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CN107417566B - 一种可见光催化卤代芳烃和腙类化合物合成n-芳基腙的方法 - Google Patents

一种可见光催化卤代芳烃和腙类化合物合成n-芳基腙的方法 Download PDF

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CN107417566B
CN107417566B CN201710453387.XA CN201710453387A CN107417566B CN 107417566 B CN107417566 B CN 107417566B CN 201710453387 A CN201710453387 A CN 201710453387A CN 107417566 B CN107417566 B CN 107417566B
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薛东
余树生
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Abstract

本发明公开了一种可见光催化卤代芳烃和腙类化合物合成N‑芳基取代腙的方法，该方法利用多取代BODIPY有机化合物作为光催化剂和镍协同催化实现了N‑芳基腙的合成。与现有合成方法相比，本发明利用过渡金属镍在无配体下和有机光敏剂实现了C‑N偶联反应，该方法所用催化剂廉价易得、催化效率高，且反应条件温和，环境友好，产物产率高，底物适用范围广。

Description

一种可见光催化卤代芳烃和腙类化合物合成N-芳基腙的方法
技术领域
本发明涉及一种在可见光照射条件下，采用多取代BODIPY有机光催化剂和过渡金属镍催化剂高效催化卤代芳烃和二苯甲酮腙类化合物合成N-芳腙的方法。
背景技术
多数含氮杂环化合物都具有生理活性，是一些天然产物、功能材料和药物分子的重要结构片段，而芳基腙及其衍生物在合成含氮杂环化合物中起着重要作用。目前合成N-芳基腙的方法可以分为两大类，第一类是非金属催化的方法，主要通过酸碱催化(Resnicket al.,J.Org.Chem.,1965,30,2832-2834；Bigdeli et al.,J.Chem.Res.1999,9,570-571)和微波催化(Silvestri et al.,Acs Combinatorial Science,2011,13,2-6)，虽然反应操作简单但是官能团的耐受性不好，底物适用性不广。第二类是过渡金属催化的方法，主要有钯催化(Hartwig et al.,Angew.Chem.Int.Ed.,1998,37,2090-2093；C.Mauger,G.Mignani.Syn.Commun.,2006,36,1123-1129.)、铜催化(Buchwald et al.,J.Am.Chem.Soc.2001,123,7727-7729)和镍催化(Yang et al.,RSC Adv.,2014,4,3364-3367.)三种体系，钯催化虽然反应效果较好但是钯比较贵，铜催化对于底物要求较高只有高活性的碘代芳烃才能反应，目前报道的镍催化的方法底物实用性较差，对于含有羰基、氰基的底物不能反应，而且过渡金属催化的都需要配体调控，配体通常比较昂贵。因此，发展一种无配体参与的方法合成N-芳基腙具有非常重要的意义。
近年来，可见光催化反应因其绿色、高效、条件温和，在有机合成领域得到了广泛应用，过渡金属催化和光催化协同双催化的方法在偶联反应中也发挥着很重要的作用。传统的光催化剂一般是钌和铱的络合物，这类催化剂在可见光下有很强的吸收，性质稳定且有很长的生命周期，但其使用贵金属，合成成本高。因此，用廉价的光敏剂和过渡金属通过可见光催化卤代芳烃和二苯甲酮腙类化合物合成N-芳基腙具有很大的应用前景。
发明内容
本发明所要解决的技术问题在于提供一种在可见光照射下，用有机光敏剂和镍在无外加配体的条件下高效合成N-芳基腙的方法。
解决上述技术问题所采用的技术方案是：在惰性气体保护下，将式I所示的卤代芳烃、式II所示的腙类化合物、碱、多取代BODIPY有机光催化剂和镍催化剂溶于有机溶剂中，在可见光照射下30～100℃搅拌反应，反应完后分离纯化，得到式III所示的N-芳基腙。
Figure BDA0001323082360000021
式中Ar代表芳基，具体如苯基、C1～C4烷基取代苯基、C1～C4烷氧基取代苯基、卤代苯基、三氟甲基取代苯基、氰基取代苯基、苯甲酰胺基、苯乙酰胺基、苯甲酰基、苯乙酰基、苯甲酸甲酯基、萘基、菲基、芴基、吡啶基、卤代吡啶基、氰基取代吡啶基、C1～C4烷基取代吡啶基、C1～C4烷氧基取代吡啶基、三氟甲基取代吡啶基、噻吩基、苯并噻吩基、卤代苯并噻吩基、氰基取代苯并噻吩基、C1～C4烷基取代苯并噻吩基、C1～C4烷氧基取代苯并噻吩基、三氟甲基取代苯并噻吩基、喹啉基、卤代喹啉基、氰基取代喹啉基、C1～C4烷基取代喹啉基、C1～C4烷氧基取代苯基、喹啉基、三氟甲基取代喹啉基、N-叔丁氧羰基吲哚基、苯并吡唑基-4-酮基、1,3-苯并二噁唑基、苯酞基等，X代表Br或I，R1、R2各自独立的代表C1～C6烷基、苯基、C1～C4烷基取代苯基、C1～C4烷氧基取代苯基、卤代苯基、三氟甲基取代苯基、萘基中的任意一种。
上述的多取代BODIPY有机光催化剂的结构式如下所示：
Figure BDA0001323082360000022
式中R3、R6、R7各自独立的代表C1～C6烷基、C1～C6烷氧基、苯基、C1～C4烷基取代苯基、C1～C4烷氧基取代苯基、卤代苯基、三氟甲基取代苯基中的任意一种，R4代表F、Cl、苯基、C1～C4烷基取代苯基、C1～C4烷氧基取代苯基、卤代苯基、萘基中的任意一种，R5代表C1～C6烷基。
上述多取代BODIPY有机光催化剂的结构式中，优选R3、R6、R7各自独立的代表甲基或苯基，R4代表F、苯基、C1～C4烷基取代苯基中的任意一种，R5代表乙基。
上述的卤代芳烃与腙类化合物、碱、多取代BODIPY有机光催化剂、镍催化剂的摩尔比优选为1:(1.1～3):(1.1～3):(0.01～0.03):(0.01～0.03)。
上述的镍催化剂为NiBr2、NiI2、NiCl2、双-(1,5-环辛二烯)镍、三氟甲磺酸镍、乙酰丙酮镍等，碱为1,8-二氮杂二环十一碳-7-烯、三乙烯二胺、N-乙基二异丙胺、三乙胺、N-甲基二环己基胺等，有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、1,4-二氧六环等。
上述制备方法中，进一步优选在可见光照射下50～70℃搅拌反应的时间为5～10小时。
本发明利用过渡金属镍在无配体下和有机光敏剂实现了C-N偶联反应，该方法催化效率高，且反应条件温和，环境友好，产物产率高。与现有合成N-芳基腙的方法相比，该方法最大的特点是无需使用配体，反应条件温和，产物产率高，底物适用范围广。
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
合成结构式如下化合物(1)
Figure BDA0001323082360000031
将二苯甲酮腙(196mg，1mmol)、溴苯(62.8mg，0.4mmol)、多取代BODIPY有机光催化剂(3.4mg，0.008mmol)、NiBr2(1.8mg，0.008mmol)、N-甲基二环己基胺(210μL，1mmol)、DMF(3mL)加入到Schlenk反应管中，通氮气保护，在60℃下用四个4W的LED灯近距离照射反应10h，反应结束后冷却到室温，将反应液用乙酸乙酯萃取(10mL)后用饱和食盐水洗三次(10mL×3)，收集有机相用无水硫酸钠干燥，过滤，用旋转蒸发仪浓缩后用石油醚和乙酸乙酯体积比为200:1的混合液作为洗脱剂进行柱层析分离，得到黄色油状化合物(1)102mg，其产率为94％，表征数据为：1H NMR(400MHz,CDCl3):δ7.61-7.57(m,4H),7.55-7.50(m,2H),7.36-7.29(m,5H),7.28-7.24(m,2H),7.09(d,J＝7.64Hz,2H),6.86(t,J＝7.28Hz,1H)；13CNMR(100MHz,CDCl3):δ144.7,144.3,138.5,132.9,129.8,129.4,129.3,129.2,128.3,128.1,126.6,120.2,113.0；HRMS(m/z,ESI+)理论值C19H16BrN2 +[M+H]+:351.0497,实测值:351.0493。
本实施例中所用的多取代BODIPY有机光催化剂为结构式如下的BODIPY-1：
Figure BDA0001323082360000041
实施例2
本实施例中，用等摩尔量的BODIPY-2替换实施例1中的BODIPY-1，其他步骤与实施例1相同，得到黄色油状化合物(1)89mg，其产率为82％。
Figure BDA0001323082360000042
实施例3
本实施例中，用等摩尔量的BODIPY-3替换实施例1中的BODIPY-1，其他步骤与实施例1相同，得到黄色油状化合物(1)82mg，其产率为76％。
Figure BDA0001323082360000043
实施例4
本实施例中，用等摩尔量的BODIPY-4替换实施例1中的BODIPY-1，其他步骤与实施例1相同，得到黄色油状化合物(1)98mg，其产率为90％。
Figure BDA0001323082360000051
实施例5
本实施例中，用等摩尔量的双-(1,5-环辛二烯)镍替换实施例1中的NiBr2，其他步骤与实施例1相同，得到黄色油状化合物(1)87mg，其产率为80％。
实施例6
本实施例中，用等摩尔量的三氟甲磺酸镍替换实施例1中的NiBr2，其他步骤与实施例1相同，得到黄色油状化合物(1)97mg，其产率为89％。
实施例7
本实施例中，用等摩尔量的乙酰丙酮镍替换实施例1中的NiBr2，其他步骤与实施例1相同，得到黄色油状化合物(1)90mg，其产率为83％。
实施例8
合成结构式如下的化合物(2)
Figure BDA0001323082360000052
本实施例中，用等摩尔量的对溴苯乙酮替换实施例1中的溴苯，其他步骤与实施例1相同，得到黄色粘稠状化合物(2)，其产率为92％，表征数据为：1H NMR(400MHz,CDCl3):δ7.90(d,J＝8.7Hz,2H),7.75(s,1H),7.61-7.55(m,5H),7.35-7.33(m,5H),7.09(d,J＝8.7Hz,2H),2.54(s,3H)；13C NMR(100MHz,CDCl3):δ196.7,148.4,147.0,138.0,132.3,130.7,130.0,129.8,129.5,129.1,128.8,128.4,127.0,112.3,26.3；HRMS(m/z,ESI+)理论值C21H19N2O+[M+H]+:315.1497,实测值:315.1494。
实施例9
合成结构式如下的化合物(3)
Figure BDA0001323082360000061
本实施例中，用等摩尔量的对氟溴苯替换实施例1中的溴苯，其他步骤与实施例1相同，得到黄色粘稠状化合物(3)，其产率为95％，表征数据为：1H NMR(400MHz,CDCl3):δ7.61-7.53(m,5H),7.43(s,1H),7.35-7.29(m,5H),7.05-7.02(m,2H),6.96(t,J＝8.4,2H)；13C NMR(100MHz,CDCl3):δ157.4(JC-F＝236.1),144.5,141.14(JC-F＝1.8),138.4,132.8,129.8,129.4,129.2,128.3,128.2,126.6,115.8(JC-F＝22.5),113.8(JC-F＝7.5)；HRMS(m/z,ESI+)理论值C19H16FN2 +[M+H]+:291.1298,实测值:291.1291。
实施例10
合成结构式如下的化合物(4)
Figure BDA0001323082360000062
本实施例中，用等摩尔量的2-甲氧基苯替换实施例1中的溴苯，其他步骤与实施例1相同，得到黄色固体化合物(4)，其产率为86％，表征数据为：1HNMR(400MHz,CDCl3):δ8.0(s,1H),7.67(d,J＝8.0,1H),7.63-7.56(m,4H),7.53-7.51(m,1H),7.37-7.28(m,5H),6.98(m,1H),6.80-6.75(m,2H),3.68(s,3H)；13C NMR(100MHz,CDCl3):δ145.6,145.0,138.7,134.4,133.2,129.7,129.2,128.3,128.0,126.7,121.7,119.3,112.5,110.2,55.7。
实施例11
合成结构式如下的化合物(5)
本实施例中，用等摩尔量的1-溴萘替换实施例1中的溴苯，其他步骤与实施例1相同，得到黄色的固体化合物(5)，其产率为92％，表征数据为：1H NMR(400MHz,CDCl3):δ8.19(s,1H),7.78(t,J＝1.2,3H),7.69-7.63(m,4H),7.60-7.57(m,1H),7.49-7.41(m,3H),7.40-7.36(m,3H),7.34-7.28(m,3H),7.24(m,1H)；13C NMR(100MHz,CDCl3):δ146.5,139.4,138.3,134.3,133.0,130.0,129.7,129.2,128.9,128.5,128.4,126.9,125.7,125.1,122.0,120.0,119.0,108.2；HRMS(m/z,ESI+)理论值C23H19N2 +[M+H]+:323.1548,实测值:323.1552。
实施例12
合成结构式如下的化合物(6)
Figure BDA0001323082360000072
本实施例中，用等摩尔量的3-溴吡啶替换实施例1中的溴苯，其他步骤与实施例1相同，得到白色固体化合物(6)，其产率为77％，表征数据为：1H NMR(400MHz,CDCl3):δ8.30(d,J＝2.5Hz,1H),8.11(d,J＝4.6Hz,1H),7.63-7.51(m,5H),7.49(s,1H),7.36-7.31(m,5H),7.18(dd,J＝4.7Hz,J＝8.3Hz,1H)；13C NMR(100MHz,CDCl3):δ146.4,141.6,141.0,138.0,135.9,132.4,130.0,129.7,129.0,128.6,128.4,126.8,123.9,119.7；HRMS(m/z,ESI+)理论值C18H16N3 +[M+H]+:274.1344,实测值:274.1341。
实施例13
合成结构式如下的化合物(7)
Figure BDA0001323082360000081
本实施例中，用等摩尔量的3-溴噻吩替换实施例1中的溴苯，其他步骤与实施例1相同，得到黄色粘稠状化合物(7)，其产率为84％，表征数据为：1H NMR(400MHz,CDCl3):δ7.60-7.57(m.6H),7.35-7.28(m,5H),7.20(dd,J＝3.32Hz,J＝5.04Hz,1H),6.86(d,J＝5.12Hz,1H),6.61(d,J＝1.92Hz,1H)；13C NMR(100MHz,CDCl3):δ145.0,144.7,138.2,132.8,129.7,129.2,129.1,128.2,128.0,126.5,125.4,118.1,99.0；HRMS(m/z,ESI+)理论值C17H14N2NaS+[M+H]+:301.0775,实测值:301.0770。
实施例14
合成结构式如下的化合物(8)
Figure BDA0001323082360000082
本实施例中，用等摩尔量的N-叔丁氧羰基-5-溴吲哚替换实施例1中的溴苯，其他步骤与实施例1相同，得到棕色固体化合物(8)，其产率为80％，表征数据为：1HNMR(400MHz,CDCl3):δ7.98(s,1H),7.62-7.56(m,4H),7.53-7.50(m,3H),7.36-7.24(m,6H),6.97(dd,J＝1.8Hz,J＝8.9Hz,1H),6.48(d,J＝3.7,1H),1.65(s,9H)；13C NMR(100MHz,CDCl3):δ149.9,143.7,140.8,138.7,133.1,131.7,130.2,129.8,129.3,128.3,128.0,126.5,115.8,111.3,107.4,104.0,83.4,28.4；HRMS(m/z,ESI+)理论值C26H25N3O2 +[M+H]+:412.2025,实测值：412.2035。
实施例15
合成结构式如下的化合物(9)
本实施例中，用等摩尔量的对三氟甲基苯替换实施例1中的溴苯，其他步骤与实施例1相同，得到黄色固体化合物(9)，其产率为92％，表征数据为：1HNMR(400MHz,CDCl3):δ7.65-7.55(m,6m),7.48(d,J＝8.4Hz,2H),7.35-7.33(m,5H),7.12(d,J＝8.4Hz,2H)；13CNMR(100MHz,CDCl3):δ147.2,146.4,138.0,132.5,130.0,129.7,129.1,128.7,128.4,126.9,126.7(q,JC-F＝3.8Hz),124.9(q,JC-F＝269.1Hz),121.8(q,JC-F＝32.3Hz),112.6；HRMS(m/z,ESI+)理论值C20H15F3N2Na+[M+Na]+:363.1085,实测值:363.1083。
实施例16
合成结构式如下的化合物(10)
Figure BDA0001323082360000092
本实施例中，用等摩尔量的对溴苯甲酰胺替换实施例1中的溴苯，其他步骤与实施例1相同，得到白色固体化合物(10)，其产率为94％，表征数据为：1HNMR(400MHz,CDCl3):δ7.73(d,J＝8.8Hz,2H),6.69(s,1H),6.61-7.52(m,5H),7.35-7.32(m,5H),7.10-7.08(m,2H),5.90(br.,NH2),13C NMR(100MHz,CDCl3):δ169.3,147.6,146.4,138.0,132.4,129.9,129.7,129.3,129.1,128.7,128.4,126.9,124.4,112.5。
实施例17
合成结构式如下的化合物(11)
Figure BDA0001323082360000101
本实施例中，用等摩尔量的邻溴苯腈替换实施例1中的溴苯，其他步骤与实施例1相同，得到黄色粘稠状化合物(11)，其产率为83％，表征数据为：1H NMR(400MHz,CDCl3):δ8.2(s,1H),7.74(d,J＝8.5,1H),7.66-7.62(m,4H),7.59-7.57(m,1H),7.53-7.49(m,1H),7.39-7.35(m,5H),6.83(t,J＝7.2,1H)；13C NMR(100MHz,CDCl3):δ148.4,146.9,137.7,134.4,132.3,131.8,130.0,129.0,128.7,128.4,127.2,119.5,116.7,113.7,94.9；HRMS(m/z,ESI+)理论值C20H15N3Na+[M+Na]+:320.1164,实测值:320.1162。
实施例18
合成结构式如下的化合物(12)
本实施例中，用等摩尔量的3-溴-5-氯苯甲醚替换实施例1中的溴苯，其他步骤与实施例1相同，得到棕色固体化合物(12)，其产率为90％，表征数据为：1HNMR(400MHz,CDCl3):δ7.61-7.52(m,5H),7.46(s,1H),7.33-7.32(m,5H),6.66(s,1H),6.57(s,1H),6.40(s,1H)；13C NMR(100MHz,CDCl3):δ161.4,146.6,145.5,138.1,135.6,132.6,129.9,129.6,129.1,128.5,128.4,126.8,106.1,106.1,97.4,55.6；HRMS(m/z,ESI+)理论值C20H17ClN2O+[M+H]+:337.1108,实测值:337.1108。
实施例19
合成结构式如下的化合物(13)
本实施例中，用等摩尔量的3-溴-5-甲氧基苯乙酮替换实施例1中的溴苯，其他步骤与实施例1相同，得到黄色固体化合物(13)，其产率为92％，表征数据为：1HNMR(400MHz,CDCl3):δ7.61-7.57(m,4H),7.54-7.51(m,2H),7.38-7.29(m,7H),7.23(br,s,NH),3.88(s,3H),2.37(s,3H)；13C NMR(100MHz,CDCl3):δ167.5,145.2,144.8,139.6,138.3,132.8,131.0,129.9,129.5,129.2,128.4,126.7,122.0,117.9,111.4,52.2,21.7；HRMS(m/z,ESI+)理论值C22H20N2NaO2 +:367.1422,实测值:367.1430。
实施例20
合成结构式如下的化合物(14)
Figure BDA0001323082360000112
本实施例中，用等摩尔量的9-溴菲替换实施例1中的溴苯，其他步骤与实施例1相同，得到黄色固体化合物(14)，其产率为54％，表征数据为：1H NMR(400MHz,CDCl3):δ8.71(d,J＝8.3Hz,1H),8.56(d,J＝8.2Hz,1H),8.17(s,1H),7.9(s,1H),7.89(d,J＝8.0,1H),7.70-7.66(m,2H),7.64-7.60(m,2H),7.57-7.54(m,1H),7.50-7.45(m,4H),7.42-7.35(m,3H),7.33-7.29(m,1H)；13C NMR(100MHz,CDCl3):δ147.3,138.3,137.1,133.5,133.8,133.0,131.3,130.0,129.7,129.2,128.6,128.5,127.7,127.2,127.0,126.6,126.4,123.9,123.8,123.7,122.5,119.6,106.4；HRMS(m/z,ESI+)理论值C27H20N2Na+[M+H]+:395.1524,实测值:395.1515。
实施例21
合成结构式如下的化合物(15)
Figure BDA0001323082360000121
本实施例中，用等摩尔量的2-溴芴替换实施例1中的溴苯，其他步骤与实施例1相同，得到黄色固体化合物(15)，其产率为86％，表征数据为：1HNMR(400MHz,CDCl3):δ6.69-6.59(m,7H),7.57-7.53(m,1H),7.50(d,J＝8.0Hz,1H),7.39-7.29(m,7H),7.24-7.20(m,1H),7.03(dd,J＝1.6Hz,J＝8.4Hz,1H)；13C NMR(100MHz,CDCl3):δ145.2,144.4,144.1,142.7,142.2,138.5,134.5,133.0,129.9,129.4,129.3,128.3,128.1,126.8,126.6,125.4,124.9,120.6,118.9,112.1,109.7,37.2。
实施例22
合成结构式如下的化合物(16)
Figure BDA0001323082360000122
本实施例中，用等摩尔量的6-溴-4-二氢色原酮替换实施例1中的溴苯，其他步骤与实施例1相同，得到白色固体化合物(16)，其产率为92％，表征数据为：1HNMR(400MHz,CDCl3):δ7.60-7.50(m,5H),7.47-7.44(m,2H),7.35-7.26(m,6H),6.93(d,J＝8.9Hz,1H),4.5(t,J＝6.5Hz,2H),2.8(t,J＝6.5Hz,2H)；13C NMR(100MHz,CDCl3):δ192.3,156.2,144.7,139.5,138.2,132.8,129.9,129.5,129.1,128.3,128.2,126.6,122.0,121.5,118.9,109.2,67.2,38.1。
实施例23
合成结构式如下化合物(17)
本实施例中，用等摩尔量的6-溴-苯并噻吩替换实施例1中的溴苯，其他步骤与实施例1相同，得到白色固体化合物(17)，其产率为89％，表征数据为：1H NMR(400MHz,CDCl3):δ7.69(d,J＝8.8Hz,1H),7.63-7.56(m,6H),7.54-7.51(m,1H),7.40-7.29(m,6H),7.24(t,J＝5.2Hz,1H),7.09(dd,J＝2.0Hz,J＝8.7Hz,1H)；13C NMR(100MHz,CDCl3):δ144.2,142.3,140.9,138.5,132.9,131.8,129.9,129.4,129.3,128.4,128.1,127.4,126.6,123.7,123.0,112.5,106.4；HRMS(m/z,ESI+)理论值C21H16N2NaS+[M+Na]+:351.0932,实测值:351.0926。
实施例24
合成结构式如下的化合物(18)
Figure BDA0001323082360000132
本实施例中，用等摩尔量的3-溴喹啉替换实施例1中的溴苯，其他步骤与实施例1相同，得到黄色固体化合物(18)，其产率为80％，表征数据为：1H NMR(400MHz,CDCl3):δ8.63(d,J＝2.6Hz,1H),7.99-7.97(m,1H),7.85(d,J＝2.4Hz,1H),7.75-7.73(m,1H),7.70(s,1H),7.65-7.62(m,4H),7.59-7.56(m,1H),7.47(t,J＝3.8Hz,2H),7.40-7.34(m,5H)；13CNMR(100MHz,CDCl3):δ147.1,143.9,141.1,138.3,138.0,132.4,130.0,129.8,129.3,128.8,128.5,127.2,127.0,126.7,126.2；HRMS(m/z,ESI+)理论值C22H18N3 +[M+H]+:324.1501,实测值:324.1494。
实施例25
合成结构式如下的化合物(19)
Figure BDA0001323082360000141
本实施例中，用等摩尔量的N-叔丁氧羰基-5-溴吲哚替换实施例1中的溴苯，其他步骤与实施例1相同，得到棕色固体化合物(19)，其产率为80％，表征数据为：1HNMR(400MHz,CDCl3):δ7.98(s,1H),7.62-7.56(m,4H),7.53-7.50(m,3H),7.36-7.24(m,6H),6.97(dd,J＝1.8Hz,J＝8.9Hz,1H),6.48(d,J＝3.7,1H),1.65(s,9H)；13C NMR(100MHz,CDCl3):δ149.9,143.7,140.8,138.7,133.1,131.7,130.2,129.8,129.3,128.3,128.0,126.5,115.8,111.3,107.4,104.0,83.4,28.4；HRMS(m/z,ESI+)理论值C26H25N3O2 +[M+H]+:412.2025,实测值:412.2035。
实施例26
合成结构式如下的化合物(20)
Figure BDA0001323082360000142
本实施例中，用等摩尔量的4-溴-1,2-亚甲二氧基苯替换实施例1中的溴苯，其他步骤与实施例1相同，得到黄色固体化合物(20)，其产率为90％，表征数据为：1H NMR(400MHz,CDCl3):δ7.60-7.56(m,4H),7.53-7.50(m,1H),7.38(s,1H),7.34-7.27(m,5H),6.87(d,J＝2.2Hz,1H),6.69(d,J＝8.4Hz,1H),6.36(dd,J＝2.2Hz,J＝8.4Hz,1H),5.90(s,2H)；13C NMR(100MHz,CDCl3):δ148.6,143.7,141,4,140.5,138.5,132.9,129.8,129.3,129.2,128.3,128.0,126.5,108.6,104.9,101.0,96.0；HRMS(m/z,ESI+)理论值C20H17N2O2 +[M+H]+:317.1290,实测值：317.1283。
实施例27
合成结构式如下的化合物(21)
Figure BDA0001323082360000151
本实施例中，用等摩尔量的9-(4-溴苯基)咔唑替换实施例1中的溴苯，其他步骤与实施例1相同，得到黄色粘稠状化合物(21)，其产率为91％，表征数据为：1H NMR(400MHz,CDCl3):δ8.12(d,J＝7.7Hz,2H),7.65-7.59(m,5H),7.56-7.54(m,1H),7.40-7.37(m,6H),7.34-7.30(m,4H),7.29-7.23(m,3H)；13C NMR(100MHz,CDCl3):δ145.4,144.2,141.6,138.3,132.8,130.0,129.7,129.6,129.3,128.5,128.4,126.8,126.0,123.2,120.0,119.7,114.0,109.9。
实施例28
合成结构式如下的化合物(22)
本实施例中，用等摩尔量的6-溴苯酞替换实施例1中的溴苯，其他步骤与实施例1相同，得到白色固体化合物(22)，其产率为74％，表征数据为：1HNMR(400MHz,CDCl3):δ7.66(s,1H),7.63-7.59(m,5H),7.57-7.53(m,1H),7.38-7.30(m,7H),5.25(s,2H)；13C NMR(100MHz,CDCl3):δ171.5,146.2,146.0,138.0,137.7 132.5,130.0,129.7,129.1,128.4,127.0,126.9,122.7,120.0,108.5,69.7.HRMS(m/z,ESI+)理论值C21H17N2O2 +[M+H]+:329.1290,实测值：329.1292。

Claims (3)

1.一种可见光催化卤代芳烃和腙类化合物合成N-芳基腙的方法，其特征在于：在惰性气体保护下，将式I所示的卤代芳烃、式II所示的腙类化合物、碱、多取代BODIPY有机光催化剂和镍催化剂溶于有机溶剂中，在可见光照射下30～100℃搅拌反应，反应完后分离纯化，得到式III所示的N-芳基腙；
Figure 144432DEST_PATH_IMAGE001
式中Ar代表苯基、C1～C4烷基取代苯基、C1～C4烷氧基取代苯基、卤代苯基、三氟甲基取代苯基、氰基取代苯基、萘基、菲基、芴基、吡啶基、卤代吡啶基、氰基取代吡啶基、C1～C4烷基取代吡啶基、C1～C4烷氧基取代吡啶基、三氟甲基取代吡啶基、噻吩基、苯并噻吩基、卤代苯并噻吩基、氰基取代苯并噻吩基、C1～C4烷基取代苯并噻吩基、C1～C4烷氧基取代苯并噻吩基、三氟甲基取代苯并噻吩基、喹啉基、卤代喹啉基、氰基取代喹啉基、C1～C4烷基取代喹啉基、三氟甲基取代喹啉基、N-叔丁氧羰基吲哚基、苯并吡唑基-4-酮基、1,3-苯并二噁唑基、苯酞基中的任意一种，X代表Br或I，R1、R2各自独立的代表C1～C6烷基、苯基、C1～C4烷基取代苯基、C1～C4烷氧基取代苯基、卤代苯基、三氟甲基取代苯基、萘基中的任意一种；
上述的多取代BODIPY有机光催化剂的结构式如下所示：
Figure 658590DEST_PATH_IMAGE002
式中所述的R3、R6、R7各自独立的代表甲基或苯基，R4代表F、苯基、C1～C4烷基取代苯基中的任意一种，R5代表乙基；
上述的卤代芳烃与腙类化合物、碱、多取代BODIPY有机光催化剂、镍催化剂的摩尔比为1:（1.1～3）:（1.1～3）:（0.01～0.03）:（0.01～0.03），其中所述的镍催化剂为NiBr2、NiI2、NiCl2、双-(1,5-环辛二烯)镍、三氟甲磺酸镍、乙酰丙酮镍中的任意一种，所述的碱为N-甲基二环己基胺。
2.根据权利要求1所述的可见光催化卤代芳烃和腙类化合物合成N-芳基腙的方法，其特征在于：在可见光照射下50～70℃搅拌反应的时间为5～10小时。
3.根据权利要求1所述的可见光催化卤代芳烃和腙类化合物合成N-芳基腙的方法，其特征在于：所述的有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、1,4-二氧六环中的任意一种。
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