CN104030974A - 一种含芳基取代的三联吡啶类化合物及其制备方法和应用 - Google Patents

一种含芳基取代的三联吡啶类化合物及其制备方法和应用 Download PDF

Info

Publication number
CN104030974A
CN104030974A CN201410287370.8A CN201410287370A CN104030974A CN 104030974 A CN104030974 A CN 104030974A CN 201410287370 A CN201410287370 A CN 201410287370A CN 104030974 A CN104030974 A CN 104030974A
Authority
CN
China
Prior art keywords
aryl
compound
terpyridine
formula
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410287370.8A
Other languages
English (en)
Inventor
朱红军
刘宇剑
刘睿
郭军
朱晓林
黄海
金晓东
李炜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Tech University
Original Assignee
Nanjing Tech University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Tech University filed Critical Nanjing Tech University
Priority to CN201410287370.8A priority Critical patent/CN104030974A/zh
Publication of CN104030974A publication Critical patent/CN104030974A/zh
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/26—Radicals substituted by halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/127—Preparation from compounds containing pyridine rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
    • C07D213/22—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing two or more pyridine rings directly linked together, e.g. bipyridyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/36—Radicals substituted by singly-bound nitrogen atoms
    • C07D213/38—Radicals substituted by singly-bound nitrogen atoms having only hydrogen or hydrocarbon radicals attached to the substituent nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • 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
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • 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
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Pyridine Compounds (AREA)

Abstract

本发明提供了一种含芳基取代的三联吡啶类化合物、制备方法及应用。以2-溴苯基-2，2’：6’2”-三联吡啶(II)与芳基硼酸酯为原料，在经超声除气的甲苯∶水＝4∶1的混合溶剂体系中，四(三苯基膦)钯为催化剂，碳酸钾为碱，回流反应18-24h而得。该类化合物适用于有机发光材料和荧光材料的开发与制备。

Description

一种含芳基取代的三联吡啶类化合物及其制备方法和应用
技术领域
本发明涉及一种含芳基取代的三联吡啶类化合物、制备方法及其作为光电材料在电致发光中的应用。
技术背景
三联吡啶类化合物具有σ给电子能力及π受电子能力，能够与多种金属形成稳定的配合物。此外，三联吡啶类化合物与其他化合物相比，具有独特的磁、光物理和电化学性质。对三联吡啶结构进行修饰，可以方便地调控化合物的光物理和电化学性质，因此利用这些特性可以设计出很多新颖的功能化材料，用于光电子器件、信息存储、分子开关、分子机器和太阳能电池等(Synth.Met.，2004，146，11-15；J.Am.Chem.Soc.，2004，126，4958-4971；Chem.Mat.，2010，22，6384-6492)。
三联吡啶最早是由于1796年在Sythesis杂志上报道的。以2-乙酰基吡啶和取代芳香醛为原料，在碱的作用下，一分子2-乙酰基吡啶与芳香醛发生羟醛缩合，生成α，β-不饱和酮，另一分子的2-乙酰基吡啶在碱的作用下产生含碳负离子的中间体，与α，β-不饱和酮进行不饱和羰基化合物的1，4-加成，反应产生1，5-二酮。1，5-二酮在胺的作用下，形成1，4-二氢吡啶环，接着1，4-二氢吡啶环在加热条件下，发生氧化脱氢，形成一个具有芳香性的吡啶环，最终得到三联吡啶类化合物(Synthesis，1976，1，1-24)。之后Newkome等人于1972年报道了肼盐热裂解法来合成三联吡啶类化合物(J.Org.Chem.，1972，37，1329-1336)，但其反应条件苛刻，原料复杂，路线较为繁琐。
三联吡啶类化合物的结构主要可以通过Stille偶联反应、Ulmann偶联反应和Suzuki偶联反应等修饰(Angew.Chem.Int.Ed.2004，43，4704-4734；Angew. Chem.Int.Ed.2009，48，6954-6971)。
Stille偶联反应是有机锡化合物和不含β-氢的卤代烃(或三氟甲磺酸酯)在钯催化下发生的交叉偶联反应。是由Stille等人于20世纪70年代首先发现，该反应一般在无水无氧条件下进行，但实验中常见的有机锡化合物通常具有较大的毒性，因而限制了其应用。
Ulmann偶联反应是卤代芳香族化合物与铜粉共热生成联芳类化合物的反应，该反应是由德国化学家Ulmann于1901年发现的，但是该反应大都需要较高的反应温度。由于其反应条件不太温和，因而限制了其应用。
Suzuki偶联反应是芳基硼酸或硼酸酯与卤代芳烃或烯烃在钯配合物的催化下发生交叉偶联反应，该反应是由日本化学家铃木章在1979年首先报道，在有机合成中的用途非常广泛(Chem.Rev.，1995，95，2457-2483)。此外，Suzuki偶联反应对官能团的耐受性非常好，反应物可以带着-CHO、-COCH3、、-CN、-NO2等官能团进行反应而不受影响。该反应中常用的催化剂有Pd(PPh3)4与Pd(dppf)Cl2等；碱也有很多选择，常用的有碳酸钠、碳酸铯、碳酸钾、碳酸锂等。反应中催化剂和碱的最优选择，因反应底物不同而不同。
有文献报道，三联吡啶类化合物在电致发光方面有着较优良的性能(ACS Appl.Mat.Interfaces，2012，4，2877-2880)。本发明的目的是提供一种新型的含芳基取代的三联吡啶化合物，及其最优的制备方法和在光电材料方面的应用。
发明内容
本发明的目的在于提供一种含芳基取代的三联吡啶类化合物、制备方法及其作为光电材料在电致发光中的应用。
本发明采用的技术方案是：
如式I所示的含芳基取代的三联吡啶类化合物
式I中R1选自：
其中R2为H、碳原子数1至12的烷基、碳原子数7至12的芳香基。
本发明还提供所述如式I所示的含芳基取代的三联吡啶类化合物的制备方法，所述方法为：
式II所示化合物与式III所示化合物在氮气保护下进行Suzuki偶联反应，以四(三苯基膦)钯为催化剂，在超声除气的甲苯∶水＝4∶1的混合溶剂中，在碱性条件下，回流反应18-24h，反应结束后反应液后处理得到式I所示化合物；所述式II所示化合物与式III所示化合物的物质的量之比为1∶1.5；
式III中R1选自：
其中R2为H、碳原子数1至12的烷基、碳原子数7至12的芳香基。
所述催化剂四(三苯基膦)钯的物质的量用量通常为式II所示化合物的物质的量的5％。
所述碱性条件，即加入常用碱类例如碳酸钾、碳酸钠或氢氧化钠等，保持反应液的pH值为碱性即可。所述反应液后处理方法为：反应结束后，反应液加水淬灭反应，加入二氯甲烷稀释，过滤掉不溶物，滤液用无水硫酸镁干燥，除去溶剂，得到式I所示化合物粗品，式I所示化合物粗品以石油醚∶二氯甲烷＝5∶1混合溶液为洗脱剂，经柱层析分离提纯，得到式I所示化合物纯品。
所述式II所示化合物通常可按以下方法制备得到：4-溴苯甲醛的甲醇溶液中，依次加入2-乙酰基吡啶、氢氧化钠和浓氨水，加热回流反应72～80h，然后冷却到室温，得到灰色沉淀物。过滤，滤饼依次用水、甲醇洗涤后干燥得到式II所示化合物，所述的4-溴苯甲醛、2-乙酰基吡啶、氢氧化钠和浓氨水中的NH3·H2O的物质的量之比为1∶2∶1～2∶70～100。
所述反应式如下。
这是本领域技术人员公知的制备方法。
所述式III所示化合物通常可按以下方法制备得到：式IV所示化合物和联硼酸频哪醇酯在以[1，1′-双(二苯基磷)二茂铁]二氯化钯为催化剂，以醋酸钾为碱，以二甲亚砜为溶剂条件下，加热回流反应8～10h，然后加入甲苯萃取，取有机层用水洗涤后干燥，减压除去溶剂后得到式V所示粗产物，以石油醚∶乙酸乙酯＝4∶1的混合溶液为洗脱剂，经柱层析提纯，得到式V所示化合物纯产物，所述式IV所示化合物、联硼酸频哪醇酯、[1，1′-双(二苯基磷)二茂铁]二氯化钯、醋酸钾的物质的量之比为1∶1～1.1∶0.005～0.01∶2～4。
所述反应式如下：
式IV中R1选自：
其中R2为H、碳原子数1至12的烷基、碳原子数7至12的芳香基。
这是本领域技术人员公知的制备方法。
本发明提供式I所示的含芳基取代的三联吡啶类化合物通过测试，具有发光性能，可用作发光材料，且具有反应条件简单，原料易得，产率较高等优点。
附图说明
图1归一化的化合物VI-XI在二氯甲烷溶液中的紫外-可见吸收光谱(1×10-5M)
图2归一化的化合物VI-XI在二氯甲烷溶液中的荧光发射光谱(1×10-7M)
图3归一化的化合物VI-XI在不同溶剂中的荧光发射光谱(1×10-7M)
具体实施方式
下面结合具体实例对本发明作进一步阐述，但本发明的保护范围不限于此。
下述制备例中所用试剂，均为市售试剂：
实施例1：2-溴苯基-2，2’：6’2”-三联吡啶(II)的制备
向装有200mL甲醇的圆底烧瓶中，依次加入4-溴苯甲醛(2.0g，10.80mmol)、2-乙酰基吡啶(4.4g，21.6mmol)、氢氧化钠(0.44g，10.80mmol)和60mL的浓氨水(28％)，加热到70℃，回流72h。冷却到室温后，得到灰色沉淀物，过滤，滤饼依次用水洗，甲醇洗，干燥得到2-溴苯基-2，2’：6’2”-三联吡啶(3.8g，89％)。 1H NMR(CDCl3，400MHz)：δppm7.36-7.40(m，3H)，7.48(t，J＝8.0Hz，2H)，7.67(d，J＝8.0Hz，2H)，7.74(d，J＝8.0Hz，2H)，7.87-7.91(m，2H)，8.00(d，J＝8.0Hz，2H)，8.68(d，J＝8.0Hz，2H)，8.73-8.76(m，2H)，8.80(s，2H).
实施例2：式VI所示化合物的合成：
在氮气保护下，将II(388mg，1mmol)，碳酸钾(552mg，4.0mmol)，四(三苯基膦)钯(46mg，0.04mmol)，萘硼酸酯(1.75g，7.0mmol)全部加入到史莱克管中，抽真空，用氮气置换三次。在N2保护的氛围下，取10mL经超声除气的甲苯∶水＝4∶1的混合溶剂，注射到史莱克管中，随后加热至回流，反应20h以上。TLC跟踪，显示无原料残留，则反应结束。关闭加热装置，待反应体系降至室温，用20mL二氯甲烷稀释，并用饱和食盐水洗涤3次，过滤掉不溶物，收集有机相。再用无水硫酸镁干燥，减压除去溶剂，得到粗产品。用石油醚∶二氯甲烷＝1∶1的混合溶剂为洗脱剂，利用200-300目的氧化铝进行柱层析，分离得到白色固体0.36g，产率为83.5％，熔点为220-221℃。1H NMR(CDCl3，400MHz)：δppm7.36-7.40(m，3H)，7.48(t，J＝8.0Hz，2H)，7.57(d，J＝8.0Hz，2H)，7.67(d，J＝8.0Hz，2H)，7.74(d，J＝8.0Hz，2H)，7.87-7.94(m，4H)，8.00(d，J＝8.0Hz，2H)，8.68(d，J＝8.0Hz，2H)，8.73-8.76(m，2H)，8.80(s，2H).TOF-MS(ES+)calcd.for C27H19N3[M+1]+：453.1，found453.3.
取10mg样品放入日本滨松Quantaurus-Tau C11367-1型荧光寿命系统的样品腔，测得该产物的荧光寿命为2.64ns。
实施例3：式VII所示化合物的合成：
在氮气保护下，按实施例2中方法合成得到化合物VII，产品为白色固体，产率为85.0％，熔点为229-231℃。1H NMR(CDCl3，400MHz)：δppm7.01(d，J＝2.0Hz，2H)，7.34-7.38(m，2H)，7.62(dd，J＝2.0Hz，2H)，7.7(d，J＝8.0Hz，2H)，7.85-7.90(m，2H)，7.95-8.03(m，4H)，8.69(d，J＝8.0Hz，2H)，8.73-8.77(m，3H)，8.80(s，2H).TOF-MS(ES+)calcd.for C28H21N3O[M+1]+：462.2，found462.1.
该产物的荧光寿命为2.15ns，测试方法同实施例2。
实施例4：式III所示化合物的制备
其中，R1为取代咔唑基，结构如下：
其中，R2为碳原子数为6的烷基链。
N-溴代丁二酰亚胺溴代：在室温条件下，将咔唑(15.0g，89.88mmol)溶于150mL N，N-二甲基甲酰胺中，再加入N-溴代丁二酰亚胺(15.9g，90mmol)，反应搅拌过夜。反应液用乙酸乙酯萃取3次，合并有机层，用饱和食盐水洗涤3 次，再用无水硫酸镁干燥有机相，减压除去溶剂。得到的粗产品用乙醇重结晶，得到淡黄色固体11.5g。产率为66.8％。
烷基链取代：在室温条件下，将溴代的咔唑(4.10g，16.66mmol)加入到二甲基亚砜(80mL)中，搅拌至固体全部溶解，再依次加入溴己烷(2.49mL，17.49mmol)、氢氧化钾(7.46g，133.28mmol)和碘化钾(0.28g，1.67mmol)，混合搅拌24h以上。然后用饱和食盐水充分洗涤，再用二氯甲烷萃取，分离出有机相，无水硫酸镁干燥，得到粗产品。以石油醚作为洗脱剂，柱层析得到淡黄色油状液体5.0g，产率为90.9％。1H NMR(CDCl3，400MHz)：δppm0.85(s，3H)，1.24(s，12H)，1.25-1.52(m，8H)，4.15(m，2H)，7.57(m，2H)，7.67-7.73(m，5H).
实施例5：式VIII所示化合物的合成：
将得到的溴代的碳六链取代咔唑(1.5g，4.53mmol)，[1，1′-双(二苯基磷)二茂铁]二氯化钯(116mg，0.038mmol)，醋酸钾(1.35g，13.8mmol)和双戊酰二硼(1.2g，4.83mmol)置于100mL圆底烧瓶中，加入20mL的二甲亚砜，在95℃下反应8h后，加入100mL甲苯萃取，取有机层，用水洗去二甲亚砜后干燥，除去溶剂，得到粗产品。粗产品用柱层析提纯，以石油醚∶二氯甲烷＝4∶1为洗脱剂，得到纯产物，产率为75％。1H NMR(CDCl3，400MHz)：δppm0.85(s，4H)，1.25-1.52(m，7H)，1.92-1.95(m，2H)，4.35(s，2H)，7.33(s，1H)，7.45-7.57(m，3H)，8.34(d，J＝8.0Hz，1H)，8.45(s，1H，J＝8.0Hz)，9.10(s，1H).
该产物的荧光寿命为2.08ns，测试方法同实施例2。
实施例6：式IX所示化合物的合成：
烷基链取代：合成方法同实施例4中的烷基链取代。经后处理得到淡黄色油状液体，产率为86.9％。
N-溴代丁二酰亚胺溴代：合成方法同实施例4中的溴代。经后处理得到黄色油状液体，产率为84.2％。
溴代碳链芴硼酸的合成方法同实施例4。得到的粗产品通过柱层析分离提纯，洗脱剂为石油醚，得到无色油状液体6.8g，产率为50.4％。1H NMR(CDCl3，400MHz)：δppm 0.57(s，4H)，0.72-0.76(m，6H)，0.88-1.26(m，12H)，1.38(s，12H)，1.98(d，4H)，7.29(m，3H)，7.70(m，1H)，7.79(s，1H)，7.81(d，1H).
在氮气保护下，按实施例2中方法合成得到化合物IX，产品为白色固体，产率为80％，熔点为110-111℃。1H NMR(CDCl3，400MHz)：δppm 0.76-0.80(m，6H，CH3)，1.07-1.44(m，16H，CH2)，1.95-2.05(m，4H，CH2)，7.34-7.38(m，5H)，7.64-7.71(m，2H)，7.72-7.81(m，4H)，7.85-7.95(m，2H)，8.04-8.06(m，2H)，8.69-8.74(m，2H)，8.75-8.80(dd，2H)，8.83(s，2H).TOF-MS(ES+)calcd.for C46H47N3[M+1]+：642.4，found 642.1.
该产物的荧光寿命为2.45ns，测试方法同实施例2。
实施例7：式X所示化合物的合成：
在氮气保护下，按实施例2中方法合成得到化合物X，产品为白色固体，产率为82％，熔点为217-218℃。1H NMR(CDCl3，400MHz)：δppm7.04-7.08(m，2H)，7.15-7.19(m，6H)，7.27-7.31(m，4H)，7.35-7.38(m，2H)，7.56(d，J＝8.0Hz，2H)，7.71(d，J＝8.0Hz，2H)，7.87-7.91(m，2H)，7.98(d，J＝8.0Hz，2H)，8.68(d，J＝8.0Hz，2H)，8.74-8.76(m，2H)，8.80(s，2H).TOF-MS(ES+)calcd.for C39H28N4[M+1]+：553.3，found 553.8.
该产物的荧光寿命为3.15ns，测试方法同实施例2。
实施例8：式XI所示化合物的合成：
在氮气保护下，按实施例2中方法合成得到化合物XI，产品为白色固体，产率为84％，熔点为198-199℃。1H NMR(CDCl3，400MHz)：δppm 7.12-7.14(m，5H)，7.16-7.19(m，6H)，7.27-7.31(m，4H)，7.35-7.38(m，2H)，8.68(d，J＝8.0Hz，2H)，8.74-8.76(m，2H)，8.80(s，2H).TOF-MS(ES+)calcd.for C39H28N4[M+1]+：478.5，found 478.8.
该产物的荧光寿命为2.45ns，测试方法同实施例2。
虽然已经用优选实施例详述了本发明，然而其并非用于限定本发明。任何本领域的技术人员，在不脱离本发明的精神和范围的情况下，应当可以做出各种修改与变更。因此本发明的保护范围应当视为所附的权利要求书所限定的范围。

Claims (3)

1.一种含芳基取代的三联吡啶类化合物，其结构通式为：
其中R1选自：
其中R2为H，碳原子数1至12的烷基，碳原子数7至12的芳香基。
2.一种如权利要求1所述的含芳基取代的三联吡啶类化合物的合成方法，其特征是：2-溴苯基-2，2’：6’2”-三联吡啶(II)与芳基硼酸酯在经超声除气的甲苯∶水＝4∶1的混合溶剂体系中，四(三苯基膦)钯为催化剂，碳酸钾为碱，回流反应18-24h，得到目标化合物。
3.一种含芳基取代的三联吡啶类化合物作为发光材料的应用，可用作荧光材料和制作有机发光二极管中的发光层。
CN201410287370.8A 2014-06-23 2014-06-23 一种含芳基取代的三联吡啶类化合物及其制备方法和应用 Pending CN104030974A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410287370.8A CN104030974A (zh) 2014-06-23 2014-06-23 一种含芳基取代的三联吡啶类化合物及其制备方法和应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410287370.8A CN104030974A (zh) 2014-06-23 2014-06-23 一种含芳基取代的三联吡啶类化合物及其制备方法和应用

Publications (1)

Publication Number Publication Date
CN104030974A true CN104030974A (zh) 2014-09-10

Family

ID=51461997

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410287370.8A Pending CN104030974A (zh) 2014-06-23 2014-06-23 一种含芳基取代的三联吡啶类化合物及其制备方法和应用

Country Status (1)

Country Link
CN (1) CN104030974A (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019026619A (ja) * 2017-08-03 2019-02-21 国立大学法人山形大学 ターピリジン誘導体、及びそれを用いた有機電子素子
WO2019123190A1 (ja) * 2017-12-22 2019-06-27 株式会社半導体エネルギー研究所 発光素子、発光装置、電子機器、及び照明装置
CN112062752A (zh) * 2020-09-08 2020-12-11 吉林大学 一种有机荧光分子及其制备方法、荧光传感器及其应用、标准荧光卡片
CN113512000A (zh) * 2021-04-29 2021-10-19 河南阿尔法医药科技有限公司 一种规模化生产4’-溴-2,2’:6’,2”-三联吡啶的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100343668C (zh) * 2002-03-08 2007-10-17 松本和子 荧光标识化合物及其应用
US20130059392A1 (en) * 2011-09-06 2013-03-07 The Hong Kong University Of Science And Technology Aggregation-induced emission luminogens for metal ion detection

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100343668C (zh) * 2002-03-08 2007-10-17 松本和子 荧光标识化合物及其应用
US20130059392A1 (en) * 2011-09-06 2013-03-07 The Hong Kong University Of Science And Technology Aggregation-induced emission luminogens for metal ion detection

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
CONGBIN FAN ET. AL.: "Synthesis, photophysical and iron-sensing properties of terpyridyl-based triphenylamine derivatives", 《DYES AND PIGMENTS》 *
DIFENG WU ET. AL.: "Superaromatic terpyridines based on corannulene responsive to metal ions", 《DALTON TRANS》 *
SI-CHUN YUAN ET. AL.: "Rigid Linear and Star-Shaped π-Conjugated 2,2’:6’,2’’-Terpyridine Ligands with Blue Emission", 《ORG. LETT.》 *
YOUNG HOON LEE ET. AL.: "Synthesis, structure and luminescence properties of Cu(II), Zn(II) and Cd(II) complexes with 4′-terphenylterpyridine", 《DALTON TRANS.》 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019026619A (ja) * 2017-08-03 2019-02-21 国立大学法人山形大学 ターピリジン誘導体、及びそれを用いた有機電子素子
WO2019123190A1 (ja) * 2017-12-22 2019-06-27 株式会社半導体エネルギー研究所 発光素子、発光装置、電子機器、及び照明装置
JPWO2019123190A1 (ja) * 2017-12-22 2020-12-24 株式会社半導体エネルギー研究所 発光素子、発光装置、電子機器、及び照明装置
US11404656B2 (en) 2017-12-22 2022-08-02 Semiconductor Energy Laboratory Co., Ltd. Light-emitting device, light-emitting apparatus, electronic device, and lighting device
JP7304818B2 (ja) 2017-12-22 2023-07-07 株式会社半導体エネルギー研究所 発光素子、発光装置、電子機器、及び照明装置
JP7601956B2 (ja) 2017-12-22 2024-12-17 株式会社半導体エネルギー研究所 発光素子、発光装置、電子機器、及び照明装置
CN112062752A (zh) * 2020-09-08 2020-12-11 吉林大学 一种有机荧光分子及其制备方法、荧光传感器及其应用、标准荧光卡片
CN112062752B (zh) * 2020-09-08 2021-09-14 吉林大学 一种有机荧光分子及其制备方法、荧光传感器及其应用、标准荧光卡片
CN113512000A (zh) * 2021-04-29 2021-10-19 河南阿尔法医药科技有限公司 一种规模化生产4’-溴-2,2’:6’,2”-三联吡啶的方法

Similar Documents

Publication Publication Date Title
Dyker et al. Palladium‐Catalyzed Arylation of Cyclopentadienes
JP4908882B2 (ja) ベンゾビスアゾール骨格をもつ有機π電子系材料およびその製造方法
CN101967147B (zh) 均三氮杂蒄化合物及其合成方法和应用
KR20210148364A (ko) 아다만틸을 함유하는 트리페닐아민 유도체의 제조 방법
CN107935812B (zh) 钌催化烷基芳酮与二苯乙炔反应制备多芳取代萘衍生物的方法
CN104030974A (zh) 一种含芳基取代的三联吡啶类化合物及其制备方法和应用
CN114057775A (zh) 一种超级碱材料及其制备方法与有机发光二极管
CN104370930A (zh) 基于铑催化的c–h/c–h氧化偶联反应高效制备双(杂)芳环并吡喃酮/环戊酮衍生物的方法
CN110117237B (zh) 一种芳香腈或烯基腈类化合物的制备方法
CN103373892A (zh) 一种基于三蝶烯的三维纳米石墨烯及其制备方法
CN103113174B (zh) 一种酚类化合物的制备方法
CN107188906A (zh) 二苯并磷杂茂化合物及其合成方法和应用
KR102651502B1 (ko) 유기 붕소 화합물 및 그의 제조 방법
CN103242379B (zh) 2-二茂铁基-芳基喹啉及其制备方法
CN108864070B (zh) 一种含吡啶基团的吩噁嗪化合物及其制备方法
JP2012176928A (ja) ピレン誘導体、ピレン誘導体の製造方法、錯体、触媒、電子材料、発光材料および色素
KR101983796B1 (ko) 다이사이안스티릴 벤젠 유도체 및 이를 포함하는 형광재료
CN103435542B (zh) 2-联芳基-6-芳基喹啉及其制备方法
CN108997431B (zh) 对苯二甲醇衍生的双齿亚磷酸酯配体的合成方法及其应用
CN102516284B (zh) 含联三吡啶的取代噻咯类化合物及其制备和应用
CN104003827A (zh) 一种端炔的合成方法
CN115380017B (zh) 用于制备氘化化合物的方法
WO2022233178A1 (zh) 一种有机金属化合物及其应用
CN106366069A (zh) 一种n‑杂芳基咔唑类化合物的制备方法
KR20230096064A (ko) 나선형 디스피로디인데노피리딘 및 디스피로디인데노피리다진, 및 이의 제조 및 용도

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20140910