CN117466745A - 一种光化学锰催化合成芳胺类化合物的方法 - Google Patents

一种光化学锰催化合成芳胺类化合物的方法 Download PDF

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CN117466745A
CN117466745A CN202311448035.7A CN202311448035A CN117466745A CN 117466745 A CN117466745 A CN 117466745A CN 202311448035 A CN202311448035 A CN 202311448035A CN 117466745 A CN117466745 A CN 117466745A
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manganese
aromatic amine
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薛东
宋戈洋
宋佳萌
李琪
农定展
黄柠
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Shaanxi Normal University
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Abstract

本发明公开了一种光化学廉价锰催化合成芳胺类化合物的方法，以联吡啶为配体，锰盐为催化剂，以廉价且来源丰富的芳基溴化物和胺类化合物为反应物，并添加1,8‑二氮杂环[5,4,0]十一烯‑7等作为有机碱，在氩气氛围中通过光促进锰催化芳基溴化物和胺类化合物的C‑N偶联反应实现了芳胺类化合物的合成。本发明反应体系简单、操作简便、反应条件温和，后处理简单，目标化合物选择性好、收率高，避免了传统的昂贵金属催化剂以及无机碱的使用造成催化体系反应复杂、官能团兼容性差等问题，具有很好的应用价值和市场前景。

Description

一种光化学锰催化合成芳胺类化合物的方法
技术领域
本发明属于芳胺类化合物的合成技术领域，具体涉及一种通过光化学锰催化合成芳胺类化合物的方法。
背景技术
芳基卤化物的胺化反应是合成含有N-芳基的有机化合物的方法之一，在合成化学中得到广泛应(Nature 2008,455,314；Org.Process Res.Dev.2019,23,1529)。经过20多年的发展，通过设计特定的配体策略，Pd(Chem.Soc.Rev.2013,42,9283；Chem.Rev.2016,116,12564；Angew.Chem.Int.Ed.2019,58,17118)、Cu(Angew.Chem.Int.Ed.2009,48,6954；Chem.Soc.Rev.2014,43,3525；Angew.Chem.Int.Ed.2017,56,16136)、Ni(Org.ProcessRes.Dev.2022,26,2281；Org.Chem.Front.2023,10,548)催化的芳基卤化物与N-亲核试剂的交叉偶联反应为合成芳基胺提供了重要途径。因此，发展高效的芳胺合成方法在药物化学和合成化学中具有十分重要的意义，受到合成化学家的广泛关注。随着光化学(Chem.Rev.2016,116,10075；Angew.Chem.Int.Ed.2019,58,6152；Chem.Rev.2013,113,5322)和电化学(Angew.Chem.Int.Ed.2017,56,13088；J.Am.Chem.Soc.2019,141,6392；JACS Au 2021,1,1057)的发展，为C-N偶联反应中存在的科学问题提出了新的解决方案，实现了一些难以在单一催化体系中完成的反应，但仍需要开发使用廉价和可持续的金属催化新策略。
锰是继铁和钛之后第三丰富的过渡金属，在地壳中的丰度约为1000ppm的低毒性金属与其他3d金属催化(Pd、Ni、Cu)形成碳-杂原子键相比较，Mn催化的交叉偶联反应仍然处于发展期，在过渡金属催化领域中的应用研究较少(Eur.J.Org.Chem.2016,3912)。2009年，Teo(Chem.Commun.2009,6258-6260)报道了N-亲核试剂和芳基碘化物的C-N交叉偶联反应，该反应采用MnCl2·4H2O作为催化剂，反式1,2二氨基环己烷作为配体，K3PO4为碱，水作为溶剂。然而邻位取代的芳基碘化物产物收率较差。接着，为了扩展N-亲核试剂的范围，该小组(Tetrahedron Lett.2010,51,3910–3912)提出了一种基于MnCl2·4H2O并以L-脯氨酸为配体的催化体系，用于使用芳基卤化物对脂肪胺进行N-芳基化。该方法一系列脂肪胺(例如吗啉和几种伯胺和仲胺)提供了良好到中等的产率。2012年Teo和Yong(Synlett 2012,23,2106–2110)报道了在水相中使用MnF2和Cs2CO3将亲核试剂扩展到吲哚、7-氮杂吲哚和吲唑衍生物与吡啶和噻吩碘化物的偶联。为了降低先前反应中的高温并进一步拓宽底物范围，随后该课题组开发了双金属体系MnF2/CuI(Eur.J.Org.Chem.2013,3,515–524)，在该条件下，许多C-N偶联反应在60℃可以进行。此外，该催化体系还能够实现苯甲酰胺和磺酰胺衍生物与各种芳基卤的偶联。然而，在2017年，Madsen和同事发现Teo等人在水相的锰催化C-N偶联可能是金属污染导致的催化反应，其中活性成分是可能是铜盐(Eur.J.Org.Chem.2017.5269)。在此之后，锰催化的C-N偶联反应几乎停滞不前。与Pd或Ni催化的过程相比，Mn催化的反应从机理的角度不太清楚，范围没有得到充分利用。现有的锰催化体系底物受限，仅限于芳基碘化物。因此，开发温和条件下通用锰催化偶联反应仍然十分最重要。
发明内容
本发明的目的是提供一种使用廉价的锰盐与联吡啶催化体系，实现芳基溴化物与胺类化合物的C-N偶联合成芳胺类化合物的方法。
针对上述目的，本发明所采用的技术方案是：将式I所示(杂)芳基溴化物与式II所示胺类化合物、联吡啶、锰催化剂、有机碱加入有机溶剂中，在氩气氛围中加热并光照反应，反应完后分离纯化产物，得到式III所示芳胺类化合物；
式中，所述Ar代表苯基、噻吩基、噻唑基、吡啶基、吡唑基、嘧啶基、哌啶基、吡嗪基、喹啉基、苯丙噻吩基、苯并呋喃基、二苯并噻吩基、喹喔啉基中任意一种，或者含C1～C6烷基、C6～环烷基、叔丁基二甲基硅氧基、磺酰基、苯氧基、四氢萘基、吖啶基、哌啶基、三甲基甲硅烷基、卤素、三氟甲氧基、三氟甲基、氰基、酯基、酰基、羰基、硼酯基中至少1种取代基的苯基或者吡啶基；HNNu代表芳胺、取代芳胺、杂环芳胺、吡唑、酰胺、磺酰胺、脂肪胺中任意一种。
上述合成方法中，优选胺类化合物的用量为芳基溴化物摩尔量的1.1～2倍。
上述合成方法中，优选联吡啶的用量为芳基溴化物摩尔量的5％～10％。
上述合成方法中，优选锰催化剂为溴化锰、碳酸锰、醋酸锰、氯化锰、高氯酸锰等中任意一种，其用量为芳基溴化物摩尔量的5％～10％。
上述合成方法中，优选有机碱为1,8-二氮杂二环十一碳-7-烯(DBU)、四甲基胍(TMG)、7-甲基-1,5,7-三氮杂二环[4.4.0]癸-5-烯(MTBD)、1,2-二甲基-1,4,5,6-四氢嘧啶(DMTHPM)等中任意一种，其用量为芳基溴化物摩尔量的2～3倍。
上述合成方法中，优选有机溶剂为二甲基亚砜、甲苯、异丙醇、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中任意一种或两种。
上述合成方法中，优选在氩气氛围中，在波长为360～430nm的紫外光照射下80～90℃反应24～36小时。
本发明的有益效果如下：
本发明使用锰盐与联吡啶催化体系，在光照条件下实现芳基溴化物与胺类化合物的C-N偶联反应合成芳胺类化合物。本发明反应体系简单，反应经济效益较高、对环境无害，反应后处理简单，芳胺类化合物具有收率好、官能团兼容性优异等优点，是一种简单、高效合成芳胺类化合物的方法，与目前追求环保、经济、绿色的化学概念相符合，具有非常重要的应用前景。
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并不仅限于这些实施例。
实施例1
在氩气氛围中，将31.4mg(0.2mmol)溴苯、29.4mg(0.4mmol)正丁胺、1.9mg(0.01mmol)联吡啶、2.6mg(0.01mmol)醋酸锰、60mg(0.6mmol)DBU、2mL N,N-二甲基甲酰胺、磁子加入反应管中，在波长为390～395nm的紫外光照射下，85℃反应24小时。反应完后冷却至室温，加入饱和氯化钠水溶液和乙酸乙酯稀释萃取得到有机相，有机相减压蒸馏得到粗产物，以石油醚与乙酸乙酯体积比为100:1至10:1的混合液为淋洗剂，柱层析分离粗产物，得到结构式如下的淡黄色油状产物，其产率为86％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.17(t,J＝7.6Hz,2H),6.69(t,J＝7.3Hz,1H),6.61(d,J＝8.4Hz,2H),3.12(t,J＝7.1Hz,2H),1.66-1.57(m,2H),1.52-1.37(m,2H),0.96(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ148.7,129.4,117.2,112.9,43.9,31.9,20.5,14.0；HRMS(ESI)m/z calc.for C10H16N[M+H]+:理论值150.1277,实测值150.1279。
实施例2
本实施例中，用等摩尔4-甲基溴苯替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为88％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.04(d,J＝8.5Hz,2H),6.58(d,J＝8.3Hz,2H),3.38(br,1H),3.13(t,J＝7.1Hz,2H),2.29(s,3H),1.69-1.69(m,2H),1.54-1.42(m,2H),1.01(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ146.4,129.8,126.4,113.0,44.2,31.8,20.5,20.4,14.0；HRMS(ESI)m/z C11H18N[M+H]+:理论值164.1434,实测值164.1435。
实施例3
本实施例中，用等摩尔3-(4-溴苯基)丙酸乙酯苯替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为93％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.01(d,J＝8.3Hz,2H),6.54(d,J＝8.4Hz,2H),4.13(q,J＝7.1Hz,2H),3.09(t,J＝7.1Hz,2H),2.89-2.78(m,2H),2.62-2.52(m,2H),1.65-1.54(m,2H),1.50-1.37(m,2H),1.24(t,J＝7.1Hz,3H),0.96(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ173.3,147.1,129.2,113.0,60.4,44.0,36.6,31.9,30.3,20.4,14.3,14.0；HRMS(ESI)m/z C15H24NO2[M+H]+:理论值250.1802,实测值250.1803。
实施例4
本实施例中，用等摩尔4-溴联苯醚替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为88％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.35-7.18(m,2H),6.98(t,J＝7.3Hz,1H),6.99-6.84(m,4H),6.57(d,J＝8.8Hz,2H),3.35(br,1H),3.08(t,J＝7.1Hz,2H),1.66-1.52(m,2H),1.51-1.35(m,2H),0.96(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ159.3,147.4,145.3,129.5,121.9,121.3,117.1,113.7,44.2,31.8,20.4,14.0；HRMS(ESI)m/z C16H20NO[M+H]+:理论值242.1539,实测值242.1535。
实施例5
本实施例中，用等摩尔4-氯溴苯替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为83％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.11(d,J＝8.7Hz,2H),6.51(d,J＝8.7Hz,2H),3.60(br,1H),3.08(t,J＝7.1Hz,2H),1.64-1.55(m,2H),1.48-1.37(m,2H),0.96(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ147.2,129.1,121.7,113.8,43.9,31.7,20.4,14.0；HRMS(ESI)m/z C10H15ClN[M+H]+:理论值184.0888,实测值184.0886。
实施例6
本实施例中，用等摩尔4-氟溴苯替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为84％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ6.88(t,J＝8.7Hz,2H),6.59-6.49(m,2H),3.47(br,1H),3.07(t,J＝7.1Hz,2H),1.64-1.55(m,2H),1.48-1.38(m,2H),0.96(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ155.7(d,J＝233.0Hz),144.9,115.6(d,J＝22.0Hz),113.5(d,J＝7.5Hz),44.4,31.7,20.3,13.9；19F NMR(376MHz,CDCl3)δ-128.59(s,F)；HRMS(ESI)m/z C10H15FN[M+H]+:理论值168.1183,实测值168.1185。
实施例7
本实施例中，用等摩尔6-溴-1,1,4-4-四甲基-1,2,3,4-四氢萘替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为82％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.13(t,J＝7.5Hz,1H),6.55(t,J＝3.2Hz,1H),6.50-6.43(m,1H),3.11(t,J＝7.0Hz,2H),1.73-1.76(m,4H),1.64-1.57(m,2H),1.52-1.39(m,2H),1.36-1.00(m,12H),0.98(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ146.3,145.8,134.0,127.4,111.2,110.5,44.1,35.5,35.4,34.4,33.6,32.2,32.0,32.0,20.5,14.1；HRMS(ESI)m/z C18H30N[M+H]+:理论值260.2373,实测值260.2374。
实施例8
本实施例中，用等摩尔2,4,5-三甲基溴苯替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为80％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ6.84(s,1H),6.46(s,1H),3.16(t,J＝7.0Hz,2H),2.24(s,3H),2.17(s,3H),2.10(s,3H),1.72-1.62(m,2H),1.54-1.41(m,2H),0.99(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ144.6,134.8,131.6,124.4,119.3,111.9,44.2,32.0,20.5,20.0,18.7,17.0,14.1；HRMS(ESI)m/z C13H22N[M+H]+:理论值192.1747,实测值192.1750。
实施例9
本实施例中，用等摩尔2-氧三氟甲基溴苯替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为84％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.10-7.01(m,2H),6.65(d,J＝8.0Hz,1H),6.61-6.48(m,1H),3.98(br,1H),3.08(t,J＝7.1Hz,2H),1.61-1.50(m,2H),1.47-1.30(m,2H),0.89(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ140.8,136.1),127.7,122.2,121.0(q,J＝126.3Hz),120.8 116.0,112.0,43.2,31.4,20.2,13.8；HRMS(ESI)m/zC11H15F3NO[M+H]+:理论值234.1100,实测值234.1098。
实施例10
本实施例中，用等摩尔2-三氟甲基-4-溴吡啶替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为86％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ8.17(d,J＝5.2Hz,1H),6.74(s,1H),6.48(d,J＝5.6Hz,1H),4.91(br,1H),3.18-3.10(m,2H),1.64-1.49(m,2H),1.43-1.30(m,2H),0.91(t,J＝7.3Hz,3H)；13C NMR(150MHz,CDCl3)δ154.6,149.9,148.6(q,J＝33.0Hz),122.1(q,J＝115.5Hz),108.9,104.2,42.5,30.9,20.1,13.7；HRMS(ESI)m/zC10H14F3N2[M+H]+:理论值219.1104,实测值219.1106。
实施例11
本实施例中，用等摩尔2,6-二甲基-4-溴吡啶替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为89％。
所得产物的核磁波谱数据为：1H NMR(600MHz,CDCl3)δ6.14(s,2H),4.16(br,1H),3.11(m,2H),2.37(s,6H),1.62-1.54(m,2H),1.45-1.36(m,2H),0.95(t,J＝7.4Hz,3H)；13CNMR(150MHz,CDCl3)δ157.5,154.6,104.1,42.4,31.3,24.2,20.2,13.8；HRMS(ESI)m/zC11H19N2[M+H]+:理论值179.1543,实测值179.1545。
实施例12
本实施例中，用等摩尔2-溴吡啶替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为80％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ8.05(d,J＝4.3Hz,1H),7.41(t,J＝7.7Hz,1H),6.60-6.48(m,1H),6.37(d,J＝8.4Hz,1H),4.63(br,1H),3.24(t,J＝6.9Hz,2H),1.67-1.54(m,2H),1.49-1.37(m,2H),0.95(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ158.9,148.0,137.5,112.5,106.3,42.0,31.6,20.2,13.8；HRMS(ESI)m/z C9H15N2[M+H]+:理论值151.1230,实测值151.1233。
实施例13
本实施例中，用等摩尔2-溴-6-甲氧基吡啶替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为83％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.34(t,J＝7.9Hz,1H),6.00(d,J＝7.9Hz,1H),5.92(d,J＝7.9Hz,1H),4.36(br,1H),3.84(s,3H),3.23(m,2H),1.65-1.55(m,2H),1.49-1.37(m,2H),0.95(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ164.8,159.1,141.1,98.4,98.2,54.5,43.2,32.9,21.4,15.0；HRMS(ESI)m/z C10H17N2O[M+H]+:理论值181.1335,实测值181.1338。
实施例14
本实施例中，用等摩尔2-溴嘧啶替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为78％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)1H NMR(400MHz,CDCl3)δ8.18(d,J＝4.4Hz,2H),6.41(t,J＝4.6Hz,1H),5.54(br,1H),3.36-3.27(m,2H),1.62-1.43(m,2H),1.39 -1.27(m,2H),0.86(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ162.5,157.9,110.1,41.2,31.7,20.1,13.8；HRMS(ESI)m/z calc.for C8H14N3[M+H]+:理论值152.1182,实测值152.1185。
实施例15
本实施例中，用等摩尔2-甲基-4-溴-吡啶替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为85％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.97(s,2H),3.67(br,1H),3.05(t,J＝7.1Hz,2H),2.52(s,3H),1.59-1.50(m,2H),1.41-1.34(m,2H),0.89(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ156.6,141.1,139.6,43.1,31.3,24.5,20.1,13.8；HRMS(ESI)m/z C10H20N3[M+H]+:理论值182.1652,实测值182.1654。
实施例16
本实施例中，用等摩尔溴代雌酚酮替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色固体，其产率为76％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.09(d,J＝8.4Hz,1H),6.44(dd,J＝8.4,2.4Hz,1H),6.36(d,J＝2.2Hz,1H),3.44(br,1H),3.09(t,J＝7.1Hz,2H),2.92-2.84(m,2H),2.59-2.42(m,1H),2.42-2.32(m,1H),2.22(t,J＝10.2Hz,1H),2.11 -2.06(m,2H),2.01-1.91(m,2H),1.75-1.54(m,11H),0.95(t,J＝7.3Hz,3H),0.90(s,3H)；13CNMR(100MHz,CDCl3)δ221.1,146.6,137.2,128.6,126.1,112.75,110.9,50.4,48.1,44.0,43.9,38.6,35.9,31.9,31.8,29.7,26.7,26.0,21.6,20.3,14.0,13.9；HRMS(ESI)m/zC22H32N2O[M+H]+:理论值326.2478,实测值326.2480。
实施例17
本实施例中，用等摩尔溴代吉非罗齐甲酯替换实施例1中的溴苯，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为73％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ6.59(s,1H),6.44(s,1H),3.84(d,J＝4.5Hz,2H),3.65(s,3H),3.09(t,J＝7.1Hz,2H),2.91-2.86(m,1H),2.19(s,3H),2.09(s,3H),1.75-1.65(m,4H),1.67-1.55(m,2H),1.52-1.36(m,2H),1.21(s,6H),0.96(t,J＝7.3Hz,3H)；13C NMR(100MHz,CDCl3)δ178.4,148.8,140.5,125.3,120.0,115.8,113.3,69.6,51.7,44.6,42.1,37.2,32.0,25.5,25.2,20.4,17.4,16.1,14.0；HRMS(ESI)m/z C20H34NO3[M+H]+:理论值336.2533,实测值336.2535。
实施例18
本实施例中，用等摩尔4-叔丁基溴苯实施例1中的溴苯，用等摩尔甲胺替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为92％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.22(d,J＝8.5Hz,2H),6.58(d,J＝8.6Hz,2H),2.81(s,3H),1.28(s,9H)；13C NMR(100MHz,CDCl3)δ147.2,140.2,126.1,112.4,34.0,31.7,31.1；HRMS(ESI)m/z C11H18N[M+H]+:理论值164.1434,实测值164.1435。
实施例19
本实施例中，用等摩尔4-叔丁基溴苯替换实施例1中的溴苯，用等摩尔2-甲基丙-2-烯-1-胺替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为93％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.20(d,J＝8.6Hz,2H),6.57(d,J＝8.6Hz,2H),4.50-4.86(m,2H),3.67(s,2H),1.79(s,3H),1.28(s,9H)；13C NMR(100MHz,CDCl3)δ146.0,143.1,140.1,125.9,112.54,110.8,50.3,33.8,31.6,20.5；HRMS(ESI)m/z C14H22N[M+H]+:理论值204.1747,实测值204.1750。
实施例20
本实施例中，用等摩尔4-叔丁基溴苯换实施例1中的溴苯，用等摩尔2-(1,3-二氧戊环-4-基)乙烷-1-胺替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为90％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.20(d,J＝8.5Hz,2H),6.58(d,J＝8.5Hz,2H),4.98(t,J＝4.4Hz,1H),3.98(t,J＝6.9Hz,2H),3.91-3.83(m,2H),3.25(t,J＝6.5Hz,2H),2.03-1.97(m,2H),1.27(s,9H)；13C NMR(100MHz,CDCl3)δ146.2,140.2,126.1,112.7,103.9,65.0,39.6,34.0,33.7,33.2,31.7；HRMS(ESI)m/z C15H24NO2[M+H]+:理论值250.1802,实测值250.1805。
实施例21
本实施例中，用等摩尔4-叔丁基溴苯换实施例1中的溴苯，用等摩尔3-氨基丙酸叔丁酯替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色固体，其产率为91％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.21(d,J＝8.3Hz,2H),6.59(d,J＝8.3Hz,2H),3.39(t,J＝6.3Hz,2H),2.52(t,J＝6.3Hz,2H),1.46(s,9H),1.28(s,9H)；13C NMR(100MHz,CDCl3)δ171.8,145.4,140.5,126.6,112.9,80.8,40.0,35.3,33.9,31.9,28.1；HRMS(ESI)m/z C17H28NO2[M+H]+:理论值278.2115,实测值278.2110。
实施例22
本实施例中，用等摩尔4-叔丁基溴苯换实施例1中的溴苯，用等摩尔4-氨基丁腈替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为93％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.51(d,J＝8.8Hz,2H),7.38(d,J＝8.8Hz,2H),3.85(t,J＝7.0Hz,2H),2.60(t,J＝8.1Hz,2H),2.22-2.09(m,2H),1.31(s,9H)；13C NMR(100MHz,CDCl3)δ174.1,147.5,136.8,125.7,119.9,48.9,34.4,32.7,31.3,18.1；HRMS(ESI)m/z C14H21N2[M+H]+:理论值217.1699,实测值217.1696。
实施例23
本实施例中，用等摩尔4-叔丁基溴苯换实施例1中的溴苯，用等摩尔2,2,2-三氟乙烷-1-胺替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为85％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.16(d,J＝8.7Hz,2H),6.56(d,J＝8.6Hz,2H),3.65(q,J＝9.0Hz,2H),1.20(s,9H)；13C NMR(100MHz,CDCl3)δ143.9,142.0,126.9,125.1(q,J＝278.6Hz),112.9,46.3(q,J＝33.4Hz),33.9,31.5；HRMS(ESI)m/z C12H17F3N[M+H]+:理论值232.1308,实测值232.1305。
实施例24
本实施例中，用等摩尔4-叔丁基溴苯换实施例1中的溴苯，用等摩尔脱氢松香胺替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为82％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.21(d,J＝8.6Hz,3H),7.04(s,1H),6.92(s,1H),6.60(d,J＝8.5Hz,2H),3.55(br,1H),3.12-3.06(m,1H),2.95-2.81(m,4H),2.39-2.42(m,1H),1.85-1.75(m,3H),1.74-1.61(m,2H),1.55-1.44(m,3H),1.30(s,9H),1.32-1.21(m,9H),1.04(s,3H)；13C NMR(100MHz,CDCl3)δ147.4,146.6,145.7,139.8,134.8,126.9,126.0,124.3,123.9,112.5,55.3,45.3,38.5,37.5,37.4,36.3,33.8,33.5,31.6,30.1,25.3,24.0,19.4,18.9,18.8；HRMS(ESI)m/z C30H44N[M+H]+:理论值418.3468,实测值418.3471。
实施例25
本实施例中，用等摩尔4-叔丁基溴苯换实施例1中的溴苯，用等摩尔3,3-二氟环丁胺替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为82％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.31(d,J＝8.6Hz,2H),6.49(d,J＝8.6Hz,2H),4.21(t,J＝11.9Hz,4H),1.31(s,9H)；13C NMR(100MHz,CDCl3)δ147.6,141.8,126.0,116.1(q,J＝273Hz),112.2,63.5(q,J＝25Hz),34.0,31.5；19F NMR(376MHz,CDCl3)δ-99.21(p,J＝11.8Hz)；HRMS(ESI)m/z C14H20F2N[M+H]+:理论值240.1558,实测值240.1555。
实施例26
本实施例中，用等摩尔4-叔丁基溴苯换实施例1中的溴苯，用等摩尔3-氟氮杂环丁烷替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为84％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.18(d,J＝8.6Hz,2H),6.36(d,J＝8.6Hz,2H),5.44-5.12(m,1H),4.16-3.93(m,2H),3.91-3.75(m,2H),1.21(s,9H)；13CNMR(100MHz,CDCl3)δ149.0,141.0,125.9,111.7,82.9(d,J＝204.3Hz),59.8(d,J＝23.2Hz),34.0,31.6；HRMS(ESI)m/z C13H19FN[M+H]+:理论值208.1496,实测值208.1493。
实施例27
本实施例中，用等摩尔4-叔丁基溴苯换实施例1中的溴苯，用等摩尔三氟甲基乙酰胺替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为88％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ8.06(br,1H),7.49(d,J＝8.2Hz,2H),7.40(d,J＝8.3Hz,2H),1.32(s,9H)；13C NMR(100MHz,CDCl3)δ155.0,(q,J＝40Hz),132.6,126.3,120.5,120.3,116.0(q,J＝286.9Hz),34.7,31.4；HRMS(ESI)m/zC12H15F3NO[M+H]+:理论值246.1100,实测值246.1103。
实施例28
本实施例中用等摩尔4-叔丁基溴苯换实施例1中的溴苯，用等摩尔吡唑替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为91％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.89(d,J＝2.4Hz,1H),7.71(d,J＝1.1Hz,1H),7.61(d,J＝8.7Hz,2H),7.46(d,J＝8.7Hz,2H),6.44(t,J＝2.0Hz,1H)；1.34(s,9H)；13C NMR(100MHz,CDCl3)δ149.6,140.8,137.9,126.7,126.3,118.9,107.3,34.5,31.4；HRMS(ESI)m/z C13H17N2[M+H]+:理论值201.1386,实测值201.1389。
实施例29
本实施例中用等摩尔4-叔丁基溴苯换实施例1中的溴苯，用等摩尔对甲基苯胺替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为90％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.31(d,J＝3.0Hz,2H),7.11(d,J＝6.2Hz,2H),7.06-6.98(m,4H),2.34(s,3H),1.36(s,9H)；13C NMR(100MHz,CDCl3)δ143.5,141.2,141.0,130.3,129.8,126.1,118.2,117.2,34.2,31.5,20.7；HRMS(ESI)m/zC17H22N[M+H]+:理论值240.1747,实测值240.1749。
实施例30
本实施例中用等摩尔4-叔丁基溴苯换实施例1中的溴苯，用等摩尔联苯胺替换实施例1中的正丁胺，其他步骤与实施例1相同，得到结构式如下的淡黄色油状物，其产率为88％。
所得产物的核磁波谱数据为：1H NMR(400MHz,CDCl3)δ7.56(d,J＝7.3Hz,2H),7.48(d,J＝8.5Hz,2H),7.44-7.37(m,2H),7.36-7.24(m,3H),7.07(t,J＝8.7Hz,4H),5.70(br,1H),1.32(s,9H)；13C NMR(100MHz,iCDCl3)δ144.5,143.2,141.0,140.1,133.2,128.8,128.0,126.5,126.2,118.5,117.2,34.2,31.5；HRMS(ESI)m/zC22H24N[M+H]+:理论值302.1903,实测值302.1907。

Claims (8)

1.一种光化学廉价锰催化合成芳胺类化合物的方法，其特征在于：将式I所示芳基溴化物与式II所示胺类化合物、联吡啶、锰催化剂、有机碱加入有机溶剂中，在氩气氛围中加热并光照反应，反应完后分离纯化产物，得到式III所示芳胺类化合物；
式中，Ar代表芳基、取代芳基、杂环芳基、取代杂环芳基中任意一种，HNNu代表芳胺、取代芳胺、杂环芳胺、吡唑、酰胺、磺酰胺、脂肪胺中任意一种；
所述锰催化剂为溴化锰、碳酸锰、醋酸锰、氯化锰、三氟磺酸锰中任意一种；
所述有机碱为1,8-二氮杂二环十一碳-7-烯、四甲基胍、7-甲基-1,5,7-三氮杂二环[4.4.0]癸-5-烯、1,2-二甲基-1,4,5,6-四氢嘧啶中任意一种。
2.根据权利要求1所述的光化学廉价锰催化合成芳胺类化合物的方法，其特征在于：所述Ar代表苯基、噻吩基、噻唑基、吡啶基、吡唑基、嘧啶基、哌啶基、吡嗪基、喹啉基、苯丙噻吩基、苯并呋喃基、二苯并噻吩基、喹喔啉基中任意一种，或者含C1～C6烷基、C6～环烷基、叔丁基二甲基硅氧基、磺酰基、苯氧基、四氢萘基、吖啶基、哌啶基、三甲基甲硅烷基、卤素、三氟甲氧基、三氟甲基、氰基、酯基、酰基、羰基、硼酯基中至少1种取代基的苯基或者吡啶基。
3.根据权利要求1或2所述的光化学廉价锰催化合成芳胺类化合物的方法，其特征在于：所述胺类化合物的用量为芳基溴化物摩尔量的1.1～2倍。
4.根据权利要求1或2所述的光化学廉价锰催化合成芳胺类化合物的方法，其特征在于：所述联吡啶的用量为芳基溴化物摩尔量的5％～15％。
5.根据权利要求1或2所述的光化学廉价锰催化合成芳胺类化合物的方法，其特征在于：所述锰催化剂的用量为芳基溴化物摩尔量的5％～15％。
6.根据权利要求1或2所述的光化学廉价锰催化合成芳胺类化合物的方法，其特征在于：所述有机碱的用量为芳基溴化物摩尔量的2～3倍。
7.根据权利要求1或2所述的光化学廉价锰催化合成芳胺类化合物的方法，其特征在于：所述有机溶剂为二甲基亚砜、甲苯、异丙醇、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中任意一种或两种。
8.根据权利要求1或2所述的光化学廉价锰催化合成芳胺类化合物的方法，其特征在于：所述光照反应是在波长为360～430nm的紫外光照射下80～90℃反应24～36小时。
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