CN114853794B - 一种将吡咯和硼氮单元嵌入苝的稠环芳烃的制备方法 - Google Patents
一种将吡咯和硼氮单元嵌入苝的稠环芳烃的制备方法 Download PDFInfo
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Abstract
本发明属于有机光电功能材料技术领域,具体公开了一种在苝的两侧海湾区分别嵌入吡咯、硼氮单元的新型稠环芳烃BN‑NP的制备方法。该化合物为具有吡咯和硼氮单元掺杂的锯齿状边缘稠环芳烃,具有二维平面弯曲结构和大共轭体系。本发明使用化合物A为原料,通过过渡金属催化下的C‑N偶联反应和亲电硼化反应得到化合物BN‑NP,反应方程式如下:本发明通过自下而上的合成策略,将五元吡咯环、BN单元分别引入苝的两侧湾区位置,从而得到苝的新型衍生物BN‑NP。同时此化合物BN‑NP具有灵敏的氟离子(F‑)监测、吡啶(pyridine)监测、准分子发射、全局抗磁性以及弯曲结构等性能。本发明提供的BN‑NP的制备方法合理,操作简便,产率高,并且在有机光电材料方面具有广阔的应用前景。
Description
技术领域
本发明涉及一种在苝的海湾区嵌入吡咯及硼氮单元的稠环芳烃BN-NP的制备方法,属于有机光电材料领域。
背景技术
稠环芳烃被认为是由sp2杂化碳原子组成的二维石墨烯片段。它具有大离域的π电子共轭体系,在晶体中的排列一般呈现强烈的π-π相互作用,因此稠环芳烃在有机光电材料领域具有广泛的应用前景。以杂原子代替稠环芳烃化合物中部分碳原子,形成含杂原子的共轭骨架分子,是调控稠环芳烃性能的有力方法。其中,将硼氮单元引入稠环芳烃被认为是一种很独特的调节性能的方法。与全碳稠环芳烃相比,硼氮单元的引入具有许多优势:1.硼氮(B-N)和碳碳(C=C)结构单元互为等电子体;2.硼氮(B-N)单元引入不会改变相应全碳化合物原来的分子骨架;3.分子荧光量子产率被显著提高;4.硼氮(B-N)引入使稠环芳烃分子骨架具有更多反应活性差异较大的可修饰位点,从而更容易进行进一步结构修饰;5.引入分子偶极矩和离子特征;6.增强与其它杂原子(如氮、硫等)间的相互作用,从而使化合物具有丰富的自组装行为、固态堆积、外界刺激下的性能响应等。由此,将硼氮单元引入稠环芳烃在有机功能材料领域具有重要的意义。
本发明通过自下而上的合成策略,将五元吡咯环、BN单元分别引入苝的两侧湾区位置,从而得到苝的新型衍生物BN-NP。此化合物BN-NP具有灵敏的氟离子(F-)监测、吡啶(pyridine)监测、准分子发射、全局抗磁性等性能。总而言之,本发明提供的BN-NP的制备方法简单,操作简便,反应产率高,并且BN-NP分子具有优异的氟离子(F-)监测、吡啶(pyridine)监测、准分子发射、全局抗磁性等性能,在有机光电材料方面具有广阔的应用前景。
发明内容
本发明设计并合成一种结构新颖的硼氮单元和氮原子掺杂的稠环芳烃,属于有机光电材料领域。本发明使用化合物A为原料,通过过渡金属催化下的C-N偶联反应,以及亲电硼化反应得到目标物BN-NP,该化合物的反应方程式如下:
本发明的优势在于:合成方法简便,反应条件温和,成本低;所得的产品具有优异的氟离子(F-)监测、吡啶(pyridine)监测、准分子发射、全局抗磁性等性能,在有机光电材料方面具有广阔的应用前景。
本发明的合成工艺及条件是通过以下步骤实现的:
步骤一、按照质量比,二(三叔丁基膦)钯:四丁氧基苯胺:叔丁醇钠:化合物A=1:3.56:3.764:7.421,在氮气的氛围下溶解在无水甲苯中,反应混合液在130℃下搅拌反应12小时;反应结束后,将反应液经硅藻土抽滤,收集滤液,通过减压蒸馏回收溶剂;以体积比为5:1的石油醚与二氯甲烷的混合溶剂为淋洗剂,使用200~300目的中性硅胶柱层析分离,收集第四个黄绿色带,得到化合物B的溶液,然后经减压蒸馏回收溶剂,且真空干燥后得到橘红色固体化合物B。
步骤二、按照质量比,三乙胺:化合物B:苯基二氯化硼=1:6.944:13.069,在氮气的氛围下溶解在无水氯苯中,反应混合液在140℃下搅拌反应5小时;反应结束后,将反应液经硅藻土抽滤,收集滤液,通过减压蒸馏回收溶剂;以体积比为7:1的石油醚与二氯甲烷的混合溶剂为淋洗剂,使用200~300目的中性硅胶柱层析分离,收集第一个黄绿色带,得到化合物BN-NP的溶液,然后经减压蒸馏回收溶剂,且真空干燥后得到淡黄色固体目标物BN-NP。
附图说明
1.图1为化合物B的核磁共振氢谱图。
2.图2为化合物BN-NP的核磁共振氢谱图。
3.图3为化合物BN-NP的1H-1H COSY图。
4.图4(A)为化合物BN-NP的1H-1H NOESY图;(B)为化合物BN-NP部分放大的1H-1HNOESY图。
5.图5为化合物BN-NP的核磁共振碳谱图。
6.图6为化合物BN-NP的MALDI-TOF质谱图。
7.图7为化合物BN-NP在不同溶剂中的紫外吸收光谱图。
8.图8为化合物BN-NP在不同溶剂中的荧光发射光谱图。
9.图9为化合物BN-NP在吡啶与THF不同比例的混合溶液中的紫外吸收光谱。
10.图10为化合物BN-NP在吡啶与THF不同比例的混合溶液中的荧光发射光谱。
11.图11为化合物BN-NP在DMSO与THF不同比例的混合溶液中的荧光发射光谱。
12.图12(A)为TBAF滴定BN-NP溶液的紫外吸收光谱;(B)为依次加入TBAF和BF3OEt2的BN-NP溶液的紫外吸收光谱。
13.图13(A)为TBAF滴定BN-NP溶液的荧光发射光谱;(B)依次加入TBAF和BF3OEt2的BN-NP溶液的荧光发射光谱。
具体实施方式
实施例1.化合物B的合成
将80mg(0.105mmol)化合物A,38.28mg(0.232mmol)四丁氧基苯胺,10.77mg(0.021mmol)二(三叔丁基膦)钯,40.58mg(0.422mmol)叔丁醇钠加入到8ml无水甲苯中,使用液氮将反应混合物冷冻并抽真空3min,自然回到室温后充入氮气,重复该操作3次,反应混合物在130℃下搅拌反应12小时;反应结束后,将反应液经硅藻土抽滤,收集滤液,通过减压蒸馏回收溶剂;以体积比为5:1的石油醚与二氯甲烷的混合溶剂为淋洗剂,使用200~300目的中性硅胶柱层析分离,收集第四个黄绿色带,得到化合物B的溶液,然后经减压蒸馏回收溶剂,且真空干燥后得到橘红色固体化合物B,共63.87mg,产率为72%。
实施例2.化合物B的合成
将80mg(0.105mmol)化合物A,38.30mg(0.232mmol)四丁氧基苯胺,10.75mg(0.021mmol)二(三叔丁基膦)钯,40.60mg(0.422mmol)叔丁醇钠加入到8ml无水甲苯中,使用液氮将反应混合物冷冻并抽真空3min,自然回到室温后充入氮气,重复该操作3次,反应混合物在130℃下搅拌反应12小时;反应结束后,将反应液经硅藻土抽滤,收集滤液,通过减压蒸馏回收溶剂;以体积比为5:1的石油醚与二氯甲烷的混合溶剂为淋洗剂,使用200~300目的中性硅胶柱层析分离,收集第四个黄绿色带,得到化合物B的溶液,然后经减压蒸馏回收溶剂,且真空干燥后得到橘红色固体化合物B,共62.8mg,产率为70.5%。
实施例3.化合物BN-NP的合成
将100mg(0.119mmol)化合物B,10ml无水氯苯,加入50ml双口瓶中,使用液氮将反应混合物冷冻并抽真空3min,自然回到室温后充入氮气,重复该操作3次;待反应混合物恢复至室温后,向其中加入0.02ml(0.1422mmol)三乙胺,然后在氩气保护下,将0.152ml(1.185mmol)苯基二氯化硼加入双口瓶中,反应混合物在140℃下搅拌反应5小时;反应结束后,将反应液经硅藻土抽滤,收集滤液,通过减压蒸馏回收溶剂;按照体积比为7:1的石油醚与二氯甲烷的混合溶剂为淋洗剂,使用200~300目的中性硅胶柱层析分离,收集第一个黄绿色带,得到化合物BN-NP的溶液,然后经减压蒸馏回收溶剂,且真空干燥后得到淡黄色固体目标化合物BN-NP,共108mg,产率为97.5%。
实施例4.化合物BN-NP的合成
将20mg(0.024mmol)化合物B,4ml无水氯苯,加入25ml双口瓶中,使用液氮将反应混合物冷冻并抽真空3min,自然回到室温后充入氮气,重复该操作3次;待反应混合物恢复至室温后,向其中加入0.004ml(0.028mmol)三乙胺,然后在氩气保护下,将0.03ml(0.237mmol)苯基二氯化硼加入双口瓶中,反应混合物在140℃下搅拌反应5小时;反应结束后,将反应液经硅藻土抽滤,收集滤液,通过减压蒸馏回收溶剂;按照体积比为7:1的石油醚与二氯甲烷的混合溶剂为淋洗剂,使用200~300目的中性硅胶柱层析分离,收集第一个黄绿色带,得到化合物BN-NP的溶液,然后经减压蒸馏回收溶剂,且真空干燥后得到淡黄色固体目标化合物BN-NP,共17.6mg,产率为78.8%。
实施例5.化合物BN-NP的合成
将100mg(0.119mmol)化合物B,16ml无水氯苯,加入50ml双口瓶中,使用液氮将反应混合物冷冻并抽真空3min,自然回到室温后充入氮气,重复该操作3次;待反应混合物恢复至室温后,向其中加入0.02ml(0.1422mmol)三乙胺,然后在氩气保护下,将0.03ml(0.237mmol)苯基二氯化硼加入双口瓶中,反应混合物在140℃下搅拌反应5小时;反应结束后,将反应液经硅藻土抽滤,收集滤液,通过减压蒸馏回收溶剂;按照体积比为7:1的石油醚与二氯甲烷的混合溶剂为淋洗剂,使用200~300目的中性硅胶柱层析分离,收集第一个黄绿色带,得到化合物BN-NP的溶液,然后经减压蒸馏回收溶剂,且真空干燥后得到淡黄色固体目标化合物BN-NP,共13.7mg,产率为12.4%。
图1为化合物B的核磁共振氢谱图;1H NMR(500MHz,CDCl3):δ(ppm)=9.07(d,J=7.6Hz,1H),7.87(s,1H),7.78(t,J=7.9Hz,1H),7.69(t,J=10.7Hz,3H),7.63(d,J=8.8Hz,1H),7.13(d,J=8.3Hz,2H),6.92(d,J=8.7Hz,2H),6.44(s,1H),4.74(t,J=7.0Hz,2H),3.97(t,J=6.4Hz,2H),2.12(p,J=7.2Hz,2H),1.83–1.74(m,2H),1.51(q,J=7.5Hz,1H),1.42(q,J=7.5Hz,1H),1.33(d,J=8.0Hz,1H),1.27(d,J=7.9Hz,3H),0.99(t,J=7.4Hz,2H),0.83(t,J=7.2Hz,2H).
图2为化合物BN-NP的核磁共振氢谱图;1H NMR(600MHz,CD2Cl2)):δ(ppm)=8.37(d,J=8.5Hz,1H),8.21(s,1H),8.04(s,1H),7.97(d,J=4.8Hz,2H),7.59(d,J=9.1Hz,1H),7.41(d,J=6.4Hz,2H),7.19(d,J=5.6Hz,3H),7.12(d,J=8.2Hz,2H),6.81(d,J=8.2Hz,2H),4.79(t,J=7.1Hz,2H),3.87(t,J=6.4Hz,2H),2.13(t,J=7.6Hz,2H),1.67(t,J=7.4Hz,2H),1.44–1.39(m,2H),1.37–1.32(m,2H),1.24(t,J=7.7 Hz,2H),1.17–1.13(m,2H),0.89(t,J=7.4 Hz,3H),0.71(t,J=7.4 Hz,3H).
Claims (4)
1.一种在苝的两侧湾区分别嵌入吡咯及硼氮单元的稠环芳烃,简称化合物BN-NP,结构式如下:
2.一种4-丁氧基苯胺取代的吡咯苝衍生物,简称化合物B,结构式如下:
3.如权利要求1所述化合物BN-NP的制备方法,其特征在于:反应物料的质量比为,三乙胺:4-丁氧基苯胺取代的吡咯苝衍生物:苯基二氯化硼=1:6.944:13.069,其中4-丁氧基苯胺取代的吡咯苝衍生物为权利要求2中所述的化合物B。
4.如权利要求3所述的制备方法,其特征在于,反应在氮气的保护下进行,反应温度为140℃,反应时间为5小时。
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