CN112174972A - 氮杂咔咯化合物及其制备方法 - Google Patents
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Abstract
Description
技术领域
本发明属于有机合成技术领域,具体涉及一种氮杂咔咯化合物及其制备方法。
背景技术
与去甲咔咯相比,氮杂咔咯在吡咯-吡咯键间插入一个氮原子,表现出明显的芳香性,成为与普通卟啉相似的18π芳香族共轭的新型分子。而卟啉类化合物的性质很大程度上受其骨架和结构的影响,因此氮原子的插入大大的改变了其性质与电子结构,使其具有更加新颖的性质,在化学催化、电极材料、电池和分子自组装、生物传感器以及配位化学等领域具有潜在的应用前景,逐渐成为人们关注的焦点。
目前,氮杂咔咯的合成方法已有少量文献报道(Chem.Commun.,2016,52,3540—3543;Chem.Eur.J.2012,18,5919-5923;Org.Lett.2016,18,2978–2981),但其合成方法颇为复杂繁琐。传统的方法需要经过多步合成,使用价格相对较高的钯作催化剂,反应温度高,收率低,且只能合成苄基氮杂咔咯。因此申请人经过大量实验探索和研究,得到了一条简单的合成路线,只需通过一步法便合成得到了芳基氮杂咔咯化合物,此类化合物为我们首次合成,没有文献报导。为氮杂咔咯化合物的功能化提供一种全新的合成途径。
发明内容
本发明的目的之一在于提供上述经过一步法合成的氮杂咔咯化合物。
本发明的氮杂咔咯化合物,其结构式如式(1)所示:
其中,R为式(2)至式(6)结构式中之一所示:
本发明的目的之二在于提供上述氮杂咔咯化合物的制备方法,它包括如下顺序的步骤:
(1)称取一定量的去甲咔咯和胺类化合物置于反应瓶中,以二氯甲烷作溶剂;其中,去甲咔咯的结构式如式(7)所示:
(2)在常温搅拌下加入一定量的亚碘酰苯反应2小时,用色谱方法跟踪反应;
(3)待反应完全后,浓缩反应液,直接用层析柱加以分离,收集绿色带即为粗产品,经浓缩、干燥后得所需化合物。
优选地,步骤(1)中,胺类化合物和去甲咔咯两种反应物的物质的量之比为4.5:1。
优选地,步骤(2)中,去甲咔咯与亚碘酰苯的物质的量之比为3.5:1。
优选地,步骤(2)中,跟踪反应的色谱方法是薄层色谱法、气相色谱法和高效液相色谱法中的任意一种,从而判断反应是否完成。
优选地,步骤(3)中,柱层析中所用洗脱剂是体积比为4:1的石油醚与二氯甲烷的混合溶剂,分离采用柱层析法,以便提高产物纯度。
本发明与现有技术相比,具有如下有益效果:
(1)具有反应选择性好、操作简便等优点。
(2)本发明方法通过选择不同的芳胺类化合物,可制备得到不同取代基的氮杂咔咯化合物。
(3)制备的氮杂咔咯化合物在化学催化和光电子领域有潜在的应用前景。
(4)利用本发明合成方法得到氮杂咔咯化合物具有优异的产率,且能在产业上实现批量生产。
附图说明
图1为本发明实施例3所制备产品的单晶X-射线衍射图。
具体实施方式
下面结合附图和具体实验实例对本发明做进一步的详细描述,具体实施例并不对本发明做任何限定。
实施例1:
称取去甲咔咯(30mg,0.052mmol)和4-氨基苯甲醛(0.234mmol)于10mL小瓶中,向上述小瓶中加入二氯甲烷(5ml),在室温搅拌下再加入亚碘酰苯(0.18mmol)反应2小时,用薄层色谱(TLC)跟踪反应,待反应完全后,用200-300目硅胶进行柱层析,用体积比为4:1或者5:1的石油醚和二氯甲烷的混合溶剂作为洗脱剂,收集绿色带,收集到的溶液经浓缩、干燥后得到绿色产物4-甲酰基苯基氮杂咔咯化合物,产率为94%。
产物波谱表征数据如下:1H NMR(500MHz,CDCl3,298K)δ:1.92(s,12H,-CH3),2.51(s,6H,-CH3),7.13(s,4H,ArH),7.16(d,J=4.5Hz,2H,pyrrH),7.91(d,J=4.0Hz,2H,pyrrH),8.01(d,J=8.0Hz,2H,ArH),8.08(d,J=4.5Hz,2H,pyrrH),8.23(d,J=8.0Hz,2H,ArH),8.28(d,J=4.0Hz,2H,pyrrH),10.27(s,1H,-CHO);13C NMR(125MHz,CDCl3,298K)δ:19.67,20.10,111.44,116.02,124.20,126.45,127.37,128.90,129.68,130.57,131.83,131.85,133.82,136.08,136.31,137.16,141.78,143.59,145.81,189.71.UV-vis(CH2Cl2)λmax/nm(logε):396(5.08),438(4.49),561(3.95),594(3.87),637(3.90).ESI-HRMScalc.for C43H36N5NiO+[M+H]+:696.2268,Found:696.2268。
光谱数据表明上述制备方法得到了4-甲酰基苯基氮杂咔咯化合物。
实施例2:
本实施例采用与实施例1基本相同的合成工艺,原料改为对氰基苯胺用量为0.234mmol,得绿色产物,即得产品氮杂咔咯化合物,产率为73%。
产物波谱表征数据如下:1H NMR(500MHz,CDCl3,298K)δ:1.92(s,12H,-CH3),2.51(s,6H,-CH3),7.12(d,J=5.0Hz,2H,pyrrH),7.13(s,4H,ArH),7.90(d,J=4.5Hz,2H,pyrrH),7.98(d,J=8.5Hz,2H,ArH),8.04(d,J=8.5Hz,2H,ArH),8.08(d,J=5.0Hz,2H,pyrrH),8.27(d,J=4.5Hz,2H,pyrrH);13C NMR(125MHz,CDCl3,298K)δ:19.65,20.10,111.10,113.26,116.16,116.46,124.39,126.46,127.61,129.83,130.64,131.68,131.82,131.89,133.72,136.37,137.13,141.61,143.73,144.68.UV-vis(CH2Cl2)λmax/nm(logε):394(5.03),438(4.45),565(3.93),592(3.77),640(3.91).ESI-HRMS calc.for C43H35N6Ni+[M+H]+:693.2271,Found:693.2268。
光谱数据表明上述制备方法得到了4-氰基苯基氮杂咔咯化合物。
实施例3:
本实施例采用与实施例1基本相同的合成工艺,原料改为对硝基苯胺,用量为0.234mmol,得绿色产物,即得产品4-硝基苯基氮杂咔咯化合物,产率为71%。
产物波谱表征数据如下:1H NMR(500MHz,CDCl3,298K)δ:1.92(s,12H,-CH3),2.51(s,6H,-CH3),7.13(s,4H,ArH),7.14(d,J=4.5Hz,2H,pyrrH),7.90(d,J=4.5Hz,2H,pyrrH),8.03(d,J=9.0Hz,2H,ArH),8.09(d,J=4.5Hz,2H,pyrrH),8.27(d,J=4.5Hz,2H,pyrrH),8.59(d,J=9.0Hz,2H,ArH);13C NMR(125MHz,CDCl3,298K)δ:19.65,20.10,111.02,116.22,122.69,123.04,123.56,124.46,126.48,127.72,129.99,130.68,131.82,131.92,133.70,136.39,137.12,141.52,143.79,146.18,147.49.UV-vis(CH2Cl2)λmax/nm(logε):394(5.01),439(4.47),565(4.01),591(3.85),640(3.95).ESI-HRMS calc.forC42H35N6NiO2 +[M+H]+:713.2169,Found:713.2166。
光谱数据表明上述制备方法得到了4-硝基苯基氮杂咔咯化合物。图1所示为本实施例所制得产品的单晶X射线衍射图。
实施例4:
本实施例采用与实施例1基本相同的合成工艺,原料改为3-氟苯胺,用量为0.234mmol,得绿色产物,即得产品氮杂咔咯化合物,产率为82%。
产物波谱表征数据如下:1H NMR(500MHz,CDCl3,298K)δ:1.92(s,12H,-CH3),2.51(s,6H,-CH3),7.13(s,4H,ArH),7.22(d,J=4.0Hz,2H,pyrrH),7.50-7.51(m,1H,ArH),7.61-7.63(m,1H,ArH),7.67-7.68(m,2H,ArH),7.90(d,J=4.0Hz,2H,pyrrH),8.08(d,J=4.5Hz,2H,pyrrH),8.28(d,J=4.0Hz,2H,pyrrH));13C NMR(125MHz,CDCl3,298K)δ:19.68,20.13,111.69,115.85,116.25(d,J=21Hz),116.66(d,J=23Hz),123.99,124.81,124.84,126.42,126.45,127.19,128.82,128.89,130.51,131.73,131.89,133.90,136.27,137.18,137.23,142.13,142.21,142.28,143.45,161.15(d,J=250Hz).UV-vis(CH2Cl2)λmax/nm(logε):393(5.01),439(4.43),563(3.94),590(3.83),635(3.94).ESI-HRMS calc.forC42H34FN5Ni+[M]+:685.2146,Found:685.2145。
光谱数据表明上述制备方法得到了3-氟苯基氮杂咔咯化合物。
实施例5:
本实施例采用与实施例1基本相同的合成工艺,原料改为4-甲氧羰基苯胺,用量为0.234mmol,得绿色产物,即得产品氮杂咔咯化合物,产率为72%。
产物波谱表征数据如下:1H NMR(500MHz,CDCl3,298K)δ:1.92(s,12H,-CH3),2.51(s,6H,-CH3),4.05(s,3H,-OCH3),7.13(s,4H,ArH),7.19(d,J=4.5Hz,2H,pyrrH),7.90(d,J=4.0Hz,2H,pyrrH),7.94(d,J=8.0Hz,2H,ArH),8.08(d,J=4.5Hz,2H,pyrrH),8.28(d,J=4.0Hz,2H,pyrrH),8.41(d,J=8.0Hz,2H,ArH);13C NMR(125MHz,CDCl3,298K)δ:19.68,20.11,51.45,111.63,115.91,124.05,126.44,127.20,128.95,129.08,130.52,130.69,131.78,131.88,133.89,136.28,137.19,141.96,143.49,144.77,164.88;UV-vis(CH2Cl2)λmax/nm(logε):394(5.03),438(4.45),561(3.97),590(3.81),635(3.93).ESI-HRMScalc.for C44H38N5NiO2 +[M+H]+:726.2373,Found:726.2377。
光谱数据表明上述制备方法得到了4-甲氧羰基苯基氮杂咔咯化合物。
Claims (6)
3.根据权利要求2所述氮杂咔咯化合物的制备方法,其特征在于:步骤(1)中,胺类化合物和去甲咔咯两种反应物的物质的量之比为4.5:1。
4.根据权利要求2所述氮杂咔咯化合物的制备方法,其特征在于:步骤(2)中,去甲咔咯与亚碘酰苯的物质的量之比为3.5:1。
5.根据权利要求2所述氮杂咔咯化合物的制备方法,其特征在于:步骤(2)中,跟踪反应的色谱方法是薄层色谱法、气相色谱法和高效液相色谱法中的任意一种。
6.根据权利要求2所述氮杂咔咯化合物的制备方法,其特征在于:步骤(3)中,柱层析中所用洗脱剂是体积比为4:1的石油醚与二氯甲烷的混合溶剂。
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