.2mg,1.0 mmol)，配合物1a(10.8mg,0.02mmol)和KHMDS(1mL,1.0mmol)。在氮气气氛下，加入2mL 甲苯并在110℃下加热12h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10mL) 萃取。合并的有机相在减压下浓缩。然后将残余物通过快速柱色谱纯化(石油醚：乙酸乙酯 100∶1,v/v)，得到白色固体4s(166mg,76％)。1H NMR(400MHz,CDCl3):δ8.38(d,J＝7.5 Hz,2H),8.17(d,J＝8.6Hz,1H),7.92(d,J＝8.6Hz,1H),7.70(d,J＝8.1Hz,1H),7.66(d,J＝6.4 Hz,1H),7.62(d,J＝8.0Hz,2H),7.56(t,J＝7.2Hz,1H),7.48(t,J＝7.6Hz,1H),3.05(s,3H).13C NMR(101MHz,CDCl3):δ155.6,147.3,139.9,137.7,137.0,129.9,129.0,128.8,127.5,127.2, 126.3,125.6,118.3,18.2.
(20)化合物4t的催化合成
将反应容器中加入3-氨基-3-苯基-1-丙醇2t(151.2mg,1.0mmol)，苯乙酮3a(120.2mg,1.0 mmol)，配合物1a(10.8mg,0.02mmol)和KHMDS(1mL,1.0mmol)。在氮气气氛下，加入2mL 甲苯并在110℃下加热12h。冷却至室温后，添加10mL水，并将混合物用EtOAc(3×10mL) 萃取。合并的有机相在减压下浓缩。然后将残余物通过快速柱色谱纯化(石油醚：乙酸乙酯 100∶1,v/v)，得到黄色油状物4t(164mg,71％)。1H NMR(400MHz,CDCl3):δ8.17(d,J＝7.3 Hz,4H),7.86–7.78(m,1H),7.70(d,J＝7.8Hz,2H),7.51(t,J＝7.5Hz,4H),7.44(t,J＝7.3Hz, 2H).13C NMR(101MHz,CDCl3):δ156.9,139.5,137.5,129.0,128.7,127.0,118.7.
配合物1b、1c、1d对上述喹啉及其衍生物也具有较优异的催化性能，化合物4a的催化合成为例，四种配合物的对比如下。
Figure BDA0002739835360000231
Figure BDA0002739835360000232
aReaction conditions:2a(1.0mmol),3a(1.0mmol),KHMDS(1.0mmol),tolueue(2.0mL), 110℃,0.1MPa N2.bIsolsted yields.
上述实施例的作用在于具体介绍本发明的实质性内容，但本领域技术人员应当知道，不应将本发明的保护范围局限于该具体实施例。

Claims (10)

1.一种钌配合物，其特征在于，其化学结构如下式所示：
Figure FDA0002739835350000011
2.一种权利要求1所述配合物1a的制备方法，其特征在于，合成路线如下：
Figure FDA0002739835350000012
3.根据权利要求2所述的制备方法，其特征在于，化合物L1H的合成路线如下：
Figure FDA0002739835350000013
4.一种权利要求1所述配合物1b的制备方法，其特征在于，合成路线如下：
Figure FDA0002739835350000014
5.根据权利要求4所述的制备方法，其特征在于，化合物L2H的合成路线如下：
Figure FDA0002739835350000015
6.一种权利要求1所述配合物1c的制备方法，其特征在于，合成路线如下：
Figure FDA0002739835350000021
7.根据权利要求6所述的制备方法，其特征在于，化合物L3H的合成路线如下：
Figure FDA0002739835350000022
8.一种权利要求1所述配合物1d的制备方法，其特征在于，合成路线如下：
Figure FDA0002739835350000023
9.根据权利要求8所述的制备方法，其特征在于，化合物L4H的合成路线如下：
Figure FDA0002739835350000024
10.权利要求1所述的钌配合物用作催化合成喹唑啉及其衍生物的催化剂的用途，或用作催化合成喹啉及其衍生物的催化剂的用途。
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CN107406427A (zh) * 2015-02-25 2017-11-28 豪夫迈·罗氏有限公司 炔基醇及其使用方法
WO2018135506A1 (ja) * 2017-01-19 2018-07-26 日本曹達株式会社 ルテニウム錯体を用いた還元方法
EP3450441A1 (en) * 2017-09-05 2019-03-06 Samsung Electronics Co., Ltd. Organometallic compound, organic light-emitting device including the organometallic compound, and diagnostic composition including the organometallic compound

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102648540A (zh) * 2009-12-05 2012-08-22 默克专利有限公司 包含金属络合物的电子器件
CN107406427A (zh) * 2015-02-25 2017-11-28 豪夫迈·罗氏有限公司 炔基醇及其使用方法
WO2018135506A1 (ja) * 2017-01-19 2018-07-26 日本曹達株式会社 ルテニウム錯体を用いた還元方法
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