WO2022110381A1 - 氧杂环型化合物及其应用和使用其的电子器件 - Google Patents

氧杂环型化合物及其应用和使用其的电子器件 Download PDF

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WO2022110381A1
WO2022110381A1 PCT/CN2020/137385 CN2020137385W WO2022110381A1 WO 2022110381 A1 WO2022110381 A1 WO 2022110381A1 CN 2020137385 W CN2020137385 W CN 2020137385W WO 2022110381 A1 WO2022110381 A1 WO 2022110381A1
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heterocyclic compound
oxygen heterocyclic
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compound
oxygen
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白科研
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Definitions

  • the present application relates to the technical field of organic optoelectronic materials, and more particularly, the present application relates to an oxygen heterocyclic compound and its application and electronic devices using the same.
  • Organic electronic devices refer to devices composed of an anode, a cathode and an organic layer sandwiched between the anode and the cathode, including organic light-emitting diodes, organic solar cells, organic semiconductors, organic crystals, and the like. Its working principle is to apply an external voltage on the electrode, inject holes and electrons into the organic layer to form excitons, thereby radiating light, such as organic light-emitting diodes; or external light sources are absorbed by organic materials to form excitons, and excitons are separated into empty spaces. Holes and electrons are transferred to electrodes for storage, such as organic solar cells.
  • the organic light emitting diode is mainly described below.
  • An organic light-emitting diode is a device that converts electrical energy into light energy, and its structure usually includes an anode, a cathode, and one or more layers of organic materials interposed therebetween.
  • the organic material layer is classified into a hole injection material layer, a hole transport material layer, an electron injection material layer, an electron transport material layer and a light emitting material layer according to functions.
  • luminescent materials are further classified into luminescent materials such as blue, sky blue, green, yellow, red, and deep red according to the luminescent color.
  • the evaluation indicators of organic light-emitting diodes are mainly voltage, efficiency and life. How to develop low-voltage, high-efficiency and long-life organic light-emitting diode devices has always been the goal pursued by the R&D and commercial circles, which requires high mobility of electrons/holes Injecting and transporting materials, high-efficiency light-emitting materials and an effective balance of electrons and holes in the device are also required.
  • the type of vapor deposition sublimation type or fusion type
  • decomposition temperature, glass transition temperature, outgassing phenomenon, etc. of the material must also be considered.
  • thicker hole transport materials need to be evaporated. The sublimation material in this material will seriously affect the uniformity of mass production film thickness, so the development of molten hole transport materials has also become an important direction.
  • the embodiments of the present application innovatively provide an oxygen heterocyclic compound, its application, and an electronic device using the same.
  • the organic material includes an aromatic amine and an oxygen heterocyclic ring, and the aromatic amine can effectively improve the hole injection and transport properties of the organic material.
  • Oxygen heterocycles are favorable for the formation of molten-type evaporation materials.
  • the embodiments of the present application disclose an oxygen heterocyclic compound.
  • the general structural formula of the oxygen heterocyclic compound is shown in the following formula 1:
  • Ar 1 and Ar 2 are independently selected from single or multiple substituted or unsubstituted aryl groups, or substituted or unsubstituted heteroaryl groups, or Ar 1 and Ar 2 are adjacent aryl groups or heteroaryl groups When the base is connected to each other to form a monocyclic or fused ring of an aromatic ring or a heterocyclic ring, wherein, the heteroatom of the heteroaryl group is O, N, F, S or Si;
  • Ar 3 and Ar 4 are independently selected from the number of carbon atoms Alkyl with 1-22 carbons, alkoxy with 1-22 carbons, heteroalkyl with 1-22 carbons, single or multiple substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl base, or when Ar 3 and Ar 4 are adjacent aryl groups or heteroaryl groups, they are connected to each other to form a monocyclic or fused ring of an aromatic ring or a heterocyclic ring, wherein the heteroatom of the heteroalky
  • Ar 1 and Ar 2 are independently represented by any one of Formula 301 to Formula 332:
  • Ar 3 and Ar 4 are independently represented by any one of Formula 301-Formula 332 and Formula 401-403:
  • the structure of the oxygen heterocyclic compound is represented by any one of the following general formulas 501-508:
  • the structure of the oxygen heterocyclic compound is represented by any one of the following general formulas 601-617:
  • the structure of the oxygen heterocyclic compound is represented by any one of the following general formulas 701-722:
  • the structure of the oxygen heterocyclic compound is represented by any one of the following general formulas 801 to 819:
  • the embodiments of the present application disclose the application of the above-mentioned oxygen heterocyclic compound as an electroluminescent organic material in an electronic device.
  • the embodiment of the present application discloses an electronic device.
  • the electronic device includes a substrate, an anode, a cathode, and one or more organic material layers disposed between the anode and the cathode, at least one of the one or more organic material layers comprising the above-mentioned oxygen heterocyclic type compound.
  • the oxygen heterocyclic compound comprises an aromatic amine and an oxygen heterocycle, and the aromatic amine can effectively improve the hole injection and transport properties of organic materials, Thus, the balance of electrons and holes in the organic light-emitting diode is improved, and lower voltage and higher efficiency are achieved; while the oxygen heterocycle is beneficial to the formation of a molten type evaporation material, which is beneficial to the stability of mass production evaporation.
  • This kind of material can realize the preparation of high-efficiency electroluminescent devices, which can be used in the manufacture of display devices.
  • Ar 1 and Ar 2 are independently selected from single or multiple substituted or unsubstituted aryl groups, or substituted or unsubstituted heteroaryl groups, or Ar 1 and Ar 2 are adjacent aryl groups or heteroaryl groups.
  • the heteroatom of the heteroaryl group is O, N, F, S or Si
  • Ar 3 and Ar 4 are independently selected from C1-C22 Alkyl, C1-C22 alkoxy, C1-C22 heteroalkyl, single or multiple substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, or Ar 3 and Ar 4 are in phase
  • the heteroatom of the heteroalkyl group is O, N, F, S or Si.
  • Ar 1 and Ar 2 can be independently represented by any one of the following formulas 301-332:
  • Ar 3 and Ar 4 can be independently represented by any one of the above formulas 301-332 and the following formulas 401-403:
  • the structure of the oxygen heterocyclic compound can be represented by any one of the following general formulas 501-508:
  • the structure of the oxygen heterocyclic compound can be represented by any one of the following general formulas 601-617:
  • the structure of the oxygen heterocyclic compound can be represented by any one of the following general formulas 701-722:
  • the structure of the oxygen heterocyclic compound can be represented by any one of the following general formulas 801 to 819:
  • Another embodiment of the embodiments of the present application provides the application of the above-mentioned oxygen heterocyclic compounds as electroluminescent organic materials in electronic devices.
  • an electronic device including a substrate, an anode, a cathode, and one or more organic material layers disposed between the anode and the cathode, at least one of the one or more organic material layers Oxygen heterocyclic compounds of the above examples are included.
  • the organic material layer may include a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer and a light-emitting layer.
  • the electronic device may be an electroluminescent device, such as an organic light emitting diode device.
  • the preparation method of the oxygen heterocyclic compound of target structure 1 provided by embodiment 1 is as follows:
  • the obtained intermediate compound (3) was added to 100 mL of acetonitrile, 2 mmol of boron tribromide was added, stirred for 12 h, dissolved in dichloromethane (300 mL) and added with saturated NH 4 Cl (200 mL) solution, extracted with dichloromethane, organic The phase was dried over anhydrous sodium sulfate, concentrated and then subjected to column separation. Using 200-300 mesh silica gel as the stationary phase and dichloromethane as the eluent, 1.3 mmol of the target structure 1 was obtained with a yield of 77%.
  • Matrix-assisted laser desorption ionization time-of-flight mass spectrometer MALDI-TOF: calculated m/z, 501.63; found m/z, 501.42. Elemental Analysis (EA): Calculated Carbon C, 88.59; Hydrogen H, 5.43; Nitrogen N, 2.79; Found C, 88.25; H, 5.51; N, 2.83.
  • the step of producing the product of the previous step—the compound (2) in Example 2 can be similar to the step of producing the product of the previous step—the compound (2) in Example 1.
  • the oxygen heterocyclic compound of the target structure 2 provided in Example 2 has The preparation method is as follows:
  • the obtained intermediate compound (5) was added to 100 mL of acetonitrile, 2.5 mmol of boron tribromide was added, stirred for 12 h, dissolved in dichloromethane (300 mL) and added with saturated NH 4 Cl (200 mL) solution, extracted with dichloromethane, The organic phase was dried over anhydrous sodium sulfate, concentrated and then subjected to column separation. Using 200-300 mesh silica gel as the stationary phase and dichloromethane as the eluent, 1.6 mmol of the target structure 2 was obtained with a yield of 81%.
  • Matrix-assisted laser desorption ionization time-of-flight mass spectrometer MALDI-TOF: calculated m/z, 668.84; found m/z, 668.24. Elemental Analysis (EA): Calculated Carbon C, 87.99; Hydrogen H, 5.43; Nitrogen N, 4.19; Found C, 87.84; H, 5.26; N, 4.01.
  • the step of producing the product of the previous step—the compound (2) in Example 3 can be similar to the step of producing the product of the previous step—the compound (2) in Example 1.
  • the oxygen heterocyclic compound of the target structure 3 provided in Example 3 has The preparation method is as follows:
  • the obtained intermediate compound (7) was added to 100 mL of acetonitrile, 2.5 mmol of boron tribromide was added, stirred for 12 h, dissolved in dichloromethane (300 mL) and added with saturated NH 4 Cl (200 mL) solution, extracted with dichloromethane, The organic phase was dried over anhydrous sodium sulfate, concentrated and then subjected to column separation. Using 200-300 mesh silica gel as the stationary phase and dichloromethane as the eluent, 1.7 mmol of the target structure 3 was obtained with a yield of 85%.
  • Matrix-assisted laser desorption ionization time-of-flight mass spectrometer MALDI-TOF: calculated m/z, 784.35; found m/z, 784.12. Elemental Analysis (EA): Calculated Carbon C, 88.74; Hydrogen H, 5.65; Nitrogen N, 3.57; Found C, 88.56; H, 5.37; N, 3.89.
  • the step of producing the product of the previous step—the compound (2) in Example 4 can be similar to the step of producing the product of the previous step—the compound (2) in Example 1.
  • the oxygen heterocyclic compound of the target structure 4 provided in Example 4 has a similar
  • the preparation method is as follows:
  • the obtained intermediate compound (9) was added to 100 mL of acetonitrile, 2.5 mmol of boron tribromide was added, stirred for 12 h, dissolved in dichloromethane (300 mL) and added with saturated NH4Cl (200 mL) solution, extracted with dichloromethane, the organic phase was After drying over anhydrous sodium sulfate, column separation was carried out after concentration. Using 200-300 mesh silica gel as the stationary phase and dichloromethane as the eluent, 1.7 mmol of the target structure 4 was obtained with a yield of 85%.
  • Matrix-assisted laser desorption ionization time-of-flight mass spectrometer MALDI-TOF: calculated m/z, 784.35; found m/z, 784.12. Elemental Analysis (EA): Calculated Carbon C, 88.74; Hydrogen H, 5.65; Nitrogen N, 3.57; Found C, 88.56; H, 5.37; N, 3.89.
  • the step of producing the product of the previous step—the compound (2) in Example 5 can be similar to the step of producing the product of the previous step—the compound (2) in Example 1.
  • the oxygen heterocyclic compound of the target structure 5 provided in Example 5 has The preparation method is as follows:
  • the obtained intermediate compound (11) was added to 100 mL of acetonitrile, 2.5 mmol of boron tribromide was added, stirred for 12 h, dissolved in dichloromethane (300 mL) and added with saturated NH 4 Cl (200 mL) solution, extracted with dichloromethane, The organic phase was dried over anhydrous sodium sulfate, concentrated and then subjected to column separation. Using 200-300 mesh silica gel as the stationary phase and dichloromethane as the eluent, 1.4 mmol of the target structure 5 was obtained with a yield of 80%.
  • Matrix-assisted laser desorption ionization time-of-flight mass spectrometer MALDI-TOF: calculated m/z, 667.27; found m/z, 667.31. Elemental Analysis (EA): Calculated Carbon C, 88.26; Hydrogen H, 5.14; Nitrogen N, 4.20; Found C, 88.31; H, 5.21; N, 4.19.
  • the step of producing the product of the previous step—the compound (2) in Example 6 can be similar to the step of producing the product of the previous step—the compound (2) in Example 1.
  • the oxygen heterocyclic compound of the target structure 6 provided in Example 6 has a similar
  • the preparation method is as follows:
  • the obtained intermediate compound (13) was added to 100 mL of acetonitrile, 2.5 mmol of boron tribromide was added, stirred for 12 h, dissolved in dichloromethane (300 mL) and added with saturated NH4Cl (200 mL) solution, extracted with dichloromethane, the organic phase was After drying over anhydrous sodium sulfate, column separation was carried out after concentration. Using 200-300 mesh silica gel as the stationary phase and dichloromethane as the eluent, 1.6 mmol of the target structure 6 was obtained in a yield of 74%.
  • Matrix-assisted laser desorption ionization time-of-flight mass spectrometer MALDI-TOF: calculated m/z, 744.31; found m/z, 744.31. Elemental Analysis (EA): Calculated for Carbon C, 88.68; Hydrogen H, 5.41; Nitrogen N, 3.76; Found C, 88.52; H, 5.29; N, 3.87.
  • the step of producing the product of the previous step—the compound (2) in Example 7 can be similar to the step of producing the product of the previous step—the compound (2) in Example 1.
  • the oxygen heterocyclic compound of the target structure 7 provided in Example 7 has The preparation method is as follows:
  • the obtained intermediate compound (15) was added to 100 mL of acetonitrile, 2.5 mmol of boron tribromide was added, stirred for 12 h, dissolved in dichloromethane (300 mL) and added with saturated NH4Cl (200 mL) solution, extracted with dichloromethane, the organic phase was After drying over anhydrous sodium sulfate, column separation was carried out after concentration. Using 200-300 mesh silica gel as the stationary phase and dichloromethane as the eluent, 1.5 mmol of the target structure 7 was obtained in a yield of 65%.
  • Matrix-assisted laser desorption ionization time-of-flight mass spectrometer MALDI-TOF: calculated m/z, 784.35; found m/z, 784.13. Elemental Analysis (EA): Calculated for Carbon C, 88.74; Hydrogen H, 5.65; Nitrogen N, 3.57; Found C, 88.69; H, 5.37; N, 3.48.
  • the step of producing the product of the previous step—the compound (2) in Example 8 can be similar to the step of producing the product of the previous step—the compound (2) in Example 1.
  • the oxygen heterocyclic compound of the target structure 8 provided in Example 8 has The preparation method is as follows:
  • the obtained intermediate compound (17) was added to 100 mL of acetonitrile, 2.5 mmol of boron tribromide was added, stirred for 12 h, dissolved in dichloromethane (300 mL) and added with saturated NH 4 Cl (200 mL) solution, extracted with dichloromethane, The organic phase was dried over anhydrous sodium sulfate, concentrated and then subjected to column separation. Using 200-300 mesh silica gel as the stationary phase and dichloromethane as the eluent, 1.5 mmol of the target structure 7 was obtained with a yield of 65%.
  • Matrix-assisted laser desorption ionization time-of-flight mass spectrometer MALDI-TOF: calculated m/z, 733.96; found m/z, 733.79. Elemental Analysis (EA): Calculated Carbon C, 90.01; Hydrogen H, 5.91; Nitrogen N, 1.91; Found C, 89.87; H, 6.05; N, 1.88.
  • Target structure 9 is shown in formula 17, and its synthetic route refers to target structure 1. Yield 65%.
  • Matrix-assisted laser desorption ionization time-of-flight mass spectrometer MALDI-TOF: calculated m/z, 577.73; found m/z, 577.35.
  • Elemental Analysis EA: Calculated Carbon C, 89.40; Hydrogen H, 5.41; Nitrogen N, 2.42; Found C, 89.24; H, 5.32; N, 2.59.
  • the target structure 10 is shown in formula 18, and its synthetic route refers to the target structure 1. Yield 71%.
  • Matrix-assisted laser desorption ionization time-of-flight mass spectrometer MALDI-TOF: calculated m/z, 617.79; found m/z, 617.54.
  • Elemental Analysis EA: Calculated Carbon C, 89.43; Hydrogen H, 5.71; Nitrogen N, 2.27; Found C, 89.21; H, 5.85; N, 2.19.
  • the target structure 11 is shown in formula 19, and its synthetic route refers to the target structure 1. Yield 74%.
  • Matrix-assisted laser desorption ionization time-of-flight mass spectrometer MALDI-TOF: calculated m/z, 693.89; found m/z, 693.77.
  • Elemental Analysis EA: Calculated Carbon C, 89.43; Hydrogen H, 5.71; Nitrogen N, 2.27; Found C, 89.21; H, 5.85; N, 2.19.
  • the electronic device is fabricated according to methods known in the art.
  • the device structure may specifically include an ITO layer, a HAT-CN layer (for example, a thickness of 5 nm), and any of the above-mentioned layers.
  • an organic material layer of an oxygen heterocyclic compound of a target structure eg, a thickness of 30 nm
  • a Firpic:B3PyPB layer 12%, 10 nm
  • a TPBi layer eg, a thickness of 40 nm
  • LiF layer eg, a thickness of 2 nm
  • Aluminum Al layer eg thickness 100nm.
  • the oxygen heterocyclic compound comprises an aromatic amine and an oxygen heterocycle, and the aromatic amine can effectively improve the hole injection and transport properties of organic materials, Thus, the balance of electrons and holes in the organic light-emitting diode is improved, and lower voltage and higher efficiency are achieved; while the oxygen heterocycle is beneficial to the formation of a molten type evaporation material, which is beneficial to the stability of mass production evaporation.
  • This kind of material can realize the preparation of high-efficiency electroluminescent devices, which can be used in the manufacture of display devices.

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Abstract

一种氧杂环型化合物及其应用和使用其的电子器件。氧杂环型化合物包含芳胺和氧杂环，芳胺能有效提高有机材料的空穴注入和传输性能；氧杂环有利于形成熔融型蒸镀材料。氧杂环型化合物的结构通式如式1所示。

Description

氧杂环型化合物及其应用和使用其的电子器件 技术领域
本申请涉及有机光电材料技术领域，更为具体来说，本申请涉及一种氧杂环型化合物及其应用和使用其的电子器件。
背景技术
有机电子器件是指由阳极、阴极及夹在阳极和阴极之间的有机层构成的器件，包括有机发光二极管、有机太阳能电池、有机半导体、有机晶体等。其工作原理为在电极上施加外加电压，将空穴和电子注入有机层中形成激子，从而辐射发光，比如有机发光二极管；或外部光源被有机材料吸收形成激子，而激子分离成空穴、电子被传递至电极而储存，比如有机太阳能电池。以下主要描述有机发光二极管。
有机发光二极管是将电能转化为光能的器件，其结构通常包括阳极、阴极及置于其之间的一层或多层有机材料层。有机材料层根据功能分为空穴注入材料层、空穴传输材料层、电子注入材料层、电子传输材料层和发光材料层。此外，发光材料根据发光颜色又分为蓝色、天蓝色、绿色、黄色、红色和深红色等发光材料。
有机发光二极管的评价指标主要为电压、效率和寿命，如何开发低电压、高效率和长寿命的有机发光二极管器件一直是研发界和商业界追求的目标，这需要高迁移率的电子/空穴注入和传输材料，还需要高效率的发光材料以及器件中电子和空穴的有效平衡。另外，从有机材料的可量产性角度出发，也必须考虑材料的蒸镀类型(升华型或熔融型)、分解温度、玻璃化转变温度和放气现象等。特别是量产中需要蒸镀较厚的空穴传输材料，这种材料中的升华型材料会严重影响量产膜厚的均匀性，所以开发熔融型的空穴传输材料也成为一个重要方向。
技术问题
本申请实施例创新地提供了一种氧杂环型化合物及其应用和使用其的电子器件，有机材料包含芳胺和氧杂环，其芳胺能够有效提高有机材料的空穴注 入和传输性能，氧杂环有利于形成熔融型蒸镀材料。
技术解决方案
为实现上述的技术目的，一方面，本申请实施例公开了一种氧杂环型化合物。所述氧杂环型化合物的结构通式如下述式1所示：
Figure PCTCN2020137385-appb-000001
式1
式中，Ar 1和Ar 2相互独立地选自单个或多个取代或未取代的芳基、或者取代或未取代的杂芳基，或者Ar 1和Ar 2为相邻的芳基或杂芳基时相互连接形成芳环或杂环的单环或稠环，其中，所述杂芳基的杂原子为O、N、F、S或Si；Ar 3和Ar 4相互独立地选自碳数为1～22的烷基、碳数为1～22的烷氧基、碳数为1～22的杂烷基、单个或多个取代或未取代的芳基、或者取代或未取代的杂芳基，或者Ar 3和Ar 4为相邻的芳基或杂芳基时相互连接形成芳环或杂环的单环或稠环，其中，所述杂烷基的杂原子为O、N、F、S或Si。
进一步地，对于所述氧杂环型化合物，所述氧杂环型化合物的结构通式如下述式2所示：
Figure PCTCN2020137385-appb-000002
式2
进一步地，对于所述氧杂环型化合物，Ar 1和Ar 2相互独立地由式301-式332中的任一式表示：
Figure PCTCN2020137385-appb-000003
进一步地，对于所述氧杂环型化合物，Ar 3和Ar 4相互独立地由式301-式332和式401-403中的任一式表示：
Figure PCTCN2020137385-appb-000004
进一步地，对于所述氧杂环型化合物，所述氧杂环型化合物的结构由下述 通式501-式508中的任一式表示：
Figure PCTCN2020137385-appb-000005
进一步地，对于所述氧杂环型化合物，所述氧杂环型化合物的结构由下述通式601-式617中的任一式表示：
Figure PCTCN2020137385-appb-000006
进一步地，对于所述氧杂环型化合物，所述氧杂环型化合物的结构由下述通式701-式722中的任一式表示：
Figure PCTCN2020137385-appb-000007
进一步地，对于所述氧杂环型化合物，所述氧杂环型化合物的结构由下述通式801-式819中的任一式表示：
Figure PCTCN2020137385-appb-000008
为实现上述的技术目的，另一方面，本申请实施例公开了一种上述氧杂环型化合物在电子器件中作为电致发光有机材料的应用。
为实现上述的技术目的，又一方面，本申请实施例公开了一种电子器件。所述电子器件包括基底、阳极、阴极和置于所述阳极和所述阴极之间的一个或多个有机材料层，所述一个或多个有机材料层中至少一层包含上述氧杂环型化合物。
有益效果
本申请实施例提供的氧杂环型化合物及其应用和使用其的电子器件，氧杂 环型化合物包含芳胺和氧杂环，其芳胺能够有效提高有机材料的空穴注入和传输性能，从而改善有机发光二极管的电子和空穴平衡，达到较低的电压和较高的效率；而氧杂环有利于形成熔融型蒸镀材料，从而有利于量产蒸镀的稳定性。这类材料能够实现高效率的电致发光器件制备,该材料可用于显示设备的制造。
本发明的实施方式
下面对本申请实施例提供的氧杂环型化合物及使用其的电子器件进行详细的解释和说明。
本申请一个实施例的氧杂环型化合物的结构通式如下述式1所示：
Figure PCTCN2020137385-appb-000009
式1
式1中，Ar 1和Ar 2相互独立地选自单个或多个取代或未取代的芳基、或者取代或未取代的杂芳基，或者Ar 1和Ar 2为相邻的芳基或杂芳基时相互连接形成芳环或杂环的单环或稠环，其中，杂芳基的杂原子为O、N、F、S或Si；Ar 3和Ar 4相互独立地选自C1～C22的烷基、C1～C22的烷氧基、C1～C22的杂烷基、单个或多个取代或未取代的芳基、或者取代或未取代的杂芳基，或者Ar 3和Ar 4为相邻的芳基或杂芳基时相互连接形成芳环或杂环的单环或稠环，其中，杂烷基的杂原子为O、N、F、S或Si。
作为本申请实施例的一个优选方案，氧杂环型化合物的结构通式可以如下述式2所示：
Figure PCTCN2020137385-appb-000010
式2
可见，在该优选方案中，氧杂环型化合物中芳胺取代位置固定。
作为本申请实施例的一个优选方案，Ar 1和Ar 2可以相互独立地由下面的式301-式332中的任一式表示：
Figure PCTCN2020137385-appb-000011
作为本申请实施例的一个优选方案，Ar 3和Ar 4可以相互独立地由上面的式301-式332和下面的式401-403中的任一式表示：
Figure PCTCN2020137385-appb-000012
作为本申请实施例的一个进一步优选的方案，氧杂环型化合物的结构可以由下述通式501-式508中的任一式表示：
Figure PCTCN2020137385-appb-000013
作为本申请实施例的另一个进一步优选的方案，氧杂环型化合物的结构可以由下述通式601-式617中的任一式表示：
Figure PCTCN2020137385-appb-000014
作为本申请实施例的又一个进一步优选的方案，氧杂环型化合物的结构可以由下述通式701-式722中的任一式表示：
Figure PCTCN2020137385-appb-000015
作为本申请实施例的再一个进一步优选的方案，氧杂环型化合物的结构可以由下述通式801-式819中的任一式表示：
Figure PCTCN2020137385-appb-000016
本申请实施例的另一个实施例提供上述氧杂环型化合物在电子器件中作为电致发光有机材料的应用。
本申请的又一个实施例提供一种电子器件，该电子器件包括基底、阳极、阴极和置于阳极和阴极之间的一个或多个有机材料层，一个或多个有机材料层中至少一层包含上述实施例的氧杂环型化合物。其中，有机材料层可以包括空穴注入层、空穴传输层、电子注入层、以及电子传输层和发光层。在此，电子器件可以为电致发光器件，例如有机发光二极管器件。
下面，对本申请上述实施例提供的氧杂环型化合物的制备方法进行说明。
实施例1
目标结构1的氧杂环型化合物的合成如过程式9所示：
Figure PCTCN2020137385-appb-000017
过程式9
实施例1提供的目标结构1的氧杂环型化合物的制备方法如下：
在100mL的两口瓶中加入化合物(1)(3mmol)、Pd(OAc) 2(0.15mmol)、PPh 3(0.3mmol)、CsCO 3(6.0mmol)和50mL甲苯，在氩气氛围下，搅拌升温至100℃，反应12h。用二氯甲烷(300mL)溶解并加入饱和NH 4Cl(200mL)溶液，二氯甲烷萃取，有机相无水硫酸钠干燥，浓缩后进行柱分离，以200-300目的硅胶为固定相，二氯甲烷为淋洗剂，得到中间体2.7mmol的化合物(2)，产率90％。
在250mL的两口瓶中加入上步产物——化合物(2)、镁Mg(3mmol)、以及I2一粒，在氩气环境下加入10mL除水除氧的THF溶剂，搅拌至碘褪色，反应0.5h；将二苯甲酮(3mmol)溶解于50mL除水除氧的THF溶剂中，然后将混合液在氩气下导入上步制成的混合液中，反应12h，用二氯甲烷(300mL)溶解并加入饱和NH4Cl(200mL)溶液，二氯甲烷萃取，有机相无水硫酸钠干燥，浓缩后进行柱分离，以200-300目的硅胶为固定相，二氯甲烷为淋洗剂，得到中间体1.9mmol的化合物(3)，产率70％。
将得到的中间体的化合物(3)加入100mL乙腈中，加入2mmol三溴化硼，搅拌12h，用二氯甲烷(300mL)溶解并加入饱和NH 4Cl(200mL)溶液，二氯甲烷萃取，有机相无水硫酸钠干燥，浓缩后进行柱分离，以200-300目的硅胶为固定相，二氯甲烷为淋洗剂，得到1.3mmol的目标结构1，产率77％。基质辅 助激光解析电离飞行时间质谱仪(MALDI-TOF)：计算值m/z，501.63；实测值m/z，501.42。元素分析法(EA)：计算值碳C,88.59；氢H,5.43；氮N,2.79；实测值C,88.25；H,5.51；N,2.83。
实施例2
目标结构2的氧杂环型化合物的合成如过程式10所示：
Figure PCTCN2020137385-appb-000018
过程式10
实施例2产生上步产物——化合物(2)的步骤可以与实施例1中产生上步产物——化合物(2)的步骤类似，实施例2提供的目标结构2的氧杂环型化合物的制备方法如下：
在250mL的两口瓶中加入上步产物——化合物(2)(3mmol)、镁Mg(3.3mmol)、以及I 2一粒，在氩气环境下加入10mL除水除氧的THF溶剂，搅拌至碘褪色，反应0.5h；将化合物(4)(3.2mmol)溶解于50mL除水除氧的THF溶剂中，然后将混合液在氩气下导入上步制成的混合液中，反应12h，用二氯甲烷(300mL)溶解并加入饱和NH 4Cl(200mL)溶液，二氯甲烷萃取，有机相无水硫酸钠干燥，浓缩后进行柱分离，以200-300目的硅胶为固定相，二氯甲烷为淋洗剂，得到中间体2.0mmol的化合物(5)，产率67％。
将得到的中间体的化合物(5)加入100mL乙腈中，加入2.5mmol三溴化硼，搅拌12h，用二氯甲烷(300mL)溶解并加入饱和NH 4Cl(200mL)溶液，二氯甲烷萃取，有机相无水硫酸钠干燥，浓缩后进行柱分离，以200-300目的硅胶为固定相，二氯甲烷为淋洗剂，得到1.6mmol的目标结构2，产率81％。基质辅助激光解析电离飞行时间质谱仪(MALDI-TOF)：计算值m/z，668.84；实测值m/z，668.24。元素分析法(EA)：计算值碳C,87.99；氢H,5.43；氮N,4.19；实测值C,87.84；H,5.26；N,4.01。
实施例3
目标结构3的氧杂环型化合物的合成如过程式11所示：
Figure PCTCN2020137385-appb-000019
过程式11
实施例3产生上步产物——化合物(2)的步骤可以与实施例1中产生上步产物——化合物(2)的步骤类似，实施例3提供的目标结构3的氧杂环型化合物的制备方法如下：
在250mL的两口瓶中加入上步产物——化合物(2)(3mmol)、镁Mg(3.3mmol)、以及I 2一粒，在氩气环境下加入10mL除水除氧的THF溶剂，搅拌至碘褪色，反应0.5h；将化合物(6)(3.2mmol)溶解于50mL除水除氧的THF溶剂中，然后将混合液在氩气下导入上步制成的混合液中，反应12h，用二氯甲烷(300mL)溶解并加入饱和NH 4Cl(200mL)溶液，二氯甲烷萃取，有机相无水硫酸钠干燥，浓缩后进行柱分离，以200-300目的硅胶为固定相，二氯甲烷为淋洗剂，得到中间体1.95mmol的化合物(7)，产率65％。
将得到的中间体的化合物(7)加入100mL乙腈中，加入2.5mmol三溴化硼，搅拌12h，用二氯甲烷(300mL)溶解并加入饱和NH 4Cl(200mL)溶液，二氯甲烷萃取，有机相无水硫酸钠干燥，浓缩后进行柱分离，以200-300目的硅胶为固定相，二氯甲烷为淋洗剂，得到1.7mmol的目标结构3，产率85％。基质辅助激光解析电离飞行时间质谱仪(MALDI-TOF)：计算值m/z，784.35；实测值m/z，784.12。元素分析法(EA)：计算值碳C,88.74；氢H,5.65；氮N,3.57；实测值C,88.56；H,5.37；N,3.89。
实施例4
目标结构4的氧杂环型化合物的合成如过程式12所示：
Figure PCTCN2020137385-appb-000020
过程式12
实施例4产生上步产物——化合物(2)的步骤可以与实施例1中产生上步产物——化合物(2)的步骤类似，实施例4提供的目标结构4的氧杂环型化合物的制备方法如下：
在250mL的两口瓶中加入上步产物——化合物(2)(3mmol)、镁Mg(3.3mmol)、以及I 2一粒，在氩气环境下加入10mL除水除氧的THF溶剂，搅拌至碘褪色，反应0.5h；将化合物(8)(3.2mmol)溶解于50mL除水除氧的THF溶剂中，然后将混合液在氩气下导入上步制成的混合液中，反应12h，用二氯甲烷(300mL)溶解并加入饱和NH 4Cl(200mL)溶液，二氯甲烷萃取，有机相无水硫酸钠干燥，浓缩后进行柱分离，以200-300目的硅胶为固定相，二氯甲烷为淋洗剂，得到中间体1.95mmol的化合物(9)，产率65％。
将得到的中间体的化合物(9)加入100mL乙腈中，加入2.5mmol三溴化硼，搅拌12h，用二氯甲烷(300mL)溶解并加入饱和NH4Cl(200mL)溶液，二氯甲烷萃取，有机相无水硫酸钠干燥，浓缩后进行柱分离，以200-300目的硅胶为固定相，二氯甲烷为淋洗剂，得到1.7mmol的目标结构4，产率85％。基质辅助激光解析电离飞行时间质谱仪(MALDI-TOF)：计算值m/z，784.35；实测值m/z，784.12。元素分析法(EA)：计算值碳C,88.74；氢H,5.65；氮N,3.57；实测值C,88.56；H,5.37；N,3.89。
实施例5
目标结构5的氧杂环型化合物的合成如过程式13所示：
Figure PCTCN2020137385-appb-000021
过程式13
实施例5产生上步产物——化合物(2)的步骤可以与实施例1中产生上步产物——化合物(2)的步骤类似，实施例5提供的目标结构5的氧杂环型化合物的制备方法如下：
在250mL的两口瓶中加入上步产物——化合物(2)(3mmol)、镁Mg(3.3mmol)、以及I 2一粒，在氩气环境下加入10mL除水除氧的THF溶剂，搅拌至碘褪色，反应0.5h；将化合物(10)(3.2mmol)溶解于50mL除水除氧的THF溶剂中，然后将混合液在氩气下导入上步制成的混合液中，反应12h，用二氯甲烷(300mL)溶解并加入饱和NH 4Cl(200mL)溶液，二氯甲烷萃取，有机相无水硫酸钠干燥，浓缩后进行柱分离，以200-300目的硅胶为固定相，二氯甲烷为淋洗剂，得到中间体1.8mmol的化合物(11)，产率60％。
将得到的中间体的化合物(11)加入100mL乙腈中，加入2.5mmol三溴化硼，搅拌12h，用二氯甲烷(300mL)溶解并加入饱和NH 4Cl(200mL)溶液，二氯甲烷萃取，有机相无水硫酸钠干燥，浓缩后进行柱分离，以200-300目的硅胶为固定相，二氯甲烷为淋洗剂，得到1.4mmol的目标结构5，产率80％。基质辅助激光解析电离飞行时间质谱仪(MALDI-TOF)：计算值m/z，667.27；实测值m/z，667.31。元素分析法(EA)：计算值碳C,88.26；氢H,5.14；氮N,4.20；实测值C,88.31；H,5.21；N,4.19。
实施例6
目标结构6的氧杂环型化合物的合成如过程式14所示：
Figure PCTCN2020137385-appb-000022
过程式14
实施例6产生上步产物——化合物(2)的步骤可以与实施例1中产生上步产物——化合物(2)的步骤类似，实施例6提供的目标结构6的氧杂环型化合物的制备方法如下：
在250mL的两口瓶中加入上步产物——化合物(2)(3mmol)、镁Mg(3.3mmol)、以及I 2一粒，在氩气环境下加入10mL除水除氧的THF溶剂，搅拌至碘褪色，反应0.5h；将化合物(12)(3.2mmol)溶解于50mL除水除氧的THF溶剂中，然后将混合液在氩气下导入上步制成的混合液中，反应12h，用二氯甲烷(300mL)溶解并加入饱和NH 4Cl(200mL)溶液，二氯甲烷萃取，有机相无水硫酸钠干燥，浓缩后进行柱分离，以200-300目的硅胶为固定相，二氯甲烷为淋洗剂，得到中间体2.2mmol的化合物(13)，产率72％。
将得到的中间体的化合物(13)加入100mL乙腈中，加入2.5mmol三溴化硼，搅拌12h，用二氯甲烷(300mL)溶解并加入饱和NH4Cl(200mL)溶液，二氯甲烷萃取，有机相无水硫酸钠干燥，浓缩后进行柱分离，以200-300目的硅胶为固定相，二氯甲烷为淋洗剂，得到1.6mmol的目标结构6，产率74％。基质辅助激光解析电离飞行时间质谱仪(MALDI-TOF)：计算值m/z，744.31；实测值m/z，744.31。元素分析法(EA)：计算值碳C,88.68；氢H,5.41；氮N,3.76；实测值C,88.52；H,5.29；N,3.87。
实施例7
目标结构7的氧杂环型化合物的合成如过程式15所示：
Figure PCTCN2020137385-appb-000023
过程式15
实施例7产生上步产物——化合物(2)的步骤可以与实施例1中产生上步产物——化合物(2)的步骤类似，实施例7提供的目标结构7的氧杂环型化合物的制备方法如下：
在250mL的两口瓶中加入上步产物——化合物(2)(3mmol)、镁Mg(3.3mmol)、以及I 2一粒，在氩气环境下加入10mL除水除氧的THF溶剂，搅拌至碘褪色，反应0.5h；将化合物(14)(3.2mmol)溶解于50mL除水除氧的THF溶剂中，然后将混合液在氩气下导入上步制成的混合液中，反应12h，用二氯甲烷(300mL)溶解并加入饱和NH 4Cl(200mL)溶液，二氯甲烷萃取，有机相无水硫酸钠干燥，浓缩后进行柱分离，以200-300目的硅胶为固定相，二氯甲烷为淋洗剂，得到中间体2.4mmol的化合物(15)，产率79％。
将得到的中间体的化合物(15)加入100mL乙腈中，加入2.5mmol三溴化硼，搅拌12h，用二氯甲烷(300mL)溶解并加入饱和NH4Cl(200mL)溶液，二氯甲烷萃取，有机相无水硫酸钠干燥，浓缩后进行柱分离，以200-300目的硅胶为固定相，二氯甲烷为淋洗剂，得到1.5mmol的目标结构7，产率65％。基质辅助激光解析电离飞行时间质谱仪(MALDI-TOF)：计算值m/z，784.35；实测值m/z，784.13。元素分析法(EA)：计算值碳C,88.74；氢H,5.65；氮N,3.57；实测值C,88.69；H,5.37；N,3.48。
实施例8
目标结构8的氧杂环型化合物的合成如过程式16所示：
Figure PCTCN2020137385-appb-000024
过程式16
实施例8产生上步产物——化合物(2)的步骤可以与实施例1中产生上步产物——化合物(2)的步骤类似，实施例8提供的目标结构8的氧杂环型化合物的制备方法如下：
在250mL的两口瓶中加入上步产物——化合物(2)(3mmol)、镁Mg(3.3mmol)、以及I 2一粒，在氩气环境下加入10mL除水除氧的THF溶剂，搅拌至碘褪色，反应0.5h；将化合物(16)(3.2mmol)溶解于50mL除水除氧的THF溶剂中，然后将混合液在氩气下导入上步制成的混合液中，反应12h，用二氯甲烷(300mL)溶解并加入饱和NH4Cl(200mL)溶液，二氯甲烷萃取，有机相无水硫酸钠干燥，浓缩后进行柱分离，以200-300目的硅胶为固定相，二氯甲烷为淋洗剂，得到中间体2.1mmol的化合物(17)，产率70％。
将得到的中间体的化合物(17)加入100mL乙腈中，加入2.5mmol三溴化硼，搅拌12h，用二氯甲烷(300mL)溶解并加入饱和NH 4Cl(200mL)溶液，二氯甲烷萃取，有机相无水硫酸钠干燥，浓缩后进行柱分离，以200-300目的硅胶为固定相，二氯甲烷为淋洗剂，得到1.5mmol的目标结构7，产率65％。基质辅助激光解析电离飞行时间质谱仪(MALDI-TOF)：计算值m/z，733.96；实测值m/z，733.79。元素分析法(EA)：计算值碳C,90.01；氢H,5.91；氮N,1.91；实测值C,89.87；H,6.05；N,1.88。
实施例9
目标结构9如式17所示，其合成路线参照目标结构1。产率65％。基质辅助激光解析电离飞行时间质谱仪(MALDI-TOF)：计算值m/z，577.73；实测值m/z，577.35。元素分析法(EA)：计算值碳C,89.40；氢H,5.41；氮N,2.42；实测值C,89.24；H,5.32；N,2.59。
Figure PCTCN2020137385-appb-000025
式17
实施例10
目标结构10如式18所示，其合成路线参照目标结构1。产率71％。基质辅助激光解析电离飞行时间质谱仪(MALDI-TOF)：计算值m/z，617.79；实测值m/z，617.54。元素分析法(EA)：计算值碳C,89.43；氢H,5.71；氮N,2.27；实测值C,89.21；H,5.85；N,2.19。
Figure PCTCN2020137385-appb-000026
式18
实施例11
目标结构11如式19所示，其合成路线参照目标结构1。产率74％。基质辅助激光解析电离飞行时间质谱仪(MALDI-TOF)：计算值m/z，693.89；实测值m/z，693.77。元素分析法(EA)：计算值碳C,89.43；氢H,5.71；氮N,2.27；实测值C,89.21；H,5.85；N,2.19。
Figure PCTCN2020137385-appb-000027
式19
检测和实验验证
经检测和实验验证，上述各个目标结构1-11的氧杂环型化合物的能级如下表1所示：
表1
Figure PCTCN2020137385-appb-000028
按本领域已知方法制作本申请实施例提供的电子器件，以电子器件是电致发光器件为例，器件结构具体可以依次包括ITO层、HAT-CN层(比如厚度为5nm)、包含上述任一目标结构(比如厚度为30nm)的氧杂环型化合物的有机材料层、Firpic:B3PyPB层(12％,10nm)、TPBi层(比如厚度为40nm)、LiF层(比如厚度为2nm)、以及铝Al层(比如厚度为100nm)。经检测和实验验证，对于上述各个目标结构1-11的氧杂环型化合物，有机材料层包含该目标结构的氧杂环型化合物的该电致发光器件的性能数据如下表2所示：
表2
Figure PCTCN2020137385-appb-000029
Figure PCTCN2020137385-appb-000030
本申请实施例提供的氧杂环型化合物及其应用和使用其的电子器件，氧杂环型化合物包含芳胺和氧杂环，其芳胺能够有效提高有机材料的空穴注入和传输性能，从而改善有机发光二极管的电子和空穴平衡，达到较低的电压和较高的效率；而氧杂环有利于形成熔融型蒸镀材料，从而有利于量产蒸镀的稳定性。这类材料能够实现高效率的电致发光器件制备,该材料可用于显示设备的制造。
综上所述，虽然本申请已以优选实施例揭露如上，但上述优选实施例并非用以限制本申请，本领域的普通技术人员，在不脱离本申请的精神和范围内，均可作各种更动与润饰，因此本申请的保护范围以权利要求界定的范围为准。

Claims (10)

  1. 一种氧杂环型化合物，所述氧杂环型化合物的结构通式如下述式1所示：
    Figure PCTCN2020137385-appb-100001
    式中，Ar 1和Ar 2相互独立地选自单个或多个取代或未取代的芳基、或者取代或未取代的杂芳基，或者Ar 1和Ar 2为相邻的芳基或杂芳基时相互连接形成芳环或杂环的单环或稠环，其中，所述杂芳基的杂原子为O、N、F、S或Si；
    Ar 3和Ar 4相互独立地选自碳数为1～22的烷基、碳数为1～22的烷氧基、碳数为1～22的杂烷基、单个或多个取代或未取代的芳基、或者取代或未取代的杂芳基，或者Ar 3和Ar 4为相邻的芳基或杂芳基时相互连接形成芳环或杂环的单环或稠环，其中，所述杂烷基的杂原子为O、N、F、S或Si。
  2. 根据权利要求1所述的氧杂环型化合物，其中，所述氧杂环型化合物的结构通式如下述式2所示：
    Figure PCTCN2020137385-appb-100002
  3. 根据权利要求1所述的氧杂环型化合物，其中，Ar 1和Ar 2相互独立地由式301-式332中的任一式表示：
    Figure PCTCN2020137385-appb-100003
  4. 根据权利要求1所述的氧杂环型化合物，其中，Ar 3和Ar 4相互独立地由式301-式332和式401-403中的任一式表示：
    Figure PCTCN2020137385-appb-100004
  5. 根据权利要求2所述的氧杂环型化合物，其中，所述氧杂环型化合物的结构由下述通式501-式508中的任一式表示：
    Figure PCTCN2020137385-appb-100005
  6. 根据权利要求2所述的氧杂环型化合物，其中，所述氧杂环型化合物的结构由下述通式601-式617中的任一式表示：
    Figure PCTCN2020137385-appb-100006
  7. 根据权利要求2所述的氧杂环型化合物，其中，所述氧杂环型化合物的结构由下述通式701-式722中的任一式表示：
    Figure PCTCN2020137385-appb-100007
  8. 根据权利要求2所述的氧杂环型化合物，其中，所述氧杂环型化合物的结构由下述通式801-式819中的任一式表示：
    Figure PCTCN2020137385-appb-100008
  9. 一种如权利要求1-8中任一项所述的氧杂环型化合物在电子器件中作为电致发光有机材料的应用。
  10. 一种电子器件，包括基底、阳极、阴极和置于所述阳极和所述阴极之间的一个或多个有机材料层，所述一个或多个有机材料层中至少一层包含如权利要求1-8中任一项所述的氧杂环型化合物。
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