CN115197184A - A kind of luminescent auxiliary material and its preparation method and application - Google Patents
A kind of luminescent auxiliary material and its preparation method and applicationDownload PDFInfo
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Abstract
Description
Translated fromChinese技术领域technical field
本发明涉及有机光电材料技术领域，具体涉及一种发光辅助材料及其制备方法和应用。The invention relates to the technical field of organic optoelectronic materials, in particular to a luminescence auxiliary material and a preparation method and application thereof.
背景技术Background technique
自2000年以来有机电致发光器件(OLED)受到了极大的关注，高速发展至今以其自发光、发光效率高、全色彩显示、低功耗、低驱动电压等优势被显示、照明等领域广泛应用。有机电致发光利用有机半导体材料的光电功能特性，将电能直接转换为光能，其属于载流子注入型发光，通过从阳极注入的空穴与从阴极注入的电子在发光层复合形成激子，并以光能的形式释放能量。OLED器件从结构上分为单层器件结构、双层器件结构、三层以及多层器件结构等，目前使用最为广泛的为三层器件结构即同时拥有电子传输层、发光层和空穴传输层等多中功能层结构，三个功能层各司其职使其性能达到优化。Since 2000, organic electroluminescent devices (OLEDs) have received great attention, and they have developed rapidly so far in display, lighting and other fields due to their advantages such as self-luminescence, high luminous efficiency, full-color display, low power consumption, and low driving voltage. widely used. Organic electroluminescence utilizes the optoelectronic functional properties of organic semiconductor materials to directly convert electrical energy into light energy. It belongs to the carrier injection type luminescence. The holes injected from the anode and the electrons injected from the cathode recombine in the light-emitting layer to form excitons. , and release energy in the form of light energy. OLED devices can be divided into single-layer device structure, double-layer device structure, three-layer and multi-layer device structure from the structure. Equipped with a multi-functional layer structure, the three functional layers perform their own duties to optimize their performance.
空穴传输层(HTL)负责调节空穴的注入速度和注入量，然而目前大多数空穴传输层材料，在高电流下驱动OLED时，在阳极与空穴注入层之间出现热应力，并且所述热应力显著降低装置的使用寿命；由于空穴传输区域中使用的有机材料具有非常高的空穴迁移率，所以可能破坏空穴-电子电荷平衡并且量子效率(cd/A)可能降低。The hole transport layer (HTL) is responsible for regulating the injection rate and amount of holes, however, for most of the current hole transport layer materials, thermal stress occurs between the anode and the hole injection layer when driving OLEDs at high currents, and The thermal stress significantly reduces the lifetime of the device; since the organic materials used in the hole transport region have very high hole mobility, the hole-electron charge balance may be disrupted and the quantum efficiency (cd/A) may be reduced.
为了解决上述问题，一般会在空穴输送层和发光层之间加入发光辅助层(即设置上述提到的多层空穴输送层)提高器件寿命和效率。发光辅助层能够增加空穴利用率，从而改善发光效率及寿命，降低驱动电压。但如今发光辅助层材料较少并且面临着有增益效果不明显的问题。开发性能更高的有机功能材料迫在眉睫。In order to solve the above problems, a light-emitting auxiliary layer is generally added between the hole-transporting layer and the light-emitting layer (ie, the above-mentioned multi-layer hole-transporting layers are provided) to improve the life and efficiency of the device. The light-emitting auxiliary layer can increase the utilization rate of holes, thereby improving the light-emitting efficiency and lifespan, and reducing the driving voltage. However, nowadays, there are few materials for the light-emitting auxiliary layer and there is a problem that the gain effect is not obvious. The development of organic functional materials with higher performance is imminent.
因此，研发一种能够显著提高蓝光器件寿命，同时发光效率，BI值，驱动电压也能得到一定程度的改善的发光辅助材料是本领域人员亟需解决的技术问题。Therefore, developing a luminescent auxiliary material that can significantly improve the lifespan of blue-light devices and at the same time improve the luminous efficiency, BI value, and driving voltage to a certain extent is a technical problem that those skilled in the art need to solve urgently.
发明内容SUMMARY OF THE INVENTION
有鉴于此，本发明提供了一种发光辅助材料及其制备方法和应用。In view of this, the present invention provides a luminescence auxiliary material and a preparation method and application thereof.
本发明提供的发光辅助材料，能够显著提高蓝光器件寿命，同时发光效率，BI值，驱动电压也得到了一定程度的改善。The luminescent auxiliary material provided by the present invention can significantly improve the lifetime of the blue light device, and meanwhile, the luminous efficiency, BI value and driving voltage are also improved to a certain extent.
为了实现上述目的，本发明采用如下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
一种发光辅助材料，上述发光辅助材料的结构通式如式I所示：A light-emitting auxiliary material, the general structural formula of the above-mentioned light-emitting auxiliary material is shown in formula I:
其中，in,
环B选自碳原子数为6～20的芳基；Ring B is selected from aryl groups having 6 to 20 carbon atoms;
X选自O、-NR2、-C(R3)(R4)-或S；X is selected from O,-NR2 , -C(R3 )(R4)- or S;
R1选自氢、取代或非取代的碳原子数为1～12的烷基、取代或非取代的碳原子数为6～30的芳基、或取代或非取代的3～30元杂芳基；R1 is selected from hydrogen, substituted or unsubstituted alkyl group with 1-12 carbon atoms, substituted or unsubstituted aryl group with 6-30 carbon atoms, or substituted or unsubstituted 3-30-membered heteroaryl base;
R2选自取代或非取代的碳原子数为6～30的芳基、或取代或非取代的3～30元杂芳基；R2 is selected from substituted or unsubstituted aryl groups with 6-30 carbon atoms, or substituted or unsubstituted 3-30-membered heteroaryl groups;
R3-R4各自独立的选自取代或非取代的碳原子数为1～20的烷基、取代或非取代的碳原子数为6～30的芳基、或取代或非取代的3～30元杂芳基；R3 -R4 are each independently selected from substituted or unsubstituted alkyl groups with 1-20 carbon atoms, substituted or unsubstituted aryl groups with 6-30 carbon atoms, or substituted or unsubstituted 3- 30-membered heteroaryl;
Ar1、Ar2各自独立的选自取代或非取代的碳原子数为3～20的环烷基、取代或非取代的碳原子数为3～30的杂环烷基，其中杂原子选自N、O、S、Si、P或Se；取代或非取代的碳原子数为6～30的芳基、取代或非取代的碳原子数为3～20的杂芳基，其中杂原子选自N、O、S、Si、P或Se；取代或非取代的碳原子数为10～30稠环基、或取代或非取代的碳原子数为5～30螺环基。Ar1 and Ar2 are each independently selected from substituted or unsubstituted cycloalkyl groups with 3-20 carbon atoms and substituted or unsubstituted heterocycloalkyl groups with 3-30 carbon atoms, wherein the hetero atoms are selected from N, O, S, Si, P or Se; substituted or unsubstituted aryl group with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group with 3 to 20 carbon atoms, wherein the heteroatom is selected from N, O, S, Si, P or Se; a substituted or unsubstituted fused ring group with 10-30 carbon atoms, or a substituted or unsubstituted spirocyclic group with 5-30 carbon atoms.
进一步，上述发光辅助材料的结构式选自下述结构式中的任一种：Further, the structural formula of the above-mentioned luminescent auxiliary material is selected from any one of the following structural formulas:
进一步，上述环B为苯基。Furthermore, the above-mentioned ring B is a phenyl group.
进一步，上述R1为氢，甲基，乙基，叔丁基，甲基苯，甲氧基，苯基，联苯基，三联苯基，萘基，菲基，咔唑基，芴基，二甲基芴，苯并呋喃，苯并噻吩，吡啶基中的任意一种；Further, the above R1 is hydrogen, methyl, ethyl, tert-butyl, methylbenzene, methoxy, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, carbazolyl, fluorenyl, Any one of dimethylfluorene, benzofuran, benzothiophene and pyridyl;
上述R2为苯基、萘基，联苯基，菲基，咔唑基，芴基，二甲基芴，三联苯基，苯并呋喃，苯并噻吩、吡啶基中的任意一种。The above R2 is any one of phenyl, naphthyl, biphenyl, phenanthryl, carbazolyl, fluorenyl, dimethylfluorene, terphenyl, benzofuran, benzothiophene, and pyridyl.
进一步，上述R3-R4各自独立的选自甲基，乙基，苯基，甲基苯，联苯基或萘基。Further, the above R3 -R4 are each independently selected from methyl, ethyl, phenyl, methylbenzene, biphenyl or naphthyl.
进一步，上述Ar1与Ar2在任意可连接位置与N进行连接，Ar1、Ar2各自独立的选自以下基团：Further, the above-mentioned Ar1 and Ar2 are connected to N at any connectable position, and Ar1 and Ar2 are each independently selected from the following groups:
更进一步，上述发光辅助材料的结构式选自下述结构式中的任一种：Further, the structural formula of the above-mentioned luminescent auxiliary material is selected from any one of the following structural formulas:
在本说明书中，术语“取代或非取代的”意指被选自以下的一个、两个或更多个取代基取代：氘；卤素基团；腈基；甲硅烷基；硼基；C1-C6的烷基；C3-C10环烷基；C6-C18的芳基；C3-C30的杂环基，或者被以上所示的取代基中的两个或更多个取代基相连接的取代基取代，或者不具有取代基。In this specification, the term "substituted or unsubstituted" means substituted with one, two or more substituents selected from the group consisting of: deuterium; halogen group; nitrile group; silyl group; boron group; C1- C6 alkyl; C3-C10 cycloalkyl; C6-C18 aryl; C3-C30 heterocyclyl, or a substituent connected by two or more of the substituents shown above Substituted or unsubstituted.
更进一步，上述发光辅助材料的结构式选自下述结构式中的任一种：Further, the structural formula of the above-mentioned luminescent auxiliary material is selected from any one of the following structural formulas:
本发明还提供一种如上述发光辅助材料的制备方法，包括以下步骤：The present invention also provides a preparation method of the above-mentioned luminescent auxiliary material, comprising the following steps:
(1)在氮气的保护下，将反应物A-I、反应物B-I、四(三苯基膦)钯和碳酸钾分别加入到甲苯、乙醇、水的混合溶剂中，升温，反应，反应结束后，冷却至室温，待固体析出完毕后抽滤，然后用水洗涤除去盐，再用乙醇淋洗，干燥滤饼，置于1,4-二氧六环中重结晶，得到中间体C-I所示化合物；(1) under the protection of nitrogen, reactant A-I, reactant B-1, tetrakis (triphenylphosphine) palladium and potassium carbonate are respectively added in the mixed solvent of toluene, ethanol, water, heat up, react, after reaction finishes, Cool to room temperature, after the solid precipitation is completed, suction filtration, then wash with water to remove salt, rinse with ethanol, dry the filter cake, place in 1,4-dioxane for recrystallization to obtain the compound shown in intermediate C-I;
(2)在反应容器中加入中间体C-I和反应物D-I溶于甲苯之后，在氮气保护下加入Pd2(dba)3、P(t-Bu)3、t-BuONa；添加后使反应温度缓慢升温，并且搅拌混合物；使用硅藻土趁热抽滤，除去盐和催化剂，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，并且使用旋转式蒸发器去除溶剂；以二氯甲烷、石油醚作为洗脱剂，用管柱色谱法纯化剩余物质，获得化合物中间体E-I；(2) After adding intermediate CI and reactant DI to the reaction vessel and dissolving in toluene, add Pd2 (dba)3 , P(t-Bu)3 , t-BuONa under nitrogen protection; make the reaction temperature slow after adding The temperature was raised, and the mixture was stirred; use diatomaceous earth to filter while hot to remove salt and catalyst, after the filtrate was cooled to room temperature, then distilled water was added to the filtrate for washing, the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate Then use magnesium sulfate to dry the combined organic layers, and use a rotary evaporator to remove the solvent; use dichloromethane and petroleum ether as eluents, and purify the remaining material by column chromatography to obtain compound intermediate EI;
(3)在反应容器中加入中间体E-I和反应物F-I溶于甲苯之后，在氮气保护下加入Pd2(dba)3、P(t-Bu)3、t-BuONa；添加后使反应温度缓慢升温，并且搅拌混合物；使用硅藻土趁热抽滤，除去盐和催化剂，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，并且使用旋转式蒸发器去除溶剂；以二氯甲烷、石油醚作为洗脱剂，用管柱色谱法纯化剩余物质，获得通式I所示发光辅助材料；(3) After adding intermediate EI and reactant FI to the reaction vessel and dissolving in toluene, add Pd2 (dba)3 , P(t-Bu)3 , t-BuONa under nitrogen protection; make the reaction temperature slow after adding The temperature was raised, and the mixture was stirred; use diatomaceous earth to filter while hot to remove salt and catalyst, after the filtrate was cooled to room temperature, then distilled water was added to the filtrate for washing, the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate Then use magnesium sulfate to dry the combined organic layers, and use a rotary evaporator to remove the solvent; use dichloromethane and petroleum ether as eluents, purify the remaining material by column chromatography, and obtain the luminescence auxiliary shown in general formula I Material;
上述Hal2为氯、溴、或碘中的任意一种；Above-mentioned Hal2 is any one in chlorine, bromine or iodine;
上述通式I所示发光辅助材料的合成路线为：The synthetic route of the luminescent auxiliary material shown in the above general formula I is:
进一步，步骤(1)中，上述反应物A-I、反应物B-I、四(三苯基膦)钯和碳酸钾的摩尔比为1:(1.1-1.2):(0.01-0.02):(2.0-2.3)。Further, in step (1), the molar ratio of above-mentioned reactant A-I, reactant B-1, tetrakis(triphenylphosphine) palladium and potassium carbonate is 1:(1.1-1.2):(0.01-0.02):(2.0-2.3 ).
进一步，步骤(1)中，上述甲苯、乙醇、水的体积比为(2-4):1:1。Further, in step (1), the volume ratio of above-mentioned toluene, ethanol and water is (2-4):1:1.
进一步，步骤(1)中，上述升温至80-100℃，反应8-12h。Further, in step (1), the temperature is raised to 80-100° C., and the reaction is performed for 8-12 hours.
进一步，步骤(2)中，上述中间体C-I、反应物D-I、Pd2(dba)3、P(t-Bu)3、t-BuONa的摩尔比为1.0:(1.0-1.4):0.01:(0.02-0.04):(2.0-2.4)。Further, in step (2), the molar ratio of the above-mentioned intermediate CI, reactant DI, Pd2 (dba)3 , P(t-Bu)3 and t-BuONa is 1.0:(1.0-1.4):0.01:( 0.02-0.04):(2.0-2.4).
进一步，步骤(2)中，上述二氯甲烷、石油醚的体积比为1:(1-9)。Further, in step (2), the volume ratio of above-mentioned dichloromethane and petroleum ether is 1:(1-9).
进一步，步骤(2)中，上述反应温度缓慢升温到105-115℃，并且搅拌混合物8-12h。Further, in step (2), the above reaction temperature is slowly raised to 105-115° C., and the mixture is stirred for 8-12 h.
进一步，步骤(3)中，上述中间体E-I、反应物F-I、Pd2(dba)3、P(t-Bu)3、t-BuONa的摩尔比为1.0:(1.0-1.4):0.01:(0.02-0.04):(2.0-2.4)。Further, in step (3), the molar ratio of the above-mentioned intermediate EI, reactant FI, Pd2 (dba)3 , P(t-Bu)3 , and t-BuONa is 1.0:(1.0-1.4):0.01:( 0.02-0.04):(2.0-2.4).
进一步，步骤(3)中，上述二氯甲烷、石油醚的体积比为1:(2-7)。Further, in step (3), the volume ratio of above-mentioned dichloromethane and sherwood oil is 1:(2-7).
进一步，步骤(3)中，上述反应温度缓慢升温到105-115℃，并且搅拌混合物8-12h。Further, in step (3), the above reaction temperature is slowly raised to 105-115° C., and the mixture is stirred for 8-12 h.
进一步，上述中间体B-I的制备方法，包括以下步骤：Further, the preparation method of above-mentioned intermediate B-I, comprises the following steps:
1)在氮气保护下，将反应物1加入到四氢呋喃中，降温，缓慢滴加n-BuLi，得到中间体2的反应液；1) Under nitrogen protection, reactant 1 was added to tetrahydrofuran, cooled, and n-BuLi was slowly added dropwise to obtain the reaction solution of intermediate 2;
2)在氮气保护下，将含有中间体2的反应液、反应物3、醋酸钯(Pd(OAc)2)，2-环己基-2,4,6-三异丙基联苯(X-Phos)，碳酸铯溶于四氢呋喃中，升温，反应，冷却至室温，加入H2O，分液，将有机层用旋转式蒸发器去除溶剂，得到的固体用甲苯加热溶解，趁热过硅胶漏斗，用甲醇和二氯甲烷作为展开剂，将得到的旋转式蒸发器去除溶剂，得到的固体干燥，得到中间体4；2) Under nitrogen protection, the reaction solution containing intermediate 2, reactant 3, palladium acetate (Pd(OAc)2 ), 2-cyclohexyl-2,4,6-triisopropylbiphenyl (X- Phos), cesium carbonate was dissolved in tetrahydrofuran, heated up, reacted, cooled to room temperature, added H2 O, separated, the organic layer was removed from the solvent by a rotary evaporator, the obtained solid was heated and dissolved in toluene, passed through a silica gel funnel while hot , using methanol and dichloromethane as a developing agent, the obtained rotary evaporator is removed the solvent, and the obtained solid is dried to obtain intermediate 4;
3)在氮气保护下，将中间体4溶于THF中降温，缓慢滴加n-BuLi，反应，升至室温，将反应物5硼酸三异丙酯混合溶剂中，过夜充分反应，加入盐酸，将溶液PH值调到1-2之间进行酸化，分液，合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂，得到固体有机物，使用的二氯甲烷将固体有机物完全溶解，然后缓慢滴加到石油醚溶液中，搅拌均匀，有沉淀析出，抽滤得固体，依次用无水乙醇、石油醚淋洗，烘干，得到反应物B-I；3) Under nitrogen protection, the intermediate 4 was dissolved in THF to cool down, n-BuLi was slowly added dropwise, the reaction was raised to room temperature, the reactant 5 was in a mixed solvent of triisopropyl borate, fully reacted overnight, and hydrochloric acid was added, The pH value of the solution is adjusted to be between 1-2 for acidification, liquid separation, after combining the organic phases, use anhydrous magnesium sulfate to dry, and use a rotary evaporator to remove the solvent to obtain solid organic matter, and the dichloromethane used is used to convert the solid. The organic matter is completely dissolved, then slowly added dropwise to the petroleum ether solution, stirred evenly, precipitated out, filtered to obtain a solid, rinsed with absolute ethanol and petroleum ether successively, and dried to obtain reactant B-I;
上述Hal1选自氯、溴、碘中的任意一种；Above-mentioned Hal1 is selected from any one in chlorine, bromine, iodine;
中间体B-I的合成路线如下：The synthetic route of intermediate B-I is as follows:
进一步，步骤1)中，上述反应物1和n-BuLi的摩尔比为1.0:(1.1-1.5)。Further, in step 1), the molar ratio of the above-mentioned reactant 1 and n-BuLi is 1.0:(1.1-1.5).
进一步，步骤1)中，上述降温至-78℃。Further, in step 1), the above temperature is lowered to -78°C.
进一步，步骤2)中，上述中间体2、反应物3、醋酸钯、2-环己基-2,4,6-三异丙基联苯、碳酸铯的摩尔比为1.0:(1-1.2):(0.01-0.05):(0.01-0.05):(2.0-2.3)。Further, in step 2), the mol ratio of above-mentioned intermediate 2, reactant 3, palladium acetate, 2-cyclohexyl-2,4,6-triisopropylbiphenyl and cesium carbonate is 1.0:(1-1.2) :(0.01-0.05):(0.01-0.05):(2.0-2.3).
进一步，步骤2)中，上述甲醇和二氯甲烷的体积比为1:(40-60)。Further, in step 2), the volume ratio of the above methanol and dichloromethane is 1:(40-60).
进一步，步骤2)中，上述升温至40-70℃，反应2-8h。Further, in step 2), the temperature is raised to 40-70° C., and the reaction is performed for 2-8 h.
进一步，步骤3)中，上述中间体4、n-BuLi、反应物5的摩尔比为1.0:(1.1-1.5):(1.1-1.4)。Further, in step 3), the molar ratio of the above-mentioned intermediate 4, n-BuLi, and reactant 5 is 1.0:(1.1-1.5):(1.1-1.4).
本发明的上述术语中，“缓慢升温”是根据实际操作情况进行升温速度的调节，其缓慢有助于反应充分及反应的顺利进行。In the above-mentioned terms of the present invention, "slowly heating up" refers to the adjustment of the heating rate according to the actual operation conditions, and the slowness is helpful for the sufficient reaction and the smooth progress of the reaction.
本发明还提供一种上述发光辅助材料或上述方法制备的发光辅助材料在制备有机电致发光器件中的应用。The present invention also provides an application of the above-mentioned light-emitting auxiliary material or the light-emitting auxiliary material prepared by the above-mentioned method in preparing an organic electroluminescence device.
进一步，上述有机电致发光器件包括第一电极、与上述第一电极对置设置的第二电极、以及在上述第一电极与第二电极之间的1层以上的有机物层，上述有机物层中的至少1层包含上述发光辅助材料。Further, the organic electroluminescence device includes a first electrode, a second electrode disposed opposite to the first electrode, and more than one organic layer between the first electrode and the second electrode, wherein the organic layer is At least one layer of the above-mentioned light-emitting auxiliary material.
进一步，上述有机物层还包括空穴注入层、空穴传输层、电子阻挡层、发光辅助层、发光层、空穴阻挡层、电子传输层、电子注入层中的一种或几种。Further, the above organic layer further includes one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting auxiliary layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.
进一步，上述有机物层可以由相同物质或不同物质组成。Further, the above-mentioned organic substance layers may be composed of the same substance or different substances.
进一步，上述发光辅助材料在制造有机电致发光器件时，利用真空蒸镀法或溶液涂布法来制备有机物层。Further, when the above-mentioned light-emitting auxiliary material is used to manufacture an organic electroluminescent device, the organic layer is prepared by a vacuum evaporation method or a solution coating method.
进一步，上述溶液涂布法为旋涂法、浸涂法、刮涂法、喷墨印刷法、丝网印刷法、喷雾法或辊涂法中的任一种。Further, the above-mentioned solution coating method is any one of spin coating, dip coating, blade coating, inkjet printing, screen printing, spraying, or roll coating.
进一步，上述有机电致发光器件为顶部发光型、底部发光型或双向发光型。Further, the above-mentioned organic electroluminescent device is a top emission type, a bottom emission type or a bidirectional emission type.
进一步，上述有机电致发光器件用于制备有机发光器件、有机太阳电池、电子纸、有机感光体或有机薄膜晶体管。Further, the above organic electroluminescent device is used for preparing organic light-emitting device, organic solar cell, electronic paper, organic photoreceptor or organic thin film transistor.
本发明的有益效果是：本发明以二苯并呋喃、二苯并噻吩、咔唑、二甲基芴为骨架通过具有桥联π基团的苯基与芳胺基团和金刚烷基连接，其中，金刚烷具有高空间对称性和刚性结构，将其引入稠环单元中，可以有效的提升材料的热稳定性，同时金刚烷构筑单元的引入显著改善了材料理化性能，有利于提升器件性能，延长器件寿命。The beneficial effects of the present invention are: the present invention uses dibenzofuran, dibenzothiophene, carbazole, and dimethyl fluorene as the skeleton to connect with the arylamine group and the adamantyl group through the phenyl group with a bridged π group, Among them, adamantane has high spatial symmetry and rigid structure. The introduction of it into the fused ring unit can effectively improve the thermal stability of the material. At the same time, the introduction of the adamantane building unit significantly improves the physical and chemical properties of the material, which is conducive to improving device performance. , prolong device life.
芳胺基团使得其有很强的空穴传输能力，三芳胺结构能够降低分子的结晶性，降低分子的平面性，阻止分子在平面上移动的同时，高的空穴传输速率能够降低器件的驱动电压，提高有机电致发光器件的效率，寿命。The arylamine group makes it have strong hole transport ability. The triarylamine structure can reduce the crystallinity of the molecule, reduce the planarity of the molecule, and prevent the molecule from moving on the plane. At the same time, the high hole transport rate can reduce the device performance. Driving voltage, improving the efficiency and lifespan of organic electroluminescent devices.
附图说明Description of drawings
附图1为化合物22核磁共振氢谱；Accompanying drawing 1 is compound 22 hydrogen nuclear magnetic resonance spectrum;
附图2为化合物41核磁共振氢谱。Figure 2 is the hydrogen nuclear magnetic resonance spectrum of compound 41.
具体实施方式Detailed ways
以下的实施例在于详细说明本发明，只是本发明的较佳实施例，并非限制本发明。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The following examples are intended to illustrate the present invention in detail, but are only preferred embodiments of the present invention, and do not limit the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
反应物B-1的合成路线如下：The synthetic route of reactant B-1 is as follows:
CAS：反应物b-1：397243-08-2CAS: reactant b-1: 397243-08-2
CAS：反应物b-3：13101-40-1CAS: reactant b-3: 13101-40-1
步骤1：step 1:
在氮气保护下，将反应物b-1(400mmol)加入到四氢呋喃中，降温至-78℃，缓慢滴加n-BuLi(440mmol)，得到中间体b-2的反应液；Under nitrogen protection, reactant b-1 (400 mmol) was added to tetrahydrofuran, cooled to -78°C, and n-BuLi (440 mmol) was slowly added dropwise to obtain the reaction solution of intermediate b-2;
步骤2：Step 2:
在氮气保护下，将含有中间体b-2的反应液(400mmol)、反应物b-3(480mmol)、醋酸钯(Pd(OAc)2)(4mmol)，2-环己基-2,4,6-三异丙基联苯(X-Phos)(8mmol)，碳酸铯(840mmol)溶于四氢呋喃中，升温至50℃，反应4h，冷却至室温，加入H2O，分液，将有机层用旋转式蒸发器去除溶剂，得到的固体用甲苯加热溶解，趁热过硅胶漏斗，用甲醇：二氯甲烷体积比为1:(40-60)作为展开剂，将得到的旋转式蒸发器去除溶剂，得到的固体干燥，得到中间体b-4(45.62g，Mw:325.91，产率：35％)；Under nitrogen protection, the reaction solution (400 mmol) containing intermediate b-2, reactant b-3 (480 mmol), palladium acetate (Pd(OAc)2 ) (4 mmol), 2-cyclohexyl-2,4, 6-Triisopropylbiphenyl (X-Phos) (8 mmol), cesium carbonate (840 mmol) were dissolved in tetrahydrofuran, the temperature was raised to 50 ° C, the reaction was performed for 4 h, cooled to room temperature, H2 O was added, the layers were separated, and the organic layer was separated. The solvent was removed with a rotary evaporator, and the obtained solid was heated and dissolved in toluene, passed through a silica gel funnel while still hot, and a volume ratio of methanol: dichloromethane was 1: (40-60) as a developing agent, and the obtained rotary evaporator was removed. solvent, the resulting solid was dried to give intermediate b-4 (45.62 g, Mw: 325.91, yield: 35%);
步骤3：Step 3:
在氮气保护下，将中间体b-4(140mmol)溶于1400ml的THF中降温至-78℃，缓慢滴加n-BuLi(154mmol)，反应2h，升至室温，将反应物b-5(154mmol)(硼酸三异丙酯)混合溶剂中，过夜充分反应，加入盐酸，将溶液PH值调到1-2之间进行酸化。分液，合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂，得到固体有机物。使用的二氯甲烷将固体有机物完全溶解，然后缓慢滴加到石油醚溶液中，搅拌均匀，有沉淀析出，抽滤得固体，依次用无水乙醇、石油醚淋洗，烘干，得到反应物B-1(34.20g，Mw：290.87，产率：84％)。Under nitrogen protection, the intermediate b-4 (140 mmol) was dissolved in 1400 ml of THF and the temperature was lowered to -78 ° C, n-BuLi (154 mmol) was slowly added dropwise, the reaction was carried out for 2 h, and the temperature was raised to room temperature, and the reactant b-5 ( 154mmol) (triisopropyl borate) mixed solvent, fully react overnight, add hydrochloric acid, and adjust the pH value of the solution to 1-2 for acidification. After liquid separation, the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain solid organic matter. The dichloromethane used completely dissolves the solid organic matter, then slowly drips it into the petroleum ether solution, stirs evenly, and precipitates out, the solid is obtained by suction filtration, rinsed with absolute ethanol and petroleum ether in turn, and dried to obtain the reactant. B-1 (34.20 g, Mw: 290.87, yield: 84%).
实施例1：化合物1的合成Example 1: Synthesis of Compound 1
步骤1：step 1:
在氮气的保护下，将反应物A-1(100mmol)、反应物B-1(110mmol)，四(三苯基膦)钯(1mmol)和碳酸钾(210mmol)，分别加入甲苯(4ml)、乙醇(200ml)、水(200ml)的混合溶剂中，升温至95℃，反应8h，反应结束后，冷却至室温，待固体析出完毕后抽滤，然后用水洗涤除去盐，再用乙醇淋洗，干燥滤饼，置于1,4-二氧六环中重结晶，得到中间体C-1所示化合物(23.13g、产率：56％、Mw:413.12)。Under the protection of nitrogen, reactant A-1 (100 mmol), reactant B-1 (110 mmol), tetrakis (triphenylphosphine) palladium (1 mmol) and potassium carbonate (210 mmol) were added with toluene (4 ml), In a mixed solvent of ethanol (200ml) and water (200ml), the temperature was raised to 95°C, and the reaction was carried out for 8 hours. After the reaction was completed, it was cooled to room temperature. After the solid was precipitated, it was filtered with suction, washed with water to remove the salt, and rinsed with ethanol. The filter cake was dried and recrystallized in 1,4-dioxane to obtain the compound represented by Intermediate C-1 (23.13 g, yield: 56%, Mw: 413.12).
步骤2：Step 2:
在反应容器中加入中间体C-1(40mmol)和反应物D-1(46mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.4mmol)、P(t-Bu)3(0.8mmol)、t-BuONa(80mmol)；添加后使反应温度缓慢升温到110℃，并且搅拌混合物8h；使用硅藻土趁热抽滤，除去盐和催化剂，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，并且使用旋转式蒸发器去除溶剂；以体积比为1：(1-9)的二氯甲烷、石油醚作为洗脱剂，用管柱色谱法纯化剩余物质，获得化合物中间体E-1(18.36g、产率：82％、Mw：559.86)。After the intermediate C-1 (40 mmol) and the reactant D-1 (46 mmol) were added to the reaction vessel and dissolved in toluene, Pd2 (dba)3 (0.4 mmol) and P(t-Bu)3 were added under nitrogen protection. (0.8 mmol), t-BuONa (80 mmol); after the addition, the reaction temperature was slowly raised to 110° C., and the mixture was stirred for 8 h; celite was used for hot suction filtration to remove salts and catalysts, the filtrate was cooled to room temperature, and then the Distilled water was added to the filtrate for washing, the organic phase was retained after the separation, and the aqueous phase was extracted with ethyl acetate; then the combined organic layers were dried using magnesium sulfate, and the solvent was removed using a rotary evaporator; the volume ratio was 1:( 1-9) of dichloromethane and petroleum ether were used as eluents, and the remaining material was purified by column chromatography to obtain compound intermediate E-1 (18.36 g, yield: 82%, Mw: 559.86).
步骤3：Step 3:
在反应容器中加入中间体E-1(30mmol)和反应物F-1(36mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.3mmol)、P(t-Bu)3(0.6mmol)、t-BuONa(60mmol)；添加后使反应温度缓慢升温到105℃，并且搅拌混合物12h；使用硅藻土趁热抽滤，除去盐和催化剂，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，并且使用旋转式蒸发器去除溶剂；以体积比为1：(2-7)的二氯甲烷、石油醚作为洗脱剂，用管柱色谱法纯化剩余物质，获得化合物1(18.58g、产率：87％、Mw：712.08)。After intermediate E-1 (30 mmol) and reactant F-1 (36 mmol) were added to the reaction vessel and dissolved in toluene, Pd2 (dba)3 (0.3 mmol) and P(t-Bu)3 were added under nitrogen protection. (0.6 mmol), t-BuONa (60 mmol); after the addition, the reaction temperature was slowly raised to 105° C., and the mixture was stirred for 12 h; diatomaceous earth was used for hot suction filtration to remove salts and catalysts, the filtrate was cooled to room temperature, and then the Distilled water was added to the filtrate for washing, the organic phase was retained after the separation, and the aqueous phase was extracted with ethyl acetate; then the combined organic layers were dried using magnesium sulfate, and the solvent was removed using a rotary evaporator; the volume ratio was 1:( 2-7) dichloromethane and petroleum ether were used as eluents, and the remaining material was purified by column chromatography to obtain compound 1 (18.58 g, yield: 87%, Mw: 712.08).
上述各步骤中的产率为相应步骤的分产率。The yield in each of the above steps is the sub-yield of the corresponding step.
表征：Characterization:
HPLC纯度：＞99.7％。HPLC purity: >99.7%.
质谱测试：理论值为711.91；测试值为712.08。Mass spectrometry test: the theoretical value is 711.91; the test value is 712.08.
元素分析：Elemental analysis:
理论值：C,87.73；H,5.81；N,1.97；O,4.49Theoretical value: C, 87.73; H, 5.81; N, 1.97; O, 4.49
测试值：C,87.62；H,5.92；N,2.05；O,4.58Tested values: C, 87.62; H, 5.92; N, 2.05; O, 4.58
实施例2：化合物22的合成Example 2: Synthesis of Compound 22
与实施例1中间体C-1的反应一致，得到中间体C-22；Consistent with the reaction of Example 1 intermediate C-1, intermediate C-22 was obtained;
步骤2：Step 2:
在反应容器中加入中间体C-22(42mmol)和反应物D-22(54.6mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.42mmol)、P(t-Bu)3(1.05mmol)、t-BuONa(88.2mmol)；添加后使反应温度缓慢升温到105℃，并且搅拌混合物12h；使用硅藻土趁热抽滤，除去盐和催化剂，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，并且使用旋转式蒸发器去除溶剂；以体积比为1：(1-9)的二氯甲烷、石油醚作为洗脱剂，用管柱色谱法纯化剩余物质，获得化合物中间体E-22(21.34g、产率：86.7％、Mw：586.02)；After the intermediate C-22 (42 mmol) and the reactant D-22 (54.6 mmol) were added to the reaction vessel and dissolved in toluene, Pd2 (dba)3 (0.42 mmol) and P(t-Bu) were added under nitrogen protection.3 (1.05 mmol), t-BuONa (88.2 mmol); after the addition, the reaction temperature was slowly raised to 105 ° C, and the mixture was stirred for 12 h; celite was used for hot suction filtration to remove salt and catalyst, and the filtrate was cooled to room temperature, Then, distilled water was added to the filtrate for washing, the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate; then the combined organic layers were dried with magnesium sulfate, and the solvent was removed using a rotary evaporator; the volume ratio was 1 : (1-9) dichloromethane and petroleum ether were used as eluents, and the remaining material was purified by column chromatography to obtain compound intermediate E-22 (21.34 g, yield: 86.7%, Mw: 586.02);
步骤3：Step 3:
在反应容器中加入中间体E-22(30mmol)和反应物F-22(39mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.3mmol)、P(t-Bu)3(1.2mmol)、t-BuONa(63mmol)；添加后使反应温度缓慢升温到115℃，并且搅拌混合物9h；使用硅藻土趁热抽滤，除去盐和催化剂，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，并且使用旋转式蒸发器去除溶剂；以体积比为1：(2-7)的二氯甲烷、石油醚作为洗脱剂，用管柱色谱法纯化剩余物质，获得化合物22(19.38g、产率：85.9％、Mw：752.23)。After the intermediate E-22 (30 mmol) and the reactant F-22 (39 mmol) were added to the reaction vessel and dissolved in toluene, Pd2 (dba)3 (0.3 mmol) and P(t-Bu)3 were added under nitrogen protection. (1.2 mmol), t-BuONa (63 mmol); after the addition, the reaction temperature was slowly raised to 115° C., and the mixture was stirred for 9 h; diatomaceous earth was used for hot suction filtration to remove salt and catalyst, the filtrate was cooled to room temperature, and then the Distilled water was added to the filtrate for washing, the organic phase was retained after the separation, and the aqueous phase was extracted with ethyl acetate; then the combined organic layers were dried using magnesium sulfate, and the solvent was removed using a rotary evaporator; the volume ratio was 1:( 2-7) dichloromethane and petroleum ether were used as eluents, and the remaining material was purified by column chromatography to obtain compound 22 (19.38 g, yield: 85.9%, Mw: 752.23).
上述各步骤中的产率为相应步骤的分产率。The yield in each of the above steps is the sub-yield of the corresponding step.
表征：Characterization:
HPLC纯度：＞99.8％。HPLC purity: >99.8%.
质谱测试：理论值为751.97；测试值为752.23。Mass spectrometry test: the theoretical value is 751.97; the test value is 752.23.
元素分析：Elemental analysis:
理论值：C,87.85；H,6.03；N,1.86；O,4.26Theoretical value: C, 87.85; H, 6.03; N, 1.86; O, 4.26
测试值：C,87.59；H,6.24；N,1.92；O,4.38Tested: C, 87.59; H, 6.24; N, 1.92; O, 4.38
核磁共振氢谱：如附图1所示。H NMR spectrum: as shown in Figure 1.
实施例3：化合物41的合成Example 3: Synthesis of Compound 41
步骤1：step 1:
与实施例1中间体C-1的反应一致，得到中间体C-41；Consistent with the reaction of intermediate C-1 in Example 1, intermediate C-41 was obtained;
步骤2：Step 2:
在反应容器中加入中间体C-41(42mmol)和反应物D-41(54.6mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.42mmol)、P(t-Bu)3(1.05mmol)、t-BuONa(88.2mmol)；添加后使反应温度缓慢升温到105℃，并且搅拌混合物12h；使用硅藻土趁热抽滤，除去盐和催化剂，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，并且使用旋转式蒸发器去除溶剂；以体积比为1：(1-9)的二氯甲烷、石油醚作为洗脱剂，用管柱色谱法纯化剩余物质，获得化合物中间体E-41(21.2g、产率：84.7％、Mw：595.97)；After the intermediate C-41 (42 mmol) and the reactant D-41 (54.6 mmol) were added to the reaction vessel and dissolved in toluene, Pd2 (dba)3 (0.42 mmol) and P(t-Bu) were added under nitrogen protection.3 (1.05 mmol), t-BuONa (88.2 mmol); after the addition, the reaction temperature was slowly raised to 105 ° C, and the mixture was stirred for 12 h; celite was used for hot suction filtration to remove salt and catalyst, and the filtrate was cooled to room temperature, Then, distilled water was added to the filtrate for washing, the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate; then the combined organic layers were dried with magnesium sulfate, and the solvent was removed using a rotary evaporator; the volume ratio was 1 : (1-9) dichloromethane and petroleum ether were used as eluents, and the remaining material was purified by column chromatography to obtain compound intermediate E-41 (21.2 g, yield: 84.7%, Mw: 595.97);
步骤3：Step 3:
在反应容器中加入中间体E-41(30mmol)和反应物F-41(39mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.3mmol)、P(t-Bu)3(1.2mmol)、t-BuONa(63mmol)；添加后使反应温度缓慢升温到115℃，并且搅拌混合物9h；使用硅藻土趁热抽滤，除去盐和催化剂，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，并且使用旋转式蒸发器去除溶剂；以体积比为1：(2-7)的二氯甲烷、石油醚作为洗脱剂，用管柱色谱法纯化剩余物质，获得化合物41(18.4g、产率：82％、Mw：748.34)。After the intermediate E-41 (30 mmol) and the reactant F-41 (39 mmol) were added to the reaction vessel and dissolved in toluene, Pd2 (dba)3 (0.3 mmol) and P(t-Bu)3 were added under nitrogen protection. (1.2 mmol), t-BuONa (63 mmol); after the addition, the reaction temperature was slowly raised to 115° C., and the mixture was stirred for 9 h; diatomaceous earth was used for hot suction filtration to remove salt and catalyst, the filtrate was cooled to room temperature, and then the Distilled water was added to the filtrate for washing, the organic phase was retained after the separation, and the aqueous phase was extracted with ethyl acetate; then the combined organic layers were dried using magnesium sulfate, and the solvent was removed using a rotary evaporator; the volume ratio was 1:( 2-7) dichloromethane and petroleum ether were used as eluents, and the remaining material was purified by column chromatography to obtain compound 41 (18.4 g, yield: 82%, Mw: 748.34).
上述各步骤中的产率为相应步骤的分产率。The yield in each of the above steps is the sub-yield of the corresponding step.
表征：Characterization:
HPLC纯度：＞99.8％。HPLC purity: >99.8%.
质谱测试：理论值为747.98；测试值为748.34。Mass spectrometry test: the theoretical value is 747.98; the test value is 748.34.
元素分析：Elemental analysis:
理论值：C,89.92；H,6.06；N,1.87；O,2.14Theoretical value: C, 89.92; H, 6.06; N, 1.87; O, 2.14
测试值：C,89.61；H,6.28；N,1.95；O,2.28Tested values: C, 89.61; H, 6.28; N, 1.95; O, 2.28
核磁共振氢谱：如附图2所示。H NMR spectrum: as shown in Figure 2.
实施例4：化合物52的合成Example 4: Synthesis of Compound 52
步骤1：step 1:
与实施例1中间体C-1的反应一致，得到中间体C-52；Consistent with the reaction of intermediate C-1 in Example 1, intermediate C-52 is obtained;
步骤2：Step 2:
在反应容器中加入中间体C-52(30mmol)和反应物D-52(36mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.3mol)、P(t-Bu)3(0.6mmol)、t-BuONa(66mmol)；添加后使反应温度缓慢升温到105℃，并且搅拌混合物12h；使用硅藻土趁热抽滤，除去盐和催化剂，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，并且使用旋转式蒸发器去除溶剂；以体积比为1：(1-9)的二氯甲烷、石油醚作为洗脱剂，用管柱色谱法纯化剩余物质，获得化合物中间体E-52(15.20g、产率：85％、Mw：595.94)；After the intermediate C-52 (30 mmol) and the reactant D-52 (36 mmol) were added to the reaction vessel and dissolved in toluene, Pd2 (dba)3 (0.3 mol) and P(t-Bu)3 were added under nitrogen protection. (0.6 mmol), t-BuONa (66 mmol); after the addition, the reaction temperature was slowly raised to 105° C., and the mixture was stirred for 12 h; hot suction filtration was used on diatomaceous earth to remove salt and catalyst, the filtrate was cooled to room temperature, and then the Distilled water was added to the filtrate for washing, the organic phase was retained after the separation, and the aqueous phase was extracted with ethyl acetate; then the combined organic layers were dried using magnesium sulfate, and the solvent was removed using a rotary evaporator; the volume ratio was 1:( 1-9) dichloromethane and petroleum ether were used as eluents, and the remaining material was purified by column chromatography to obtain compound intermediate E-52 (15.20 g, yield: 85%, Mw: 595.94);
步骤3：Step 3:
在反应容器中加入中间体E-52(20mmol)和反应物F-52(26mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.2mmol)、P(t-Bu)3(0.8mmol)、t-BuONa(44mmol)；添加后使反应温度缓慢升温到110℃，并且搅拌混合物10h；使用硅藻土趁热抽滤，除去盐和催化剂，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，并且使用旋转式蒸发器去除溶剂；以体积比为1：(2-7)的二氯甲烷、石油醚作为洗脱剂，用管柱色谱法纯化剩余物质，获得化合物52(13.55g、产率：88.9％、Mw：762.25)。After the intermediate E-52 (20 mmol) and the reactant F-52 (26 mmol) were added to the reaction vessel and dissolved in toluene, Pd2 (dba)3 (0.2 mmol) and P(t-Bu)3 were added under nitrogen protection. (0.8 mmol), t-BuONa (44 mmol); after the addition, the reaction temperature was slowly raised to 110° C., and the mixture was stirred for 10 h; celite was used for hot suction filtration to remove salts and catalysts, the filtrate was cooled to room temperature, and then the Distilled water was added to the filtrate for washing, the organic phase was retained after the separation, and the aqueous phase was extracted with ethyl acetate; then the combined organic layers were dried using magnesium sulfate, and the solvent was removed using a rotary evaporator; the volume ratio was 1:( 2-7) dichloromethane and petroleum ether were used as eluents, and the remaining material was purified by column chromatography to obtain compound 52 (13.55 g, yield: 88.9%, Mw: 762.25).
上述各步骤中的产率为相应步骤的分产率。The yield in each of the above steps is the sub-yield of the corresponding step.
表征：Characterization:
HPLC纯度：＞99.7％。HPLC purity: >99.7%.
质谱测试：理论值为761.97；测试值为762.25。Mass spectrometry test: the theoretical value is 761.97; the test value is 762.25.
元素分析：Elemental analysis:
理论值：C,88.27；H,5.69；N,1.84；O,4.20Theoretical value: C, 88.27; H, 5.69; N, 1.84; O, 4.20
测试值：C,88.06；H,5.83；N,1.91；O,4.31Tested values: C, 88.06; H, 5.83; N, 1.91; O, 4.31
实施例5：化合物188的合成Example 5: Synthesis of Compound 188
反应物B-188的合成路线如下：The synthetic route of reactant B-188 is as follows:
CAS：反应物b-8：148836-41-3CAS: reactant b-8: 148836-41-3
步骤1：step 1:
在氮气保护下，将反应物b-6(400mmol)加入到四氢呋喃中，降温至-78℃，缓慢滴加n-BuLi(440mmol)，得到中间体b-7的反应液；Under nitrogen protection, reactant b-6 (400 mmol) was added to tetrahydrofuran, cooled to -78°C, and n-BuLi (440 mmol) was slowly added dropwise to obtain the reaction solution of intermediate b-7;
步骤2：Step 2:
在氮气保护下，将含有中间体b-7的反应液(400mmol)、反应物b-8(480mmol)、醋酸钯(Pd(OAc)2)(4mmol)，2-环己基-2,4,6-三异丙基联苯(X-Phos)(8mmol)，碳酸铯(840mmol)溶于四氢呋喃中，升温至50℃，反应4h，冷却至室温，加入H2O，分液，将有机层用旋转式蒸发器去除溶剂，得到的固体用甲苯加热溶解，趁热过硅胶漏斗，用甲醇：二氯甲烷体积比为1:(40-60)作为展开剂，将得到的旋转式蒸发器去除溶剂，得到的固体干燥，得到中间体b-9(49.54g，Mw:325.93，产率：38％)；Under nitrogen protection, the reaction solution containing intermediate b-7 (400 mmol), reactant b-8 (480 mmol), palladium acetate (Pd(OAc)2 ) (4 mmol), 2-cyclohexyl-2,4, 6-Triisopropylbiphenyl (X-Phos) (8 mmol), cesium carbonate (840 mmol) were dissolved in tetrahydrofuran, the temperature was raised to 50 ° C, the reaction was performed for 4 h, cooled to room temperature, H2 O was added, the layers were separated, and the organic layer was separated. The solvent was removed with a rotary evaporator, and the obtained solid was heated and dissolved in toluene, passed through a silica gel funnel while still hot, and a volume ratio of methanol: dichloromethane was 1: (40-60) as a developing agent, and the obtained rotary evaporator was removed. solvent, the obtained solid was dried to give intermediate b-9 (49.54 g, Mw: 325.93, yield: 38%);
步骤3：Step 3:
在氮气保护下，将中间体b-9(140mmol)溶于1400ml的THF中降温至-78℃，缓慢滴加n-BuLi(154mmol)，反应2h，升至室温，将反应物b-10(154mmol)(硼酸三异丙酯)混合溶剂中，过夜充分反应，加入盐酸，将溶液PH值调到1-2之间进行酸化。分液，合并有机相后，使用无水硫酸镁进行干燥，并且使用旋转式蒸发器去除溶剂，得到固体有机物。使用的二氯甲烷将固体有机物完全溶解，然后缓慢滴加到石油醚溶液中，搅拌均匀，有沉淀析出，抽滤得固体，依次用无水乙醇、石油醚淋洗，烘干，得到反应物B-188(32.99g，Mw：290.89，产率：81％)。Under the protection of nitrogen, the intermediate b-9 (140 mmol) was dissolved in 1400 ml of THF and cooled to -78°C, n-BuLi (154 mmol) was slowly added dropwise, the reaction was carried out for 2 h, and the temperature was raised to room temperature, and the reactant b-10 ( 154mmol) (triisopropyl borate) mixed solvent, fully react overnight, add hydrochloric acid, and adjust the pH value of the solution to 1-2 for acidification. After liquid separation, the organic phases were combined, dried using anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator to obtain solid organic matter. The used dichloromethane dissolves the solid organic matter completely, then slowly drips it into the petroleum ether solution, stirs evenly, and precipitates out, the solid is obtained by suction filtration, rinsed with absolute ethanol and petroleum ether in turn, and dried to obtain the reactant. B-188 (32.99 g, Mw: 290.89, yield: 81%).
步骤1：step 1:
在氮气的保护下，将反应物A-188(100mmol)、反应物B-188(110mmol)、四(三苯基膦)钯(1mmol)和碳酸钾(210mmol)，分别加入甲苯(4ml)、乙醇(200ml)、水(200ml)的混合溶剂中，升温至95℃，反应8h，反应结束后，冷却至室温，待固体析出完毕后抽滤，然后用水洗涤除去盐，再用乙醇淋洗，干燥滤饼，置于1,4-二氧六环中重结晶，得到中间体C-188所示化合物(24.90g、产率51％、Mw：488.25)；Under the protection of nitrogen, reactant A-188 (100 mmol), reactant B-188 (110 mmol), tetrakis(triphenylphosphine) palladium (1 mmol) and potassium carbonate (210 mmol) were added with toluene (4 ml), In a mixed solvent of ethanol (200ml) and water (200ml), the temperature was raised to 95°C, and the reaction was carried out for 8 hours. After the reaction was completed, it was cooled to room temperature. After the solid was precipitated, it was filtered with suction, washed with water to remove the salt, and rinsed with ethanol. The filter cake was dried and placed in 1,4-dioxane for recrystallization to obtain the compound represented by intermediate C-188 (24.90 g, yield 51%, Mw: 488.25);
步骤2：Step 2:
在反应容器中加入中间体C-188(40mmol)和反应物D-188(46mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.4mmol)、P(t-Bu)3(1.12mmol)、t-BuONa(80mmol)；添加后使反应温度缓慢升温到110℃，并且搅拌混合物8h；使用硅藻土趁热抽滤，除去盐和催化剂，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，并且使用旋转式蒸发器去除溶剂；以体积比为1：(1-9)的二氯甲烷、石油醚作为洗脱剂，用管柱色谱法纯化剩余物质，获得化合物中间体E-188(21.61g、产率87％、Mw：621.03)；After the intermediate C-188 (40 mmol) and the reactant D-188 (46 mmol) were added to the reaction vessel and dissolved in toluene, Pd2 (dba)3 (0.4 mmol) and P(t-Bu)3 were added under nitrogen protection. (1.12 mmol), t-BuONa (80 mmol); after the addition, the reaction temperature was slowly raised to 110° C., and the mixture was stirred for 8 h; hot suction filtration was used on diatomaceous earth to remove salt and catalyst, the filtrate was cooled to room temperature, and then the Distilled water was added to the filtrate for washing, the organic phase was retained after the separation, and the aqueous phase was extracted with ethyl acetate; then the combined organic layers were dried using magnesium sulfate, and the solvent was removed using a rotary evaporator; the volume ratio was 1:( 1-9) dichloromethane and petroleum ether were used as eluents, and the remaining material was purified by column chromatography to obtain compound intermediate E-188 (21.61 g, yield 87%, Mw: 621.03);
步骤3：Step 3:
在反应容器中加入中间体E-188(30mmol)和反应物F-188(34.5mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.3mmol)、P(t-Bu)3(0.84mmol)、t-BuONa(60mmol)；添加后使反应温度缓慢升温到115℃，并且搅拌混合物8.5h；使用硅藻土趁热抽滤，除去盐和催化剂，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，并且使用旋转式蒸发器去除溶剂；以体积比为1：(1-9)的二氯甲烷、石油醚作为洗脱剂，用管柱色谱法纯化剩余物质，获得化合物188(20.26g、产率：85.8％、Mw：787.33)After the intermediate E-188 (30 mmol) and the reactant F-188 (34.5 mmol) were added to the reaction vessel and dissolved in toluene, Pd2 (dba)3 (0.3 mmol) and P(t-Bu) were added under nitrogen protection.3 (0.84 mmol), t-BuONa (60 mmol); after the addition, the reaction temperature was slowly raised to 115 ° C, and the mixture was stirred for 8.5 h; celite was used for hot suction filtration to remove salt and catalyst, and the filtrate was cooled to room temperature. Then, distilled water was added to the filtrate for washing, the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate; then the combined organic layers were dried with magnesium sulfate, and the solvent was removed using a rotary evaporator; the volume ratio was 1 : (1-9) dichloromethane and petroleum ether were used as eluents, and the remaining material was purified by column chromatography to obtain compound 188 (20.26 g, yield: 85.8%, Mw: 787.33)
上述各步骤中的产率为相应步骤的分产率。The yield in each of the above steps is the sub-yield of the corresponding step.
表征：Characterization:
HPLC纯度：＞99.7％。HPLC purity: >99.7%.
质谱测试：理论值为787.02；测试值为787.33。Mass spectrometry test: the theoretical value is 787.02; the test value is 787.33.
元素分析：Elemental analysis:
理论值：C,88.52；H,5.89；N,3.56；O,2.03Theoretical value: C, 88.52; H, 5.89; N, 3.56; O, 2.03
测试值：C,88.28；H,6.10；N,3.61；O,2.10Tested values: C, 88.28; H, 6.10; N, 3.61; O, 2.10
实施例6：化合物268的合成Example 6: Synthesis of Compound 268
步骤1：step 1:
在氮气的保护下，将反应物A-268(100mmol)、反应物B-268(110mmol)、四(三苯基膦)钯(1mmol)和碳酸钾(210mmol)，分别加入甲苯(4ml)、乙醇(200ml)、水(200ml)的混合溶剂中，升温至95℃，反应8h，反应结束后，冷却至室温，待固体析出完毕后抽滤，然后用水洗涤除去盐，再用乙醇淋洗，干燥滤饼，置于1,4-二氧六环中重结晶，得到中间体C-268所示化合物(24.16g、产率：55％、Mw：439.26)；Under the protection of nitrogen, reactant A-268 (100 mmol), reactant B-268 (110 mmol), tetrakis(triphenylphosphine) palladium (1 mmol) and potassium carbonate (210 mmol) were added with toluene (4 ml), In a mixed solvent of ethanol (200ml) and water (200ml), the temperature was raised to 95°C, and the reaction was carried out for 8 hours. After the reaction was completed, it was cooled to room temperature. After the solid was precipitated, it was filtered with suction, washed with water to remove the salt, and rinsed with ethanol. The filter cake was dried and recrystallized in 1,4-dioxane to obtain the compound represented by intermediate C-268 (24.16 g, yield: 55%, Mw: 439.26);
步骤2：Step 2:
在反应容器中加入中间体C-268(42mmol)和反应物D-268(46.2mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.42mmol)、P(t-Bu)3(1.2mmol)、t-BuONa(84mmol)；添加后使反应温度缓慢升温到105℃，并且搅拌混合物12h；使用硅藻土趁热抽滤，除去盐和催化剂，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，并且使用旋转式蒸发器去除溶剂；以体积比为1：(1-9)的二氯甲烷、石油醚作为洗脱剂，用管柱色谱法纯化剩余物质，获得化合物中间体E-268(21.34g、产率：83％、Mw：612.05)；After the intermediate C-268 (42 mmol) and the reactant D-268 (46.2 mmol) were added to the reaction vessel and dissolved in toluene, Pd2 (dba)3 (0.42 mmol) and P(t-Bu) were added under nitrogen protection.3 (1.2 mmol), t-BuONa (84 mmol); after the addition, the reaction temperature was slowly raised to 105° C., and the mixture was stirred for 12 h; celite was used for hot suction filtration to remove salt and catalyst, and the filtrate was cooled to room temperature, followed by Distilled water was added to the filtrate for washing, the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate; then the combined organic layers were dried with magnesium sulfate, and the solvent was removed using a rotary evaporator; the volume ratio was 1: (1-9) dichloromethane and petroleum ether were used as eluents, and the remaining material was purified by column chromatography to obtain compound intermediate E-268 (21.34 g, yield: 83%, Mw: 612.05);
步骤3：Step 3:
在反应容器中加入中间体E-268(30mmol)和反应物F-268(33mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.3mmol)、P(t-Bu)3(0.9mmol)、t-BuONa(60mmol)；添加后使反应温度缓慢升温到110℃，并且搅拌混合物10h；使用硅藻土趁热抽滤，除去盐和催化剂，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，并且使用旋转式蒸发器去除溶剂；以体积比为1：(2-7)的二氯甲烷、石油醚作为洗脱剂，用管柱色谱法纯化剩余物质，获得化合物268(20.20g、产率：86.5％、Mw：778.41)。After the intermediate E-268 (30 mmol) and the reactant F-268 (33 mmol) were added to the reaction vessel and dissolved in toluene, Pd2 (dba)3 (0.3 mmol) and P(t-Bu)3 were added under nitrogen protection. (0.9 mmol), t-BuONa (60 mmol); after the addition, the reaction temperature was slowly raised to 110° C., and the mixture was stirred for 10 h; diatomaceous earth was used for hot suction filtration to remove salts and catalysts, the filtrate was cooled to room temperature, and then the Distilled water was added to the filtrate for washing, the organic phase was retained after the separation, and the aqueous phase was extracted with ethyl acetate; then the combined organic layers were dried using magnesium sulfate, and the solvent was removed using a rotary evaporator; the volume ratio was 1:( 2-7) dichloromethane and petroleum ether were used as eluents, and the remaining material was purified by column chromatography to obtain compound 268 (20.20 g, yield: 86.5%, Mw: 778.41).
上述各步骤中的产率为相应步骤的分产率。The yield in each of the above steps is the sub-yield of the corresponding step.
表征：Characterization:
HPLC纯度：＞99.8％。HPLC purity: >99.8%.
质谱测试：理论值为778.05；测试值为778.41。Mass spectrometry test: the theoretical value is 778.05; the test value is 778.41.
元素分析：Elemental analysis:
理论值：C,89.54；H,6.61；N,1.8；O,2.06Theoretical value: C, 89.54; H, 6.61; N, 1.8; O, 2.06
测试值：C,89.23；H,6.84；N,1.84；O,2.22Tested values: C, 89.23; H, 6.84; N, 1.84; O, 2.22
实施例7：化合物274的合成Example 7: Synthesis of Compound 274
步骤1：step 1:
在氮气的保护下，将反应物A-274(100mmol)、反应物B-274(110mmol)、四(三苯基膦)钯(1mmol)和碳酸钾(210mmol)，分别加入甲苯(4ml)、乙醇(200ml)、水(200ml)的混合溶剂中，升温至95℃，反应8h，反应结束后，冷却至室温，待固体析出完毕后抽滤，然后用水洗涤除去盐，再用乙醇淋洗，干燥滤饼，置于1,4-二氧六环中重结晶，得到中间体C-274所示化合物(22.32g、产率：52％、Mw：429.22)；Under the protection of nitrogen, reactant A-274 (100 mmol), reactant B-274 (110 mmol), tetrakis (triphenylphosphine) palladium (1 mmol) and potassium carbonate (210 mmol) were added with toluene (4 ml), In a mixed solvent of ethanol (200ml) and water (200ml), the temperature was raised to 95°C, and the reaction was carried out for 8 hours. After the reaction was completed, it was cooled to room temperature. After the solid was precipitated, it was filtered with suction, washed with water to remove the salt, and rinsed with ethanol. The filter cake was dried and recrystallized in 1,4-dioxane to obtain the compound represented by intermediate C-274 (22.32 g, yield: 52%, Mw: 429.22);
步骤2：Step 2:
在反应容器中加入中间体C-274(40mmol)和反应物D-274(46mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.4mmol)、P(t-Bu)3(1.12mmol)、t-BuONa(80mmol)；添加后使反应温度缓慢升温到110℃，并且搅拌混合物8h；使用硅藻土趁热抽滤，除去盐和催化剂，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，并且使用旋转式蒸发器去除溶剂；以体积比为1：(1-9)的二氯甲烷、石油醚作为洗脱剂，用管柱色谱法纯化剩余物质，获得化合物中间体E-274(28.68g、产率：83％、Mw：575.98)；After the intermediate C-274 (40 mmol) and the reactant D-274 (46 mmol) were added to the reaction vessel and dissolved in toluene, Pd2 (dba)3 (0.4 mmol) and P(t-Bu)3 were added under nitrogen protection. (1.12 mmol), t-BuONa (80 mmol); after the addition, the reaction temperature was slowly raised to 110° C., and the mixture was stirred for 8 h; hot suction filtration was used on diatomaceous earth to remove salt and catalyst, the filtrate was cooled to room temperature, and then the Distilled water was added to the filtrate for washing, the organic phase was retained after the separation, and the aqueous phase was extracted with ethyl acetate; then the combined organic layers were dried using magnesium sulfate, and the solvent was removed using a rotary evaporator; the volume ratio was 1:( 1-9) dichloromethane and petroleum ether were used as eluents, and the remaining material was purified by column chromatography to obtain compound intermediate E-274 (28.68g, yield: 83%, Mw: 575.98);
步骤3：Step 3:
在反应容器中加入中间体E-274(30mmol)和反应物F-274(33mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.3mmol)、P(t-Bu)3(0.9mmol)、t-BuONa(60mmol)；添加后使反应温度缓慢升温到110℃，并且搅拌混合物10h；使用硅藻土趁热抽滤，除去盐和催化剂，滤液冷却至室温后，接着将蒸馏水添加到滤液中进行洗涤，分液后保留有机相，用乙酸乙酯萃取水相；接着使用硫酸镁干燥合并后的有机层，并且使用旋转式蒸发器去除溶剂；以体积比为1：(2-7)的二氯甲烷、石油醚作为洗脱剂，用管柱色谱法纯化剩余物质，获得化合物274(28.18g、产率：86％、Mw：728.16)。After the intermediate E-274 (30 mmol) and the reactant F-274 (33 mmol) were added to the reaction vessel and dissolved in toluene, Pd2 (dba)3 (0.3 mmol) and P(t-Bu)3 were added under nitrogen protection. (0.9 mmol), t-BuONa (60 mmol); after the addition, the reaction temperature was slowly raised to 110° C., and the mixture was stirred for 10 h; diatomaceous earth was used for hot suction filtration to remove salts and catalysts, the filtrate was cooled to room temperature, and then the Distilled water was added to the filtrate for washing, the organic phase was retained after the separation, and the aqueous phase was extracted with ethyl acetate; then the combined organic layers were dried using magnesium sulfate, and the solvent was removed using a rotary evaporator; the volume ratio was 1:( 2-7) dichloromethane and petroleum ether were used as eluents, and the remaining material was purified by column chromatography to obtain compound 274 (28.18 g, yield: 86%, Mw: 728.16).
上述各步骤中的产率为相应步骤的分产率。The yield in each of the above steps is the sub-yield of the corresponding step.
表征：Characterization:
HPLC纯度：＞99.7％。HPLC purity: >99.7%.
质谱测试：理论值为727.97；测试值为728.16。Mass spectrometry test: the theoretical value is 727.97; the test value is 728.16.
元素分析：Elemental analysis:
理论值：C,85.80；H,5.68；N,1.92；O,2.20；S,4.40Theoretical: C, 85.80; H, 5.68; N, 1.92; O, 2.20; S, 4.40
测试值：C,85.45；H,5.87；N,1.99；O,2.31；S,4.46Tested: C, 85.45; H, 5.87; N, 1.99; O, 2.31; S, 4.46
实施例8-70Examples 8-70
参照实施例1-7的合成方法完成对如下化合物的制备，化合物分子式、质谱如表1所示：The following compounds were prepared with reference to the synthetic methods of Examples 1-7, and the molecular formulas and mass spectra of the compounds are shown in Table 1:
表1实施例8-70化合物的分子式、质谱Table 1 Molecular formula and mass spectrum of the compounds of Examples 8-70
另外，需要说明，本发明其他化合物参照上述所列举的实施例的合成方法即可获得，所以在此不再一一例举。In addition, it should be noted that other compounds of the present invention can be obtained by referring to the synthesis methods of the above-mentioned examples, so they will not be listed one by one here.
[应用例1]有机电致发光器件制备：[Application example 1] Preparation of organic electroluminescent device:
a、ITO阳极：将涂层厚度为150nm的ITO(氧化铟锡)-Ag-ITO(氧化铟锡)玻璃基板在蒸馏水中清洗2次，超声波洗涤30min，再用蒸馏水反复清洗2次，超声波洗涤10min，洗涤结束后，然后转移至等甩干机内进行甩干，最后用真空烘箱220℃烘烤2小时，烘烤结束后降温即可使用。以该基板为阳极，使用蒸镀机进行蒸镀器件工艺，在其上依次蒸镀其它功能层。a. ITO anode: The ITO (indium tin oxide)-Ag-ITO (indium tin oxide) glass substrate with a coating thickness of 150nm was washed twice in distilled water, ultrasonically washed for 30min, and then repeatedly washed with distilled water twice, and ultrasonically washed After washing for 10 minutes, transfer it to a drying machine for drying, and finally bake it in a vacuum oven at 220°C for 2 hours. After baking, it can be used after cooling down. The substrate is used as the anode, and the device is vapor-deposited using a vapor-coating machine, and other functional layers are sequentially vapor-deposited on it.
b、HIL(空穴注入层)：以
c、HTL(空穴传输层)：以
d、发光辅助层：以
e、EML(发光层)：然后在上述发光辅助层上，以
f、HB(空穴阻挡层)：以
g、ETL(电子传输层)：以
h、EIL(电子注入层)：以
i、阴极：以
j、光取出层：以
k、将蒸镀完成的基板进行封装。首先采用涂胶设备将清洗后盖板用UV胶进行涂覆工艺，然后将涂覆完成的盖板移至压合工段，将蒸镀完成的基板置于盖板上端，最后将基板和盖板在贴合设备作用下进行贴合，同时完成对UV胶光照固化。k. Encapsulate the vapor-deposited substrate. First, use the glue coating equipment to coat the cleaned cover plate with UV glue, then move the coated cover plate to the pressing section, place the evaporated substrate on the top of the cover plate, and finally put the substrate and cover plate Lamination is carried out under the action of the laminating equipment, and the UV glue is cured by light at the same time.
器件结构：Device structure:
ITO/Ag/ITO/HT:P-dopant(10nm,2％)/HT(120nm)/化合物1(10nm)/Host:Dopant(25nm,3％)/HB(5nm)/ET:Liq(35nm,50％)/Yb(1nm)/Mg:Ag(18nm,1:9)/CPL(70nm)。ITO/Ag/ITO/HT:P-dopant(10nm,2%)/HT(120nm)/Compound 1(10nm)/Host:Dopant(25nm,3%)/HB(5nm)/ET:Liq(35nm, 50%)/Yb(1 nm)/Mg:Ag(18 nm, 1:9)/CPL(70 nm).
[应用例2-70][Application example 2-70]
按照上述有机电致发光器件的制备方法制备应用例2-70的有机电致发光器件，区别在于将应用例1中的化合物1分别替换为对应的化合物，形成发光辅助层。The organic electroluminescent devices of application examples 2-70 were prepared according to the above-mentioned preparation method of organic electroluminescent devices, the difference being that compound 1 in application example 1 was respectively replaced with the corresponding compound to form a light-emitting auxiliary layer.
对比例1Comparative Example 1
按照上述含发光辅助材料的有机电致发光器件的制备方法制备有机电致发光器件，区别在于将应用例1中的化合物替换为比较化合物1。An organic electroluminescent device was prepared according to the above-mentioned preparation method of an organic electroluminescent device containing a light-emitting auxiliary material, except that the compound in Application Example 1 was replaced with Comparative Compound 1.
对比例2Comparative Example 2
按照上述含发光辅助材料的有机电致发光器件的制备方法制备有机电致发光器件，区别在于将应用例1中的化合物替换为比较化合物2。An organic electroluminescent device was prepared according to the above-mentioned preparation method of an organic electroluminescent device containing a luminescent auxiliary material, except that the compound in the application example 1 was replaced with the comparative compound 2.
对比例3Comparative Example 3
按照上述含发光辅助材料的有机电致发光器件的制备方法制备有机电致发光器件，区别在于将应用例1中的化合物替换为比较化合物3。An organic electroluminescent device was prepared according to the above-mentioned preparation method of an organic electroluminescent device containing a light-emitting auxiliary material, except that the compound in Application Example 1 was replaced with Comparative Compound 3.
对比例4Comparative Example 4
按照上述含发光辅助材料的有机电致发光器件的制备方法制备有机电致发光器件，区别在于将应用例1中的化合物替换为比较化合物4。An organic electroluminescent device was prepared according to the above-mentioned preparation method of an organic electroluminescent device containing a light-emitting auxiliary material, except that the compound in Application Example 1 was replaced with the comparative compound 4.
对比例5Comparative Example 5
按照上述含发光辅助材料的有机电致发光器件的制备方法制备有机电致发光器件，区别在于将应用例1中的化合物替换为比较化合物5。An organic electroluminescent device was prepared according to the above-mentioned preparation method of an organic electroluminescent device containing a light-emitting auxiliary material, except that the compound in Application Example 1 was replaced with the comparative compound 5.
对比例6Comparative Example 6
按照上述含发光辅助材料的有机电致发光器件的制备方法制备有机电致发光器件，区别在于将应用例1中的化合物替换为比较化合物6。An organic electroluminescent device was prepared according to the above-mentioned preparation method of an organic electroluminescent device containing a luminescent auxiliary material, except that the compound in Application Example 1 was replaced with Comparative Compound 6.
对比例7Comparative Example 7
按照上述含发光辅助材料的有机电致发光器件的制备方法制备有机电致发光器件，区别在于将应用例1中的化合物替换为比较化合物7。An organic electroluminescent device was prepared according to the above-mentioned preparation method of an organic electroluminescent device containing a light-emitting auxiliary material, except that the compound in Application Example 1 was replaced with the
对比例8Comparative Example 8
按照上述含发光辅助材料的有机电致发光器件的制备方法制备有机电致发光器件，区别在于将应用例1中的化合物替换为比较化合物8。An organic electroluminescent device was prepared according to the above-mentioned preparation method of an organic electroluminescent device containing a light-emitting auxiliary material, except that the compound in Application Example 1 was replaced with Comparative Compound 8.
对比例9Comparative Example 9
按照上述含发光辅助材料的有机电致发光器件的制备方法制备有机电致发光器件，区别在于将应用例1中的化合物替换为比较化合物9。An organic electroluminescent device was prepared according to the above-mentioned preparation method of an organic electroluminescent device containing a light-emitting auxiliary material, except that the compound in Application Example 1 was replaced with Comparative Compound 9.
比较化合物1-9的结构式如下：The structural formulas of comparative compounds 1-9 are as follows:
在1000(nits)亮度下对上述器件应用例1～70以及器件对比例1～9得到的有机电致发光器件的驱动电压、发光效率、BI值以及寿命进行表征，测试结果如下表2：The driving voltage, luminous efficiency, BI value and lifetime of the organic electroluminescent devices obtained from the above device application examples 1 to 70 and device comparative examples 1 to 9 were characterized at a brightness of 1000 (nits), and the test results are shown in Table 2:
表2发光特性测试结果(亮度：1000nits)Table 2 Test results of luminous characteristics (brightness: 1000nits)
本发明以二苯并呋喃、二苯并噻吩、咔唑、二甲基芴为骨架通过具有桥联π基团的苯基与芳胺基团和金刚烷基连接，其中，金刚烷具有高空间对称性和刚性结构，将其引入稠环单元中，可以有效的提升材料的热稳定性，同时金刚烷构筑单元的引入显著改善了材料理化性能，得到具有优异性能的用于蓝光发光辅助层的有机电致发光化合物，In the present invention, dibenzofuran, dibenzothiophene, carbazole and dimethyl fluorene are used as skeletons to connect with arylamine groups and adamantyl groups through a phenyl group with a bridged π group, wherein adamantane has high steric Symmetry and rigid structure, the introduction of it into the fused ring unit can effectively improve the thermal stability of the material, and the introduction of the adamantane building unit significantly improves the physical and chemical properties of the material, resulting in excellent performance for blue light emitting auxiliary layer. organic electroluminescent compounds,
从上表可知，对比例1-9与应用例1-70所用发光辅助材料器件性能在寿命上取得了显著提高。发光效率，BI值，驱动电压也得到了一定程度的改善。It can be seen from the above table that the device performance of the luminescent auxiliary materials used in Comparative Examples 1-9 and Application Examples 1-70 has been significantly improved in terms of life. Luminous efficiency, BI value, and driving voltage have also been improved to a certain extent.
从实验数据来看，化合物35与对比例2，对比例3相比的主要差别在于金刚烷的使用，在蓝光器件的寿命上延长了60h左右，提高了近40％。其他带有金刚烷的本发明化合物与比较化合物相比，普遍提高寿命在20-40％左右，在蓝光寿命上已经取得了显著提高。From the experimental data, the main difference between compound 35 and comparative example 2 and comparative example 3 is the use of adamantane, which prolongs the life of the blue light device by about 60h, and increases by nearly 40%. Compared with the comparative compounds, the other compounds of the present invention with adamantane generally improve the lifetime by about 20-40%, and have achieved a significant improvement in the blue light lifetime.
在本领域中，蓝光器件寿命短的问题一直是本领域技术人员急需解决的问题之一，对于本发明中金刚烷能够显著提高化合物结构稳定性，显著提高了蓝光器件的寿命，有利于在实际生产上应用。In this field, the problem of short lifespan of blue light devices has always been one of the urgent problems to be solved by those skilled in the art. For the adamantane in the present invention, the stability of the compound structure can be significantly improved, and the lifespan of blue light devices can be significantly improved, which is beneficial to practical applications. application in production.
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。The above description of the disclosed embodiments enables any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
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