CN113045566B - 一种π共轭多环氨基异喹啉类化合物及其合成方法和用途 - Google Patents

一种π共轭多环氨基异喹啉类化合物及其合成方法和用途 Download PDF

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CN113045566B
CN113045566B CN202010877037.8A CN202010877037A CN113045566B CN 113045566 B CN113045566 B CN 113045566B CN 202010877037 A CN202010877037 A CN 202010877037A CN 113045566 B CN113045566 B CN 113045566B
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刘蕾
李�杰
王大伟
张钊
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Abstract

本发明公开了一种π共轭多环氨基异喹啉类化合物及其合成方法和用途，属于有机化学和材料学领域。本发明提供了一种具有良好的原子和反应步骤经济性的、高效的、绿色的合成该新型π共轭多环氨基异喹啉类化合物的方法，合成得到的新型π共轭多环氨基异喹啉类化合物的结构具有较强的荧光量子产率，以及较长的光致发光寿命，能够用于小分子荧光标记物、新型光电材料等领域，具有良好的应用前景。

Description

一种π共轭多环氨基异喹啉类化合物及其合成方法和用途
技术领域
本发明涉及一种π共轭多环氨基异喹啉类化合物及其合成方法和用途，属于有机化学和材料学领域。
背景技术
稠合的含N杂环由于其结构具有各种特殊的光电性能和电磁特性而成为材料科学应用中的重要结构单元。在这种情况下，对新型含N杂环的设计和有效合成就具有持续而强烈需求。在许多合成方法中，过渡金属催化的碳氢键活化最近已重组为一种越来越可行的工具，用于制备具有扩展π共轭体系的稠合含N杂环化合物。尽管取得了长足的进步，但过渡金属催化剂的使用，特别是贵金属Ru-，Rh-，Pd-和Ir-复合物的使用使得该策略仍然存在着明显的缺陷。值得注意的是，6π电子环化反应已广泛用于制备复杂分子，并且在当代合成化学中发挥了重要作用，从而可以在无过渡金属参与的条件下实现分子内碳氢键加成。但是，目前为止该领域的成就主要集中于热致电环化过程，而仅零星地报道了相应的光致电环化反应的实例。值得注意的是，为了避免了使用高强度的紫外线，在光敏剂Ir(Fppy)3存在的情况下，可见光可以促进2-芳氧基酮类化合物进行有效的6π电环化反应。而通过光诱导氧化脱氢的6π电子环化策略可以为直接扩展芳香环，从而获得各种稠合的π-共轭多环烃提供一种快速，有效和方便的方法。但是，这些光致电环化反应通常需要外源氧化剂、昂贵的过渡金属催化剂或高强度紫外线参与。考虑到这些缺点，本发明从开发实现这一有价值策略的替代方法为目标，发展新型无过渡金属参与的、温和的、绿色的反应条件实现氧化电环化策略，从而提高了官能团耐受性和合成方法的实用性。
近年来，芳基脒在过渡金属催化C-H/N-H键活化策略下实现了与炔烃、重氮化合物、α-氧化酮等亲电试剂反应用于合成可药学有用的1-氨基异喹啉类衍生物。另一方面，因为马来酰亚胺具有潜在的、优越的生物学活性，并且可用于药理学上有用的琥珀酰亚胺和吡咯烷的合成。然而，利用这些缺电子的内烯烃进行的氧化[4+2]环化是非常具有挑战性的，因为两个偶联试剂更优先进行氮杂-迈克尔加成反应。
发明内容
技术问题：
为了解决上述问题，本发明设计了一种温和的合成方法，基于特定的底物结构，不使用过渡金属催化剂，并利用可见光或阳光替代高强度紫外光，以催化量的氧化剂构建得到共轭N-杂环，并实现异常宽的底物范围和出色的官能团耐受性。同时，本发明设计的一类新型含氮杂环骨架，可作为小分子荧光标记物应用于新型材料领域。
技术方案：
本发明首先设计、发展了铜催化芳基脒(1)与马来酰亚胺(2)间的氧化氨基化制备原料化合物(3)；随后发展了以分子氧和催化量的TEMPO作为氧化剂，通过可见光促进分子内氧化电环化的策略绿色、高效地构建新型氨基异喹啉类稠合杂环骨架及其衍生物，具体方案如图1所示。
本发明的第一个目的是提供一种合成式(I)所示的π共轭多环氨基异喹啉类化合物的方法，所述方法的合成路线如下所示：
Figure BDA0002652905520000021
其中，所述芳基Ar为有取代基取代或者未取代的芳基，取代基包括单取代、二取代或者三取代的卤素、C1-8烷基、卤代烷基、环烷基；所述取代为邻位、间位或者对位取代；R1选自：氢、C1-8烷基、烷氧基取代的C1-8烷基、C3-6环烷基、苄基、α-酯基取代烷基、α-酯基取代-烷氧基取代手性烷基；R2、R3分别独立的选自：氢、C1-8烷基；
所述方法包括如下过程：
(1)在氧气环境下，利用铜催化剂催化化合物1与化合物2发生氧化氨基化反应，制得化合物3；
(2)然后化合物3与氧化剂在可见光照射下，反应得到式(I)所示的π共轭多环氨基异喹啉化合物。
在本发明的一种实施方式中，所述R1选自：氢、甲基、乙基、环己基、苄基、α-酯基取代烷基、手性烷基。其中，α-酯基取代烷基包括-C(Ra)(Rb)C(O)O-Rc；Ra、Rb分别独立的选自：氢、C1-8烷基、烷氧基烷基、取代或未取代的苄基、取代或未取代的芳基；苄基或芳基涉及取代的取代基选自：卤素、C1-8烷氧基、C1-8烷基。
在本发明的一种实施方式中，所述R2、R3分别独立优选自：氢、叔丁基。
在本发明的一种实施方式中，所述芳基Ar的芳环为苯环或者萘环。
在本发明的一种实施方式中，所述步骤(1)中的氧化氨基化反应是在有机溶剂中进行的，溶剂选自如下任意一种或多种：二氯甲烷(DCE)、异丙醇(i-propanol)、甲苯。优选二氯甲烷。
在本发明的一种实施方式中，所述步骤(1)中的铜催化剂选自如下任意一种或多种：Cu(OAc)2、CuBr、Cu(OTf)2、Cu。优选Cu(OAc)2、CuBr。
在本发明的一种实施方式中，所述步骤(1)中的铜催化剂的添加量为相对化合物1的20mol％。
在本发明的一种实施方式中，所述步骤(1)中的氧化氨基化反应还包括加入配体，配体的添加量为相对化合物1的30mol％。
在本发明的一种实施方式中，所述步骤(1)中的铜催化剂与配体的摩尔比为1:1.5。
在本发明的一种实施方式中，所述步骤(1)中的配体选自如下任意一种或多种：2,2'-联吡啶(bpy)、4,4'-二甲基-2,2'-联吡啶(dmbbpy)、1,10-菲罗啉(phen)、4,7-二苯基-1,10-菲啰啉(4,7-diphenyl phen)。
在本发明的一种实施方式中，所述步骤(1)中的氧化氨基化反应的反应温度为100-120℃，优选120℃；反应时间为12-20h；优选12-20h；进一步优选12h。
在本发明的一种实施方式中，所述步骤(2)中的氧化剂选自如下任意一种或者多种：TEMPO、O2。
在本发明的一种实施方式中，所述步骤(2)中的反应是在溶剂中进行的，所述溶剂选自如下任意一种或多种：异丙醇、乙二醇、四氟乙烯。
在本发明的一种实施方式中，所述步骤(2)中反应的温度为20-30℃；反应的时间为10-20h；优选12-20h；进一步优选12h。
在本发明的一种实施方式中，所述步骤(2)中的可见光为：20W白光灯或者太阳光。
本发明的第二个目的是提供一种π共轭多环氨基异喹啉类化合物，所述化合物的结构如式(I)所示：
Figure BDA0002652905520000031
其中，所述芳基Ar为有取代基取代或者未取代的芳基，取代基包括单取代、二取代或者三取代的卤素、C1-8烷基、卤代烷基、环烷基；所述取代为邻位、间位或者对位取代；R1选自：甲基、乙基、环己基、苄基、α-酯基取代烷烃、手性烷基；R2、R3分别独立的选自：氢、叔丁基。
在本发明的一种实施方式中，所述R1选自：氢、甲基、乙基、环己基、苄基、α-酯基取代烷基、手性烷基。其中，α-酯基取代烷基包括-C(Ra)(Rb)C(O)O-Rc；Ra、Rb分别独立的选自：氢、C1-8烷基、烷氧基烷基、取代或未取代的苄基、取代或未取代的芳基；苄基或芳基涉及取代的取代基选自：卤素、C1-8烷氧基、C1-8烷基。
本发明的第三个目的是将上述π共轭多环氨基异喹啉类化合物作为小分子荧光标记物应用于荧光标记示踪领域中。
本发明的第四个目的是将上述π共轭多环氨基异喹啉类化合物应用于光电材料领域中。
有益效果：
本发明提供了一种具有良好的原子和反应步骤经济性的、高效的、绿色的合成该新型π共轭多环氨基异喹啉类化合物的方法，该方法不使用过渡金属催化剂，并利用可见光或阳光替代高强度紫外光。本发明合成得到的新型π共轭多环氨基异喹啉类化合物的结构具有较强的荧光量子产率，以及较长的光致发光寿命，能够用于小分子荧光标记物、新型光电材料等领域，具有着良好的潜在应用前景。
附图说明
图1为铜催化氧化氨基化与可见光诱导的6π氧化杂环化合成异喹啉类杂环化合物的路线图。
图2为12种π共轭多环氨基异喹啉类化合物的UV-Vis吸收和光致发光(PL)光谱(样品50μM in CHCl3)。
具体实施方式
以下实施例涉及到的反应过程如下所示：
Figure BDA0002652905520000041
该合成方法学具有广泛的底物适用性，以及官能团耐受性，涉及到的化合物如下所示：
Figure BDA0002652905520000051
其中，[a]表示不添加TEMPO(20mol％)作为添加物的反应过程。
通过引入手性天然氨基酸的芳基脒为原料，该合成方法具有优秀的官能团耐受性和立体稳定性如下为涉及到的新型手性异喹啉类杂环化合物：
Figure BDA0002652905520000061
通过实施例详细描述本发明涉及的以上异喹啉类杂环化合物的合成方法：
实施例1π共轭多环氨基异喹啉类化合物的合成
(1)氧化氨基化反应合成化合物3：将称量好的芳基脒1(0.25mmol，1.0当量)，马来酰亚胺2(0.50mmol，2.0当量)，Cu(OAc)2(9.0mg，20.0mol％)和2,2'-二联吡啶(11.7mg，30.0mol)置于干燥的反应管中，通过双排管进行真空-氧气的置换(三次)后，加入无水DCE(1.0mL)，在氧气(1atm)氛围下于120℃下搅拌12h。室温下，真空蒸发溶剂，并将残留的残余物通过硅胶柱色谱纯化(正己烷/EtOAc作为洗脱剂)得到原料3。
(2)合成化合物4：将称量好的原料3(0.15mmol，1.0当量)，TEMPO(0.03mmol，20mol％)置于干燥的反应管中，通过双排管进行真空-氧气的置换(三次)后，加入异丙醇(3.0mL)，在可见光(20W)与氧气(1atm)氛围下，于23℃下用搅拌12小时。室温下，真空蒸发溶剂，并将剩余的残余物通过硅胶上的柱色谱法纯化(正己烷/EtOAc作为洗脱剂)，得到目标产物4。
中间体化合物3-a：
Figure BDA0002652905520000071
Yellow solid.M.p.＝161-163℃.1H-NMR(DMSO,400MHz):δ＝7.98(s,1H),7.48(d,J＝8.5Hz,2H),7.34(d,J＝8.5Hz,2H),5.03(s,1H),2.70(s,3H),1.43(s,9H).13C-NMR(DMSO,100MHz):δ＝172.4,168.8,161.3,154.4,135.3,133.9,130.7,128.8,102.6,53.2,28.5,23.5.IR(ATR):3343,2922,1699,1536,1382,1204cm-1.HR-MS(ESI)m/z calcd forC16H19ClN3O2 +[M+H+]320.1160,found 320.1168[M+H+].
5-(tert-Butylamino)-8-chloro-2-methyl-1H-pyrrolo[3,4-c]isoquinoline-1,3(2H)-dione(化合物4)
Figure BDA0002652905520000072
Yellow solid.收率80％.M.p.＝222-224℃.1H-NMR(CDCl3,400MHz):δ＝8.60(d,J＝2.1Hz,1H),7.67(d,J＝9.0Hz,1H),7.50(dd,J＝9.0,2.1Hz,1H),5.83(s,1H),3.17(s,3H),1.65(s,9H).13C-NMR(CDCl3,100MHz):δ＝169.0,168.1,159.2,149.6,138.6,132.6,128.4,123.9,123.7,116.8,109.2,53.8,28.9,23.5.IR(ATR):3428,2973,1696,1538,1434,1205cm-1.HR-MS(ESI)m/z calcd for C16H17ClN3O2 +[M+H+]318.1009,found 318.1014[M+H+].
化合物5的合成：
合成过程同化合物4，仅将原料由对位氯取代的芳基脒替换为对位氟取代的芳基脒。制得中间体3-b及目标产物化合物5。
中间体化合物3-b：
Figure BDA0002652905520000073
Yellow solid.M.p.＝186-189℃.1H-NMR(CDCl3,400MHz):δ＝7.37–7.30(m,2H),7.05(t,J＝8.6Hz,2H),5.22(s,1H),5.16(s,1H),2.84(s,3H),1.52(s,9H).13C-NMR(CDCl3,100MHz):δ＝172.81,168.83,163.73(d,JC-F＝251.7Hz),160.11,153.50,131.78(d,JC-F＝3.4Hz),129.78(d,JC-F＝8.6Hz),116.01(d,JC-F＝21.9Hz),104.61,53.54,28.51,23.38.19F-NMR(CDCl3,376MHz):δ＝-108.51(s).IR(ATR):3318,2960,1749,1538,1382,1211cm-1.HR-MS(ESI)m/z calcd for C16H19FN3O2 +[M+H+]304.1456,found 304.1451[M+H+].
5-(tert-Butylamino)-8-fluoro-2-methyl-1H-pyrrolo[3,4-c]isoquinoline-1,3(2H)-dione(化合物5)
Figure BDA0002652905520000074
Yellow solid.收率85％.M.p.＝243-244℃.1H-NMR(CDCl3,400MHz):δ＝8.23(dd,J＝9.3,2.6Hz,1H),7.78(dd,J＝9.2,5.0Hz,1H),7.30(dd,J＝8.6,2.2Hz,1H),5.84(s,1H),3.17(s,3H),1.65(s,9H).13C-NMR(CDCl3,100MHz):δ＝169.1,168.2,164.4(d,JC-F＝254.5Hz),159.2,149.7,133.6(d,JC-F＝11.6Hz),125.0(d,JC-F＝9.8Hz),117.2(d,JC-F＝24.8Hz),115.5(d,JC-F＝1.7Hz),109.8(d,JC-F＝4.5Hz),109.3(d,JC-F＝22.3Hz),53.8,29.0,23.5.19F-NMR(CDCl3,376MHz):δ＝-105.05(s).IR(ATR):3360,2971,1698,1522,1347,1199cm-1.HR-MS(ESI)m/z calcd for C16H17FN3O2 +[M+H+]302.1305,found 302.1311[M+H+].
化合物6的合成：
合成过程同化合物4，将原料由对位氯取代的芳基脒替换为对位溴取代的芳基脒。
中间体化合物3-c：
Figure BDA0002652905520000081
Yellow solid.M.p.＝162-164℃.1H-NMR(CDCl3,400MHz):δ＝7.50(d,J＝8.4Hz,2H),7.21(d,J＝8.4Hz,2H),5.23(s,1H),5.15(s,1H),2.84(s,3H),1.51(s,9H).13C-NMR(CDCl3,100MHz):δ＝172.7,168.8,159.9,153.3,134.4,132.1,129.2,125.0,104.8,53.6,28.4,23.4.IR(ATR):3344,2918,1699,1534,1382,1204,1112cm-1.HR-MS(ESI)m/z calcdfor C16H19BrN3O2 +[M+H+]364.0655,found 364.0663[M+H+].
8-Bromo-5-(tert-butylamino)-2-methyl-1H-pyrrolo[3,4-c]isoquinoline-1,3(2H)-dione(化合物6)
Figure BDA0002652905520000082
Yellow solid.收率89％.M.p.＝250-251℃.1H-NMR(CDCl3,400MHz):δ＝8.75(d,J＝2.1Hz,1H),7.64–7.58(m,2H),5.87(s,1H),3.16(s,3H),1.64(s,9H).13C-NMR(CDCl3,100MHz):δ＝168.9,168.0,159.3,149.5,132.8,132.7,131.0,127.1,123.7,117.1,109.0,53.8,28.9,23.5.IR(ATR):3456,2987,1706,1539,1429,1215cm-1.HR-MS(ESI)m/z calcdfor C16H17BrN3O2 +[M+H+]362.0504,found 362.0501[M+H+].
化合物7的合成：
合成过程同化合物4，仅替换相应芳基脒原料。
中间体化合物3-d：
Figure BDA0002652905520000083
Yellow solid.M.p.＝100-102℃.1H-NMR(CDCl3,400MHz):7.46–7.29(m,5H),5.21(s,1H),5.13(s,1H),2.84(s,3H),1.52(s,9H).13C-NMR(CDCl3,100MHz):δ＝172.9,169.1,161.3,153.7,135.5,130.6,128.8,127.6,104.3,53.5,28.5,23.3.IR(ATR):3350,2974,1698,1523,1379,1286,1112cm-1.HR-MS(ESI)m/z calcd for C16H20N3O2 +[M+H+]286.1550,found 286.1557[M+H+].
5-(tert-Butylamino)-2-methyl-1H-pyrrolo[3,4-c]isoquinoline-1,3(2H)-dione(化合物7)
Figure BDA0002652905520000084
Yellow solid.收率71％.M.p.＝220-222℃.1H-NMR(CDCl3,400MHz):δ＝8.61(d,J＝8.0Hz,1H),7.74(t,J＝8.0Hz,2H),7.56(td,J＝8.0,1.5Hz,1H),5.90(s,1H),3.17(s,3H),1.65(s,9H).13C-NMR(CDCl3,100MHz):δ＝169.5,168.5,159.3,148.6,131.8,131.6,127.8,124.9,122.0,118.8,110.2,53.5,29.0,23.4.IR(ATR):3467,2918,1684,1521,1363,1211cm-1.HR-MS(ESI)m/z calcd for C16H18N3O2 +[M+H+]284.1399,found 284.1403[M+H+].
化合物8的合成：
合成过程同化合物4，仅替换相应芳基脒原料。
中间体化合物3-e：
Figure BDA0002652905520000091
Yellow solid.M.p.＝142-144℃.1H-NMR(CDCl3,400MHz):δ＝7.22(d,J＝8.0Hz,2H),7.15(d,J＝8.0Hz,2H),5.21(s,1H),5.11(s,1H),2.84(s,3H),2.35(s,3H),1.51(s,9H).13C-NMR(CDCl3,100MHz):δ＝173.1,169.2,161.6,154.0,141.0,132.6,129.5,127.5,103.9,53.4,28.6,23.3,21.4.IR(ATR):3348,2976,1701,1535,1381,1203,1111cm-1.HR-MS(ESI)m/z calcd for C17H22N3O2 +[M+H+]300.1707,found 300.1703[M+H+].
5-(tert-Butylamino)-2,8-dimethyl-1H-pyrrolo[3,4-c]isoquinoline-1,3(2H)-dione(化合物8)
Figure BDA0002652905520000092
Yellow solid.收率75％.M.p.＝288-290℃.1H-NMR(CDCl3,400MHz):δ＝8.40(s,1H),7.62(d,J＝8.6Hz,1H),7.38(dd,J＝8.6,1.3Hz,1H),5.79(s,1H),3.16(s,3H),2.54(s,3H),1.64(s,9H).13C-NMR(CDCl3,100MHz):δ＝169.7,168.6,159.2,148.7,142.6,131.8,129.6,124.1,121.8,116.8,109.9,53.4,29.0,23.4,21.8.IR(ATR):3608,2919,1685,1508,1430,1361,1059cm-1.HR-MS(ESI)m/z calcd for C17H20N3O2 +[M+H+]298.1556,found 298.1553[M+H+].
化合物9的合成：
合成过程同化合物4，仅替换相应芳基脒原料。
中间体化合物3-f：
Figure BDA0002652905520000093
Yellow solid.M.p.＝155-157℃.1H-NMR(CDCl3,400MHz):δ＝7.29(d,J＝8.7Hz,2H),6.85(d,J＝8.7Hz,2H),5.20(s,1H),5.16(s,1H),3.81(s,3H),2.85(s,3H),1.51(s,9H).13C-NMR(CDCl3,100MHz):δ＝173.1,169.0,161.4,161.3,154.1,129.2,127.9,114.1,103.6,55.3,53.3,28.5,23.3.IR(ATR):3352,2976,1698,1505,1381,1257,1173cm-1.HR-MS(ESI)m/z calcd for C17H22N3O3 +[M+H+]316.1656,found 316.1657[M+H+].
5-(tert-Butylamino)-8-methoxy-2-methyl-1H-pyrrolo[3,4-c]isoquinoline-1,3(2H)-dione(化合物9)
Figure BDA0002652905520000101
Yellow solid.收率77％.M.p.＝230-232℃.1H-NMR(CDCl3,400MHz):δ＝7.92(d,J＝2.6Hz,1H),7.64(d,J＝9.3Hz,1H),7.13(dd,J＝9.3,2.6Hz,1H),5.73(s,1H),3.97(s,3H),3.16(s,3H),1.63(s,9H).13C-NMR(CDCl3,100MHz):δ＝169.8,168.5,162.2,159.2,149.4,133.9,123.8,119.4,113.1,109.6,103.3,55.7,53.4,29.1,23.4.IR(ATR):3426,2920,1704,1538,1433,1229cm-1.HR-MS(ESI)m/z calcd for C17H20N3O3 +[M+H+]314.1505,found 314.1506[M+H+].
化合物10的合成：
合成过程同化合物4，仅替换相应芳基脒原料。
Figure BDA0002652905520000102
中间体化合物3-g：Yellow solid.M.p.＝144-146℃.1H-NMR(CDCl3,400MHz):δ＝7.42-7.35(m,1H),7.24(td,J＝7.0,1.4Hz,1H),7.14(t,J＝7.3Hz,1H),7.08(t,J＝9.0Hz,1H),5.19(s,1H),5.08(s,1H),2.84(s,3H),1.53(s,9H).13C-NMR(CDCl3,100MHz):δ＝172.7,169.3,158.7(d,JC-F＝250.3Hz),155.4,153.2,132.1(d,JC-F＝8.2Hz),129.5(d,JC-F＝3.0Hz),124.5(d,JC-F＝3.6Hz),122.7(d,JC-F＝16.1Hz),116.3(d,JC-F＝21.5Hz),104.8,53.8,28.5,23.3.19F-NMR(CDCl3,376MHz):δ＝-114.35(s).IR(ATR):3347,2960,1693,1537,1435,1206,1116cm-1.HR-MS(ESI)m/z calcd for C16H19FN3O2 +[M+H+]304.1456,found304.1459[M+H+].
Figure BDA0002652905520000103
5-(tert-Butylamino)-6-fluoro-2-methyl-1H-pyrrolo[3,4-c]isoquinoline-1,3(2H)-dione(化合物10)
Yellow solid.收率70％.M.p.＝196-198℃.1H-NMR(CDCl3,400MHz):δ＝8.40(d,J＝8.1Hz,1H),7.65(td,J＝8.1,5.5Hz,1H),7.19(dd,J＝14.7,8.0Hz,1H),7.09(s,1H),3.16(s,3H),1.63(s,9H).13C-NMR(CDCl3,100MHz):δ＝169.1,168.0,160.1(d,JC-F＝248.7Hz),158.5(d,JC-F＝6.0Hz),149.8,134.2(d,JC-F＝2.5Hz),132.6(d,JC-F＝10.9Hz),120.7(d,JC-F＝4.1Hz),113.2(d,JC-F＝25.6Hz),108.9(d,JC-F＝8.9Hz),108.4(d,JC-F＝3.5Hz),53.8,28.9,23.5.19F-NMR(CDCl3,376MHz):δ＝-111.17(s).IR(ATR):2918,1698,1540,1497,1448cm-1.HR-MS(ESI)m/z calcd for C16H17FN3O2 +[M+H+]302.1305,found302.1309[M+H+].
化合物11的合成：
合成过程同化合物4，仅替换相应芳基脒原料。
中间体化合物3-h：
Figure BDA0002652905520000104
Yellow solid.M.p.＝184-186℃.1H-NMR(CDCl3,400MHz):δ＝7.26–7.18(m,2H),7.11(d,J＝9.6Hz,2H),5.20(s,1H),5.09(s,1H),2.85(s,3H),2.34(s,3H),1.52(s,9H).13C-NMR(CDCl3,100MHz):δ＝173.0,169.2,161.6,153.8,138.7,135.4,131.3,128.7,127.9,124.7,104.0,53.4,28.5,23.3,21.4.IR(ATR):3347,2930,1698,1526,1363,1235,1112cm-1.HR-MS(ESI)m/z calcd for C17H22N3O2 +[M+H+]300.1707,found 300.1713[M+H+].
Figure BDA0002652905520000111
5-(tert-Butylamino)-2,6-dimethyl-1H-pyrrolo[3,4-c]isoquinoline-1,3(2H)-dione(化合物11)
Yellow solid.收率54％.M.p.＝204-206℃.1H-NMR(CDCl3,400MHz):δ＝8.51(d,J＝7.7Hz,1H),7.55(t,J＝7.7Hz,1H),7.30(d,J＝7.7Hz,1H),6.31(s,1H),3.15(s,3H),2.91(s,3H),1.64(s,9H).13C-NMR(CDCl3,100MHz):δ＝169.5,168.4,160.8,148.3,133.7,133.6,131.6,131.2,122.8,119.5,109.8,54.0,29.0,24.9,23.4.IR(ATR):3453,2918,1674,1531,1363,cm-1.HR-MS(ESI)m/z calcd for C17H20N3O2 +[M+H+]298.1556,found298.1563[M+H+].
化合物12的合成：
合成过程同化合物4，仅替换相应芳基脒原料。
中间体化合物3-i：
Figure BDA0002652905520000112
Yellow solid.M.p.＝155-156℃.1H-NMR(CDCl3,400MHz):δ＝7.70–7.64(m,1H),7.59(s,1H),7.53–7.49(m,2H),5.21(s,1H),5.18(s,1H),2.83(s,3H),1.54(s,9H).13C-NMR(CDCl3,100MHz):δ＝172.5,168.7,159.2,153.0,136.2,131.4(q,JC-F＝32.9Hz),131.0,129.5,127.2(q,JC-F＝3.7Hz),124.4(q,JC-F＝3.8Hz),123.5(q,JC-F＝272.0Hz),105.2,53.8,28.5,23.4.19F-NMR(CDCl3,376MHz):δ＝-62.76(s).IR(ATR):3320,2964,1702,1513,1389,1286,1110cm-1.HR-MS(ESI)m/z calcd for C17H19F3N3O2 +[M+H+]354.1424,found354.1422[M+H+].
5-(tert-Butylamino)-2-methyl-7-(trifluoromethyl)-1H-pyrrolo[3,4-c]isoquinoline-1,3(2H)-dione(化合物12)
Figure BDA0002652905520000113
Yellow solid.收率71％.M.p.＝233-235℃.1H-NMR(CDCl3,400MHz):δ＝8.75(d,J＝8.6Hz,1H),7.98(s,1H),7.94(d,J＝8.6Hz,1H),5.94(s,1H),3.19(s,3H),1.68(s,9H).13C-NMR(CDCl3,100MHz):δ＝168.8,167.8,159.5,150.4,133.7,129.3(q,JC-F＝32.8Hz),127.8(q,JC-F＝3.2Hz),125.9,123.7(q,JC-F＝272.7Hz),119.7(q,JC-F＝4.1Hz),117.8,109.5,54.1,28.9,23.6.19F-NMR(CDCl3,376MHz):δ＝-62.37(s).IR(ATR):3393,2921,1705,1543,1434,1298,1121cm-1.HR-MS(ESI)m/z calcd for C17H17F3N3O2 +[M+H+]352.1273,found352.1279[M+H+].
化合物13的合成：
合成过程同化合物4，仅替换相应芳基脒原料。
中间体化合物3-j：
Figure BDA0002652905520000121
Yellow solid.M.p.＝186-188℃.1H-NMR(CDCl3,400MHz):δ＝6.85(dd,J＝8.0,1.6Hz,1H),6.79(d,J＝1.6Hz,1H),6.76(d,J＝8.0Hz,1H),6.00(s,2H),5.19(s,1H),2.87(s,3H),1.50(s,9H).13C-NMR(CDCl3,100MHz):δ＝173.1,169.1,160.9,153.8,149.6,148.0,129.5,122.2,108.5,108.0,103.9,101.7,53.4,28.5,23.4.IR(ATR):3349,2958,1694,1535,1377,1250,1112cm-1.HR-MS(ESI)m/z calcd for C17H20N3O4 +[M+H+]330.1448,found 330.1454[M+H+].
5-(tert-Butylamino)-2-methyl-1H-[1,3]dioxolo[4,5-g]pyrrolo[3,4-c]isoquinoline-1,3(2H)-dione(化合物13)
Figure BDA0002652905520000122
Yellow solid.收率67％.M.p.＝267-269℃.1H-NMR(CDCl3,400MHz):δ＝7.97(s,1H),7.01(s,1H),6.12(s,2H),5.37(s,1H),3.14(s,3H),1.62(s,9H).13C-NMR(CDCl3,100MHz):δ＝169.6,168.6,158.4,151.8,149.1,129.6,114.8,110.7,102.2,101.9,99.5,53.3,29.7,29.2,23.4.IR(ATR):3433,2920,1694,1511,1363,1245cm-1.HR-MS(ESI)m/zcalcd for C17H18N3O4 +[M+H+]328.1297,found 328.1303[M+H+].
化合物14和化合物14’的合成：
合成过程同化合物4，仅替换相应芳基脒原料。
中间体化合物3-k：
Figure BDA0002652905520000123
Yellow solid.M.p.＝188-190℃.1H-NMR(CDCl3,400MHz):δ＝7.25–7.19(m,2H),7.15–7.09(m,2H),5.19(s,1H),5.09(s,1H),2.85(s,3H),2.34(s,3H),1.52(s,9H).13C-NMR(CDCl3,100MHz):δ＝173.1,169.3,161.6,153.8,138.8,135.4,131.3,128.7,127.9,124.7,104.0,53.4,28.5,23.3,21.4.IR(ATR):3352,2971,1698,1522,1374,1085cm-1.HR-MS(ESI)m/z calcd for C17H22N3O2 +[M+H+]300.1707,found 300.1703[M+H+].
Figure BDA0002652905520000124
5-(tert-Butylamino)-2,9-dimethyl-1H-pyrrolo[3,4-c]isoquinoline-1,3(2H)-dione(化合物14)&5-(tert-butylamino)-2,7-dimethyl-1H-pyrrolo[3,4-c]isoquinoline-1,3(2H)-dione(化合物14’)
Yellow solid.1H-NMR(CDCl3,400MHz):δ＝8.49(d,J＝8.4Hz,1.4H),7.62-7.53(m,3.4H),7.50(s,1.4H),7.48–7.42(m,1H),5.90(s,1H),5.81(s,1.4H),3.17(s,3H),3.15(s,4.2H),3.00(s,3H),2.54(s,4.2H),1.65(s,21.7H).13C-NMR(CDCl3,100MHz):δ＝169.6,168.8,168.7,167.9,159.8,158.8,149.9,147.7,138.1,136.5,134.3,133.7,132.4,129.5,127.6,124.6,121.4,119.8,119.7,118.9,110.8,110.4,53.5,53.3,29.0,29.0,25.0,23.8,23.4,22.1.IR(ATR):3338,2920,1684,1523,1355,1206cm-1.HR-MS(ESI)m/zcalcd for C17H20N3O2 +[M+H+]298.1556,found 298.1557[M+H+].
化合物15和化合物15’的合成：
合成过程同化合物4，仅替换相应芳基脒原料。
Figure BDA0002652905520000131
中间体化合物3-l：Yellow solid.M.p.＝165-167℃.1H-NMR(CDCl3,400MHz):δ＝7.34(td,J＝8.0,5.7Hz,1H),7.15–7.08(m,2H),7.08–7.02(m,1H),5.22(s,1H),5.18(s,1H),2.85(s,3H),1.52(s,9H).13C-NMR(CDCl3,100MHz):δ＝172.73,168.85,162.53(d,JC-F＝249.3Hz),159.43,153.22,137.46(d,JC-F＝7.1Hz),130.66(d,JC-F＝8.2Hz),123.40(d,JC-F＝3.2Hz),117.67(d,JC-F＝21.1Hz),114.84(d,JC-F＝22.8Hz),104.83,53.63,28.47,23.39.19F-NMR(CDCl3,376MHz):δ＝-110.69(s).IR(ATR):3341,2964,1695,1540,1362,1287,1187cm-1.HR-MS(ESI)m/z calcd for C16H19FN3O2 +[M+H+]304.1456,found 304.1458[M+H+].
Figure BDA0002652905520000132
5-(tert-Butylamino)-9-fluoro-2-methyl-1H-pyrrolo[3,4-c]isoquinoline-1,3(2H)-dione(化合物15)
Yellow solids.M.p.＝253-256℃.1H-NMR(CDCl3,400MHz):δ＝8.66(dd,J＝9.0,5.8Hz,1H),7.53(td,J＝9.0,2.4Hz,1H),7.38(dd,J＝9.0,2.3Hz,1H),5.65(s,1H),3.17(s,3H),1.65(s,9H).13C-NMR(CDCl3,100MHz):δ＝169.2,168.3,161.7(d,JC-F＝250.9Hz),158.6,147.8(d,JC-F＝2.3Hz),128.4,127.6(d,JC-F＝8.5Hz),121.4(d,JC-F＝23.6Hz),120.0(d,JC-F＝7.3Hz),110.3,107.2(d,JC-F＝22.7Hz),53.67,28.92,23.47.19F-NMR(CDCl3,376MHz):δ＝-109.11(s).IR(ATR):3491,2919,1698,1522,1362,1207cm-1.HR-MS(ESI)m/z calcd for C16H17FN3O2 +[M+H+]302.1305,found 302.1308[M+H+].
5-(tert-Butylamino)-7-fluoro-2-methyl-1H-pyrrolo[3,4-c]isoquinoline-1,3(2H)-dione(化合物15’)
M.p.＝265-267℃.1H-NMR(CDCl3,400MHz):δ＝7.55(dd,J＝5.5,3.2Hz,2H),7.51–7.43(m,1H),5.91(s,1H),3.20(s,3H),1.66(s,9H).13C-NMR(CDCl3,100MHz):δ＝167.6,166.6,158.7,158.3(d,JC-F＝260.1Hz),150.0,128.32(d,JC-F＝7.5Hz),121.81(d,JC-F＝22.2Hz),120.62(d,JC-F＝6.7Hz),117.91(d,JC-F＝4.2Hz),117.45(d,JC-F＝20.4Hz),108.14(d,JC-F＝6.0Hz),53.8,28.9,23.8.19F-NMR(CDCl3,376MHz):δ＝-102.84(s).IR(ATR):3483,2918,1698,1498,1362,1206cm-1.HR-MS(ESI)m/z calcd for C16H17FN3O2 +[M+H+]302.1305,found302.1311[M+H+].
化合物16的合成：
合成过程同化合物4，替换相应芳基脒原料和马来酰亚胺原料。
Figure BDA0002652905520000141
中间体化合物3-m：Yellow solid.M.p.＝165-167℃.1H-NMR(CDCl3,400MHz):δ＝7.37–7.31(m,2H),7.29–7.25(m,2H),5.21(s,1H),5.14(s,1H),3.39(q,J＝7.2Hz,2H),1.52(s,9H),1.04(t,J＝7.2Hz,3H).13C-NMR(CDCl3,100MHz):δ＝172.5,168.6,159.9,153.3,136.7,134.1,129.1,129.0,105.0,53.6,32.4,28.5,13.9.IR(ATR):3343,2974,1693,1533,1397,1202cm-1.HR-MS(ESI)m/z calcd for C17H21ClN3O2 +[M+H+]334.1317,found 334.1319[M+H+].
Figure BDA0002652905520000142
5-(tert-Butylamino)-8-chloro-2-ethyl-1H-pyrrolo[3,4-c]isoquinoline-1,3(2H)-dione(化合物16)
Yellow solid.收率85％.M.p.＝204-206℃.1H-NMR(CDCl3,400MHz):δ＝8.59(d,J＝2.0Hz,1H),7.70(d,J＝9.0Hz,1H),7.48(dd,J＝9.0,2.0Hz,1H),5.89(s,1H),3.73(q,J＝7.2Hz,2H),1.64(s,9H),1.28(t,J＝7.2Hz,3H).13C-NMR(CDCl3,100MHz):δ＝168.8,167.8,159.3,149.5,138.6,132.6,128.4,123.9,123.8,116.9,109.1,53.7,32.5,28.9,14.2.IR(ATR):3407,2973,1701,1537,1434,1206cm-1.HR-MS(ESI)m/z calcd forC17H19ClN3O2 +[M+H+]332.1166,found 332.1170[M+H+].
化合物17的合成：
合成过程同化合物4，仅替换相应芳基脒原料和马来酰亚胺原料。
Figure BDA0002652905520000143
中间体化合物3-n：Yellow solid.M.p.＝160-162℃.1H-NMR(CDCl3,400MHz):δ＝7.33(d,J＝8.5Hz,2H),7.26(d,J＝8.5Hz,2H),5.20(s,1H),5.12(s,1H),3.73(tt,J＝12.3,3.8Hz,1H),1.95–1.81(m,2H),1.74(d,J＝13.1Hz,2H),1.51(s,9H),1.51–1.38(m,2H),1.33–1.06(m,4H).13C-NMR(CDCl3,100MHz):δ＝172.6,168.6,159.8,152.9,136.6,134.2,129.0,129.0,105.0,53.5,50.1,30.0 28.5,26.0,25.1.IR(ATR):3336,2932,1698,1576,1363,1206,1090cm-1.HR-MS(ESI)m/z calcd for C21H26ClN3O2 +[M+H+]387.1714,found 387.1721[M+H+].
Figure BDA0002652905520000144
5-(tert-Butylamino)-8-chloro-2-cyclohexyl-1H-pyrrolo[3,4-c]isoquinoline-1,3(2H)-dione(化合物17)
Yellow solid.收率71％.M.p.＝240-242℃.1H-NMR(CDCl3,400MHz):δ＝8.61(d,J＝2.1Hz,1H),7.68(d,J＝9.0Hz,1H),7.48(dd,J＝9.0,2.1Hz,1H),5.83(s,1H),4.10(tt,J＝12.4,3.5Hz,1H),2.21(td,J＝12.4,3.5Hz,2H),1.87(d,J＝13.3Hz,2H),1.75(d,J＝10.9Hz,2H),1.64(s,9H),1.45–1.17(m,4H).13C-NMR(CDCl3,100MHz):δ＝169.1,168.0,159.2,149.1,138.6,132.6,128.3,123.9,123.7,117.0,108.8,53.7,50.5,30.2,28.9,26.1,25.3.13C-NMR(CDCl3,100MHz):δ＝169.08,167.95,159.24,149.10,138.55,132.65,128.27,123.92,123.70,116.98,108.83,53.72,50.45,30.21,28.96,26.14,25.27.IR(ATR):2919,1700,1507,1363,1176cm-1.HR-MS(ESI)m/z calcd for C21H25ClN3O2 +[M+H+]386.1635,found 386.1632[M+H+].
化合物18的合成：
合成过程同化合物4，仅替换相应芳基脒原料和马来酰亚胺原料。
Figure BDA0002652905520000151
中间体化合物3-o：Yellow solid.M.p.＝176-178℃.1H-NMR(CDCl3,400MHz):δ＝7.34–7.26(m,4H),7.25–7.18(m,3H),7.09–7.03(m,2H),5.34(s,1H),5.18(s,1H),4.49(s,2H),1.50(s,9H).13C-NMR(CDCl3,100MHz):δ＝172.0,168.2,160.02 153.5,136.9,136.6,134.3,129.1,129.0,128.4,127.8,127.3,105.3,53.6,40.9,28.5.IR(ATR):3346,2919,1695,1530,1385,1204,1090cm-1.HR-MS(ESI)m/z calcd for C22H23ClN3O2 +[M+H+]396.1479,found 396.1483[M+H+].
Figure BDA0002652905520000152
2-Benzyl-5-(tert-butylamino)-8-chloro-1H-pyrrolo[3,4-c]isoquinoline-1,3(2H)-dione(化合物18)
Yellow solid.收率82％.M.p.＝228-230℃.1H-NMR(CDCl3,400MHz):δ＝8.58(d,J＝2.0Hz,1H),7.63(d,J＝9.0Hz,1H),7.46(dd,J＝9.0,2.0Hz,3H),7.31(t,J＝7.5Hz,2H),7.24(d,J＝7.5Hz,1H),5.83(s,1H),4.84(s,2H),1.63(s,9H).13C-NMR(CDCl3,100MHz):δ＝168.5,167.6,159.2,149.4,138.7,136.9,132.6,128.6,128.6,128.4,127.7,124.0,123.7,116.9,109.1,53.8,41.2,28.9.IR(ATR):2972,1704,1539,1392,1208cm-1.HR-MS(ESI)m/z calcd for C22H21ClN3O2 +[M+H+]394.1322,found 394.1324[M+H+].
化合物19的合成：
合成过程同化合物4，仅替换相应芳基脒原料和马来酰亚胺原料。
Figure BDA0002652905520000153
中间体化合物3-p：Yellow solid.M.p.＝135-137℃.1H-NMR(CDCl3,400MHz):δ＝7.35(d,J＝8.5Hz,2H),7.29(d,J＝8.5Hz,2H),5.30(s,1H),5.23(s,1H),4.10(s,2H),3.65(s,3H),1.52(s,9H).13C-NMR(CDCl3,100MHz):δ＝171.3,168.0,167.9,160.1,153.6,136.8,133.8,129.1,129.0,105.1,53.7,52.3,38.3,28.5.IR(ATR):3344,2975,1694,1533,1397,1283,1202cm-1.HR-MS(ESI)m/z calcd for C18H21ClN3O4 +[M+H+]378.1221,found 378.1230[M+H+].
Figure BDA0002652905520000161
Methyl
2-[5-(tert-butylamino)-8-chloro-1,3-dioxo-1,3-dihydro-2H-pyrrolo[3,4-c]isoquinolin-2-yl]acetat e(化合物19)
Yellow solid.收率81％.M.p.＝222-225℃.1H-NMR(CDCl3,400MHz):δ＝8.37(d,J＝2.0Hz,1H),7.72(d,J＝9.0Hz,1H),7.46(dd,J＝9.0,2.0Hz,1H),6.08(s,1H),4.45(s,2H),3.81(s,3H),1.61(s,9H).13C-NMR(CDCl3,100MHz):δ＝168.6,167.7,167.1,159.4,149.3,138.7,132.3,128.7,123.9,123.7,116.8,109.0,54.00 52.7,38.4,28.9.IR(ATR):3416,2919,1706,1539,1435,1206cm-1.HR-MS(ESI)m/z calcd for C18H19ClN3O4 +[M+H+]376.1064,found 376.1067[M+H+].
化合物20的合成：
合成过程同化合物4，仅替换相应芳基脒原料和马来酰亚胺原料。
Figure BDA0002652905520000162
中间体化合物3-q：Yellow solid.M.p.＝223-224℃.1H-NMR(CDCl3,400MHz):δ＝7.35(d,J＝8.5Hz,2H),7.29(d,J＝8.5Hz,2H),5.31(s,1H),5.19(s,1H),4.61(q,J＝7.3Hz,1H),3.59(s,3H),1.52(s,9H),1.46(d,J＝7.3Hz,3H).13C-NMR(CDCl3,100MHz):δ＝171.4,170.6,167.7,160.1,153.4,136.7,134.0,129.1,129.0,105.2,53.7,52.5,46.8,28.5,15.2.IR(ATR):3342,2967,1698,1521,1388,1082cm-1.HR-MS(ESI)m/z calcd forC19H23ClN3O4 +[M+H+]392.1377,found392.1369[M+H+].
Figure BDA0002652905520000163
Methyl 2-[5-(tert-butylamino)-8-chloro-1,3-dioxo-1,3-dihydro-2H-pyrrolo[3,4-c]isoquinolin-2-yl]propanoate(化合物20)
Yellow solid.收率75％.M.p.＝292-294℃.1H-NMR(CDCl3,400MHz):δ＝8.48(d,J＝2.0Hz,1H),7.71(d,J＝9.0Hz,1H),7.48(dd,J＝9.0,2.0Hz,1H),5.97(s,1H),4.98(q,J＝7.3Hz,1H),3.77(s,3H),1.72(d,J＝7.3Hz,3H),1.63(s,9H).13C-NMR(CDCl3,100MHz):δ＝170.8,167.9,167.0,159.4,149.2,138.7,132.4,128.6,123.9,123.8,117.0,109.0,53.9,52.7,47.1,28.9,15.5.IR(ATR):3430,2918,1694,1551,1333,1271cm-1.HR-MS(ESI)m/z calcd for C19H21ClN3O4 +[M+H+]390.1221,found 390.1227[M+H+].
化合物21的合成：
合成过程同化合物4，仅替换相应芳基脒原料和马来酰亚胺原料。
Figure BDA0002652905520000171
中间体化合物3-r：Yellow solid.M.p.＝126-128℃.1H-NMR(CDCl3,400MHz):δ＝7.35(d,J＝8.5Hz,2H),7.27(d,J＝8.5Hz,2H),5.23(s,1H),5.13(s,1H),3.58(s,3H),1.58(s,6H),1.51(s,9H).13C-NMR(CDCl3,100MHz):δ＝173.7,172.3,168.3,159.9,152.8,136.6,134.2,129.1,129.0,105.4,59.4,53.6,52.4,28.5,24.3.IR(ATR):3360,2963,1747,1615,1417,1267,1089cm-1.HR-MS(ESI)m/z calcd for C20H25ClN3O4 +[M+H+]406.1534,found 406.1537[M+H+].
Figure BDA0002652905520000172
Methyl
2-[5-(tert-butylamino)-8-chloro-1,3-dioxo-1,3-dihydro-2H-pyrrolo[3,4-c]isoquinolin-2-yl]-2-me thylpropanoate(化合物21)
Yellow solid.收率81％.M.p.＝192-194℃.1H-NMR(CDCl3,400MHz):δ＝8.52(d,J＝2.0Hz,1H),7.70(d,J＝9.0Hz,1H),7.48(dd,J＝9.0,2.0Hz,1H),5.92(s,1H),3.79(s,3H),1.85(s,6H),1.63(s,9H).13C-NMR(CDCl3,100MHz):δ＝173.8,168.9,167.7,159.4,148.9,138.7,132.4,128.5,123.9,123.8,117.1,108.5,59.9,53.8,52.7,28.9,24.7.IR(ATR):3429,2921,1698,1542,1334,1267,1149cm-1.HR-MS(ESI)m/z calcd forC20H23ClN3O4 +[M+H+]404.1377,found404.1381[M+H+].
化合物22的合成：
合成过程同化合物4，仅替换相应芳基脒原料和马来酰亚胺原料。
Figure BDA0002652905520000173
中间体化合物3-s：Yellow solid.M.p.＝225-227℃.1H-NMR(CDCl3,400MHz):δ＝7.35(d,J＝8.5Hz,2H),7.29(d,J＝8.5Hz,2H),5.31(s,1H),5.19(s,1H),4.61(q,J＝7.3Hz,1H),3.59(s,3H),1.52(s,9H),1.46(d,J＝7.3Hz,3H).13C-NMR(CDCl3,100MHz):δ＝171.4,170.6,167.7,160.0,153.4,136.7,134.0,129.1,129.0,105.2,53.7,52.5,46.8,28.5,15.2.IR(ATR):3335,2931,1697,1531,1345,1205,1090cm-1.HR-MS(ESI)m/z calcdfor C19H23ClN3O4 +[M+H+]392.1377,found 392.1378[M+H+].
Figure BDA0002652905520000174
Methyl
(S)-2-[5-(tert-butylamino)-8-chloro-1,3-dioxo-1,3-dihydro-2H-pyrrolo[3,4-c]isoquinolin-2-yl]pr opanoate(化合物22)
Yellow solid.收率73％.M.p.＝292-294℃.1H-NMR(CDCl3,400MHz):δ＝8.52(d,J＝2.0Hz,1H),7.69(d,J＝9.0Hz,1H),7.49(dd,J＝9.0,2.0Hz,1H),5.93(s,1H),4.98(q,J＝7.3Hz,1H),3.77(s,3H),1.72(d,J＝7.3Hz,3H),1.64(s,9H).13C-NMR(CDCl3,100MHz):δ＝170.7,167.9,167.0,159.3,149.2,138.7,132.5,128.6,123.9,123.7,117.0,109.0,53.9,52.7,47.1,28.9,15.5.IR(ATR):3430,2918,1694,1551,1333,1271cm-1.HR-MS(ESI)m/z calcd for C19H21ClN3O4 +[M+H+]390.1221,found 390.1228[M+H+].
化合物23的合成：
合成过程同化合物4，仅替换相应芳基脒原料和马来酰亚胺原料。
Figure BDA0002652905520000181
中间体化合物3-t：Yellow solid.M.p.＝144-147℃.1H-NMR(CDCl3,400MHz):δ＝7.35–7.27(m,4H),5.46(s,1H),5.17(s,1H),4.24(d,J＝8.6Hz,1H),3.57(s,3H),2.34–2.17(m,1H),1.52(s,9H),0.90(d,J＝6.0Hz,3H),0.73(d,J＝6.0Hz,3H).13C-NMR(CDCl3,100MHz):δ＝171.6,169.7,167.5,160.0,153.3,136.6,134.6,129.3,128.9,105.5,56.3,53.6,52.0,34.2,28.5,25.4,16.6.IR(ATR):3340,2969,1698,1522,1385,1086cm-1.HR-MS(ESI)m/z calcd for C21H27ClN3O4 +[M+H+]420.1690,found 420.1693[M+H+].
Figure BDA0002652905520000182
Methyl
(S)-2-[5-(tert-butylamino)-8-chloro-1,3-dioxo-1,3-dihydro-2H-pyrrolo[3,4-c]isoquinolin-2-yl]-3-methylbutan oate(化合物23)
Yellow solid.收率78％.M.p.＝175-177℃.1H-NMR(CDCl3,400MHz):δ＝8.57(d,J＝2.2Hz,1H),7.70(d,J＝9.0Hz,1H),7.49(dd,J＝9.0,2.2Hz,1H),5.94(s,1H),4.66(d,J＝8.2Hz,1H),3.73(s,3H),2.65–2.47(m,1H),1.65(s,9H),1.13(d,J＝7.0Hz,3H),0.90(d,J＝7.0Hz,3H).13C-NMR(CDCl3,100MHz):δ＝169.8,168.2,167.3,159.4,149.0,138.7,132.5,128.6,124.1,123.7,117.1,108.9,56.7,53.9,52.3,34.7,29.0,25.9,16.9.IR(ATR):3467,2901,1704,1540,1436,1248cm-1.HR-MS(ESI)m/z calcd for C21H25ClN3O4 +[M+H+]418.1534,found418.1531[M+H+].
化合物24的合成：
合成过程同化合物4，仅替换相应芳基脒原料和马来酰亚胺原料。
Figure BDA0002652905520000191
中间体化合物3-u：Yellow solid.M.p.＝80-81℃.1H-NMR(CDCl3,400MHz):δ＝7.35–7.27(m,4H),5.49(s,1H),5.17(s,1H),4.23(s,1H),3.50(s,3H),1.52(s,9H),0.91(s,9H).13C-NMR(CDCl3,100MHz):δ＝171.7,168.6,167.7,159.9,153.3,136.7,134.6,129.3,128.9,105.6,58.8,53.6,51.7,35.4,28.5,27.4.IR(ATR):3351,2962,1749,1525,1382,1207cm-1.HR-MS(ESI)m/z calcd for C22H29ClN3O4 +[M+H+]434.1847,found 434.1849[M+H+].
Figure BDA0002652905520000192
Methyl
(S)-2-[5-(tert-butylamino)-8-chloro-1,3-dioxo-1,3-dihydro-2H-pyrrolo[3,4-c]isoquinolin-2-yl]-3,3-dimethylbutanoate(化合物24)
Yellow solid.收率87％.M.p.＝93-95℃.1H-NMR(CDCl3,400MHz):δ＝8.59(d,J＝2.1Hz,1H),7.71(d,J＝9.0Hz,1H),7.49(dd,J＝9.0,2.1Hz,1H),5.94(s,1H),4.63(s,1H),3.68(s,3H),1.65(s,9H),1.20(s,9H)..13C-NMR(CDCl3,100MHz):δ＝168.7,168.4,167.6,159.5,149.0,138.7,132.6,128.6,124.1,123.7,117.1,108.9,59.4,53.9,51.9,35.7,28.9,27.9.IR(ATR):3447,2966,1699,1540,1339,1207cm-1.HR-MS(ESI)m/z calcd forC22H27ClN3O4 +[M+H+]432.1690,found 432.1694[M+H+].
化合物25的合成：
合成过程同化合物4，仅替换相应芳基脒原料和马来酰亚胺原料。
Figure BDA0002652905520000193
中间体化合物3-v：Yellow solid.M.p.＝92-94℃.1H-NMR(CDCl3,400MHz):δ＝7.35–7.27(m,4H),5.36(s,1H),5.14(s,1H),4.67(dd,J＝9.7,5.0Hz,1H),3.86(dd,J＝9.7,5.0Hz,1H),3.77(t,J＝9.7Hz,1H),3.61(s,3H),1.51(s,9H),1.04(s,9H).13C-NMR(CDCl3,100MHz):δ＝171.5,168.7,167.7,159.8,153.0,136.6,134.1,129.1,129.0,105.2,73.3,59.0,53.6,52.3,52.2,28.5,27.3.IR(ATR):3348,2988,1708,1573,1379,1276cm-1.HR-MS(ESI)m/z calcd for C23H31ClN3O5 +[M+H+]464.1952,found 464.1953[M+H+].
Figure BDA0002652905520000194
Methyl
(S)-3-(tert-butoxy)-2-[5-(tert-butylamino)-8-chloro-1,3-dioxo-1,3-dihydro-2H-pyrrolo[3,4-c]isoquinolin-2-yl]propanoate(化合物25)
Yellow solid.收率82％.M.p.＝173-175℃.1H-NMR(CDCl3,400MHz):δ＝8.52(d,J＝2.1Hz,1H),7.71(d,J＝9.0Hz,1H),7.47(dd,J＝9.0,2.1Hz,1H),5.95(s,1H),5.04(dd,J＝8.4,6.5Hz,1H),4.10(s,1H),4.08(d,J＝1.9Hz,1H),3.77(s,3H),1.64(s,9H),1.14(s,9H).13C-NMR(CDCl3,100MHz):δ＝168.9,168.0,167.1,159.4,149.1,138.6,132.5,128.5,123.9,123.8,117.0,109.0,73.7,59.2,53.6,52.7,52.6,28.9,27.5.IR(ATR):3412,2920,1705,1539,1392,1208cm-1.HR-MS(ESI)m/z calcd for C23H29ClN3O5 +[M+H+]462.1796,found 462.1794[M+H+].
化合物26的合成：
合成过程同化合物4，仅替换相应芳基脒原料和马来酰亚胺原料。
Figure BDA0002652905520000201
中间体化合物3-w：Yellow solid.M.p.＝122-125℃.1H-NMR(CDCl3,400MHz):δ＝7.34–7.27(m,4H),5.45(d,J＝12.5Hz,1H),5.16(s,1H),4.24(d,J＝8.6Hz,1H),3.57(s,3H),2.32–2.20(m,1H),1.63–1.58(m,2H),1.52(s,9H),0.90(d,J＝6.7Hz,3H),0.73(t,J＝6.3Hz,3H).13C-NMR(CDCl3,100MHz):δ＝171.6,169.7,167.4,160.0,153.3,136.6,134.5,129.2,128.9,105.5,56.3,53.6,52.0,34.1,28.5,25.3,16.5,10.8.IR(ATR):3355,2968,1697,1522,1386,1285,1199cm-1.HR-MS(ESI)m/z calcd for C22H29ClN3O4 +[M+H+]434.1841,found 434.1844[M+H+].
Figure BDA0002652905520000202
Methyl
(2S,3R)-2-[5-(tert-butylamino)-8-chloro-1,3-dioxo-1,3-dihydro-2H-pyrrolo[3,4-c]isoquinolin-2-yl]-3-methylpentanoate(化合物26)
Yellow solid.收率81％.M.p.＝116-118℃.1H-NMR(CDCl3,400MHz):δ＝8.55(d,J＝1.8Hz,1H),7.71(d,J＝9.0Hz,1H),7.48(dd,J＝9.0,1.8Hz,1H),5.97(s,1H),4.66(d,J＝8.2Hz,1H),3.73(s,3H),2.65–2.47(m,1H),1.64(s,9H),1.62–1.51(m,2H),1.13(d,J＝7.0Hz,3H),0.90(d,J＝7.0Hz,3H).13C-NMR(CDCl3,100MHz):δ＝169.9,168.2,167.3,159.5,149.0,138.7,132.5,128.6,124.0,123.8,117.1,108.9,56.7,53.9,52.3,34.7,28.9,25.9,16.8,11.0.IR(ATR):3420,2968,1706,1540,1373,1207cm-1.HR-MS(ESI)m/zcalcd for C22H27ClN3O4 +[M+H+]432.1690,found 432.1694[M+H+].
化合物27的合成：
合成过程同化合物4，仅替换相应芳基脒原料和马来酰亚胺原料。
Figure BDA0002652905520000211
中间体化合物3-x：Yellow solid.M.p.＝172-174℃.1H-NMR(CDCl3,400MHz):δ＝7.34–7.27(m,4H),5.44(s,1H),5.16(s,1H),4.54(dd,J＝11.9,4.2Hz,1H),3.60(s,3H),2.03(ddd,J＝14.2,11.0,4.0Hz,1H),1.68(ddd,J＝14.2,11.0,4.0Hz,1H),1.52(s,9H),1.14–1.01(m,1H),0.81(d,J＝6.5Hz,3H),0.75(d,J＝6.5Hz,3H).13C-NMR(CDCl3,100MHz):δ＝171.6,170.7,167.6,159.9,153.4,136.6,134.5,129.2,128.9,105.7,53.6,52.4,49.9,37.1,28.5,24.9,23.1,20.8.IR(ATR):3347,2963,1698,1522,1394,1207cm-1.HR-MS(ESI)m/z calcd for C22H29ClN3O4 +[M+H+]434.1847,found 434.1845[M+H+].
Figure BDA0002652905520000212
Methyl
(S)-2-[5-(tert-butylamino)-8-chloro-1,3-dioxo-1,3-dihydro-2H-pyrrolo[3,4-c]isoquinolin-2-yl]-4-methylpentanoate(化合物27)
Yellow solid.收率79％.M.p.＝97-99℃.1H-NMR(CDCl3,400MHz):δ＝8.50(d,J＝2.1Hz,1H),7.71(d,J＝9.0Hz,1H),7.47(dd,J＝9.0,2.1Hz,1H),5.98(s,1H),4.95(dd,J＝11.7,4.3Hz,1H),3.76(s,3H),2.37(ddd,J＝14.3,11.7,4.3Hz,1H),1.96(ddd,J＝14.3,11.7,4.3Hz,1H),1.63(s,9H),1.53(dd,J＝6.7,2.7Hz,1H),0.97(d,J＝6.7Hz,3H),0.94(d,J＝6.7Hz,3H).13C-NMR(CDCl3,100MHz):δ＝170.9,168.2,167.3,159.4,149.1,138.7,132.4,128.6,123.9,123.8,117.0,108.9,53.9,52.6,50.3,37.5,28.9,25.1,23.2,21.0.IR(ATR):3411,2958,1707,1539,1435,1207cm-1.HR-MS(ESI)m/z calcd forC22H27ClN3O4 +[M+H+]432.1690,found 432.1697[M+H+].
化合物28的合成：
合成过程同化合物4，仅替换相应芳基脒原料和马来酰亚胺原料。
Figure BDA0002652905520000213
中间体化合物3-y：Yellow solid.M.p.＝161-164℃.1H-NMR(CDCl3,400MHz):δ＝7.39–7.31(m,2H),7.20–7.14(m,2H),6.91–6.79(m,4H),5.12(s,1H),5.10(s,1H),4.77(dd,J＝11.4,5.1Hz,1H),3.65(s,3H),3.33(dd,J＝14.3,5.1Hz,1H),3.23(dd,J＝14.2,11.5Hz,1H),1.49(s,9H),1.31(s,9H).13C-NMR(CDCl3,100MHz):δ＝171.1,169.8,167.7,159.9,154.0,153.0,136.6,133.7,131.9,129.3,129.1,129.0,124.1,104.8,78.2,53.6,52.6,52.5,33.9,28.8,28.5.IR(ATR):3336,2984,1684,1522,1361,1236cm-1.HR-MS(ESI)m/z calcd for C29H35ClN3O5 +[M+H+]540.2265,found 540.2269[M+H+].
Figure BDA0002652905520000221
Methyl
(S)-3-[4-(tert-butoxy)phenyl]-2-[5-(tert-butylamino)-8-chloro-1,3-dioxo-1,3-dihydro-2H-pyrrol o[3,4-c]isoquinolin-2-yl]propanoate(化合物28)
Yellow solid.收率73％.M.p.＝114-116℃.1H-NMR(CDCl3,400MHz):δ＝8.43(d,J＝2.2Hz,1H),7.64(d,J＝9.0Hz,1H),7.44(dd,J＝9.0,2.2Hz,1H),7.08(d,J＝8.4Hz,2H),6.80(d,J＝8.4Hz,2H),5.88(s,1H),5.11(dd,J＝10.8,5.8Hz,1H),3.79(s,3H),3.59–3.46(m,2H),1.60(s,9H),1.20(s,9H).13C-NMR(CDCl3,100MHz):δ＝169.9,167.8,166.9,159.3,154.0,148.8,138.6,132.4,131.9,129.4,128.5,124.3,123.9,123.7,116.9,108.7,78.2,53.8,52.9,52.7,34.2,28.9,28.7.IR(ATR):3407,2923,1705,1540,1435,1206cm-1.HR-MS(ESI)m/z calcd for C29H33ClN3O5 +[M+H+]538.2109,found 538.2116[M+H+].
化合物29的合成：
合成过程同化合物4，仅替换相应芳基脒原料和马来酰亚胺原料。
Figure BDA0002652905520000222
中间体化合物3-z：Yellow solid.M.p.＝85-87℃.1H-NMR(CDCl3,400MHz):δ＝7.31–7.26(m,2H),7.23–7.14(m,5H),7.01–6.96(m,2H),5.20(s,1H),5.11(s,1H),4.80(dd,J＝11.5,5.0Hz,1H),3.66(s,3H),3.43–3.27(m,2H),1.49(s,9H).13C-NMR(CDCl3,100MHz):δ＝171.3,169.8,167.7,159.8,153.0,137.1,136.6,133.9,129.0,128.8,128.4,128.3,126.6,105.0,53.6,52.7,52.6,34.6,28.5.IR(ATR):3350,2971,1704,1521,1388,1205,1088cm-1.HR-MS(ESI)m/z calcd for C25H27ClN3O4 +[M+H+]468.1690,found 468.1692[M+H+].
Figure BDA0002652905520000223
Methyl
(S)-2-[5-(tert-butylamino)-8-chloro-1,3-dioxo-1,3-dihydro-2H-pyrrolo[3,4-c]isoquinolin-2-yl]-3-phenylpropanoate(化合物29)
Yellow solid.收率74％.M.p.＝183-185℃.1H-NMR(CDCl3,400MHz):δ＝8.46(d,J＝1.1Hz,1H),7.63(d,J＝9.0Hz,1H),7.44(dd,J＝9.0,1.4Hz,1H),7.26(s,1H),7.22(s,1H),7.22–7.18(m,2H),7.17–7.10(m,1H),5.88(s,1H),5.17(dd,J＝10.4,5.9Hz,1H),3.79(s,3H),3.65–3.44(m,2H),1.61(s,9H).13C-NMR(CDCl3,100MHz):δ＝169.9,167.9,167.1,159.3,149.0,138.6,137.1,132.5,129.0,128.9,128.6,126.7,124.0,123.7,117.0,108.9,53.9,52.9,52.8,34.9,28.9.IR(ATR):3427,2918,1702,1541,1363,1208cm-1.HR-MS(ESI)m/z calcd for C25H25ClN3O4 +[M+H+]466.1534,found 466.1538[M+H+].
化合物30的合成：
合成过程同化合物4，仅替换相应芳基脒原料和马来酰亚胺原料。
Figure BDA0002652905520000231
中间体化合物3-I：Yellow solid.M.p.＝291-293℃.1H-NMR(CDCl3,400MHz):δ＝7.29–7.09(m,7H),7.12(d,J＝6.5Hz,2H),5.32(s,1H),5.18(dd,J＝14.7,7.4Hz,1H),5.14(s,1H),1.66(d,J＝7.4Hz,3H),1.50(s,9H).13C-NMR(CDCl3,100MHz):δ＝172.1,168.1,159.9,153.2,141.0,136.5,134.4,129.0,128.9,128.2,127.1,126.7,105.3,53.5,48.8,28.5,17.7.IR(ATR):3344,2973,1690,1578,1352,1205cm-1.HR-MS(ESI)m/z calcd forC23H25ClN3O2 +[M+H+]410.1635,found 410.1637[M+H+].
Figure BDA0002652905520000232
(S)-5-(Tert-butylamino)-8-chloro-2-(1-phenylethyl)-1H-pyrrolo[3,4-c]isoquinoline-1,3(2H)-dio ne(化合物30)
Yellow solid.收率93％.M.p.＝181-183℃.1H-NMR(CDCl3,400MHz):δ＝8.60(d,J＝2.1Hz,1H),7.63(d,J＝9.0Hz,1H),7.54(d,J＝7.5Hz,2H),7.47(dd,J＝9.0,2.1Hz,1H),7.33(t,J＝7.5Hz,2H),7.25–7.18(m,1H),5.80(s,1H),5.56(q,J＝7.3Hz,1H),1.94(d,J＝7.3Hz,3H),1.63(s,9H).13C-NMR(CDCl3,100MHz):δ＝168.7,167.7,159.2,149.1,149.0,140.8,138.6,132.6,128.4,128.4,127.5,124.0,123.6,117.0,108.9,53.8,49.2,29.0,17.7.IR(ATR):3417,2973,1697,1533,1337,1222cm-1.HR-MS(ESI)m/z calcd forC23H23ClN3O2 +[M+H+]408.1479,found408.1482[M+H+].
化合物33合成过程：化合物4(96.0mg，0.30mmol)和TBDMSOTf(79.0mg，0.30mmol)溶于10mL DCM(二氯甲烷)溶液中，在23℃下搅拌12h。通过硅胶柱色谱法纯化(正己烷/乙酸乙酯＝1∶2；5％Et3N)，得到目标化合物33(72mg，92％收率)为黄色固体。M.p.>300℃。
化合物35合成过程：化合物4(48mg，0.15mmol)，N-苯基吡唑(14.0mg，0.10mmol)[RuCl2(p-cymene)]2(3.0mg，5mmol％)和K2CO3(28.0mg，0.20mmol)的甲苯悬浮液(2mL)在氩气保护下在120℃搅拌12h。在室温下，真空去除残余溶剂，并将剩余的残余物进行硅胶柱色谱纯化(正己烷/乙酸乙酯＝4∶1)，得到目标化合物35(17mg，40％收率)为黄色固体。M.p.>300℃。
Figure BDA0002652905520000241
5-Amino-8-chloro-2-methyl-1H-pyrrolo[3,4-c]isoquinoline-1,3(2H)-dione(化合物33)
Yellow solid.M.p.>300℃.1H-NMR(DMSO,400MHz):δ＝8.39(s,1H),8.37(s,2H),8.27(d,J＝2.2Hz,1H),7.68(dd,J＝9.0,2.2Hz,1H),2.99(s,3H).13C-NMR(DMSO,100MHz):δ＝168.8,167.9,163.1,151.2,138.3,132.8,128.2,128.0,122.0,116.2,108.4,23.7.IR(ATR):3344,2973,1689,1521,1362,1205cm-1.HR-MS(ESI)m/z calcd for C12H9ClN3O2 +[M+H+]262.0383,found 262.0391[M+H+].
8-[2-(1H-Pyrazol-1-yl)phenyl]-5-(tert-butylamino)-2-methyl-1H-pyrrolo[3,4-c]isoquinoline-1,3(2H)-dione(化合物35)
Yellow solid.1H-NMR(CDCl3,400MHz):δ＝8.61(d,J＝1.8Hz,1H),7.65–7.50(m,6H),7.20(d,J＝2.3Hz,1H),7.03(dd,J＝8.7,1.8Hz,1H),6.22(t,J＝2.3Hz,1H),5.81(s,1H),3.17(s,3H),1.63(s,9H).13C-NMR(CDCl3,100MHz):δ＝169.3,168.4,159.1,149.0,142.7,140.5,138.7,135.3,131.9,131.4,131.3,129.4,128.7,128.2,126.8,124.2,121.8,117.6,110.1,106.8,53.6,28.9,23.5.IR(ATR):3438,2971,1682,1543,1205cm- 1.HR-MS(ESI)m/z calcd for C25H24N5O2 +[M+H+]426.1930,found 426.1937[M+H+].
实施例2探究氧化氨基化反应过程中溶剂选用对合成中间体化合物的影响
参照实施例1的制备过程，当各反应条件选用表1所示的条件时，相应的合成中间体化合物3-a的结果如表1所示：
表1不同氧化氨基化反应溶剂体系合成中间体化合物3-a的结果
Figure BDA0002652905520000242
实施例3探究氧化氨基化反应过程中催化剂选用对合成中间体化合物的影响
参照实施例1的制备过程，当各反应条件选用表2所示的条件时，相应的合成中间体化合物3-a的结果如表2所示：
表2不同氧化氨基化反应催化体系合成中间体化合物3-a的结果
Figure BDA0002652905520000251
实施例4探究氧化氨基化反应过程中配体选用对合成中间体化合物的影响
参照实施例1的制备过程，当各反应条件选用表3所示的条件时，相应的合成中间体化合物3-a的结果如表3所示：
表3不同氧化氨基化反应催化体系合成中间体化合物3-a的结果
Figure BDA0002652905520000252
其中，涉及的DCE为二氯甲烷；TFE为四氟乙烯；DMF为N,N-二甲基甲酰胺；
i-propanol为异丙醇；toluene为甲醇；NMP为N-甲基吡咯烷酮；THF为四氢呋喃；
pyridine为吡啶；dmbbpy＝4,4'-di-methyl-2,2'-bipyridine，即4,4'-二甲基-2,2'-联吡啶；
dtbbpy＝4,4'-di-tert-butyl-2,2'-bipyridine，即4,4'-二叔丁基-2,2'-二吡啶；
bpy＝2,2’-bipyridine，即2,2'-联吡啶；phen＝1,10-phenanthroline，即1,10-菲罗啉；
TMEDA＝tetramethylethylenediamine，即N,N,N',N'-四甲基乙二胺
3,4,7,8-tetramethyl phen为3,4,7,8-四甲基-1,10-菲罗；4,7-diphenyl phen为4,7-二苯基-1,10-菲啰啉；
L-Ala为L-丙氨酸。
实施例5探究步骤(2)中溶剂选择对合成目标化合物的影响
参照实施例1的制备过程，当各反应条件选用表4所示的条件时，相应的合成目标化合物4的结果如表4所示：
表4不同溶剂体系合成目标体化合物4的结果
Figure BDA0002652905520000253
Figure BDA0002652905520000261
实施例6探究步骤(2)中反应光照环境对合成目标化合物的影响
参照实施例1的制备过程，当各反应条件选用表5所示的条件时，相应的合成目标化合物4的结果如表5所示：
表5不同溶剂体系合成目标体化合物4的结果
Figure BDA0002652905520000262
实施例7π共轭多环氨基异喹啉类化合物的性能应用
UV-VIS-NIR谱图：使用配备150mm积分球，光电倍增管(PMT)和InGaAs检测器的Perkin-Elmer Lambda 1050光谱仪记录UV-VIS-NIR光谱。
光致发光谱图：使用配备378nm皮秒二极管激光器(脉冲功率0.99nJ cm-2，脉冲频率40MHz)的PicoQuant FluoTime 300光谱仪进行稳态光致发光(PL)测量和与时间相关的单光子计数(TCSPC)测量。
PLQY产率：使用PicoQuant FluoTime 300光谱仪和软件easytau测量了光致发光量子产率PLQY。
探究π共轭多环氨基异喹啉类化合物在光学领域中的应用：
为了考察该方法学合成的新型含氮杂环化合物作为各种光学应用候选对象的可能性。为此，借助于UV-Vis吸收和光致发光(PL)光谱对其中的12个目标化合物(化合物4、5、6、7、8、9、13、22、23、25、30和33)进行了光学表征。通过时间相关的单光子计数(TCSPC)和PL量子产率测量进一步研究了PL动力学。值得注意的是，所研究的化合物仅表现出较小的光谱变化，在UV区域具有强吸收，在450nm以下的吸收带强度较小(见图2)。化合物13和33在可见光范围内分别显示出轻微的谱带偏移，分别变为红色和蓝色，这是可以预期的，因为化合物13具有最大的共轭体系，而33则缺少推电子的叔丁基基团。其中化合物13的PL最大值位于其中515nm，而化合物33的PL最大值位于475nm。而且PL谱带与吸收谱带重叠很小，在室温下有明显的红移并且没有振动的精细结构。
为了进一步研究结构变化对异喹啉衍生物光物理的影响，我们研究了溶液中化合物的PL量子产率(PLQY)(表6)。值得注意的是，所有化合物均显示出高于40％的高量子产率。该数据表明与具有其他取代基团的杂环相比，氯原子取代的杂环化合物30可导致高达70％的更高PL量子产率(PLQY)最高。溴原子取代的化合物6由于自旋轨道耦合从而会导致荧光猝灭。因此，与之相比，PLQY较低，为47.9％。而化合物4和5的PLQY分别为66.1％和59.5％。总而言之，高量子产率，吸收谱带和PL谱带几乎没有重叠，以及PL信号缺乏振动精细结构，表明这些化合物可以用作荧光量子产率参照材料。研究PLQY标准的进一步要求(例如发射的去极化)不在这项工作的范围之内。但是，连同本发明中包括的有效合成途径，这些化合物可能成为PLQY标准的候选者。
表6不同化合物的荧光量子产率.
Figure BDA0002652905520000271

Claims (4)

1.一种合成式(I)所示的π共轭多环氨基异喹啉类化合物的方法，其特征在于，所述方法的合成路线如下所示：
Figure FDA0003591843260000011
其中，所述芳基Ar为有取代基取代或者未取代的芳基，取代基选自单取代、二取代或者三取代的卤素、C1-8烷基；所述取代为邻位、间位或者对位取代；R1选自：氢、C1-8烷基、C3-6环烷基、苄基；R2、R3分别独立的选自：氢、叔丁基；
芳基为苯环；
所述方法包括如下过程：
(1)在氧气环境下，利用铜催化剂催化化合物1与化合物2发生氧化氨基化反应，制得化合物3；
(2)然后利用化合物3与氧化剂在可见光照射下，反应得到式(I)所示的π共轭多环氨基异喹啉化合物；
步骤(1)中的氧化氨基化反应是在有机溶剂中进行的，溶剂选自如下任意一种或多种：二氯甲烷、异丙醇、甲苯；
所述步骤(1)中的铜催化剂选自如下任意一种或多种：Cu(OAc)2、CuBr、Cu(OTf)2、Cu；
步骤(1)中还包括加入配体，配体选自如下任意一种或多种：2,2'-联吡啶、4,4'-二甲基-2,2'-联吡啶、1,10-菲罗啉、4,7-二苯基-1,10-菲啰啉；
步骤(2)中的氧化剂选自如下任意一种或者多种：TEMPO、O2；
步骤(2)中的反应是在溶剂中进行的，所述溶剂选自如下任意一种或多种：异丙醇、乙二醇、四氟乙烯。
2.一种合成式(I)所示的π共轭多环氨基异喹啉类化合物的方法，其特征在于，所述方法的合成路线如下所示：
Figure FDA0003591843260000021
式(I)所示的π共轭多环氨基异喹啉化合物为：
Figure FDA0003591843260000022
所述方法包括如下过程：
(1)在氧气环境下，利用铜催化剂催化化合物1与化合物2发生氧化氨基化反应，制得化合物3；
(2)然后利用化合物3与氧化剂在可见光照射下，反应得到式(I)所示的π共轭多环氨基异喹啉化合物；
步骤(1)中的氧化氨基化反应是在有机溶剂中进行的，溶剂选自如下任意一种或多种：二氯甲烷、异丙醇、甲苯；
所述步骤(1)中的铜催化剂选自如下任意一种或多种：Cu(OAc)2、CuBr、Cu(OTf)2、Cu；
步骤(1)中还包括加入配体，配体选自如下任意一种或多种：2,2'-联吡啶、4,4'-二甲基-2,2'-联吡啶、1,10-菲罗啉、4,7-二苯基-1,10-菲啰啉；
步骤(2)中的氧化剂选自如下任意一种或者多种：TEMPO、O2；
步骤(2)中的反应是在溶剂中进行的，所述溶剂选自如下任意一种或多种：异丙醇、乙二醇、四氟乙烯。
3.根据权利要求1所述的方法，其特征在于，所述步骤(1)中的铜催化剂的添加量为化合物1的20mol％。
4.根据权利要求1所述的方法，其特征在于，所述步骤(1)中的氧化氨基化反应还包括加入配体，配体的添加量为相对化合物1的30mol％。
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