CN108558788A - 一种新型具有聚集诱导发光现象的荧光染料合成方法 - Google Patents
一种新型具有聚集诱导发光现象的荧光染料合成方法 Download PDFInfo
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- CN108558788A CN108558788A CN201810309246.5A CN201810309246A CN108558788A CN 108558788 A CN108558788 A CN 108558788A CN 201810309246 A CN201810309246 A CN 201810309246A CN 108558788 A CN108558788 A CN 108558788A
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Classifications
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- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/0019—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules
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- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P35/00—Antineoplastic agents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/14—Styryl dyes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
一种新型具有聚集诱导发光现象的荧光染料合成方法,涉及材料科学领域,所得荧光染料结构通式为以下中的一种:
Description
技术领域
本发明涉及材料科学领域,特别是一种含四苯乙烯结构、用于合成具有聚集诱导发光现象的高性能功能化化合物(尤其是具有单线态氧产生能力的化合物)及其制备方法。
背景技术
恶性肿瘤严重危害我国人民的生命与健康。2017年中国癌症数据统计报告指出,目前我国癌症发病率和死亡率持续上升,已经成为最主要的疾病死亡原因;中国新发癌症病例占全世界的四分之一。因此,提高癌症的早期诊断与精准诊疗水平符合当今我国的重大战略需求。分子影像学是传统的医学影像技术与现代分子生物学相结合产生的一门新兴学科。近年来,由于重大疾病精准诊疗的迫切需求使得分子影像技术及其相关材料领域快速发展,单光子发射计算机断层成像(SPECT),正电子发射计算机断层成像(PET-CT)、核磁共振成像(MRI)以及光学成像等分子影像技术已经被广泛地应用于癌症的临床诊断、治疗评估以及癌症发生发展机制的研究中。
肿瘤的早期诊断和精准分期、图像引导下的手术精准切除等是目前临床上提高患者治疗疗效及生存周期的挑战性难题。目前传统成像技术灵敏度和特异性、空间分辨率较低,同时存在电离辐射危害等瓶颈问题。而相比于其他分子影像技术,光学成像特别是荧光成像技术具有高灵敏度、高瞬时分辨率、价格低廉、高效低毒以及设备简便移动灵活等特点和优势。迄今为止,荧光材料包括传统有机小分子荧光染料(通常具有平面的分子结构)、荧光蛋白、无机半导体量子点、半导体共轭高分子以及“聚集诱导发光”(Aggregation-Induced Emission;简称AIE)材料等被大量应用于癌症诊疗的研究中。其中,每种荧光材料各具特色和优缺点。具有平面分子结构的有机小分子荧光染料通常在高浓度和聚集状态下发生荧光淬灭,即“聚集导致荧光淬灭(Aggregation-Caused Quenching;简称ACQ)”效应。这是因为在聚集状态下,分子之间的相互作用(例如π-π堆积)导致了非辐射能量转换,从而淬灭了荧光发射。毫无疑问,ACQ效应不利于荧光传感与成像,它迫使研究者在生物传感与成像方面的研究只能够使用比较稀的探针溶液,这样就导致了探针灵敏度的降低并且提高了对生物分子的追踪分析的难度。为了解决ACQ效应,AIE荧光材料应运而生,它们展现出了与ACQ材料截然相反的现象。AIE荧光分子(例如四苯基乙烯)通常具有分子内的可旋转单元(通常为苯环)。当其在溶液中以单分子状态存在时,AIE分子内的苯环就能够自由旋转,导致激发态能量大多以非辐射方式衰减,因而分子几乎不产生荧光发射。然而,在聚集状态下,AIE分子之间的空间位阻使得AIE分子内的苯环旋转受阻,非辐射衰减受到抑制,激发态能量以辐射方式产生强荧光。近年来,AIE领域特别是AIE分子在荧光检测与成像方面的相关研究取得了快速的发展,因为相比于传统的荧光材料,AIE荧光材料同时具备聚集态下荧光亮度高、抵制光漂白能力强、细胞/体内毒性低、便于实现荧光开启式检测等诸多优势。尽管目前还不够深入,AIE荧光材料在癌症诊疗领域的研究中也进行了许多尝试,并且取得了一系列重要的进展。其中非常重要的一点是,由于纳米材料的EPR效应(EnhancedPermeability and Retention Effect)是其应用于癌症诊疗的重要基础,因此,越聚越亮的AIE荧光材料特别适用于构建具有高荧光量子产率的荧光纳米材料/探针,有助于实现癌症的高灵敏检测。
发明内容
本发明的目的是发挥聚集诱导发光(AIE)现象优势,提供了一种含有四苯乙烯结构的新型功能化荧光染料。
本发明的另外一个目的在于提供上述新型荧光染料的制备方法。
本发明还有一个目的是在于提供上述一些新型荧光染料应用于制备功能化小分子荧光探针的制备方法。
本发明的技术方案:一种新型荧光染料,其结构通式为I、II中的一种:
其中Ar选自下列结构式中的任一种:
其中Acceptor选自下列结构式中的任一种:
通式中R为:
方式I:包括以下步骤:(A1)利用二苯甲酮通过锌粉-四氯化钛还原偶联反应合成具有四苯乙烯结构的含有一个卤原子的大共轭体系分子.(A2)通过正丁基锂反应将四苯乙烯结构上的卤原子溴替换硼酸基。(A3)为通过一步Suzuki反应与4-溴苯甲醛或5-溴噻吩-2-甲醛偶联形成更大体系共轭的含有四苯乙烯结构的酮中间体。
方式II:包括以下步骤:(B1)利用二苯甲酮通过锌粉-四氯化钛还原偶联反应合成具有四苯乙烯结构的含有一个卤原子的大共轭体系分子.(B2)通过正丁基锂反应将2-(3,4-乙烯基双氧噻吩)甲醛附加正三丁基锡结构。(B3)将B1步骤得到的TPE-Br与B2得到的产物通过一步Suzuki反应偶联形成一种新的含有更大共轭体系的酮中间体。
方式III:包括以下步骤:(C1)利用方法I、方法II得到的中间体与所接电子受体(acceptor)通过哌啶与乙腈体系进行回流反应得到目标终产物。
方式IV:包括以下步骤:(D1)利用方法I、方法II得到的中间体与所接电子受体(acceptor)通过醋酸与醋酸铵体系进行回流反应得到含羧基的中间体。(D2)由上一步反应得到的中间体与带有功能基团的支链通过缩合反应进行染料功能化得到目标终产物。
其中Acceptor为如下三种时采用方法III:
其中Acceptor为如下两种时采用方法IV:
本发明的优点是:相较于传统的荧光染料,本发明中的新型染料,不仅可以解决高浓度下聚集诱导淬灭的问题,通过荧光分子的重新生成,对NO等连接到染料上的功能基团释放过程进行示踪监测,同时可依靠荧光分子在病灶部位产生的ROS,对癌症部位进行治疗,实现染料多功能化的目的。
具体实施方式
下面给出实例对本发明作更详细的说明,有必要指出的是以下实施例不能解释为对发明保护范围的限制,该领域的技术熟练人员根据上述发明内容对本发明作出的一些非本质的改进和调整,仍应属于本发明的保护范围。
实施例1
(E)-2-((2-(2-(5-((4'-(2,2-bis(4-methoxyphenyl)-1-phenylvinyl)-[1,1'-biphenyl]-4-yl)methylene)-4-oxo-2-thioxothiazolidin-3-yl)acetamido)ethyl)disulfanyl)ethylnitrate的合成
(1)合成中间体
4,4'-(2-(4-bromophenyl)-2-phenylethene-1,1-diyl)bis(methoxybenzene) [1a]:
将24.2g(372mmol)锌粉悬浮于250mL四氢呋喃(THF)加入1L三口瓶中,磁子搅拌并通入氩气。将体系降至0℃滴加21mL(186mmol)四氯化钛,滴加完成后将体系恢复室温反应30min,再油浴加热升至70℃,反应3h。之后再次降至0℃,先滴加7.4g(93mmol)吡啶,后滴加溶于200mL四氢呋喃(THF)的4,4'-二甲氧基二苯甲酮9g(37.2mmol)与4-溴二苯甲酮12.6g(48.4mmol),滴加完成后油浴升温至70℃反应8h过夜。待反应完全后,将体系再次降温至0℃,加入200mL饱和碳酸氢钠溶液淬灭,过硅藻土,使用乙酸乙酯200mL洗净滤饼,将滤液分液,旋干有机相,硅胶拌样,过柱得产物9.9g,产率为57%。1HNMR:(400MHz,CDCl3)δ7.24–7.18(m,2H),7.11–6.86(m,11H),6.69–6.60(m,4H),3.75(t,J=9.2Hz,6H).解析该中间体结构如下:
(2)合成中间体(4-(2,2-bis(4-methoxyphenyl)-1-phenylvinyl)phenyl)boronic acid [1b]:
将1.2g(2.55mmol)实施例2中间体[2a]溶于20mL四氢呋喃(THF)中放入100mL两口瓶中,磁子搅拌并通入氩气。将体系降低至-78℃,向其中缓慢滴入浓度为2.4M正丁基锂己烷溶液1.3mL,反应2h。然后,维持体系-78℃,向体系中缓慢滴入530mg(5.10mmol)硼酸三甲酯,缓慢恢复室温反应4h。待反应完全,降低体系温度至0℃,向体系中滴入浓度为3M的盐酸10mL,反应两小时。向体系中加入20mL水,用乙酸乙酯3*20mL萃取分液,用旋转蒸发仪旋干有机相,硅胶拌样,过柱得产物600mg,产率为54%。该中间体结构如下:
合成中间体
4'-(2,2-bis(4-methoxyphenyl)-1-phenylvinyl)-[1,1'-biphenyl]-4-carbaldehyde [1c]:
将5.76g(14.6mmol)中间体[1b]与2.46g(13.27mmol)4-溴苯甲醛混合加入250mL两口瓶中,并向其中加入催化量的四三苯基膦钯153mg(132.7μmol)、2M浓度的碳酸钾水溶液26mL、相转移催化剂四丁基溴化铵(TBAB)428mg(1.33mmol)与100mL甲苯。磁子搅拌并通入氩气,油浴加热至80℃回流8h过夜。待反应完全后,使用分液漏斗分液,并用50mL乙酸乙酯洗水相3次,之后将有机相旋干,硅胶拌样,过柱得5.8g产物,产率80%。1H NMR(400MHz,CDCl3)δ10.03(s,1H),7.91(d,J=8.2Hz,2H),7.72(d,J=8.2Hz,2H),7.40(d,J=8.3Hz,2H),7.15–6.92(m,11H),6.65(t,J=8.6Hz,4H),3.74(s,6H).解析该中间体结构如下:
(1)合成中间体
(E)-2-(5-((4'-(2,2-bis(4-methoxyphenyl)-1-phenylvinyl)-[1,1'-biphenyl]-4-yl)methylene)-4-oxo-2-thioxothiazolidin-3-yl)acetic acid [1d]:
将2g(4mmol)中间体[1c]与2.3g(12mmol)3-羧甲基绕丹宁混合加入100mL两口瓶中,并向其中加入930mg(12mmol)醋酸铵和30mL醋酸,磁子搅拌并通入氩气,油浴加热至120℃回流,反应8h过夜。待反应停止,恢复室温,向体系中加入50mL乙酸乙酯和50mL水,使用分液漏斗分液,并用乙酸乙酯洗水相3次。将有机相旋干,使用石油醚:乙酸乙酯=40:1的浓度重结晶,得到产物2.55g,产率95%。1H NMR(400MHz,CDCl3)δ7.81(s,1H),7.69(d,J=8.4Hz,2H),7.60–7.51(m,2H),7.40(d,J=8.4Hz,2H),7.18–7.03(m,7H),6.96(dd,J=14.6,8.8Hz,4H),6.65(t,J=8.5Hz,4H),4.94(s,2H),3.75(s,6H),2.10(s,1H).解析该中间体结构如下:
(2)合成中间体tert-butyl(2-((2-hydroxyethyl)disulfanyl)ethyl)carbamate [1e]:
将10g(65mmol)2-羟乙基二硫化物与7.9g(70mmol)半胱胺盐酸盐混合加入100mL两口瓶中,向体系中加入13.2g三乙胺(TEA)与40mL无水甲醇,磁子搅拌并通入氩气,避光条件下室温反应4h。待反应完全后,将体系降至0℃,将21.3g(97.5mmol)二碳酸二叔丁酯溶于20mL无水甲醇中,滴入体系后恢复反应体系至室温8h过夜。待反应完全后,使用旋转蒸发仪旋干体系,使用乙酸乙酯与水将体系分液,并用乙酸乙酯洗水相3次后旋干,硅胶拌样,过柱得到产品8.53g,产率52%。1H NMR(300MHz,CDCl3):d 1.43(s,9H),2.79(t,J=6.5Hz,2H),2.87(t,J=5.7Hz,2H),3.48(q,J=6.0Hz,2H),3.88(t,J=5.5Hz,2H),4.8(bs,1H).解析该中间体结构如下:
(3)合成中间体2-((2-((tert-butoxycarbonyl)amino)ethyl)disulfanyl)ethylmethanesulfonate [1f]:
将8.53g(33.7mmol)中间体[1e]溶于盛有50mL二氯甲烷(DCM)的250mL两口瓶中,向其中加入6.81g(67.4mmol)三乙胺(TEA),磁子搅拌并通入氩气,将体系降至0℃,滴加5.77g(50.6mmol)甲基磺酰氯,体系逐渐浑浊,0℃反应1h。待反应完全后,加入盐水洗,使用二氯甲烷(DCM)分液,同样用二氯甲烷洗水相3次,旋干有机相,硅胶拌样,过柱得产物8g,产率为72%。1H NMR(300MHz,CDCl3):d 1.43(s,9H),2.80(t,J=6.4Hz,2H),2.98(t,J=5.7Hz,2H),3.05(s,3H),3.35-3.45(m,2H),4.45(t,J=6.7Hz,2H),4.78(bs,1H).解析该中间体结构如下:
(4)合成中间体tert-butyl(2-((2-bromoethyl)disulfanyl)ethyl)carbamate [1g]:
将8g(24.17mmol)中间体[1g]溶于40mL丙酮中,磁子搅拌并通入氩气,向体系内缓慢滴加4.2g(48.34mmol)溴化锂,油浴加热45℃回流8h过夜。待反应完全,旋干,硅胶拌样,过柱得产物6.2g,产率为81%。1H NMR(300MHz,CDCl3):d 1.44(s,9H),2.80(t,J=6.3Hz,2H),3.06(t,J=6.7Hz,2H),3.44(m,2H),3.61(t,J=7.6Hz,2H),4.87(bs,1H).解析该中间体结构如下:
(5)合成中间体tert-butyl(2-((2-(nitrooxy)ethyl)disulfanyl)ethyl)carbamate [1h]:
将1g(3.16mmol)中间体[1g]溶于10mL无水乙腈加入50mL试管中,向其中加入646mg(3.8mmol)硝酸银,磁子搅拌并通入氩气,避光条件下反应3h。待反应完全后,抽滤,旋干有机相,硅胶拌样,过柱得产物400mg,产率为42%。1HNMR(300MHz,CDCl3):d 1.44(s,9H),2.80(t,J=6.3Hz,2H),3.06(t,J=6.7Hz,2H),3.44(q,J=6.1Hz,2H),4.70(t,J=7.62Hz,2H),4.87(br s,1H).解析该中间体结构如下:
(6)合成中间体(E)-2,5-dioxopyrrolidin-1-yl
2-(5-((4'-(2,2-bis(4-methoxyphenyl)-1-phenylvinyl)-[1,1'-biphenyl]-4-yl)methylene)-4-oxo-2-thioxothiazolidin-3-yl)acetate [1i]:
将700mg(1.04mmol)中间体[1d]溶于5mL二氯甲烷(DCM)中,倒入50mL两口瓶中,向其中加入239mg(2.08mmol)N-羟基丁二酰亚胺(NHS),磁子搅拌并通入氩气。将体系降低至0℃,向体系中滴加溶于5mL二氯甲烷的二环己基碳二亚胺(DCC)435mg(2.08mmol),缓慢将反应体系恢复室温8h过夜。将550mg(1.85mmol)中间体溶于8mL的二氯甲烷(DCM)中,倒入另一50mL两口瓶中,将体系降低至0℃,滴加溶于2mL二氯甲烷(DCM)的842mg(7.38mmol)三氟乙酸,缓慢恢复室温8h过夜。待两体系反应完全,分别使用旋转蒸发仪旋干,将两体系旋干得到的粗品混合加入一个新的两口瓶中,向其中加入三乙胺(TEA)630mg(6.24mmol)和溶剂N,N-二甲基甲酰胺(DMF)10mL,维持室温反应8h过夜。待反应完全后旋干,HPLC纯化,得到终产物300mg,产率为34%,1H NMR(400MHz,CDCl3)δ7.83(s,1H),7.72(d,J=8.4Hz,2H),7.61–7.53(m,2H),7.43(d,J=8.4Hz,2H),7.15(dd,J=8.1,6.3Hz,5H),7.10–7.07(m,2H),6.99(dd,J=14.4,8.8Hz,5H),6.68(t,J=8.5Hz,4H),4.83(s,2H),4.73(t,J=6.7Hz,2H),3.77(d,J=1.2Hz,6H),3.00(t,J=6.7Hz,2H),2.88(t,J=6.2Hz,2H),2.03(d,J=5.7Hz,2H).
该终产物结构如下:
实施例2
(E)-2-(2-(2-(7-(4-(2,2-bis(4-methoxyphenyl)-1-phenylvinyl)phenyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)vinyl)-4H-chromen-4-ylidene)malononitrile的合成:
(1)合成中间体2,3-dihydrothieno[3,4-b][1,4]dioxine-5-carbaldehyde [2a]:
将5g(35.21mmol)3,4-乙烯二氧噻吩溶于70mLN,N-二甲基甲酰胺(DMF)放入两口瓶,磁子搅拌并通入氩气。将反应体系降至0℃,向体系中滴加10.8g(70.42mmol)的三氯氧磷。缓慢恢复体系至室温反应8h过夜。待反应完全后,使用旋转蒸发仪旋干DMF,将体系降至0℃加入50mL饱和碳酸氢钠溶液淬灭过量的三氯氧磷,使用3*50mL二氯甲烷萃取并分液,旋干有机相。硅胶拌样,过柱得产物4g,产率67%。1H NMR(400MHz,CDCl3)δ9.91(d,J=1.0Hz,1H),6.79(d,J=1.0Hz,1H),4.39–4.24(m,4H).解析得该中间体结构如下:
(2)合成中间体
7-(tributylstannyl)-2,3-dihydrothieno[3,4-b][1,4]dioxine-5-carbaldehyde [2b]:
将2.04g(12mmol)中间体[2a]溶于20mL氯仿与50mL甲醇的混合溶液中,装入两口瓶,向体系中加入1.908g(18mmol)原甲酸三甲酯与催化量2,3-二氯-5,6-二氰基-1,4-苯醌18.6mg(0.6mmol),磁子搅拌并通入氩气,油浴升温至50℃反应2h。待反应完全后,将体系用旋转蒸发仪旋干,向体系中加入60mL四氢呋喃(THF),磁子搅拌并通入氩气。将体系温度降至-78℃,滴加浓度为2.4M的正丁基锂己烷溶液7.5mL,维持体系温度反应2h,将7.8g(24mmol)正三丁基锡加入体系,缓慢恢复至室温,反应16h后加入浓度为2.5M的硫酸氢钾96mL,继续反应2h。待反应完全后向体系中加入50mL饱和碳酸氢钠溶液,使用3*50mL乙酸乙酯分液,使用旋转蒸发仪旋干有机相,得到粗产物备用,无法计算产率。该中间体结构如下:
(3)合成中间体
7-(4-(2,2-bis(4-methoxyphenyl)-1-phenylvinyl)phenyl)-2,3-dihydrothieno[3,4-b][1,4]dioxine-5-carbaldehyde [2c]:
将2g(4.36mmol)中间体[2a]与4g粗品中间体[2c]称入两口瓶中,加入40mL甲苯作为溶剂,向体系中称入催化量的四三苯基膦钯101mg(0.0872mmol),磁子搅拌并通入氩气,油浴加热至80℃反应8h过夜。待反应完全,用旋转蒸发仪旋干体系,硅胶拌样,过柱得产物1.32g,产率54%。1H NMR(400MHz,CDCl3)δ9.93–9.88(m,1H),7.54(t,J=8.6Hz,2H),7.14–7.08(m,3H),7.03(dd,J=12.6,5.0Hz,4H),6.95(dd,J=16.4,8.8Hz,4H),6.64(dd,J=12.4,8.8Hz,4H),4.36(dd,J=13.7,5.3Hz,4H),3.74(d,J=5.0Hz,6H).解析该中间体结构如下:
(4)合成终产物
(E)-2-(2-(2-(7-(4-(2,2-bis(4-methoxyphenyl)-1-phenylvinyl)phenyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)vinyl)-4H-chromen-4-ylidene)malononitrile [2d]
将1g(1.78mmol)中间体[2c]与452mg(2.16mmol)2-(2-甲基-4H-1-苯并吡喃-4-基)-丙二腈称入两口瓶中混合,向体系加入20mL乙腈将其溶解,再向体系中加入16mg(0.18mmol)吡啶,磁子搅拌并通入氩气,油浴升温至85℃回流,反应8h过夜。待反应完全,用旋转蒸发仪将体系旋干,硅胶拌样,过柱得产物620mg,产率46%。1H NMR(400MHz,CDCl3)δ7.72(t,J=7.8Hz,1H),7.65–7.51(m,4H),7.44(t,J=7.8Hz,1H),7.12(dd,J=12.9,7.5Hz,4H),7.06(d,J=8.2Hz,4H),7.01(d,J=8.7Hz,2H),6.96(d,J=8.7Hz,2H),6.81(s,1H),6.71–6.62(m,5H),5.40–5.31(m,1H),4.41(dd,J=21.6,3.7Hz,4H),3.77(d,J=6.4Hz,6H).该终产物结构如下:
Claims (5)
1.一种新型具有聚集诱导发光现象的荧光染料,其结构通式为:
其中Ar选自下列结构式中的任一种:
其中Acceptor选自下列结构式中的任一种:
2.一种新型具有聚集诱导发光现象的荧光染料,其结构通式为:
其中Ar选自下列结构式中的Ar1或Ar2或Ar3任一种:
Acceptor选自下列结构式中的任一种:
通式中R为:
3.一种新型具有聚集诱导发光现象的荧光染料合成方法,其特征是:包括中间体的合成方法及目标终产物的合成方法,所得目标终产物为以下通式中的一种
其中Ar选自下列结构式中的Ar1或Ar2或Ar3任一种:
Acceptor选自下列结构式中的任一种:
通式中R为:
4.根据权利要求3所述的新型具有聚集诱导发光现象的荧光染料合成方法,其特征是:所述的中间体的合成方法包括
方式I:包括以下步骤:(A1)利用二苯甲酮通过锌粉-四氯化钛还原偶联反应合成具有四苯乙烯结构的含有一个卤原子的大共轭体系分子,(A2)通过正丁基锂反应将四苯乙烯结构上的卤原子溴替换硼酸基,(A3)为通过一步Suzuki反应与4-溴苯甲醛或5-溴噻吩-2-甲醛偶联形成更大体系共轭的含有四苯乙烯结构的酮中间体。
方式II:包括以下步骤:(B1)利用二苯甲酮通过锌粉-四氯化钛还原偶联反应合成具有四苯乙烯结构的含有一个卤原子的大共轭体系分子,(B2)通过正丁基锂反应将2-(3,4-乙烯基双氧噻吩)甲醛附加正三丁基锡结构,(B3)将B1步骤得到的TPE-Br与B2得到的产物通过一步Suzuki反应偶联形成一种新的含有更大共轭体系的酮中间体。
5.根据权利要求3所述的新型具有聚集诱导发光现象的荧光染料合成方法,其特征是:
其中Acceptor为如下三种时
目标终产物的合成方法包括以下步骤:(C1)利用权利要求4的方法I或方法II之一得到的中间体与所接电子受体(acceptor)通过哌啶与乙腈体系进行回流反应得到目标终产物;
其中Acceptor为如下两种时
目标终产物的合成方法包括以下步骤:(D1)利用权利要求4的方法I或方法II之一得到的中间体与所接电子受体(acceptor)通过醋酸与醋酸铵体系进行回流反应得到含羧基的中间体,(D2)由上一步(D1)得到的中间体与带有功能基团的支链通过缩合反应进行染料功能化得到目标终产物。
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