CN108558677A - 一种高度回旋交叉共轭有机化合物及其合成方法 - Google Patents
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 10
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 claims abstract description 7
- BRUOAURMAFDGLP-UHFFFAOYSA-N 9,10-dibromoanthracene Chemical class C1=CC=C2C(Br)=C(C=CC=C3)C3=C(Br)C2=C1 BRUOAURMAFDGLP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- OOMZKLJLVGQZGV-UHFFFAOYSA-N (2,5-dimethylphenyl)boronic acid Chemical class CC1=CC=C(C)C(B(O)O)=C1 OOMZKLJLVGQZGV-UHFFFAOYSA-N 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 28
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 claims description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 20
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- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
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- VZGDMQKNWNREIO-UHFFFAOYSA-N carbon tetrachloride Substances ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 5
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- 238000000034 method Methods 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical class [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 4
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 2
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- VWSUVZVPDQDVRT-UHFFFAOYSA-N phenylperoxybenzene Chemical compound C=1C=CC=CC=1OOC1=CC=CC=C1 VWSUVZVPDQDVRT-UHFFFAOYSA-N 0.000 claims 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 2
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
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- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
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- 239000007850 fluorescent dye Substances 0.000 description 2
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- RSSDWSPWORHGIE-UHFFFAOYSA-N $l^{1}-phosphanylbenzene Chemical compound [P]C1=CC=CC=C1 RSSDWSPWORHGIE-UHFFFAOYSA-N 0.000 description 1
- ZYYANAWVBDFAHY-UHFFFAOYSA-N (2,3-dimethylphenyl)boronic acid Chemical compound CC1=CC=CC(B(O)O)=C1C ZYYANAWVBDFAHY-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical class BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 1
- ODJZWVFLHZHURI-UHFFFAOYSA-M [Br-].C(CCC)[P+](CCCC)(CCCC)CCCC.[NH4+].[Br-] Chemical compound [Br-].C(CCC)[P+](CCCC)(CCCC)CCCC.[NH4+].[Br-] ODJZWVFLHZHURI-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了具有高度回旋交叉共轭有机化合物,涉及共轭有机分子合成领域。本发明的有机化合物结构式为
Description
技术领域
本发明属于共轭有机分子合成领域,具体涉及了一种具有高度回旋交叉共轭有机化合物及其合成方法。
背景技术
自21世纪以来,聚集诱导发光现象(aggregation-induced emission,AIE)的发现,即在在溶液态几乎不发光或弱荧光,而在纳米聚集态和固态下荧光效率显著增强的现象,让科研工作者们对共轭骨架扭曲分子有了新的认识和思考。与传统的线型平面结构共轭有机分子相比,使得它们在新型荧光传感、压致荧光变色等材料开发方面具有独特的优点,因此作为一类新型的共轭有机荧光材料,从而成为新一代共轭骨架分子的主流。
而绝大多数的共轭有机荧光材料的高荧光性主要表现在结晶态而不是无定形态,从而限制了其作为共轭荧光材料的发展。目前,大部分共轭有机荧光材料主要局限于具有平面结构。而合成具有高度扭曲的共轭骨架有机分子是目前应急需解决的问题。
目前已报道的高度回旋交叉扭曲骨架共轭有机荧光材料非常有限。主要是由于回旋交叉扭曲的限制使分子在构筑与设计过程中面临许多限制,更是在合成过程中面临许多未知的困难。因此,能够构筑设计出一种具有高度扭曲的有机荧光分子,以弥补现阶段有机荧光分子玻璃化转变温度过低,分子设计困难等方面提供了一个解决之道。
发明内容
本发明的目的在于克服现有的共轭有机荧光材料玻璃化转变温度低,荧光效率低等缺点,提供了一种新型的回旋交叉有机共轭分子及其制备方法,本发明合成的回旋交叉共轭有机化合物具有优异的热稳定性和良好的荧光特性,可用于制备新型有机电致发光器件(OLEDs)及有机荧光染料。
为达到上述目的,本发明提供的新型技术方案为:
本发明提供一种新型回旋交叉共轭化合物,该化合物的结构式为:
更进一步的,该化合物的NMR、MS参数如下:
1H NMR(500MHz,CDCl3,ppm)δ=8.04(d,J=8.3Hz,1H),7.72(d,J=14.6,7.7,2.6Hz,3H),7.54(d,J=2.0Hz,1H),7.43(d,J=8.6Hz,2H),7.39–7.30(m,4H),7.17–7.08(m,3H),7.03(d,J=8.5Hz,2H),6.95(d,J=8.1Hz,2H),6.59(d,J=16.2Hz,1H),1.32(s,9H),1.13(s,9H);
13C NMR(126MHz,CDCl3)δ=147.51,147.41,147.27,146.94,137.87,136.84,136.49,135.52,131.44,131.34,130.15,129.26,129.11,128.39,127.34,127.10,126.42,126.12,125.52,125.44,124.56,124.44,123.43,123.05,122.84,77.25,77.00,76.74;
MS(EI)(m/z):calcd for C106H78N4,1407.63;found 1407.36([M+H]+)。
本发明还提供上述新型回旋交叉系列共轭化合物的合成方法,其步骤为:
(1)将14.8g K2CO3、43mL水加入1000ml的单口圆底烧瓶中,再依次加入四丁基溴化铵TBAB(少量)、反应物6g 9,10-二溴蒽、反应物6.7g 2,5-二甲基苯硼酸,后加入130mL甲苯/水混合溶液,加入0.6g四(三苯基磷)钯(Pd(PPh3)4),无氧惰性气体保护下,110℃下反应72h。
反应结束后,真空旋蒸,水和二氯甲烷进行萃取。石油醚为淋洗剂进行柱层析得到白色固体6.2g,得到结构式为的化合物1。
(2)将步骤(1)获得的5g化合物1、10.36g N-溴代丁二酰亚胺NBS、0.156g过氧化二苯甲酰依次加入到1000mL单口圆底烧瓶中,再加入400mL CCl4溶液,100℃下避光回流搅拌反应10h。
反应结束后冷却至室温,过滤并用CCl4溶液冲洗白色固体,粗产物用丙酮/三氯甲烷重结晶得淡黄色固体7.5g,得到结构式为的化合物2。
(3)将步骤(2)获得的10g化合物2、14.2mL亚磷酸三乙酯P(OEt)3加入到250mL单口圆底烧瓶中150℃下回流搅拌反应8h。
反应结束后冷却至室温。通过减压蒸馏将反应体系中多余的亚磷酸三乙酯除掉,采用柱色谱乙酸乙酯:二氯甲烷作为淋洗剂,旋干后获得黄色固体2.1g,得到结构式为的化合物3。
(4)将步骤(3)获得的5g化合物3、8.7g4-二苯胺基苯甲醛、9.6g叔丁醇钾加入到100mL单口圆底烧瓶中,无氧惰性气体保护下,常温搅拌反应6h。
反应结束后,真空旋蒸,再用甲醇冲洗过滤得到黄色固体,进一步用石油醚:二氯甲烷作为淋洗剂进行层析柱色谱提纯,得到黄色固体3.2g,最终得到结构式为的新型回旋交叉共轭有机化合物。
更进一步的通过该方法合成的新型回旋交叉共轭有机化合物NMR、MS参数如下:
1H NMR(500MHz,CDCl3,ppm)δ=8.04(d,J=8.3Hz,1H),7.72(d,J=14.6,7.7,2.6Hz,3H),7.54(d,J=2.0Hz,1H),7.43(d,J=8.6Hz,2H),7.39–7.30(m,4H),7.17–7.08(m,3H),7.03(d,J=8.5Hz,2H),6.95(d,J=8.1Hz,2H),6.59(d,J=16.2Hz,1H),1.32(s,9H),1.13(s,9H);
13C NMR(126MHz,CDCl3)δ=147.51,147.41,147.27,146.94,137.87,136.84,136.49,135.52,131.44,131.34,130.15,129.26,129.11,128.39,127.34,127.10,126.42,126.12,125.52,125.44,124.56,124.44,123.43,123.05,122.84,77.25,77.00,76.74;
MS(EI)(m/z):calcd for C106H78N4,1407.63;found 1407.36([M+H]+)。
更进一步的步骤(1)加入甲苯与水的体积比为3:1。
更进一步的步骤(2)中采用硅胶色谱层析柱分离时,淋洗剂为丙酮与三氯甲烷按照2:1的体积比组成的混合物。
更进一步的步骤(3)中采用硅胶色谱层析柱分离时,淋洗剂为乙酸乙酯和二氯甲烷按照5:4的体积比组成的混合物。
更进一步的步骤(4)中采用硅胶色谱层析柱分离时,淋洗剂为石油醚和二氯甲烷按照5:1的体积比组成的混合物。
有益效果
通过采用本发明提供的技术方案,具有以下显著的效果。
(1)通过本发明合成的回旋交叉共轭荧光有机化合物,能够克服现有的AIE分子常常存在的化合物分子的缺点,具有优异的热稳定性、较高的玻璃化转变温度、良好的荧光特性,可用于有机电致发光(OLEDs)和有机染料的制备当中,具有非常潜在的应用价值。
(2)本发明采用的合成方法,合成工艺简单,原料易得,合成的收率较高,成本较低,适用于大型产业化合成。
附图说明
图1为本发明合成的新型回旋交叉共轭化合物的合成路线图;
图2为本发明合成的新型回旋交叉共轭化合物的固态荧光发射/紫外吸收光谱图;
图3为本发明合成的新型回旋交叉共轭化合物的在四氢呋喃中的荧光发射/紫外吸收光谱图;
图4为本发明合成的新型回旋交叉共轭化合物的溶剂化效应(在不同溶剂中的荧光发射)光谱图。
具体实施方式
为进一步了解本发明的内容,结合附图和实施例进一步详细阐释本发明的技术方案。
实施例1
本实施例的一种新型回旋交叉共轭化合物,该化合物的结构式为:
该有机化合物的NMR、MS参数如下:
1H NMR(500MHz,CDCl3,ppm)δ=8.04(d,J=8.3Hz,1H),7.72(d,J=14.6,7.7,2.6Hz,3H),7.54(d,J=2.0Hz,1H),7.43(d,J=8.6Hz,2H),7.39–7.30(m,4H),7.17–7.08(m,3H),7.03(d,J=8.5Hz,2H),6.95(d,J=8.1Hz,2H),6.59(d,J=16.2Hz,1H),1.32(s,9H),1.13(s,9H);
13C NMR(126MHz,CDCl3)δ=147.51,147.41,147.27,146.94,137.87,136.84,136.49,135.52,131.44,131.34,130.15,129.26,129.11,128.39,127.34,127.10,126.42,126.12,125.52,125.44,124.56,124.44,123.43,123.05,122.84,77.25,77.00,76.74;
MS(EI)(m/z):calcd for C106H78N4,1407.63;found 1407.36([M+H]+)。
本实施例的一种新型的回旋交叉有机共轭分子,能够克服现有的共轭有机荧光材料玻璃化转变温度低,荧光效率低等缺点,具有优异的热稳定性和良好的荧光特性,可用于制备新型有机电致发光器件(OLEDs)及有机荧光染料,具有相当高的推广价值。
本实施例的一种新型的回旋交叉有机共轭分子的合成方法(合成方法如图1所示),其步骤为:
(1)将K2CO3(14.8g,107mmol)、43mL水加入带有磁力搅拌子的1000ml的单口圆底烧瓶中,再依次加入少量四丁基溴化铵TBAB、反应物9,10-二溴蒽(6g,17.9mmol)、反应物2,5-二甲基苯硼酸(6.7g,44.7mmol)。再加入130mL甲苯溶液(V甲苯:V水=3:1),加入催化剂四(三苯基磷)钯(Pd(PPh3)4)(0.6g,0.52mmol),无氧惰性气体保护下,110℃下反应72h。反应液为淡黄色澄清溶液,反应结束后冷却至室温,有机相用二氯甲烷和水萃取,无水硫酸镁MgSO4干燥,过滤、旋干后得到灰色粗产物。粗产物采用柱色谱进行分离提纯,淋洗液为石油醚。旋干后得到6.2g结构式为的化合物1,化合物1的产率为89%。
(2)将步骤(1)中获得的化合物(15g,12.9mmol)、反应物N-溴代丁二酰亚胺(NBS)(10.36g,58.2mmol)、催化剂过氧化二苯甲酰(0.156g,0.6mmol)依次加入到1000mL单口圆底烧瓶中,加入400mLCCl4溶液,100℃下避光回流搅拌反应10h。反应液呈淡黄色透明溶液,反应结束后冷却至室温,过滤并用CCl4溶液冲洗白色固体粗产物,后用丙酮/三氯重结晶=2/1得7.5g淡黄色结构式为的化合物2,化合物的产率为83%。
(3)将步骤(2)中获得的化合物2(10g,14.2mmol),亚磷酸三乙酯P(OEt)3(14.2mmol,85.5mmol),150℃下回流搅拌反应8h,反应结束后冷却至室温。减压蒸馏除去多余的亚磷酸三乙酯采用柱色谱进行分离,淋洗剂为乙酸乙酯:二氯甲烷=5:4,干燥后得到2.1g结构式为的黄色固体固体化合物3,化合物的产率为16%。化合物3的NMR参数如下:
1H NMR(500MHz,CDCl3,ppm)δ=7.85(d,J=9.9Hz,1H),7.62–7.46(m,3H),7.32(t,J=4.6Hz,2H),4.05(q,J=7.1Hz,4H),3.89–3.57(m,4H),3.21(d,J=21.5Hz,2H),2.80(d,J=21.8Hz,2H),1.22(d,J=7.1Hz,6H),1.12–0.84(m,6H).
(4)将步骤(3)中获得的化合物3(5g,5.4mmol)、4-二苯胺基苯甲醛(8.7g,53.6mmol)加入100mL单口圆底烧瓶中,再加入叔丁醇钾(t-BuOK)(9.6g,85.6mmol),抽入适量四氢呋喃(THF)溶液作反应溶剂,无氧惰性气体保护下,常温搅拌反应6h。反应结束后用加入甲醇终止反应,用甲醇冲洗过滤得到黄色固体,用石油醚:二氯甲烷=5:1的淋洗剂进行硅胶色谱层析柱提纯得到2.4g结构式为的新型回旋交叉共轭有机化合物,该化合物的产率为32%。
通过该方法制备的新型回旋交叉共轭有机化合物的NMR、MS参数如下:
1H NMR(500MHz,CDCl3,ppm)δ=8.04(d,J=8.3Hz,1H),7.72(d,J=14.6,7.7,2.6Hz,3H),7.54(d,J=2.0Hz,1H),7.43(d,J=8.6Hz,2H),7.39–7.30(m,4H),7.17–7.08(m,3H),7.03(d,J=8.5Hz,2H),6.95(d,J=8.1Hz,2H),6.59(d,J=16.2Hz,1H),1.32(s,9H),1.13(s,9H);
13C NMR(126MHz,CDCl3)δ=147.51,147.41,147.27,146.94,137.87,136.84,136.49,135.52,131.44,131.34,130.15,129.26,129.11,128.39,127.34,127.10,126.42,126.12,125.52,125.44,124.56,124.44,123.43,123.05,122.84,77.25,77.00,76.74;
MS(EI)(m/z):calcd for C106H78N4,1407.63;found 1407.36([M+H]+)。
在F-4600荧光分光光度计上测定制备的新型回旋交叉共轭有机化合物的荧光发射光谱,发射光谱的测量范围为300-800nm,狭缝宽度为5nm或10nm,电压为500V或750V,使用四面透光的比色皿宽度尺寸为1cm,溶液浓度均为1×10-5mol/L,该新型回旋交叉共轭有机化合物在不同的溶剂中的液态量子效率数据如表一所示。从表一中我们可以看出,在不同的溶剂中其液态荧光量子效率不尽相同。
表一为新型回旋交叉共轭有机化合物在不同溶剂中的荧光量子效率。
其中,n-Hexane表示正己烷,Toluene表示甲苯,Triethylamine表示三乙胺,n-Butyl Ether表示正丁醚,Isopropyl Ether表示异丙醚,Chloroform表示三氯甲烷,Diethyl Ether表示乙醚,EA表示乙酸乙酯,THF表示四氢呋喃,DCM表示二氯甲烷,DMF表示N,N-二甲基甲酰胺,Acetone表示丙酮,MeCN表示乙腈。
本实施例中新型回旋交叉共轭有机化合物的归一化的固态荧光发射/紫外吸收光谱图如图2所示;图3为本实施例中合成的新型回旋交叉共轭化合物的在四氢呋喃中的归一化的荧光发射/紫外吸收光谱图;将合成的新型回旋交叉共轭化合物加入到不同极性的有机溶剂中,配成浓度为随着有机溶剂1×10-5mol/L的稀溶液。从图4中我们可以发现,当有机溶剂极性较小时,其荧光发射波长较短,但是随着有机溶剂极性的不断增大,其荧光发射波长逐渐增大,由450nm逐渐红移至510nm,其红移高达55nm。这表明,在极性较小的有机溶剂中,合成的新型回旋交叉共轭化合物显示出较强的局域态发光(LE),而当有机溶剂极性不断增大时,逐渐表现出强的分子内电荷转移态(ICT)发光。因此本实施例中合成的新型回旋交叉共轭化合物可用于有机电致发光(OLEDs)和有机染料的制备当中具有非常潜在的应用价值。
上述实施例中的一种新型回旋交叉共轭化合物具有优异的热稳定性、较高的玻璃化转变温度、良好的荧光特性,可用于有机电致发光(OLEDs)和有机染料的制备当中,具有非常潜在的应用价值。且采用的合成方法合成工艺简单,原料易得,合成的收率较高,成本较低,适用于大型产业化生产。
Claims (6)
1.一种具有高度回旋交叉共轭有机化合物,其特征在于:该有机化合物的结构式为:
2.如权利要求1所述的一种具有高度回旋交叉共轭有机化合物,其特征在于:该有机化合物的NMR、MS参数如下:
1H NMR(500MHz,CDCl3,ppm)δ=8.04(d,J=8.3Hz,1H),7.72(d,J=14.6,7.7,2.6Hz,3H),7.54(d,J=2.0Hz,1H),7.43(d,J=8.6Hz,2H),7.39–7.30(m,4H),7.17–7.08(m,3H),7.03(d,J=8.5Hz,2H),6.95(d,J=8.1Hz,2H),6.59(d,J=16.2Hz,1H),1.32(s,9H),1.13(s,9H);
13C NMR(126MHz,CDCl3)δ=147.51,147.41,147.27,146.94,137.87,136.84,136.49,135.52,131.44,131.34,130.15,129.26,129.11,128.39,127.34,127.10,126.42,126.12,125.52,125.44,124.56,124.44,123.43,123.05,122.84,77.25,77.00,76.74.
MS(EI)(m/z):calcd for C106H78N4,1407.63;found 1407.36([M+H]+)。
3.一种具有高度回旋交叉共轭有机化合物的合成方法,其步骤为:
(1)将14.8g K2CO3、43mL水加入1000ml的单口圆底烧瓶中,再依次加入四丁基溴化铵TBAB(少量)、反应物6g 9,10-二溴蒽、反应物6.7g 2,5-二甲基苯硼酸,后加入130mL甲苯/水混合溶液,加入0.6g四(三苯基磷)钯(Pd(PPh3)4),无氧惰性气体保护下,110℃下反应72h;
反应结束后,真空旋蒸,水和二氯甲烷进行萃取,石油醚为淋洗剂进行柱层析得到白色固体6.2g,得到结构式为的化合物1;
(2)将步骤(1)获得的5g化合物1、10.36g N-溴代丁二酰亚胺NBS、0.156g过氧化二苯甲酰依次加入到1000mL单口圆底烧瓶中,再加入400mL CCl4溶液,100℃下避光回流搅拌反应10h;
反应结束后冷却至室温,过滤并用CCl4溶液冲洗白色固体,粗产物用丙酮/三氯甲烷重结晶得淡黄色固体7.5g,得到结构式为的化合物2;
(3)将步骤(2)获得的10g化合物2、14.2mL亚磷酸三乙酯P(OEt)3加入到250mL单口圆底烧瓶中150℃下回流搅拌反应8h;
反应结束后冷却至室温,通过减压蒸馏将反应体系中多余的亚磷酸三乙酯除掉,采用柱色谱乙酸乙酯:二氯甲烷作为淋洗剂,旋干后获得黄色固体2.1g,得到结构式为的化合物3;
(4)将步骤(3)获得的5g化合物3、8.7g4-二苯胺基苯甲醛、9.6g叔丁醇钾加入到100mL单口圆底烧瓶中,无氧惰性气体保护下,常温搅拌反应6h;
反应结束后,真空旋蒸,再用甲醇冲洗过滤得到黄色固体,进一步用石油醚:二氯甲烷作为淋洗剂进行层析柱色谱提纯,得到黄色固体3.2g,最终得到结构式为的新型回旋交叉共轭有机化合物。
4.根据权利要求3所述的一种具有高度回旋交叉共轭有机化合物的合成方法,其特征在于:通过该方法制备的具有高度回旋交叉共轭有机化合物的NMR参数如下:
1H NMR(500MHz,CDCl3,ppm)δ=8.04(d,J=8.3Hz,1H),7.72(d,J=14.6,7.7,2.6Hz,3H),7.54(d,J=2.0Hz,1H),7.43(d,J=8.6Hz,2H),7.39–7.30(m,4H),7.17–7.08(m,3H),7.03(d,J=8.5Hz,2H),6.95(d,J=8.1Hz,2H),6.59(d,J=16.2Hz,1H),1.32(s,9H),1.13(s,9H);
13C NMR(126MHz,CDCl3)δ=147.51,147.41,147.27,146.94,137.87,136.84,136.49,135.52,131.44,131.34,130.15,129.26,129.11,128.39,127.34,127.10,126.42,126.12,125.52,125.44,124.56,124.44,123.43,123.05,122.84,77.25,77.00,76.74.
MS(EI)(m/z):calcd for C106H78N4,1407.63;found 1407.36([M+H]+)。
5.根据权利要求4所述的一种具有高度回旋交叉共轭有机化合物的合成方法,其特征在于:步骤(1)加入甲苯与水的体积比为3:1。
6.根据权利要求5所述的一种具有高度回旋交叉共轭有机化合物的合成方法,其特征在于:步骤(2)中采用硅胶色谱层析柱分离时,淋洗剂由丙酮和三氯甲烷按照2:1的体积比组成;步骤(3)中采用硅胶色谱层析柱分离时,淋洗剂由乙酸乙酯和二氯甲烷按照5:4的体积比组成;步骤(4)中采用硅胶色谱层析柱分离时,淋洗剂由石油醚和二氯甲烷按照5:1的体积比组成。
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