CN113444088A - 一种苯并[4,5]咪唑并[2,1-a]异喹啉-6(5H)-酮及其衍生物、制备方法 - Google Patents
一种苯并[4,5]咪唑并[2,1-a]异喹啉-6(5H)-酮及其衍生物、制备方法 Download PDFInfo
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Abstract
本发明提供了一种苯并[4,5]咪唑并[2,1‑a]异喹啉‑6(5H)‑酮及其衍生物、制备方法;所述本发明将物质(I)和物质(II)作为反应原料,加入溶剂、光催化剂和碱,在惰性气体和蓝光光照条件下室温搅拌反应,得到苯并[4,5]咪唑并[2,1‑a]异喹啉‑6(5H)‑酮及其衍生物;本发明采用的原料磺酰氯在本发明中作为磺酰化试剂,该原料磺酰氯为市售产品,其经济廉价易得;本发明方法操作简单,条件温和,且产率高。本发明具由良好的官能团耐受性,可以实现多种不同基团的底物的偶联,本发明制备的得到的化合物在医药合成中间体具有良好的应用前景,对复杂的苯并咪唑稠合的多环化合物具有十分重要的意义。
Description
技术领域
本发明属于有机合成领域,具体涉及一种苯并[4,5]咪唑并[2,1-a]异喹啉-6(5H)-酮及其衍生物、制备方法。
背景技术
苯并咪唑稠合的多环骨架,特别是苯并[4,5]咪唑并[2,1-a]异喹啉-6(5H)-酮衍生物,广泛存在于多种合成中间体、药物和有机材料中。因此,苯并咪唑稠合的多环化合物的制备具有重要意义。这些年来,已有多种制备苯并咪唑稠合的多环化合物的方法;包括:缩合、金属催化的交叉偶联和自由基级联反应。但上述现有的方法通常需要使用金属催化剂、化学计量氧化剂、酸/碱反应介质和高反应温度等工艺条件,这些条件都会对其进一步的合成应用造成一定的阻碍。因此,开发一种条件温和且环境友好的方法是当前迫切的需求。
可见光是一种环境友好且无限可用的能源,可用于激活化学转化,它引发的有机反应已成为有机合成的有力工具。通过单电子转移、能量转移或氢原子转移过程的各种可见光诱导的有机转化已受到化学家的广泛关注。在2019年,Yu课题组实现了全氟烷基取代的苯并咪唑并[2,1-a]异喹啉-6(5H)-酮的快速制备(Adv.Synth.Catal.,2019,361,5176-5181.)。之后,Li课题组报道了在芳基重氮盐的存在下,新的可见光诱导的N-甲基苯甲酰基-2-芳基苯并咪唑的二芳基化反应(Chin.Chem.Lett.,2020,32,1229-1232.)。考虑到高反应效率,在光解催化条件下,扩大使用N-甲基丙烯酰基-2-芳基苯并咪唑来构建苯并[4,5]咪唑并[2,1-a]异喹啉-6(5H)-酮衍生物的策略是非常理想的。
近年来,磺酰氯作为一种廉价易得的反应伙伴,已被广泛用于在各种反应中快速构建双键和/或C-S键。在含有磺酰氯的光解转化中,主要过程是在失去SO2后形成碳-碳键,形成C-S键的方法非常少。具有巨大合成潜力的砜官能团广泛应用于农业化学和天然产物合成领域,并且许多磺酰基官能化的化合物具有优异的生物性能。
发明内容
为了克服现有技术中存在的不足,本发明提供一种新颖的、高效的可见光诱导的磺酰化/环化反应,该反应以磺酰氯作为磺化试剂和氧化剂,在温和的反应条件下得到一系列磺酰化的苯并[4,5]咪唑并[2,1-a]异喹啉-6(5H)-酮及其衍生物,所述方法操作简单,反应条件温和,原料廉价易得,并具有良好的产率。
本发明涉及一种苯并[4,5]咪唑并[2,1-a]异喹啉-6(5H)-酮及其衍生物,其结构式为如下:
其中,
R1为Cl,
R2为H、Me、tBu、OMe、F、Cl或Br;
R5为Me、F或CN,R6为F或Br。
本发明还涉及前述苯并[4,5]咪唑并[2,1-a]异喹啉-6(5H)-酮及其衍生物的制备方法,所述方法包括如下步骤:
将物质(I)和物质(II)作为反应原料,加入溶剂、光催化剂和碱,在惰性气体和蓝光光照条件下室温搅拌反应,得到苯并[4,5]咪唑并[2,1-a]异喹啉-6(5H)-酮及其衍生物,其反应式为:
其中,物质(I)为N-甲基丙烯酰基-2-芳基苯并咪唑或其衍生物;物质(II)为带有R3基团的磺酰氯。
优选地,所述方法中的各物质的用量如下:
所述物质(I)的用量为1.0当量,0.1mmol,所述物质(II)的用量为2.0当量,0.2mmol,所述光催化剂的用量为5mol%,所述碱的用量为2.0当量,0.2mmol,所述溶剂的用量为1mL。
优选地,所述蓝光光照条件为在5W的蓝光照射下,所述室温搅拌的时间为24小时。
优选地,所述光催化剂为fac-Ir(ppy)3,所述溶剂为二氯甲烷,所述碱为2,6-二甲基吡啶。
本发明具有以下优点:
(1)本发明采用的原料磺酰氯在本发明中作为磺酰化试剂,该原料磺酰氯为市售产品,其经济廉价易得。
(2)本发明的制备方法的是以可见光催化系统进行磺酰化/环化,本发明方法操作简单,条件温和,且产率高。
(3)本发明具由良好的官能团耐受性,可以实现多种不同基团的底物的偶联,本发明制备的得到的化合物在医药合成中间体具有良好的应用前景,对复杂的苯并咪唑稠合的多环化合物具有十分重要的意义。
附图说明
图1是实施例2采用N-甲基丙烯酰-2-苯基苯并咪唑对可见光驱动磺酰化/环化的底物范围的实验对比图;
图2是实施例4采用不同的磺酰氯反应产生多种磺酰基取代的苯并[4,5]咪唑并[2,1-a]异喹啉-6(5H)-酮及其衍生物的实验对比图;
图3是本发明制备原理图。
具体实施方式
下面结合具体实施例对本发明进行详细说明。应当指出的是,以下的实施实例只是对本发明的进一步说明,但本发明的保护范围并不限于以下实施例。
实施例1
本实施例以N-甲基丙烯酰基-2-苯基苯并咪唑1a和对甲苯磺酰氯2a作为模型底物制备苯并[4,5]咪唑并[2,1-a]异喹啉-6(5H)-酮及其衍生物,其反应过程如下:
在氩气氛围下向一个10mL的玻璃瓶中加入1a(1.0当量,0.1mmol),2a(2.0当量,0.2mmol),光催化剂(5mol%),碱(2.0当量,0.2mmol)和1mL的溶剂。在5W的蓝光照射下,室温搅拌24小时。反应结束后,通过旋转蒸发减压出去溶剂,然后通过硅胶柱色谱分离纯化得到目标产物。所述柱层析色谱法为:以纯石油醚等浓度洗脱,收集合并目标化合物的洗脱液,旋转蒸发去除溶剂后干燥。
实施例2
在实施例1为对照试验,对不同反应条件包括光催化剂、溶剂和碱进行筛选,其结果如下表1:
表1
由表1的数据可以看出:
条目1-5,所述的光催化剂为fac-Ir(ppy)3、Ru(bpy)3Cl2·6H2O、[Ir{dF(CF3ppy)}2(dtbbpy)]PF6、Ir(ppy)2(dtbbpy)(PF6)、Eosin Y。
条目6-9,所述的溶剂为DMSO、THF、DCM、MeOH。
条目10-16,所述的碱为2,6-二甲基吡啶、DBU、Na2CO3、K2CO3、NaHCO3、Cs2CO3、KH2PO4。
通过条件筛选表明,条目10为更优选,所以,本发明选取光催化剂为fac-Ir(ppy)3,溶剂为二氯甲烷、碱为2,6-二甲基吡啶。
实施例3
在实施例1为对照试验,本实施例涉及N-甲基丙烯酰-2-苯基苯并咪唑对可见光驱动磺酰化/环化的底物范围。
本实施例对应的结果见图1所示。
通过上述实验数据,可以得到最优的条件:
在氩气氛围下向一个10mL的玻璃瓶中加入N-甲基丙烯酰-2-苯基苯并咪唑1(1.0当量,0.1mmol),2a(2.0当量,0.2mmol),光催化剂fac-Ir(ppy)3(5mol%),2,6-二甲基吡啶(2.0当量,0.2mmol)和1mL的二氯甲烷。在5W的蓝光照射下,室温搅拌24小时。反应结束后,通过旋转蒸发减压出去溶剂,然后通过硅胶柱色谱分离纯化得到目标产物。
所获产物的1H NMR、13C NMR和HRMS的数据表征如下:
1、3aa,其结构式如下:
黄色固体,mp=199.0-203.6℃.1H NMR(600MHz,CD2Cl2)δH 8.45(dd,J=7.8,1.1Hz,1H),8.31-8.19(m,1H),7.83-7.75(m,1H),7.46-7.40(m,3H),7.32-7.28(m,1H),7.21(dd,J=12.6,8.1Hz,3H),7.01(d,J=7.9Hz,2H),4.47(d,J=14.9Hz,1H),3.99(d,J=14.9Hz,1H),2.19(s,3H),1.65(s,3H);13C NMR(151MHz,CD2Cl2)δc 170.7,149.4,144.9,144.1,137.3,136.4,131.6,131.2,129.6,128.3,127.6,127.0,126.0,125.9,125.6,123.0,119.8,115.6,64.7,46.9,31.0,21.1;HRMS m/z(ESI)calcd for C24H20N2NaO3S+[M+Na]+:439.1087,found:439.1103.
2、3ba,其结构式如下:
淡黄色固体,mp=238.7-241.1℃.1H NMR(600MHz,CD2Cl2)δHδ8.24(d,J=8.0Hz,1H),8.22-8.07(m,1H),7.72-7.67(m,1H),7.35(m,2H),7.15-7.12(m,1H),7.12-7.07(m,2H),6.94(d,J=8.0Hz,2H),6.73(s,1H),4.39(d,J=15.1Hz,1H),3.92(d,J=15.0Hz,1H),2.17(s,3H),2.06(s,3H),1.56(s,3H);13C NMR(151MHz,CD2Cl2)δC 170.9,149.6,144.6,144.2,142.0,136.9,136.7,131.6,129.5,129.3,127.4,125.9,125.8,125.4,120.4,119.6,115.6,64.7,46.8,30.9,21.2,21.1;HRMS m/z(ESI)calcd for C25H22N2NaO3S+[M+Na]+:453.1243,found:453.1260.
3、3ca,其结构式如下:
棕色固体,mp=165.3-172.6℃.1H NMR(600MHz,CD2Cl2)δH 8.37(d,J=8.3Hz,1H),8.29-8.22(m,1H),7.79-7.74(m,1H),7.49(dd,J=8.3,1.8Hz,1H),7.42(m,2H),7.21-7.16(m,3H),7.00(d,J=7.9Hz,2H),4.49(d,J=15.0Hz,1H),4.04(d,J=15.0Hz,1H),2.17(s,3H),1.66(s,3H),1.21(s,9H);13C NMR(151MHz,CD2Cl2)δC 171.0,155.1,149.5,144.8,144.2,137.0,136.7,131.6,129.6,127.7,125.9,125.8,125.3,123.6,120.4,119.6,115.5,65.2,47.1,35.0,31.1,30.7,21.1;HRMS m/z(ESI)calcd for C28H28N2NaO3S+[M+Na]+:495.1713,found:495.1728.
4、3da,其结构式如下:
淡黄色固体,mp=204.1-206.2℃.1H NMR(600MHz,CD2Cl2)δH 8.37(d,J=8.7Hz,1H),8.24(d,J=7.9Hz,1H),7.73(d,J=7.5Hz,1H),7.43-7.36(m,2H),7.21(d,J=8.1Hz,2H),7.05(dd,J=17.3,8.0Hz,2H),6.97(dd,J=8.7,2.3Hz,1H),6.51(d,J=2.3Hz,1H),4.47(d,J=15.0Hz,1H),3.94(d,J=15.0Hz,1H),3.69(s,3H),2.22(s,3H),1.63(s,3H);13CNMR(151MHz,CD2Cl2)δC 170.7,162.1,149.5,144.8,144.2,139.0,136.7,131.5,129.5,127.9,127.6,125.7,125.1,119.4,115.8,115.4,114.6,112.1,64.7,55.3,47.0,31.0,21.1;HRMS m/z(ESI)calcd for C25H22N2NaO4S+[M+Na]+:469.1192,found:469.1208.
5、3ea,其结构式如下:
白色固体,mp=217.6-224.3℃;1H NMR(600MHz,CD2Cl2)δH 8.46(dd,J=8.7,5.8Hz,1H),8.27-8.21(m,1H),7.80-7.75(m,1H),7.46-7.41(m,2H),7.26(d,J=8.3Hz,2H),7.16(td,J=8.5,2.4Hz,1H),7.06(d,J=7.9Hz,2H),6.84(dd,J=9.7,2.4Hz,1H),4.47(d,J=15.0Hz,1H),3.90(d,J=15.0Hz,1H),2.23(s,3H),1.65(s,3H);13C NMR(151MHz,CD2Cl2)δC 170.1,164.4(d,J=252.2Hz),148.6,145.2,144.0,139.9(d,J=9.1Hz),136.4,131.5,129.7,128.5(d,J=9.1Hz),127.5,126.0,125.6,119.8,119.6(d,J=3.0Hz),116.3(d,J=22.7Hz),115.6,114.0(d,J=24.2Hz),64.5,47.0(d,J=1.5Hz),30.8,21.1;HRMS m/z(ESI)calcd for C24H19FN2NaO3S+[M+Na]+:457.0993,found:457.1006.
6、3fa,其结构式如下:
黄色固体,mp=170.3-175.2℃.1H NMR(600MHz,CD2Cl2)δH 8.31-8.19(m,2H),7.78(dd,J=6.7,1.9Hz,1H),7.45-7.39(m,2H),7.26-7.20(m,2H),7.08-6.99(m,4H),4.54(d,J=15.2Hz,0.09H),4.44(d,J=14.9Hz,0.97H),4.40(d,J=15.2Hz,0.1H),3.97(d,J=14.9Hz,0.94H),2.45(s,0.23H),2.43(s,2.80H),2.22(s,2.81H),2.15(s,0.21H),1.76(s,0.21H),1.63(s,2.81H);13C NMR(151MHz,CD2Cl2)δC 171.7,170.9,149.5,145.1,144.8,144.2,144.1,138.6,137.0,136.5,136.3,135.9,135.0,134.3,132.2,131.6,129.5,129.4,128.5,127.8,127.6,126.9,126.0,125.9,125.8,125.5,125.3,125.0,122.7,119.8,119.7,115.6,64.8,61.8,47.8,46.6,30.9,27.0,22.5,21.2,21.1,20.8;HRMS m/z(ESI)calcd for C25H22N2NaO3S+[M+Na]+:453.1243,found:453.1265.
7、3ga,其结构式如下:
白色固体,mp=243.2-251.8℃;1H NMR(600MHz,CD2Cl2)δH 8.59(d,J=2.1Hz,1H),8.29-8.24(m,1H),7.82-7.78(m,1H),7.48-7.43(m,2H),7.30(dd,J=8.5,2.2Hz,1H),7.21(d,J=8.2Hz,2H),7.07(d,J=7.9Hz,2H),6.98(d,J=8.5Hz,1H),4.45(d,J=15.0Hz,1H),3.94(d,J=15.0Hz,1H),2.26(s,3H),1.64(s,3H);13C NMR(151MHz,CD2Cl2)δC 170.1,147.9,145.1,143.9,136.3,135.9,133.9,131.6,129.7,128.7,128.4,127.5,126.1,126.0,124.9,122.5,120.0,115.6,64.7,46.6,30.5,21.2;HRMS m/z(ESI)calcd forC24H19BrN2NaO3S+[M+Na]+:517.0192,found:517.0205.
8、3ha,其结构式如下:
淡黄色固体,mp=232.9-235.8℃;1H NMR(600MHz,CD2Cl2)δH 8.29-8.25(m,1H),7.89-7.84(m,1H),7.497.44(m,2H),7.33-7.27(m,3H),7.22-7.17(m,1H),7.07(dd,J=12.8,7.9Hz,3H),4.49(d,J=14.9Hz,1H),3.98(d,J=14.9Hz,1H),2.21(s,3H),1.66(s,3H);13C NMR(151MHz,CD2Cl2)δC 170.1,160.4(d,J=261.2Hz),145.5(d,J=8.7Hz),145.1,144.3(d,J=3.0Hz),139.8,136.5,131.9(d,J=10.6Hz),130.5,129.6,127.6,126.1,126.0,123.0(d,J=3.0Hz),120.4,116.1(d,J=21.1Hz),115.6,112.3(d,J=10.6Hz),64.8,46.8(d,J=1.5Hz),31.3,21.1;HRMS m/z(ESI)calcd for C24H19FN2NaO3S+[M+Na]+:457.0993,found:457.1010.
9、3ia,其结构式如下:
黄色固体,mp=177.1-184.6℃;1H NMR(600MHz,CD2Cl2)δH 8.32-8.28(m,1H),7.89-7.84(m,1H),7.49(m,3H),7.27(d,J=8.2Hz,2H),7.21-7.18(m,2H),7.06(d,J=8.0Hz,2H),4.48(d,J=15.0Hz,1H),3.98(d,J=15.0Hz,1H),2.22(s,3H),1.66(s,3H);13CNMR(151MHz,CD2Cl2)δC 169.9,146.8,145.1,143.8,140.2,136.4,133.5,131.8,130.7,130.5,129.6,127.6,126.3,126.0,126.0,120.9,120.5,115.7,64.8,47.1,31.4,21.2;HRMS m/z(ESI)calcd for C24H19ClN2NaO3S+[M+Na]+:473.0697,found:473.0713.
10、3ja,其结构式如下:
白色固体,mp=178.9-182.0℃;1H NMR(600MHz,DMSO)δH 8.30(s,1H),8.27(dd,J=7.8,1.2Hz,1H),8.16(s,1H),7.54(d,J=7.9Hz,1H),7.45-7.42(m,1H),7.27(td,J=8.0,1.4Hz,1H),7.11(q,J=8.3Hz,4H),4.79(d,J=15.3Hz,1H),4.25(d,J=15.3Hz,1H),2.23(s,3H),1.65(s,3H);13C NMR(151MHz,DMSO)δC 171.5,152.0,144.7,143.9,138.6,136.9,132.4,130.9,130.0,128.8,128.7,128.6,128.0,127.5,125.7,122.0,121.5,116.8,64.3,47.0,30.1,21.4;HRMS m/z(ESI)calcd for C24H18Cl2N2NaO3S+[M+Na]+:507.0307,found:507.0318.
实施例4
在实施例1为对照试验,不同的磺酰氯反应产生多种磺酰基取代的苯并[4,5]咪唑并[2,1-a]异喹啉-6(5H)-酮及其衍生物;
本实施例对应的结果见图2所示。
通过上述实验数据,可以得到最优的条件:
在氩气氛围下向一个10mL的玻璃瓶中加入1a(1.0当量,0.1mmol),磺酰氯2(2.0当量,0.2mmol),光催化剂fac-Ir(ppy)3(5mol%),2,6-二甲基吡啶(2.0当量,0.2mmol)和1mL的二氯甲烷。在5W的蓝光照射下,室温搅拌24小时。反应结束后,通过旋转蒸发减压出去溶剂,然后通过硅胶柱色谱分离纯化得到目标产物。
所获产物的1H NMR、13C NMR和HRMS的数据表征如下:
1、3ab,其结构式如下:
淡黄色固体,mp=225.1-231.3℃;1H NMR(600MHz,CDCl3)δH 8.60(d,J=7.7Hz,1H),8.27(d,J=7.6Hz,1H),7.87(d,J=7.7Hz,1H),7.54-7.41(m,4H),7.31(dd,J=8.6,2.9Hz,3H),6.63(d,J=8.8Hz,2H),4.54(d,J=14.8Hz,1H),4.00(d,J=14.8Hz,1H),3.64(s,3H),1.69(s,3H);13C NMR(151MHz,CDCl3)δc 170.5,163.6,149.0,137.5,131.9,131.1,130.4,130.1,128.7,127.1,126.7,126.4,126.1,119.4,115.9,114.1,64.7,55.5,47.0,31.5;HRMS m/z(ESI)calcd for C24H20N2NaO4S+[M+Na]+:455.1036,found:455.1053.
2、3ac,其结构式如下:
白色固体,mp=186.9-188.2℃;1H NMR(400MHz,CDCl3)δH 8.50(d,J=7.9Hz,1H),8.32-8.28(m,1H),7.85-7.80(m,1H),7.46-7.38(m,3H),7.30(d,J=8.2Hz,2H),7.28-7.20(m,1H),7.17(d,J=7.9Hz,1H),7.06(d,J=8.3Hz,2H),4.53(d,J=14.7Hz,1H),4.00(d,J=14.8Hz,1H),2.78(dt,J=13.8,6.9Hz,1H),1.65(s,3H),1.13(dd,J=6.9,4.4Hz,6H);13CNMR(101MHz,CDCl3)δC 170.6,155.1,149.2,143.56,137.1,136.8,131.38,131.29,128.4,127.8,127.1,127.1,126.8,126.2,126.1,125.8,122.7,119.7,115.8,64.4,46.9,34.0,31.3,23.5,23.4;HRMS m/z(ESI)calcd for C26H24N2NaO3S+[M+Na]+:467.1400,found:467.1409.
3、3ad,其结构式如下:
淡黄色固体,mp=191.5-195.6℃;1H NMR(600MHz,CDCl3)δH 8.51(d,J=7.6Hz,1H),8.36-8.29(m,1H),7.87-7.81(m,1H),7.49-7.39(m,3H),7.33(d,J=8.5Hz,2H),7.25(dd,J=7.6,5.6Hz,3H),7.19(d,J=7.9Hz,1H),4.56(d,J=14.9Hz,1H),4.02(d,J=14.9Hz,1H),1.68(s,3H),1.22(s,9H);13C NMR(151MHz,CDCl3)δC 170.6,157.4,149.2,143.7,137.2,136.5,131.4,131.2,128.4,127.5,126.8,126.2,126.1,126.0,125.8,122.8,119.8,115.8,64.4,46.9,35.1,31.4,30.9;HRMS m/z(ESI)calcd for C27H26N2NaO3S+[M+Na]+:481.1556,found:481.1567.
4、3ae,其结构式如下:
淡黄色固体,mp=185.1-190.3℃.1H NMR(400MHz,CDCl3)δH 8.52(d,J=7.9Hz,1H),8.36-8.28(m,1H),7.87-7.81(m,1H),7.50-7.39(m,5H),7.35-7.28(m,1H),7.18(d,J=7.9Hz,1H),6.92(t,J=8.5Hz,2H),4.54(d,J=14.8Hz,1H),4.02(d,J=14.8Hz,1H),1.68(s,3H);13C NMR(101MHz,CDCl3)δC 170.7,165.6(d,J=257.6Hz),149.2,143.8,137.2,135.8(d,J=3.0Hz),131.5(d,J=2.0Hz),130.7,130.6,129.3(d,J=18.2Hz),128.7,126.8,126.4,126.3,126.0,122.9,120.0,116.5,116.3,115.9,64.8,47.0,31.2;HRMS m/z(ESI)calcd for C23H17FN2NaO3S+[M+Na]+:443.0836,found:443.0850.
5、3af,其结构式如下:
黄色固体,mp=207.9-215.5℃;1HNMR(400MHz,CDCl3)δH 8.54(dd,J=7.9,1.0Hz,1H),8.33-8.28(m,1H),7.88-7.83(m,1H),7.51-7.43(m,3H),7.37-7.30(m,3H),7.24-7.16(m,3H),4.54(d,J=14.8Hz,1H),4.02(d,J=14.8Hz,1H),1.69(s,3H);13CNMR(101MHz,CDCl3)δC 170.6,149.1,143.5,140.5,138.1,137.2,131.6,131.4,129.4,129.2,128.7,126.8,126.5,126.4,126.1,122.8,119.9,115.9,64.7,47.0,47.0,31.2;HRMS m/z(ESI)calcd for C23H17ClN2NaO3S+[M+Na]+:459.0541,found:459.0553.
6、3ag,其结构式如下:
黄色油状.1H NMR(400MHz,CDCl3)δH 8.53(dd,J=7.9,0.9Hz,1H),8.34-8.29(m,1H),7.87-7.84(m,1H),7.58-7.41(m,7H),7.25-7.18(m,1H),7.12(d,J=8.0Hz,1H),4.57(d,J=14.9Hz,1H),4.06(d,J=14.9Hz,1H),1.69(s,3H);13C NMR(101MHz,CDCl3)δC170.5,149.0,143.6,143.2(d,J=1.0Hz),137.0,135.1(q,J=33.3Hz),131.5,131.4,128.8,128.3,126.7,126.5,126.4,126.3,126.2,126.1,123.0(q,J=273.7Hz),122.9,120.0,115.8,64.7,47.0,31.1;HRMS m/z(ESI)calcd for C24H17F3N2NaO3S+[M+Na]+:493.0804,found:493.0804.
7、3ah,其结构式如下:
淡黄色固体,mp=166.9-171.1℃;1H NMR(600MHz,CDCl3)δH 8.51(d,J=7.7Hz,1H),8.31(d,J=7.3Hz,1H),7.83(d,J=7.5Hz,1H),7.44(m,3H),7.29-7.23(m,2H),7.19-7.12(m,3H),7.09(s,1H),4.54(d,J=14.9Hz,1H),4.02(d,J=14.9Hz,1H),2.18(s,3H),1.67(s,3H);13C NMR(151MHz,CDCl3)δC 170.5,149.2,143.7,139.3,139.2,137.1,134.3,131.4,131.2,128.9,128.4,128.0,126.8,126.1,126.0,125.7,124.8,122.8,119.8,115.8,64.6,46.8,31.2,21.1;HRMS m/z(ESI)calcd for C24H20N2NaO3S+[M+Na]+:439.1087,found:439.1102.
8、3ai,其结构式如下:
淡黄色固体,mp=200.7-203.7℃;1H NMR(600MHz,CDCl3)δH 8.55(d,J=7.7Hz,1H),8.35(dd,J=7.0,1.9Hz,1H),7.85(dd,J=6.8,1.5Hz,1H),7.49-7.43(m,3H),7.30-7.23(m,3H),7.17(d,J=7.9Hz,1H),7.13(dd,J=7.9,2.3Hz,2H),4.56(d,J=14.9Hz,1H),4.04(d,J=14.9Hz,1H),1.69(s,3H);13C NMR(151MHz,CDCl3)δC 170.6,162.1(d,J=252.2Hz),149.1,143.6,141.9(d,J=7.6Hz),137.0,131.4,131.3,130.9(d,J=7.6Hz),128.7,126.5,126.4,126.2,125.9,123.4(d,J=4.5Hz),122.8,120.8(d,J=22.7Hz),119.9,115.8,115.0(d,J=24.2Hz),64.7,47.0,31.0;HRMS m/z(ESI)calcd forC23H17FN2NaO3S+[M+Na]+:443.0836,found:443.0836.
9、3aj,其结构式如下:
黄色固体,mp=225.0-227.4℃;1H NMR(600MHz,CDCl3)δH 8.62(d,J=7.7Hz,1H),8.34(dd,J=6.9,2.0Hz,1H),7.91–7.86(m,1H),7.69(t,J=7.9Hz,2H),7.65(s,1H),7.56–7.41(m,4H),7.31(t,J=7.4Hz,1H),7.17(d,J=7.7Hz,1H),4.60(d,J=15.0Hz,1H),4.06(d,J=15.0Hz,1H),1.72(s,3H);13C NMR(151MHz,CDCl3)δC 170.4,148.8,143.4,141.5,136.8,136.5,131.5,131.5,131.4,131.2,130.1,129.0,126.7,126.5,126.4,126.2,122.9,119.9,116.6,115.8,113.8,64.8,47.0,31.0;HRMS m/z(ESI)calcd forC24H17N3NaO3S+[M+Na]+:450.0883,found:450.0883.
10、3ak,其结构式如下:
黄色固体,mp=191.6-197.2℃;1H NMR(600MHz,CDCl3)δH 8.43(d,J=7.7Hz,1H),8.33(dd,J=7.1,1.6Hz,1H),7.84(dd,J=7.0,1.3Hz,1H),7.48-7.42(m,2H),7.41-7.36(m,1H),7.31-7.24(m,1H),7.15(d,J=7.8Hz,1H),7.08(td,J=8.9,8.5,3.3Hz,2H),6.98(td,J=7.8,1.6Hz,1H),6.86-6.81(m,1H),4.60(d,J=15.3Hz,1H),4.25(d,J=15.3Hz,1H),1.74(s,3H);13C NMR(151MHz,CDCl3)δC 170.4,158.9(d,J=255.2Hz),149.0,143.4,136.8,135.9(d,J=9.1Hz),131.3,131.2,129.5,128.6,127.6(d,J=15.1Hz),126.3,126.2,126.1,126.0,124.7(d,J=3.0Hz),122.7,119.7,116.6(d,J=21.1Hz),115.9,64.3(d,J=3.0Hz),46.6,30.4;HRMS m/z(ESI)calcd for C23H17FN2NaO3S+[M+Na]+:443.0836,found:443.0849.
11、3al,其结构式如下:
淡黄色固体,mp=245.7-250.3℃;1H NMR(600MHz,CDCl3)δH 8.43(d,J=7.7Hz,1H),8.37(dd,J=6.9,2.0Hz,1H),7.85(dd,J=6.8,1.7Hz,1H),7.63-7.59(m,1H),7.49-7.43(m,2H),7.23(m,2H),7.14(dd,J=7.9,1.5Hz,1H),7.09(d,J=7.8Hz,1H),7.01(m,2H),4.63(dd,J=38.8,15.4Hz,2H),1.74(s,3H);13C NMR(151MHz,CDCl3)δC 170.5,149.0,143.6,138.9,136.9,134.8,134.2,131.4,131.1,131.0,128.6,127.9,126.2,126.1,126.0,126.0,122.9,120.1,119.8,115.9,62.3,46.8,30.6;HRMS m/z(ESI)calcd forC23H17BrN2NaO3S+[M+Na]+:503.0035,found:503.0052.
12、3am,其结构式如下:
白色固体,mp=198.5-202.3℃;1H NMR(600MHz,CDCl3)δH 8.59-8.55(m,1H),8.39-8.34(m,1H),7.88-7.84(m,1H),7.50-7.44(m,3H),7.38(t,J=1.8Hz,1H),7.30-7.25(m,1H),7.22(d,J=1.8Hz,2H),7.13(d,J=7.9Hz,1H),4.57(d,J=15.1Hz,1H),4.05(d,J=15.1Hz,1H),1.70(s,3H);13C NMR(151MHz,CDCl3)δC 170.3,148.9,143.7,142.5,136.5,136.0,133.6,131.3,131.1,129.1,126.4,126.4,126.3,126.1,126.0,123.0,119.9,115.8,65.0,46.9,30.8;HRMS m/z(ESI)calcd for C23H16Cl2N2NaO3S+[M+Na]+:493.0151,found:493.0151.
13、3an,其结构式为如下:
淡黄色固体,mp=179.1-184.6℃;1H NMR(600MHz,CDCl3)δH 8.48(d,J=7.4Hz,1H),8.19(d,J=7.9Hz,1H),7.82-7.76(m,2H),7.73(dd,J=12.2,8.5Hz,2H),7.66(d,J=8.1Hz,1H),7.53(m,3H),7.43-7.39(m,1H),7.37-7.33(m,1H),7.28-7.22(m,1H),7.16(d,J=7.8Hz,1H),7.08(t,J=7.5Hz,1H),4.61(d,J=15.0Hz,1H),4.07(d,J=15.0Hz,1H),1.67(s,3H);13C NMR(151MHz,CDCl3)δC 170.4,149.1,143.7,137.0,136.0,135.0,131.7,131.3,131.1,129.9,129.5,129.4,129.3,128.5,127.6,127.5,126.7,126.1,126.0,125.8,122.8,122.1,119.8,115.7,64.4,46.9,31.3,;HRMS m/z(ESI)calcd forC27H20N2NaO3S+[M+Na]+:475.1087,found:475.1104.
14、3ao,其结构式为如下:
淡黄色固体,mp=204.6-207.8℃;1H NMR(600MHz,CDCl3)δH 8.54(d,J=7.8Hz,1H),8.38-8.32(m,1H),7.84(d,J=7.2Hz,1H),7.51-7.41(m,4H),7.34(t,J=7.6Hz,1H),7.28-7.22(m,1H),7.07(d,J=3.6Hz,1H),6.79(t,J=4.3Hz,1H),4.65(d,J=14.9Hz,1H),4.13(d,J=14.9Hz,1H),1.71(s,3H);13C NMR(151MHz,CDCl3)δC 170.5,149.2,143.7,140.9,137.2,134.3,134.3,131.4,131.4,128.5,127.7,126.5,126.4,126.1,125.9,122.8,119.8,115.8,65.9,47.1,31.2;HRMS m/z(ESI)calcd for C21H16N2NaO3S2 +[M+Na]+:431.0495,found:431.0508.
15、3ap,其结构式为如下:
白色固体,mp=207.8-209.6℃;1H NMR(600MHz,CDCl3)δH 8.58(d,J=7.7Hz,1H),8.39-8.34(m,1H),7.84(dd,J=6.4,2.4Hz,1H),7.61(dd,J=10.9,4.0Hz,1H),7.58-7.52(m,2H),7.48-7.42(m,2H),4.48(d,J=14.7Hz,1H),3.97(d,J=14.7Hz,1H),2.00-1.95(m,1H),1.75(s,3H),1.04-0.98(m,2H),0.84-0.79(m,2H);13C NMR(151MHz,CDCl3)δC 171.0,149.2,143.6,138.3,131.6,131.4,128.7,126.8,126.5,126.1,125.9,122.7,119.8,115.7,62.7,47.1,32.1,31.0,5.37,5.07;HRMS m/z(ESI)calcd for C20H18N2NaO3S+[M+Na]+:389.0930,found:389.0930.
16、3aq,其结构式为如下:
淡黄色固体,mp=205.7-208.7℃;1H NMR(600MHz,CDCl3)δH 8.57(d,J=7.7Hz,1H),8.38-8.31(m,1H),7.87-7.81(m,1H),7.62(t,J=7.5Hz,1H),7.55(dd,J=14.8,7.6Hz,2H),7.47-7.41(m,2H),4.34(d,J=14.6Hz,1H),3.88(d,J=14.6Hz,1H),2.69-2.59(m,2H),1.77-1.68(m,5H),0.94(t,J=7.4Hz,3H);13C NMR(151MHz,CDCl3)δC 171.1,149.3,143.7,138.2,131.7,131.4,128.7,126.8,126.1,126.1,125.8,122.8,119.9,115.7,61.0,57.5,47.0,30.9,15.6,12.9;HRMS m/z(ESI)calcd for C20H20N2NaO3S+[M+Na]+:391.1087,found:391.1087.
17、3ar,其结构式为如下:
黄色固体,mp=170.9-175.8℃;1H NMR(600MHz,CDCl3)δH 8.56(d,J=7.7Hz,1H),8.37-8.30(m,1H),7.86-7.81(m,1H),7.63-7.59(m,1H),7.57-7.52(m,2H),7.43(m,2H),4.37(d,J=14.3Hz,1H),3.83(d,J=14.3Hz,1H),2.88-2.81(m,1H),1.72(s,3H),1.28(dd,J=17.9,6.8Hz,6H);13C NMR(151MHz,CDCl3)δC 171.2,149.4,143.7,138.2,131.6,131.4,128.6,126.6,126.4,126.0,125.7,122.6,119.9,115.6,57.4,55.5,46.9,31.1,15.1,14.8;HRMS m/z(ESI)calcd for C20H20N2NaO3S+[M+Na]+:391.1087,found:391.1100.
本发明的反应原理为:以原料1a和2a的反应过程来描述此类反应的机理,如下图,首先,在5W蓝色发光二极管的照射下,光敏化剂fac-[IrIII(ppy)3]被激发成fac-[IrIII(ppy)3]*,该fac-[IrIII(ppy)3]*容易被对甲苯磺酰氯2a氧化以产生相应的自由基A。随后,自由基A被底物1a捕获,形成自由基中间体B。在与苯环的分子内加成环化之后,所得中间体C经历单电子氧化以产生阳离子中间体D,并且光敏化剂fac-[IrIII(ppy)3]被再生用于下一次运行。在提取一个质子后,阳离子中间体D转化为最终产物3aa。
以上对本发明的具体实施例进行了描述。需要理解的是,本发明并不局限于上述特定实施方式,本领域技术人员可以在权利要求的范围内做出各种变形或修改,这并不影响本发明的实质。
Claims (5)
2.一种如权利要求1所述的苯并[4,5]咪唑并[2,1-a]异喹啉-6(5H)-酮及其衍生物的制备方法,其特征在于,所述方法包括如下步骤:
将物质(I)和物质(II)作为反应原料,加入溶剂、光催化剂和碱,在惰性气体和蓝光光照条件下室温搅拌反应,得到苯并[4,5]咪唑并[2,1-a]异喹啉-6(5H)-酮及其衍生物;
其中,所述物质(I)为N-甲基丙烯酰基-2-芳基苯并咪唑或其衍生物;所述物质(II)为带有R3基团的磺酰氯。
3.如权利要求2所述的苯并[4,5]咪唑并[2,1-a]异喹啉-6(5H)-酮及其衍生物的制备方法,其特征在于,所述方法中的各物质的用量如下:
所述物质(I)的用量为1.0当量,0.1mmol,所述物质(II)的用量为2.0当量,0.2mmol,所述光催化剂的用量为5mol%,所述碱的用量为2.0当量,0.2mmol,所述溶剂的用量为1mL。
4.如权利要求2所述的苯并[4,5]咪唑并[2,1-a]异喹啉-6(5H)-酮及其衍生物的制备方法,其特征在于,所述蓝光光照条件为在5W的蓝光照射下,所述室温搅拌的时间为24小时。
5.如权利要求2所述的苯并[4,5]咪唑并[2,1-a]异喹啉-6(5H)-酮及其衍生物的制备方法,其特征在于,所述光催化剂为fac-Ir(ppy)3,所述溶剂为二氯甲烷,所述碱为2,6-二甲基吡啶。
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