CN114671800B - 一种咔唑类衍生物及其制备方法与应用 - Google Patents

一种咔唑类衍生物及其制备方法与应用 Download PDF

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CN114671800B
CN114671800B CN202210389073.9A CN202210389073A CN114671800B CN 114671800 B CN114671800 B CN 114671800B CN 202210389073 A CN202210389073 A CN 202210389073A CN 114671800 B CN114671800 B CN 114671800B
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王辉
谢星冰
杜磊
赵大斌
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

本发明公开了一种咔唑类衍生物，结构通式如式I所示：其中，R表示‑L‑(A)n或‑CX1X2中的任意一种；L为单键、取代或未取代的C1～C30亚烷基、取代或未取代的C6～C30亚芳基、取代或未取代的3元～30元亚杂芳基和取代或未取代的C3～C30亚环烷基中的任意一种；A为取代或未取代的C6～C30芳基、取代或未取代的3元～30元杂芳基和‑NX3X4中的任意一种；n为整数1或者2。本发明咔唑衍生物用于有机电致发光器件等光电器件后，可降低光电器件的驱动电压、显著提高光电器件的发光效率以及延长光电器件的的使用寿命。

Description

一种咔唑类衍生物及其制备方法与应用
技术领域
本发明涉及有机发光材料技术领域，更具体的说是涉及一种咔唑类衍生物及其制备方法与应用。
背景技术
有机电致发光技术作为最新一代显示技术，由其制备的光电器件由于有着功耗低、响应速度快、宽视角、高分辨率、宽温度特性、质量轻以及可卷曲等特点而逐渐被大众认可，有机电致发光显示技术与传统的LCD显示方式不同，无需背光灯，采用非常薄的有机材料涂层和玻璃基板，当有电流通过时，这些有机材料就会发光。近些年国际各大企业都在不断加强对OLED技术的研究，OLED技术得到了进一步的完善。
目前，有机发光器件的材料主要存在寿命短的技术问题，而且发光效率和功率效率低以及驱动电压高，造成该类材料的使用成本增加，后期的使用对于市场的发展存在很大的障碍。
因此，如何提供一种寿命长效率高的咔唑类衍生物是本领域技术人员亟需解决的问题。
发明内容
有鉴于此，本发明提供了一种咔唑类衍生物及其制备方法与应用，本发明咔唑衍生物用于有机电致发光器件等光电器件后，可降低光电器件的驱动电压、显著提高光电器件的发光效率以及延长光电器件的的使用寿命。另外，本发明提供的咔唑衍生物制备方法，具有合成步骤简单、易提纯，且目标产物收率高的特点，适于推广与应用。
为了达到上述目的，本发明采用如下技术方案：
一种咔唑类衍生物，所述咔唑类衍生物的结构通式如式I所示：
其中，R表示-L-(A)n或-CX1X2中的任意一种；
L为单键、取代或未取代的C1～C30亚烷基、取代或未取代的C6～C30亚芳基、取代或未取代的3元～30元亚杂芳基和取代或未取代的C3～C30亚环烷基中的任意一种；
A为取代或未取代的C6～C30芳基、取代或未取代的3元～30元杂芳基和-NX3X4中的任意一种；
n为整数1或者2；当n是2时，每个A可以相同或不同；
X1-X4为氢、氘、卤素、氰基、取代或未取代的C1～C30烷基、取代或未取代的C6～C30的稠环、取代或未取代的C6～C30芳基、取代或未取代的3元～30元杂芳基、取代或未取代的C3～C30环烷基中的任意一种，或与相邻取代基连接形成一个或多个环。
优选的，所述取代或未取代的C3～C30环烷基为单环烷基、多环烷基和螺烷基中的任意一种，且所述取代的C3～C30环烷基上的碳原子被至少一个杂原子取代；所述杂原子为N、O、S、Si、S和Ge中的至少一种。
优选的，所述C6～C30芳基为单环基团或多环基团；
其中，所述多环基团具有两个碳为两个邻接环共用的多个环，至少一个环是芳香族环，其它环为环烷基、环烯基、芳基和杂芳基中的至少一种。
优选的，所述芳基为单环芳基和多环芳基；
其中，所述多环芳基具有两个以上的环，其中两个碳为两个邻接环共用，所述环至少一个是芳基，其它环选自环烷基、环烯基、芳基和杂芳基中的至少一种；
所述杂芳基为呋喃、噻吩、吡啶和三嗪中的任意一种。
优选的，所述C1～C30烷基为甲基、乙基、丙基、异丙基、丁基、异丁基和叔丁基中的任意一种；
所述环烷基为单环、多环和螺烷基中的任意一种；所述环烷基优选为C3～C30的环烷基，更具体地包括环丙基、环戊基、环己基和金刚烷胺基中的任意一种；
所述杂环烷基为至少含有一个杂原子的环烷基；所述杂环烷基优选为含有包括至少一个所述杂原子的3到7个环原子的杂环烷基，并且包括环胺；更具体地包括吗啉基、哌啶基、吡咯烷基、四氢呋喃和四氢吡喃中的任意一种，所述杂原子选自N、O、S、P、B、Si、Se和Ge中的至少一种；所述杂原子优选为N、O、S中的至少一种；
所述C6～C30芳基为苯、联苯、三联苯、萘、蒽、菲和芘中的任意一种。
需要说明的是，上述的“取代”是指与化合物的碳原子键合的氢原子变成另外的取代基，并且取代的位置没有限制，只要该位置为氢原子被取代的位置即可，即取代基可以取代的位置，并且当两个或更多个取代基取代时，两个或更多个取代基可以彼此相同或不同。
优选的，所述咔唑类衍生物结构式为式F001～F087所示：
一种上述所述咔唑类衍生物的制备方法，合成路径为：
其中，R如上述所述式I中所定义一致；
制备方法包括如下步骤：
在氮气或者氩气保护下，在化合物A和化合物B中加入溶剂和催化剂后在90～140℃反应20～30h，然后依次进行冷却、沉淀、抽滤、洗涤、烘干、层析和浓缩后即得一种咔唑类衍生物。
优选的，所述化合物A与所述化合物B的摩尔比为1:(1.05～1.3)；优选为1:1.1；
所述溶剂为DMSO，所述化合物A与所述溶剂的摩尔体积比为4.3mmol:20～30mL；
所述催化剂为4-二甲氨基吡啶，所述催化剂与所述化合物A的摩尔比为(0.01～0.1):1，优选为0.05:1。
优选的，所述干燥的温度为70～80℃。
优选的，所述柱层析以二氯甲烷和石油醚按照一定比例(1～15均可)混合作为溶剂，采用硅胶柱层析。
优选的，所述R表示以下结构式所示基团中的任一种：
上述为基团连接位置。
上述所述一种咔唑类衍生物的应用，其特征在于，上述所述的咔唑类衍生物或者上述所述制备方法得到的所述咔唑类衍生物在制备有机电致发光器件中的应用。
上述所述一种有机电致发光器件，包括：第一电极、有机物层、第二电极；其特征在于，所述有机物层包含上述所述的咔唑类衍生物或者上述所述制备方法得到的所述咔唑类衍生物。
上述所述一种咔唑类衍生物用于制备有机电致发光器件的应用。
优选的，所述有机物层包括发光层；所述发光层包括所述咔唑衍生物和掺杂材料，掺杂材料采用在欧洲专利申请07102949.0的化合物作为发光层中的掺杂剂；
需要说明的是，有机物层还可包括空穴注入层、空穴传输层、空穴注入和空穴传输技能层的复合层、电子阻挡层、空穴阻挡层、电子传输层、电子注入层、电子传输层和电子注入技能层的复合层中的至少一层，且其中的至少一层可包含或不包含上述咔唑衍生物化合物，但不限于此。
另外，掺杂可以选择其他类型的有机化合物，并不只限于上述掺杂化合物。
优选的，所述有机咔唑衍生物与掺杂材料的质量比为(90～99.5):(0.5～10)。
经由上述的技术方案可知，与现有技术相比，本发明的有益效果如下：本发明提供了一种咔唑衍生物，将该咔唑衍生物用于有机电致发光器件等光电器件后，可降低光电器件的驱动电压、显著提高光电器件的发光效率以及延长光电器件的的使用寿命；另外，本发明提供的咔唑衍生物制备方法，具有合成步骤简单、易提纯，且目标产物收率高的特点，适于推广与应用。
具体实施方式
下面将对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
制备化合物F001，其合成路线如下：
具体的制备方法包括以下步骤：
(1)在氮气保护体系下，按摩尔比1：4称取化合物S1与氟化铯，将丁二腈与1，2-二甲氧基乙烷按体积比1：1加入到体系中，加热至60℃，滴加化合物S2(S2与S1的摩尔比为4：1)，60℃反应24h；减压蒸馏出去溶液，粗品依次用正庚烷萃取3次，水萃取2次，乙醚萃取2次得到化合物S3；
在氮气保护体系下，将化合物S3(15mmol)加入烧瓶中，加入48mL亚磷酸三乙酯和48mL 1,2-二氯苯溶解，回流反应3h；反应结束后，减压蒸馏除去溶液，用乙酸乙酯萃取，有机相用无水硫酸镁干燥；旋干溶液，粗品通过柱色谱法纯化，得到化合物A001；
(2)在氮气保护体系下，称取化合物A001(29.46mmol，10g)，B001(32.41mol，7.8g)，碳酸铯(88.39mol，28.8g)放入反应体系中，接着往反应体系中加入300mL二甲基亚砜，4-二甲氨基吡啶(1.47mmol，0.18g)使反应体系在氮气保护下90℃反应24小时，反应停止后体系冷却至室温，有沉淀析出，将沉淀抽滤，用无水乙醇冲洗烘干，得到固体粉末，用二氯甲烷做溶剂，用硅胶柱层析，滤液浓缩固体析出，得到咔唑衍生物F001(12.2g，产率：76.17％)。
HPLC纯度：大于99％；
质谱：计算值为543.17，测试值为543.63；
元素分析：
计算值C：88.38％；H：3.89％；N：7.73％；
测试值C：88.36％；H：3.90％；N：7.74％。
实施例2
制备化合物F005，其合成如下：
A005的制备如上述实施例1中A001的制备方法；
F005具体的制备方法包括以下步骤：
在氮气保护体系下，称取化合物A005(29.46mmol，10g)，B005(32.41mol，12.34g)，碳酸铯(88.39mol，28.8g)放入反应体系中，接着往反应体系中加入300mL二甲基亚砜，4-二甲氨基吡啶(1.47mmol，0.18g)使反应体系在氮气保护下90℃反应24小时，反应停止后体系冷却至室温，有沉淀析出，将沉淀抽滤，用无水乙醇冲洗烘干，得到固体粉末，用二氯甲烷做溶剂，用硅胶柱层析，滤液浓缩固体析出，得到咔唑衍生物F005(15.1g，产率：74.95％)；
HPLC纯度：大于99％；
质谱：计算值为683.2，测试值为683.77；
元素分析：
计算值C：87.83％；H：3.69％；N：6.15％；O：2.34％；
测试值C：87.84％；H：3.70％；N：6.13％；O：2.34％。
实施例3
制备化合物F011，其合成路线如下：
A011的制备如上述实施例1中A001的制备方法；
F011具体的制备方法包括以下步骤：
在氮气保护体系下，称取化合物A011(29.46mmol，10g)，B011(32.41mol，9.10g)，碳酸铯(88.39mol，28.8g)放入反应体系中，接着往反应体系中加入300mL二甲基亚砜，4-二甲氨基吡啶(1.47mmol，0.18g)使反应体系在氮气保护下90℃反应24小时，反应停止后体系冷却至室温，有沉淀析出，将沉淀抽滤，用无水乙醇冲洗烘干，得到固体粉末，用二氯甲烷做溶剂，用硅胶柱层析，滤液浓缩固体析出，得到咔唑衍生物F011(12.1g，产率：70.36％)；
HPLC纯度：大于99％；
质谱：计算值为583.17，测试值为583.65；
元素分析：
计算值C：86.43％；H：3.63％；N：7.20％；O：2.74％；
测试值C：86.41％；H：3.64％；N：7.20％；O：2.75％。
实施例4
制备化合物F013，其合成路线如下：
A013的制备如上述实施例1中A001的制备方法；
F013具体的制备方法包括以下步骤：
在氮气保护体系下，称取化合物A013(29.46mmol，10g)，B013(32.41mol，8.68g)，碳酸铯(88.39mol，28.8g)放入反应体系中，接着往反应体系中加入300mL二甲基亚砜，4-二甲氨基吡啶(1.47mmol，0.18g)使反应体系在氮气保护下90℃反应24小时，反应停止后体系冷却至室温，有沉淀析出，将沉淀抽滤，用无水乙醇冲洗烘干，得到固体粉末，用二氯甲烷做溶剂，用硅胶柱层析，滤液浓缩固体析出，得到咔唑衍生物F013(12.7g，产率：75.53％)；
HPLC纯度：大于99％；
质谱：计算值为570.18，测试值为570.66；
元素分析：
计算值C：86.30％；H：3.89％；N：9.82％；
测试值C：86.32％；H：3.88％；N：9.81％。
实施例5
制备化合物F014，其具体步骤如下：
A014的制备如上述实施例1中A001的制备方法；
F014具体的制备方法包括以下步骤：
在氮气保护体系下，称取化合物A014(29.46mmol，10g)，B014(32.41mol，9g)，碳酸铯(88.39mol，28.8g)放入反应体系中，接着往反应体系中加入300mL二甲基亚砜，4-二甲氨基吡啶(1.47mmol，0.18g)使反应体系在氮气保护下90℃反应24小时，反应停止后体系冷却至室温，有沉淀析出，将沉淀抽滤，用无水乙醇冲洗烘干，得到固体粉末，用二氯甲烷做溶剂，用硅胶柱层析，滤液浓缩固体析出，得到咔唑衍生物F014(13.4g，产率：78.32％)；
HPLC纯度：大于99％；
HPLC纯度：大于99％；
质谱：计算值为580.25，测试值为580.72；
元素分析：
计算值C：84.80％；H：5.55％；N：9.65％；
测试值C：84.81％；H：5.56％；N：9.64％。
实施例6
制备化合物F019，其具体步骤如下：
A019的制备如上述实施例1中A001的制备方法；
F014具体的制备方法包括以下步骤：
在氮气保护体系下，称取化合物A019(29.46mmol，10g)，B019(32.41mol，13.61g)，碳酸铯(88.39mol，28.8g)放入反应体系中，接着往反应体系中加入300mL二甲基亚砜，4-二甲氨基吡啶(1.47mmol，0.18g)使反应体系在氮气保护下90℃反应24小时，反应停止后体系冷却至室温，有沉淀析出，将沉淀抽滤，用无水乙醇冲洗烘干，得到固体粉末，用二氯甲烷做溶剂，用硅胶柱层析，滤液浓缩固体析出，得到咔唑衍生物F019(15.3g，产率：71.84％)；
HPLC纯度：大于99％；
质谱：计算值为722.25，测试值为722.85；
元素分析：
计算值C：88.07％；H：4.18％；N：7.75％；
测试值C：88.05％；H：4.19％；N：7.76％。
实施例7-23
按照实施例1中的合成方法，仅将相应反应物替换，可以合成实施例7-23的目标化合物，其FD-MS(即质谱)的结果如表1所示，
表1实施例7-23的目标化合物的FD-MS的结果
此外，为了进一步说明本发明公开制备的咔唑类衍生物在电致发光器件中的应用效果，还进行了下述测试实验，具体如下：
有机电致发光器件包括：第一电极、第二电极和置于所述两电极之间的一个或者更多个有机物层，其中，所述有机物层的一个或更多个层包含有本发明化学式1所示的化合物；本发明化学式1所示化合物可以是单一形态或与其它物质混合存在于有机物层中；
有机物层至少包括空穴注入层、空穴传输层、既具备空穴注入又具备空穴传输技能层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层和既具备电子传输又具备电子注入技能层中的一种或几种。
器件实施例1
利用发光化合物制备有机电致发光器件(OLED)，所制备OLED器件的结构为：
ITO阳极/HIL/HTL/EML/HBL/ETL/EIL/阴极
具体步骤为：
a、ITO阳极：将涂层厚度为的ITO(氧化铟锡)玻璃基板在蒸馏水中清洗2次，超声波洗涤30min，再用蒸馏水反复清洗2次，超声波洗涤10min，洗涤结束后，用甲醇、丙酮、异丙醇依次超声波洗涤(每次洗涤5min)，干燥，然后转移至等离子体清洗机内洗涤5min，再送至蒸镀机中，以该基板为阳极，在其上依次蒸镀其它功能层；
b、HIL(空穴注入层)：真空蒸镀2-TNATA(即N1-(2-萘基)-N4，N4-二(4-(2-萘基(苯基)氨基)苯基)-N1-苯基苯-1，4-二胺)形成空穴注入层；
c、HTL(空穴传输层)：真空蒸镀NPB(即N，N'-二苯基-N，N'-(1-萘基)-1，1'-联苯-4，4'-二胺)形成空穴传输层；
d、EML(发光层)：主体材料采用F001，掺杂材料采用如下所示E，作为发光层中的掺杂剂，以重量比90:10混合蒸镀形成发光层；
e、HBL(空穴阻挡层)：真空蒸镀BAlq形成空穴阻挡层；
f、ETL(电子传输层)：真空蒸镀Alq3形成电子传输层；
g、EIL(电子注入层)：真空蒸镀LiF形成电子注入层；
h、阴极：蒸镀Al形成阴极，得到OLED器件；
器件实施例2-23
参照上述方法，将F001分别替换为F005、F009、F011、F013、F014、F017、F019、F023、F027、F029、F031、F032、F037、F039、F042、F043、F045、F050、F058、F062、F073、F083，制备得到相应化合物的有机电致发光器件。
对比例
参照上述方法，将F001替换为RH，具体结构式如下：
对器件实施例1-23和对比例中得到的OLED器件进行发光性能检测，采用KEITHLEY2400型测量单元，CS-2000分光辐射亮度计，测试驱动电压、发光寿命及发光效率，测试结果参见表2。
表2器件实施例1-23和对比例中有机电致发光器件检测结果
由表2可以看出，在发光亮度均为5000cd/cm2，与对比例相比，本发明提供的器件的驱动电压明显小于对比例的驱动电压，而效率及寿命远高于对比例。由此可知，使用本发明提供的化合物作为发光层材料所制备的有机电致发光器件与使用比较化合物RH作为发光层材料所制备的有机电致发光器件相比，驱动电明显降低，发光效率以及寿命得到显著提高。
本说明书中各个实施例采用递进的方式描述，每个实施例重点说明的都是与其他实施例的不同之处，各个实施例之间相同相似部分互相参见即可。对于实施例公开的装置而言，由于其与实施例公开的方法相对应，所以描述的比较简单，相关之处参见方法部分说明即可。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (3)

1.一种咔唑类衍生物，其特征在于，所述咔唑类衍生物结构式为式F001～F087所示：
2.一种咔唑类衍生物的应用，其特征在于，权利要求1所述的咔唑类衍生物在制备有机电致发光器件中的应用。
3.一种有机电致发光器件，包括：第一电极、有机物层、第二电极；其特征在于，所述有机物层包含权利要求1所述的咔唑类衍生物。
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