CN108997346B - 一种基于苝酰亚胺c3对称的螺浆烷衍生物及其合成与应用 - Google Patents
一种基于苝酰亚胺c3对称的螺浆烷衍生物及其合成与应用 Download PDFInfo
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- CN108997346B CN108997346B CN201811048989.8A CN201811048989A CN108997346B CN 108997346 B CN108997346 B CN 108997346B CN 201811048989 A CN201811048989 A CN 201811048989A CN 108997346 B CN108997346 B CN 108997346B
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Abstract
Description
技术领域
本发明涉及有机材料技术领域,具体涉及一种基于苝酰亚胺C3对称的螺浆烷衍生物及其合成与应用。
背景技术
C3对称的三维材料因其在传感器、光电转换、能量存储、超分子自组装等方面的具有重要的意义,近期备受关注。这类材料的一个显著的特点是分子结构中含有三个互成120°的结构单元,因此这类分子一般具有较大的分子内自由体积(intramolecular freevolume),是制备分子笼、二维聚合物(2D polymers)的重要结构单元。这类结构独特的化合物通常含有较多的活性位点,通过化合物的活性位点进行适当的化学修饰,可以赋予化合物一些特殊的性能。例如,可以引入共轭π体系,增加化合物的共轭长度、提高化合物的结晶性能及分子间作用力,提高载流子的传输能力。其中,分子中三个互成120°共轭结构的π电子有一定的相互影响,这些空间弱相互作用(through-space interactions)对有机器件(有机场效应晶体管、有机太阳能电池等)的性能有很重要的影响。
苝酰亚胺类衍生物是一类常见的工业颜料,这类特殊的稠环化合物通常具有优异的光稳定性、热稳定性和化学稳定性。同时,化合物中共轭的大π体系赋予了它较强的荧光性能和光电性能,使这类化合物作为光电材料广泛应用于有机场效应晶体管、有机太阳能电池、光导体、电致发光、自组装及生物荧光探针等领域。特别是近几年,随着有机电子学的不断发展,苝酰亚胺类化合物因其较高的电子传输效率和光电转化效率成为最重要的n型半导体之一,受到了学术界和工业界的广泛关注。其中,二维结构的苝酰亚胺类化合物具有较大的分子间作用力,易于结晶与组装,该类化合物通常具有较高的电子传输效率,而作为电池的受体材料,其电荷转化效率相对较低。而具有三维立体结构的苝酰亚胺类衍生物的研究相对较少,其电子结构、聚集状态和作为光电材料的性能很少为人所知。由鉴于此,本课题组在专利号为“201711286168.3”的中国专利中首次设计合成了一类基于苝酰亚胺C3对称的螺浆烷;本发明在此基础上,进一步在该螺浆烷中的苝酰亚胺的侧面活性位点引入官能团,进一步的扩大共轭π体系,以获得更优异的电子传输效率。
发明内容
基于以上背景技术,本发明提供一种基于苝酰亚胺C3对称的螺浆烷衍生物及其合成与应用。本发明在专利号为“201711286168.3”专利中公开的化合物 1(式1所示)的基础上,在苝中的两个萘环之间引入环结构,进一步扩大共轭π体系,以获得更优异的电子传输效率。
为实现以上目的,本发明采用以下技术方案:
本发明第一个方面提供一种基于苝酰亚胺C3对称的螺浆烷衍生物,其结构式如式2所示:
该结构是由苯环、噻吩、双键构成大共轭体系,其在溶剂中溶解性很差, R、R1、R2和R3的引入增大了其溶解性,以使得该分子可以溶解于溶剂中,对其性能研究以及应用都有所帮助。R、R1、R2和R3各自独立的选自:C2-60烷基、含取代基的C2-60烷基、C2-60烷氧基、含取代基的C2-60烷氧基、C2-60硅烷基、芳香基、含取代基的芳香基、烷基芳香基、含取代基的烷基芳香基、烷基杂芳香基、含取代基的烷基杂芳香基、烷基杂环基和含取代基的烷基杂环基。
优选地,所述取代基选自:甲基、乙基、丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、羟基、巯基、氟原子、氯原子、溴原子、碘原子、氰基、醛基、脂基、磺基、亚磺基、硝基、氨基、亚氨基、羧基和肼基中的至少一种。
优选地,所述烷氧基选自:甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、仲丁氧基、异丁氧基、叔丁氧基、戊氧基、己氧基、庚氧基、辛氧基、壬氧基、癸氧基、十一碳烷氧基、十二碳烷氧基、十三碳烷氧基、十四碳烷氧基、十五碳烷氧基、十六碳烷氧基、十七碳烷氧基、十八碳烷氧基、十九碳烷氧基和二十碳烷氧基中的任一种。
优选地,所述芳香基选自:苯基、萘基、蒽基、菲基、并四苯基、并五苯基、三苯胺基、芘基、茚基、联苯基和芴基中的至少一种。
所述杂环基、杂芳香基均选自:噻吩、苯并噻吩、吡喃、苯并吡喃、呋喃、苯并呋喃、咪唑、苯并咪唑、吡唑、苯并吡唑、吡咯、苯并吡咯、吡啶、苯并吡啶、吡嗪、苯并吡嗪、吲哚、异吲哚、苯并吲哚、嘧啶、苯并嘧啶、萘啶、苯并萘啶、哒嗪、苯并哒嗪、吲唑、苯并吲唑、嘌呤、苯并嘌呤、喹嗪、苯并喹嗪、喹啉、苯并喹啉、吲嗪、苯并吲嗪、酞嗪、苯并酞嗪、喹喔啉、苯并喹喔啉、噻唑、苯并噻唑、咔啉、苯并咔啉、菲啶、苯并菲啶、菲咯啉、苯并菲咯啉、吖啶、苯并吖啶、吩嗪、苯并吩嗪、吩噻嗪、苯并吩噻嗪、咔唑、苯并咔唑、二并噻吩、二噻吩并吡咯、三并噻吩、四并噻吩和五并噻吩中的任一种。
优选地,所述R、R1、R2和R3各自独立的选自:C2-60烷基、含取代基的 C2-60烷基、C2-60硅烷基;所述烷基选自直链或支链烷基。此处的R基团是为了增加化合物在溶剂中的溶解性。
本发明第二个方面提供以上基于苝酰亚胺C3对称的螺浆烷衍生物的合成方法,该方法的步骤包括:
化合物1进行溴化反应得到化合物2;
其中,各化合物结构如下所示:
优选地,所述Suzuki偶联反应的条件包括:Pd(PPh3)4作为催化剂,K2CO3作为碱,THF和水作为溶剂。
优选地,当X基团为时,所述Stille偶联反应的条件包括:Pd(PPh3)4和CuI作为催化剂,THF和NEt3作为溶剂。
优选地,当X基团为时,所述关环反应的条件包括:DBU作为碱,甲苯作为溶剂。
本发明第三个方面提供以上式2化合物在有机光电器件中的应用。
本发明的有益效果
本发明首次合成公开了一系列基于苝酰亚胺C3对称的螺浆烷衍生物。本发明在化合物1的基础上,在苝中的两个萘环之间引入环结构,进一步扩大共轭π体系,以获得更优异的电子传输效率。
附图说明
图1为本发明合成路线图。
具体实施方式
下面通过实施例对本发明进行具体描述,有必要在此指出的是本实施例只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限制,该领域的技术熟练人员可以根据以上发明的内容做出一些非本质的改进和调整。在不冲突的情况下,本发明中的实施例及实施例中的特征可以相互组合。
本发明的技术方案的设计思路为:在化合物1的基础上,通过三条合成路线,如图1所示,分别在化合物1的苝中的两个萘环之间引入环结构,进一步扩大共轭π体系,以期获得更优异的电子传输效率。
该系列化合物的分子是由苯环、噻吩、双键构成大共轭体系,其在溶剂中的溶解性很差,为了研究其化学性质,分子中引入的R、R1、R2和R3均为了提高其在有机溶剂中的溶解性,其选择范围非常广,包括:C2-60烷基、含取代基的C2-60烷基、C2-60烷氧基、含取代基的C2-60烷氧基、C2-60硅烷基、芳香基、含取代基的芳香基、烷基芳香基、含取代基的烷基芳香基、烷基杂芳香基、含取代基的烷基杂芳香基、烷基杂环基和含取代基的烷基杂环基。
其中,所述取代基选自:甲基、乙基、丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、羟基、巯基、氟原子、氯原子、溴原子、碘原子、氰基、醛基、脂基、磺基、亚磺基、硝基、氨基、亚氨基、羧基和肼基中的至少一种。
所述烷氧基选自:甲氧基、乙氧基、丙氧基、异丙氧基、正丁氧基、仲丁氧基、异丁氧基、叔丁氧基、戊氧基、己氧基、庚氧基、辛氧基、壬氧基、癸氧基、十一碳烷氧基、十二碳烷氧基、十三碳烷氧基、十四碳烷氧基、十五碳烷氧基、十六碳烷氧基、十七碳烷氧基、十八碳烷氧基、十九碳烷氧基和二十碳烷氧基中的任一种。
所述芳香基选自:苯基、萘基、蒽基、菲基、并四苯基、并五苯基、三苯胺基、芘基、茚基、联苯基和芴基中的至少一种。
所述杂环基、杂芳香基均选自:噻吩、苯并噻吩、吡喃、苯并吡喃、呋喃、苯并呋喃、咪唑、苯并咪唑、吡唑、苯并吡唑、吡咯、苯并吡咯、吡啶、苯并吡啶、吡嗪、苯并吡嗪、吲哚、异吲哚、苯并吲哚、嘧啶、苯并嘧啶、萘啶、苯并萘啶、哒嗪、苯并哒嗪、吲唑、苯并吲唑、嘌呤、苯并嘌呤、喹嗪、苯并喹嗪、喹啉、苯并喹啉、吲嗪、苯并吲嗪、酞嗪、苯并酞嗪、喹喔啉、苯并喹喔啉、噻唑、苯并噻唑、咔啉、苯并咔啉、菲啶、苯并菲啶、菲咯啉、苯并菲咯啉、吖啶、苯并吖啶、吩嗪、苯并吩嗪、吩噻嗪、苯并吩噻嗪、咔唑、苯并咔唑、二并噻吩、二噻吩并吡咯、三并噻吩、四并噻吩和五并噻吩中的任一种。
本发明实施例中列举几种选择对本发明的合成过程具体说明,在此不再一一列出所有可能的基团。本领域的技术人员根据本发明中公开的合成步骤,可根据自己的需求更换R、R1、R2和R3的选择,更换过程只需更换相应的原料中的R、R1、R2和R3即可,所对应的原料均为商业可直接购买或者根据现有文献报道的合成方法直接简单的合成。
实施例1
化合物2a的合成
在两口瓶中加入化合物1a(100mg,69.27mmol)和100mL氯仿溶剂。加热升温回流之后,缓慢加入溴素(0.97g,超过120eq.)。回流6小时,冷却,反应液用饱和亚硫酸钠水溶液萃取,干燥后除去溶剂,剩余残渣在硅胶色谱柱上纯化分离,展开剂为石油醚/三氯甲烷(1:1到3:1,v/v),得到紫红色的化合物2a(60mg,45%)。
其中的溴素作为溴化试剂,而溴化试剂还可以为其它常用的溴化试剂,只是效果有所差异,经试验验证溴素的效果比较好。
2a:1H NMR(400MHz,CDCl3,300K)δ9.57(d,J=8.0Hz,6H),8.80(s, 6H),8.33(d,J=8.0Hz,6H),5.17-5.09(m,3H),2.26-2.16(m,6H),1.86-1.76 (m,6H),1.32-1.20(m,36H),0.81(t,J=6.5Hz,18H);
13C NMR(126MHz,CDCl2CDCl2,373K):δ=163.62,147.52,139.07, 137.23,134.81,132.55,131.81,130.03,128.10,127.84,122.34,120.88,119.51, 56.06,33.26,32.42,30.37,27.35,23.12,14.53;
HRMS(MALDI(N),100%):calcd(%)for C101H87Br6N3O6:1911.1695;found,1911.1714.
其中1a的合成如下:
在250mL三颈烧瓶中通氮气30min后,加入双戊二酰硼(33mmol)、适量的PdC12与dppf、90mmol醋酸钾、1,3,5-溴苯(10mmol)、120mL二甲基亚砜(DMSO),70℃下加热搅拌至原料1,3,5-溴苯消失,结束反应。待反应液冷却至室温,过滤,滤液减压蒸馏除去二甲基亚砜(DMSO)。蒸干物与滤饼一起水洗,用苯萃取,萃取液用无水硫酸镁干燥。减压蒸馏除去溶剂,硅胶柱层析,用石油醚与二氯甲烷混合溶剂洗脱,得无色针状晶体TNP 1-1,产率87%。
在100mL单口瓶中通氮气30min后,加入TNP 1-1(0.84g,2.1mmol), 50mL二氯甲烷,适量的溴素(1.0g,6.5mmol),将溶液在室温下避光搅拌 72小时。用饱和亚硫酸钠水溶液淬灭后,水层用二氯甲烷萃取。合并的有机层用盐水洗涤,然后用无水硫酸钠干燥。过滤后,蒸发滤液,得到三溴-TNP异构体混合物1-2,为褐色粉末,1.3g,定量。
在100mL两口瓶中加入三溴-TNP异构体混合物1-2(1.1g,1.7mmol)、双(频那醇合)二硼(1.6g,6.2mmol)、[1,1’-双(二苯基膦基)二茂铁] 二氯化钯(0.06g,0.1mmol)、乙酸钾(1.5g,0.02mmol)、N,N-二甲基甲酰胺(15mL),搅拌均匀后在90℃下反应过夜,冷却至室温。加入适量二氯甲烷,用水萃取三遍,饱和氯化钠溶液萃取一遍,干燥,硅胶柱提纯,二氯甲烷/石油醚作展开剂,得到三硼酯-TNP异构体混合物1-3,为灰色固体,收率为 61.8%。
将四(三苯基膦)钯(0.03g,0.03mmol)和4-溴-1,8-二萘甲酸酐(0.64 g,2.3mmol)加入到三硼酯-TNP异构体混合物1-3(0.5g,0.6mL)的甲苯溶液中,在氮气保护下回流12h,反应结束后,减压旋蒸除去溶剂,粗产品用甲醇洗涤,干燥,溶解在二氯甲烷中,硅胶柱提纯,二氯甲烷/石油醚作展开剂,得到化合物三萘甲酸酐-TNP异构体混合物1-4,为灰色固体,收率为96%。
在100mL两口瓶中加入三萘甲酸酐-TNP异构体混合物1-4(0.3g,0.3 mmol),三氯化铝(0.6g,4.5mmol),1-氯苯50mL,然后在氮气保护下,回流12h,冷却到室温,加入稀盐酸搅拌2h,减压除去溶剂,粗产品用甲醇洗涤,干燥,粗产物溶解在二氯甲烷中,硅胶柱提纯,二氯甲烷作展开剂,得到基于苝酰亚胺C3对称的螺浆烷的中间体1-5,为黑色固体,收率为60%。
在100mL两口瓶中加入基于苝酰亚胺C3对称的螺浆烷的中间体1-5(0.04 g,0.041mmol),(0.07g,0.041mmoL),N,N-二甲基甲酰胺15mL 然后在氮气保护下,回流12h,待冷却至室温后,加入二氯甲烷、稀盐酸萃取,分液取有机相干燥后,硅胶柱提纯,二氯甲烷作展开剂,得到相应的基于苝酰亚胺C3对称的螺浆烷1a(20mg),为红色晶体,收率为30%。
1a:1H NMR(400MHz,CDCl3,300K)δ=8.51(s,6H),8.41(d,J=7.7Hz, 6H),8.26(d,J=8.1Hz,6H),8.21(d,J=7.7Hz,6H),5.20-5.13(m,3H),2.27- 2.17(m,6H),1.87-1.77(m,6H),1.37-1.17(m,36H),0.83-0.76(m,18H).
13C NMR(101MHz,CDCl3,300K)δ=165.08,164.03,146.27,137.79, 135.74,131.98,131.13,130.34,128.74,127.27,127.23,125.23,122.28,121.31, 120.24,81.23,54.68,32.94,32.57,31.99,27.63,26.88,22.81,14.26,0.21.
HRMS(MALDI(N),100%):calcd(%)for C101H93N3O6:1444.8700;found,1444.7104.
实施例2
化合物3a的合成
将化合物2a(80mg,0.04mmol)、4-叔丁基苯硼酸(9eq.,64.12mg,0.36 mmol)和四(三苯基膦)钯(30%eq.,13.85mg,0.01mmol)加入到一个充满氮气的史莱克瓶中,然后依次加入四氢呋喃(20mL),2M的碳酸钾水溶液(10 mL)。反应液加热到55℃反应12小时,然后用分液漏斗除去水相保留有机相,减压蒸干溶剂,用甲醇洗涤滤渣,干燥。干燥后的粗产品使用硅胶柱进一步提纯得到紫色产物3a(53mg,59%),整个后处理过程需要避光。
3a:1H NMR(500MHz,CDCl2CDCl2,373K)δ=8.41(s,6H),7.80(d,J= 8.1Hz,6H),7.56(d,J=8.1Hz,12H),7.40(dd,J=7.8,5.4Hz,18H),5.18-5.14 (m,3H),2.28-2.21(m,6H),1.93-1.88(m,6H),1.53(s,54H),1.38-1.30(m, 36H),0.93-0.87(m,18H);
13C NMR(125MHz,CDCl2CDCl2,373K):δ=165.15,152.14,146.54, 141.94,139.61,137.67,136.31,134.86,132.48,131.27,131.18,130.37,130.33, 129.33,128.98,127.51,124.11,121.47,120.36,55.47,35.45,33.35,32.47,32.26, 27.39,23.15,14.55;
HRMS(MALDI(N),100%):calcd(%)for C161H165N3O6:2236.2698;found,2236.2717.
实施例3
化合物4a的合成
在标准的光化学反应管中,加入化合物3a(2×40mg,35.77mmol), 甲苯(2×40mL)和碘单质(5mg)。反应液在95℃,蓝光灯(460-465nm) 下照射12小时。然后,反应液用饱和亚硫酸钠水溶液萃取,然后用分液漏斗除去水相保留有机相,减压蒸干溶剂,用甲醇洗涤滤渣,干燥。干燥后的粗产品使用硅胶柱进一步提纯(PE:DCM=2:1,v:v),得到黄色的化合物4a(60mg, 75%)。
4a:1H NMR(400MHz,CDCl3,300K)δ=10.90(s,6H),10.54(d,J=15.1 Hz,6H),9.96(s,6H),9.53(d,J=8.8Hz,6H),8.32(d,J=8.7Hz,6H),5.49- 5.42(m,3H),2.47-2.37(m,6H),2.14-1.87(m,60H),1.34-1.18(m,36H),0.83 -0.74(m,18H);
13C NMR(125MHz,CDCl2CDCl2,373K):δ=166.38,152.24,147.07, 134.79,133.12,130.52,129.05,127.49,127.08,126.63,125.87,125.68,125.63, 124.69,124.26,122.58,122.09,120.21,116.32,56.02,36.52,33.64,33.09,32.54, 30.37,27.56,23.16,14.53;
HRMS(MALDI(N),100%):calcd(%)for C161H153N3O6:2224.1759;found,2224.1761.
实施例4
化合物5a的合成
将化合物2a(80mg,0.04mmol),三甲基[5-[三(1-甲基乙基)甲硅烷基] -2-噻吩基]-锡烷(9eq.,147mg,0.37mmol),碘化亚铜(30%eq.,2.32mg, 0.01mmol)和四(三苯基膦)钯(30%eq.,11.59mg,0.01mmol)加入到一个充满氮气的史莱克瓶中,然后加入干燥的甲苯(20mL)。反应液加热到110℃反应12小时,反应结束后减压蒸干溶剂,用甲醇洗涤滤渣,干燥。粗产品使用硅胶柱进一步提纯得到紫色产物5a(42mg,37%),整个后处理过程需要避光 (PE/DCM=4:1,v/v)。
5a:1H NMR(500MHz,CDCl2CDCl2,373K)δ=8.58(s,6H),7.85(d,J= 8.2Hz,6H),7.53-7.42(m,12H),7.35(d,J=3.3Hz,6H),5.21-5.15(m,3H), 2.29-2.21(m,6H),1.97-1.90(m,6H),1.50-1.46(m,18H),1.39-1.34(m, 36H),1.33-1.28(m,108H),0.93-0.89(m,18H);
13C NMR(126MHz,CDCl2CDCl2,373K)δ=164.93,151.17,146.88,137.86, 137.74,137.38,136.67,136.41,132.66,132.05,131.10,130.17,129.94,128.66, 128.55,121.43,120.35,55.67,33.38,32.49,30.37,27.43,23.14,19.74,19.57, 14.55,13.24,12.97,12.87,12.77;
HRMS(MALDI(N),100%):calcd(%)for C179H225N3O6S6Si6:2872.4333; found,2872.4326.
实施例5
化合物6a的合成
在标准的光化学反应管中,加入化合物5a(2×40mg,35.77mmol), 甲苯(2×40mL)和碘单质(5mg)。反应液在95℃,蓝光灯(460-465nm) 下照射6小时。然后,反应液用饱和亚硫酸钠水溶液萃取,有机相浓缩后在二氯甲烷和甲醇的混合溶剂中热重结晶两次,得到纯为黄色固体的化合物6a (60mg,75%).
6a:1H NMR(400MHz,CDCl3,300K)δ=10.43(s,6H),10.16(d,J=8.8 Hz,6H),9.15(s,6H),5.52-5.42(m,3H),2.48-2.44(m,6H),1.99-1.92(m,6H), 1.86-1.80(m,18H),1.49-1.46(m,108H),1.29-1.23(m,36H),0.79-0.76(m, 18H);
13C NMR(125MHz,CDCl2CDCl2,373K):δ=166.20,146.87,144.20, 140.34,138.30,133.32,131.18,130.87,127.28,124.92,124.72,124.60,123.87, 123.68,122.34,121.20,117.07,56.16,33.64,32.53,30.37,27.54,23.16,19.87, 19.24,14.53,13.30;
HRMS(MALDI(N),100%):calcd(%)for C179H213N3O6S6Si6:2860.3394;found,2860.3408.
实施例6
化合物7a的合成
将化合物2a(80mg,0.042mmol)、辛基-乙炔(15eq.,69.2mg,0.62mmol)、碘化亚铜(30%eq.,2.32mg,0.01mmol)和四(三苯基膦)钯(30%eq.,11.59mg, 0.01mmol)加入到一个充满氮气的史莱克瓶中,然后加入四氢呋喃(15mL)和三乙胺(15mL)。反应液加热到80℃反应12小时,反应结束降至室温后,将反应液倒入稀盐酸溶液中搅拌,再用二氯甲烷萃取,然后将有机相干燥后减压蒸干溶剂。粗产品使用硅胶柱进一步提纯(PE/DCM=3:1,v/v),得到紫色产物7a(50mg,57%)。
7a:1H NMR(500MHz,CDCl2CDCl2,373K)δ=10.35(d,J=8.0Hz,6H), 8.71(s,6H),8.36(d,J=8.1Hz,6H),5.19-5.14(m,3H),2.81-2.75(m,12H), 2.28-2.22(m,6H),1.95-1.90(m,18H),1.75-1.70(m,12H),1.60-1.53(m, 24H),1.37-1.33(m,36H),1.11–1.05(m,18H),0.92-0.87(m,18H);
13C NMR(125MHz,CDCl2CDCl2,373K):δ=164.56,147.71,139.21, 137.60,136.19,130.23,129.89,129.57,129.38,129.30,128.55,121.51,121.03, 119.36,100.78,100.57,84.15,57.76,55.63,33.31,32.46,32.23,30.37,29.67, 29.34,27.36,23.32,23.14,21.11,14.71,14.54;
HRMS(MALDI(N),100%):calcd(%)for C149H165N3O6:2092.2698;found,2092.2714.
实施例7
化合物8a的合成
将化合物7a(80mg,0.026mmol)加入到一个充满氮气的史莱克瓶中,然后加入干燥的甲苯(15mL)和1,8-二氮杂二环十一碳-7-烯(0.2mL)。反应液加热到110℃反应3天,反应结束后减压蒸干溶剂,用甲醇洗涤滤渣,干燥。粗产品使用硅胶柱进一步提纯(PE:DCM=3:1,v/v),得到浅黄色产物8a(20mg, 25%)。
8a:1H NMR(500MHz,CDCl2CDCl2,373K)δ=10.47(s,6H),9.90(s, 6H),9.04(s,6H),5.50-5.44(m,3H),4.28(t,J=7.6Hz,12H),2.50-2.43(m, 12H),2.50-2.43(m,6H),2.14-2.07(m,6H),1.99-2.06(m,12H),1.78-1.85 (m,12H),1.67-1.61(m,12H),1.42-1.31(m,36H),1.11(t,J=7.3Hz,18H), 0.88(t,J=7.2Hz,18H);
13C NMR(125MHz,CDCl2CDCl2,373K):δ=166.57,146.73,140.51, 133.49,133.44,130.32,128.90,128.49,124.00,123.92,122.96,122.77,122.13, 121.95,117.11,87.70,55.93,35.44,33.66,32.80,32.55,32.34,30.62,30.47, 30.38,29.99,27.55,23.53,23.31,23.17,14.73,14.64,14.53;
HRMS(MALDI(N),100%):calcd(%)for C149H165N3O6:2092.2698;found,2092.2693.
实施例8
化合物2b的合成
在两口瓶中加入化合物1b(100mg,50.24mmol)和100mL氯仿溶剂。加热升温回流之后,缓慢加入溴素(1.33g,超过120eq.)。回流6小时,冷却,反应液用饱和亚硫酸钠水溶液萃取,干燥后除去溶剂,剩余残渣在硅胶色谱柱上纯化分离,展开剂为石油醚/三氯甲烷(1:1到3:1,v/v),得到紫红色的化合物2b(80mg,60%)。
2b:1H NMR(400MHz,CDCl3,300K)δ=9.56(d,J=8.0Hz,6H),8.77(s, 6H),8.33(d,J=8.0Hz,6H),4.07(d,J=7.2Hz,6H),2.00-1.90(m,3H),1.32- 1.20(m,120H),0.83-0.80(m,18H);
13C NMR(101MHz,CDCl3,300K)δ=162.83,146.72,138.46,136.41, 134.27,131.75,131.24,129.09,127.20,126.89,121.01,120.27,118.85,81.32, 45.03,36.83,32.13,32.11,31.92,30.25,29.90,29.86,29.56,27.15,26.72,22.88, 14.31;
HRMS(MALDI(N),100%):calcd(%)for C140H165Br6N3O6:2457.7799; found,2457.7828.
其中1b的合成参见1a的合成,不同之处在于最后一步:
在100mL两口瓶中加入基于苝酰亚胺C3对称的螺浆烷的中间体1-5(0.04 g,0.041mmol),(0.09g,0.041mmoL),N,N-二甲基甲酰胺15mL 然后在氮气保护下,回流12h,待冷却至室温后,加入二氯甲烷、稀盐酸萃取,分液取有机相干燥后,硅胶柱提纯,二氯甲烷作展开剂,得到相应的基于苝酰亚胺C3对称的螺浆烷1b(25mg),为红色晶体,收率为30%。
1b:1H NMR(400MHz,CDCl3,300K)δ8.54(d,J=8.1Hz,6H),8.45(d,J =7.7Hz,6H),8.29(d,J=8.1Hz,6H),8.23(d,J=7.7Hz,6H),4.10(d,J=7.1 Hz,6H),2.01-1.95(m,3H),1.35-1.17(m,120H),0.83-0.78(m,J=6.8Hz, 18H);
13C NMR(101MHz,CDCl3,300K)δ=164.25,146.46,137.86,136.12, 131.65,130.29,128.79,127.39,127.32,125.46,121.59,121.37,120.30,81.31, 77.55,77.23,76.92,44.80,36.85,32.11,32.09,31.98,30.29,29.88,29.84,29.55, 29.53,27.15,26.77,22.86,14.28;
HRMS(MALDI(N),100%):calcd(%)for C140H171N3O6:1991.9230;found,1991.3199.
实施例9
化合物3b的合成
将化合物2b(100mg,0.04mmol)、4-叔丁基苯硼酸(9eq.,65.23mg,0.37 mmol)和四(三苯基膦)钯(30%eq.,13.85mg,0.01mmol)加入到一个充满氮气的史莱克瓶中,然后依次加入四氢呋喃(20mL),2M的碳酸钾水溶液(10 mL)。反应液加热到55℃反应12小时,然后用分液漏斗除去水相保留有机相,减压蒸干溶剂,用甲醇洗涤滤渣,干燥。干燥后的粗产品使用硅胶柱进一步提纯得到紫色产物3a(85mg,76%),整个操作过程需要避光。
3b:1H NMR(500MHz,CDCl2CDCl2,373K)δ=8.44(s,6H),7.80(d,J= 8.0Hz,6H),7.56(d,J=7.9Hz,12H),7.40(t,J=8.9Hz,18H),4.15(d,J=5.8 Hz,6H),2.11-2.06(m,3H),1.53(s,54H),1.36-1.28(m,120H),0.90-0.88(m, 18H);
13C NMR(125MHz,CDCl2CDCl2,373K):δ=164.90,152.17,146.58, 141.90,139.64,137.64,136.32,135.08,132.72,132.57,131.38,130.29,129.28, 128.96,127.53,121.16,120.35,45.67,37.65,35.46,33.01,32.56,32.26,30.76, 30.38,30.38,30.32,30.28,29.93,27.45,23.25,14.58;
HRMS(MALDI(N),100%):calcd(%)for C200H243N3O6:2782.8802;found,2782.8826.
实施例10
化合物4b的合成
在标准的光化学反应管中,加入化合物3a(2×50mg,35.91mmol), 甲苯(2×40mL)和碘单质(5mg)。反应液在95℃,蓝光灯(460-465nm) 下照射12小时。然后,反应液用饱和亚硫酸钠水溶液萃取,然后用分液漏斗除去水相保留有机相,减压蒸干溶剂,用甲醇洗涤滤渣,干燥。干燥后的粗产品使用硅胶柱进一步提纯(PE:DCM=2:1,v:v),得到黄色的化合物4b(90mg, 90%)。
4b:1H NMR(500MHz,CDCl2CDCl2,373K)δ=8.44(s,6H),7.80(d,J= 8.0Hz,6H),7.56(d,J=7.9Hz,12H),7.40(t,J=8.9Hz,18H),4.15(d,J=5.8 Hz,6H),2.11-2.06(m,3H),1.53(s,54H),1.36-1.28(m,120H),0.90-0.88(m, 18H);
13C NMR(125MHz,CDCl2CDCl2,373K):δ=164.90,152.17,146.58, 141.90,139.64,137.64,136.32,135.08,132.72,132.57,131.38,130.29,129.28, 128.96,127.53,121.16,120.35,45.67,37.65,35.46,33.01,32.56,32.26,30.76, 30.38,30.38,30.32,30.28,29.93,27.45,23.25,14.58;
HRMS(MALDI(N),100%):calcd(%)for C200H243N3O6:2770.7863;found,2770.7833.
实施例11
化合物5b的合成
将化合物2b(100mg,0.04mmol),三甲基[5-[三(1-甲基乙基)甲硅烷基] -2-噻吩基]-锡烷(9eq.,147mg,0.37mmol),碘化亚铜(30%eq.,2.32mg, 0.01mmol)和四(三苯基膦)钯(30%eq.,11.59mg,0.01mmol)加入到一个充满氮气的史莱克瓶中,然后加入干燥的甲苯(20mL)。反应液加热到110℃反应12小时,反应结束后减压蒸干溶剂,用甲醇洗涤滤渣,干燥。粗产品使用硅胶柱进一步提纯得到紫色产物5b(76mg,56%),整个后处理过程需要避光 (PE/DCM=4:1,v/v)。
5b:1H NMR(400MHz,CDCl3,300K)δ=8.57(s,6H),7.69(d,J=8.0Hz, 6H),7.43–7.35(m,12H),7.31(d,J=3.3Hz,6H),4.10(d,J=7.2Hz,6H),1.99 -1.93(m,3H),1.37–1.34(m,18H),1.22-1.13(m,228H),0.82-0.77(m,18H);
13C NMR(126MHz,CDCl2CDCl2,373K)δ=164.70,151.08,146.92, 137.96,137.86,137.34,136.64,136.60,132.77,132.07,131.20,130.12,129.86, 128.72,128.63,121.09,120.33,45.80,37.68,32.98,32.55,30.77,30.38,30.30, 29.93,27.44,23.25,19.74,19.56,19.49,14.57,12.86,12.74;
HRMS(MALDI(N),100%):calcd(%)for C218H303N3O6S6Si6:3419.0437; found,3419.0373.
实施例12
化合物6b的合成
在标准的光化学反应管中,加入化合物5b(2×50mg,35.91mmol), 甲苯(2×40mL)和碘单质(5mg)。反应液在95℃,蓝光灯(460-465nm) 下照射6小时。然后,反应液用饱和亚硫酸钠水溶液萃取,有机相浓缩后在二氯甲烷和甲醇的混合溶剂中热重结晶两次,得到纯为黄色固体的化合物6b (90mg,90%).
6b:1H NMR(400MHz,CDCl3,300K)δ=10.41(s,6H),10.18(s,6H), 9.14(s,6H),4.37(d,J=6.8Hz,6H),2.18-2.12(m,3H),1.85-1.78(m,18H), 1.48-1.45(m,108H),1.20-1.04(m,120H),0.74-0.70(m,18H);
13C NMR(125MHz,CDCl2CDCl2,373K):δ=165.90,146.87,144.22, 140.42,138.33,131.16,130.91,127.30,124.90,124.58,123.80,122.04,121.19, 117.08,100.78,46.31,37.88,33.17,32.45,30.77,30.37,30.25,30.21,30.17, 29.81,27.58,23.15,19.85,14.49,13.29;
HRMS(MALDI(N),100%):calcd(%)for C218H291N3O6S6Si6:3406.9498; found,3406.9450.
实施例13
化合物7b的合成
将化合物2b(100mg,0.040mmol)、辛基-乙炔(15eq.,69.2mg,0.62mmol)、碘化亚铜(30%eq.,2.32mg,0.01mmol)和四(三苯基膦)钯(30%eq.,11.59mg, 0.01mmol)加入到一个充满氮气的史莱克瓶中,然后加入四氢呋喃(15mL)和三乙胺(15mL)。反应液加热到80℃反应12小时,反应结束降至室温后,将反应液倒入稀盐酸溶液中搅拌,再用二氯甲烷萃取,然后将有机相干燥后减压蒸干溶剂。粗产品使用硅胶柱进一步提纯(PE/DCM=3:1,v/v),得到紫色产物7b(80mg,76%)。
7b:1H NMR(500MHz,CDCl2CDCl2,373K)δ=10.36(d,J=8.0Hz,6H), 8.74(s,6H),8.36(d,J=8.1Hz,6H),4.15(d,J=7.0Hz,6H),2.78(t,J=7.0Hz, 12H),2.12-2.07(m,3H),1.95-1.89(m,12H),1.76-1.71(m,12H),1.59-1.54 (m,24H),1.35-1.28(m,120H),1.08(t,J=6.9Hz,18H),0.92-0.89(m,18H);
13C NMR(125MHz,CDCl2CDCl2,373K):δ=164.31,147.76,139.21,137.59,136.37,130.31,130.00,129.35,129.26,128.43,121.20,121.02,119.38,100.56, 84.13,45.75,37.94,37.61,32.99,32.56,32.23,30.75,30.37,30.28,29.93,29.66, 29.33,27.44,23.31,23.25,21.11,14.70,14.57;
HRMS(MALDI(N),100%):calcd(%)for C188H243N3O6:2638.8802;found,2638.8752.
实施例14
化合物8b的合成
将化合物7b(100mg,0.040mmol)加入到一个充满氮气的史莱克瓶中,然后加入干燥的甲苯(15mL)和1,8-二氮杂二环十一碳-7-烯(0.2mL)。反应液加热到110℃反应3天,反应结束后减压蒸干溶剂,用甲醇洗涤滤渣,干燥。粗产品使用硅胶柱进一步提纯(PE:DCM=3:1,v/v),得到浅黄色产物8b(50mg, 50%)。
8b:1H NMR(500MHz,CDCl2CDCl2,373K)δ=10.44(s,6H),9.84(s, 6H),8.96(s,6H),4.46-4.42(m,6H),4.28-4.20(m,12H),2.65-2.55(m,12H), 2.28-2.24(m,3H),2.04-1.96(m,12H),1.83-1.75(m,12H),1.65-1.57(m, 12H),1.37-1.17(m,120H),1.12-1.06(m,18H),0.84-0.77(m,18H).
13C NMR(125MHz,CDCl2CDCl2,373K):δ=166.13,146.51,140.42, 140.32,133.29,133.29,130.10,128.75,128.57,128.19,123.64,123.57,122.62, 122.47,121.70,121.58,117.23,46.07,37.88,35.30,33.08,32.74,32.46,32.17, 30.77,30.52,30.38,30.24,30.19,29.82,27.49,23.49,23.15,14.70,14.47.
HRMS(MALDI(N),100%):calcd(%)for C188H243N3O6:2638.8802;found,2638.8827.
显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定,对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动,这里无法对所有的实施方式予以穷举,凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。
Claims (8)
2.根据权利要求1所述的基于苝酰亚胺C3对称的螺浆烷衍生物,其特征在于,所述R为所述R4、R5选自C3-12烷基,R4、R5相同或不同。
5.根据权利要求4所述的方法,其特征在于,所述Suzuki偶联反应的条件包括:Pd(PPh3)4作为催化剂,K2CO3作为碱,THF和水作为溶剂。
8.权利要求1-3任一项所述基于苝酰亚胺C3对称的螺浆烷衍生物在有机光电器件中的应用。
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