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Numéro de publicationCN103189469 A
Type de publicationDemande
Numéro de demandeCN 201180051960
Numéro PCTPCT/KR2011/006314
Date de publication3 juil. 2013
Date de dépôt26 août 2011
Date de priorité27 août 2010
Numéro de publication201180051960.5, CN 103189469 A, CN 103189469A, CN 201180051960, CN-A-103189469, CN103189469 A, CN103189469A, CN201180051960, CN201180051960.5, PCT/2011/6314, PCT/KR/11/006314, PCT/KR/11/06314, PCT/KR/2011/006314, PCT/KR/2011/06314, PCT/KR11/006314, PCT/KR11/06314, PCT/KR11006314, PCT/KR1106314, PCT/KR2011/006314, PCT/KR2011/06314, PCT/KR2011006314, PCT/KR201106314
Inventeurs慎孝壬, 李秀镛, 安熙春, 金荣佶, 徐美兰, 赵英俊, 权赫柱, 李暻周, 金奉玉
Déposant罗门哈斯电子材料韩国有限公司
Exporter la citationBiBTeX, EndNote, RefMan
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Novel organic electroluminescent compounds and organic electroluminescent device using the same
CN 103189469 A
Résumé
Provided are novel organic electroluminescent compounds and an organic electroluminescent device using the same. Because the organic electroluminescent device using the organic electroluminescent compound as a hole transport material or a hole injection material exhibits good luminous efficiency and excellent lifetime properties, it is used to manufacture OLED devices having superior operating lifetimes and that consume less power due to improved power efficiency.
Revendications(10)  Langue du texte original : Chinois
1.一种由如下化学式I表示的有机电致发光化合物: 化学式I A has the following Formula I represented by the organic electroluminescent compound: of formula I
Figure CN103189469AC00021
其中,环A和环C独立地表示 Among them, the rings A and C independently represent
Figure CN103189469AC00022
环B表示 Ring B represents
Figure CN103189469AC00023
X1和X2独立地表示CR3或N ; Y1 和Y2 独立地表示化学键、-0-、-S-、-C (R11R12)-、-Si (R13R14)-或者-N(R15)-,仅排除Y1和Y2都是化学键的情况; R1至R3独立地表不氢、氣、齒素、取代或未取代的(C1-C30)烧基、取代或未取代的(C6-C30)芳基、取代或未取代的(C2-C30)杂芳基、取代或未取代的(C3-C30)环烷基、取代或未取代的5-元至7-元杂环烷基、取代或未取代的(C6-C30)芳基(C1-C30)烷基、取代或未取代的(C1-C30)烷基甲硅烷基、氰基、硝基或羟基,并且当具有两个或更多个R1或R2时,它们相互连接形成环结构; L表示取代或未取代的(C6-C30)亚芳基或者取代或未取代的(C2-C30)杂亚芳基,并且当具有两个或更多个L时,它们相互连接形成环结构; Ar1和Ar2独立地表示取代或未取代的 X1 and X2 independently represent CR3 or N; Y1 and Y2 independently represents a bond, -0 -, - S -, - C (R11R12) -, - Si (R13R14) - or -N (R15) -, only exclude Y1 Y2 is a bond and circumstances; R1 to R3 independently represent hydrogen does, gas, halogen, a substituted or unsubstituted (C1-C30) firing group, a substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted substituted (C2-C30) heteroaryl, a substituted or unsubstituted (C3-C30) cycloalkyl group, a substituted or unsubstituted 5-membered to 7-membered heterocycloalkyl, substituted or unsubstituted (C6- C30) aryl (C1-C30) alkyl, optionally substituted (C1-C30) alkylsilyl, cyano, nitro or hydroxyl, and when two or more R1 or R2, they are interconnected to form a ring structure; L represents a substituted or unsubstituted (C6-C30) arylene group or a substituted or unsubstituted (C2-C30) heteroarylene group, and when two or more L, they are interconnected to form a ring structure; Ar1 and Ar2 independently represent a substituted or unsubstituted of substituted
Figure CN103189469AC00024
Y4.Y3 和Y4 独立地表示化学键、-0-、-S-、-C (R16R17)-,-Si (R18R19)-或者-N(R20)-,仅排除Y3和Y4都是化学键的情况; R11至R2tI独立地表示氢、氣、卤素、取代或未取代的(C1-C30)烧基、取代或未取代的(C6-C30)芳基或者取代或未取代的(C2-C30)杂芳基,或者它们可分别通过具有或不具有稠环的取代或未取代的(C3-C30)亚烷基或者具有或不具有稠环的取代或未取代的(C3-C30)亚烯基与相邻取代基连接形成脂环、单环或多环芳环; m和η独立地表示0-4的整数,当m和η是大于或等于2的整数时,每个R1和L可相同或不同; P表示0-2的整数,当ρ=2时,每个R2可相同或不同;以及所述杂环烷基、杂芳基和杂亚芳基包含一个或多个选自B、N、O、S、P (=0)、Si和P的杂原子。 Y4.Y3 and Y4 independently represents a bond, -0 -, - S -, - C (R16R17) -, - Si (R18R19) - or -N (R20) -, to exclude only the situation Y3 and Y4 are chemical bonds; to R2tI R11 independently represent hydrogen, gas, halogen, a substituted or unsubstituted (C1-C30) burning group, a substituted or unsubstituted (C6-C30) aryl group, or a substituted or unsubstituted (C2-C30) heteroaryl group, or they may be separately through with or without a fused ring of a substituted or unsubstituted (C3-C30) alkylene or a fused ring with or without a substituted or unsubstituted (C3-C30) alkenylene with phase ortho-substituted aliphatic groups joined to form a ring, mono- or polycyclic aromatic ring; m and η are independently an integer of 0-4, and when m and η is an integer greater than or equal to 2, each R1 and L may be the same or different ; P represents an integer of 0 to 2, when ρ = 2, each R2 may be the same or different; and the heterocycloalkyl, heteroaryl and heteroarylene containing one or more selected from B, N, O, S, P (= 0), Si and P heteroatoms.
2.如权利要求1所述的有机电致发光化合物,其特征在于,所述RpHUAivAr2以及R11至R2tl的取代基可分别被选自下组的一个或多个取代基进一步取代:氘、卤素、卤素取代或未取代的(C1-C30)烷基、(C6-C30)芳基、(C6-C30)芳基取代或未取代的(C2-C30)杂芳基、5-元至7-元杂环烷基、与一个或多个芳环稠合的5-元至7-元杂环烷基、(C3-C30)环烷基、与一个或多个芳环稠合的(C6-C30)环烷基、(C2-C30)烯基、(C2-C30)炔基、 2. The claim 1 wherein the organic electroluminescent compounds, characterized in that said RpHUAivAr2 to R2tl and R11 substituents may respectively be selected from one or more of the group further substituted: deuterium, halogen, halogen-substituted or unsubstituted (C1-C30) alkyl, (C6-C30) aryl, (C6-C30) aryl substituted or unsubstituted (C2-C30) heteroaryl, 5- membered to 7-membered heterocycloalkyl, with one or more aromatic rings fused 5- to 7-membered heterocyclic group, (C3-C30) cycloalkyl, with one or more aromatic rings fused (C6-C30 ) cycloalkyl, (C2-C30) alkenyl, (C2-C30) alkynyl,
Figure CN103189469AC00031
氰基、咔唑基、(C6-C30)芳基(C1-C30)烷基、(C1-C30)烷基(C6-C30)芳基、-0R21、-SR22' -NR23R24' -PR25R26, -SiR27R28R29' 硝基和羟基,且Y11 和Y12 独立地表示化学键、-C(R31R32)-、-0-、-S-或-N(R33)-,仅排除Y11和Y12都是化学键的情况;并且R21至R29以及R31至R33独立地表示(C1-C30)烷基、(C6-C30)芳基、(C2-C30)杂芳基或者(C3-C30)环烧基。 Cyano, carbazolyl, (C6-C30) aryl (C1-C30) alkyl, (C1-C30) alkyl (C6-C30) aryl, -0R21, -SR22 '-NR23R24' -PR25R26, - SiR27R28R29 'nitro and hydroxyl, and Y11 and Y12 independently represents a bond, -C (R31R32) -, - 0 -, - S- or -N (R33) -, Y11 and Y12 are only exclude the case of chemical bonds; and R21 to R29 and R31 to R33 independently represent (C1-C30) alkyl, (C6-C30) aryl, (C2-C30) heteroaryl or (C3-C30) cycloalkyl group burned.
3.如权利要求1所述的有机电致发光化合物,其特征在于, 所述化学式I的 According to claim 1, wherein the organic electroluminescent compound wherein Formula I
Figure CN103189469AC00032
选自以下结构: Is selected from the following structures:
Figure CN103189469AC00041
其中,RyR11至R15、以及P的定义与权利要求1的定义相同。 Wherein, RyR11 to R15, and the definition of the rights defined P 1 is the same requirements.
4.如权利要求1所述的有机电致发光化合物,其特征在于,所述化合物选自下述化合物: As claimed in claim 1 wherein the organic electroluminescent compounds, wherein the compound is selected from the following compounds:
Figure CN103189469AC00051
Figure CN103189469AC00061
Figure CN103189469AC00071
Figure CN103189469AC00081
Figure CN103189469AC00091
Figure CN103189469AC00101
Figure CN103189469AC00111
Figure CN103189469AC00121
Figure CN103189469AC00131
Figure CN103189469AC00141
5.一种有机电致发光器件,所述器件包含权利要求1-4中任一项所述的有机电致发光化合物。 An organic electroluminescent device, the device comprising to claim any one of claims 1-4 wherein the organic electroluminescent compound.
6.如权利要求5所述的有机电致发光器件,其特征在于,所述有机电致发光化合物用作空穴注入材料或者空穴传输材料。 The organic electroluminescent device as claimed in claim 5, characterized in that said organic electroluminescent compounds as the hole injecting material or a hole transporting material.
7.如权利要求6所述的有机电致发光器件,其特征在于,该器件包含第一电极;第二电极;插入所述第一电极和第二电极之间的一层或多层有机层,所述有机层包含化学式I表/Jn的一种或多种有机电致发光化合物。 Inserting one or more layers of the first electrode and the second electrode of the organic layer; claim 7. The organic electroluminescent device of claim 6, characterized in that the device comprises a first electrode; a second electrode , the organic layer comprises a chemical formula I table / Jn one or more organic electroluminescent compound.
8.如权利要求7所述的有机电致发光器件,其特征在于,所述有机层还包含选自元素周期表中第I族、第2族的有机金属、第四周期和第五周期的过渡金属、镧系金属和d-过渡元素的一种或多种金属或络合物。 Claim 8. The organic electroluminescence device according to 7, wherein the organic layer further comprises a Group I of the periodic table is selected from organometallic Group 2, the fourth cycle and the fifth cycle transition metals, lanthanide metals and transition elements of d- or more metals or complexes.
9.如权利要求7所述的有机电致发光器件,其特征在于,所述有机层包含电致发光层和电荷产生层。 A process as claimed in claim 7 organic electroluminescent device wherein the organic layer comprises an electroluminescent layer and a charge generating layer.
10.如权利要求7所述的有机电致发光器件,其特征在于,所述有机层还包含一层或多层发射红光、绿光和蓝光的有机电致发光层,以发射白光。 10. The as claimed in claim 7 An organic electroluminescent device, characterized in that the organic layer further comprises one or more layers emit red, green and blue organic electroluminescent layer to emit white light.
Description  Langue du texte original : Chinois

新有机电致发光化合物和使用该化合物的有机电致发光器 The new organic electroluminescent compounds and using the compounds are organic electroluminescence

Item

技术领域 Technical Field

[0001] 本发明涉及新有机电致发光化合物和包含该化合物的有机电致发光器件,更具体地涉及适合用作空穴传输材料或空穴注入材料的新有机电致发光化合物和使用该化合物的有机电致发光器件。 [0001] The present invention relates to novel organic electroluminescent compounds and compounds containing the organic electroluminescent devices, and more particularly to suitable for use as a hole transport material or a hole injection material new organic electroluminescent compounds and using the compounds The organic electroluminescent device.

技术背景 BACKGROUND

[0002]目前广泛使用液晶显示器(IXD),其是具有低功耗和轻量化的非发射性显示器,但是其具有复杂的运行系统和包括响应时间和对比度在内的并不令人满意的性能。 [0002] There are currently widely used in liquid crystal displays (IXD), which is a low power consumption and weight of the non-emissive display, but it has a complex operational systems and include response time and contrast, including unsatisfactory performance . 因此,目前有机电致发光器件作为下一代平板显示器正受到关注,并对它们进行深入研究。 Therefore, it is an organic electroluminescent device as a next-generation flat panel display positive attention, and their in-depth study.

[0003] 在显示器件中,电致发光(EL)器件是优选的,因为它们作为自发射显示器件提供宽视角、优异的对比度和快速响应速率。 [0003] In the display device, an electroluminescent (EL) devices are preferred because they are self-emitting display devices provide a wide viewing angle, excellent contrast and rapid response rate. 伊斯曼柯达公司(Eastman Kodak)在1987年首先开发了一种有机EL器件,该器件使用低分子量芳族二胺和铝配合物作为形成电致发光层的物质[App1.Phys.Lett.51,913,1987]。 Eastman Kodak Company (Eastman Kodak) first developed in 1987 an organic EL device which use a low molecular weight aromatic diamine and an aluminum complex as material form an electroluminescent layer [App1.Phys.Lett.51 , 913,1987].

[0004] 有机电致发光器件的发光机制是:当电荷注入到形成在电子注入电极(阴极)和空穴注入电极(阳极)之间的有机层时,形成电子-空穴对,电子-空穴对湮灭时发光。 [0004] The organic electroluminescent device emitting mechanism: when the charge is injected into the formation in the electron injection electrode (cathode) and a hole organic layer electrode (anode) between the injected form an electron - hole pair, e - empty Point on when annihilation light. 所述器件可以在挠性透明基材(例如塑料)上形成,也可在相比等离子体显示平板或无机电致发光显示器低的电压(IOV或更低)下运行,需要较少的功耗并具有优异的色彩。 The device may be a flexible transparent substrate (such as plastic) are formed, can also be displayed to run flat or inorganic electroluminescent displays low voltage (IOV or lower) in plasma compared, it requires less power consumption and has excellent color.

[0005] 可以将有机EL器件的有机材料大体分为电致发光材料和电荷传输材料。 [0005] The organic material can be divided into organic EL devices electroluminescent material and a charge transport material. 所述电致发光材料直接涉及电致发光颜色和发光效率,需要以下数种特性,例如固态的高荧光量子产率、电子和空穴的高迁移率、真空沉积时的低降解性、均匀薄膜成型性和稳定性。 The electroluminescent material directly related to the electroluminescent color and luminous efficiency caused, the following several characteristics, such as solid state high fluorescence quantum yield, high electron and hole mobility, low degradation during vacuum deposition, a uniform thin film moldability and stability.

[0006] 同时,空穴注入和传输材料包括铜酞菁(CuPc)、NPB, TPD、MTDATA (4,4',4' ' -三(3-甲基苯基苯基氨基)三苯基胺)等。 [0006] Meanwhile, the hole injecting and transporting material include copper phthalocyanine (CuPc), NPB, TPD, MTDATA (4,4 ', 4' '- tris (3-methylphenyl phenylamino) triphenylamine ) and so on. 空穴注入或传输层中使用这些材料的器件在效率和操作寿命上有问题。 Hole injection or transport layer devices using these materials in terms of efficiency and operating life problems. 这是因为当有机EL器件在高电流条件下驱动时,在阳极和空穴注入层之间产生了热应力。 This is because when the organic EL device is driven at high current conditions, between the anode and the hole injection layer produces a thermal stress. 所述热应力明显降低了器件的工作寿命。 The heat stress significantly reduced the working life of the device. 另外,由于用于空穴注入层的有机材料具有非常高的空穴迁移性,可打破所述空穴-电子的电荷平衡,并降低量子产率(cd/A)。 Further, since the organic material used for the hole injection layer having a very high hole mobility, the hole may break - electron charge balance, and reduce the quantum yield (cd / A).

[0007] 已知使薄膜具有良好稳定性的无定形化合物提高了有机EL器件的工作寿命。 [0007] known in the film having a good stability of the amorphous compound improves the working life of the organic EL device. 玻璃化转变温度(Tg)是无定形态的量度。 The glass transition temperature (Tg) is a measure of an amorphous state. MTDATA的玻璃化转变温度为76° C,并不能具有高的无定形态。 MTDATA glass transition temperature of 76 ° C, and can not have a high amorphous. 这些材料在有机EL设备的工作寿命以及发光效率方面并不令人满意,这是由空穴注入和传输性质决定的。 These materials are in the working life of the organic EL device and a light emitting efficiency is not satisfactory, which is a hole injection and transport properties of the decision.

发明内容 DISCLOSURE

[0008] 抟术问是页 [0008] The technique asked Tuan page

[0009] 因此,本发明针对现有技术存在的问题,本发明的一个目的是提供具有比常规空穴注入或空穴传输材料更好的发光效率和器件使用寿命且具有优异主链结构的有机电致发光化合物,并提供采用此新有机电致发光化合物作为空穴注入层或空穴传输层的新有机电致发光器件。 [0009] Accordingly, the present invention addresses the problems of the prior art, an object of the present invention is to provide a ratio of a conventional hole injecting or hole transporting material better luminous efficiency and device lifetime and having a main chain structure have an excellent The organic electroluminescent compounds, and delivers this new organic electroluminescent compounds as the hole injection layer or hole transport layer new organic electroluminescent devices.

[0010] 技术方案 [0010] Technical Solution

[0011] 本发明提供如下化学式I表示的有机电致发光化合物,以及包含所述有机电致发光化合物的有机电致发光器件。 [0011] The present invention provides the following formula I represent organic electroluminescent compounds, and comprising the organic electroluminescent compounds are organic electroluminescent devices. 在有机电致发光器件的空穴注入层或空穴传输层中含有本发明的有机电致发光化合物,从而降低了装置的运行电压并增加了装置的发光效率。 In an organic electroluminescent device hole injection layer or the hole transport layer comprising the inventive organic electroluminescent compounds, thereby reducing the operating voltage of the device and increase the luminous efficiency of the device.

[0012] 在一个方面,本发明提供用如下化学式I表示的有机电致发光化合物。 [0012] In one aspect, the present invention is provided by the following formula I represent organic electroluminescent compounds.

[0013] 化学式I [0013] The formula I

[0014] [0014]

Figure CN103189469AD00161

[0015] 其中,环A和环C独立地表示 [0015] wherein rings A and C independently represent

Figure CN103189469AD00162

[0016]环 B 表 [0016] Ring B table

Figure CN103189469AD00163

[0017] X1和X2独立地表示CR3或N ; [0017] X1 and X2 independently represent CR3 or N;

[0018] Y1 和Y2 独立地表示化学键、-0-、-S-、-C (R11R12)-、_Si (R13R14)-或者-N(R15)-,仅排除Y1和Y2同时是化学键的情况; [0018] Y1 and Y2 independently represents a bond, -0 -, - S -, - C (R11R12) -, _ Si (R13R14) - or -N (R15) -, Y1 and Y2 only exclusion is also the case of a chemical bond;

[0019] R1至R3独立地表述氢、氘、卤素、取代或未取代的(C1-C30)烷基、取代或未取代的(C6-C30)芳基、取代或未取代的(C2-C30)杂芳基、取代或未取代的(C3-C30)环烷基、取代或未取代的5-元至7-元杂环烷基、取代或未取代的(C6-C30)芳基(C1-C30)烷基、取代或未取代的(C1-C30)烷基甲硅烷基、氰基、硝基或羟基,并且当具有两个或更多个R1或R2时,它们相互连接形成环结构; [0019] R1 to R3 independently express hydrogen, deuterium, halogen, a substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted (C2-C30 ) heteroaryl, substituted or unsubstituted (C3-C30) cycloalkyl group, a substituted or unsubstituted 5-membered to 7-membered heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl (C1 -C30) alkyl group, a substituted or unsubstituted (C1-C30) alkylsilyl group, a cyano group, a nitro group or a hydroxyl group, and when two or more R1 or R2 when they are connected to each other to form a ring structure ;

[0020] L表示取代或未取代的(C6-C30)亚芳基或者取代或未取代的(C2-C30)杂亚芳基,并且当具有两个或更多个L时,它们相互连接形成环结构; [0020] L represents a substituted or unsubstituted (C6-C30) arylene group or a substituted or unsubstituted (C2-C30) heteroarylene group, and when two or more of L, they are interconnected to form ring structure;

[0021] Ar1和Ar2独立地表示取代或未取代的(C6-C30)芳基、取代或未取代的(C2-C30) [0021] Ar1 and Ar2 independently represent a substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted (C2-C30)

杂芳基,或者 Heteroaryl, or

[0022] [0022]

Figure CN103189469AD00164

[0023] Y3 和Y4 独立地表示化学键、-O-、-S-、-C (R16R17) _、-Si (R18R19)-或者-N(R2tl)-,仅排除Y3和Y4同时是化学键的情况; [0023] Y3 and Y4 independently represents a bond, -O -, - S -, - C (R16R17) _, - Si (R18R19) - or -N (R2tl) -, to exclude only the Y3 and Y4 is also the case of chemical bonds ;

[0024] R11至R2tl独立地表示氢、氘、卤素、取代或未取代的(C1-C30)烷基、取代或未取代的(C6-C30)芳基或者取代或未取代的(C2-C30)杂芳基,或者它们可分别通过具有或不具有稠环的取代或未取代的(C3-C30)亚烷基或者具有或不具有稠环的取代或未取代的(C3-C30)亚烯基与相邻取代基连接形成脂环、单环或多环芳环; [0024] R11 to R2tl independently represent hydrogen, deuterium, halogen, a substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl group, or a substituted or unsubstituted (C2-C30 ) heteroaryl, or they may be separately through with or without a fused ring of a substituted or unsubstituted (C3-C30) alkylene or a fused ring with or without a substituted or unsubstituted (C3-C30) alkenylene adjacent substituent group to form an alicyclic ring, a monocyclic or polycyclic aromatic ring;

[0025] m和η独立地表示0_4的整数,当m和η是大于或等于2的整数时,每个R1和L可相同或不同; [0025] m and η independently represents an integer 0_4 when m and η is an integer greater than or equal to 2, each R1 and L may be the same or different;

[0026] P表示0-2的整数,当ρ=2时,每个R2可相同或不同;以及 [0026] P is an integer of 0-2, and when ρ = 2, each R2 may be the same or different; and

[0027] 所述杂环烷基、杂芳基和杂亚芳基包含一个或多个选自B、N、O、S、P (=0)、Si和P的杂原子; [0027] The heterocycloalkyl, heteroaryl and heteroarylene containing one or more selected from B, N, O, S, P (= 0), Si and P heteroatoms;

[0028] 本文所用术语“烷基”和其他含有“烷基”部分的取代基包括直链和支链部分,并且“环烷基”包括单环烃以及多环烃,例如取代或未取代的金刚烷基或者取代或未取代的(C7-C30) 二环烷基。 [0028] As used herein the term "alkyl" and the other containing "alkyl" moiety include both linear and branched moieties, and "cycloalkyl" includes monocyclic hydrocarbons and polycyclic hydrocarbons, e.g., a substituted or unsubstituted adamantyl, or a substituted or unsubstituted (C7-C30) bicycloalkyl group. 本文所用术语“芳基”指的是通过从芳香烃去除一个氢原子得到的有机基团,包括4元至7元、具体为5元或6元的单环或稠环,甚至还可以包括通过单键连接的多个芳基的结构。 As used herein, the term "aryl" refers to an aromatic hydrocarbon by removing one hydrogen atom from an organic group, including 4-7 yuan, in particular 5- or 6-membered single ring or a condensed ring, and even including through Speed connection structure more aromatic groups. 它们的具体例子包括但不限于:苯基、萘基、联苯基(biphenyl)、三联苯基(terphenyl)、蒽基、却基、荷基、菲基(phenanthryl)、苯并[9,10]菲基 Specific examples thereof include, but are not limited to: phenyl, naphthyl, biphenyl (biphenyl), terphenyl (terphenyl), an anthryl group, but group, menthyl, phenanthryl (phenanthryl), benzo [9,10 ] phenanthryl

(triphenylenyl )、花基、花基(perylenyl )、蔚基(chrysenyl )、并四苯基(naphthacenyl )、荧蒽基(fluoranthenyl)等。 (Triphenylenyl), flower group, flower base (perylenyl), Wei group (chrysenyl), and tetraphenyl (naphthacenyl), fluoranthenyl (fluoranthenyl) and so on. 所述萘基包括1_萘基和2-萘基,所述蒽基包括1-蒽基、2-蒽基和9-蒽基,所述芴基包括1-芴基、2-芴基、3-芴基、4-芴基和9-芴基,所述并四苯基(naphthacenyl)包括1-并四苯基、2-并四苯基和9_并四苯基。 The naphthyl group includes 1_ naphthyl and 2-naphthyl, the anthryl includes 1-anthryl, 2-anthryl and 9-anthryl group, a fluorenyl group include 1-fluorenyl, 2-fluorenyl, 3- fluorenyl, 4-fluorenyl and 9-fluorenyl, said phenyl and four (naphthacenyl) and tetraphenyl including 1-, 2- and 9-stage and four-tetraphenyl and phenyl. 所述花基包括1-花基、2-芘基和4-芘基,所述联苯基包括2-联苯基、3-联苯基和4-联苯基,所述三联苯基包括对_ 二联苯基~4~基、对-二联苯基-3-基、对-二联苯基~2~基、间-二联苯基~4~基、间_ 二联苯基_3-基和间_ 二联苯基-2-基,所述荷基包括1_荷基、2-荷基、3-荷基、4-荷基和9-芴基。 The spent flowers group include 1-yl, 2-pyrenyl group and 4-pyrenyl group, a biphenyl group include 2-biphenylyl, 3-biphenylyl and 4-biphenylyl, terphenyl group comprising the _ two of biphenyl - 4 - based on - two biphenyl-3-yl, for - two biphenyl ~ 2 ~ groups, between - two biphenyl ~ 4 ~ group, between _ two biphenyl _3- groups and between _ two biphenyl-2-yl, which includes 1_-charged-charged, 2-charged, 3-charged, 4-charged and the 9-fluorenyl.

[0029] 本文所用术语“杂芳基”表示包含1-4个选自B、N、O、S、P、P(=0)、Si和Se的杂原子作为芳环骨架原子,并且其他芳环骨架原子为碳的芳基基团。 [0029] As used herein the term "heteroaryl" represents containing 1-4 heteroatoms selected from B, N, O, S, P, P (= 0), Si and Se heteroatoms as aromatic ring backbone atoms, and other aryl ring backbone atoms of carbon aryl group. 它可以是与一个或多个苯环缩合得到的5元或6元单环杂芳基或多环杂芳基,且可以是部分饱和的。 It can be associated with one or more benzene condensation of 5- or 6-membered monocyclic heteroaryl or polycyclic heteroaryl, and may be partially saturated. 在本发明中,“杂芳基”包含一个或多个杂芳基通过单键连接的结构。 In the present invention, the term "heteroaryl" containing one or more hetero-aryl structures connected by a single bond. 所述杂芳基包括二价芳基,其中环中的杂原子可被氧化或季铵化以形成例如N-氧化物或季铵盐。 The heteroaryl groups include bivalent aryl group, wherein the ring heteroatoms may be oxidized or quaternized to form, for example a quaternary ammonium salt or N- oxide. 它们具体例子包括但并不限于,单环杂芳基例如呋喃基、噻吩基、吡咯基、咪唑基、吡唑基、噻唑基、噻二唑基、异噻唑基、异噁唑基、噁唑基、噁二唑基、三嗪基、四嗪基、三唑基、呋咱基(furazanyl)、吡啶基、吡嗪基、喃唳基、咕嗪基等;多环杂芳基例如苯并呋喃基(benzofuranyl)、苯并苯硫基、二苯并呋喃基、二苯并苯硫基、异苯并呋喃基、苯并咪唑基、苯并噻唑基、苯并异噻唑基、苯并异噁唑基、苯并噁唑基、异吲哚基、吲哚基、吲唑基、苯并噻二唑基、喹啉基、异喹啉基、噌啉基(cinnolinyl )、喹唑啉基、喹喔啉基(quinoxalinyl )、咔唑基、菲唳基(phenanthridinyl )、苯并间二氧杂环戊烯基(benzodioxolyl )、吖啶基、菲咯啉基、吩嗪基、吩噻嗪基、吩噁嗪基等;及其N-氧化物(例如吡啶基N-氧化物、喹啉基N-氧化物);或其季铵盐等。 Specific examples include, but are not limited to, a monocyclic heteroaryl group such as furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl group, oxadiazolyl, triazinyl, tetrazine, triazolyl, furazanyl (furazanyl), pyridyl, pyrazinyl, Nan Li group, cushions, piperazinyl and the like; polycyclic heteroaryl groups such as benzo furanyl (benzofuranyl), benzothiophenyl, dibenzofuryl dibenzo phenylthio, isobenzofuran group, benzimidazolyl, benzothiazolyl, benzisothiazole group, benzoisoxazole oxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzo-thiadiazolyl, quinolyl, isoquinolyl, cinnolinyl (cinnolinyl), quinazolinyl , quinoxaline (quinoxalinyl), carbazolyl, Philippines 唳 group (phenanthridinyl), between Benzodioxol alkenyl (benzodioxolyl), acridinyl, phenanthroline group, phenazine group, phenothiazines group, phenoxazine group and the like; and N- oxides (e.g., pyridyl N- oxide, quinolinyl N- oxide); or a quaternary ammonium salt. 吡咯基包括:1-吡咯基、2-吡咯基和3-吡咯基; 吡啶基包括2-吡啶基、3-吡啶基和4-吡啶基;喷哚基包括1-吲哚基、2-吲哚基、3-吲哚基、4-吲哚基、5-吲哚基、6-吲哚基和7-吲哚基;异吲哚基包括1-异吲哚基、2-异吲哚基、3-异吲哚基、4-异吲哚基、5-异吲哚基、6-异吲哚基和7-异吲哚基;呋喃基包括2-呋喃基和3-呋喃基;苯并呋喃基包括2-苯并呋喃基、3-苯并呋喃基、4-苯并呋喃基、5-苯并呋喃基、6-苯并呋喃基和7-苯并呋喃基;异苯并呋喃基包括1-异苯并呋喃基、3-异苯并呋喃基、4-异苯并呋喃基、5-异苯并呋喃基、6-异苯并呋喃基和7-异苯并呋喃基;喹啉基包括3-喹啉基、4-喹啉基、5-喹啉基、6-喹啉基、7-喹啉基和8-喹啉基;异喹啉基包括1-异喹啉基、3-异喹啉基、4-异喹啉基、5-异喹啉基、6-异喹啉基、7-异喹啉基和8-异喹啉基;喹喔啉基包括2-喹喔啉基、5-喹喔啉基和6-喹喔啉基;咔唑基包括1-咔唑基、2-咔唑基、3-咔唑基、4-咔唑基和9-咔唑基;菲基包括1-菲基、2-菲基、3-菲基、4-菲基、6-菲基、7-菲基、8-菲基、9-菲基和10-菲基;吖啶基包括1-吖啶基、2-吖啶基、3-吖啶基、4-吖啶基和9-吖啶基;菲咯啉基包括I,7-菲咯啉-2-基、I, 7-菲咯啉-3-基、I, 7-菲咯啉-4-基、I, 7-菲咯啉-5-基、I, 7-菲咯啉-6-基、I, 7-菲咯啉-8-基、1,7-菲咯啉-9-基、1,7-菲咯啉-10-基、1,8-菲咯啉-2-基、1,8-菲咯啉-3-基、I, 8-菲咯啉-4-基、I, 8-菲咯啉-5-基、I, 8-菲咯啉-6-基、I, 8-菲咯啉-7-基、I, 8-菲咯啉-9-基、1,8-菲咯啉-10-基、1,9-菲咯啉-2-基、1,9-菲咯啉-3-基、1,9-菲咯啉-4-基、I, 9-菲咯啉-5-基、I, 9-菲咯啉-6-基、I, 9-菲咯啉-7-基、I, 9-菲咯啉_8_基、I, 9-菲咯啉-10-基、1,10-菲咯啉-2-基、1,10-菲咯啉-3-基、1,10-菲咯啉-4-基、1,10-菲咯啉-5-基、2,9-菲咯啉-1-基、2,9-菲咯啉-3-基、2,9-菲咯啉_4_基、2,9-菲咯啉_5_基、2,9-菲咯啉-6-基、2,9-菲咯啉-7-基、2,9-菲咯啉_8_基、2,9-菲咯啉-10-基、2,8-菲咯啉-1-基、2,8-菲咯啉-3-基、2,8-菲咯啉-4-基、2,8-菲咯啉_5_基、2,8-菲咯啉_6_基、2,8-菲咯啉-7-基、2,8-菲咯啉-9-基、2,8-菲咯啉-10-基、2,7-菲咯啉-1-基、2,7-菲咯啉-3-基、2,7-菲咯啉-4-基、2,7-菲咯啉-5-基、2,7-菲咯啉-6-基、2,7-菲咯啉-8-基、2,7-菲咯啉-9-基和2,7-菲咯啉-10-基;吩嗪基包括1-吩嗪基和2-吩嗪基;吩噻嗪基包括1-吩噻嗪基、2-吩噻嗪基、3-吩噻嗪基、4-吩噻嗪基和I O-吩噻嗪基;吩噁嗪基包括1-吩噁嗪基、2-吩噁嗪基、3-吩噁嗪基、4-吩噁嗪基和10-吩噁嗪基;噁唑基包括2-噁唑基、4-噁唑基和5-噁唑基;噁二唑包括2-噁二唑基和5-噁二唑基;呋咱基包括3-呋咱基;二苯并呋喃基包括1- 二苯并呋喃基、2- 二苯并呋喃基、3- 二苯并呋喃基和4- 二苯并呋喃基;二苯并苯硫基包括1- 二苯并苯硫基、2- 二苯并苯硫基、3- 二苯并苯硫基和4- 二苯并苯硫基。 Pyrrolyl include: 1-pyrrolyl, 2-pyrrolyl and 3-pyrrolyl; pyridyl group include 2-pyridyl, 3-pyridyl and 4-pyridyl; spray indolyl includes 1-indolyl, 2-indole indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl and 7-indolyl; isoindolyl includes 1-isoindolyl, 2 isoindole group, 3-isoindolyl, 4 isoindolyl, 5 isoindolyl, 6 and 7 isoindolyl isoindolyl; furyl group includes 2-furyl and 3-furyl; benzofuranyl include 2-benzofuranyl, 3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl and 7-benzofuranyl; isobenzofuran benzofuranyl includes 1-isobenzofuran group, 3 isobenzofuran, 4-isobenzofuran group, 5-isobenzofuran, 6- and 7-isobenzofuranyl isobenzofuranyl ; quinoline groups include 3-quinolyl, 4-quinolyl, 5-quinolinyl, 6-quinolyl, quinolyl 7- and 8-quinolinyl; isoquinolinyl includes 1-isoquinolyl isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolinyl, 6-isoquinolyl, 7-isoquinolyl and 8-isoquinolyl; quinoxalinyl include 2- quinoxalinyl, 5- and 6-quinoxalinyl quinoxalinyl; carbazolyl group include 1-carbazolyl, 2- carbazolyl, 3- carbazolyl, 4-carbazolyl and 9 - carbazolyl; phenanthryl include 1-phenanthryl, 2- phenanthryl, 3- phenanthryl, 4-phenanthryl, phenanthryl 6-, 7- phenanthryl, 8- phenanthryl, 9-phenanthryl and 10- phenanthryl; acridine acridine groups include 1-piperidinyl, 2-acridinyl, 3- acridinyl, 4-acridinyl and 9-acridinyl; phenanthroline group include I, 7- phenanthroline - 2- group, I, 7- phenanthroline-3-yl, I, 7- phenanthroline-4-yl, I, 7- phenanthroline-5-yl, I, 7- phenanthroline -6- group, I, 7- 8-phenanthroline, 1,7-phenanthroline-9-yl, 1,7-phenanthroline-10-yl, 1,8-phenanthroline-2-yl, 1,8-phenanthroline-3-yl, I, 8- phenanthroline-4-yl, I, 8- phenanthroline-5-yl, I, 8- 6-phenanthroline, I, 8- phenanthroline-7-yl, I, 8- phenanthroline-9-yl, 1,8-phenanthroline-10-yl, 1,9-phenanthroline-2-yl, 1,9 phenanthroline-3-yl, 1,9-phenanthroline-4-yl, I, 9- phenanthroline-5-yl, I, 9- phenanthroline-6-yl, I, 9- phenanthroline 7-yl, I, 9- phenanthroline _8_ group, I, 9- 10-yl phenanthroline, 1,10-2-yl, 1,10 - 3-yl, 1,10-4-yl, 1,10-5-yl, 2,9-phenanthroline-1-yl, 2,9-phenanthroline -3- group, 2,9-phenanthroline _4_ group, 2,9-phenanthroline _5_ group, 6-yl 2,9-phenanthroline, 2,9-phenanthroline-7-yl, 2,9-phenanthroline _8_ group, 10-yl 2,9-phenanthroline, 2,8-phenanthroline-1-yl, 2,8-phenanthroline-3-yl, 2, 8- 4-phenanthroline, 2,8-phenanthroline _5_ group, 2,8-phenanthroline _6_ group, 2,8-phenanthroline-7-yl, 2,8 phenanthroline-9-yl, 2,8-phenanthroline-10-yl, 2,7-phenanthroline-1-yl, 2,7-phenanthroline-3-yl, 2,7-phenanthroline 4-yl, 2,7-phenanthroline-5-yl, 2,7-phenanthroline-6-yl, 2,7-phenanthroline-8-yl, 2,7-phenanthroline - 9- yl and 2,7-phenanthroline-10-yl; phenazine phenazine group include 1- and 2-phenazine group; phenothiazine phenothiazine group include 1-yl, 2- phenothiazine group , 3- phenothiazine group, 4- phenothiazine group and I O- phenothiazine group; phenoxazine phenoxazine group include 1-yl, 2-phenoxazine group, 3- phenoxazine group, 4 - 10- phenoxazine group and a phenoxazine group; oxazolyl group include 2-oxazolyl, 4-oxazolyl and 5-oxazolyl; oxadiazol including 2- and 5-oxadiazolyl oxadiazol oxazolyl; furazanyl include 3 furazanyl; dibenzofuranyl include 1 dibenzofuranyl, 2 dibenzofuranyl, 3- and 4-dibenzofuranyl dibenzofuranyl ; include 1-phenylthio-dibenzo dibenzo phenylthio, 2-dibenzo-phenylthio, 3- and 4-phenylthio-dibenzo dibenzo phenylthio.

[0030] 本文所用术语“(C1-C30)烷基”包括(C1-C20)烷基或(Cl-ClO)烷基,且术语“(C6-C30)芳基”包括(C6-C20)芳基或(C6-C12)芳基。 [0030] As used herein the term "(C1-C30) alkyl" includes (C1-C20) alkyl or (Cl-ClO) alkyl, and the term "(C6-C30) aryl" includes (C6-C20) aryl group or (C6-C12) aryl. 术语“(C2-C30)杂芳基”包括(C2-C20)杂芳基或(C2-C12)杂芳基,术语“(C3-C30)环烷基”可包括(C3-C20)环烷基或(C3-C7)环烷基。 The term "(C2-C30) heteroaryl" include (C2-C20) heteroaryl or (C2-C12) heteroaryl, the term "(C3-C30) cycloalkyl" may include (C3-C20) cycloalkyl group or (C3-C7) cycloalkyl. 术语“(C2-C30)烯基或炔基”包括(C2-C20)烯基或炔基或者(C2-C10) The term "(C2-C30) alkenyl or alkynyl group" include (C2-C20) alkenyl or alkynyl, or (C2-C10)

烯基或炔基。 Alkenyl or alkynyl group.

[0031] 在本文所用表述“取代或未取代的”或者“有或没有取代基”中,术语“取代的(有取代基)”表示未取代的取代基进一步被取代基取代。 [0031] As used herein, the expression "substituted or unsubstituted" or "with or without substituent" in the term "substituted (substituted)" means an unsubstituted substituents further substituents. RpRyRyUArpAr2以及R11至R2tl的取代基可分别被选自下组的一个或多个取代基进一步取代:氘、卤素、卤素取代或未取代的(C1-C30)烷基、(C6-C30)芳基、(C6-C30)芳基取代或未取代的(C2-C30)杂芳基、5-元至7-元杂环烷基、与一个或多个芳环稠合的5-元至7-元杂环烷基、(C3-C30)环烷基、与一个或多个芳环稠合的(C6-C30)环烷基、(C2-C30)烯基、(C2-C30)炔基、 RpRyRyUArpAr2 to R2tl and R11 substituents may respectively be selected from one or more of the group further substituted: deuterium, halogen, halogen-substituted or unsubstituted (C1-C30) alkyl, (C6-C30) aryl , (C6-C30) aryl optionally substituted (C2-C30) heteroaryl, 5- to 7-membered heterocyclic group with one or more aromatic rings fused 5- to 7- membered heterocyclic group, (C3-C30) cycloalkyl, with one or more aromatic rings fused (C6-C30) cycloalkyl, (C2-C30) alkenyl, (C2-C30) alkynyl,

[0032] [0032]

Figure CN103189469AD00191

[0033]氰基、咔唑基、(C6-C30)芳基(C1-C30)烷基、(C1-C30)烷基(C6-C30)芳基、-OR21, -SR22, _NR23R24、-PR25R26, -SiR27R28R29、硝基和羟基,且Y11 和Y12 独立地表示化学键、-C(R31R32)-、-0-、-S-或-N(R33)-,仅排除Y11和Y12都是化学键的情况;并且R21至R29以及R31至R33独立地表示(C1-C30)烷基、(C6-C30)芳基、(C2-C30)杂芳基或者(C3-C30)环烧基。 [0033] cyano, carbazolyl, (C6-C30) aryl (C1-C30) alkyl, (C1-C30) alkyl (C6-C30) aryl group, -OR21, -SR22, _NR23R24, -PR25R26 , -SiR27R28R29, nitro and hydroxyl, and Y11 and Y12 independently represents a bond, -C (R31R32) -, - 0 -, - S- or -N (R33) -, Y11 and Y12 are only exclude bond case ; and R21 to R29 and R31 to R33 independently represent (C1-C30) alkyl, (C6-C30) aryl, (C2-C30) heteroaryl or (C3-C30) cycloalkyl group burned.

[0034] 在化学式I中,环 [0034] In Formula I, Ring

Figure CN103189469AD00192

与二氢吲哚环稠合,表示6-元芳环或6-元含氮杂 Indoline ring and fused aromatic ring represents a 6-membered or 6-membered nitrogen-containing

Figure CN103189469AD00193

与环A稠合,表示5-元或6-元环,环C A fused ring represents a 5- or 6-membered ring, C

Figure CN103189469AD00194

与环B稠合,表示6-元 Fused ring B represents a 6-membered

芳环或6-元含氮杂芳环。 Or 6-membered aromatic nitrogen-containing aromatic ring.

[0035] 此外,化学式I的 [0035] In addition, the formula I

Figure CN103189469AD00195

选自以下结构,但不限于此。 It is selected from the following structures, but not limited thereto.

[0036] [0036]

Figure CN103189469AD00201

[0037] 其中,R2、R11至R15、以及p的定义与化学式I相同。 [0037] wherein, R2, R11 to R15, and p is the same as defined in formula I.

[0038] 具体来说,L表示(C6-C30)亚芳基;ArjPAr2独立地表示(C6-C30)芳基、(C2-C30) [0038] More specifically, L represents (C6-C30) arylene; ArjPAr2 independently represent (C6-C30) aryl, (C2-C30)

杂芳基、 Heteroaryl,

Figure CN103189469AD00202

[0040] Y3 和Y4 独立地表不_0-、-S-、-C (R16R17) _ 或-N (R20) - ;R16、R17 和R2q 独立地表不(C1-C30)烷基、(C6-C30)芳基或(C2-C30)杂芳基,或者R16和17可通过取代或未取代的有或没有稠环的(C3-C30)亚烷基或者通过取代或未取代的有或没有稠环的(C3-C30)亚烯基连接形成脂环或者单环或多环芳环况表示氢、(C6-C30)芳基或(C2-C30)杂芳基,或者可 [0040] Y3 and Y4 independently represent not _0 -, - S -, - C (R16R17) _ or -N (R20) -; R16, R17 and R2q not independently represent (C1-C30) alkyl, (C6- C30) aryl or (C2-C30) heteroaryl, or R16 and 17 can be substituted or unsubstituted fused ring with or without a (C3-C30) alkylene or with or without a substituted or unsubstituted fused by Central (C3-C30) alkenylene to form an alicyclic ring or a mono- or polycyclic aromatic ring case represents hydrogen, (C6-C30) aryl or (C2-C30) heteroaryl, or may be

Figure CN103189469AD00211

与相邻取代基连接;L的亚芳基,Ar1和Ar2芳基、杂芳 Connected with the adjacent substituents; L arylene group, Ar1 and Ar2 aryl, heteroaryl

基,R16、R17和R2tl的烷基、芳基或杂芳基,R1的芳基或杂芳基可以被一个或多个选自下组的取代基进一步取代:氘、卤素、卤素取代或未取代的(C6-C30)芳基、(C1-C30)烷基、(C6-C30)芳基取代或未取代的(C2-C30)杂芳基、5-元至7-元杂环烷基、与一个或多个芳环稠合的 Group, R16, R17 and R2tl alkyl, aryl or heteroaryl group, R1 aryl or heteroaryl group optionally substituted by one or more substituents selected from the group further substituted: deuterium, halo, halo-substituted or unsubstituted substituted (C6-C30) aryl, (C1-C30) alkyl, (C6-C30) aryl substituted or unsubstituted (C2-C30) heteroaryl, 5- membered to 7-membered heterocycloalkyl , with one or more aromatic rings fused

5-元至7-元杂环烷基 5- to 7-membered heterocyclic group

Figure CN103189469AD00212

、咔唑基,以及-NR23R24- Y11和Y12独立地表 , Carbazolyl, and -NR23R24- Y11 and Y12 independently represent

示-C (R31R32)-、-O-、-S-或者-N(R3tl)- ;R23、R24, R31、R32 和R33 独立地表示(C1-C30)烷基、(C6-C30)芳基或者(C2-C30)杂芳基。 Illustrates -C (R31R32) -, - O -, - S- or -N (R3tl) -; R23, R24, R31, R32 and R33 independently represent (C1-C30) alkyl, (C6-C30) aryl or (C2-C30) heteroaryl.

[0041] 本发明的有机电致发光化合物可列举为下述化合物,但它们并不对本发明构成限制: [0041] The present invention has the organic electroluminescent compounds include the following compounds, but they are not to be construed to limit the present invention:

[0042] [0042]

Figure CN103189469AD00213

[0043] [0043]

Figure CN103189469AD00221
Figure CN103189469AD00231
Figure CN103189469AD00241
Figure CN103189469AD00251
Figure CN103189469AD00261
Figure CN103189469AD00271
Figure CN103189469AD00281

[0050] [0050]

Figure CN103189469AD00291
Figure CN103189469AD00301
Figure CN103189469AD00311

[0053] 本发明的有机电致发光化合物可例如下述方案I所示来制备,但不限于此。 [0053] The present invention has the organic electroluminescent compounds can be prepared as shown below in Scheme I, for example, but not limited thereto.

[0054][方案 I] [0054] [program I]

[0055] [0055]

Figure CN103189469AD00312

[0056] 其中,A、B、C、R” L、Ar” Ar2、m和n与化学式I的定义相同。 [0056] wherein like A, B, C, R "L, Ar" Ar2, m and n are as defined in formula I.

[0057] 此外,本发明提供一种有机电致发光器件,其中本发明的有机电致发光化合物用作空穴注入材料或空穴传输材料。 [0057] Further, the present invention provides an organic electroluminescent device, wherein the present invention is an organic electroluminescent compounds as the hole injection material or a hole transport material.

[0058] 当化学式I表示的本发明的有机电致发光化合物用于空穴注入层或者空穴传输层时,它可用于制造由于改善的功率效率而消耗更少功率的OLED器件。 [0058] When Formula I of the present invention is represented when the organic electroluminescent compound for the hole injection layer or a hole transport layer, which can be used in the manufacture of power due to the improvement of the efficiency of OLED devices consume less power.

[0059] 本发明的有机电致发光器件包含第一电极;第二电极;插入所述第一电极和第二电极之间的一层或多层有机层,所述有机层包括化学式I表不的一种或多种有机电致发光化合物。 [0059] The present invention has an organic electroluminescent device comprising a first electrode; a second electrode; inserting one or more layers of the first electrode and the second electrode of the organic layer, the organic layer comprises a sheet of Formula I is not of one or more organic electroluminescent compound. [0060] 此外,除了包含化学式I的一种或多种有机电致发光化合物层之外,有机层还可包含一层或多层电致发光层。 [0060] In addition to formula I comprising one or more organic electroluminescent compound layer other than the organic layer may further comprise one or more layers of an electroluminescent layer. 电致发光层还可包含一种或多种掺杂剂或基质。 The electroluminescent layer may further comprise one or more dopants or matrix. 用于本发明的有机电致发光器件的掺杂剂或基质没有特别的限制,但是可选自如下化学式2-6: Used in the present invention is an organic electroluminescent device or matrix dopant is not particularly limited, but may be selected from the following formula 2-6:

[0061] 化学式2 [0061] Formula 2

[0062] MiL101L102L103 [0062] MiL101L102L103

[0063]其中, [0063] where

[0064] M1 表示Ir、Pt、Pd 或者Os ; [0064] M1 represents Ir, Pt, Pd or Os;

[0065] 配体Llt11、L102和Llt13独立地选自下述结构: [0065] Ligand Llt11, L102 and Llt13 independently selected from the following structures:

[0066] [0066]

Figure CN103189469AD00321

[0068] R201至R2tl3独立地表示氢、氘、卤素取代或未取代的(C1-C30)烷基、(C1-C30)烷基取代或未取代的(C6-C30)芳基或卤素; [0068] R201 to R2tl3 independently represent hydrogen, deuterium, halogen-substituted or unsubstituted (C1-C30) alkyl, (C1-C30) alkyl optionally substituted (C6-C30) aryl or halogen;

[0069] R2tl4至R219独立地表示氢、氘、取代或未取代的(C1-C30)烷基、取代或未取代的(C1-C30)烷氧基、取代或未取代的(C3-C30)环烷基、取代或未取代的(C2-C30)烯基、取代或未取代的(C6-C30)芳基、取代或未取代的单-(C1-C30)烷基氨基或者取代或未取代的二-(C1-C30)烷基氨基、取代或未取代的单-(C6-C30)芳基氨基或者取代或未取代的二-(C6-C30)芳基氨基、SF5、取代或未取代的三(C1-C30)烷基甲硅烷基、取代或未取代的二(C1-C30)烷基(C6-C30)芳基甲硅烷基、取代或未取代的三(C6-C30)芳基甲硅烷基、氰 [0069] R2tl4 to R219 independently represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) a cycloalkyl group, a substituted or unsubstituted (C2-C30) alkenyl, substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted mono - (C1-C30) alkylamino group or a substituted or unsubstituted di - (C1-C30) alkylamino group, a substituted or unsubstituted mono - (C6-C30) arylamino or a substituted or unsubstituted di - (C6-C30) arylamino, SF5, a substituted or unsubstituted three (C1-C30) alkylsilyl group, a substituted or unsubstituted di (C1-C30) alkyl (C6-C30) aryl silyl group, a substituted or unsubstituted three (C6-C30) aryl a silyl group, a cyano

基或者齒素; Group or tooth elements;

[0070] R220至R223独立地表示氢、氘、卤素取代或未取代的(C1-C30)烷基或者(C1-C30)烷基取代或未取代的(C6-C30)芳基; [0070] R220 to R223 independently represent hydrogen, deuterium, halogen-substituted or unsubstituted (C1-C30) alkyl or (C1-C30) alkyl substituted or unsubstituted (C6-C30) aryl;

[0071] R224和R225独立地表示氢、氘、取代或未取代的(C1-C30)烷基、卤素取代或未取代的(C6-C30)芳基或者卤素,或者R224和R225可通过具有或不具有稠环的取代或未取代的(C3-C12)亚烷基或者具有或不具有稠环的取代或未取代的(C3-C12)亚烯基与相邻取代基连接形成脂环、单环或多环芳环; [0071] R224 and R225 independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, halo-substituted or unsubstituted (C6-C30) aryl or halogen, or R224 and R225 can be with or It does not have a condensed ring substituted or unsubstituted (C3-C12) alkylene or fused ring with or without a substituted or unsubstituted (C3-C12) alkenylene with an adjacent substituent to form an alicyclic ring, single or polycyclic aromatic ring;

[0072] R226表示取代或未取代的(C1-C30)烷基、取代或未取代的(C6-C30)芳基、取代或未取代的(C2-C30)杂芳基或卤素; [0072] R226 represents a substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted (C2-C30) heteroaryl or halogen;

[0073] R227至R229独立地表示氢、氘、取代或未取代的(C1-C30)烷基、取代或未取代的(C6-C30)芳基或卤素;以及 [0073] R227 to R229 independently represent hydrogen, deuterium, a substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or halogen; and

R233 R234 R237.R238 2\^J<2A2 R233 R234 R237.R238 2 \ ^ J <2A2

[0074] Q 表示 [0074] Q represents

Figure CN103189469AD00331

[0075] 其中,R231至R242独立地表示氢、氘、卤素取代或未取代的(C1-C30)烷基、(C1-C30)烷氧基、卤素、取代或未取代的(C6-C30)芳基、氰基、取代或未取代的(C3-C30)环烷基,或者它们可通过亚烷基或者亚烯基与相邻取代基连接形成螺环或稠环,或者通过亚烷基或者亚烯基与R2tl7或R2tl8连接形成饱和或不饱和稠环。 [0075] wherein, R231 through R242 independently represent hydrogen, deuterium, halogen-substituted or unsubstituted (C1-C30) alkyl, (C1-C30) alkoxy, halo, a substituted or unsubstituted (C6-C30) an aryl group, a cyano group, a substituted or unsubstituted (C3-C30) cycloalkyl, or they may be substituted by alkylene or alkenylene group to form an adjacent ring or a spiro fused ring, or through an alkylene group or alkenylene and R2tl7 or R2tl8 to form a saturated or unsaturated condensed ring.

[0076] 化学式3 [0076] Chemical Formula 3

[0077] [0077]

Figure CN103189469AD00332

[0078]其中, [0078] where

[0079] Z 表示-O-、-S-、-C (R41R42) -、-Si (R43R44) _ 或者-N (R45)-; [0079] Z represents -O -, - S -, - C (R41R42) -, - Si (R43R44) _ or -N (R45) -;

[0080] 环D和环F独立地表示 [0080] ring D and ring F independently represent

Figure CN103189469AD00333

[0081]环 E 表 [0081] ring E table

Figure CN103189469AD00334

Y21和Y22独立地表示CH或N ; Y21 and Y22 independently represent CH or N;

[0083] Y23 和Y24 独立地表不化学键、_0-、-S-、-C (R41R42) -、Si (R43R44)_ 或者-N (R45)-,仅排除Y23和Y24都是化学键的情况;[0084] R31和R32独立地表不氢、氣、齒素、取代或未取代的(C1-C30)烧基、取代或未取代的(C6-C30)芳基、取代或未取代的(C2-C30)杂芳基、取代或未取代的(C3-C30)环烷基、取代或未取代的5-元至7-元杂环烷基、取代或未取代的(C6-C30)芳基(C1-C30)烷基、取代或未取代的(C1-C30)烷基甲硅烷基、取代或未取代的(C6-C30)芳基甲硅烷基、取代或未取代的(C1-C30)烷基(C6-C30)芳基甲硅烷基、氰基、硝基或者羟基,或者它们可以通过有或没有稠环的取代或未取代的(C3-C30)亚烷基或者有或没有稠环的取代或未取代的(C3-C30)亚烯基与相邻取代基连接以形成脂环、单环或多环芳环; [0083] Y23 and Y24 independently represent no bond, _0 -, - S -, - C (R41R42) -, Si (R43R44) _ or -N (R45) - situation Y23 and Y24 are chemical bonds, excluding only; [ 0084] R31 and R32 are not independently represent hydrogen, gas, halogen, a substituted or unsubstituted (C1-C30) firing group, a substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted (C2-C30 ) heteroaryl, substituted or unsubstituted (C3-C30) cycloalkyl group, a substituted or unsubstituted 5-membered to 7-membered heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl (C1 -C30) alkyl group, a substituted or unsubstituted (C1-C30) alkylsilyl group, a substituted or unsubstituted (C6-C30) aryl silyl group, a substituted or unsubstituted (C1-C30) alkyl (C6-C30) aryl silyl group, a cyano group, a nitro group or a hydroxyl group, or they may be with or without a fused ring of a substituted or unsubstituted (C3-C30) alkylene or substituted fused ring with or without the (C3-C30) alkenylene with adjacent or unsubstituted aliphatic substituents linked to form a ring, a monocyclic or polycyclic aromatic ring;

[0085] R41至R45独立地表示氢、氘、卤素、取代或未取代的(C1-C30)烷基、取代或未取代的(C6-C30)芳基、取代或未取代的(C2-C30)杂芳基、取代或未取代的5-元至7-元杂环烷基或者有或没有取代基的取代或未取代的(C3-C30)环烷基,或者它们可分别与相邻取代基连接以形成环; [0085] R41 to R45 independently represent hydrogen, deuterium, halogen, a substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted (C2-C30 ) heteroaryl, a substituted or unsubstituted 5-membered to 7-membered heterocyclic group with or without substituent or a substituted or unsubstituted (C3-C30) cycloalkyl, or they may be substituted, respectively, with an adjacent group is attached to form a ring;

[0086] r和q独立地表示0_4的整数,并且当r和q是大于或等于2的整数时,每个R31和R32可以相同或不同,或者它们可分别与相邻取代基连接以形成环; [0086] r and q independently represents an integer 0_4, and when r and q is an integer greater than or equal to 2, each of R31 and R32 may be the same or different, or they may be separately connected to the adjacent substituent to form a ring ;

[0087] 所述杂环烷基和杂芳基包含一个或多个选自B、N、O、S、P (=0)、Si和P的杂原子。 [0087] The heterocycloalkyl and heteroaryl include one or more selected from B, N, O, S, P (= 0), Si and P heteroatoms.

[0088] 化学式4 [0088] Formula 4

[0089] (Cz-L2) aM [0089] (Cz-L2) aM

[0090] 化学式5 [0090] Chemical Formula 5

[0091] (Cz)b_L2_M [0091] (Cz) b_L2_M

[0092]其中, [0092] where

[0093] Cz选自以下结构: [0093] Cz selected from the following structures:

[0094] [0094]

Figure CN103189469AD00341

[0095] 环G表示(C6-C30)脂环、(C6-C30)芳环或者(C2-C30)杂芳环; [0095] Ring G represents (C6-C30) cycloaliphatic, (C6-C30) aromatic ring or a (C2-C30) heteroaryl ring;

[0096] R51和R53独立地表示氢、氘、卤素、取代或未取代的(C1-C30)烷基、取代或未取代的(C6-C30)芳基、取代或未取代的(C2-C30)杂芳基、取代或未取代的5-元至7-元杂环烷基、与一个或多个取代或未取代的(C3-C30)环烷基稠合的取代或未取代的(C6-C30)芳基、与一个或多个取代或未取代的芳环稠合的5-元至7-元杂环烷基、取代或未取代的(C3-C30)环烷基、与一个或多个取代或未取代的芳环稠合的(C3-C30)环烷基、取代或未取代的(C6-C30)芳基(C1-C30)烷基、氰基、硝基、羟基、-BR61R62, -PR63R64、-P(=0)R65R66,R67R68R69S1-、-NR7(lR71或-YR72,或者它们可通过取代或未取代的有或没有稠环的(C3-C30)亚烷基或者取代或未取代的有或没有稠环的(C3-C30)亚烯基与相邻取代基连接形成脂环、单环或多环芳环,所形成的脂环、单环或多环芳环的碳原子被选自氮、氧、硫的一个或多个杂原子取代;并且每个R52和R53可相互相同或不同; [0096] R51 and R53 independently represent hydrogen, deuterium, halogen, a substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted (C2-C30 ) heteroaryl, a substituted or unsubstituted 5-membered to 7-membered heterocycloalkyl group, with one or more substituted or unsubstituted (C3-C30) cycloalkyl fused to a substituted or unsubstituted (C6 -C30) aryl, with one or more optionally substituted aryl rings fused 5- to 7-membered heterocyclic group, optionally substituted (C3-C30) cycloalkyl, with one or a plurality of substituted or unsubstituted aryl ring fused (C3-C30) cycloalkyl, substituted or unsubstituted (C6-C30) aryl (C1-C30) alkyl, cyano, nitro, hydroxy, - BR61R62, -PR63R64, -P (= 0) R65R66, R67R68R69S1 -, - NR7 (lR71 or -YR72, or they can be optionally substituted with or without a fused ring (C3-C30) alkylene or a substituted or There is not substituted or (C3-C30) alkenylene not fused ring with an adjacent substituent to form an alicyclic, mono- or polycyclic aromatic ring formed alicyclic, mono- or polycyclic aromatic ring carbon atoms selected from substituted nitrogen, oxygen, sulfur or a plurality of hetero atoms; and each of R52 and R53 may be the same or different from each other;

[0097] Y 表示O 或S ; [0097] Y represents O or S;

[0098] R61至R72独立地表示氢、氘、卤素、取代或未取代的(C1-C30)烷基、取代或未取代的(C6-C30)芳基、取代或未取代的(C2-C30)杂芳基、取代或未取代的5-元至7-元杂环烷基、与一个或多个取代或未取代的(C3-C30)环烷基稠合的取代或未取代的(C6-C30)芳基、与一个或多个取代或未取代的芳环稠合的5-元至7-元杂环烷基、取代或未取代的(C3-C30)环烷基、与一个或多个取代或未取代的芳环稠合的(C3-C30)环烷基、取代或未取代的(C6-C30)芳基(C1-C30)烷基、氰基、硝基或羟基; [0098] R61 to R72 independently represent hydrogen, deuterium, halogen, a substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted (C2-C30 ) heteroaryl, a substituted or unsubstituted 5-membered to 7-membered heterocycloalkyl group, with one or more substituted or unsubstituted (C3-C30) cycloalkyl fused to a substituted or unsubstituted (C6 -C30) aryl, with one or more optionally substituted aryl rings fused 5- to 7-membered heterocyclic group, optionally substituted (C3-C30) cycloalkyl, with one or a plurality of substituted or unsubstituted aryl ring fused (C3-C30) cycloalkyl, substituted or unsubstituted (C6-C30) aryl (C1-C30) alkyl group, a cyano group, a nitro group or a hydroxyl group;

[0099] L2表示化学键、取代或未取代的(C6-C30)芳基或者取代或未取代的(C2-C30)杂 [0099] L2 represents a bond, a substituted or unsubstituted (C6-C30) aryl group, or a substituted or unsubstituted (C2-C30) heteroaryl

芳基; Aryl;

[0100] M表示取代或未取代的(C6-C30)芳基或者取代或未取代的(C2-C30)杂芳基; [0100] M represents a substituted or unsubstituted (C6-C30) aryl group, or a substituted or unsubstituted (C2-C30) heteroaryl;

[0101] a, b, c和d独立地表示0-4的整数。 [0101] a, b, c and d are independently an integer of 0-4.

[0102] 化学式6 [0102] Formula 6

[0103] [0103]

Figure CN103189469AD00351

[0104]其中, [0104] where

[0105] A1至A19独立地表示CR81或N ; [0105] A1 to A19 independently represents CR81 or N;

[0106] X 表示-C (R82R83) -、-N (R84) -、-S-、_0_、-Si (R85) (R86) -、-P (R87) -、-P (=0) (R88)-或者-B (R89)-; [0106] X represents -C (R82R83) -, - N (R84) -, - S -, _ 0 _, - Si (R85) (R86) -, - P (R87) -, - P (= 0) (R88 ) - or -B (R89) -;

[0107] Ar11表示取代或未取代的(C6-C40)亚芳基或者取代或未取代的(C2-C40)杂亚芳基;仅排除e=0且A15至A19同时是CR81的情况; [0107] Ar11 represents a substituted or unsubstituted (C6-C40) arylene group or a substituted or unsubstituted (C2-C40) heteroarylene group; e = 0 and only excluded A15 to A19 is also the case CR81;

[0108] R81至R89独立地表示氢、氘、卤素、取代或未取代的(C1-C30)烷基、取代或未取代的(C6-C30)芳基、与一个或多个取代或未取代的(C3-C30)环烷基稠合的取代或未取代的(C6-C30)芳基、取代或未取代的(C2-C30)杂芳基、取代或未取代的5-元至7-元杂环烷基、与一个或多个取代或未取代的芳环稠合的5-元至7-元杂环烷基、取代或未取代的(C3-C30)环烷基、与一个或多个取代或未取代的芳环稠合的(C3-C30)环烷基、氰基、三氟甲基、-NR91R92、-BR93R94、-PR95R96、-P (=0) R97R98、R99R100R101Si' R102Y2卜、R103C (=0) 'R104C (=0) O-、取代或未取代的(C6-C30)芳基(C1-C30)烷基、取代或未取代的(C2-C30)烯基、取代或未取代的(C2-C30)炔基、羧基、硝基或者羟基,或者它们可通过取代或未取代的有或没有稠环的(C3-C30)亚烷基或者取代或未取代的有或没有稠环的(C3-C30)亚烯基与相邻取代基连接形成脂环、单环或多环芳环; [0108] R81 to R89 independently represent hydrogen, deuterium, halogen, a substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted with one or more The (C3-C30) cycloalkyl fused optionally substituted (C6-C30) aryl, optionally substituted (C2-C30) heteroaryl, optionally substituted 5- to 7- membered heterocyclic group, with one or more optionally substituted aryl rings fused 5- to 7-membered heterocyclic group, optionally substituted (C3-C30) cycloalkyl, with one or more substituted or unsubstituted aromatic ring fused (C3-C30) cycloalkyl, cyano, trifluoromethyl, -NR91R92, -BR93R94, -PR95R96, -P (= 0) R97R98, R99R100R101Si 'R102Y2 Bu , R103C (= 0) 'R104C (= 0) O-, substituted or unsubstituted (C6-C30) aryl (C1-C30) alkyl, substituted or unsubstituted (C2-C30) alkenyl, substituted or unsubstituted (C2-C30) alkynyl group, a carboxyl group, a nitro group or a hydroxyl group, or they may be substituted by a substituted or unsubstituted fused ring with or without a (C3-C30) alkylene or a substituted or unsubstituted, with or without fused ring of (C3-C30) alkenylene with an adjacent substituent to form an alicyclic ring, a monocyclic or polycyclic aromatic ring;

[0109] R91至R98独立地表示取代或未取代的(C1-C30)烷基、取代或未取代的(C6-C30)芳基或者取代或未取代的(C2-C30)杂芳基; [0109] R91 to R98 independently represent a substituted or unsubstituted (C1-C30) alkyl, optionally substituted (C6-C30) aryl or optionally substituted (C2-C30) heteroaryl;

[0110] R99至Rltll独立地表示取代或未取代的(C1-C30)烷基或者取代或未取代的(C6-C30)芳基;[0111] Y21表示S或者O ; [0110] R99 to Rltll independently represent a substituted or unsubstituted (C1-C30) alkyl group or a substituted or unsubstituted (C6-C30) aryl; [0111] Y21 represents S or O;

[0112] R102表示取代或未取代的(C1-C30)烷基或者取代或未取代的(C6-C30)芳基; [0112] R102 represents a substituted or unsubstituted (C1-C30) alkyl group or a substituted or unsubstituted (C6-C30) aryl;

[0113] Rltl3表示取代或未取代的(C1-C30)烷基、取代或未取代的(C1-C30)烷氧基、取代或未取代的(C6-C30)芳基或者取代或未取代的(C6-C30)芳氧基; [0113] Rltl3 represents a substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C6-C30) aryl group, or a substituted or unsubstituted (C6-C30) aryloxy;

[0114] Rltl4表示取代或未取代的(C1-C30)烷基、取代或未取代的(C1-C30)烷氧基、取代或未取代的(C6-C30)芳基或者取代或未取代的(C6-C30)芳氧基; [0114] Rltl4 represents a substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C6-C30) aryl group, or a substituted or unsubstituted (C6-C30) aryloxy;

[0115] e表示0-2的整数。 [0115] e represents an integer of 0-2.

[0116] 所述杂环烷基、杂芳基和杂亚芳基包含一个或多个选自B、N、O、S、P(=0)、Si和P的杂原子; [0116] The heterocycloalkyl, heteroaryl and heteroarylene containing one or more selected from B, N, O, S, P (= 0), Si and P heteroatoms;

[0117] 在化学式2-6所用术语“取代或未取代的”中,术语“取代的”表示未取代的取代基被取代基进一步取代。 [0117] In Chemical Formula 2-6 The term "optionally substituted", the term "substituted" means unsubstituted substituent is further substituted. 所述取代基表示选自化学式I中基团所表示的相同基团的一个或多个取代基。 The substituents represent one or more groups selected from the group of formula I represented the same group of substituents.

[0118] 具体来说,化学式2-6可用如下化合物: [0118] Specifically, the following compounds of formula 2-6 can be used:

[0119] [0119]

Figure CN103189469AD00361

[0120] [0120]

Figure CN103189469AD00371
Figure CN103189469AD00381
Figure CN103189469AD00391
Figure CN103189469AD00401

[0124] [0124]

Figure CN103189469AD00411
Figure CN103189469AD00421

[0126] 本发明的有机电致发光器件包含化学式I表示的有机电致发光化合物,还可包含一种或多种选自芳胺化合物和苯乙烯基胺化合物的化合物,所述芳胺化合物和苯乙烯基胺化合物的具体例子如韩国专利申请第10-2008-0060393号的说明书第212至224段所述,但不限于此。 [0126] The present invention is an organic electroluminescent device comprising a compound of the organic electroluminescent compounds, it may further comprise one or more selected from aromatic amine compounds and styryl amine compounds are represented by formula I, wherein the aromatic amine compound and Specific examples of the styryl amine compound, such as Korean Patent Application 212 to 224 of the first paragraph of the specification No. 10-2008-0060393, but is not limited thereto.

[0127] 在本发明的有机电致发光器件中,除了化学式I表示的有机电致发光化合物以夕卜,有机层还可包括一种或多种选自元素周期表第I族、第2族的有机金属、第四周期和第五周期的过渡金属、镧系金属和d-过渡元素的金属或络合化合物。 [0127] In the present invention, there is an organic electroluminescent device, in addition to organic electroluminescent compounds Xi Bu, the organic layer may further comprise one or more compounds selected from the Periodic Table Group I, Group 2 represented by the formula I The transition metal organometallic the fourth period and the fifth cycle, metal or complex lanthanide metals and d- transition element compounds. 所述有机层可包括电致发光层和电荷产生层。 The organic layer may comprise an electroluminescent layer and a charge generating layer. [0128] 可实现具有独立发光模式的像素结构的有机电致发光器件,其中同时平行图案化(pattern)包含本发明化学式I的有机电致发光化合物作为子像素的有机电致发光器件,所述一个或多个子像素包含一种或多种选自Ir、Pt、Pd、Rh、Re、Os、Tl、Pb、B1、In、Sn、Sb、Te、Au和Ag的金属化合物。 [0128] can be achieved having a pixel structure of independent light organic electroluminescent device wherein simultaneous parallel patterning (pattern) comprising the present invention of formula I are organic electroluminescent compounds as the sub-pixel organic electroluminescent device, the one or more sub-pixel comprises one or more selected from Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, B1, In, Sn, Sb, Te, Au and Ag metal compound.

[0129] 另外,除了所述化学式I表示的有机电致发光化合物之外,所述有机层还可同时包括一种或多种发射蓝光、绿光或红光的有机电致发光层,以实现发射白光的有机电致发光器件。 [0129] Further, in addition to the Formula I compound represented by the organic electroluminescent addition, the organic layer may further comprise one or more simultaneously emit blue, green or red organic electroluminescent layer, in order to achieve emitting white organic electroluminescent devices. 发蓝光、绿光或红光的化合物的例子可以是韩国专利申请第10-2008-0123276、10-2008-0107606或10-2008-0118428号所述的化合物,但不限于此。 Emitting blue, green, red or compound examples may be a compound or a number of the first 10-2008-0123276,10-2008-0107606 the Korean Patent Application 10-2008-0118428, but is not limited thereto.

[0130] 在本发明的有机电致发光器件中,选自硫属化物层、金属卤化物层和金属氧化物层的层(以下称为“表面层”)可设置在电极对中的一个或两个电极的内表面上。 [0130] In the present invention, there is an organic electroluminescent device, selected from chalcogenide layers, metal halide layers and metal oxide layers layer (hereinafter referred to as "surface layer") may be disposed in a pair of electrodes or two electrodes on the inner surface. 更具体地说,硅或铝的金属硫属化物(包括氧化物)层可置于电致发光介质层的阳极表面上,且金属卤化物层或金属氧化物层可置于所述电致发光介质层的阴极表面上。 More specifically, silicon or aluminum metal chalcogenide (including oxide) layer may be disposed on the electroluminescent dielectric layer surface of the anode, and a metal halide layer or a metal oxide layer may be interposed between the electroluminescent cathode surface of the dielectric layer. 从而得到工作稳定性。 Resulting in job stability. 例如,硫属化物可以是SiOx (I彡X彡2)、AlOx (I彡X彡1.5)、Si0N、SiA10N等。 For example, chalcogenide may be SiOx (I San San X 2), AlOx (I San San X 1.5), Si0N, SiA10N like. 例如,金属卤化物可以是LiF、MgF2、CaF2、稀土金属氟化物等。 For example, the metal halide may be LiF, MgF2, CaF2, fluorides of rare earth metal. 例如,金属氧化物可以是Cs20、Li20、Mg0、Sr0、Ba0、Ca0 等。 For example, the metal oxide can be Cs20, Li20, Mg0, Sr0, Ba0, Ca0 like.

[0131] 在本发明的有机电致发光器件中,也优选在所制备的电极对的至少一个表面上设置电子传输化合物和还原性掺杂剂的混合区,或者空穴传输化合物和氧化性掺杂剂的混合区。 [0131] In the present invention, an organic electroluminescent device, it is preferable to set the mixing zone electron transport compound and a reductive dopant on at least one surface of the electrode prepared for, or the hole transport compound and oxidative doping dopant mixing zone. 在该情况下,由于电子传输化合物被还原成阴离子,从而促进电子从混合区注入以及传输到电致发光介质。 In this case, since the electron transport compound is reduced to an anion, so as to facilitate electron injection from the mixing zone and transferred to the electroluminescent medium. 另外,由于空穴传输化合物被氧化形成阳离子,从而促进空穴从混合区注入和传输到电致发光介质。 Further, since the hole transport compound is oxidized to form a cation, thereby facilitating hole injection and transport to the electroluminescent media from the mixing zone. 优选的氧化性掺杂剂包括各种路易斯酸和受体化合物。 Preferable oxidative dopants include various Lewis acids and acceptor compounds. 优选的还原性掺杂剂包括碱金属、碱金属化合物、碱土金属、稀土金属及其混合物。 Preferable reductive dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals and mixtures thereof. 此外,具有两层或更多层电致发光层的发白光的电致发光器件可使用还原性掺杂剂层作为电荷产生层来制备。 In addition, having two or more layers of the electroluminescent layer emits white light electroluminescent devices can be prepared using reductive dopant layer as the charge generating layer.

[0132]发明的有益.的效果 [0132] useful invention. The effect

[0133] 根据本发明,有机电致发光化合物可用作空穴传输材料或者空穴注入材料,从而得到的有机电致发光器件可以具有良好的发光效率,并具有优异的材料使用寿命性能,并可用于制造具有非常优异运行寿命且由于提高了功率效率而降低功率消耗的OLED器件。 [0133] According to the present invention, the organic electroluminescent compounds useful as hole transport material or a hole injection material, to thereby obtain the organic electroluminescence device may have excellent luminous efficiency and excellent life property of material, and It can be used to make a very good operating life due to increased power efficiency and reduced power consumption of the OLED device.

[0134] 发明的具体实施方式 [0134] Specific embodiments of the invention

[0135] 下文参照本发明的代表性化合物进一步描述本发明的有机电致发光化合物,及其制备方法和器件的电致发光性能。 [0135] Referring to the present invention, representative compounds of the present invention is further described below, the organic electroluminescent compounds, and electrical preparation and luminescent properties of the device. 但是这些实施例仅用于描述实施方式目的,并没有限制本发明的范围。 However, these examples are only for the purpose of describing the embodiment, and not to limit the scope of the invention.

[0136][制备例I]制备化合物I [0136] [Preparation Example I] Preparation of Compound I

[0137] [0137]

Figure CN103189469AD00441

[0138] 化合物1-1的制备 [0138] Preparation of Compound 1-1

[0139]向 5OOmL 甲苯中加入2_ 鹏苯30g(120.4mmoI)、4_ 漠苯基砸酸26g(132.5mmol)、Pd (PPh3) 46.9g(6.02mmol)和2M的Na2C03150mL,混合物在100°C加热。 [0139] To 5OOmL 2_ Peng benzene toluene was added 30g (120.4mmoI), 4_ desert phenyl drop acid 26g (132.5mmol), Pd (PPh3) 46.9g (6.02mmol) and 2M of Na2C03150mL, the mixture was heated at 100 ° C . 4小时之后,将混合物在室温下冷却,并用乙酸乙酯萃取。 After four hours, the mixture was cooled at room temperature and extracted with ethyl acetate. 在用蒸馏水清洗,用MgSO4去除水分并在减压下进行蒸懼之后,通过柱分离得到化合物l_l,28g(100.68mmol, 83.33%)。 With distilled water, and the water is removed over MgSO4 fear evaporated under reduced pressure after separated by column to give compound l_l, 28g (100.68mmol, 83.33%).

[0140] 化合物1-2的制备 [0140] Preparation of Compound 1-2

[0141] 向300mL亚磷酸三乙酯中加入化合物l_128g(100.68mmol),并在150°C搅拌6小时。 [0141] Compound l_128g (100.68mmol) to 300mL triethyl phosphite and stirred at 150 ° C 6 hours. 在室温冷却后,混合物减压蒸发,并用乙酸乙酯萃取。 After cooling at room temperature, the mixture was evaporated under reduced pressure, and extracted with ethyl acetate. 所得物质用蒸馏水清洗。 The resulting material was washed with distilled water. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物1-2,IIg(44.69mmol, 44.38%)。 MgSO4 followed by removal of the water and subjected to distillation under reduced pressure, separated by column to give compound 1-2, IIg (44.69mmol, 44.38%).

[0142] 化合物1-3的制备 Preparation of [0142] Compound 1-3

[0143]混合化合物 l-230g(101.29mmol)、碘苯41.3g (202.59mmol)、CuI9.6g(50.64mmol) ,Cs2C0382.5g(253.2mmol)以及甲苯600mL,并在50°C加热。 [0143] mixing the compound l-230g (101.29mmol), iodobenzene 41.3g (202.59mmol), CuI9.6g (50.64mmol), Cs2C0382.5g (253.2mmol) and toluene 600mL, and heated at 50 ° C. 向混合物中加入乙二胺6.8mL(101.29mmol),回流搅拌混合物。 To the mixture was added ethylenediamine 6.8mL (101.29mmol), the mixture was stirred at reflux. 14小时后,混合物在室温下冷却,并向其中加入蒸馏水。 After 14 hours, the mixture was cooled at room temperature, distilled water was added thereto. 用乙酸乙酯萃取所得混合物。 The resulting mixture was extracted with ethyl acetate. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物l_3,32g(85.96mmol, 84.86%)。 After removal of water with MgSO4 and distilled under reduced pressure to give compound l_3,32g (85.96mmol, 84.86%) by column separation.

[0144] 化合物1-4的制备 [0144] Preparation of Compound 1-4

[0145] 将化合物l-332g(85.96mmol)溶于300mL THF,并在-78°C向混合物中缓慢加入正丁基锂37.8mL(94.55mmol,2.5M在己烷中)。 [0145] The compound l-332g (85.96mmol) was dissolved in 300mL THF, at -78 ° C and n-butyllithium was slowly added to the mixture 37.8mL (94.55mmol, 2.5M in hexane). I小时后,向混合物中加入硼酸三甲酯 I h, the mixture was added trimethyl borate

12.4mL(lll.7mmol)。 12.4mL (lll.7mmol). 在室温下搅拌混合物12小时之后,向经过搅拌的混合物中加入蒸懼水,用乙酸乙酯萃取混合物。 After the mixture was stirred at room temperature for 12 hours, the stirred mixture was added through fear distilled water, the mixture was extracted with ethyl acetate. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物l_4,20g(59.31_1,69.00%)。 After removal of water with MgSO4 and distilled under reduced pressure to give compound l_4,20g (59.31_1,69.00%) by column separation.

[0146] 化合物1-5的制备 [0146] Preparation of Compound 1-5

[0147]混合化合物 l_420g (59.31mmol)、1-漠~2~ 硝基苯14.3g (71.17mmol)、Pd(PPh3)42.7g(2.37mmol)、2M 的Na2C0375mL、甲苯300mL 以及乙醇70mL,回流搅拌。 [0147] mixing the compound l_420g (59.31mmol), 1- nitrobenzene desert ~ 2 ~ 14.3g (71.17mmol), Pd (PPh3) 42.7g (2.37mmol), 2M of Na2C0375mL, 300mL of toluene and ethanol 70mL, was stirred under reflux . 5 小时后,混合物在室温下冷却,并向混合物中加入蒸馏水。 After 5 hours, the mixture was cooled at room temperature, distilled water was added to the mixture. 用乙酸乙酯萃取该混合物。 The mixture was extracted with ethyl acetate. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物l_5,20g(48.25mmol, 81.36%)。 After removal of water with MgSO4 and distilled under reduced pressure to give compound l_5,20g (48.25mmol, 81.36%) by column separation.

[0148] 化合物1-6的制备 [0148] Preparation of Compound 1-6

[0149] 在向化合物l-520g(48.25mmol)加入200mL亚磷酸三乙酯后,混合物在150°C搅拌6小时,并在室温下冷却。 [0149] After the compound l-520g (48.25mmol) of triethyl phosphite was added 200mL, the mixture was stirred for 6 hours at 150 ° C, and cooled at room temperature. 在进行减压蒸馏之后,用乙酸乙酯萃取混合物,所得物质用蒸馏水清洗。 After conducting distillation under reduced pressure, the mixture was extracted with ethyl acetate, the resulting material washed with distilled water. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物1-6,7g (18.30mmol, 37.93%)。 After removal of water with MgSO4 and distilled under reduced pressure to give compound 1-6,7g (18.30mmol, 37.93%) by column separation.

[0150] 化合物I的制备 [0150] Preparation of Compound I

[0151]混合化合物 l~67g (18.30mmol)、4_ 漠-N, N- 二苯基苯胺11.9g (36.60mmol)、Cull.7g(9.15mmol) ,K3PO4Il.6g(54.90mmol)以及甲苯lOOmL,并在50°C加热。 [0151] mixing the compound l ~ 67g (18.30mmol), 4_ desert -N, N- diphenyl aniline 11.9g (36.60mmol), Cull.7g (9.15mmol), K3PO4Il.6g (54.90mmol) and toluene lOOmL, and 50 ° C and heating. 向混合物中加入乙二胺1.2mL(18.30mmol)之后,回流搅拌混合物。 After the mixture was added ethylenediamine 1.2mL (18.30mmol) to the refluxed mixture was stirred. 14小时后,混合物在室温下冷却,并向混合物中加入蒸馏水。 After 14 hours, the mixture was cooled at room temperature, distilled water was added to the mixture. 用乙酸乙酯萃取该混合物。 The mixture was extracted with ethyl acetate. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物l,8g(17.44mmol, 95.33%)。 MgSO4 followed by removal of the water and subjected to distillation under reduced pressure, separated by column to give compound l, 8g (17.44mmol, 95.33%).

[0152] MS/FAB 实测值576,理论值575.70 [0152] MS / FAB found 576, the theoretical value of 575.70

[0153][制备例2]制备化合物15 [0153] [Preparation Example 2] Preparation of Compound 15

[0154] [0154]

Figure CN103189469AD00451

[0155] 化合物2-1的制备 [0155] Preparation of Compound 2-1

[0156] 向IL双颈RBF中加入1-溴_2_硝基苯15g(0.074mol)之后,混合9,9_ 二甲基-9H-芴-2-基硼酸23g(0.096mol)、Pd (PPh3) 44.2g(0.003mol) 'Na2CO3 (2M) IllmL 和乙醇lllmL。 After [0156] 1-bromo-nitrobenzene _2_ 15g (0.074mol) to a two-neck IL RBF was mixed 9,9_ dimethyl -9H- fluoren-2-yl boronic acid 23g (0.096mol), Pd ( PPh3) 44.2g (0.003mol) 'Na2CO3 (2M) IllmL and ethanol lllmL. 向混合物加入200mL甲苯之后,将混合物在120°C搅拌加热3小时。 After 200mL of toluene was added to the mixture, and the mixture was stirred and heated at 120 ° C for 3 hours. 反应完成之后,用蒸馏水清洗所得物质,用乙酸乙酯萃取。 After the reaction was completed, the resulting material washed with distilled water, extracted with ethyl acetate. 用MgSO4去除有机层的水分并用旋转蒸发器去除溶剂之后,通过柱色谱法纯化得到化合物2-l,22g(95%)。 After removal of water and the organic layer with MgSO4 and solvent was removed on a rotary evaporator to give compound 2-l was purified by column chromatography, 22g (95%).

[0157] 化合物2-2的制备 Preparation of [0157] Compound 2-2

[0158] 向IL双颈RBF加入化合物2_124g(0.076mol)之后,向混合物中加入亚磷酸三乙酯200mL和1,2_ 二氯苯200mL,在140°C搅拌加热12小时。 [0158] After the two-neck IL RBF was added compound 2_124g (0.076mol), to the mixture was added triethyl phosphite and 1,2_ dichlorobenzene 200mL 200mL, stirred and heated at 140 ° C for 12 hours. 反应完成后,蒸馏溶剂。 After completion of the reaction, the solvent was distilled. 用蒸馏水清洗所得物质,并用乙酸乙酯萃取。 The resulting material was washed with distilled water, and extracted with ethyl acetate. 用MgSO4去除有机层的水分并用旋转蒸发器去除溶剂之后,通过柱色谱法纯化得到化合物2-2,7g(33%)。 After removal of water and the organic layer with MgSO4 and solvent was removed on a rotary evaporator, and purified by column chromatography to give compound 2-2,7g (33%).

[0159] 化合物15的制备 [0159] Preparation of Compound 15

[0160] 混合化合物2-27g(18.30mmol)、N-(4-溴苯基)-N_苯基萘_2_胺(N_(4_溴苯基)-N-苯基蔡-2-胺)13.7g(36.60mmol)、Cull.7g(9.15mmol)、K3PO4Il.6g(54.90mmol)以及甲苯lOOmL,并在50°C加热。 [0160] mixing the compound 2-27g (18.30mmol), N- (4- bromophenyl) -N_ _2_ phenyl naphthyl amine (N_ (4_ bromophenyl) -N- phenyl CAI -2- amine) 13.7g (36.60mmol), Cull.7g (9.15mmol), K3PO4Il.6g (54.90mmol) and toluene lOOmL, and heated at 50 ° C. 向混合物中加入乙二胺1.2mL(18.30mmol),回流搅拌混合物。 To the mixture was added ethylenediamine 1.2mL (18.30mmol), the mixture was stirred at reflux. 14小时后,混合物在室温下冷却,并向混合物中加入蒸馏水。 After 14 hours, the mixture was cooled at room temperature, distilled water was added to the mixture. 用乙酸乙酯萃取该混合物。 The mixture was extracted with ethyl acetate. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物15,8g (17.44mmo1, 95.33%)。 After removal of water with MgSO4 and distilled under reduced pressure to give compound 15,8g (17.44mmo1, 95.33%) by column separation.

[0161] MS/FAB 实测值577,理论值576.73 [0161] MS / FAB found 577, the theoretical value of 576.73

[0162][制备例3]制备化合物22 [0162] [Preparation Example 3] Preparation of Compound 22

[0163] [0163]

Figure CN103189469AD00461

[0164] 化合物3-1的制备 [0164] Preparation of Compound 3-1

[0165]混合 2-溴-9H-咔唑7g (18.30mmol)、N_ (4- (9H-咔唑-9-基)苯基)-4-溴-N-苯基苯胺13.7g(36.60mmol)、Cull.7g(9.15mmol)、K3PO4Il.6g(54.90mmol)以及甲苯IOOmL,并在50°C加热。 [0165] 2-bromo -9H- carbazole mixing 7g (18.30mmol), N_ (4- (9H- carbazol-9-yl) phenyl) -4-bromo-phenyl aniline -N- 13.7g (36.60mmol ), Cull.7g (9.15mmol), K3PO4Il.6g (54.90mmol) and toluene IOOmL, and heated at 50 ° C. 加入乙二胺1.2mL(18.30mmol)之后,回流搅拌混合物。 After addition of ethylenediamine 1.2mL (18.30mmol), the mixture was stirred at reflux. 14小时后,混合物在室温下冷却,并向混合物中加入蒸馏水。 After 14 hours, the mixture was cooled at room temperature, distilled water was added to the mixture. 用乙酸乙酯萃取该混合物。 The mixture was extracted with ethyl acetate. 用18504去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物3-l,8g(17.44mmol, 95.33%)。 After removal of water by 18,504 and distilled under reduced pressure to give compound 3-l by column separation, 8g (17.44mmol, 95.33%).

[0166] 化合物3-2的制各 [0166] The compound prepared each 3-2

[0167]混合化合物 3_112g(37.42mmol)、2_(甲硫基)苯基硼酸7.5g(44.69mmol)、Pd(PPh3)42.15g(l.6mmol)、2M 的Na2CO3 水溶液45ml 和THF200ml,然后回流搅拌。 [0167] mixing the compound 3_112g (37.42mmol), 2_ (methylthio) phenylboronic acid 7.5g (44.69mmol), Pd (PPh3) 42.15g (l.6mmol), 2M aqueous solution of Na2CO3 and 45ml THF200ml, then stirred at reflux . 5 小时之后,将混合物在室温下冷却,并用乙酸乙酯萃取。 After five hours, the mixture was cooled at room temperature and extracted with ethyl acetate. 所得物质用蒸馏水清洗。 The resulting material was washed with distilled water. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物3-2,IOg (27.36mmol, 73.47%)。 MgSO4 followed by removal of the water and subjected to distillation under reduced pressure, to give a compound isolated by column 3-2, IOg (27.36mmol, 73.47%).

[0168] 化合物3-3的制各 [0168] The compound prepared each 3-3

[0169] 向IOOml乙酸中加入化合物3_210g(27.36mmol),并向混合物中缓慢加入H2022.65ml (30.09mmol, 35%)。 [0169] Compound 3_210g (27.36mmol) to IOOml acetic acid, was slowly added to the mixture H2022.65ml (30.09mmol, 35%). 混合物在室温下搅拌12小时,减压蒸馏掉乙酸。 The mixture was stirred at room temperature for 12 hours, acetic acid was distilled off under reduced pressure. 用二氯甲烷萃取所得物质,并用NaHCO3溶液中和。 The resulting material was extracted with dichloromethane and treated with NaHCO3 solution. 用MgSO4去除水分并在减压下进行蒸馏之后,得到化合物3-3,IOg (26.21mmol, 95.79%)。 MgSO4 followed by removal of the water and subjected to distillation under reduced pressure, to give compound 3-3, IOg (26.21mmol, 95.79%).

[0170] 化合物22的制各 [0170] Each compound of 22

[0171] 化合物3-310g(26.21mmol)与三氟甲磺酸70mL混合,在100°C搅拌5小时。 [0171] Compound 3-310g (26.21mmol) and trifluoromethanesulfonic acid 70mL mixing, at 100 ° C for 5 hours. 经过搅拌的混合物在室温下冷却,加入到IOOmL的混合物(吡啶:蒸馏水=1:5)。 After stirring the mixture was cooled at room temperature, the mixture was added to IOOmL (pyridine: distilled water = 1: 5). 混合物回流搅拌并在室温下冷却之后,加压过滤所得固体。 The mixture was stirred under reflux and cooled at room temperature, the resulting solid was filtered pressure. 通过柱分离得到化合物22,6g(17.16mmol, 65.47%)。 To give compound 22,6g (17.16mmol, 65.47%) by column separation.

[0172] MS/FAB 实测值682,理论值681.84 [0172] MS / FAB found 682, the theoretical value of 681.84

[0173][制备例4]制备化合物32 [0173] [Preparation Example 4] Preparation of Compound 32

[0174] [0174]

Figure CN103189469AD00471

[0175] 化合物4-1的制备 [0175] Preparation of Compound 4-1

[0176] 混合二苯并[b, d]噻吩-4-基硼酸10g(43.84mmol)、溴代硝基苯 [0176] Mixed-dibenzo [b, d] thiophen-4-yl boronic acid 10g (43.84mmol), bromo-nitrobenzene

8.85g(43.84mmol)、2M的Na2CO3溶液70ml、甲苯200ml和乙醇70ml,并回流搅拌。 8.85g (43.84mmol), Na2CO3 solution of 70ml 2M, 200ml of toluene and ethanol 70ml, and stirred under reflux. 5小时之后,将混合物在室温下冷却,并用乙酸乙酯萃取混合物。 After 5 hours, the mixture was cooled at room temperature, the mixture was extracted with ethyl acetate. 所得物质用蒸馏水清洗。 The resulting material was washed with distilled water. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物4-1,IOg(32.74mmol, 74.68%)。 MgSO4 followed by removal of the water and subjected to distillation under reduced pressure, to give a compound isolated by column 4-1, IOg (32.74mmol, 74.68%).

[0177] 化合物4-2的制备 [0177] Preparation of Compound 4-2

[0178] 混合化合物4-110g(32.74mmol)与IOOmL亚磷酸三乙酯,并在150°C搅拌7小时。 [0178] mixing the compound 4-110g (32.74mmol) and IOOmL triethyl phosphite and stirred at 150 ° C 7 hours. 在室温下冷却混合物并进行减压蒸馏之后,使用乙酸乙酯通过重结晶得到化合物4-2,7g (25.60mmol, 78.19%)。 After cooling at room temperature, and the mixture was evaporated under reduced pressure, ethyl acetate to give compound 4-2,7g (25.60mmol, 78.19%) by recrystallization.

[0179] 化合物32的制各 [0179] Compound 32 is prepared for each

[0180]混合化合物 4-27g(25.60mmol)、N-(4-溴苯基)-N, 9- 二苯基-9H-咔唑-3-胺10.44g(51.21mmol)、CuI2.5g(12.80mmol)、Κ3Ρ0416.30g(76.82mmol)以及甲苯200mL,并在50°C加热。 [0180] mixing the compound 4-27g (25.60mmol), N- (4- bromophenyl) -N, 9- diphenyl -9H- carbazol-3-amine 10.44g (51.21mmol), CuI2.5g ( 12.80mmol), Κ3Ρ0416.30g (76.82mmol) and toluene 200mL, and heated at 50 ° C. 向混合物中加入乙二胺1.72mL(25.60mmol)。 To the mixture was added ethylene diamine 1.72mL (25.60mmol). 混合物回流搅拌12小时,在室温下冷却,并用乙酸乙酯萃取。 The mixture was stirred at reflux for 12 hours, cooled to room temperature, and extracted with ethyl acetate. 用NaHCO3溶液清洗所得物质。 The resulting material was cleaned NaHCO3 solution. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物32,8g(22.89mmol, 89.41%)。 MgSO4 followed by removal of the water and subjected to distillation under reduced pressure, to give a compound isolated by column 32,8g (22.89mmol, 89.41%).

[0181] MS/FAB 实测值682,理论值681.84 [0181] MS / FAB found 682, the theoretical value of 681.84

[0182][制备例5]制备化合物41 [0182] [Preparation Example 5] Preparation of Compound 41

[0183] [0183]

Figure CN103189469AD00472

[0184] 化合物5-1的制备 [0184] Preparation of Compound 5-1

[0185] 将2_(苯基氨基)苯甲酸50g(0.23mol)溶于IL的MeOH之后,将混合物加入冰浴中,并在(TC搅拌10分钟。在(TC缓慢加入S0Cl260mL(0.58mol)之后,混合物在90°C回流搅拌12小时。反应完成之后,用蒸馏水清洗所得混合物,用乙酸乙酯萃取。用MgSO4去除有机层的水分并用旋转蒸发器去除溶剂之后,通过柱色谱法使用乙酸乙酯作为洗脱溶剂纯化得到化合物5-l,47g(92%)。 After [0185] The 2_ (phenylamino) benzoic acid 50g (0.23mol) was dissolved in IL of MeOH, the mixture was added to an ice bath, and (TC was stirred for 10 minutes. After (TC slowly added S0Cl260mL (0.58mol) After the mixture was stirred at 90 ° C under reflux for 12 hours. After completion of the reaction, the resulting mixture was washed with distilled water, extracted with ethyl acetate. The organic layer over MgSO4 and removal of the water the solvent was removed on a rotary evaporator, purified by column chromatography using ethyl acetate as the eluting solvent to give the compound 5-l, 47g (92%).

[0186] 化合物5-2的制各 [0186] The compound braking 5-2 each

[0187] 将化合物5_190g(0.3mol)加入1.5L的THF之后,向混合物中缓慢加入MeMgBr (3.0M)462mL(l.38mol),混合物在室温下搅拌12小时。 After [0187] Compound 5_190g (0.3mol) was added 1.5L of THF, was slowly added to the mixture MeMgBr (3.0M) 462mL (l.38mol), the mixture was stirred at room temperature for 12 hours. 反应完成之后,用蒸馏水中和所得混合物,用乙酸乙酯萃取。 After the reaction was completed, distilled water and the resulting mixture was extracted with ethyl acetate. 用MgSO4去除有机层的水分并用旋转蒸发器去除溶剂之后,通过柱色谱法使用乙酸乙酯作为洗脱溶剂纯化得到化合物5-2,80g(90%)。 After removal of water and the organic layer with MgSO4 and solvent was removed on a rotary evaporator, purified by column chromatography using ethyl acetate as the eluting solvent to give compound 5-2,80g (90%).

[0188] 化合物5-3的制各 [0188] The compound prepared each 5-3

[0189] 将化合物5_280g(0.35mol)加入1.7L的H3PO4之后,混合物在室温下搅拌12小时。 After [0189] Compound 5_280g (0.35mol) was added 1.7L of H3PO4, the mixture was stirred at room temperature for 12 hours. 反应完成之后,用蒸馏水中和所得的混合物。 After the reaction was completed, distilled water and the resultant mixture. 过滤所产生的固体,同时用水清洗。 The resulting solid was filtered, and washed with water. 用二氯甲烷溶解固体,用NaOH萃取并中和。 Dissolved solids with dichloromethane, and neutralized with NaOH and extracted. 用MgSO4去除有机层的水分并用旋转蒸发器去除溶剂之后,使用己烷通过重结晶得到化合物5-3,64g(87%)。 After removal of water and the organic layer with MgSO4 and solvent was removed on a rotary evaporator, using hexane to give compound 5-3,64g (87%) by recrystallization.

[0190] 化合物5-4的制各 [0190] The compound prepared each 5-4

[0191]将化合物 5~364g(0.30mol)、漠苯52.8g(0.33mol)、Pd(OAc)2L 37g(6.1ImmoI)、P(t-Bu)350%7.3mL(15.28mmol)以及Na0t_Bu58g(0.61mol)溶于1.2L 甲苯中,混合物在120°C搅拌12小时。 [0191] Compound 5 ~ 364g (0.30mol), desert benzene 52.8g (0.33mol), Pd (OAc) 2L 37g (6.1ImmoI), P (t-Bu) 350% 7.3mL (15.28mmol) and Na0t_Bu58g ( 0.61mol) was dissolved in 1.2L of toluene, the mixture was stirred at 120 ° C 12 hours. 反应完成之后,用蒸馏水中和所得混合物,用乙酸乙酯萃取。 After the reaction was completed, distilled water and the resulting mixture was extracted with ethyl acetate. 用MgSO4去除有机层的水分并用旋转蒸发器去除溶剂之后,通过柱色谱法使用乙酸乙酯作为洗脱溶剂纯化得到化合物5-4,71g(81%)。 After removal of water and the organic layer with MgSO4 and solvent was removed on a rotary evaporator, purified by column chromatography using ethyl acetate as the eluting solvent to give compound 5-4,71g (81%).

[0192] 化合物5-5的制各 [0192] The compound prepared 5-5 each

[0193] 将化合物5-420g(0.07mol)溶于800mL的DMF中,在(TC搅拌10分钟。缓慢加入NBS12.5g(0.07mol)的350mL的DMF溶液之后,混合物在(TC搅拌6小时。反应完成之后,用蒸馏水中和所得混合物,用乙酸乙酯萃取。用MgSO4去除有机层的水分并用旋转蒸发器去除溶剂之后,通过柱色谱法使用乙酸乙酯作为洗脱溶剂纯化得到化合物5-5,21g(84%)。 [0193] Compound 5-420g (0.07mol) was dissolved in 800mL of DMF, after (TC stirred for 10 min. Was slowly added NBS12.5g (0.07mol) in 350mL of DMF, and the mixture (TC was stirred for 6 hours. After completion of the reaction, the resulting mixture was distilled water, extracted with ethyl acetate. The organic layer over MgSO4 and remove the water solvent was removed on a rotary evaporator and then, by column chromatography using ethyl acetate as the eluting solvent to give compound 5-5 , 21g (84%).

[0194] 化合物5-6的制各 [0194] The compound prepared each 5-6

[0195]将化合物 5-520g (0.054mol)、2-氯苯胺8.4g (0.065mo I)、Pd (OAc) 22,370mg(l.64mmol)、P (t-Bu) 350%3.6mL (5.49mmol)以及Cs2C0335.7g(0.109mol)溶于300mL甲苯中,在120°C搅拌4小时。 [0195] Compound 5-520g (0.054mol), 2- chloroaniline 8.4g (0.065mo I), Pd (OAc) 22,370mg (l.64mmol), P (t-Bu) 350% 3.6mL (5.49 mmol) and Cs2C0335.7g (0.109mol) was dissolved in 300mL of toluene and stirred at 120 ° C 4 hours. 反应完成之后,用蒸馏水中和所得混合物,用乙酸乙酯萃取。 After the reaction was completed, distilled water and the resulting mixture was extracted with ethyl acetate. 用MgSO4去除有机层的水分并用旋转蒸发器去除溶剂之后,通过柱色谱法使用乙酸乙酯作为洗脱溶剂纯化得到化合物5-6,13.6g(60%)。 After removal of water and the organic layer with MgSO4 and solvent was removed on a rotary evaporator, purified by column chromatography using ethyl acetate as the eluting solvent to give compound 5-6,13.6g (60%).

[0196] 化合物5-7的制各 [0196] The compound prepared each 5-7

[0197]将化合物 5-612.6g(0.03mol)、Pd(OAc)2L 37mg(6.13mmol)、四氟硼酸二-叔丁基-(甲基)膦3g(12.26mmol)以及Cs2C0350g(0.15mol)溶于240mL 的DMA,在190°C搅拌4小时。 [0197] Compound 5-612.6g (0.03mol), Pd (OAc) 2L 37mg (6.13mmol), tetrafluoroborate two - tert-butyl - (methyl) phosphine 3g (12.26mmol) and Cs2C0350g (0.15mol) was dissolved in 240mL of DMA, stirred at 190 ° C 4 hours. 反应完成之后,用蒸馏水中和所得混合物,用乙酸乙酯萃取。 After the reaction was completed, distilled water and the resulting mixture was extracted with ethyl acetate. 用MgSO4去除有机层的水分并用旋转蒸发器去除溶剂之后,通过柱色谱法使用乙酸乙酯作为洗脱溶剂纯化得到化合物5-7,7g (70%)。 After removal of water and the organic layer with MgSO4 and solvent was removed on a rotary evaporator, purified by column chromatography using ethyl acetate as the eluting solvent to give compound 5-7,7g (70%). [0198] 化合物41的制各 System [0198] Compound 41 each

[0199]混合化合物 5-77g (25.60mmol)、N- ( 二苯基_4_ 基)-N- (4_ 溴苯基)_9,9- 二甲基-9H-芴-2-胺10.44g(51.21mmol)、CuI2.5g(12.80mmol)、K3P0416.30g(76.82mmol)以及甲苯200mL,并在50°C加热。 [0199] mixing the compound 5-77g (25.60mmol), N- (diphenylphosphino _4_-yl) -N- (4_ bromophenyl) _9,9- dimethyl -9H- fluorene-2-amine 10.44g ( 51.21mmol), CuI2.5g (12.80mmol), K3P0416.30g (76.82mmol) and toluene 200mL, and heated at 50 ° C. 向混合物中加入乙二胺1.72mL(25.60mmol)。 To the mixture was added ethylene diamine 1.72mL (25.60mmol). 混合物回流搅拌12小时之后,在室温下冷却混合物,并用乙酸乙酯萃取。 After the mixture was stirred at reflux for 12 hours, the mixture was cooled at room temperature, and extracted with ethyl acetate. 用NaHCO3溶液清洗所得物质。 The resulting material was cleaned NaHCO3 solution. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物41,8g (22.89mmol, 89.41%)。 MgSO4 followed by removal of the water and subjected to distillation under reduced pressure, to give a compound isolated by column 41,8g (22.89mmol, 89.41%).

[0200] MS/FAB 实测值811,理论值810.04 [0200] MS / FAB found 811, the theoretical value of 810.04

[0201][制备例6]制备化合物51 [0201] [Preparation Example 6] Preparation of Compound 51

[0202] [0202]

Figure CN103189469AD00491

[0203] 化合物6-1的制各 [0203] The compound prepared each 6-1

[0204] 将化合物2-28.1g (0.028mol)加入IL双颈RBF中,向混合物中加入300mL的DMF。 [0204] Compound 2-28.1g (0.028mol) was added bis IL-neck RBF, to the mixture was added 300mL of DMF. 混合物在(TC回流搅拌10分钟。将NBS5.08g(0.028mol)溶于300mL的DMF并将混合物缓慢地加入到反应物之后,混合物在0°C回流搅拌6小时。反应完成之后,用蒸馏水中和所得混合物,用乙酸乙酯萃取。用MgSO4去除有机层的水分并用旋转蒸发器去除溶剂之后,通过柱色谱法使用乙酸乙酯作为洗脱溶剂纯化得到化合物6-l,9g(87%)。 After the mixture (TC was stirred at reflux for 10 minutes. The NBS5.08g (0.028mol) was dissolved in 300mL of DMF and the mixture was slowly added to the reaction mixture was stirred for 6 hours at 0 ° C to reflux. After completion of the reaction, distilled water and the resulting mixture was extracted with ethyl acetate. The organic layer over MgSO4 and removal of the water the solvent was removed on a rotary evaporator then, by column chromatography using ethyl acetate as the eluting solvent to give the compound 6-l, 9g (87%).

[0205] 化合物6-2的制各 [0205] The compound prepared each 6-2

[0206] 混合化合物6_17g(18.30mmol)、N-(4-溴苯基)_N_苯基萘-2-胺 [0206] mixing the compound 6_17g (18.30mmol), N- (4- bromophenyl) _N_-phenyl-2-amine

13.7g(36.60mmol)、Cull.7g(9.15mmol)、K3PO4Il.6g(54.90mmol)以及甲苯IOOmL,并在50°C加热。 13.7g (36.60mmol), Cull.7g (9.15mmol), K3PO4Il.6g (54.90mmol) and toluene IOOmL, and heated at 50 ° C. 向混合物中加入乙二胺1.2mL(18.30mmol),回流搅拌。 To the mixture was added ethylenediamine 1.2mL (18.30mmol), stirred under reflux. 14小时后,混合物在室温下冷却,并向混合物中加入蒸馏水。 After 14 hours, the mixture was cooled at room temperature, distilled water was added to the mixture. 用乙酸乙酯萃取该混合物。 The mixture was extracted with ethyl acetate. 用MgSO4去除水分并在减压下进行蒸懼之后,通过柱分离得到化合物6-2,8g(17.44mmol, 95.33%)。 After removal of water with MgSO4 and evaporated under reduced pressure to fear, to give compound 6-2,8g (17.44mmol, 95.33%) by column separation.

[0207] 化合物51的制备 [0207] Preparation of Compound 51

[0208]混合化合物 6-27g(18.30mmol)、9H-咔唑13.7g (36.60mmol)、Cull.7g(9.15mmol) ,K3PO4Il.6g(54.90mmol)以及甲苯lOOmL,并在50°C加热。 [0208] mixing the compound 6-27g (18.30mmol), 9H- carbazole 13.7g (36.60mmol), Cull.7g (9.15mmol), K3PO4Il.6g (54.90mmol) and toluene lOOmL, and heated at 50 ° C. 向混合物中加入乙二胺1.2mL(18.30mmol),回流搅拌。 To the mixture was added ethylenediamine 1.2mL (18.30mmol), stirred under reflux. 14小时后,混合物在室温下冷却,并向混合物中加入蒸馏水。 After 14 hours, the mixture was cooled at room temperature, distilled water was added to the mixture. 用乙酸乙酯萃取该混合物。 The mixture was extracted with ethyl acetate. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物51,8g(17.44mmol, 95.33%)。 After removal of water with MgSO4 and distilled under reduced pressure to give compound 51,8g (17.44mmol, 95.33%) by column separation.

[0209] MS/FAB 实测值742,理论值741.92 [0209] MS / FAB found 742, the theoretical value of 741.92

[0210][制备例7]制备化合物53 [0210] [Preparation Example 7] Preparation of Compound 53

[0211] [0211]

Figure CN103189469AD00501

[0212] 化合物7-1的制各 [0212] The compound prepared each 7-1

[0213] 将2-溴二苯并[b, d]噻吩74g(216.3mmol)溶于1.5L的THF中,在_78°C缓慢加入正丁基锂86.5mL(216.3mmol,2.5M在己烷中)。 [0213] 2-bromo-dibenzo [b, d] thiophene 74g (216.3mmol) was dissolved in 1.5L of THF, at _78 ° C was slowly added n-butyl lithium 86.5mL (216.3mmol, 2.5M in already dioxane). I小时后,向混合物中加入硼酸三甲酯28.9mL(259.6mmol),在室温下搅拌12小时。 I h, the mixture was added trimethyl borate 28.9mL (259.6mmol), stirred at room temperature for 12 hours. 向混合物中加入蒸懼水,所述混合物用乙酸乙酯萃取。 To the mixture was added distilled water fear, the mixture was extracted with ethyl acetate. 用MgSO4去除水分并在减压下进行蒸馏之后,使用乙酸乙酯和己烷进行重结晶得到化合物7-l,40g(136.8_1,62.96%)。 MgSO4 followed by removal of the water and subjected to distillation under reduced pressure, ethyl acetate and hexane to give Compound 7-l, 40g (136.8_1,62.96%).

[0214] 化合物7-2的制各 [0214] The compound prepared each 7-2

[0215]混合化合物 7_140g (136.8mmol)、碘硝基苯37.4g (150.5mmol)、Pd(PPh3)46.32g(5.47mmol)、2M 的Na2CO3170mL 以及甲苯700mL,在100°C搅拌4 小时。 [0215] mixing the compound 7_140g (136.8mmol), iodine nitrobenzene 37.4g (150.5mmol), Pd (PPh3) 46.32g (5.47mmol), Na2CO3170mL and 700mL 2M in toluene at 100 ° C for 4 hours. 混合物在室温下冷却之后,向其中加入蒸馏水,并用乙酸乙酯萃取所述混合物。 After the mixture was cooled to room temperature, distilled water was added thereto, and the mixture was extracted with ethyl acetate. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物7-2,28g(72.86mmol, 52.94%)。 MgSO4 followed by removal of the water and subjected to distillation under reduced pressure, to give a compound isolated by column 7-2,28g (72.86mmol, 52.94%).

[0216] 化合物7-3的制各 [0216] Each compound of 7-3

[0217] 混合化合物7-228g(72.86mmol)与300mL亚磷酸三乙酯,并在150°C搅拌12小时。 [0217] mixing the compound 7-228g (72.86mmol) of triethyl phosphite 300mL, and stirred at 150 ° C 12 hours. 混合物在室温下冷却并进行减压蒸馏之后,用乙酸乙酯萃取所述混合物,并用所得物质清洗所得物质。 The mixture was cooled to room temperature and then distilled under reduced pressure, the mixture was extracted with ethyl acetate, and the resulting material was obtained cleaning material. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物7-3,IIg (31.22mmol, 43.05%)。 MgSO4 followed by removal of the water and subjected to distillation under reduced pressure, to give a compound isolated by column 7-3, IIg (31.22mmol, 43.05%).

[0218] 化合物53的制各 [0218] Compound 53 of each system

[0219]混合化合物 7_37g(18.30mmol)、4_ 溴-N-(4_( 二苯并[b, d]噻吩-4-基)苯基)-N-苯基苯胺13.7g(36.60mmol) >Cull.7g(9.15mmol)、K3PO4I1.6g(54.90mmol)以及甲苯IOOmL,并在50°C加热。 [0219] mixing the compound 7_37g (18.30mmol), 4_ bromo -N- (4_ (dibenzo [b, d] thiophen-4-yl) phenyl) -N- phenyl aniline 13.7g (36.60mmol)> Cull .7g (9.15mmol), K3PO4I1.6g (54.90mmol) and toluene IOOmL, and heated at 50 ° C. 加入乙二胺1.2ml (18.30mmol),并回流搅拌。 Ethylenediamine 1.2ml (18.30mmol), and stirred under reflux. 14小时后,混合物在室温下冷却,并向混合物中加入蒸馏水。 After 14 hours, the mixture was cooled at room temperature, distilled water was added to the mixture. 用乙酸乙酯萃取该混合物。 The mixture was extracted with ethyl acetate. 用18504去除水分并在减压下进行蒸懼之后,通过柱分离得到化合物53,8g(17.44mmol, 95.33%)。 After removal of water by 18,504 fear and evaporated under reduced pressure to give compound 53,8g (17.44mmol, 95.33%) by column separation.

[0220] MS/FAB 实测值699,理论值698.90 [0220] MS / FAB found 699, the theoretical value of 698.90

[0221][制备例8]制备化合物54 [0221] [Preparation Example 8] Preparation of Compound 54

[0222] [0222]

Figure CN103189469AD00511

[0223] 化合物8-1的制各 [0223] The compound prepared each 8-1

[0224]混合 2,5- 二溴硝基苯50g(177.99mol)、1_ 萘硼酸36.7g(213.59mmol)、Pd(PPh3)4I0.28g(8.89mmol)、2M 的Na2CO3 (533.97mmol)、甲苯700mL 以及乙醇200mL,在100°C搅拌5小时。 [0224] 2,5-dibromo nitrobenzene mixing 50g (177.99mol), 1_ naphthalene boronic acid 36.7g (213.59mmol), Pd (PPh3) 4I0.28g (8.89mmol), 2M of Na2CO3 (533.97mmol), toluene 700mL ethanol and 200mL, stirred at 100 ° C for 5 hours. 混合物在室温下冷却之后,向其中加入蒸馏水,并用乙酸乙酯萃取所述混合物。 After the mixture was cooled to room temperature, distilled water was added thereto, and the mixture was extracted with ethyl acetate. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物8-1,50g (152.36mmol, 85.60%)。 After removal of water with MgSO4 and distilled under reduced pressure to give compound 8-1,50g (152.36mmol, 85.60%) by column separation.

[0225] 化合物8-2的制各 [0225] The compound prepared each 8-2

[0226] 混合化合物8-150g(152.36mmol)和亚磷酸三乙酯500mL,在150°C搅拌7小时。 [0226] mixing the compound 8-150g (152.36mmol) and triethylphosphite 500mL, stirred at 150 ° C for 7 hours. 混合物在室温冷却并进行减压蒸馏之后,用乙酸乙酯萃取所述混合物。 After the mixture was cooled and distilled under reduced pressure at room temperature, the mixture was extracted with ethyl acetate. 所得物质用蒸馏水清洗。 The resulting material was washed with distilled water. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物8-2,30g(101.29mmol, 66.64%)。 After removal of water with MgSO4 and distilled under reduced pressure to give compound 8-2,30g (101.29mmol, 66.64%) by column separation.

[0227] 化合物8-3的制各 [0227] The compound prepared 8-3 each

[0228]混合化合物 8-230g(101.29mmol)、N_ (4-(9H-咔唑-9-基)苯基)_4_ 溴-N-(4_ 叔丁基-苯基)苯胺41.3g (202.59mmol)、CuI9.6g (50.64mmol)、Cs2C0382.5g (253.2mmol)以及甲苯600mL,并在50°C加热。 [0228] mixing the compound 8-230g (101.29mmol), N_ (4- (9H- carbazol-9-yl) phenyl) _4_ bromo -N- (4_ tert-butyl - phenyl) aniline 41.3g (202.59mmol ), CuI9.6g (50.64mmol), Cs2C0382.5g (253.2mmol) and toluene 600mL, and heated at 50 ° C. 加入乙二胺6.8mL(101.29mmol),并回流搅拌。 Ethylenediamine 6.8mL (101.29mmol), and stirred under reflux. 14小时后,混合物在室温下冷却,并向混合物中加入蒸馏水。 After 14 hours, the mixture was cooled at room temperature, distilled water was added to the mixture. 用乙酸乙酯萃取该混合物。 The mixture was extracted with ethyl acetate. 用18504去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物8-3,32g(85.96mmol, 84.86%)。 After removal of water by 18,504 and distilled under reduced pressure to give compound 8-3,32g (85.96mmol, 84.86%) by column separation.

[0229] 化合物8-4的制各 [0229] The compound prepared 8-4 each

[0230] 将化合物8-332g (85.96mmol)溶于300mL的THF中,并在-78 V缓慢加入正丁基锂37.8mL(94.55mmol,2.5M在己烷中)。 [0230] Compound 8-332g (85.96mmol) was dissolved in 300mL of THF, and slowly added n-butyllithium 37.8mL at -78 V (94.55mmol, 2.5M in hexane). I小时后,向混合物中加入硼酸三甲酯 I h, the mixture was added trimethyl borate

12.4mL(lll.7mmol)。 12.4mL (lll.7mmol). 在室温下搅拌混合物12小时之后,向混合物中加入蒸懼水,用乙酸乙酯萃取混合物。 After the mixture was stirred at room temperature for 12 hours, to the mixture was added distilled water fear, the mixture was extracted with ethyl acetate. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物8-4,20g (59.3ImmoI, 69.00%)。 After removal of water with MgSO4 and distilled under reduced pressure to give compound 8-4,20g (59.3ImmoI, 69.00%) by column separation. [0231] 化合物8-5的制各 [0231] The compound prepared each 8-5

[0232]混合化合物 8-420g(59.31mmol)、1-溴-2-硝基苯14.3g (71.17mmol)、Pd(PPh3)42.7g(2.37mmol)、2M 的Na2C0375mL、甲苯300mL 以及乙醇70mL,回流搅拌。 [0232] mixing the compound 8-420g (59.31mmol), 1- bromo-2-nitrobenzene 14.3g (71.17mmol), Pd (PPh3) 42.7g (2.37mmol), 2M of Na2C0375mL, 300mL of toluene and ethanol 70mL, reflux stirring. 5 小时后,混合物在室温下冷却,并向混合物中加入蒸馏水。 After 5 hours, the mixture was cooled at room temperature, distilled water was added to the mixture. 用乙酸乙酯萃取该混合物。 The mixture was extracted with ethyl acetate. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物8-5,20g(48.25mmol, 81.36%)。 After removal of water with MgSO4 and distilled under reduced pressure to give compound 8-5,20g (48.25mmol, 81.36%) by column separation.

[0233] 化合物8-6的制各 [0233] The compound prepared 8-6 each

[0234] 混合化合物8-520g(48.25mmol)与200mL亚磷酸三乙酯,并在150°C搅拌6小时。 [0234] mixing the compound 8-520g (48.25mmol) of triethyl phosphite 200mL, and stirred at 150 ° C 6 hours. 混合物在室温冷却并进行减压蒸馏之后,用乙酸乙酯萃取所述混合物。 After the mixture was cooled and distilled under reduced pressure at room temperature, the mixture was extracted with ethyl acetate. 所得物质用蒸馏水清洗。 The resulting material was washed with distilled water. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物8-6,7g (18.30mmol, 37.93%)。 After removal of water with MgSO4 and distilled under reduced pressure to give compound 8-6,7g (18.30mmol, 37.93%) by column separation. [0235] 化合物54的制各 [0235] Compound 54 is prepared for each

[0236]混合化合物 8-630g(101.29mmol)、碘苯41.3g (202.59mmol)、CuI9.6g(50.64mmol) ,Cs2C0382.5g(253.2mmol)以及甲苯600mL,并在50°C加热。 [0236] mixing the compound 8-630g (101.29mmol), iodobenzene 41.3g (202.59mmol), CuI9.6g (50.64mmol), Cs2C0382.5g (253.2mmol) and toluene 600mL, and heated at 50 ° C. 向混合物中加入乙二胺6.8mL(101.29mmol),回流搅拌。 To the mixture was added ethylenediamine 6.8mL (101.29mmol), stirred at reflux. 14小时后,混合物在室温下冷却,并向混合物中加入蒸馏水。 After 14 hours, the mixture was cooled at room temperature, distilled water was added to the mixture. 用乙酸乙酯萃取该混合物。 The mixture was extracted with ethyl acetate. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物54,32g(85.96mmol, 84.86%)。 After removal of water with MgSO4 and distilled under reduced pressure to give compound 54,32g (85.96mmol, 84.86%) by column separation.

[0237] MS/FAB 实测值848,理论值847.06 [0237] MS / FAB found 848, the theoretical value of 847.06

[0238][制备例9]制备化合物58 [0238] [Preparation Example 9] Preparation of Compound 58

[0239] [0239]

Figure CN103189469AD00521

[0240] 化合物9-1的制各 [0240] The compound prepared each 9-1

[0241]混合 1-蔡删酸10.2g (59.4mmol)、1-漠_2_ 硝基苯10.0g (49.5mmol)、Pd(PPh3)4L 7g(l.4mmol)、2M 的K2CO3 水溶液75mL、甲苯200mL 以及乙醇lOOmL,回流搅拌12小时。 [0241] mixing 1- Cai deleted acid 10.2g (59.4mmol), 1- desert _2_ nitrobenzene 10.0g (49.5mmol), Pd (PPh3) 4L 7g (l.4mmol), 2M aqueous solution of K2CO3 75mL, toluene 200mL and ethanol lOOmL, stirred under reflux for 12 hours. 混合物用蒸馏水清洗,并用乙酸乙酯萃取。 The mixture was washed with distilled water, extracted with ethyl acetate. 用无水MgSO4去除水分并在减压下进行蒸馏之后,在所得残留物上通过柱分离得到化合物9-l,9.0g(73.7%)。 After removal of water and dried over anhydrous MgSO4 and distilled under a reduced pressure, the resulting residue to give Compound 9-l by column separation, 9.0g (73.7%).

[0242] 化合物9-2的制各 [0242] The compound prepared each 9-2

[0243] 将化合物9-19.0g (36.1mmol)和N-溴代琥珀酰亚胺7.6g (43.3mmol)溶于二氯甲烷300mL中,在室温下搅拌12小时。 [0243] Compound 9-19.0g (36.1mmol) and N- bromosuccinimide 7.6g (43.3mmol) was dissolved in 300mL of dichloromethane and stirred at room temperature for 12 hours. 在减压蒸馏所得固体之后,用蒸馏水、甲醇和己烷清洗,得到化合物9-2,9.6g(81.3%)。 After the resulting solid was distilled off under reduced pressure, with distilled water, methanol and washed with hexane to give compound 9-2,9.6g (81.3%).

[0244] 化合物9-3的制各 [0244] The compound prepared each 9-3

[0245]混合化合物 9-29.6g(29.3mmol)和Fe [C2O4].2H20 (二水合草酸铁)72.2g(175.5mmol),在205°C加热30分钟。 [0245] mixing the compound 9-29.6g (29.3mmol) and Fe [C2O4] .2H20 (iron oxalate dihydrate) 72.2g (175.5mmol), heated at 205 ° C 30 minutes. 混合物在室温下冷却之后,用乙酸乙酯萃取所述混合物,用蒸馏水清洗所得物质。 After the mixture was cooled to room temperature, the mixture was extracted with ethyl acetate, washed with distilled water resulting material. 使用甲苯重结晶得到化合物9-3,5.2g(60.5%)。 Recrystallized from toluene to give Compound 9-3,5.2g (60.5%).

[0246] 化合物9-4的制各 [0246] The compound braking 9-4 each

[0247]混合化合物 9_330g(101.29mmol)、4_ 溴-N-苯基-N_(4_(9-苯基-9H-咔唑-3-基)苯基)苯胺)41.3g(202.59mmol)、CuI9.6g(50.64mmol)、Cs2C0382.5g (253.2mmol)以及甲苯600mL,并在50°C加热。 [0247] mixing the compound 9_330g (101.29mmol), 4_ bromo -N- phenyl -N_ (4_ (9- phenyl -9H- carbazol-3-yl) phenyl) aniline) 41.3g (202.59mmol), CuI9 .6g (50.64mmol), Cs2C0382.5g (253.2mmol) and toluene 600mL, and heated at 50 ° C. 向混合物中加入乙二胺 To the mixture was added ethylenediamine

6.8mL(101.29mmol),回流搅拌。 6.8mL (101.29mmol), stirred at reflux. 14小时后,混合物在室温下冷却,并向混合物中加入蒸馏水。 After 14 hours, the mixture was cooled at room temperature, distilled water was added to the mixture. 用乙酸乙酯萃取该混合物。 The mixture was extracted with ethyl acetate. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物9-4,32g(85.96_1,84.86%)。 MgSO4 followed by removal of the water and subjected to distillation under reduced pressure, to give a compound isolated by column 9-4,32g (85.96_1,84.86%).

[0248] 化合物9-5的制各 [0248] The compound prepared each 9-5

[0249] 将化合物9-423.1g (62.07mmol)溶于500mL的THF,并在_78°C向混合物中缓慢加入正丁基锂29.79mL(74.48mmol, 2.5M在己烷中)。 [0249] Compound 9-423.1g (62.07mmol) was dissolved in 500mL of THF, and at _78 ° C was slowly added to the mixture, n-butyllithium 29.79mL (74.48mmol, 2.5M in hexane). I小时后,向混合物中加入硼酸三甲酯 I h, the mixture was added trimethyl borate

10.38mL (93.1Ommol)。 10.38mL (93.1Ommol). 在室温下搅拌混合物12小时之后,向混合物中加入蒸懼水,用乙酸乙酯萃取混合物。 After the mixture was stirred at room temperature for 12 hours, to the mixture was added distilled water fear, the mixture was extracted with ethyl acetate. 用MgSO4去除水分并在减压下进行蒸馏之后,使用乙酸乙酯和己烷进行重结晶得到化合物9-5,14g(67%)。 MgSO4 followed by removal of the water and subjected to distillation under reduced pressure, ethyl acetate and hexane to give Compound 9-5,14g (67%).

[0250] 化合物9-6的制各 [0250] The compound prepared 9-6 each

[0251]混合化合物 9_514g(41.79mmol)、2_ 漠苯甲酸甲酷13.51g(45.97mmol)、Pd(PPh3)4L 9g(l.67mmol)、2M的Na2C0360mL以及甲苯200mL,回流搅拌。 [0251] mixing the compound 9_514g (41.79mmol), 2_ desert benzoic acid methyl cool 13.51g (45.97mmol), Pd (PPh3) 4L 9g (l.67mmol), Na2C0360mL and 200mL 2M in toluene, refluxed with stirring. 12小时后,混合物在室温下冷却,并向混合物中加入蒸馏水`。 After 12 hours, the mixture was cooled at room temperature, distilled water was added to the mixture to `. 用乙酸乙酯萃取该混合物。 The mixture was extracted with ethyl acetate. 用18504去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物9-6,8.Sg (42%)。 After removal of water by 18,504 and distilled under reduced pressure to give compound isolated by column 9-6,8.Sg (42%).

[0252] 化合物9-7的制各 [0252] The compound prepared 9-7 each

[0253] 将化合物9-68.8g(17.53mmol)溶于200mL的THF中,并向混合物中加入溴化甲基镁14.60mL(43.82mmol,3.0M在二乙醚中)。 [0253] Compound 9-68.8g (17.53mmol) was dissolved in 200mL of THF and to the mixture was added methyl magnesium bromide 14.60mL (43.82mmol, 3.0M in diethyl ether). 在60°C加热混合物。 The mixture was heated at 60 ° C. 6小时后,混合物在室温下冷却,并向其中加入蒸馏水。 After 6 hours, the mixture was cooled at room temperature, distilled water was added thereto. 用乙酸乙酯萃取该混合物。 The mixture was extracted with ethyl acetate. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物9-7,6.6g(74%)。 MgSO4 followed by removal of the water and subjected to distillation under reduced pressure, to give a compound isolated by column 9-7,6.6g (74%).

[0254] 化合物58的制各 [0254] Compound 58 is prepared for each

[0255] 混合化合物9-76.6g(13.14mmol)、乙酸50mL以及磷酸50mL,在50°C搅拌5小时。 [0255] mixing the compound 9-76.6g (13.14mmol), acetic acid and phosphoric acid 50mL 50mL, at 50 ° C for 5 hours. 混合物在室温下冷却并用NaOH溶液中和。 The mixture was cooled and treated with NaOH solution at room temperature. 用乙酸乙酯萃取该混合物。 The mixture was extracted with ethyl acetate. 用MgSO4去除水分并在减压下进行蒸馏之后,通过柱分离得到化合物58,5.1g (80%)。 After removal of water with MgSO4 and distilled under reduced pressure to give compound 58,5.1g (80%) by column separation.

[0256] MS/FAB 实测值819,理论值818.01 [0256] MS / FAB found 819, the theoretical value of 818.01

[0257][制备例10]制备化合物122[0258] [0257] [Preparation Example 10] Preparation of Compound 122 [0258]

Figure CN103189469AD00541

[0259] 化合物10-1的制各 [0259] The compound 10-1 each system

[0260]混合 2-溴-9,9- 二甲基-9H-芴60g(0.219mol)、2_ 氯苯胺56g(0.439mol)、Pd(OAc)2L 5g(0.006mol)、P (t_Bu) 314mL(0.021mol)以及CsC03143g(0.439mol),向混合物中加入甲苯600mL。 [0260] 2-bromo-9,9-dimethyl-mixed -9H- fluorene 60g (0.219mol), 2_ chloroaniline 56g (0.439mol), Pd (OAc) 2L 5g (0.006mol), P (t_Bu) 314mL (0.021mol) and CsC03143g (0.439mol), was added to the mixture of toluene 600mL. 混合物在120°C搅拌12小时。 The mixture was stirred at 120 ° C 12 hours. 反应完成之后,用蒸馏水清洗所得物质,用乙酸乙酯萃取。 After the reaction was completed, the resulting material washed with distilled water, extracted with ethyl acetate. 用MgSO4去除有机层的水分并用旋转蒸发器去除溶剂之后,通过柱纯化得到化合物10-l,65g(92%)。 After removal of water and the organic layer with MgSO4 and solvent was removed on a rotary evaporator to give Compound 10-l through column purification, 65g (92%).

[0261] 化合物10-2的制各 [0261] The compound 10-2 each system

[0262]向化合物 10_165g (0.20mol)、Pd (OAc) 22.3g (0.0lmol)、四氟硼酸二-叔丁基_ (甲基)膦5.9g (0.02mol)以及Na2C0364g (0.60mol)的混合物中加入IOOOmL的DMA之后,混合物在190°C搅拌16小时。 _ The mixture tert-butyl (meth) phosphine 5.9g (0.02mol) and Na2C0364g (0.60mol) of - [0262] to a compound 10_165g (0.20mol), Pd (OAc) 22.3g (0.0lmol), bis tetrafluoroborate After adding IOOOmL the DMA, the mixture was stirred at 190 ° C 16 hours. 反应完成之后,用蒸馏水清洗所得物质,用乙酸乙酯萃取。 After the reaction was completed, the resulting material washed with distilled water, extracted with ethyl acetate. 用MgSO4去除有机层的水分并用旋转蒸发器去除溶剂之后,通过柱纯化得到化合物10-2,31g(54%)。 After removal of water and the organic layer with MgSO4 and solvent was removed on a rotary evaporator, to give compound 10-2,31g (54%) was purified by column.

[0263] 化合物10-3的制备 Preparation [0263] The compound 10-3

[0264] 向化合物10-217g(0.061mol)、CuI2.3g(0.012mol)、乙二胺3.3mL(0.049mol)以及K3P0316g(0.074mol)的混合物中加入甲苯130mL之后,混合物在120°C搅拌12小时。 [0264] After the compound of 10-217g (0.061mol), the mixture was CuI2.3g (0.012mol), ethylenediamine 3.3mL (0.049mol) and K3P0316g (0.074mol) in toluene was added 130mL, the mixture was stirred at 120 ° C 12 hours. 反应完成之后,用蒸馏水清洗所得物质,用乙酸乙酯萃取。 After the reaction was completed, the resulting material washed with distilled water, extracted with ethyl acetate. 用MgSO4去除有机层的水分并用旋转蒸发器去除溶剂之后,通过柱纯化得到化合物10-3,7.8g(72%)。 After removal of water and the organic layer with MgSO4 and solvent was removed on a rotary evaporator, to give compound 10-3,7.8g (72%) was purified by column.

[0265] 化合物122的制备 Preparation of [0265] Compound 122

[0266]化合物 10_34g(0.009mol)、4_( 二苯基氛基)苯基砸酸3.1g(0.0lOmol)、Pd(PPh3)4527mg(0.4mmol),K2CO3 (2M) 14mL、EtOH14mL 以及甲苯28mL 的混合物在120°C搅拌8小时。 [0266] The compound 10_34g (0.009mol), 4_ (diphenyl atmosphere yl) phenyl drop acid 3.1g (0.0lOmol), Pd (PPh3) 4527mg (0.4mmol), K2CO3 (2M) 14mL, EtOH14mL and 28mL of toluene The mixture was stirred at 120 ° C 8 hours. 反应完成之后,用蒸馏水清洗所得物质,用乙酸乙酯萃取。 After the reaction was completed, the resulting material washed with distilled water, extracted with ethyl acetate. 用MgSO4去除有机层的水分并用旋转蒸发器去除溶剂之后,通过柱纯化得到化合物122,2.6g(47%)。 After removal of water and the organic layer with MgSO4 and solvent was removed on a rotary evaporator, to give compound 122,2.6g (47%) was purified by column.

[0267] MS/FAB 实测值603,理论值602.76 [0267] MS / FAB found 603, the theoretical value of 602.76

[0268][制备例11]制备化合物132 [0268] [Preparation Example 11] Preparation of Compound 132

[0269] [0269]

Figure CN103189469AD00551

[0270] 化合物11-1的制各 [0270] The compound 11-1 each system

[0271]化合物 4~210g (36.Bmmol)、鹏~4~ 漠苯20g (73.2mmol)、CuI3.5g (18.3mmol)、乙二胺4.5mL(73.2mmol)、K3P0419.4g(91.5mmol)以及甲苯200mL 的混合物在120°C搅拌过夜。 [0271] The compound 4 ~ 210g (36.Bmmol), Peng ~ 4 ~ desert benzene 20g (73.2mmol), CuI3.5g (18.3mmol), ethylene diamine 4.5mL (73.2mmol), K3P0419.4g (91.5mmol) and 200mL of toluene was stirred at 120 ° C overnight. 反应完成之后,用蒸馏水清洗所得物质,用乙酸乙酯萃取。 After the reaction was completed, the resulting material washed with distilled water, extracted with ethyl acetate. 用MgSO4去除有机层的水分并用旋转蒸发器去除溶剂之后,通过柱纯化得到化合物11-1,7.7g(49%)。 After removal of water and the organic layer with MgSO4 and solvent was removed on a rotary evaporator, to give compound 11-1,7.7g (49%) was purified by column.

[0272] 化合物132的制各 [0272] Compound 132 is prepared for each

[0273]化合物 ll_17g(16.3mmol)、4_( 二苯基氛基)苯基砸酸5.6g (19.Bmmol)、Pd(PPh3)40.95g(0.82mmol)、K2C036g (40.8mmol)、甲苯60mL、Et0H20mL 以及H2020mL 的混合物在100°C搅拌过夜。 [0273] The compound ll_17g (16.3mmol), 4_ (diphenyl atmosphere yl) phenyl drop acid 5.6g (19.Bmmol), Pd (PPh3) 40.95g (0.82mmol), K2C036g (40.8mmol), toluene 60mL, mixture Et0H20mL and H2020mL at 100 ° C overnight. 反应完成之后,用蒸馏水清洗所得物质,用乙酸乙酯萃取。 After the reaction was completed, the resulting material washed with distilled water, extracted with ethyl acetate. 用MgSO4去除有机层的水分并用旋转蒸发器去除溶剂之后,通过柱纯化得到化合物132,5.4g(56%)。 After removal of water and the organic layer with MgSO4 and solvent was removed on a rotary evaporator, to give compound 132,5.4g (56%) was purified by column.

[0274] MS/FAB 实测值593,理论值592.75 [0274] MS / FAB found 593, the theoretical value of 592.75

[0275] 以下化合物是根据制备实施例1-11制备的化合物。 The following compound [0275] was prepared in accordance with the compound prepared in Example 1-11 embodiment.

[0276] [0276]

Figure CN103189469AD00552

[0277] [0277]

Figure CN103189469AD00561
Figure CN103189469AD00571
Figure CN103189469AD00581

[0280][实施例1]使用本发明的有机电致发光化合物制备OLED器件 [0280] [Example 1] The present invention is used for preparing organic electroluminescent compounds OLED devices

[0281] 通过使用本发明的电致发光材料制备OLED器件。 [0281] By using the power of the present invention for preparing organic OLED device emits light materials. 首先,将由玻璃制成的用于OLED的透明电极ITO薄膜(15 Ω/□)(购自三星康宁公司(Samsung-Corning))依次用三氯乙烯、丙酮、乙醇和蒸馏水进行超声清洗,并在使用之前储存在异丙醇中。 First, glass for OLED by a transparent electrode ITO thin film (15 Ω / □) (available from Samsung Corning Corporation (Samsung-Corning)) washed with trichlorethylene, acetone, ethanol and distilled water, subjected to ultrasonic washing, and and stored in isopropanol before use. 然后,将ITO基片装在真空沉积设备的基片固定器中,将2-TNATA(4,4',4〃-三(N,N-(2-萘基)-苯基氨基)三苯胺)置于真空沉积设备的小室(cell)中,然后排气,使室内真空度最高达到10_6托。 Then, an ITO substrate was mounted on a substrate holder in a vacuum deposition apparatus, the 2-TNATA (4,4 ', 4〃- three (N, N- (2- naphthyl) - phenylamino) triphenylamine ) was placed in a vacuum deposition apparatus chamber (cell), and then the exhaust gas, so that the degree of vacuum in the chamber up to 10_6 Torr. 接着,向所述小室施加电流以蒸发2-TNATA,从而在ITO基片上形成厚度为60nm的空穴注入层。 Then, current is applied to the chamber to evaporate 2-TNATA, thereby forming on the ITO substrate with the thickness of the hole injection layer 60nm. 然后,将化合物I放入真空沉积设备的另一个小室中,通过向所述小室施加电流来蒸发化合物I,从而在所述空穴注入层上形成厚度为20nm的空穴传输层。 Then, the compound I into another cell of the vacuum deposition apparatus, by applying a current to the cell to evaporate Compound I, thereby forming the hole injection layer on the hole transport layer to a thickness of 20nm.

[0282] 在形成空穴注入层和空穴传输层后,在其上面形成电致发光层,具体如下。 [0282] After forming the hole injection layer and a hole transport layer, thereon an electroluminescent layer is formed as follows. 将作为基质的CBP [4,4' -N, N' - 二咔唑-联苯]放置在真空气相沉积设备的小室中,将作为掺杂剂的(piq)2Ir (acac) [二-(1-苯基异喹啉基)铱(III)乙酰丙酮酸盐]放置在真空气相沉积设备的另一室中。 As a matrix CBP [4,4 '-N, N' - di-carbazole - biphenyl] placed in a small chamber in the vacuum vapor deposition apparatus, as a dopant (piq) 2Ir (acac) [two - ( 1-phenyl-isoquinolinyl) iridium (III) acetylacetonate] placed in another chamber vacuum vapor deposition apparatus. 以不同的速率蒸发两种材料,这样以4-重量%在空穴传输层上气相沉积30nm厚的电致发光层。 To evaporate two materials at different rates, so that using 4 wt% in the vapor-deposited on the hole transport layer 30nm thick electroluminescent layer.

[0283] 之后,将二(2-甲基-8-喹啉酯(quinolinato))(对苯基苯酹根合(phenolato))铝(III) (BAlq)气相沉积到电致发光层上作为空穴阻隔层,厚度为10nm。 After the [0283], the bis (2-methyl-8-quinoline ester (quinolinato)) (for phenylbenzene sprinkle root together (phenolato)) aluminum (III) (BAlq) vapor-deposited onto the electroluminescent layer as a hole blocking layer, a thickness of 10nm. 在电致发光层上气相沉积20nm厚的三(8-羟基喹啉)_铝(III) (Alq3)作为电子传输层。 In the electroluminescent layer, vapor-deposited 20nm thick tris (8-quinolinol) _ aluminum (III) (Alq3) as an electron-transporting layer. 然后,在气相沉积Inm厚的Liq (喹啉合锂)作为电子注入层后,使用另一台真空气相沉积设备形成150nm厚的Al阴极,以制造OLED。 Then, in a vapor deposition Inm thick Liq (lithium quinolinolato) as a post-electron injection layer, 150nm thick Al cathode formed using another vacuum vapor-deposit device to manufacture an OLED.

[0284] 用于OLED的每种化合物通过在10_6托条件下真空升华进行纯化。 [0284] Each compound was used by OLED at 10_6 torr vacuum sublimation purification.

[0285] 作为结果,确认6.9V的电压下电流流动为13.8mA/cm2,发射了1020cd/m2的红光。 [0285] As a result, confirmed at 6.9V of voltage and current flow of 13.8mA / cm2, emission of 1020cd / m2 red.

[0286][实施例2]使用本发明的有机电致发光化合物制备OLED器件 [0286] [Example 2] The present invention is an organic electroluminescent compounds for preparing OLED devices

[0287] 如实施例1所述相同方法来制造OLED器件,不同之处在于使用化合物19作为空穴传输材料。 [0287] OLED devices manufactured in the same manner as described in Example 1, except that Compound 19 used as a hole transporting material.

[0288] 作为结果,确认6.7V的电压下电流流动为14.3mA/cm2,发射了1060cd/m2的红光。 [0288] As a result, confirmed at 6.7V of voltage and current flow of 14.3mA / cm2, emission of 1060cd / m2 red.

[0289][实施例3]使用本发明的有机电致发光化合物制备OLED器件 [0289] [Example 3] The present invention is an organic electroluminescent compounds for preparing OLED devices

[0290] 如实施例1所述相同方法来制造OLED器件,不同之处在于使用化合物31作为空穴传输材料。 [0290] OLED devices manufactured in the same manner as described in Example 1, except that Compound 31 used as a hole transporting material.

[0291] 作为结果,确认6.7V的电压下电流流动为13.9mA/cm2,发射了1044cd/m2的红光。 [0291] As a result, confirmed at 6.7V of voltage and current flow of 13.9mA / cm2, emission of 1044cd / m2 red.

[0292][实施例4]使用本发明的有机电致发光化合物制备OLED器件 [0292] [Example 4] The present invention is an organic electroluminescent compounds for preparing OLED devices

[0293] 如实施例1所述相同方法来制造OLED器件,不同之处在于使用化合物69作为空穴传输材料。 [0293] OLED devices manufactured in the same manner as described in Example 1, except that Compound 69 used as a hole transporting material.

[0294] 作为结果,确认6.8V的电压下电流流动为14.2mA/cm2,发射了1015cd/m2的红光。 [0294] As a result, confirmed at 6.8V of voltage and current flow of 14.2mA / cm2, emission of 1015cd / m2 red. [0295][实施例5]使用本发明的有机电致发光化合物制备OLED器件 [0295] [Example 5] This invention is an organic electroluminescent compounds prepared in OLED devices

[0296] 如实施例1所述相同方法来制造OLED器件,不同之处在于使用化合物I作为空穴传输材料,并使用有机铱络合物(Ir (ppy)3 [三(2-苯基吡啶)铱]作为电致发光层上的电致发光掺杂剂,含量为15重量%。 [0296] OLED devices manufactured in the same manner as described in Example 1, except that the compound I as a hole transporting material, and an organic iridium complex (Ir (ppy) 3 [tris (2-phenylpyridine ) iridium] as the electroluminescent layer dopant in an amount of 15% by weight.

[0297] 结果,证实6.6V的电压下电流流动为3.8mA/cm2,发射了1065cd/m2的绿光。 [0297] The results confirmed that the current flow at a voltage of 6.6V is 3.8mA / cm2, emission of 1065cd / m2 of green.

[0298][实施例6]使用本发明的有机电致发光化合物制备OLED器件 [0298] [Example 6] The present invention is an organic electroluminescent compounds for preparing OLED devices

[0299] 如实施例5所述相同方法来制造OLED器件,不同之处在于使用化合物20作为空穴传输材料。 [0299] OLED devices manufactured in the same manner as described in Example 5, except that the compound 20 as a hole transporting material.

[0300] 结果,证实6.6V的电压下电流流动为3.9mA/cm2,发射了1070cd/m2的绿光。 [0300] The results confirmed that the current flow at a voltage of 6.6V is 3.9mA / cm2, emission of 1070cd / m2 of green.

[0301][实施例7]使用本发明的有机电致发光化合物制备OLED器件 [0301] [Example 7] The present invention is an organic electroluminescent compounds for preparing OLED devices

[0302] 如实施例5所述相同方法来制造OLED器件,不同之处在于使用化合物31作为空穴传输材料。 [0302] OLED devices manufactured in the same manner as described in Example 5, except that the compound 31 as a hole transporting material.

[0303] 结果,证实6.7V的电压下电流流动为3.7mA/cm2,发射了1085cd/m2的绿光。 [0303] The results confirmed that the current flow at a voltage of 6.7V is 3.7mA / cm2, emission of 1085cd / m2 of green.

[0304][实施例8]使用本发明的有机电致发光化合物制备OLED器件 [0304] [Example 8] The present invention is an organic electroluminescent compounds for preparing OLED devices

[0305] 如实施例5所述相同方法来制造OLED器件,不同之处在于使用化合物42作为空穴传输材料。 [0305] OLED devices manufactured in the same manner as described in Example 5, except that the compound 42 as a hole transporting material.

[0306] 结果,证实6.6V的电压下电流流动为3.5mA/cm2,发射了1055cd/m2的绿光。 [0306] The results confirmed that the current flow at a voltage of 6.6V is 3.5mA / cm2, emission of 1055cd / m2 of green.

[0307][实施例9]使用本发明的有机电致发光化合物制备OLED器件 [0307] [Example 9] The present invention is an organic electroluminescent compounds for preparing OLED devices

[0308] 如实施例5所述相同方法来制造OLED器件,不同之处在于使用化合物43作为空穴传输材料。 [0308] OLED devices manufactured in the same manner as described in Example 5, except that Compound 43 was used as a hole transporting material.

[0309] 结果,证实6.6V的电压下电流流动为3.6mA/cm2,发射了1080cd/m2的绿光。 [0309] The results confirmed that the current flow at a voltage of 6.6V is 3.6mA / cm2, emission of 1080cd / m2 of green.

[0310][实施例10]使用本发明的有机电致发光化合物制备OLED器件 [0310] [Example 10] The present invention is an organic electroluminescent compounds for preparing OLED devices

[0311] 如实施例5所述相同方法来制造OLED器件,不同之处在于使用化合物14代替4,4',4〃-三(N,N- (2-萘基)-苯基氨基)三苯基胺(2-TNATA)作为空穴传输材料。 [0311] OLED devices manufactured in the same manner as described in Example 5, except that Compound 14 was used in place of 4,4 ', 4〃- three (N, N- (2- naphthyl) - phenylamino) three phenylamine (2-TNATA) as a hole transport material.

[0312] 结果,证实6.6V的电压下电流流动为3.7mA/cm2,发射了1050cd/m2的绿光。 [0312] The results confirmed that the current flow at a voltage of 6.6V is 3.7mA / cm2, emission of 1050cd / m2 of green.

[0313][实施例11]使用本发明的有机电致发光化合物制备OLED器件 [0313] [Example 11] The present invention is an organic electroluminescent compounds for preparing OLED devices

[0314] (<-([1,Γ - 二苯基]-4,4'_ 二基)二况-(萘-1-基)-N4,N4- 二苯基苯-1,4-二胺)用作空穴注入材料,然后在室中排气至高达10_6托的真空。 [0314] (<- ([1, Γ - diphenyl] -4,4'_ diyl) two conditions - (naphthalen-1-yl) -N4, N4- 1,4-diphenyl benzene amines) used as a hole injection material, then vented up to 10_6 torr vacuum in the chamber. 然后向小室施加电流以蒸发N1,N1'-([1,I'- 二苯基]-4,4'-二基)二(N1-(萘-1-基)-N4,N4-二苯基苯-1,4- 二胺),从而在ITO基片上形成60nm厚的空穴注入层。 Current is then applied to the cell to evaporate N1, N1 '- ([1, I'- biphenyl] -4,4'-diyl) di (N1- (naphthalen-1-yl) -N4, N4- diphenyl benzene-1,4-diamine), 60nm thick hole injection layer is formed on the ITO substrate. 然后,将化合物122放入真空沉积器件的另一个小室中,通过向所述小室施加电流来蒸发化合物122,从而在所述空穴注入层上形成厚度为20nm的空穴传输层。 Then, the compound 122 into another cell of the vacuum deposition device by applying an electric current to the cell to evaporate Compound 122, thereby forming a hole injection layer on the hole transport layer to a thickness of 20nm.

[0315] 在形成空穴注入层和空穴传输层后,在其上面形成电致发光层,具体如下。 [0315] After forming the hole injection layer and a hole transport layer, thereon an electroluminescent layer is formed as follows. 分别在真空气相沉积设备的一个小室中加入H-31作为基质并在另一个小室中加入D-58作为掺杂剂之后,两个小室以不同速率蒸发并以15重量%进行掺杂,从而在空穴传输层上沉积30nm厚的电致发光层。 Were added after a small chamber in a vacuum vapor deposition apparatus as a matrix, and H-31 D-58 is added in another cell as a dopant, the two chambers and evaporated at different rates to carry out doping to 15% by weight, whereby 30nm thick is deposited on the hole transport layer, an electroluminescent layer. 之后将2-(4-(9, 10- 二(萘-2-基)蒽-2-基)苯基)-1-苯基-1H-苯并[d]咪唑放入空穴传输层的小室中,将喹啉酸锂(Liq)放入另一小室中。 After the 2- (4- (9,10-di (naphthalene-2-yl) anthracene-2-yl) phenyl) -1-phenyl -1H- benzo [d] imidazol-placed hole transport layer small chamber, quinoline lithium (Liq) into another small room. 两个小室以相同的速率蒸发并以50重量%掺杂,以沉积厚度为30nm的空穴传输层。 Two chambers at the same rate to 50% by weight and evaporated doping, to deposit a thickness of the hole transport layer 30nm. 然后,在气相沉积Inm厚的喹啉合锂(Liq)作为电子注入层后,使用另一台真空气相沉积设备形成150nm厚的Al阴极,以制造OLED。 Then, the quinoline synthetic thick vapor-deposited Inm lithium (Liq) as an electron injection layer after using another vacuum vapor-deposit device 150nm thick Al cathode is formed, to manufacture an OLED.

[0316] 用于OLED的每种化合物通过在10_6托条件下真空升华进行纯化。 [0316] Each compound was used by OLED at 10_6 torr vacuum sublimation purification.

[0317] 结果,证实5.4V的电压下电流流动为11.5mA/cm2,发射了6200cd/m2的绿光。 [0317] The results confirmed that the current flow at a voltage of 5.4V to 11.5mA / cm2, emission of 6200cd / m2 of green.

[0318][实施例12]使用本发明的有机电致发光化合物制备OLED器件 [0318] [Example 12] The present invention is an organic electroluminescent compounds prepared in OLED devices

[0319] 使用实施例11所述相同方法来制造OLED器件,不同之处在于化合物132用作空穴传输材料,H-1用作基质,D-71用作掺杂剂。 In the same manner as described in Example 11 [0319] OLED devices manufactured using embodiments, except that the compound used as a hole transporting material 132, H-1 used as the matrix, D-71 is used as a dopant.

[0320] 结果,证实4.0V的电压下电流流动为6.32mA/cm2,发射了3300cd/m2的绿光。 [0320] The results confirmed that the current flow at a voltage of 4.0V is 6.32mA / cm2, emission of 3300cd / m2 of green.

[0321][实施例13]使用本发明的有机电致发光化合物制备OLED器件 [0321] [Example 13] The present invention is an organic electroluminescent compounds for preparing OLED devices

[0322] 使用实施例11所述相同方法来制造OLED器件,不同之处在于化合物138用作空穴传输材料,H-34用作基质,D-31用作掺杂剂。 In the same manner as described in Example 11 [0322] OLED devices manufactured using embodiments, except that the compound used as a hole transporting material 138, H-34 is used as the matrix, D-31 is used as a dopant.

[0323] 结果,证实3.6V的电压下电流流动为2.8mA/cm2,发射了1500cd/m2的绿光。 [0323] The results confirmed that the current flow at a voltage of 3.6V is 2.8mA / cm2, emission of 1500cd / m2 of green.

[0324][实施例14]使用本发明的有机电致发光化合物制备OLED器件 [0324] [Example 14] The present invention is an organic electroluminescent compounds for preparing OLED devices

[0325] 使用实施例11所述相同方法来制造O LED器件,不同之处在于化合物149用作空穴传输材料,H-39用作基质,D-31用作掺杂剂。 In the same manner as described in Example 11 [0325] Using O LED devices fabricated embodiment, except that the compound used as a hole transporting material 149, H-39 used as a substrate, D-31 is used as a dopant.

[0326] 结果,证实3.1V的电压下电流流动为1.59mA/cm2,发射了500cd/m2的绿光。 [0326] The results confirmed that the current flow at a voltage of 3.1V is 1.59mA / cm2, emission of 500cd / m2 of green.

[0327][实施例15]使用本发明的有机电致发光化合物制备OLED器件 [0327] [Example 15] The present invention is an organic electroluminescent compounds for preparing OLED devices

[0328] 使用实施例11所述相同方法来制造OLED器件,不同之处在于化合物109用作空穴传输材料,H-45用作基质,D-6用作掺杂剂,掺杂为4重量%。 In the same manner as described in Example 11 [0328] OLED devices manufactured using embodiments, except that the compound used as a hole transporting material 109, H-45 is used as the matrix, D-6 as a dopant, doped 4 wt %.

[0329] 结果,证实4.0V的电压下电流流动为7.5mA/cm2,发射了1065cd/m2的红光。 [0329] The results confirmed that the current flow at a voltage of 4.0V is 7.5mA / cm2, emission of 1065cd / m2 red.

[0330][实施例16]使用本发明的有机电致发光化合物制备OLED器件 [0330] The present invention is an organic electroluminescent compounds for preparing OLED devices [Example 16]

[0331] 使用实施例15所述相同方法来制造OLED器件,不同之处在于化合物141用作空穴传输材料,H-49用作基质,D-6用作掺杂剂。 In the same manner as described in Example 15 [0331] OLED devices manufactured using embodiments, except that the compound used as a hole transporting material 141, H-49 is used as the matrix, D-6 as a dopant.

[0332] 结果,证实5.2V的电压下电流流动为17.0mA/cm2,发射了2210cd/m2的红光。 [0332] The results confirmed that the current flow at a voltage of 5.2V to 17.0mA / cm2, emission of 2210cd / m2 red.

[0333][实施例17]使用本发明的有机电致发光化合物制备OLED器件 [0333] [Example 17] The present invention is an organic electroluminescent compounds for preparing OLED devices

[0334] 使用实施例15所述相同方法来制造OLED器件,不同之处在于化合物142用作空穴传输材料,H-52用作基质,D-6用作掺杂剂。 In the same manner as described in Example 15 [0334] OLED devices manufactured using embodiments, except that the compound used as a hole transporting material 142, H-52 is used as the matrix, D-6 as a dopant.

[0335] 结果,证实5.6V的电压下电流流动为32.1mA/cm2,发射了3700cd/m2的红光。 [0335] The results confirmed that the current flow at a voltage of 5.6V to 32.1mA / cm2, emission of 3700cd / m2 red.

[0336][实施例18]使用本发明的有机电致发光化合物制备OLED器件 [0336] [Example 18] The present invention is an organic electroluminescent compounds for preparing OLED devices

[0337] 使用实施例15所述相同方法来制造OLED器件,不同之处在于化合物149用作空穴传输材料,H-53用作基质,D-9用作掺杂剂。 In the same manner as described in Example 15 [0337] OLED devices manufactured using embodiments, except that the compound used as a hole transporting material 149, H-53 is used as the matrix, D-9 used as a dopant.

[0338] 结果,证实6.0V的电压下电流流动为12.9mA/cm2,发射了1710cd/m2的红光。 [0338] The results confirmed that the current flow at a voltage of 6.0V to 12.9mA / cm2, emission of 1710cd / m2 red.

[0339][比较例I]使用现有技术的电致发光材料制造OLED器件 [0339] [Comparative Example I] used in the prior art electroluminescent device OLED materials

[0340] 用与实施例1相同的方法制造OLED器件,不同的是在真空气相沉积设备的一个小室内使用N,N' - 二( α -萘基)-N, N' - 二苯基-4,4' - 二胺[ΝΡΒ]代替本发明的化合物作为空穴传输材料。 [0340] The same method as described in Example 1 producing OLED device, except that N in a small vacuum vapor deposition apparatus, N '- two (α - naphthyl) -N, N' - diphenyl - 4,4 '- diamine [ΝΡΒ] instead of the compound of the present invention as a hole transporting material.

[0341] 结果,证实8.2V的电压下电流流动为20.0mA/cm2,发射了1000cd/m2的红光。 [0341] The results confirmed that the current flow at a voltage of 8.2V to 20.0mA / cm2, emission of 1000cd / m2 red.

[0342][比较例2]使用现有技术的电致发光材料制造OLED器件 [0342] [Comparative Example 2] A prior art electroluminescent device OLED materials

[0343] 用与实施例5相同的方法制造OLED器件,不同的是在真空气相沉积设备的一个小室内使用N,N' - 二( α -萘基)-N, N' - 二苯基-4,4' - 二胺[ΝΡΒ]代替本发明的化合物作为空穴传输材料。 [0343] The same method as in Example 5 An OLED was manufactured devices, except that N in a small vacuum vapor deposition apparatus, N '- two (α - naphthyl) -N, N' - diphenyl - 4,4 '- diamine [ΝΡΒ] instead of the compound of the present invention as a hole transporting material.

[0344] 结果,证实6.0V的电压下电流流动为5.0mA/cm2,发射了1183cd/m2的绿光。 [0344] The results confirmed that the current flow at a voltage of 6.0V is 5.0mA / cm2, emission of 1183cd / m2 of green.

[0345][比较例3]使用现有技术的电致发光材料制造OLED器件 [0345] [Comparative Example 3] using prior art electroluminescent material manufacturing OLED devices

[0346] 使用实施例11所述相同方法来制造OLED器件,不同之处在于NPB用作空穴传输材料,H-1用作基质,D-30用作掺杂剂。 In the same manner as described in Example 11 [0346] OLED devices manufactured using embodiments, except that NPB as a hole transporting material, H-1 used as the matrix, D-30 is used as a dopant.

[0347] 结果,证实3.0V的电压下电流流动为4.62mA/cm2,发射了1000cd/m2的绿光。 [0347] The results confirmed that the current flow at a voltage of 3.0V is 4.62mA / cm2, emission of 1000cd / m2 of green.

[0348][比较例4]使用现有技术的电致发光材料制造OLED器件 [0348] [Comparative Example 4] using prior art electroluminescent material manufacturing OLED devices

[0349] 使用实施例15所述相同方法来制造OLED器件,不同之处在于NPB用作空穴传输材料,H-46用作基质,D-9用作掺杂剂。 In the same manner as described in Example 15 [0349] OLED devices manufactured using embodiments, except that NPB as a hole transporting material, H-46 used as a substrate, D-9 used as a dopant.

[0350] 结果,证实4.6V的电压下电流流动为13.2mA/cm2,发射了1000cd/m2的红光。 [0350] The results confirmed that the current flow at a voltage of 4.6V to 13.2mA / cm2, emission of 1000cd / m2 red.

[0351] 证实相比于传统材料,本发明的有机电致发光化合物展现出优异的电致发光性质。 [0351] demonstrated compared to conventional materials, the present invention has an organic electroluminescent compounds exhibit excellent electroluminescent properties. 通过增加三重态,本发明的有机电致发光化合物能非常有效地阻挡防止三重态激子迁移离开电致发光层。 By increasing the triplet state, the present invention is an organic electroluminescent compounds are very effective barrier to prevent the migration of triplet excitons leave electroluminescent layer. 因此,还有一个好处,由于磷光的优异的电致发光效率,制造了非常优异的OLED器件。 Therefore, there is a benefit, because the excellent electrical phosphorescent luminescent efficiency, creating a very excellent OLED devices.

[0352] 虽然出于阐述的目的描述了本发明的优选实施方式,但是本领域技术人员应理解,各种改进、增加和替代方式也是可能的,它们不背离所附权利要求书所限定的本发明的范围和精神。 [0352] For illustrative purposes, although the preferred embodiment described in the present invention, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, which the appended claims without departing from the invention as defined the scope and spirit of the invention.

[0353] 工业应用件` [0353] Industrial Applicability member `

[0354] 根据本发明,有机电致发光化合物可用作空穴传输材料或者空穴注入材料,从而得到的有机电致发光器件可以具有良好的发光效率,并具有优异的材料使用寿命性能,并可用于制造具有非常优异运行寿命且由于提高了功率效率而降低功率消耗的OLED器件。 [0354] According to the present invention, the organic electroluminescent compounds useful as hole transport material or a hole injection material, to thereby obtain the organic electroluminescence device may have excellent luminous efficiency and excellent life property of material, and It can be used to make a very good operating life due to increased power efficiency and reduced power consumption of the OLED device.

Citations de brevets
Brevet cité Date de dépôt Date de publication Déposant Titre
DE19831427A1 *7 juil. 199813 janv. 2000Syntec Ges Fuer Chemie Und TecNew carbazole compounds useful for hole transport in organic electroluminescent device and electrophotography
JP2010045281A * Titre non disponible
KR20100028471A * Titre non disponible
KR20100082049A * Titre non disponible
US5843607 *2 oct. 19971 déc. 1998Xerox CorporationIndolocarbazole photoconductors
US20080124455 *22 juin 200729 mai 2008Samsung Electronics Co., Ltd.Organic light emitting compound, organic light emitting device comprising the same, and method of manufacturing the organic light emitting device
WO2010136109A1 *3 mai 20102 déc. 2010Merck Patent GmbhMaterials for organic electroluminescent devices
WO2011055933A2 *29 oct. 201012 mai 2011Cheil Industries Inc.Composition for an organic photoelectric device, organic photoelectric device using same, and display device comprising same
Référencé par
Brevet citant Date de dépôt Date de publication Déposant Titre
CN105175313A *2 sept. 201523 déc. 2015上海道亦化工科技有限公司Hole injection compound and organic electroluminescent device
CN105315194A *1 juil. 201410 févr. 2016赵晓宇Synthetic method of 2-bromocarbazole and intermediate thereof
US967676730 mai 201413 juin 2017Boe Technology Group Co., Ltd.Indoloacridine-containing derivative, preparation process and use thereof, and organic luminescent device
WO2015085728A1 *30 mai 201418 juin 2015京东方科技集团股份有限公司Indoloacridine-containing derivative, preparation method and use thereof, and organic light-emitting device
Classifications
Classification internationaleH01L51/54, C07F7/02, C07D491/02, H01L27/32, C09K11/06, C07D495/02, C07D209/70
Événements juridiques
DateCodeÉvénementDescription
3 juil. 2013C06Publication
31 juil. 2013C10Entry into substantive examination
16 nov. 2016C02Deemed withdrawal of patent application after publication (patent law 2001)