CN115304566A - Luminescent auxiliary material and preparation method and application thereof - Google Patents
Luminescent auxiliary material and preparation method and application thereofDownload 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领域，更具体的说是涉及一种发光辅助材料及其制备方法和应用。The invention relates to the field of organic photoelectric materials, and more specifically relates to a luminescence auxiliary material and its preparation method and application.
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 have been developed rapidly in the fields of display, lighting, etc. 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 photoelectric functional characteristics of organic semiconductor materials to directly convert electrical energy into light energy. It belongs to the carrier injection type of luminescence. Excitons are formed in the light-emitting layer by recombination of holes injected from the anode and electrons injected from the cathode. , and release energy in the form of light energy. OLED devices are structurally divided into single-layer device structure, double-layer device structure, three-layer and multi-layer device structure, etc. Currently, the most widely used is the three-layer device structure, which has an electron transport layer, a light-emitting layer and a hole transport layer at the same time. And other multi-functional layer structure, the three functional layers perform their own duties to optimize the 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 adjusting the injection rate and amount of holes. However, most of the current hole transport layer materials, when driving OLEDs at high currents, thermal stress occurs between the anode and the hole injection layer, and Said 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。因此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 luminescence auxiliary layer is generally added between the hole transport layer and the light-emitting layer (ie, the above-mentioned multi-layer hole transport layer is provided) to improve the device life and efficiency. The luminescence auxiliary layer can increase hole utilization rate, thereby improving luminous efficiency and lifespan, and reducing driving voltage. But now there are few materials for the luminescence auxiliary layer and it is facing the problem that the gain effect is not obvious. Therefore, it is imminent to develop organic functional materials with higher performance.
发明内容Contents of the invention
有鉴于此，本发明提供了一种发光辅助材料，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。In view of this, the present invention provides a luminescence auxiliary material, which can significantly improve the service life of blue light devices, and at the same time, 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，其分子结构通式由式I表示：A luminescent auxiliary material, the general formula of its molecular structure is represented by formula I:
其中，所述式I中，X选为O，-NR1，-C(R2)(R3)-，S中的任意一种；Wherein, in the formula I, X is selected as any one of O, -NR1 , -C(R2 )(R3 )-, S;
环A表示取代或未经取代的C6～C30芳基，A与苯环并环，且A可与苯环上的1，2位或2，3位或3，4位形成并环；Ring A represents a substituted or unsubstituted C6-C30 aryl group, A and the benzene ring form a ring, and A can form a ring with the 1,2 or 2,3 or 3,4 positions on the benzene ring;
R1表示取代或非取代的碳原子数为6～30的芳基、取代或非取代的3～30的元杂芳基；R1 represents a substituted or unsubstituted aryl group with 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group with 3 to 30 members;
R2-R3各自独立的表示取代或非取代的碳原子数为1～10的烷基、取代或非取代的碳原子数为6～30的芳基、取代或非取代的3～30的元杂芳基；R2 -R3 each independently represent a substituted or unsubstituted alkyl group with 1 to 10 carbon atoms, a substituted or unsubstituted aryl group with 6 to 30 carbon atoms, a substituted or unsubstituted 3 to 30 Metaheteroaryl;
Ar1、Ar2表示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，其中杂原子为N、O、S、Si、P、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，其中杂原子为N、O、S、Si、P、Se；取代或非取代的碳原子数为10～30稠环基、取代或非取代的碳原子数为5～30螺环基中的一种或几种。Ar1 and Ar2 represent substituted or unsubstituted cycloalkyl groups with 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl groups with 3 to 30 carbon atoms, wherein the heteroatoms are N, O, S , Si, P, Se; substituted or unsubstituted aryl groups with 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl groups with 3 to 20 carbon atoms, wherein the heteroatoms are N, O, S, Si, P, Se; one or more of substituted or unsubstituted fused ring groups with 10 to 30 carbon atoms, and substituted or unsubstituted spirocyclic groups with 5 to 30 carbon atoms.
优选的，所述式I由如下所示结构表示：Preferably, the formula I is represented by the following structure:
优选的，所述环B选为苯基；所述环A选为苯基。Preferably, the ring B is selected as phenyl; the ring A is selected as phenyl.
优选的，所述R1选为苯基、萘基、联苯基、菲基、咔唑基、芴基、二甲基芴基、三联苯基、苯并呋喃、苯并噻吩、吡啶基中的任意一种；所述R2-R3选为甲基、乙基、苯基、甲基苯、联苯基、萘基中的任意一种。Preferably, the Ris selected from phenyl, naphthyl, biphenyl, phenanthrenyl, carbazolyl, fluorenyl, dimethylfluorenyl, terphenyl, benzofuran, benzothiophene, pyridyl Any one of; said R2 -R3 is selected as any one of methyl, ethyl, phenyl, methylbenzene, biphenyl, naphthyl.
优选的，所述Ar1与Ar2在任意可连接位置与N进行连接，Ar1与Ar2选为以下基团：Preferably, the Ar1 and Ar2 are connected to N at any connectable position, and Ar1 and Ar2 are selected as the following groups:
优选的，所述式I-a选为如下结构：Preferably, the formula I-a is selected as the following structure:
优选的，所述式I-b选为如下结构：Preferably, the formula I-b is selected as the following structure:
优选的，环A、R1、Ar1、Ar2与上述中定义相同。Preferably, ring A, R1 , Ar1 and Ar2 are the same as defined above.
在本说明书中，术语“经取代或未取代的”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 by one, two or more substituents selected from: deuterium; halogen group; nitrile group; silyl group; boron group; -C6 alkyl; C3-C10 cycloalkyl; C6-C18 aryl; C3-C30 heterocyclyl, or substituted by two or more of the above substituents connected substituents, or have no substituents.
进一步的，所述发光辅助材料优选为下述结构的任意一种，但不仅限于此：Further, the luminescence auxiliary material is preferably any one of the following structures, but not limited thereto:
以上仅列举了一些具体的结构式，但本发明请求保护的系列发光辅助材料不局限上述分子结构，凡是本发明公开的基团及其取代位置的简单变换就可以得到其他具体的分子结构，本发明在此不再详细列举，但其均应落入本发明申请的保护范围。Only some specific structural formulas have been listed above, but the series of luminescent auxiliary materials claimed in the present invention are not limited to the above molecular structures, and other specific molecular structures can be obtained by simply changing the groups disclosed in the present invention and their substitution positions. They will not be listed in detail here, but all of them should fall into the protection scope of the application of the present invention.
一种所述的发光辅助材料的制备方法，所述式I的合成路线如下：A preparation method of the luminescence auxiliary material, the synthesis route of the formula I is as follows:
步骤I:Step I:
(1)：在氮气保护下，将反应物1(1.0eq)加入到四氢呋喃中，降温至-78℃，滴加n-BuLi(1.1-1.5eq)，得到中间体2的反应液；(1): Under nitrogen protection, reactant 1 (1.0eq) was added to tetrahydrofuran, cooled to -78°C, and n-BuLi (1.1-1.5eq) was added dropwise to obtain the reaction solution of intermediate 2;
(2)：在氮气保护下，将中间体2的反应液(1.0eq)、反应物3(1-1.2eq)、醋酸钯(Pd(OAc)2)(0.01-0.05eq)，2-环己基-2,4,6-三异丙基联苯(X-Phos)(0.01-0.05eq)，碳酸铯(2.0-2.3eq)溶于四氢呋喃中，升温至40-70℃，反应2-8h，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，过硅胶漏斗，用甲醇：二氯甲烷体积比为1:40-60的混合物作为展开剂，将得到的旋转式蒸发器去除溶剂，所得固体进行干燥，得到中间体4；(2): Under the protection of nitrogen, the reaction solution of intermediate 2 (1.0eq), reactant 3 (1-1.2eq), palladium acetate (Pd(OAc) 2 ) (0.01-0.05eq), 2-ring Hexyl-2,4,6-triisopropylbiphenyl (X-Phos) (0.01-0.05eq), cesium carbonate (2.0-2.3eq) dissolved in tetrahydrofuran, heated to 40-70°C, reacted for 2-8h , cooled to room temperature, added H2 O, separated, the organic layer was removed with a rotary evaporator to remove the solvent, the obtained solid was dissolved by heating with toluene, passed through a silica gel funnel, and the volume ratio of methanol:dichloromethane was 1:40-60 The mixture is used as a developing agent, and the obtained rotary evaporator is used to remove the solvent, and the obtained solid is dried to obtain intermediate 4;
(3)：在氮气保护下，将中间体4(1.0eq)溶于四氢呋喃(THF)中降温至-78℃，滴加n-BuLi(1.1-1.5eq)，反应0.5-4h，升至室温，加入反应物5(1.1-1.4eq)硼酸三异丙酯中，过夜反应充分，加入盐酸，将溶液pH值调至1-2进行酸化，分液，合并有机相后，使用无水硫酸镁进行干燥，使用旋转式蒸发器去除溶剂，得到固体有机物，使用二氯甲烷将固体有机物溶解完全，滴加到石油醚溶液中，搅拌均匀，析出沉淀，抽滤得固体，依次用无水乙醇、石油醚淋洗，烘干，得到中间体B-I。(3): Under nitrogen protection, dissolve intermediate 4 (1.0eq) in tetrahydrofuran (THF) and cool down to -78°C, add n-BuLi (1.1-1.5eq) dropwise, react for 0.5-4h, and rise to room temperature , add reactant 5 (1.1-1.4eq) to triisopropyl borate, react overnight fully, add hydrochloric acid, adjust the pH value of the solution to 1-2 for acidification, separate liquids, combine organic phases, use anhydrous magnesium sulfate Carry out drying, use a rotary evaporator to remove the solvent to obtain a solid organic matter, use dichloromethane to dissolve the solid organic matter completely, add dropwise to the petroleum ether solution, stir evenly, precipitate out, and suction filter to obtain a solid, which is sequentially washed with absolute ethanol, Rinse with petroleum ether and dry to obtain intermediate B-I.
步骤II：Step II:
(1)：在氮气的保护下，将反应物A-I(1.0eq)、反应物B-I(1.1-1.2eq)、四(三苯基膦)钯(0.01-0.02eq)和碳酸钾(2.0-2.3eq)分别加入到体积比为2-4:1:1的甲苯、乙醇、水的混合溶剂中，升温至80-100℃，反应8-12h，反应结束后，冷却至室温，待固体析出完毕后抽滤，用水洗涤除去盐，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；(1): Under the protection of nitrogen, reactant A-I (1.0eq), reactant B-I (1.1-1.2eq), tetrakis (triphenylphosphine) palladium (0.01-0.02eq) and potassium carbonate (2.0-2.3 eq) were respectively added to the mixed solvent of toluene, ethanol and water with a volume ratio of 2-4:1:1, heated to 80-100°C, and reacted for 8-12h. After the reaction, cooled to room temperature and waited for the solid precipitation to complete Afterwards, filter with suction, wash with water to remove salt, rinse with ethanol, dry the filter cake, and recrystallize in 1,4-dioxane to obtain intermediate C-I;
(2)：在反应容器中加入中间体C-I(1.0eq)和反应物D-I(1.0-1.4eq)溶于甲苯后，在氮气保护下加入Pd2(dba)3(0.01eq)、P(t-Bu)3(0.02-0.04eq)、t-BuONa(2.0-2.4eq)；添加后使反应温度升温到105-115℃，搅拌混合物8-12h；使用硅藻土抽滤，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有机层，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，获得中间体E-I；(2): After adding the intermediate CI (1.0eq) and the reactant DI (1.0-1.4eq) in toluene and dissolving them in toluene, add Pd2 (dba)3 (0.01eq), P(t -Bu)3 (0.02-0.04eq), t-BuONa(2.0-2.4eq); after addition, the reaction temperature was raised to 105-115°C, and the mixture was stirred for 8-12h; filtered with diatomaceous earth to remove salt and catalyst , after the filtrate was cooled to room temperature, distilled water was added to the filtrate for washing, and the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate; then the organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator; Dichloromethane and petroleum ether at a ratio of 1:1-9 are used as eluents, and the remaining substance is purified by column chromatography to obtain intermediate EI;
(3)：在反应容器中加入中间体E-I(1.0eq)和反应物F-I(1.0-1.4eq)溶于甲苯，在氮气保护下，加入Pd2(dba)3(0.01eq)、P(t-Bu)3(0.02-0.04eq)、t-BuONa(2.0-2.4eq)；添加后使反应温度升温到105-115℃，搅拌混合物8-12h；使用硅藻土抽滤，除去盐和催化剂，滤液冷却至室温后，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；使用硫酸镁干燥有机层，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，获得通式I的化合物；(3): Add intermediate EI (1.0eq) and reactant FI (1.0-1.4eq) in toluene to dissolve in toluene, under nitrogen protection, add Pd2 (dba)3 (0.01eq), P(t -Bu)3 (0.02-0.04eq), t-BuONa(2.0-2.4eq); after addition, the reaction temperature was raised to 105-115°C, and the mixture was stirred for 8-12h; filtered with diatomaceous earth to remove salt and catalyst , after the filtrate was cooled to room temperature, distilled water was added to the filtrate for washing, the organic phase was retained after liquid separation, and the aqueous phase was extracted with ethyl acetate; the organic layer was dried using magnesium sulfate, and the solvent was removed using a rotary evaporator; the volume ratio was 1: 2-7 dichloromethane and petroleum ether are used as eluents, and the remaining substances are purified by column chromatography to obtain the compound of general formula I;
其中，所述环A、环B、X、Ar1、Ar2如上述通式I中所定义；Hal1、和Hal2选自氯、溴、碘中的一种。Wherein, the ring A, ring B, X, Ar1 and Ar2 are as defined in the above general formula I; Hal1 and Hal2 are selected from one of chlorine, bromine and iodine.
一种发光辅助材料在有机电致发光器件中的应用，所述有机电致发光器件包括第一电极、第二电极、以及设置在所述第一电极和第二电极之间的有机物层，所述有机物层包含上述的发光辅助材料。An application of a luminescence auxiliary material in an organic electroluminescence device, the organic electroluminescence device comprising a first electrode, a second electrode, and an organic layer arranged between the first electrode and the second electrode, the The organic layer includes the above-mentioned luminescence auxiliary material.
经由上述的技术方案可知，与现有技术相比，本发明具有如下有益效果：It can be seen from the above technical solutions that, compared with the prior art, the present invention has the following beneficial effects:
本发明以萘并苯并呋喃、萘并苯并噻吩、苯并咔唑、苯并芴基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。In the present invention, naphthobenzofuran, naphthobenzothiophene, benzocarbazole and benzofluorenyl are used as skeletons to connect arylamine groups and adamantyl groups through phenyl groups with bridging π groups. Among them, adamantane has high spatial symmetry and rigid structure, and introducing it into the fused ring unit can effectively improve the thermal stability of the material. At the same time, the introduction of adamantane building unit can significantly improve the physical and chemical properties of the material, which is conducive to improving the performance of the device. , 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 a 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. The driving voltage improves the efficiency and life of the organic electroluminescent device.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据提供的附图获得其他的附图。In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only It is an embodiment of the present invention, and those skilled in the art can also obtain other drawings according to the provided drawings on the premise of not paying creative efforts.
图1附图为本发明实施例1所得化合物2的核磁共振氢谱图。Figure 1 is the H NMR spectrum of Compound 2 obtained in Example 1 of the present invention.
具体实施方式Detailed ways
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only some, not all, embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.
实施例1Example 1
化合物2的合成Synthesis of compound 2
反应物B-2的合成路线如下：The synthetic route of reactant B-2 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(300mmol)加入到四氢呋喃中，降温至-78℃，缓慢滴加n-BuLi(330mmol)，得到中间体b-2的反应液；Under nitrogen protection, reactant b-1 (300mmol) was added to THF, cooled to -78°C, and n-BuLi (330mmol) 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(300mmol)、反应物b-3(360mmol)、醋酸钯(Pd(OAc)2)(3mmol)，2-环己基-2,4,6-三异丙基联苯(X-Phos)(6mmol)，碳酸铯(630mmol)溶于2100mL的四氢呋喃中，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(36.17g，Mw:325.88，产率：37％)；Under nitrogen protection, the reaction solution (300mmol) containing intermediate b-2, reactant b-3 (360mmol), palladium acetate (Pd(OAc)2 ) (3mmol), 2-cyclohexyl-2,4, Dissolve 6-triisopropylbiphenyl (X-Phos) (6mmol), cesium carbonate (630mmol) in 2100mL of tetrahydrofuran, heat up to 50°C, react for 4h, cool to room temperature, add H2 O, separate the liquid, and The organic layer was removed with a rotary evaporator, and the obtained solid was heated and dissolved with toluene, passed through a silica gel funnel while it was hot, and the volume ratio of methanol:dichloromethane was 1:(40-60) as a developer, and the resulting solid was evaporated by rotary evaporation. The solvent was removed by an apparatus, and the obtained solid was dried to obtain intermediate b-4 (36.17g, Mw: 325.88, yield: 37%);
步骤3：Step 3:
在氮气保护下，将中间体b-4(105mmol)溶于1050ml的THF中降温至-78℃，缓慢滴加n-BuLi(115.5mmol)，反应2h，升至室温，将反应物b-5(126mmol)(硼酸三异丙酯)混合溶剂中，过夜充分反应，加入适量盐酸，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，以体积比为1：(2-7)的二氯甲烷、石油醚作为展开剂，用管柱色谱法纯化剩余物质，将得到的有机相用旋转式蒸发器去除溶剂，得到固体有机物。使用少量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-2(25.97g，Mw：291.00，产率：85％)。Under the protection of nitrogen, the intermediate b-4 (105mmol) was dissolved in 1050ml of THF and the temperature was lowered to -78°C, n-BuLi (115.5mmol) was slowly added dropwise, reacted for 2h, and raised to room temperature, and the reactant b-5 (126mmol) (triisopropyl borate) mixed solvent, fully react overnight, add an appropriate amount of hydrochloric acid, and adjust the pH value of the solution to between 1-2 for acidification. Separation, after merging the organic phases, use anhydrous magnesium sulfate to dry, use dichloromethane and petroleum ether with a volume ratio of 1: (2-7) as developing solvents, purify the remaining substances with column chromatography, and obtain The organic phase was stripped of solvent using a rotary evaporator to obtain solid organics. Use a small amount of dichloromethane to completely dissolve the solid organic matter, then slowly add it dropwise into the petroleum ether solution, stir evenly, and a precipitate is precipitated, and the solid is obtained by suction filtration, rinsed with absolute ethanol and petroleum ether in turn, and dried to obtain the reaction Substance B-2 (25.97 g, Mw: 291.00, yield: 85%).
CAS：反应物A-2：1846601-95-3CAS: Reactant A-2: 1846601-95-3
CAS：反应物D-2：1392267-83-2CAS: Reactant D-2: 1392267-83-2
步骤1：step 1:
在氮气的保护下，将反应物A-2(80mmol)、反应物B-2(88mmol)、四(三苯基膦)钯(0.8mmol)和碳酸钾(168mmol)分别加入到甲苯(450mL)、乙醇(150mL)、水(150mL)的混合溶剂中，升温至90℃，反应10h，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，再用少量乙醇淋洗，干燥滤饼，置于1,4-二氧六环中重结晶，得到中间体C-2所示化合物(22.61g，Mw：463.33，产率：61％)；Under the protection of nitrogen, reactant A-2 (80mmol), reactant B-2 (88mmol), tetrakis (triphenylphosphine) palladium (0.8mmol) and potassium carbonate (168mmol) were added to toluene (450mL) , ethanol (150mL) and water (150mL) in a mixed solvent, heat up to 90°C, and react for 10 hours. After the reaction, cool to room temperature. After the solid precipitation is complete, filter with suction, then wash with water to remove salt, and then rinse with a small amount of ethanol. Wash and dry the filter cake, place it in 1,4-dioxane and recrystallize to obtain the compound shown as intermediate C-2 (22.61g, Mw: 463.33, yield: 61%);
步骤2：Step 2:
在反应容器中加入中间体C-2(45mmol)和反应物D-2(54mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.45mol)、P(t-Bu)3(0.9mmol)、t-BuONa(99mmol)；添加后使反应温度缓慢升温到105℃，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：(1-9)的二氯甲烷、石油醚作为展开剂，用管柱色谱法纯化剩余物质，获得化合物中间体E-2(23.61g，Mw：596.15，产率：88％)；After adding intermediate C-2 (45mmol) and reactant D-2 (54mmol) dissolved in toluene in the reaction vessel, add Pd2 (dba)3 (0.45mol), P(t-Bu)3 under nitrogen protection (0.9mmol), t-BuONa (99mmol); After addition, the reaction temperature was slowly raised to 105° C., and the mixture was stirred for 10 h; the diatomaceous earth was used for suction filtration while hot to remove salt and catalyst, and after the filtrate was cooled to room temperature, the Distilled water was added to the filtrate for washing, and the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate; the combined organic layer was then 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 developing solvents, and the remaining substance was purified by column chromatography to obtain compound intermediate E-2 (23.61g, Mw: 596.15, yield: 88%);
步骤3：Step 3:
在反应容器中加入中间体E-2(35mmol)和反应物F-2(42mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.35mmol)、P(t-Bu)3(0.84mmol)、t-BuONa(80.5mmol)；添加后使反应温度缓慢升温到110℃，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、石油醚作为展开剂，用管柱色谱法纯化剩余物质，获得化合物2(22.26g，产率：85％)；After adding intermediate E-2 (35mmol) and reactant F-2 (42mmol) dissolved in toluene in the reaction vessel, add Pd2 (dba)3 (0.35mmol), P(t-Bu)3 under nitrogen protection (0.84mmol), t-BuONa (80.5mmol); after addition, the reaction temperature was slowly raised to 110° C., and the mixture was stirred for 9 h; suction filtration with diatomaceous earth was used 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; the combined organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator; with a volume ratio of 1: Dichloromethane and petroleum ether in (2-7) were used as developing solvents, and the remaining substance was purified by column chromatography to obtain compound 2 (22.26 g, yield: 85%);
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748.22。Mass spectrometry test: The theoretical value is 747.98; the test value is 748.22.
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,89.74；H,6.21；N,1.92；O,2.21Test value: C, 89.74; H, 6.21; N, 1.92; O, 2.21
化合物2的核磁共振氢谱如附图1所示。The proton nuclear magnetic resonance spectrum of compound 2 is shown in accompanying drawing 1.
实施例2Example 2
化合物83的合成Synthesis of Compound 83
CAS：反应物A-83：1256544-20-3CAS: Reactant A-83: 1256544-20-3
CAS：反应物F-83：86-76-0CAS: Reactant F-83: 86-76-0
步骤1：step 1:
在氮气的保护下，将反应物A-83(80mmol)、反应物B-83(88mmol)、四(三苯基膦)钯(0.8mmol)和碳酸钾(168mmol)分别加入到甲苯(450mL)、乙醇(150mL)、水(150mL)的混合溶剂中，升温至90℃，反应10h，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，再用少量乙醇淋洗，干燥滤饼，置于1,4-二氧六环中重结晶，得到中间体C-83所示化合物(21.50g，Mw：463.28，产率：58％)；Under the protection of nitrogen, reactant A-83 (80mmol), reactant B-83 (88mmol), tetrakis (triphenylphosphine) palladium (0.8mmol) and potassium carbonate (168mmol) were added to toluene (450mL) respectively , ethanol (150mL) and water (150mL) in a mixed solvent, heat up to 90°C, and react for 10 hours. After the reaction, cool to room temperature. After the solid precipitation is complete, filter with suction, then wash with water to remove salt, and then rinse with a small amount of ethanol. Wash and dry the filter cake, place it in 1,4-dioxane and recrystallize to obtain the compound shown as intermediate C-83 (21.50g, Mw: 463.28, yield: 58%);
步骤2：Step 2:
在反应容器中加入中间体C-83(45mmol)和反应物D-83(54mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.45mol)、P(t-Bu)3(0.9mmol)、t-BuONa(99mmol)；添加后使反应温度缓慢升温到105℃，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：(1-9)的二氯甲烷、石油醚作为展开剂，用管柱色谱法纯化剩余物质，获得化合物中间体E-83(22.26g，Mw：596.11，产率：83％)；After adding intermediate C-83 (45mmol) and reactant D-83 (54mmol) dissolved in toluene in the reaction vessel, add Pd2 (dba)3 (0.45mol), P(t-Bu)3 under nitrogen protection (0.9mmol), t-BuONa (99mmol); After addition, the reaction temperature was slowly raised to 105° C., and the mixture was stirred for 10 h; the diatomaceous earth was used for suction filtration while hot to remove salt and catalyst, and after the filtrate was cooled to room temperature, the Distilled water was added to the filtrate for washing, and the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate; the combined organic layer was then 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 developing solvents, and the remaining substance was purified by column chromatography to obtain compound intermediate E-83 (22.26g, Mw: 596.11, yield: 83%);
步骤3：Step 3:
在反应容器中加入中间体E-83(35mmol)和反应物F-83(42mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.35mmol)、P(t-Bu)3(0.84mmol)、t-BuONa(80.5mmol)；添加后使反应温度缓慢升温到110℃，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、石油醚作为展开剂，用管柱色谱法纯化剩余物质，获得化合物83(22.95g，产率：86％)；After adding the intermediate E-83 (35mmol) and the reactant F-83 (42mmol) dissolved in toluene in the reaction vessel, add Pd2 (dba) 3 (0.35mmol), P(t-Bu)3 under nitrogen protection (0.84mmol), t-BuONa (80.5mmol); after addition, the reaction temperature was slowly raised to 110° C., and the mixture was stirred for 9 h; suction filtration with diatomaceous earth was used 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; the combined organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator; with a volume ratio of 1: Dichloromethane and petroleum ether in (2-7) were used as developing solvents, and the remaining substance was purified by column chromatography to obtain compound 83 (22.95 g, yield: 86%);
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762.37。Mass spectrometry test: The theoretical value is 761.97; the test value is 762.37.
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,88.14；H,5.77；N,1.89；O,4.24Test value: C, 88.14; H, 5.77; N, 1.89; O, 4.24
实施例3Example 3
化合物162的合成Synthesis of compound 162
CAS：反应物A-162：1268271-78-8CAS: Reactant A-162: 1268271-78-8
CAS：反应物D-162：108714-73-4CAS: Reactant D-162: 108714-73-4
CAS：反应物F-162：50548-45-3CAS: Reactant F-162: 50548-45-3
步骤1：step 1:
在氮气的保护下，将反应物A-162(80mmol)、反应物B-162(88mmol)、四(三苯基膦)钯(0.8mmol)和碳酸钾(168mmol)分别加入到甲苯(450mL)、乙醇(150mL)、水(150mL)的混合溶剂中，升温至90℃，反应10h，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，再用少量乙醇淋洗，干燥滤饼，置于1,4-二氧六环中重结晶，得到中间体C-162所示化合物(25.84g，Mw：538.30，产率：60％)；Under the protection of nitrogen, reactant A-162 (80mmol), reactant B-162 (88mmol), tetrakis (triphenylphosphine) palladium (0.8mmol) and potassium carbonate (168mmol) were added to toluene (450mL) respectively , ethanol (150mL) and water (150mL) in a mixed solvent, heat up to 90°C, and react for 10 hours. After the reaction, cool to room temperature. After the solid precipitation is complete, filter with suction, then wash with water to remove salt, and then rinse with a small amount of ethanol. Wash and dry the filter cake, place it in 1,4-dioxane and recrystallize to obtain the compound shown as intermediate C-162 (25.84g, Mw: 538.30, yield: 60%);
步骤2：Step 2:
在反应容器中加入中间体C-162(45mmol)和反应物D-162(54mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.45mol)、P(t-Bu)3(0.9mmol)、t-BuONa(99mmol)；添加后使反应温度缓慢升温到105℃，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：(1-9)的二氯甲烷、石油醚作为展开剂，用管柱色谱法纯化剩余物质，获得化合物中间体E-162(27.20g，Mw：711.03，产率：85％)；After adding intermediate C-162 (45mmol) and reactant D-162 (54mmol) dissolved in toluene in the reaction vessel, add Pd2 (dba)3 (0.45mol), P(t-Bu)3 under nitrogen protection (0.9mmol), t-BuONa (99mmol); After addition, the reaction temperature was slowly raised to 105° C., and the mixture was stirred for 10 h; the diatomaceous earth was used for suction filtration while hot to remove salt and catalyst, and after the filtrate was cooled to room temperature, the Distilled water was added to the filtrate for washing, and the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate; the combined organic layer was then 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 developing solvents, and the remaining substance was purified by column chromatography to obtain compound intermediate E-162 (27.20 g, Mw: 711.03, yield: 85%);
步骤3：Step 3:
在反应容器中加入中间体E-162(35mmol)和反应物F-162(42mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.35mmol)、P(t-Bu)3(0.84mmol)、t-BuONa(80.5mmol)；添加后使反应温度缓慢升温到110℃，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、石油醚作为展开剂，用管柱色谱法纯化剩余物质，获得化合物162(24.87g，产率：81％)；After adding intermediate E-162 (35mmol) and reactant F-162 (42mmol) dissolved in toluene in the reaction vessel, add Pd2 (dba)3 (0.35mmol), P(t-Bu)3 under nitrogen protection (0.84mmol), t-BuONa (80.5mmol); after addition, the reaction temperature was slowly raised to 110° C., and the mixture was stirred for 9 h; suction filtration with diatomaceous earth was used 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; the combined organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator; with a volume ratio of 1: Dichloromethane and petroleum ether in (2-7) were used as developing solvents, and the remaining substance was purified by column chromatography to obtain compound 162 (24.87 g, yield: 81%);
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877.14；测试值为877.29。Mass spectrometry test: The theoretical value is 877.14; the test value is 877.29.
元素分析：Elemental analysis:
理论值：C,89.01；H,5.98；N,3.19；O,1.82Theoretical value: C, 89.01; H, 5.98; N, 3.19; O, 1.82
测试值：C,88.84；H,6.15；N,3.22；O,1.86Test value: C, 88.84; H, 6.15; N, 3.22; O, 1.86
实施例4Example 4
化合物209的合成Synthesis of Compound 209
CAS：反应物b-8：774608-49-0CAS: Reactant b-8: 774608-49-0
步骤1：step 1:
在氮气保护下，将反应物b-6(300mmol)加入到四氢呋喃中，降温至-78℃，缓慢滴加n-BuLi(330mmol)，得到中间体b-7的反应液；Under the protection of nitrogen, reactant b-6 (300mmol) was added to tetrahydrofuran, cooled to -78°C, and n-BuLi (330mmol) 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(300mmol)、反应物b-8(360mmol)、醋酸钯(Pd(OAc)2)(3mmol)，2-环己基-2,4,6-三异丙基联苯(X-Phos)(6mmol)，碳酸铯(630mmol)溶于2100mL的四氢呋喃中，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(33.23g，Mw:325.84，产率：34％)；Under nitrogen protection, the reaction solution (300mmol) containing intermediate b-7, reactant b-8 (360mmol), palladium acetate (Pd(OAc)2 ) (3mmol), 2-cyclohexyl-2,4, Dissolve 6-triisopropylbiphenyl (X-Phos) (6mmol), cesium carbonate (630mmol) in 2100mL of tetrahydrofuran, heat up to 50°C, react for 4h, cool to room temperature, add H2 O, separate the liquid, and The organic layer was removed with a rotary evaporator, and the obtained solid was heated and dissolved with toluene, passed through a silica gel funnel while it was hot, and the volume ratio of methanol:dichloromethane was 1:(40-60) as a developer, and the resulting solid was evaporated by rotary evaporation. The solvent was removed by an apparatus, and the obtained solid was dried to obtain intermediate b-9 (33.23g, Mw: 325.84, yield: 34%);
步骤3：Step 3:
在氮气保护下，将中间体b-9(100mmol)溶于1000ml的THF中降温至-78℃，缓慢滴加n-BuLi(120mmol)，反应2h，升至室温，将反应物b-10(120mmol)(硼酸三异丙酯)混合溶剂中，过夜充分反应，加入适量盐酸，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，以体积比为1：(2-7)的二氯甲烷、石油醚作为展开剂，用管柱色谱法纯化剩余物质，将得到的有机相用旋转式蒸发器去除溶剂，得到固体有机物。使用少量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-209(23.56g，Mw：290.89，产率：81％)。Under the protection of nitrogen, the intermediate b-9 (100mmol) was dissolved in 1000ml of THF and the temperature was lowered to -78°C, n-BuLi (120mmol) was slowly added dropwise, reacted for 2h, and raised to room temperature, and the reactant b-10 ( 120mmol) (triisopropyl borate) mixed solvent, fully react overnight, add an appropriate amount of hydrochloric acid, and adjust the pH value of the solution to between 1-2 for acidification. Separation, after merging the organic phases, use anhydrous magnesium sulfate to dry, use dichloromethane and petroleum ether with a volume ratio of 1: (2-7) as developing solvents, purify the remaining substances with column chromatography, and obtain The organic phase was stripped of solvent using a rotary evaporator to obtain solid organics. Use a small amount of dichloromethane to completely dissolve the solid organic matter, then slowly add it dropwise into the petroleum ether solution, stir evenly, and a precipitate is precipitated, and the solid is obtained by suction filtration, rinsed with absolute ethanol and petroleum ether in turn, and dried to obtain the reaction Compound B-209 (23.56 g, Mw: 290.89, yield: 81%).
CAS：反应物A-209：1642127-11-4CAS: Reactant A-209: 1642127-11-4
步骤1：step 1:
在氮气的保护下，将反应物A-209(80mmol)、反应物B-209(88mmol)、四(三苯基膦)钯(0.8mmol)和碳酸钾(168mmol)分别加入到甲苯(450mL)、乙醇(150mL)、水(150mL)的混合溶剂中，升温至90℃，反应10h，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，再用少量乙醇淋洗，干燥滤饼，置于1,4-二氧六环中重结晶，得到中间体C-209所示化合物(22.98g，Mw：463.26，产率：62％)；Under the protection of nitrogen, reactant A-209 (80mmol), reactant B-209 (88mmol), tetrakis (triphenylphosphine) palladium (0.8mmol) and potassium carbonate (168mmol) were added to toluene (450mL) , ethanol (150mL) and water (150mL) in a mixed solvent, heat up to 90°C, and react for 10 hours. After the reaction, cool to room temperature. After the solid precipitation is complete, filter with suction, then wash with water to remove salt, and then rinse with a small amount of ethanol. Wash and dry the filter cake, place it in 1,4-dioxane and recrystallize to obtain the compound shown as intermediate C-209 (22.98g, Mw: 463.26, yield: 62%);
步骤2：Step 2:
在反应容器中加入中间体C-209(45mmol)和反应物D-209(54mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.45mol)、P(t-Bu)3(0.9mmol)、t-BuONa(99mmol)；添加后使反应温度缓慢升温到105℃，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：(1-9)的二氯甲烷、石油醚作为展开剂，用管柱色谱法纯化剩余物质，获得化合物中间体E-209(23.89g，Mw：672.17，产率：79％)；After adding intermediate C-209 (45mmol) and reactant D-209 (54mmol) dissolved in toluene in the reaction vessel, add Pd2 (dba)3 (0.45mol), P(t-Bu)3 under nitrogen protection (0.9mmol), t-BuONa (99mmol); After addition, the reaction temperature was slowly raised to 105° C., and the mixture was stirred for 10 h; the diatomaceous earth was used for suction filtration while hot to remove salt and catalyst, and after the filtrate was cooled to room temperature, the Distilled water was added to the filtrate for washing, and the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate; the combined organic layer was then 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 developing solvents, and the remaining substance was purified by column chromatography to obtain compound intermediate E-209 (23.89g, Mw: 672.17, yield: 79%);
步骤3：Step 3:
在反应容器中加入中间体E-209(35mmol)和反应物F-209(42mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.35mmol)、P(t-Bu)3(0.84mmol)、t-BuONa(80.5mmol)；添加后使反应温度缓慢升温到110℃，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、石油醚作为展开剂，用管柱色谱法纯化剩余物质，获得化合物209(25.09g，产率：82％)；After adding intermediate E-209 (35mmol) and reactant F-209 (42mmol) dissolved in toluene in the reaction vessel, add Pd2 (dba)3 (0.35mmol), P(t-Bu)3 under nitrogen protection (0.84mmol), t-BuONa (80.5mmol); after addition, the reaction temperature was slowly raised to 110° C., and the mixture was stirred for 9 h; suction filtration with diatomaceous earth was used 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; the combined organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator; with a volume ratio of 1: Dichloromethane and petroleum ether in (2-7) were used as developing solvents, and the remaining substance was purified by column chromatography to obtain compound 209 (25.09 g, yield: 82%);
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874.14；测试值为874.32。Mass spectrometry test: The theoretical value is 874.14; the test value is 874.32.
元素分析：Elemental analysis:
理论值：C,90.69；H,5.88；N,1.60；O,1.83Theoretical value: C, 90.69; H, 5.88; N, 1.60; O, 1.83
测试值：C,90.53；H,6.01；N,1.64；O,1.87Test value: C, 90.53; H, 6.01; N, 1.64; O, 1.87
实施例5Example 5
化合物217的合成Synthesis of compound 217
CAS：反应物b-13：148836-41-3CAS: Reactant b-13: 148836-41-3
步骤1：step 1:
在氮气保护下，将反应物b-11(300mmol)加入到四氢呋喃中，降温至-78℃，缓慢滴加n-BuLi(330mmol)，得到中间体b-12的反应液；Under the protection of nitrogen, the reactant b-11 (300 mmol) was added to tetrahydrofuran, the temperature was lowered to -78°C, and n-BuLi (330 mmol) was slowly added dropwise to obtain the reaction solution of intermediate b-12;
步骤2：Step 2:
在氮气保护下，将含有中间体b-12的反应液(300mmol)、反应物b-13(360mmol)、醋酸钯(Pd(OAc)2)(3mmol)，2-环己基-2,4,6-三异丙基联苯(X-Phos)(6mmol)，碳酸铯(630mmol)溶于2100mL的四氢呋喃中，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-14(35.21g，Mw:325.99，产率：36％)；Under nitrogen protection, the reaction solution (300mmol) containing intermediate b-12, reactant b-13 (360mmol), palladium acetate (Pd(OAc)2 ) (3mmol), 2-cyclohexyl-2,4, Dissolve 6-triisopropylbiphenyl (X-Phos) (6mmol), cesium carbonate (630mmol) in 2100mL of tetrahydrofuran, heat up to 50°C, react for 4h, cool to room temperature, add H2 O, separate the liquid, and The organic layer was removed with a rotary evaporator, and the obtained solid was heated and dissolved with toluene, passed through a silica gel funnel while it was hot, and the volume ratio of methanol:dichloromethane was 1:(40-60) as a developer, and the resulting solid was evaporated by rotary evaporation. The solvent was removed by a machine, and the obtained solid was dried to obtain intermediate b-14 (35.21g, Mw:325.99, yield: 36%);
步骤3：Step 3:
在氮气保护下，将中间体b-14(105mmol)溶于1050ml的THF中降温至-78℃，缓慢滴加n-BuLi(126mmol)，反应2h，升至室温，将反应物b-15(126mmol)(硼酸三异丙酯)混合溶剂中，过夜充分反应，加入适量盐酸，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，以体积比为1：(2-7)的二氯甲烷、石油醚作为展开剂，用管柱色谱法纯化剩余物质，将得到的有机相用旋转式蒸发器去除溶剂，得到固体有机物。使用少量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-217(25.35g，Mw：290.85，产率：83％)。Under the protection of nitrogen, the intermediate b-14 (105mmol) was dissolved in 1050ml of THF and cooled to -78°C, slowly added dropwise n-BuLi (126mmol), reacted for 2h, raised to room temperature, and the reactant b-15 ( 126mmol) (triisopropyl borate) mixed solvent, fully react overnight, add appropriate amount of hydrochloric acid, adjust the pH value of the solution to between 1-2 for acidification. Separation, after merging the organic phases, use anhydrous magnesium sulfate to dry, use dichloromethane and petroleum ether with a volume ratio of 1: (2-7) as developing solvents, purify the remaining substances with column chromatography, and obtain The organic phase was stripped of solvent using a rotary evaporator to obtain solid organics. Use a small amount of dichloromethane to completely dissolve the solid organic matter, then slowly add it dropwise into the petroleum ether solution, stir evenly, and a precipitate is precipitated, and the solid is obtained by suction filtration, rinsed with absolute ethanol and petroleum ether in turn, and dried to obtain the reaction Compound B-217 (25.35 g, Mw: 290.85, yield: 83%).
CAS：反应物A-217：1674334-94-1CAS: Reactant A-217: 1674334-94-1
步骤1：step 1:
在氮气的保护下，将反应物A-217(80mmol)、反应物B-217(88mmol)、四(三苯基膦)钯(0.8mmol)和碳酸钾(168mmol)分别加入到甲苯(450mL)、乙醇(150mL)、水(150mL)的混合溶剂中，升温至90℃，反应10h，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，再用少量乙醇淋洗，干燥滤饼，置于1,4-二氧六环中重结晶，得到中间体C-217所示化合物(23.88g，Mw：489.30，产率：61％)；Under the protection of nitrogen, reactant A-217 (80mmol), reactant B-217 (88mmol), tetrakis (triphenylphosphine) palladium (0.8mmol) and potassium carbonate (168mmol) were added to toluene (450mL) , ethanol (150mL) and water (150mL) in a mixed solvent, heat up to 90°C, react for 10h, after the reaction, cool to room temperature, filter with suction after the solid precipitation is complete, then wash with water to remove salt, and then rinse with a small amount of ethanol Wash and dry the filter cake, place it in 1,4-dioxane and recrystallize to obtain the compound shown as intermediate C-217 (23.88g, Mw: 489.30, yield: 61%);
步骤2：Step 2:
在反应容器中加入中间体C-217(45mmol)和反应物D-217(54mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.45mol)、P(t-Bu)3(0.9mmol)、t-BuONa(99mmol)；添加后使反应温度缓慢升温到105℃，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：(1-9)的二氯甲烷、石油醚作为展开剂，用管柱色谱法纯化剩余物质，获得化合物中间体E-217(24.50g，Mw：633.13，产率：86％)；After adding intermediate C-217 (45mmol) and reactant D-217 (54mmol) dissolved in toluene in the reaction vessel, add Pd2 (dba)3 (0.45mol), P(t-Bu)3 under nitrogen protection (0.9mmol), t-BuONa (99mmol); After addition, the reaction temperature was slowly raised to 105° C., and the mixture was stirred for 10 h; the diatomaceous earth was used for suction filtration while hot to remove salt and catalyst, and after the filtrate was cooled to room temperature, the Distilled water was added to the filtrate for washing, and the organic phase was retained after separation, and the aqueous phase was extracted with ethyl acetate; the combined organic layer was then 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 developing solvents, and the remaining substance was purified by column chromatography to obtain compound intermediate E-217 (24.50 g, Mw: 633.13, yield: 86%);
步骤3：Step 3:
在反应容器中加入中间体E-217(35mmol)和反应物F-217(42mmol)溶于甲苯之后，在氮气保护下加入Pd2(dba)3(0.35mmol)、P(t-Bu)3(0.84mmol)、t-BuONa(80.5mmol)；添加后使反应温度缓慢升温到110℃，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、石油醚作为展开剂，用管柱色谱法纯化剩余物质，获得化合物217(22.52g，产率：79％)；After adding intermediate E-217 (35mmol) and reactant F-217 (42mmol) dissolved in toluene in the reaction vessel, add Pd2 (dba)3 (0.35mmol), P(t-Bu)3 under nitrogen protection (0.84mmol), t-BuONa (80.5mmol); after addition, the reaction temperature was slowly raised to 110° C., and the mixture was stirred for 9 h; suction filtration with diatomaceous earth was used 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; the combined organic layer was then dried using magnesium sulfate, and the solvent was removed using a rotary evaporator; with a volume ratio of 1: Dichloromethane and petroleum ether in (2-7) were used as developing solvents, and the remaining substance was purified by column chromatography to obtain compound 217 (22.52 g, yield: 79%);
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814.13；测试值为814.35。Mass spectrometry test: theoretical value is 814.13; test value is 814.35.
元素分析：Elemental analysis:
理论值：C,91.47；H,6.81；N,1.72Theoretical value: C,91.47; H,6.81; N,1.72
测试值：C,91.33；H,6.95；N,1.80Test value: C,91.33; H,6.95; N,1.80
实施例6-60Example 6-60
参照实施例1-5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：With reference to the synthetic method of Example 1-5, the preparation of the following compounds is completed, and the compound molecular formula and mass spectrum are as shown in Table 1:
表1实施例6-60化合物的分子式、质谱Molecular formula, mass spectrum of the compound of table 1 embodiment 6-60
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。Other compounds of the present invention can be obtained by referring to the synthesis methods of the examples listed above, so they will not be listed one by one here.
本发明还有一个目的在于提供一种含有发光辅助材料的有机电致发光器件，包括第一电极、与上述第一电极对置设置的第二电极、以及具备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层包含本发明制备的式I所示化合物。Still another object of the present invention is to provide an organic electroluminescent device containing a luminescence auxiliary material, comprising a first electrode, a second electrode opposite to the first electrode, and a Between one or more organic layers, at least one of the above organic layers contains the compound represented by formula I prepared by the present invention.
本发明的有机发光元件可以具有包含空穴注入层、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、电子注入层等作为有机物层的结构。但是，有机发光元件的结构并不限于此，可以包含数量更少或更多的有机层。The organic light-emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, an electron blocking layer, a light emission auxiliary layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like as organic layers. However, the structure of the organic light emitting element is not limited thereto, and may include fewer or more organic layers.
根据本说明书的一个实施方式，上述有机物层包含发光辅助层，发光辅助层包含本发明制备的式I所示化合物。According to one embodiment of the present specification, the above-mentioned organic layer includes a luminescence auxiliary layer, and the luminescence auxiliary layer includes the compound represented by formula I prepared in the present invention.
在上述有机发光元件包含多个有机物层的情况下，上述有机物层可以由相同物质或不同物质形成。When the above-mentioned organic light-emitting device includes a plurality of organic material layers, the above-mentioned organic material layers may be formed of the same substance or different substances.
关于上述式I所表示的化合物，在制造有机发光元件时，可以利用真空蒸镀法，也可以利用溶液涂布法来形成有机物层。其中，所谓溶液涂布法是旋涂法、浸涂法、刮涂法、喷墨印刷法、丝网印刷法、喷雾法、辊涂法等，但并非仅限于此。Regarding the compound represented by the above-mentioned formula I, when manufacturing an organic light-emitting device, a vacuum evaporation method or a solution coating method may be used to form an organic layer. Among them, the solution coating method includes spin coating, dip coating, blade coating, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited thereto.
本发明的有机发光元件根据所使用的材料，可以为顶部发光型、底部发光型或双向发光型。The organic light emitting device of the present invention may be a top emission type, a bottom emission type, or a bidirectional emission type depending on the materials used.
本发明所述的器件可以用于有机发光器件、有机太阳电池、电子纸、有机感光体或有机薄膜晶体管。The device described in the present invention can be used in organic light-emitting devices, organic solar cells, electronic paper, organic photoreceptors or organic thin film transistors.
本发明提供一种有机电致发光器件的制备方法，包括所述有机物层中包含上述的发光辅助材料。The invention provides a method for preparing an organic electroluminescence device, which comprises the above-mentioned luminescence auxiliary material in the organic layer.
应用例1：有机电致发光器件制备：Application example 1: Preparation of organic electroluminescence 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: wash the ITO (indium tin oxide)-Ag-ITO (indium tin oxide) glass substrate with a coating thickness of 150nm in distilled water twice, ultrasonically wash for 30min, then repeatedly wash twice with distilled water, ultrasonically wash After washing for 10 minutes, transfer it to a spin dryer for drying, and finally bake it in a vacuum oven at 220°C for 2 hours. After the baking is finished, it can be used after cooling down. Using the substrate as an anode, an evaporation device process is performed using an evaporation machine, and other functional layers are sequentially evaporated 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. Encapsulating the evaporated substrate. Firstly, use glue coating equipment to coat the cleaned cover with UV glue, then move the coated cover to the pressing section, place the evaporated substrate on the top of the cover, and finally put the substrate and cover together Lamination is carried out under the action of lamination equipment, and the UV glue is cured by light at the same time.
器件结构：Device structure:
ITO/Ag/ITO/HT-1：P-dopant(10nm，3％)/HT-1(120nm)/式I(10nm)/Host-1：Dopant(25nm，2％)/HB(5nm)/ET-1：Liq(35nm，50％)/Yb(1nm)/Mg：Ag(18nm，1：9)/CPL-1(70nm)。ITO/Ag/ITO/HT-1: P-dopant(10nm, 3%)/HT-1(120nm)/Formula I(10nm)/Host-1:Dopant(25nm, 2%)/HB(5nm)/ ET-1:Liq(35nm, 50%)/Yb(1nm)/Mg:Ag(18nm, 1:9)/CPL-1(70nm).
应用例2-60：Application example 2-60:
按照上述有机电致发光器件的制备方法制备应用例2-60的有机电致发光器件，区别在于将应用例1中的化合物2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 2-60 were prepared according to the above preparation method of organic electroluminescent devices, with the difference that compound 2 in application example 1 was replaced with corresponding compounds to form a luminescent 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中的化合物替换为对比化合物1。An organic electroluminescent device was prepared according to the above preparation method of an organic electroluminescent device containing a luminescence auxiliary material, except that the compound in Application Example 1 was replaced by 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中的化合物替换为对比化合物2。An organic electroluminescent device was prepared according to the method for preparing an organic electroluminescent device containing a luminescence auxiliary material, except that the compound in Application Example 1 was replaced by 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中的化合物替换为对比化合物3。An organic electroluminescent device was prepared according to the method for preparing an organic electroluminescent device containing a luminescence auxiliary material, except that the compound in Application Example 1 was replaced by 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中的化合物替换为对比化合物4。An organic electroluminescent device was prepared according to the above preparation method of an organic electroluminescent device containing a luminescence auxiliary material, except that the compound in Application Example 1 was replaced by 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中的化合物替换为对比化合物5。An organic electroluminescent device was prepared according to the above preparation method of an organic electroluminescent device containing a luminescent auxiliary material, except that the compound in Application Example 1 was replaced by
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中的化合物替换为对比化合物6。An organic electroluminescent device was prepared according to the method for preparing an organic electroluminescent device containing a luminescence auxiliary material, except that the compound in Application Example 1 was replaced by 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中的化合物替换为对比化合物7。An organic electroluminescent device was prepared according to the above preparation method of an organic electroluminescent device containing a luminescence auxiliary material, except that the compound in Application Example 1 was replaced by comparative compound 7.
对比化合物1-7的结构式如下：The structural formula of comparative compound 1-7 is as follows:
在1000(nits)亮度下对上述器件应用例1～60以及器件对比例1～7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 in the above-mentioned device application examples 1-60 and device comparative examples 1-7 were characterized at a brightness of 1000 (nits), and the test results are as follows 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)
本领域技术人员可知，受微腔效应的影响，发光效率受色度影响较大，因此引入BI值作为蓝光发光材料效率的依据，BI＝发光效率/CIEy。Those skilled in the art know that due to the effect of the microcavity, the luminous efficiency is greatly affected by the chromaticity, so the BI value is introduced as the basis for the efficiency of the blue light-emitting material, BI=luminous efficiency/CIEy.
本发明以萘并苯并呋喃、萘并苯并噻吩、苯并咔唑、苯并芴基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 present invention uses naphthobenzofuran, naphthobenzothiophene, benzocarbazole, and benzofluorenyl as the backbone to connect the arylamine group and the adamantyl group through a phenyl group with a bridging π group, wherein the adamantine Alkane has high spatial symmetry and rigid structure, and introducing 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 block can significantly improve the physical and chemical properties of the material, which is conducive to improving the performance of the device and prolonging the life of the device. life.
从上表可知，对比例1-7与应用例1-60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 luminescence auxiliary materials used in Comparative Examples 1-7 and Application Examples 1-60 has been significantly improved in terms of lifetime. The 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63与对比例5，对比例6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70h左右，提高了约14％。其他带有金刚烷的本发明化合物与对比化合物相比，普遍提高寿命在8-16％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 63 and Comparative Example 5 and Comparative Example 6 lies in the use of adamantane, which prolongs the life of the blue light device by about 70h, which is about 14%. Compared with the comparison compound, other compounds of the present invention with adamantane generally increase the lifespan by about 8-16%, and have achieved a significant improvement in the lifespan of blue light.
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 life of blue light devices has always been one of the problems that those skilled in the art urgently need to solve. For the present invention, adamantane can significantly improve the structural stability of the compound and significantly improve the life of blue light devices, which is beneficial in practice. production application.
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.
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 is provided to enable any person skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention will not 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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