CN110105230A - 一种钯/咪唑盐催化硝基芳烃和胺类化合物合成芳香胺化合物的方法 - Google Patents

一种钯/咪唑盐催化硝基芳烃和胺类化合物合成芳香胺化合物的方法 Download PDF

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CN110105230A
CN110105230A CN201910439860.8A CN201910439860A CN110105230A CN 110105230 A CN110105230 A CN 110105230A CN 201910439860 A CN201910439860 A CN 201910439860A CN 110105230 A CN110105230 A CN 110105230A
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陈万芝
陈威
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Zhejiang University ZJU
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Abstract

本发明公开了一种钯/咪唑盐催化硝基芳烃和胺类化合物合成芳香胺的方法，包括：在有机溶剂中，以钯/咪唑盐为催化剂，将硝基芳烃和胺类化合物在碱的作用下进行偶联反应，经过后处理得到芳香胺化合物。本发明方法配体合成简单，易于保存，价格便宜且配体的用量较低，产物收率高，底物适用性好，可适用于二芳基胺、N‑烷基芳胺的制备。本发明方法可用于合成一系列芳香胺化合物，该类化合物在农药、医药、材料等领域均有广泛的应用价值。

Description

一种钯/咪唑盐催化硝基芳烃和胺类化合物合成芳香胺化合 物的方法
技术领域
本发明涉及有机合成领域，具体涉及钯/咪唑盐催化硝基芳烃和胺类化合物合成芳香胺化合物的方法。
背景技术
芳香胺化合物是合成各种医药、农药、染料、聚合物以及精细化学品的重要中间体(Ruiz-Castillo,P.；Buchwald,S.L.Applications of Palladium-Catalyzed C–N Cross-Coupling Reactions，Chemical Reviews，2016,116(19),12564–12649)，而钯催化的Buchwald-Hartwig偶联反应是一种高效构建C-N键的方法。
Buchwald-Hartwig偶联反应一般由卤代芳烃作为亲电试剂，但是为了减少卤代芳烃所产生的含卤废弃物污染，化学家发展了其他拟卤芳烃如醚，酯等为亲电试剂的偶联反应。其中，硝基芳烃是基础化工原料，来源广泛，是理想的亲电偶联试剂。
硝基芳烃的Buchwald-Hartwig偶联反应已有文献报道(Inoue,F.；Kashihara,M.；Yadav,M.R.；Nakao,Y.Buchwald-Hartwig Amination of Nitroarenes，AngewandteChemie International Edition，2017,56(43),13307–13309)，该反应使用的是膦配体Brettphos(2-二环己基膦基-3,6-二甲氧基-2’,4’,6’-三异丙基联苯)。但是，上述膦配体的制备条件苛刻、对空气敏感、价格昂贵，且其催化剂的效率不高，导致该反应中的催化剂用量较大，底物范围小，因此开发新配体来实现硝基苯的Buchwald-Hartwig偶联反应有重要的意义。
N-杂环卡宾是一类强σ-给电子体，其给电子能力可以与膦配体相媲美，通过增大N-杂环卡宾配体的位阻所设计出来的N-杂环卡宾配体是膦配体强有力的竞争者，目前在许多偶联反应中，都出现了效果拔群，能够替代磷配体的N-杂环卡宾配体(Valente,C.；S.；Hoi,K.H.；Mallik,D.；Sayah,M.；Organ,M.G.The Development of BulkyPalladium NHC Complexes for the Most-Challenging Cross-Coupling Reactions，Angew.Chem.Int.Ed.2012,51(14),3314–3332)。
发明内容
本发明的目的在于提供了一种钯/咪唑盐催化硝基芳烃和胺类化合物偶联合成芳香族化合物的方法，该反应操作简单、收率高、配体用量较低、底物适用性好，适合大规模的推广应用。
为了实现上述发明目的，本发明的技术方案如下：
一种钯/咪唑盐催化硝基芳烃和胺类化合物合成芳香胺化合物的方法，包括：在有机溶剂中，以钯/咪唑盐为催化剂，将硝基芳烃和胺类化合物在碱的作用下进行偶联反应，经后处理得到芳香族化合物；
所述的硝基芳烃的结构如下式(I)所示：
Ar-NO2 (I)
所述的胺类化合物的结构如下式(II)所示：
式(I)中，Ar为芳基或杂芳基；式(II)中，R1为氢或烷基，R2为烷基、芳基或杂芳基。
作为优选，式(I)中，Ar为苯基、取代苯基或含氮杂芳基；式(II)中，R1为氢或烷基，R2为烷基、苯基、取代苯基或含氮杂环。
上述合成方法的反应方程式如下：
本发明中的钯/咪唑盐在碱作用下原位生成N-杂环卡宾零价钯配合物，然后对硝基芳烃进行氧化加成，在碱作用下与胺类化合物进行转金属化，还原消除得到芳香胺化合物，同时再生得到N-杂环卡宾零价钯配合物，完成催化循环，不仅减少了配体的用量，还提高了产物的收率。
所述的咪唑盐的结构如下式(III)所示：
式(III)中，R1、R2、R3独立的选自氢、卤素、烷基或烷氧基，Y-为Cl-、Br-、I-、PF6 -或BF4 -。
作为优选，上述咪唑盐的结构如下式中的L1～L9所示：
进一步优选，所述的咪唑盐为L1～L5，这是由于优选的配体会使产物收率更高。
所述的钯为乙酰丙酮钯(II)、醋酸钯(II)、氯化钯(II)、双(乙腈)氯化钯(II)、双(三苯基膦)氯化钯(II)、三氟乙酸钯(II)、三(二亚苄基丙酮)二钯或烯丙基氯化钯(II)二聚体中的任意一种。
作为优选，所述的钯为乙酰丙酮钯(II)、醋酸钯(II)、氯化钯(II)、双(乙腈)氯化钯(II)、三氟乙酸钯(II)或烯丙基氯化钯(II)二聚体中的任意一种，优选的钯盐制得的产物收率更高。
所述的溶剂为二氧六环、甲苯、四氢呋喃、N,N-二甲基甲酰胺、乙腈、甲基叔丁基醚、正庚烷、异丙醇或乙二醇二甲醚中的任意一种。
作为优选，所述的有机溶剂为二氧六环、甲苯或正己烷，优选的有机溶剂得到的产物收率更高。
以硝基芳烃的摩尔量计，所述有机溶剂的用量为1～10L/mol，优选为4～6L/mol。
所述的碱为磷酸三钾三水合物、无水磷酸钾、碳酸钾、氟化铯、碳酸铯、乙酸钾、磷酸氢二钾、氢氧化钾、三乙胺或1,8-二氮杂二环十一碳-7-烯中的任意一种。
作为优选，所述的碱为磷酸三钾三水合物、无水磷酸钾、氟化铯或碳酸铯中的任意一种。
所述的偶联反应的温度为100～160℃，反应时间为12～48h。
所述的钯、咪唑盐和硝基芳烃的摩尔比为1：(1～4)：(5～100)，优选为1：(1～2)：(10～100)。
所述的硝基芳烃、硼酸化合物和碱的摩尔比为1：(1～3)：(1～5)，优选为1：(1～2)：(1.5～3)。
所述的后处理包括：先利用硅藻土除去不溶物并旋干溶剂，再用硅胶柱色谱进行分离，得到产物。
与现有技术相比，本发明具有以下有益效果：本发明首次将咪唑盐作为N-杂环卡宾前体与钯原位结合后催化硝基芳烃与胺类化合物的Buchwald-Hartwig偶联反应，该反应操作简单，收率高，所用的配体合成简单、易于保存、价格便宜且配体的用量较低，底物适用性好，可用于二芳基胺、N-烷基芳胺的制备。本发明方法可用于合成一系列芳香胺化合物，该类化合物在农药、医药、材料等领域均有广泛的应用价值。
具体实施方式
通过下述实施例将有助于理解本发明，但本发明的内容并不仅限于此。下列实施例中所述的咪唑盐L1～L5的反应方程式如下所示，式(L)中，L1：R1＝R2＝R3＝Me；L2：R1＝R2＝iPr，R3＝H；L3：R1＝R2＝Et，R3＝Me；L4：R1＝R2＝Et，R3＝H；L5：R1＝R2＝Me，R3＝H。
具体合成步骤为：
(1)在史莱克管中依次加入A(1mmol,309mg)和B(1.2mmol)。在N2氛围下三抽三通，然后加入10mL甲醇和10μL甲酸(≥88％)，在60℃下反应24h。冷却至室温，反应液抽滤得淡黄固体，用甲醇(3×5mL)洗涤，真空干燥得C；
(2)将C(0.2mmol)，多聚甲醛(0.2mmol,5.9mg)，干燥甲苯(1.5mL)和三甲基氯硅烷TMSCl(0.4mmol,50μL)依次加入到封管中。室温下搅拌24h，反应液旋干后，用乙醚(3×1.5mL)，正己烷(3×1.5mL)洗涤，最后真空干燥得咪唑盐L。
实施例1
在氮气氛围中，往干燥的封管中加入92mg的上述硝基芳烃，96.4mg的芳香胺，9.2mg的Pd(acac)2，15.0mg的咪唑盐L3，480mg的磷酸三钾三水合物，3mL的二氧六环，然后拧紧封管螺纹帽，130℃下反应24h。反应结束后用硅藻土过滤，浓缩，过硅胶柱，得到产物119mg，产率93％。
对本实施例制备得到的产物进行核磁共振分析：
1H NMR(400MHz,CDCl3)δ7.12–7.04(m,4H),6.95–6.86(m,4H),5.36(bs,1H),3.83(s,3H),2.33(s,3H)；13C NMR(100MHz,CDCl3)δ154.8,142.5,136.7,129.9,129.3,121.1,116.6,114.7,55.6,20.6.
实施例2
在氮气氛围中，往干燥的封管中加入120mg的上述硝基芳烃，96.4mg的芳香胺，1.4mg的Pd(OAc)2，30.0mg的咪唑盐L3，480mg的磷酸三钾三水合物，3mL的甲苯，然后拧紧封管螺纹帽，130℃下反应24h。反应结束后用硅藻土过滤，浓缩，过硅胶柱，得到产物125.9mg，产率80％。
对本实施例制备得到的产物进行核磁共振分析：
1H NMR(400MHz,CDCl3)δ7.40–7.30(m,4H),7.29–7.20(m,2H),7.17–7.10(m,2H),6.98(d,J＝8.2Hz,2H),6.93–6.83(m,3H),5.27(bs,1H),2.20(s,3H)；13C NMR(100MHz,CDCl3)δ140.9,140.5,139.1,131.2,130.9,129.9,129.4,129.0,128.3,127.5,120.5,119.4,116.6,20.8.
实施例3
在氮气氛围中，往干燥的封管中加入92mg的上述硝基芳烃，96.4mg的芳香胺，10.6mg的PdCl2，45.0mg的咪唑盐L3，480mg的磷酸三钾三水合物，3mL的甲苯，然后拧紧封管螺纹帽，130℃下反应24h。反应结束后用硅藻土过滤，浓缩，过硅胶柱，得到产38.2mg，产率30％。
对本实施例制备得到的产物进行核磁共振分析：
1H NMR(400MHz,CDCl3)δ7.15-7.13(m,1H),7.04–6.96(m,4H),6.81–6.69(m,3H),6.01(bs,1H),3.79(s,3H),2.22(s,3H)；13C NMR(100MHz,CDCl3)δ148.0,139.9,133.7,131.2,129.8,120.9,119.7,119.4,113.9,110.4,55.6,20.8.
实施例4
在氮气氛围中，往干燥的封管中加入100.9mg的上述硝基芳烃，96.4mg的芳香胺，9.7mg的Pd(TFA)2，60.0mg的咪唑盐L3，480mg的磷酸三钾三水合物，3mL的二氧六环，然后拧紧封管螺纹帽，130℃下反应24h。反应结束后用硅藻土过滤，浓缩，过硅胶柱，得到产物54.9mg，产率40％。
对本实施例制备得到的产物进行核磁共振分析：
1H NMR(400MHz,CDCl3)δ9.46(s,1H),8.19(dd,J＝8.6,1.5Hz,1H),7.34(m,1H),7.23(d,J＝8.1Hz,2H),7.19–7.12(m,3H),6.73(m,1H),2.39(s,3H)；13C NMR(100MHz,CDCl3)δ143.7,135.9,135.7,135.7,132.8,130.3,126.6,124.8,117.1,116.0,21.0.
实施例5
在氮气氛围中，往干燥的封管中加入120mg的上述硝基芳烃，96.4mg的芳香胺，11.20mg的烯丙基氯化钯，30.0mg的咪唑盐L3，480mg的磷酸三钾三水合物，3mL的正己烷，然后拧紧封管螺纹帽，130℃下反应24h。反应结束后用硅藻土过滤，浓缩，过硅胶柱，得到产物129.6mg，产率80％。
对本实施例制备得到的产物进行核磁共振分析：
1H NMR(400MHz,CDCl3)δ7.61(d,J＝7.2Hz,2H),7.46(t,J＝7.5Hz,2H),7.41–7.31(m,2H),7.29(t,J＝1.9Hz,1H),7.19–7.01(m,6H),5.65(bs,1H),2.36(s,3H)；13C NMR(100MHz,CDCl3)δ144.3,142.6,141.3,140.1,131.4,130.0,129.8,128.7,127.4,127.2,119.5,119.3,115.9,115.7,20.8.
实施例6
在氮气氛围中，往干燥的封管中加入108.7mg的上述硝基芳烃，96.4mg的芳香胺，7.8mg的PdCl2(MeCN)2，30.0mg的咪唑盐L3，480mg的磷酸三钾三水合物，3mL的正己烷，然后拧紧封管螺纹帽，130℃下反应24h。反应结束后用硅藻土过滤，浓缩，过硅胶柱，得到产物108.9mg，产率75％。
对本实施例制备得到的产物进行核磁共振分析：
1H NMR(400MHz,CDCl3)δ7.66(s,1H),7.53(d,J＝7.6Hz,1H),7.29(t,J＝7.9Hz,1H),7.18(dd,J＝7.7,1.9Hz,1H),7.07(dd,J＝38.0,8.2Hz,4H),5.16(s,1H),3.89(s,3H),2.33(s,3H)；13C NMR(100MHz,CDCl3)δ167.2,144.3,139.5,131.8,131.3,130.0,129.3,121.2,120.6,119.5,117.3,52.1,20.8.
实施例7
在氮气氛围中，往干燥的封管中加入120mg的上述硝基芳烃，96.4mg的芳香胺，9.2mg的Pd(acac)2，30.0mg的咪唑盐L3，240mg的磷酸三钾三水合物，3mL的二氧六环，然后拧紧封管螺纹帽，130℃下反应24h。反应结束后用硅藻土过滤，浓缩，过硅胶柱，得到产物124.7mg，产率80％。
对本实施例制备得到的产物进行核磁共振分析：
1H NMR(400MHz,CDCl3)δ7.70–7.65(m,2H),7.62–7.56(m,2H),7.55–7.48(m,2H),7.43–7.36(m,1H),7.21(d,J＝8.1Hz,2H),7.19–7.11(m,4H),5.54(bs,1H),2.43(s,3H)；13CNMR(100MHz,CDCl3)δ143.4,141.0,140.1,133.2,131.3,130.1,128.9,128.1,126.6，126.6,119.3,117.1,20.9.
实施例8
在氮气氛围中，往干燥的封管中加入mg的上述硝基芳烃，96.4mg的芳香胺，9.2mg的Pd(acac)2，30.0mg的咪唑盐L3，320mg的磷酸三钾三水合物，3mL的二氧六环，然后拧紧封管螺纹帽，160℃下反应24h。反应结束后用硅藻土过滤，浓缩，过硅胶柱，得到产物72.6mg，产率60％。
对本实施例制备得到的产物进行核磁共振分析：
1H NMR(400MHz,CDCl3)δ7.11(d,J＝8.4Hz,2H),7.03-6.94(m,6H),5.18(bs,1H),2.34(s,3H)；13C NMR(100MHz,CDCl3)δ157.7(d,J＝239.0Hz,0H),141.1(s,3H),139.8(d,J＝2.4Hz,3H),130.6(s,3H),130.0(s,13H),119.5(d,J＝7.7Hz,13H),118.0(s,13H),115.9(d,J＝22.2Hz,13H),20.7(s,5H)；19F NMR(376MHz,CDCl3)δ-122.9.
实施例9
在氮气氛围中，往干燥的封管中加入99.1mg的上述硝基芳烃，96.4mg的芳香胺，1.8mg的Pd(acac)2，30.0mg的咪唑盐L3，254mg的磷酸三钾，3mL的二氧六环，然后拧紧封管螺纹帽，100℃下反应24h。反应结束后用硅藻土过滤，浓缩，过硅胶柱，得到产物27.2mg，产率20％。
对本实施例制备得到的产物进行核磁共振分析：
1H NMR(400MHz,CDCl3)δ7.84(d,J＝8.8Hz,2H),7.16(d,J＝8.2Hz,2H),7.09(d,J＝8.4Hz,2H),6.94(s,1H),6.92(s,1H),5.62(bs,1H),2.52(s,3H),2.34(s,3H)；13C NMR(100MHz,CDCl3)δ196.5,149.1,137.8,133.4,130.7,130.1,128.5,121.6,113.9,26.1,20.9.
实施例10
在氮气氛围中，往干燥的封管中加入104.5mg的上述硝基芳烃，96.4mg的芳香胺，18.4mg的Pd(acac)2，30.0mg的咪唑盐L3，273mg的氟化铯，3mL的二氧六环，然后拧紧封管螺纹帽，100℃下反应24h。反应结束后用硅藻土过滤，浓缩，过硅胶柱，得到产物84.2mg，产率60％。
对本实施例制备得到的产物进行核磁共振分析：
1H NMR(400MHz,CDCl3)δ9.22(s,1H),8.48(d,J＝6.0Hz,1H),7.77(d,J＝6.0Hz,1H),7.54(d,J＝7.4Hz,1H),7.48–7.39(m,2H),7.12(d,J＝8.1Hz,2H),7.00(d,J＝8.3Hz,2H),6.20(s,1H),2.33(s,3H)；13C NMR(100MHz,CDCl3)δ152.9,142.5,140.5,139.4,131.6,130.1,129.2,129.0,127.7,120.4,119.5,116.0,114.7,20.8.
实施例11
在氮气氛围中，往干燥的封管中加入74.5mg的上述硝基芳烃，96.4mg的芳香胺，9.2mg的Pd(acac)2，30.0mg的咪唑盐L3，137mg的碳酸铯，3mL的二氧六环，然后拧紧封管螺纹帽，130℃下反应48h。反应结束后用硅藻土过滤，浓缩，过硅胶柱，得到产物44.2mg，产率40％。
对本实施例制备得到的产物进行核磁共振分析：
1H NMR(400MHz,CDCl3)δ8.33(d,J＝2.2Hz,1H),8.08(d,J＝4.2Hz,1H),7.35(d,J＝9.7Hz,1H),7.15–7.05(m,3H),7.01(d,J＝8.4Hz,2H),6.32(bs,1H),2.31(s,3H)；13C NMR(100MHz,CDCl3)δ141.0,140.5,139.2,138.9,131.9,130.1,123.9,122.4,119.4,20.8.
实施例12
在氮气氛围中，往干燥的封管中加入103.9mg的上述硝基芳烃，194.7mg的芳香胺，9.2mg的Pd(acac)2，30.0mg的咪唑盐L3，480mg的磷酸三钾三水合物，3mL的二氧六环，然后拧紧封管螺纹帽，130℃下反应24h。反应结束后用硅藻土过滤，浓缩，过硅胶柱，得到产物138.1mg，产率80％。
对本实施例制备得到的产物进行核磁共振分析：
1H NMR(400MHz,CDCl3)δ8.22–8.16(m,1H),8.02–7.96(m,1H),7.68–7.60(m,2H),7.42(d,J＝8.1Hz,1H),7.35(t,J＝7.8Hz,1H),7.20(s,2H),6.39(dd,J＝7.5,1.0Hz,1H),5.69(bs,1H),2.86–2.59(m,4H),2.55(s,3H),1.30(t,J＝7.6Hz,6H)；13C NMR(100MHz,CDCl3)δ142.8,141.9,136.1,134.8,134.7,129.0,127.7,126.8,125.9,125.1,123.7,120.3,118.3,106.9,24.7,21.4,15.1.
实施例13
在氮气氛围中，往干燥的封管中加入103.9mg的上述硝基芳烃，111.1mg的芳香胺，9.2mg的Pd(acac)2，30.0mg的咪唑盐L5，480mg的磷酸三钾三水合物，3mL的二氧六环，然后拧紧封管螺纹帽，130℃下反应12h。反应结束后用硅藻土过滤，浓缩，过硅胶柱，得到产物163.0mg，产率87％。
对本实施例制备得到的产物进行核磁共振分析：
1H NMR(400MHz,DMSO)δ9.49(s,1H),8.03–7.96(m,2H),7.85(d,J＝7.7Hz,1H),7.78(d,J＝8.7Hz,1H),7.60–7.51(m,4H),7.31(d,J＝2.2Hz,1H),7.00(dd,J＝8.7,2.2Hz,1H)；13C NMR(100MHz,DMSO)δ150.8,136.7,135.0,134.4,132.26(q,J＝31.3Hz),128.6,128.4,126.6,126.4,126.0(d,J＝13.4Hz),124.0,122.5,121.3,121.1,116.8,115.5,111.7,94.3；19F NMR(376MHz,DMSO)δ-61.58.
实施例14
在氮气氛围中，往干燥的封管中加入103.9mg的上述硝基芳烃，128.5mg的芳香胺，9.2mg的Pd(acac)2，30.0mg的咪唑盐L4，480mg的磷酸三钾三水合物，3mL的二氧六环，然后拧紧封管螺纹帽，130℃下反应36h。反应结束后用硅藻土过滤，浓缩，过硅胶柱，得到产物135.7mg，产率97％。
对本实施例制备得到的产物进行核磁共振分析：
1H NMR(400MHz,CDCl3)δ7.97(d,J＝8.1Hz,1H),7.90(d,J＝8.4Hz,1H),7.65–7.41(m,9H),6.77(d,J＝7.4Hz,1H),4.85(bs,1H),4.59(s,2H)；13C NMR(100MHz,CDCl3)δ143.4,139.3,134.5,128.9,127.9,127.6,126.8,126.0,125.0,123.6,120.2,117.9,105.1,48.7.
实施例15
在氮气氛围中，往干燥的封管中加入103.9mg的上述硝基芳烃，78.0mg的吗啡啉，9.2mg的Pd(acac)2，30.0mg的咪唑盐L3，480mg的磷酸三钾三水合物，3mL的二氧六环，然后拧紧封管螺纹帽，130℃下反应48h。反应结束后用硅藻土过滤，浓缩，过硅胶柱，得到产物108.2mg，产率84％。
对本实施例制备得到的产物进行核磁共振分析：
1H NMR(400MHz,CDCl3)δ8.25(dd,J＝8.1,1.6Hz,1H),7.89–7.84(m,1H),7.60(d,J＝8.2Hz,1H),7.55–7.47(m,2H),7.44(t,J＝7.6Hz,1H),7.11(dd,J＝7.4,0.9Hz,1H),4.01(t,J＝4.4Hz,4H),3.14(t,J＝4.4Hz,4H)；13C NMR(100MHz,CDCl3)δ149.5,134.8,128.8,128.5,126.0,125.9,125.5,123.9,123.5,114.7,67.5,53.5.
实施例16
在氮气氛围中，往干燥的封管中加入103.9mg的上述硝基芳烃，90.1mg的N-胺基哌啶，9.2mg的Pd(acac)2，20.0mg的咪唑盐L3，480mg的磷酸三钾三水合物，3mL的二氧六环，然后拧紧封管螺纹帽，130℃下反应24h。反应结束后用硅藻土过滤，浓缩，过硅胶柱，得到产物117.5mg，产率86％。
对本实施例制备得到的产物进行核磁共振分析：
1H NMR(400MHz,CDCl3)δ7.88–7.82(m,2H),7.51–7.40(m,3H),7.39–7.30(m,2H),5.06(s,1H),2.81(s,4H),1.83–1.75(m,4H),1.52(s,2H)；13C NMR(100MHz,CDCl3)δ142.2,134.4,128.7,126.8,125.6,124.7,122.9,120.1,119.0,107.7,57.4,26.2,23.8.
实施例17
在氮气氛围中，往干燥的封管中加入103.9mg的上述硝基芳烃，96.4mg的N-甲基芳香胺，9.2mg的Pd(acac)2，15.0mg的咪唑盐L2，480mg的磷酸三钾三水合物，3mL的二氧六环，然后拧紧封管螺纹帽，130℃下反应24h。反应结束后用硅藻土过滤，浓缩，过硅胶柱，得到产物99.7mg，产率71％。
对本实施例制备得到的产物进行核磁共振分析：
1H NMR(400MHz,CDCl3)δ8.03(d,J＝8.4Hz,2H),7.91(d,J＝8.2Hz,1H),7.62(t,J＝7.8Hz,2H),7.55(t,J＝7.6Hz,1H),7.50(d,J＝7.3Hz,1H),7.29(t,J＝7.5Hz,2H),6.87(t,J＝6.8Hz,1H),6.76(d,J＝8.4Hz,2H),3.52(s,3H)；13C NMR(100MHz,CDCl3)δ150.2,145.5,135.3,131.5,129.1,128.6,126.8,126.6,126.5,126.4,125.4,124.0,117.4,113.7,40.3.
实施例18
在氮气氛围中，往干燥的封管中加入103.9mg的上述硝基芳烃，43.9mg的正丁胺，9.2mg的Pd(acac)2，20.0mg的咪唑盐L3，480mg的磷酸三钾三水合物，3mL的二氧六环，然后拧紧封管螺纹帽，130℃下反应24h。反应结束后用硅藻土过滤，浓缩，过硅胶柱，得到产物110.6mg，产率92％。
对本实施例制备得到的产物进行核磁共振分析：
1H NMR(400MHz,CDCl3)δ7.85(dd,J＝7.0,2.5Hz,2H),7.54–7.45(m,2H),7.42(t,J＝7.9Hz,1H),7.29(d,J＝8.2Hz,1H),6.68(d,J＝7.5Hz,1H),4.41(bs,1H),3.32(t,J＝7.1Hz,2H),1.80(dt,J＝14.6,7.3Hz,2H),1.57(dq,J＝14.6,7.3Hz,2H),1.06(t,J＝7.4Hz,3H)；13C NMR(100MHz,CDCl3)δ143.6,134.4,128.7,126.7,125.7,124.7,123.4,119.9,117.3,104.5,44.1,31.6,20.6,14.1.
实施例19
在氮气氛围中，往干燥的封管中加入103.9mg的上述硝基芳烃，171.8mg的5-氨基喹啉，9.2mg的Pd(acac)2，15.0mg的咪唑盐L1，480mg的磷酸三钾三水合物，3mL的二氧六环，然后拧紧封管螺纹帽，130℃下反应24h。反应结束后用硅藻土过滤，浓缩，过硅胶柱，得到产物141.8mg，产率87％。
对本实施例制备得到的产物进行核磁共振分析：
1H NMR(400MHz,CDCl3)δ8.92(dd,J＝4.2,1.6Hz,1H),8.40–8.35(m,1H),8.07(d,J＝8.4Hz,1H),7.90(d,J＝7.6Hz,1H),7.82(d,J＝8.5Hz,1H),7.59–7.45(m,4H),7.36–7.29(m,2H),7.02(d,J＝7.5Hz,1H),6.95(d,J＝7.4Hz,1H),6.44(s,1H)；13C NMR(100MHz,CDCl3)δ150.5,149.3,140.6,140.1,134.7,130.8,129.9,128.7,126.9,126.3,126.2,125.9,123.7,122.9,122.2,121.8,120.4,116.0,115.8.

Claims (10)

1.一种钯/咪唑盐催化硝基芳烃和胺类化合物合成芳香胺化合物的方法，其特征在于，包括：在有机溶剂中，以钯/咪唑盐为催化剂，将硝基芳烃和胺类化合物在碱的作用下进行偶联反应，经后处理得到芳香族化合物；
所述的硝基芳烃的结构如下式(I)所示：
Ar-NO2 (I)
所述的胺类化合物的结构如下式(II)所示：
式(I)中，Ar为芳基或杂芳基；式(II)中，R1为氢或烷基，R2为烷基、芳基或杂芳基。
2.根据权利要求1所述的合成芳香胺化合物的方法，其特征在于，式(I)中，Ar为苯基、取代苯基或含氮杂芳基；式(II)中，R1为氢或烷基，R2为烷基、苯基、取代苯基或含氮杂环。
3.根据权利要求1所述的合成芳香胺化合物的方法，其特征在于，所述的咪唑盐的结构如下式(III)所示：
式(III)中，R1、R2、R3独立的选自氢、卤素、烷基或烷氧基，Y-为Cl-、Br-、I-、PF6 -或PF4 -。
4.根据权利要求3所述的合成芳香胺化合物的方法，其特征在于，所述的咪唑盐的结构如下式L1～L9所示：
5.根据权利要求1所述的合成芳香胺化合物的方法，其特征在于，所述的钯为乙酰丙酮钯(II)、醋酸钯(II)、氯化钯(II)、双(乙腈)氯化钯(II)、双(三苯基膦)氯化钯(II)、三氟乙酸钯(II)、三(二亚苄基丙酮)二钯或烯丙基氯化钯(II)二聚体中的任意一种。
6.根据权利要求1所述的合成芳香胺化合物的方法，其特征在于，所述的有机溶剂为二氧六环、甲苯、四氢呋喃、N,N-二甲基甲酰胺、乙腈、甲基叔丁基醚、正庚烷、异丙醇或乙二醇二甲醚中的任意一种。
7.根据权利要求1所述的合成芳香胺化合物的方法，其特征在于，所述的碱为磷酸三钾三水合物、无水磷酸钾、碳酸钾、氟化铯、碳酸铯、乙酸钾、磷酸氢二钾、氢氧化钾、三乙胺或1,8-二氮杂二环十一碳-7-烯中的任意一种。
8.根据权利要求1所述的合成芳香胺化合物的方法，其特征在于，所述的偶联反应的温度为100～160℃，反应时间为12～48h。
9.根据权利要求1所述的合成芳香族化合物的方法，其特征在于，所述的钯、咪唑盐和硝基芳烃的摩尔比为1：(1～4)：(5～100)。
10.根据权利要求1所述的合成芳香族化合物的方法，其特征在于，所述的硝基芳烃、胺类化合物和碱的摩尔比为1：(1～3)：(1～5)。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116003263A (zh) * 2023-01-06 2023-04-25 中山大学 一种有机膦催化硝基芳烃、硝基烷烃与格式试剂还原偶联制备芳胺类化合物的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102770414A (zh) * 2010-04-28 2012-11-07 第一三共株式会社 ［5,6］杂环化合物
US20140248646A1 (en) * 2013-03-04 2014-09-04 Indiana University Research And Technology Corporation IMIDAZO[1,5-a]PYRIDINIUM ION FLUOROPHORES, AND METHODS OF MAKING AND USING THE SAME
JP2018070527A (ja) * 2016-10-31 2018-05-10 東ソー株式会社 芳香族アミンの製造方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102770414A (zh) * 2010-04-28 2012-11-07 第一三共株式会社 ［5,6］杂环化合物
US20140248646A1 (en) * 2013-03-04 2014-09-04 Indiana University Research And Technology Corporation IMIDAZO[1,5-a]PYRIDINIUM ION FLUOROPHORES, AND METHODS OF MAKING AND USING THE SAME
JP2018070527A (ja) * 2016-10-31 2018-05-10 東ソー株式会社 芳香族アミンの製造方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FUMIYOSHI INOUE等: "Buchwald–Hartwig Amination of Nitroarenes", 《ANGEW. CHEM. INT. ED.》 *
XIAOHUA HUANG等: "Expanding Pd-Catalyzed C-N Bond-Forming Processes: The First Amidation of Aryl Sulfonates, Aqueous Amination, and Complementarity with Cu-Catalyzed Reactions", 《J. AM. CHEM. SOC.》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116003263A (zh) * 2023-01-06 2023-04-25 中山大学 一种有机膦催化硝基芳烃、硝基烷烃与格式试剂还原偶联制备芳胺类化合物的方法

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