CN108373416B - 一种光/镍协同催化合成二芳胺的方法 - Google Patents

一种光/镍协同催化合成二芳胺的方法 Download PDF

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CN108373416B
CN108373416B CN201810396913.8A CN201810396913A CN108373416B CN 108373416 B CN108373416 B CN 108373416B CN 201810396913 A CN201810396913 A CN 201810396913A CN 108373416 B CN108373416 B CN 108373416B
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黄治炎
解昆
孟鸽
马俊杰
薛东
杨俊�
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Shaanxi Normal University
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Abstract

本发明公开了一种光/镍协同催化合成二芳胺的方法，该方法无需外加配体，直接以简单便宜的镍盐为金属催化剂，与光敏剂协同催化芳胺与溴代芳烃之间发生交叉偶联。该方法优势在于：1)BODIPY类有机光催化剂用量低，较文献报道的金属铱、钌光敏剂具有更好的催化效果；2)BODIPY类有机光敏剂容易合成；3)镍盐用量少，无需外加配体；4)反应条件温和，偶联产物收率大多高于90％。本发明方法无需高温高压设备，温度变化范围小，实验流程简单，易于操作，具有较高的应用价值和工业推广潜力。

Description

一种光/镍协同催化合成二芳胺的方法
技术领域
本发明涉及一种采用氟硼二吡咯(BODIPY)类有机光敏剂与镍盐协同催化卤代芳烃与芳胺发生Buchwald-Hartwig交叉偶联，合成二芳胺类重要中间体的方法。
背景技术
二芳胺类结构普遍存在于生物活性分子、药物分子以及功能材料分子中，其合成方法研究一直是有机合成领域的重要课题之一。其中，Buchwald-Hartwig交叉偶联反应是合成这类化合物最为重要的途径。寻找简捷高效的催化方法，通过Buchwald-Hartwig交叉偶联构建C-N键是有机合成研究领域的重要研究内容之一。目前，以芳基卤代物和芳胺为原料合成二芳胺的催化体系主要分为两大类，具体如下：
1、以金属盐与配体所形成的复合物为催化剂
1998年，Hartwig等报道(Angew.Chem.Int.Ed.1998,37,2046-2067)金属钯与双二苯基膦二茂铁配体所形成的复合物在65～100℃下催化卤代芳烃与芳胺偶联，产率介于80％～94％之间。
Figure BDA0001644785310000011
2006年，Hill等报道(J.Org.Chem.,2006,71,5117.)金属钯和烷基膦配体所形成的复合物在室温下催化对溴甲苯与苯胺偶联，产率86％。
Figure BDA0001644785310000012
2007年，Yang等报道(J.Org.Chem.,2007,72,6324-6327.)金属镍与三苯基膦所形成的复合物在100℃下催化氯代芳烃与芳胺偶联，产率介于66％～99％之间。
Figure BDA0001644785310000021
2008年，Doherty等报道(Organometallics,2008,27,1679.)金属钯和烯基膦配体所形成的复合物在80℃左右催化溴代芳烃与苯胺偶联，产率79％左右。
Figure BDA0001644785310000022
2008年，Buchwald等报道(J.Am.Chem.Soc.2008,130,13552-13554.)钯与二环己基膦配体所形成的复合物在80～110℃催化氯代芳烃与芳胺偶联，产率介于82％～99％之间。
Figure BDA0001644785310000023
2010年，Chang等报道(Org.Lett.,2010,12,1630-1643.)金属铑与1,5-环辛二烯四氟硼酸盐所形成的复合物在80℃下催化溴代芳烃与苯胺偶联，产率介于51％～81％之间。
Figure BDA0001644785310000024
2011年，Wan等报道(Appl.Organomet.Chem.2011,25,341.)铜盐与草酸二酰肼配体所形成的复合物在微波作用下，催化卤代芳烃与芳胺偶联，产率80％左右。
Figure BDA0001644785310000031
2017年，Sundaram等报道(Sundaram.G.B,Catal Lett.,2017,147,2619-2629.)钯铝非均相催化溴苯与对甲苯胺在高温下偶联，产率80％。
Figure BDA0001644785310000032
2、金属/光协同催化
2016年，Oderinde和Johannes共同报道了协同催化方法(Angew.Chem.Int.Ed.2016,55,13219–13223)，采用镍/铱光敏剂协同催化碘代芳烃与芳胺在室温下发生交叉偶联，产率介于30％～85％之间。然而，该方法以昂贵的碘代物为原料，还需使用联吡啶配体和昂贵的金属铱光敏剂，实用价值不高。
Figure BDA0001644785310000033
综述所述，以金属盐与配体所形成的复合物为催化剂一直是构建C-N键的研究重点，很多不同结构的配体得到发展，取得了很大的进展。然而，这些催化体系往往具有局限性，不同底物需要使用相应的特异性配体，且往往需要高温和强碱。镍/光协同催化是近年来发展的一种全新的催化策略，反应条件绿色温和；目前，通过光催化策略合成二芳胺的相关报道仅限于上述一篇文献，还处于技术发展的初期。
发明内容
本发明的目的在于提供一种采用镍盐和BODIPY类有机光敏剂协同催化便宜溴代芳烃与芳胺发生Buchwald-Hartwig交叉偶联，合成不同结构的二芳胺类重要有机合成中间体的方法。
解决上述技术问题所采用的技术方案为：在氮气氛围下，将式I所示的溴代芳烃和式II所示的芳胺加入有机溶剂中，再依次加入镍盐、BODIPY类有机光敏剂、有机碱和添加剂，将反应液升至50～80℃，在可见光照射下反应12～40小时，分离得到二芳胺，反应方程式如下：
Figure BDA0001644785310000041
式中Ar1和Ar2各自独立的代表苯基、吡啶基、哌啶基、萘基、噻吩基、吲哚基、苯并噻吩基、二苯并呋喃基、喹啉基、四氢萘基、吡嗪基、甲苯基中任意一种；或者C1～C4烷基、C1～C4烷氧基、C1～C4烷基取代的硅氧基、三氟甲基、醛基、氟、氯、羟基、氨基中任意一种取代的苯基、吡啶基、哌啶基、萘基、噻吩基、吲哚基、苯并噻吩基、二苯并呋喃基、喹啉基、四氢萘基、吡嗪基等；
上述制备方法中，优选所述溴代芳烃与芳胺、镍盐、BODIPY类有机光敏剂、有机碱、添加剂的摩尔比为1:1.2～1.5:0.02～0.05:0.0001～0.0002:1.5～1.8:0.02～0.05。
上述的镍盐为氯化镍、溴化镍、碘化镍及其水合物中的任意一种。
上述的BODIPY类有机光敏剂为下述化合物1a-1h中任意一种：
Figure BDA0001644785310000051
上述化合物1a-1h(不包含化合物1b，1b为已知化合物)的合成路线和合成方法如下：
Figure BDA0001644785310000052
(1)以无水二氯甲烷为溶剂，将BODIPY 2与芳基格氏试剂按摩尔比为1:8～20，在50℃下回流反应6～12小时，反应完后用1.0mol/L盐酸淬灭，并用二氯甲烷萃取，二氯甲烷萃取液用无水硫酸钠干燥后，减压蒸干，硅胶柱色谱层析分离，得到BODIPY 3，其中所述的芳基格氏试剂为苯基溴化镁、2-萘基溴化镁、3,5-二叔丁基苯基溴化镁中任意一种。
(2)以无水二氯甲烷为溶剂，将BODIPY 3和N-碘代丁二酰亚胺按摩尔比为1:3～5，在室温下搅拌反应10分钟，反应完后加水淬灭，并用二氯甲烷萃取，二氯甲烷萃取液用无水硫酸钠干燥后，减压蒸干，硅胶柱色谱层析分离，得到BODIPY4。
(3)在氮气氛围下，将BODIPY 4、芳基硼酸加入1,4-二氧六环与乙醇、水体积比为2:1:1的混合溶剂中，然后加入K3PO4、四(三苯基磷)钯，其中BODIPY 4与芳基硼酸、K3PO4、四(三苯基磷)钯的摩尔比为1:3～5:5～7:0.05～0.2，在90℃下回流反应12小时，反应完后加水淬灭，并用二氯甲烷萃取，二氯甲烷萃取液用无水硫酸钠干燥后，减压蒸干，硅胶柱色谱层析分离，得到光催化剂，其中所述的芳基硼酸为苯硼酸、2-萘硼酸、4-联苯硼酸、二苯并噻吩-2-硼酸、2-蒽硼酸中的任意一种。
上述的有机碱为N,N-二甲基环己胺、N,N-二甲基异丙胺或N,N-二环己基甲胺。
上述的添加剂为乙二醇二甲醚或二乙二醇二甲醚，优选乙二醇二甲醚。
上述的有机溶剂为N,N-二甲基甲酰胺、N,N-二乙基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮中任意一种。
上述制备方法中，所述的可见光为蓝光、白光或绿光。
本发明将芳胺与溴代芳烃在可见光、BODIPY类有机光敏剂、镍盐、有机碱及添加剂作用下发生C-N偶联反应，即可得到目标化合物二芳胺，该方法具有如下有益效果：
1、本发明直接以简单便宜的芳胺和溴代芳烃为原料，采用廉价镍盐为催化剂，使用痕量的BODIPY类有机光敏剂为光催化剂，无需外加配体，具有经济、绿色、环保的特点。
2、本发明不需要强碱、反应条件温和、操作简便、底物适用性优异，具有良好的工业生产前景。
3、本发明还可用于合成一些重要的药物前体分子和功能材料分子。
具体实施方式
下面结合实施例对本发明进一步详细说明，但本发明的保护范围不仅限于这些实施例。
实施例1
合成结构式如下的4-甲基二苯胺
Figure BDA0001644785310000061
在氮气氛围下，将苯胺(69.85mg，0.75mmol)和4-溴甲苯(85.52mg，0.5mmol)加入含有1mLN,N-二甲基甲酰胺的10mL反应瓶中，再依次加入NiBr2·3H2O(2.73mg，0.01mmol)、化合物1a(0.096mg，0.0001mmol)、乙二醇二甲醚(0.90mg，0.01mmol)、N,N-二甲基环己胺(114.5mg，0.90mmol)，将反应液升至50℃，在波长465nm的蓝光照射下反应12小时，反应完后，停止光照、加热，待反应瓶冷却至室温，将反应液减压蒸馏，除去N,N-二甲基甲酰胺、N,N-二甲基环己胺；加入正己烷稀释残留液，过滤除去残留液中的不溶性无机盐，减压蒸馏滤液，得到4-甲基二苯胺89.8mg，收率98％，结构表征数据为：1H NMR(300MHz,CDCl3):δ7.21(t,J＝7.5Hz,2H),7.06(d,J＝8.2Hz,2H),6.97(d,J＝6.4Hz,4H),6.86(t,J＝7.3Hz,1H),5.53(s,1H),2.28(s,3H).
实施例2
本实施例中，用等摩尔的化合物1b替换实施例1中的化合物1a，其他步骤与实施例1相同，得到4-甲基二苯胺，收率94％。
实施例3
本实施例中，用等摩尔的化合物1c替换实施例1中的化合物1a，其他步骤与实施例1相同，得到4-甲基二苯胺，收率93％。
实施例4
本实施例中，用等摩尔的化合物1d替换实施例1中的化合物1a，其他步骤与实施例1相同，得到4-甲基二苯胺，收率96％。
实施例5
本实施例中，用等摩尔的化合物1e替换实施例1中的化合物1a，其他步骤与实施例1相同，得到4-甲基二苯胺，收率87％。
实施例6
本实施例中，用等摩尔的化合物1f替换实施例1中的化合物1a，其他步骤与实施例1相同，得到4-甲基二苯胺，收率90％。
实施例7
本实施例中，用等摩尔的化合物1g替换实施例1中的化合物1a，其他步骤与实施例1相同，得到4-甲基二苯胺，收率93％。
实施例8
本实施例中，用等摩尔的化合物1h替换实施例1中的化合物1a，其他步骤与实施例1相同，得到4-甲基二苯胺，收率92％。
实施例9
合成结构式如下的4-甲基-4′-三氟甲基二苯胺
Figure BDA0001644785310000081
本实施例中，用等摩尔量的4-溴三氟甲苯替换实施例1中的4-溴甲苯，用等摩尔量的4-甲基苯胺替换实施例1中的苯胺，其他步骤与实施例1相同，得到4-甲基-4′-三氟甲基二苯胺123mg，产率98％，结构表征数据为：1H NMR(400MHz,CDCl3):δ147.51(d,J＝8.5Hz,2H),7.18(d,J＝8.2Hz,2H),7.08(d,J＝8.2Hz,2H),6.98(d,J＝8.5Hz,2H),5.83(s,1H),2.37(s,3H).
实施例10
合成结构式如下的4-甲基-4′-甲酰基二苯胺：
Figure BDA0001644785310000082
本实施例中，用等摩尔量的4-溴苯甲醛替换实施例1中的4-溴甲苯，用等摩尔量的4-甲基苯胺替换实施例1中的苯胺，反应温度升高至80℃，反应完后，停止光照、加热，待反应瓶冷却至室温，加入少量稀盐酸水解生成的亚胺，然后将反应液减压蒸馏，除去N,N-二甲基甲酰胺、N,N-二甲基环己胺，其他步骤与实施例1相同，得到4-甲基-4′-甲酰基二苯胺95mg，产率90％，结构表征数据为：1H NMR(400MHz,CDCl3):δ9.77(s,1H),7.72(d,J＝8.3Hz,2H),7.18(d,J＝7.9Hz,2H),7.11(d,J＝8.0Hz,2H),6.96(d,J＝8.3Hz,2H),6.37(s,1H),2.35(s,3H).
实施例11
合成结构式如下的：4-甲基-4′-氟二苯胺
Figure BDA0001644785310000083
本实施例中，用等摩尔量的4-氟溴苯替换实施例1中的4-溴甲苯，用等摩尔量的4-甲基苯胺替换实施例1中的苯胺，其他步骤与实施例1相同，得到4-甲基-4′-氟二苯胺97.6mg，产率97％，结构表征数据为：1H NMR(400MHz,CDCl3):δ7.12(d,J＝8.1Hz,2H),7.01(d,J＝0.84Hz,2H),6.99(d,J＝3.56Hz,2H),6.95(d,J＝8.4Hz,2H),5.50(s,1H),2.35(s,3H).
实施例12
合成结构式如下的：2,3-二氟-4′-甲基二苯胺
Figure BDA0001644785310000091
本实施例中，用等摩尔量的2,3-二氟溴苯替换实施例1中的4-溴甲苯，用等摩尔量的4-甲基苯胺替换实施例1中的苯胺，其他步骤与实施例1相同，得到2,3-二氟-4′-甲基二苯胺98.6mg，产率90％，结构表征数据为：1H NMR(400MHz,CDCl3):δ7.14(d,J＝8.2Hz,2H),7.06(d,J＝8.4Hz,2H),6.94-6.87(m,2H),6.65-6.58(m,1H),5.77(s,1H),2.34(s,3H).
实施例13
合成结构式如下的N-(3-吡啶基)-4-甲基苯胺
Figure BDA0001644785310000092
本实施例中，用等摩尔量的3-溴吡啶替换实施例1中的4-溴甲苯，用等摩尔量的4-甲基苯胺替换实施例1中的苯胺，其他步骤与实施例1相同，得到N-(3-吡啶基)-4-甲基苯胺87.5mg，产率95％，结构表征数据为：1H NMR(600MHz,CDCl3):δ8.33(d,J＝2.2Hz,1H),8.10(d,J＝4.26Hz,1H),7.33(d,J＝7.2Hz,1H),7.13(d,J＝4.7Hz,1H),7.11(d,J＝7.7Hz,2H),7.00(d,J＝8.2Hz,2H),6.00(s,1H),2.32(s,3H).
实施例14
合成结构式如下的N-对甲苯基-2-萘胺
Figure BDA0001644785310000093
本实施例中，用等摩尔量的2-溴萘替换实施例1中的4-溴甲苯，用等摩尔量的4-甲基苯胺替换实施例1中的苯胺，反应温度升高至80℃，其他步骤与实施例1相同，得到N-对甲苯基-2-萘胺107.3mg，产率92％。结构表征数据如下：1H NMR(400MHz,CDCl3):δ7.75(s,1H),7.73(d,J＝2.4Hz,1H),7.64(d,J＝8.2Hz,1H),7.41(t,J＝7.7Hz,1H),7.38(d,J＝1.8Hz,1H),7.30(t,J＝7.8Hz,1H),7.19(dd,J＝8.8,2.2Hz,1H),7.16(d,J＝8.4Hz,2H),7.11(d,J＝8.4Hz,2H),5.77(s,1H),2.36(s,3H).
实施例15
合成结构式如下的N-(3-噻吩基)-4-甲基苯胺
Figure BDA0001644785310000101
本实施例中，用等摩尔量的3-溴噻吩替换实施例1中的4-溴甲苯，用等摩尔量的4-甲基苯胺替换实施例1中的苯胺，反应温度升高至80℃，其他步骤与实施例1相同，得到N-(3-噻吩基)-4-甲基苯胺94.6mg，产率91％，结构表征数据为：1H NMR(600MHz,CDCl3):δ7.25(dd,J＝4.8,3.0Hz,1H),7.09(d,J＝8.0Hz,2H),6.92(d,J＝17.9Hz,2H),6.90(dd,J＝5.1,1.3Hz,1H),6.68(dd,J＝2.9,1.3Hz,1H),5.64(s,1H),2.31(s,3H).
实施例16
合成结构式如下的N-对甲苯基-5-吲哚胺
Figure BDA0001644785310000102
本实施例中，用等摩尔量的3-溴吲哚替换实施例1中的4-溴甲苯，用等摩尔量的4-甲基苯胺替换实施例1中的苯胺，反应温度升高至80℃，反应时间延长至24h，其他步骤与实施例1相同，得到N-对甲苯基-5-吲哚胺102.2mg，产率92％，结构表征数据为：1H NMR(600MHz,CDCl3):δ8.05(s,1H),7.40(s,1H),7.32(d,J＝8.5Hz,1H),7.19(t,J＝2.8Hz,1H),7.05(d,J＝8.0Hz,2H),7.01(dd,J＝1.9,8.6Hz,1H),6.90(d,J＝8.2Hz,2H),6.48(s,1H),5.52(s,1H),2.30(s,3H).
实施例17
合成结构式如下的N-对甲苯基-5-苯并噻吩胺
Figure BDA0001644785310000103
本实施例中，用等摩尔量的5-溴苯并噻吩替换实施例1中的4-溴甲苯，用等摩尔量的4-甲基苯胺替换实施例1中的苯胺，反应温度升高至80℃，其他步骤与实施例1相同，得到N-对甲苯基-5-苯并噻吩胺83.8mg，产率70％，结构表征数据为：1H NMR(600MHz,CDCl3):δ7.73(d,J＝8.6Hz,1H),7.48(d,J＝1.8Hz,1H),7.42(d,J＝5.4Hz,1H),7.19(d,J＝5.3Hz,1H),7.11(d,J＝7.9Hz,2H),7.07(dd,J＝8.6,1.9,1H),7.02(d,J＝8.2Hz,2H),5.65(s,1H),2.32(s,3H).
实施例18
合成结构式如下的N-对甲苯基-2-二苯并呋喃胺
Figure BDA0001644785310000111
本实施例中，用等摩尔量的2-溴二苯并呋喃替换实施例1中的4-溴甲苯，用等摩尔量的4-甲基苯胺替换实施例1中的苯胺，反应温度升高至80℃，其他步骤与实施例1相同，得到N-对甲苯基-2-二苯并呋喃胺116.2mg，产率85％，结构表征数据为：1H NMR(400MHz,CDCl3):δ7.87(d,J＝7.6Hz,1H),7.65(d,J＝1.9Hz,1H),7.55(d,J＝8.2Hz,1H),7.47(d,J＝8.4Hz,1H),7.44(d,J＝8.0Hz,1H),7.31(t,J＝7.5,1H),7.16(dd,J＝8.7,2.1Hz,1H),7.10(d,J＝8.0,2H),6.98(d,J＝8.0,2H),5.63(s,1H),2.32(s,3H).
实施例19
合成结构式如下的3,4,5-三甲氧基-4′-甲基二苯胺
Figure BDA0001644785310000112
本实施例中，用等摩尔量的3,4,5-三甲氧基苯胺替换实施例1中的苯胺，其他步骤与实施例1相同，得到3,4,5-三甲氧基-4′-甲基二苯胺127.1mg，产率93％，结构表征数据为：1H NMR(400MHz,CDCl3):δ7.09(d,J＝8.2Hz,2H),6.98(d,J＝8.3Hz,2H),6.28(s,2H),5.63(s,1H),3.82(s,3H),3.79(s,6H),2.31(s,3H).
实施例20
合成结构式如下的N-对甲苯基-1-萘胺
Figure BDA0001644785310000121
本实施例中，用等摩尔量的1-萘胺替换实施例1中的苯胺，其他步骤与实施例1相同，得到N-对甲苯基-1-萘胺107.32mg，产率92％，结构表征数据为：1H NMR(600MHz,CDCl3):δ8.06(d,J＝8.2Hz,1H),7.92(d,J＝8.0Hz,1H),7.58-7.51(m,3H),7.43(t,J＝7.6Hz,1H),7.35(d,J＝7.0Hz,1H),7.15(d,J＝7.9Hz,2H),7.01(d,J＝8.2Hz,2H),5.92(s,1H),2.39(s,3H).
实施例21
合成结构式如下的N-(2-吡啶基)-4-甲基苯胺
Figure BDA0001644785310000122
本实施例中，用等摩尔量的2-氨基吡啶替换实施例1中的苯胺，其他步骤与实施例1相同，得到N-(2-吡啶基)-4-甲基苯胺77.4mg，产率84％，结构表征数据为：1H NMR(400MHz,CDCl3):δ8.18(dd,J＝4.8,0.8Hz,1H),7.45(td,J＝7.7,1.8Hz,2H),7.21(d,J＝8.3Hz,2H),7.14(d,J＝8.2Hz,2H),6.88(s,1H),6.83(d,J＝8.4Hz,1H),6.69(dd,J＝7.0,5.6Hz,1H),2.34(s,3H).
实施例22
合成结构式如下的N-[2-(4-甲基吡啶基)]-4-甲基苯胺
Figure BDA0001644785310000123
本实施例中，用等摩尔量的2-氨基-4-甲基吡啶替换实施例1中的苯胺，其他步骤与实施例1相同，得到N-[2-(4-甲基吡啶基)]-4-甲基苯胺89.2mg，产率90％，结构表征数据为：1H NMR(400MHz,CDCl3):δ8.04(d,J＝5.2Hz,1H),7.20(d,J＝8.4Hz,2H),7.14(d,J＝8.3Hz,2H),6.64(s,1H),6.54(d,J＝5.1Hz,1H),2.33(s,3H),2.23(s,3H).
实施例23
合成结构式如下的4-甲基-3′-羟基二苯胺
Figure BDA0001644785310000131
本实施例中，用等摩尔量的3-氨基苄醇替换实施例1中的苯胺，其他步骤与实施例1相同，得到4-甲基-3′-羟基二苯胺98.1mg，产率92％，结构表征数据为：1HNMR(400MHz,CDCl3):δ7.23(t,J＝7.7Hz,1H),7.12(d,J＝8.2Hz,2H),7.02(d,J＝8.3Hz,2H),6.98-6.95(m,2H),6.86(s,J＝7.4Hz,1H),5.71(s,1H),4.59(s,2H),2.34(s,3H).
实施例24
合成结构式如下的4-甲基-2′-氨基二苯胺
Figure BDA0001644785310000132
本实施例中，用等摩尔量的邻苯二胺替换实施例1中的苯胺，反应温度升高至80℃，反应时间延长至36小时，其他步骤与实施例1相同，得到4-甲基-2′-氨基二苯胺88.2mg，产率89％，结构表征数据为：1H NMR(100MHz,CDCl3):δ7.14(dd,J＝7.7,1.2Hz,1H),7.08(d,J＝8.2Hz,2H),7.04(td,J＝6.4,1.1Hz,1H),6.84-6.78(m,2H),6.73(d,J＝8.4Hz,2H),5.14(s,1H),3.77(s,2H),2.33(s,3H).
实施例25
合成结构式如下的N-对甲苯基-8-喹啉胺
Figure BDA0001644785310000133
本实施例中，用等摩尔量的8-氨基喹啉替换实施例1中的苯胺，其他步骤与实施例1相同，得到N-对甲苯基-8-喹啉胺107.8mg，产率92％，结构表征数据为：1H NMR(100MHz,CDCl3):δ8.79(dd,J＝4.1,1.5Hz,1H),8.16(s,1H),8.11(dd,J＝8.2,1.4Hz,1H),7.43-7.37(m,3H),7.31(d,J＝8.3Hz,2H),7.20(d,J＝4.1Hz,3H),2.37(s,3H).
实施例26
合成结构式如下的N-对甲苯基-3,5,5,8,8-五甲基-5,6,7,8-四氢-2-萘胺
Figure BDA0001644785310000141
本实施例中，用等摩尔量的3,5,5,8,8-五甲基-5,6,7,8-四氢萘-2-胺替换实施例1中的苯胺，其他步骤与实施例1相同，得到N-对甲苯基-3,5,5,8,8-五甲基-5,6,7,8-四氢-2-萘胺141.4mg，产率92％，结构表征数据为：1H NMR(600MHz,CDCl3):δ7.25(s,1H),7.19(s,1H),7.14(d,J＝8.2Hz,2H),6.94(d,J＝8.3Hz,2H),5.29(s,1H),2.38(s,3H),2.28(s,3H),1.75(s,4H),1.37(s,6H),1.31(s,6H).
实施例27
合成结构式如下的4-[3-(3-乙基哌啶-2,6-二酮)]-4′-甲基二苯胺
Figure BDA0001644785310000142
本实施例中，用等摩尔量的3-乙基-3-(4-氨基苯基)-2,6-哌啶二酮替换实施例1中的苯胺，其他步骤与实施例1相同，得到4-[3-(3-乙基哌啶-2,6-二酮)]-4′-甲基二苯胺146.7mg，产率91％，结构表征数据为：1H NMR(400MHz,CDCl3):δ8.73(s,1H),7.11(t,J＝8.8Hz,4H),7.01(d,J＝8.3Hz,2H),6.97(d,J＝8.3Hz,2H),2.61-2.57(m,1H),2.52-2.43(m,1H),2.31(s,3H),2.17(td,J＝13.6,4.6Hz,1H),2.08-1.99(m,1H),1.95-1.86(m,1H),0.87(t,J＝7.4Hz,3H).
实施例28
合成结构式如下的N-(2-吡啶基)-3-吡啶胺
Figure BDA0001644785310000143
本实施例中，用等摩尔量的3-溴吡啶替换实施例1中的4-溴甲苯，用等摩尔量的2-氨基吡啶替换实施例1中的苯胺，其他步骤与实施例1相同，得到N-(2-吡啶基)-3-吡啶胺73.6mg，产率86％，结构表征数据为：1H NMR(100MHz,CDCl3):δ8.25(d,J＝4Hz,1H),8.23(dd,J＝4.9,0.9Hz,1H),7.04(ddd,J＝8.3,2.4,1.4Hz,1H),7.52(td,J＝1.8,7.7Hz,1H),7.24(dd,J＝8.2,4.7Hz,1H),7.12(s,1H),6.81-6.77(m,2H).
实施例29
合成结构式如下的3-甲氧基二苯胺
Figure BDA0001644785310000151
本实施例中，用等摩尔量的溴苯替换实施例1中的4-溴甲苯，用等摩尔量的3-甲氧基苯胺替换实施例1中的苯胺，其他步骤与实施例1相同，得到3-甲氧基二苯胺89.6mg，产率90％，结构表征数据为：1H NMR(400MHz,CDCl3):δ7.31(t,J＝7.7Hz,2H),7.21(t,J＝8.6Hz,1H),7.13(d,J＝7.8Hz,2H),6.99(t,J＝7.3Hz,1H),6.69(d,J＝6.9Hz,2H),6.53(dd,J＝5.8,2.2Hz,1H),5.74(s,1H),3.81(s,3H).
实施例30
合成结构式如下的N-(3,4,5-三甲氧基苯)-6-氯-2-吡嗪胺
Figure BDA0001644785310000152
本实施例中，用等摩尔量的2,6-二氯吡嗪替换实施例1中的4-溴甲苯，用等摩尔量的3,4,5-三甲氧基苯胺替换实施例1中的苯胺，其他步骤与实施例1相同，得到N-(3,4,5-三甲氧基苯)-6-氯-2-吡嗪胺118.3mg，产率80％，结构表征数据为：1HNMR(400MHz,CDCl3):δ8.06(s,1H),7.97(s,1H),6.69(s,2H),6.57(s,1H),3.86(s,6H),3.85(s,3H).
实施例31
合成结构式如下的3-苄氧基-4-甲基-3′-三异丙基硅氧基二苯胺
Figure BDA0001644785310000153
本实施例中，用等摩尔量的3-三异丙基硅氧基溴苯替换实施例1中的4-溴甲苯，用等摩尔量的3-(苄氧基)-4-甲基苯胺替换实施例1中的苯胺，反应温度升高至80℃，反应时间延长至36h，其他步骤与实施例1相同，得到3-苄氧基-4-甲基-3′-三异丙基硅氧基二苯胺138.5mg，产率60％，结构表征数据为：1H NMR(600MHz,CDCl3):δ7.47(d,J＝7.3Hz,2H),7.42(t,J＝7.4Hz,2H),7.35(t,J＝7.3Hz,1H),7.10-7.07(m,2H),6.71(d,J＝1.6Hz,1H),6.64(dd,J＝8.0,1.9Hz,1H),6.62(t,J＝2.1Hz,1H),6.58(dd,J＝8.0,1.3Hz,1H),6.47(dd,J＝8.0,1.6Hz,1H),5.60(s,1H),5.05(s,2H),2.27(s,3H),1.15(m,3H),1.14(d,J＝7.5Hz,18H).
上述实施例中NiBr2·3H2O可以替换为等摩尔量的溴化镍、氯化镍、碘化镍等镍盐及其水合物，蓝光也可以替换为白光或绿光，N,N-二甲基甲酰胺可用等体积N,N-二乙基甲酰胺或N,N-二甲基乙酰胺替换。以上列举的仅是本发明的若干个具体实例。显然，本发明不限于以上实施案例。本领域的普通技术人员能从本发明公开的内容直接导出或联想到的所有变形，均应认为是本发明的保护范围。

Claims (5)

1.一种光/镍协同催化合成二芳胺的方法，其特征在于：在氮气氛围下，将式I所示的溴代芳烃和式II所示的芳胺加入有机溶剂中，再依次加入镍盐、BODIPY类有机光敏剂、有机碱和添加剂，将反应液升至50～80℃，在可见光照射下反应12～40小时，分离得到二芳胺；
Figure 778190DEST_PATH_IMAGE001
式中Ar1和Ar2各自独立的代表苯基、哌啶基、萘基、噻吩基、吲哚基、苯并噻吩基、二苯并呋喃基、喹啉基、四氢萘基、吡嗪基、甲苯基中任意一种；或者C1～C4烷基、C1～C4烷氧基、C1～C4烷基取代的硅氧基、三氟甲基、醛基、氟、氯、羟基、氨基、吡啶基中任意一种取代的苯基、吡啶基、萘基、噻吩基、吲哚基、苯并噻吩基、二苯并呋喃基、喹啉基、四氢萘基、吡嗪基；
上述的BODIPY类有机光敏剂为下述化合物1a-1h中任意一种：
Figure 964452DEST_PATH_IMAGE002
上述的添加剂为乙二醇二甲醚或二乙二醇二甲醚；
上述的溴代芳烃与芳胺、镍盐、BODIPY类有机光敏剂、有机碱、添加剂的摩尔比为1:1.2～1.5:0.02～0.05:0.0001～0.0002:1.5～1.8:0.02～0.05；
上述的镍盐为氯化镍、溴化镍、碘化镍及其水合物中的任意一种。
2.根据权利要求1所述的光/镍协同催化合成二芳胺的方法，其特征在于：所述的有机碱为N,N-二甲基环己胺、N,N-二甲基异丙胺或N,N-二环己基甲胺。
3.根据权利要求1所述的光/镍协同催化合成二芳胺的方法，其特征在于：所述的可见光为蓝光、白光或绿光。
4.根据权利要求1所述的光/镍协同催化合成二芳胺的方法，其特征在于：所述的添加剂为乙二醇二甲醚。
5.根据权利要求1所述的光/镍协同催化合成二芳胺的方法，其特征在于：所述的有机溶剂为N,N-二甲基甲酰胺、N,N-二乙基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮中任意一种。
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