An organic compound and application thereof, an organic electroluminescence device

Abstract

The application relates to the field of organic electroluminescence devices, and discloses an organic compound and application thereof and an organic electroluminescence device. The compound contains a structure shown in ring A, and any bondable position in a structure shown in ring B is connected with any bondable position in the structure shown in ring A through an optional L connecting group. When the organic compound is used as an electron transport material in an organic electroluminescence device, the organic compound has a lower driving voltage and higher device light-emitting efficiency; when the organic compound is used as an electron blocking material in an organic electroluminescence device, the organic compound has a lower driving voltage and higher device light-emitting efficiency. Ring A: ring B:

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic electroluminescence devices, in particular to an organic compound and application thereof, and an organic electroluminescence device. BACKGROUND

[0002] The organic electroluminescence phenomenon was first discovered by Pope et al. in 1963, who found that a single crystal of anthracene could emit weak blue light under the drive of a voltage of more than 100 V, but the high driving voltage and large thickness of the single crystal anthracene did not attract widespread attention.

[0003] Until 1987, Dr. Deng Qingyun of Kodak reported that a double-layer organic electroluminescence device (Organic Light-Emitting Diodes, OLED) was prepared by vacuum thermal evaporation based on two kinds of organic semiconductor materials, 8-hydroxyquinoline aluminum with high fluorescence efficiency and good electron transport property, and aromatic diamine with good hole transport property.

[0004] The external quantum efficiency of the aforementioned OLED reached 1% and the brightness was as high as 1000 Cd / m 2 under a driving voltage of less than 10 V, which triggered a research boom in OLEDs and promoted further research on organic electroluminescence materials.

[0005] In recent years, OLEDs have gradually entered the field of vision as a new generation of display technology, and the wide application prospect and rapid technological progress have made OLEDs one of the most popular researches in the display field and scientific research product development.

[0006] At present, OLEDs or screens still have the defects of high driving voltage and low current efficiency. In order to improve these defects, on the one hand, the device structure and manufacturing process need to be further optimized, and on the other hand, the performance of the materials of each functional layer also needs to be improved.

[0007] The electron transport material and the electron blocking layer material play a crucial role in the driving voltage and luminous efficiency of the device.

[0008] Therefore, there is an urgent need in the market to develop high-performance electron transport materials and electron blocking layer materials to reduce the driving voltage and improve the luminous efficiency of the device.

[0009] CN110049986A discloses a compound with the following structure:

[0010] wherein Z is group, but the structure disclosed in the prior art has the defects of high driving voltage and low luminous efficiency when applied to OLEDs. SUMMARY

[0011] The present application aims to overcome the defects of high OLED driving voltage and low luminous efficiency provided by the prior art.

[0012] To achieve the above-mentioned object, the first aspect of the present application provides an organic compound containing a structure represented by ring A, and any bondable position in a structure represented by ring B is connected to any bondable position in the structure represented by ring A through an optional L connecting group;

[0013] Ring A: Ring B:

[0014] In ring A,

[0015] Y is O or S;

[0016] X1, X2, X3 are each independently selected from C and N, and at least one of X1, X2, X3 is N;

[0017] Any two of R1, R2, and R3 adjacent to each other are ring-closed to form a dibenzo-hexa-membered ring or ring-closed to form a dideuterated benzo-hexa-membered ring; and the remaining one is not present or is a C 6-30 aromatic group;

[0018] In ring B,

[0019] X4, X5, X6, X7, X8, X9 are each independently selected from C and N;

[0020] R4, R5, R6, and R7 are each independently selected from not present or each independently selected from a C 6-30 aromatic group with or without a heteroatom; or

[0021] Any two of R4, R5, and R6 adjacent to each other are ring-closed to form a benzene ring or ring-closed to form a C 6-30 aromatic group with or without a heteroatom; the remaining one is not present or is a C 6-30 aromatic group with or without a heteroatom; and R7 is not present or is a C 6-30 aromatic group with or without a heteroatom;

[0022] The optional L is a C 6-30 aromatic group with or without a heteroatom.

[0023] The second aspect of the present application provides the use of the organic compound of the first aspect in an organic electroluminescent device.

[0024] A third aspect of the present invention provides an organic electroluminescent device containing one or more organic compounds as described in the first aspect, wherein the organic compounds are present in at least one of the electron injection layer, electron transport layer, electron blocking layer and capping layer of the organic electroluminescent device.

[0025] When the organic compounds of the present invention are used as electron transport materials in organic electroluminescent devices, they exhibit lower driving voltage and higher device luminous efficiency.

[0026] In addition, the organic compounds of the present invention have lower driving voltage and higher device luminous efficiency when used as electron blocking materials in organic electroluminescent devices.

[0027] The present invention has at least the following specific advantages:

[0028] 1. The core structure of the compound of the present invention has electron-withdrawing properties. The oxygen and sulfur atoms in the core have high electronegativity and strong ability to attract electrons. On the one hand, adding triazine, pyrimidine, quinazoline and quinoxaline groups with deep LUMO to the core can deepen the LUMO level of the compound of the present invention and reduce the electron injection barrier. When used as an electron transport material in organic electroluminescent devices, it can reduce the driving voltage of the device and improve the luminous efficiency of the device.

[0029] On the other hand, by adding electron-donating groups to the parent core, the compound of the present invention can block electrons. When applied as an electron-blocking material to organic electroluminescent devices, it can reduce the driving voltage of the device.

[0030] 2. The core structure of the present invention has a good planar structure, which is conducive to the migration of charge carriers. When applied to organic electroluminescent devices, it can improve the luminous efficiency of the device. Detailed Implementation

[0031] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0032] The "dideuterated benzo6-membered ring" described in this invention means that the deuterium atom can replace the H atom on the group at any position where it can be substituted.

[0033] The "C" described in this invention 6-30 "Aromatic group" refers to an aryl group with a total number of carbon atoms of 6-30, including but not limited to phenyl, biphenyl, naphthyl, anthracene, phenanthryl, pyrene, etc.

[0034] In the rings A and B of the present application, "O" indicates a conjugated structure, which can form a double bond at any position capable of forming a double bond.

[0035] As described above, the first aspect of the present application provides an organic compound containing a structure represented by ring A, and a structure represented by ring B, in which any position capable of bonding is connected to any position capable of bonding in the structure represented by ring A via an optional L linking group;

[0036] Ring A: Ring B:

[0037] In ring A,

[0038] Y is O or S;

[0039] X1, X2, X3are each independently selected from C and N, and at least one of X1, X2, X3is N;

[0040] Any two of R1, R2, and R3adjacent to each other are ring-closed to form a dibenzo-hexa-membered ring or a dideuterated dibenzo-hexa-membered ring; and the remaining one is not present or is a C 6-30 aromatic group;

[0041] In ring B,

[0042] X4, X5, X6, X7, X8, X9are each independently selected from C and N;

[0043] R4, R5, R6, and R7are each independently selected from not present or each independently selected from a C 6-30 aromatic group with or without a heteroatom; or

[0044] Any two of R4, R5, and R6adjacent to each other are ring-closed to form a benzene ring or a C 6-30 aromatic group with or without a heteroatom; the remaining one is not present or is a C 6-30 aromatic group with or without a heteroatom; and R7is not present or is a C 6-30 aromatic group with or without a heteroatom;

[0045] The optional L is a C 6-30 aromatic group with or without a heteroatom.

[0046] According to one preferred embodiment, in ring A,

[0047] Y is O or S;

[0048] X1, X2, and X3 are each independently selected from C and N, and at least one of X1, X2, and X3 is N;

[0049] Any two adjacent members of R1, R2, and R3 may cyclize to form a dibenzo-6-membered ring or a dideuterated benzo-6-membered ring; the remaining member may be absent or selected from any one of phenyl, naphthyl, anthraceneyl, phenanthryl, and biphenyl.

[0050] According to another preferred embodiment, in ring B,

[0051] Any two or any three of X4, X5, X6, X7, X8, and X9 are N, and any N's adjacent ring-forming atom is C;

[0052] R4, R5, R6, and R7 are either independently absent or independently selected from phenyl, naphthyl, biphenyl, dibenzothiophene, dibenzofuranyl, or 9,9-dimethylfluorenyl; or

[0053] Any two adjacent R4, R5, and R6 cyclize to form a benzene ring; the remaining one is absent or selected from any one of phenyl, naphthyl, biphenyl, dibenzothiophene, dibenzofuran, and 9,9-dimethylfluorenyl; and R7 is absent or selected from any one of phenyl, naphthyl, biphenyl, dibenzothiophene, dibenzofuran, and 9,9-dimethylfluorenyl.

[0054] According to a particularly preferred embodiment, ring B is selected from substituted or unsubstituted carbazole, dibenzofuran, dibenzothiophene, triphenylene, naphthalene, 9,9-dimethylfluorene, substituted or unsubstituted structures of formula (Q1), substituted or unsubstituted structures of formula (Q2), substituted or unsubstituted structures of formula (Q3), substituted or unsubstituted structures of formula (Q4), substituted or unsubstituted structures of formula (Q5), substituted or unsubstituted structures of formula (Q6), substituted or unsubstituted structures of formula (Q7), substituted or unsubstituted structures of formula (Q8), and substituted or unsubstituted structures of formula (Q9).

[0055]

[0056]

[0057] Among them, Y1 and Y2 are each independently selected from N, O, S, and C;

[0058] The substituents present in ring B are optionally selected from phenyl, C 1-3 At least one of alkyl, naphthyl, biphenyl, and phenanthrene groups.

[0059] Preferably, L, if present, is a linking group selected from the structures of benzene, naphthalene, biphenyl, dibenzothiophene, dibenzofuran, 9,9-dimethylfluorene.

[0060] According to one particularly preferred embodiment, the compound is any one of the following compounds:

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070] The present application does not have particular limitation on the specific method for preparing the aforementioned compounds, and those skilled in the art can obtain the aforementioned compounds of the present application according to the specific structural formula provided by the present application, combined with the conventional process route in the field of organic synthesis. In addition, several examples are exemplarily listed in the following of the present application to illustrate the preparation method of the compounds of the present application, and those skilled in the art can also obtain the specific preparation method of all the remaining compounds by replacing the type of raw materials according to the preparation method of the compounds in the following of the present application. The present application does not further detail the preparation method of all the compounds, and those skilled in the art should not be understood as a limitation on the present application.

[0071] As described above, the second aspect of the present application provides the use of the organic compound of the first aspect in an organic electroluminescent device.

[0072] As described above, the third aspect of the present application provides an organic electroluminescent device containing one or more than two organic compounds of the first aspect, wherein the organic compound is present in at least one of the electron injection layer, the electron transport layer, the electron blocking layer and the capping layer of the organic electroluminescent device.

[0073] Preferably, the organic compound is present in the capping layer on the surface of the cathode of the organic electroluminescent device.

[0074] Particularly preferably, the organic compound is present in the electron transport layer and / or the electron blocking layer of the organic electroluminescent device.

[0075] Preferably, the organic electroluminescent device comprises, in the stated order, an anode, a hole injection layer, a hole transport layer, an optional electron blocking layer, a light-emitting layer, an optional hole blocking layer, an electron transport layer, an electron injection layer, a cathode and a cover layer.

[0076] According to some embodiments of the present application, the anode material forming the anode, generally preferably a material having a large work function, for example the anode material used in the present application is selected from one or more of the following materials, metals such as vanadium, chromium, copper and gold, or other alloys, metal oxides such as zinc oxide, indium oxide, indium tin oxide, indium zinc oxide and tin dioxide, combinations of metals and oxides such as zinc oxide: aluminum, but not limited thereto.

[0077] According to some embodiments of the present application, the material forming the hole injection layer has the ability to transport holes, and thus the material of the hole injection layer has a hole injection effect into the anode, has an excellent hole injection effect on the light-emitting layer or light-emitting material, prevents the excitons generated in the light-emitting layer from moving to the electron injection layer or electron injection material, and in addition, has an excellent thin film formation ability. The HOMO of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer.

[0078] According to some embodiments of the present application, the hole injection material and the hole transport material include at least one of an aromatic amine derivative (for example, NPB, SqMA1), a hexaazatriphenylene derivative (for example, HACTN), an indolocarbazole derivative, a conductive polymer (for example, PEDOT / PSS), a phthalocyanine or porphyrin derivative, a dibenzoindenofluorene amine, a spirobifluorene amine, but not limited thereto.

[0079] According to some embodiments of the present application, the hole injection layer and the hole transport layer can be formed, for example, using an aromatic amine derivative of the following general formula:

[0080]

[0081] The groups of R1 to R9 in the above general formula are each independently selected from a single bond, hydrogen, deuterium, an alkyl group, benzene, biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, benzophenanthrene, pyrene, fluorene, dimethylfluorene, spirobifluorene, carbazole, thiophene, benzothiophene, dibenzothiophene, furan, benzofuran, dibenzofuran, indole, indolocarbazole, indenocarbazole, pyridine, pyrimidine, imidazole, thiazole, quinoline, isoquinoline, quinoxaline, quinazoline, porphyrin, carbolin, pyrazine, pyridazine or triazine.

[0082] According to some embodiments of the present application, the material forming the electron blocking layer is not particularly limited, and in general, a compound capable of satisfying the following 1st or / and 2nd conditions can be considered for use:

[0083] 1st: having a shallow LUMO level (small absolute value), which aims to reduce the number of electrons leaving the light emitting layer, thereby increasing the recombination probability of electrons and holes in the light emitting layer.

[0084] 2nd: having a large triplet energy, which aims to reduce the number of excitons leaving the light emitting layer, thereby increasing the efficiency of exciton conversion to light.

[0085] According to some embodiments of the present application, when the light emitting material of the light emitting layer is a material capable of emitting light in the visible region by receiving holes and electrons from the hole transport layer and the electron transport layer, respectively, and combining the holes and the electrons, and preferably a material having good quantum efficiency for fluorescence or phosphorescence.

[0086] According to some embodiments of the present application, the light emitting layer can include a host material and a guest material. According to some embodiments of the present application, the host material of the device contains the compound described in the aforementioned first aspect of the present application. According to some embodiments of the present application, the guest material is preferably a compound that generates emission via at least one of phosphorescence, fluorescence, TADF (thermally activated delayed fluorescence), MLCT (metal-to-ligand charge transfer), HLCT (having a hybrid CT state), and triplet-triplet annihilation.

[0087] According to some embodiments of the present application, the guest material in the light emitting layer can include a derivative of perylene, a derivative of anthracene, a fluorene derivative, a stilbenyl aromatic derivative, an arylamine derivative, an organosilicon derivative, an organoboron derivative, a carbazole-triazine derivative, an acridine derivative, a ketone-containing derivative, a sulfone derivative, a cyano derivative, and a xanthene derivative, but is not limited thereto.

[0088] In some preferred embodiments of the present application, the sulfone derivative has the general formula shown below:

[0089]

[0090] The ketone derivative has the general formula shown below:

[0091]

[0092] In the general formula of the sulfone derivative and the ketone derivative described above, R 20 , R 21 , R 22 , and R 23each independently selected from a single bond, hydrogen, deuterium, an alkyl group, benzene, biphenyl, terphenyl, quaterphenyl, naphthalene, phenylnaphthalene, anthracene, phenanthrene, benzophenanthrene, pyrene, fluorene, carbazole, thiophene, benzothiophene, dibenzothiophene, furan, benzofuran, dibenzofuran, indole, indolecarbazole, indolocarbazole, pyridine, pyrimidine, imidazole, thiazole, quinoline, isoquinoline, quinoxaline, quinazoline, porphyrin, carbolin, pyrazine, pyridazine, or triazine, and a substituted group thereof.

[0093] According to some embodiments of the present application, the material forming the hole blocking layer can also preferably be a compound having the following first and / or second conditions:

[0094] First: having a deep HOMO energy level (large absolute value), which aims to reduce the number of holes from the light-emitting layer, thereby increasing the recombination probability of electrons and holes in the light-emitting layer.

[0095] Second: having a large triplet energy, which aims to reduce the number of excitons from the light-emitting layer, thereby increasing the efficiency of exciton conversion to light emission.

[0096] According to some embodiments of the present application, the material forming the hole blocking layer can include, for example, phenanthroline derivatives (e.g., Bphen, BCP), benzophenanthrene derivatives, and benzimidazole derivatives, but is not limited thereto.

[0097] According to some embodiments of the present application, the electron injection layer is a layer that injects electrons from the electrode, and the electron injection material is preferably a compound having the following properties: the ability to transport electrons, the effect of injecting electrons from the cathode, the excellent effect of injecting electrons into the light-emitting layer or light-emitting material, the prevention of excitons generated in the light-emitting layer from moving to the hole injection layer, and in addition, excellent thin film formation ability. The electron injection layer material can include, for example, LiF, CsF, Cs2CO3, LiQ, but is not limited thereto.

[0098] According to some embodiments of the present application, the cathode material is generally preferably a material having a small work function, which allows smooth injection of electrons into the organic material layer, and the cathode material that can be used in the present disclosure can be selected from one or more of the following materials: one or more of Al, Mg, and Ag.

[0099] The present application will be described in detail below by way of examples. In the following examples, various raw materials used are commercially available unless otherwise specified. In the following description, room temperature or ordinary temperature means 25 ± 1°C unless otherwise specified.

[0100] Preparation Example 1

[0101]

[0102] Synthesis of intermediate A-a: In a 500 ml flask, under nitrogen, intermediate A-1 (33.8 mmol) was dissolved in xylene (100 ml), intermediate A-2 (67.6 mmol), cuprous chloride (20.3 mmol), 1,10-phenanthroline hydrate (13.5 mmol), potassium hydroxide (203 mmol) were added successively and the mixture was stirred at elevated temperature. When the temperature reached 130°C, a mixture of o-chloroiodobenzene (33.8 mmol) and xylene (100 ml) was added dropwise. The reaction was maintained at reflux for 15 hours. The reaction was then quenched by the dropwise addition of 15 ml of concentrated hydrochloric acid. The mixture was stirred for 1 hour, filtered, and the filtrate was partitioned between 200 ml of water and ethyl acetate. The organic phase was washed twice with water, dried over sodium sulfate, filtered and the solvent was evaporated. The residue was purified by column chromatography on silica gel to give intermediate A-a-1 (yield: 78%).

[0103] Synthesis of compound A-a: In a 500 ml flask, under nitrogen, intermediate A-a-1 (52.7 mmol), potassium carbonate (210 mmol), 4-tricyclohexylphosphine tetrakisfluoroborate (6.3 mmol) and palladium (II) acetate (6.3 mmol) were suspended in dimethylacetamide (200 ml) and stirred at reflux for 5 hours. After cooling, the reaction mixture was mixed with 150 ml of water and 150 ml of ethyl acetate. The mixture was stirred for 30 minutes, partitioned, the organic phase was washed twice with water, dried over sodium sulfate, filtered and the solvent was evaporated. The crude product was hot extracted with toluene and recrystallized from toluene to give compound A-a (yield: 75%).

[0104] The following compounds can be obtained in a similar manner, except that intermediate A-2 is replaced by the corresponding reactant in Table 1.

[0105] Table 1

[0106]

[0107] Intermediate A-a: Mass spectrum: C21H11ClN2O, calculated: 342.06, found: 342.05. Elemental analysis: calculated: C: 73.58%, H: 3.23%, N: 8.17%; found: C: 73.59%, H: 3.21%, N: 8.16%.

[0108] Intermediate A-b: Mass spectrum: C21H11ClN2O, calculated: 342.06, found: 342.04. Elemental analysis: calculated: C: 73.58%, H: 3.23%, N: 8.17%; found: C: 73.60%, H: 3.22%, N: 8.15%.

[0109] Intermediate A-c: Mass Spec: C21H11CIN2O, Theoretical: 342.06, Found: 342.08. Elemental Analysis: Theoretical: C: 73.58%, H: 3.23%, N: 8.17%; Found: C: 73.55%, H: 3.20%, N: 8.19%.

[0110] Intermediate A-d: Mass Spec: C21H11CIN2O, Theoretical: 342.06, Found: 342.07. Elemental Analysis: Theoretical: C: 73.58%, H: 3.23%, N: 8.17%; Found: C: 73.56%, H: 3.20%, N: 8.15%.

[0111] Intermediate B-a: Mass Spec: C21H11CIN2S, Theoretical: 358.03, Found: 358.07. Elemental Analysis: Theoretical: C: 70.29%, H: 3.09%, N: 7.81%; Found: C: 70.30%, H: 3.10%, N: 7.80%.

[0112] Intermediate B-b: Mass Spec: C21H11CIN2S, Theoretical: 358.03, Found: 358.05. Elemental Analysis: Theoretical: C: 70.29%, H: 3.09%, N: 7.81%; Found: C: 70.28%, H: 3.11%, N: 7.82%.

[0113] Intermediate B-c: Mass Spec: C21H11CIN2S, Theoretical: 358.03, Found: 358.07. Elemental Analysis: Theoretical: C: 70.29%, H: 3.09%, N: 7.81%; Found: C: 70.28%, H: 3.06%, N: 7.78%.

[0114] Intermediate B-d: Mass Spec: C21H11CIN2S, Theoretical: 358.03, Found: 358.07. Elemental Analysis: Theoretical: C: 70.29%, H: 3.09%, N: 7.81%; Found: C: 70.32%, H: 3.07%, N: 7.78%.

[0115] Preparation Example 2

[0116]

[0117] Synthesis of Intermediate C-a:

[0118] Synthesis of intermediate C-a-1 : In a 500ml flask, under nitrogen protection, add intermediate A-1 (50.7mmol), intermediate C-1 (50.7mmol), a mixture of toluene (150ml), ethanol (70ml), water (35ml), potassium carbonate (127mmol), tetrakis(triphenylphosphine)palladium (0.76mmol), heat to reflux for 4h, HPLC detection of raw materials basically complete reaction, add deionized water (200ml) to the reaction solution, stir for 10min, take the organic phase with toluene wash three times, combine the organic phase, dry over anhydrous magnesium sulfate. Filter the drying agent, spin dry the organic solvent, the residue is separated by silica gel column chromatography, to obtain intermediate C-a-1 (yield: 72%).

[0119] Synthesis of intermediate C-a-2: In a 500ml flask, under nitrogen protection, add anhydrous THF (130ml) solvent, then add intermediate C-a-1 (36.5mmol), dissolve completely, then cool the mixture to -30℃, then slowly add 1M LDA (lithium diisopropylamide) solution (45ml), after adding, continue to react at -20℃ for 4h, then add iodine (55mmol) slowly to room temperature, continue to react for 4h, quench the reaction with sodium bisulfite aqueous solution, extract with dichloromethane three times, combine the organic phase, dry, spin dry the solvent, column chromatography separation, to obtain intermediate C-a-2 (yield: 68%).

[0120] Synthesis of intermediate C-a-3: In a 500ml flask, under nitrogen protection, add intermediate C-a-2 (25mmol), dichloromethane (120ml), drop BBr3 (30mmol) at 0℃, no obvious temperature during drop, after drop, warm to room temperature reaction, detect after 1h reaction, raw materials basically complete reaction. Pour the reaction solution into ice water, add 2M sodium hydroxide aqueous solution to alkaline (more than 9), separate the organic phase, add deionized water, wash twice with water, separate the organic phase, spin dry under reduced pressure to obtain the crude product, with petroleum ether to warm up, filter after cooling, dry to obtain intermediate C-a-3 (yield: 52%).

[0121] Synthesis of Intermediate C-a: In a 500 ml three-necked flask, under nitrogen protection, Intermediate C-a-3 (13 mmol) was dissolved in xylene solvent (70 ml), cuprous chloride (4 mmol), 1,10-phenanthroline hydrate (2.6 mmol), potassium hydroxide (40 mmol), and stirred at elevated temperature, and the reaction was heated to 130 °C and kept at reflux for 20 h. The reaction was monitored by TLC. After the reaction was completed, concentrated hydrochloric acid (10 ml) was added dropwise, and stirred for 1 h. The reaction mixture was filtered, and the filtrate was added to deionized water (150 ml). The organic phase was separated, washed with deionized water twice, and dried over anhydrous sodium sulfate for 2 h. The organic solvent was removed by rotary evaporation. The residue was separated by silica gel column chromatography to give Intermediate C-a (yield: 77%).

[0122] The following compounds can be obtained in a similar manner, except that Intermediate C-1 is replaced by the corresponding reactant in Table 2.

[0123] Table 2

[0124]

[0125]

[0126] Intermediate C-a: Mass spectrum: C21H11ClN2O, Theoretical value: 342.06, Found: 342.07. Elemental analysis: Theoretical value: C: 73.58%, H: 3.23%, N: 8.17%; Found: C: 73.59%, H: 3.22%, N: 8.15%.

[0127] Intermediate C-b: Mass spectrum: C21H11ClN2O, Theoretical value: 342.06, Found: 342.04. Elemental analysis: Theoretical value: C: 73.58%, H: 3.23%, N: 8.17%; Found: C: 73.57%, H: 3.21%, N: 8.18%.

[0128] Intermediate C-c: Mass spectrum: C21H11ClN2O, Theoretical value: 342.06, Found: 342.05. Elemental analysis: Theoretical value: C: 73.58%, H: 3.23%, N: 8.17%; Found: C: 73.56%, H: 3.24%, N: 8.16%.

[0129] Intermediate C-d: Mass spectrum: C21H11ClN2O, Theoretical value: 342.06, Found: 342.03. Elemental analysis: Theoretical value: C: 73.58%, H: 3.23%, N: 8.17%; Found: C: 73.60%, H: 3.20%, N: 8.20%.

[0130] Intermediate E-a: Mass Spec: C21H11CIN2S, Theoretical: 358.03, Found: 358.01. Elemental Analysis: Theoretical: C: 70.29%, H: 3.09%, N: 7.81%; Found: C: 70.30%, H: 3.10%, N: 7.80%.

[0131] Intermediate E-b: Mass Spec: C21H11CIN2S, Theoretical: 358.03, Found: 358.02. Elemental Analysis: Theoretical: C: 70.29%, H: 3.09%, N: 7.81%; Found: C: 70.28%, H: 3.08%, N: 7.82%.

[0132] Intermediate E-c: Mass Spec: C21H11CIN2S, Theoretical: 358.03, Found: 358.06. Elemental Analysis: Theoretical: C: 70.29%, H: 3.09%, N: 7.81%; Found: C: 70.31%, H: 3.11%, N: 7.82%.

[0133] Intermediate E-d: Mass Spec: C21H11CIN2S, Theoretical: 358.03, Found: 358.00. Elemental Analysis: Theoretical: C: 70.29%, H: 3.09%, N: 7.81%; Found: C: 70.27%, H: 3.06%, N: 7.78%.

[0134] Preparation Example 3

[0135] Synthesis of Intermediate F-a:

[0136]

[0137] Synthesis of Intermediate F-a-1: The synthesis method is the same as that of the synthesis of Intermediate A-a-1, except that Intermediate A-1 is replaced by Intermediate F-1 to obtain Intermediate F-a-1 (yield: 75%).

[0138] Synthesis of Intermediate F-a-2: The synthesis method is the same as that of the synthesis of Intermediate A-a, except that Intermediate A-a-1 is replaced by Intermediate F-a-1 to obtain Intermediate F-a-2 (yield: 74%).

[0139] Synthesis of intermediate F-a: In a 500 ml three-necked flask, intermediate F-a-2 (25.8 mmol) was dissolved in N,N-dimethylformamide (90 ml) under nitrogen protection, and a solution of NBS (25.8 mmol) in N,N-dimethylformamide (50 ml) was added dropwise. After the addition was completed, the temperature was raised to 100 °C and stirring was carried out for 18 h. HPLC detection showed that the reaction of the starting material was substantially complete. After the reaction solution was cooled to room temperature, water (150 ml) was added dropwise, and stirring was carried out for 30 min. The crude product was obtained by filtration, and was dried to obtain intermediate F-a (yield: 57%).

[0140] The following compounds can be obtained in a similar manner, except that intermediate A-2 is replaced by the corresponding reactant in Table 3.

[0141] Table 3

[0142]

[0143]

[0144] Intermediate F-a: Mass spectrum: C22H11BrClNO, theoretical value: 418.97, found: 418.98. Elemental analysis: theoretical value: C: 62.81%, H: 2.64%, N: 3.33%; found: C: 62.80%, H: 2.65%, N: 3.34%.

[0145] Intermediate F-b: Mass spectrum: C22H11BrClNO, theoretical value: 418.97, found: 418.95. Elemental analysis: theoretical value: C: 62.81%, H: 2.64%, N: 3.33%; found: C: 62.82%, H: 2.63%, N: 3.32%.

[0146] Intermediate F-c: Mass spectrum: C22H11BrClNO, theoretical value: 418.97, found: 418.96. Elemental analysis: theoretical value: C: 62.81%, H: 2.64%, N: 3.33%; found: C: 62.79%, H: 2.63%, N: 3.32%.

[0147] Intermediate F-d: Mass spectrum: C22H11BrClNO, theoretical value: 418.97, found: 418.94. Elemental analysis: theoretical value: C: 62.81%, H: 2.64%, N: 3.33%; found: C: 62.79%, H: 2.63%, N: 3.35%.

[0148] Intermediate G-a: Mass Spec: C22H11BrClNS, Theoretical: 434.95, Found: 434.94. Elemental Analysis: Theoretical: C: 60.50%, H: 2.54%, N: 3.21%; Found: C: 60.51%, H: 2.55%, N: 3.20%.

[0149] Intermediate G-b: Mass Spec: C22H11BrClNS, Theoretical: 434.95, Found: 434.91. Elemental Analysis: Theoretical: C: 60.50%, H: 2.54%, N: 3.21%; Found: C: 60.52%, H: 2.56%, N: 3.19%.

[0150] Intermediate G-c: Mass Spec: C22H11BrClNS, Theoretical: 434.95, Found: 434.97. Elemental Analysis: Theoretical: C: 60.50%, H: 2.54%, N: 3.21%; Found: C: 60.51%, H: 2.52%, N: 3.20%.

[0151] Intermediate G-d: Mass Spec: C22H11BrClNS, Theoretical: 434.95, Found: 434.93. Elemental Analysis: Theoretical: C: 60.50%, H: 2.54%, N: 3.21%; Found: C: 60.49%, H: 2.56%, N: 3.19%.

[0152] Preparation Example 4

[0153] Synthesis of Intermediate H-a:

[0154]

[0155] Synthesis of Intermediate H-a-1: The synthesis method is the same as that of the synthesis of Intermediate C-a-1, except that Intermediate A-1 is replaced by Intermediate F-1 to obtain Intermediate H-a-1 (yield: 75%).

[0156] Synthesis of Intermediate H-a-2: The synthesis method is the same as that of the synthesis of Intermediate C-a-2, except that Intermediate C-a-1 is replaced by Intermediate H-a-1 to obtain Intermediate H-a-2 (yield: 67%).

[0157] Synthesis of Intermediate H-a-3: The synthesis method is the same as that of the synthesis of Intermediate C-a-3, except that Intermediate C-a-2 is replaced by Intermediate H-a-2 to obtain Intermediate H-a-3 (yield: 55%).

[0158] Synthesis of intermediate H-a-4: The synthesis was performed in the same manner as that of intermediate C-a except that intermediate C-a-3 was replaced by intermediate H-a-3 to give intermediate H-a-4 (yield: 78%).

[0159] Synthesis of intermediate H-a: The synthesis was performed in the same manner as that of intermediate F-a except that intermediate F-a-2 was replaced by intermediate H-a-4 to give intermediate H-a (yield: 63%).

[0160] The following compounds can be obtained in a similar manner except that intermediate C-1 is replaced by the corresponding reactant in Table 4.

[0161] Table 4

[0162]

[0163] Intermediate H-a: Mass spectrum: C22H11BrClNO, calculated: 418.97, found: 418.93. Elemental analysis: calculated: C: 62.81%, H: 2.64%, N: 3.33%; found: C: 62.80%, H: 2.65%, N: 3.32%.

[0164] Intermediate H-b: Mass spectrum: C22H11BrClNO, calculated: 418.97, found: 418.98. Elemental analysis: calculated: C: 62.81%, H: 2.64%, N: 3.33%; found: C: 62.80%, H: 2.64%, N: 3.32%.

[0165] Intermediate H-c: Mass spectrum: C22H11BrClNO, calculated: 418.97, found: 418.96. Elemental analysis: calculated: C: 62.81%, H: 2.64%, N: 3.33%; found: C: 62.80%, H: 2.63%, N: 3.31%.

[0166] Intermediate H-d: Mass spectrum: C22H11BrClNO, calculated: 418.97, found: 418.95. Elemental analysis: calculated: C: 62.81%, H: 2.64%, N: 3.33%; found: C: 62.82%, H: 2.66%, N: 3.30%.

[0167] Intermediate I-a: Mass spectrum: C22H11BrClNS, calculated: 434.95, found: 434.93. Elemental analysis: calculated: C: 60.50%, H: 2.54%, N: 3.21%; found: C: 60.49%, H: 2.56%, N: 3.19%.

[0168] Intermediate I-b: Mass Spec: C22H11BrClNS, Theoretical: 434.95, Found: 434.94. Elemental Analysis: Theoretical: C: 60.50%, H: 2.54%, N: 3.21%; Found: C: 60.51%, H: 2.55%, N: 3.20%.

[0169] Intermediate I-c: Mass Spec: C22H11BrClNS, Theoretical: 434.95, Found: 434.92. Elemental Analysis: Theoretical: C: 60.50%, H: 2.54%, N: 3.21%; Found: C: 60.51%, H: 2.53%, N: 3.20%.

[0170] Intermediate I-d: Mass Spec: C22H11BrClNS, Theoretical: 434.95, Found: 434.93. Elemental Analysis: Theoretical: C: 60.50%, H: 2.54%, N: 3.21%; Found: C: 60.49%, H: 2.56%, N: 3.19%.

[0171] Example 1: Synthesis of compound 1-1:

[0172]

[0173] Synthesis of intermediate 1-1-1: In a 500ml three-necked flask, protected by nitrogen, 1,4-dioxane solvent (180ml) was added, followed by intermediate A-a (52.6mmol), bis(pinacolato)diboron (52.6mmol), potassium acetate (132mmol) and [1,1'-bis(diphenylphosphino)ferrocene] palladium dichloride (0.79mmol), heated to reflux for 4h, HPLC detection of raw materials reaction was completed, the reaction was reduced to room temperature, the reaction was rotary evaporated under reduced pressure to obtain the crude product, the crude product was dissolved in toluene, heated and stirred, heated to reflux, decolorized by hot silica gel column, the filtrate was rotary evaporated under reduced pressure to have a small amount of solvent, then ethanol (200ml) was added to slurry, recrystallized with toluene / ethanol to obtain intermediate 1-1-1 (yield: 88%).

[0174] Synthesis of compound 1-1: In a 500ml flask, nitrogen was bubbled, and intermediate 1-1-1 (46mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (46mmol), toluene (200ml), dicyclohexyl(2',4',6'-triisopropyl-(1,1'-biphenyl)-2-yl)phosphinic acid (2.3mmol), pd2(dba)3(tris(dibenzylideneacetone)dipalladium, 0.46mmol), aqueous solution containing potassium phosphate dibasic (115mmol) 40ml, stirring was started and heated to 90°C overnight reaction, after 17h the reaction was lowered to 40°C, kept at 0°C for 3h, filtered to get the crude, washed with water (250ml), then with methanol (250ml) to get the solid, column chromatography on silica gel with toluene as eluent to get the yellowish solid compound 1-1 (yield: 85%).

[0175] Mass: C36H21N5O, Theoretical value: 539.17, Found value: 539.20.1H-NMR (400MHz, CDC13) (ppm) δ = 7.37-7.45 (1H, m), 7.46-7.69 (10H, m), 7.75-7.84 (3H, m), 7.92-8.04 (2H, m), 8.31-8.41 (4H, m), 8.60-8.65 (1H, m).

[0176] Example 2: Synthesis of compound 1-15:

[0177]

[0178] Synthesis of intermediate 1-15-1: The synthesis method was the same as that of intermediate 1-1-1, to obtain intermediate 1-15-1 (yield: 89%).

[0179] Synthesis of compound 1-15: The synthesis method was the same as that of compound 1-1, to obtain compound 1-15 (yield: 83%).

[0180] Mass: C54H33N5O, Theoretical value: 767.27, Found value: 767.30.1H-NMR (400MHz, CDC13) (ppm) δ = 7.21-7.29 (6H, m), 7.36-7.69 (12H, m), 7.71-7.85 (6H, m), 7.91-8.04 (8H, m), 8.59-8.65 (1H, m).

[0181] Example 3: Synthesis of compound 1-22:

[0182]

[0183] Synthesis of intermediate 1-22-1: The synthesis method was the same as that of synthesis of intermediate 1-1-1 to obtain intermediate 1-22-1 (yield: 90%).

[0184] Synthesis of compound 1-22: The synthesis method was the same as that of synthesis of compound 1-1 to obtain compound 1-22 (yield: 86%).

[0185] Mass: C42H25N5O, Theoretical value: 615.21, Found value: 615.20.1H-NMR (400MHz, CDCl3) (ppm) δ = 7.21-7.28 (2H, m), 7.36-7.84 (16H, m), 7.90-8.05 (4H, m), 8.31-8.41 (2H, m), 8.59-8.65 (1H, m).

[0186] Example 4: Synthesis of compound 1-35:

[0187]

[0188] Synthesis of intermediate 1-35-1: The synthesis method was the same as that of synthesis of intermediate 1-1-1 to obtain intermediate 1-35-1 (yield: 84%).

[0189] Synthesis of compound 1-35: The synthesis method was the same as that of synthesis of compound 1-1 to obtain compound 1-35 (yield: 85%).

[0190] Mass: C42H25N5O, Theoretical value: 615.21, Found value: 615.20.1H-NMR (400MHz, CDCl3) (ppm) δ = 7.21-7.28 (2H, m), 7.36-7.84 (16H, m), 7.90-8.05 (4H, m), 8.31-8.41 (2H, m), 8.59-8.65 (1H, m).

[0191] Example 5: Synthesis of compound 1-45:

[0192]

[0193] Synthesis of compound 1-45: The synthesis method was the same as that of synthesis of compound 1-1 to obtain compound 1-45 (yield: 87%).

[0194] Mass: C42H25N5O, Theoretical value: 615.21, Found value: 615.20.1H-NMR (400 MHz, CDCI3) (ppm) δ = 7.21 ~ 7.29 (2H, m), 7.44 ~ 7.72 (11H, m), 7.75 ~ 7.85 (3H, m), 7.91 ~ 8.04 (4H, m), 8.31 ~ 8.41 (4H, m), 8.59 ~ 8.65 (1H, m).

[0195] Example 6: Synthesis of compound 1-57:

[0196]

[0197] Synthesis of compound 1-57: The synthesis method is the same as that of compound 1-1, to obtain compound 1-57 (yield: 85%).

[0198] Mass: C41H24N4O, Theoretical value: 588.20, Found value: 588.21.1H-NMR (400 MHz, CDCI3) (ppm) δ = 7.46 ~ 7.74 (11H, m), 7.75 ~ 7.85 (4H, m), 7.91 ~ 8.04 (4H, m), 8.11 ~ 8.15 (1H, m), 8.28 ~ 8.39 (3H, m), 8.60 ~ 8.64 (1H, m).

[0199] Example 7: Synthesis of compound 1-64:

[0200]

[0201] Synthesis of compound 1-64: The synthesis method is the same as that of compound 1-1, to obtain compound 1-64 (yield: 83%).

[0202] Mass: C48H29N5O, Theoretical value: 691.24, Found value: 691.30.1H-NMR (400 MHz, CDCI3) (ppm) δ = 7.46 ~ 7.74 (16H, m), 7.76 ~ 7.85 (3H, m), 7.92 ~ 8.04 (2H, m), 8.21 ~ 8.24 (1H, m), 8.31 ~ 8.41 (5H, m), 8.41 ~ 8.44 (1H, m), 8.60 ~ 8.64 (1H, m).

[0203] Example 8: Synthesis of compound 1-100:

[0204]

[0205] Synthesis of intermediate 1-100-1: The synthesis method was same as that of synthesis of intermediate 1-1-1 to obtain intermediate 1-100-1 (yield: 87%).

[0206] Synthesis of compound 1-100: The synthesis method was same as that of synthesis of compound 1-1 to obtain compound 1-100 (yield: 86%).

[0207] Mass: C36H21N5S, Theoretical value: 555.15, Found value: 555.20. 1H-NMR (400MHz, CDC13) (ppm) δ = 7.46-7.69 (10H, m), 7.76-7.85 (2H, m), 7.92-8.04 (3H, m), 8.08-8.11 (1H, m), 8.32-8.40 (4H, m), 8.60-8.64 (1H, m).

[0208] Example 9: Synthesis of compound 1-136:

[0209]

[0210] Synthesis of intermediate 1-136-1: In a 500 ml three-necked flask, under the protection of nitrogen, a mixture of intermediate G-c (34.5 mmol), phenyl boronic acid (34.5 mmol), toluene (150 ml), ethanol (30 ml), water (15 ml) was added in turn, and stirring was started. Then potassium carbonate (86.3 mmol), tetrakis (triphenylphosphine) palladium (0.35 mmol) were added in turn, and the temperature was raised to reflux for 3 h. HPLC detection showed that the raw material was substantially reacted. Deionized water (200 ml) was added to the reaction solution, and the organic phase was washed with toluene three times. The combined organic phase was dried over anhydrous magnesium sulfate. The drying agent was filtered and dried, and the organic solvent was rotary evaporated. The residue was separated by silica gel column chromatography to obtain white solid intermediate 1-136-1 (yield: 67%).

[0211] Synthesis of intermediate 1-136-2: The synthesis method was same as that of synthesis of intermediate 1-1-1 to obtain intermediate 1-136-2 (yield: 85%).

[0212] Synthesis of compound 1-136: The synthesis method was same as that of synthesis of compound 1-1 to obtain compound 1-136 (yield: 81%).

[0213] Mass: C49H30N4S, Theoretical value: 706.22, Found: 706.25.1H-NMR (400 MHz, CDCI3) (ppm) δ = 7.22-7.28 (2H, m), 7.36-7.69 (15H, m), 7.71-7.85 (4H, m), 7.91-8.04 (5H, m), 8.07-8.11 (1H, d), 8.31-8.41 (2H, m), 8.59-8.65 (1H, m).

[0214] Example 10: Synthesis of compound 1-155:

[0215]

[0216] Synthesis of intermediate 1-155-1: The synthesis method was the same as that of the synthesis of intermediate 1-1-1 to obtain intermediate 1-155-1 (yield: 87%).

[0217] Synthesis of compound 1-155: The synthesis method was the same as that of the synthesis of compound 1-1 to obtain compound 1-155 (yield: 85%).

[0218] Mass: C40H23N5S, Theoretical value: 605.17, Found: 605.20.1H-NMR (400 MHz, CDCI3) (ppm) δ = 7.42-7.70 (9H, m), 7.75-7.89 (4H, m) 7.91-8.04 (5H, m), 8.08-8.12 (1H, d), 8.31-8.41 (2H, m), 8.59-8.65 (1H, m), 8.93-9.01 (1H, m).

[0219] Example 11: Synthesis of compound 1-166:

[0220]

[0221] Synthesis of intermediate 1-166-1: The synthesis method was the same as that of the synthesis of intermediate 1-136-1 to obtain intermediate 1-166-1 (yield: 73%).

[0222] Synthesis of intermediate 1-166-2: The synthesis method was the same as that of the synthesis of intermediate 1-1-1 to obtain intermediate 1-166-2 (yield: 85%).

[0223] Synthesis of compound 1-166: The synthesis method was the same as that of the synthesis of compound 1-1 to obtain compound 1-166 (yield: 83%).

[0224] Mass: C43H26N4S, Theoretical value: 630.19, Found: 630.25. 1H-NMR (400 MHz, CDC13) (ppm) δ = 7.36 ~ 7.56 (12H, m), 7.57 ~ 7.69 (3H, m), 7.75 ~ 7.85 (2H, m), 7.91 ~ 8.04 (3H, m), 8.07 ~ 8.11 (1H, d), 8.31 ~ 8.41 (4H, m), 8.59 ~ 8.65 (1H, m).

[0225] Example 12: Synthesis of compound 1-176:

[0226]

[0227] Synthesis of intermediate 1-176-1: The synthesis method was the same as that of synthesis of intermediate 1-1-1 to obtain intermediate 1-176-1 (yield: 87%).

[0228] Synthesis of intermediate 1-176-2: The synthesis method was the same as that of synthesis of compound 1-1 to obtain intermediate 1-176-2 (yield: 83%).

[0229] Synthesis of intermediate 1-176-3: The synthesis method was the same as that of synthesis of intermediate F-a to obtain intermediate 1-176-3 (yield: 58%).

[0230] Synthesis of intermediate 1-176-4: The synthesis method was the same as that of synthesis of intermediate A-a-1 to obtain intermediate 1-176-4 (yield: 76%).

[0231] Synthesis of compound 1-176: The synthesis method was the same as that of synthesis of intermediate A-a to obtain compound 1-176 (yield: 78%).

[0232] Mass: C48H29N5O, Theoretical value: 691.24, Found: 691.20. 1H-NMR (400 MHz, CDC13) (ppm) δ = 7.18 ~ 7.32 (2H, m), 7.44 ~ 7.56 (7H, m), 7.57 ~ 7.81 (10H, m), 7.91 ~ 7.97 (1H, m), 8.17 ~ 8.21 (1H, m), 8.31 ~ 8.42 (7H, m), 8.78 ~ 8.82 (1H, d).

[0233] Example 13: Synthesis of compound 2-3:

[0234]

[0235] Synthesis of compound 2-3: The synthesis method was the same as that of compound 1-1, to obtain compound 2-3 (yield: 86%).

[0236] Mass: C39H23N3O, calc'd: 549.18, found: 549.21. 1H-NMR (400 MHz, CDC13) (ppm) δ = 7.13 ~ 7.25 (2H, m), 7.35 ~ 7.45 (1H, m) 7.46 ~ 7.56 (3H, m), 7.56 ~ 7.66 (6H, m), 7.67 ~ 7.74 (2H, m), 7.75 ~ 7.90 (4H, m), 7.91 ~ 8.05 (2H, m), 8.14 ~ 8.28 (2H, m), 8.58 ~ 8.65 (1H, m).

[0237] Example 14: Synthesis of compound 2-9:

[0238]

[0239] Synthesis of intermediate 2-9-1: The synthesis method was the same as that of intermediate 1-1-1, to obtain intermediate 2-9-1 (yield: 91%).

[0240] Synthesis of compound 2-9: The synthesis method was the same as that of compound 1-1, to obtain compound 2-9 (yield: 83%).

[0241] Mass: C39H23N3S, calc'd: 565.16, found: 565.20. 1H-NMR (400 MHz, CDC13) (ppm) δ = 7.13 ~ 7.25 (2H, m), 7.35 ~ 7.44 (1H, m) 7.46 ~ 7.53 (2H, m), 7.53 ~ 7.64 (5H, m), 7.64 ~ 7.74 (2H, m), 7.75 ~ 7.90 (3H, m), 7.91 ~ 8.05 (3H, m), 8.13 ~ 8.30 (4H, m), 8.58 ~ 8.65 (1H, m).

[0242] Example 15: Synthesis of compound 2-17:

[0243]

[0244] Synthesis of compound 2-17: The synthesis method was the same as that of compound 1-1, to obtain compound 2-17 (yield: 87%).

[0245] Mass: C51H30N4O, calculated: 714.24, found: 714.20. 1H-NMR (400 MHz, CDC13) (ppm) δ = 7.14 ~ 7.24 (2H, m), 7.35 ~ 7.44 (1H, m) 7.46 ~ 7.53 (4H, m), 7.53 ~ 7.66 (10H, m), 7.67 ~ 7.75 (2H, m), 7.76 ~ 7.90 (4H, m), 7.91 ~ 8.04 (2H, m), 8.14 ~ 8.24 (1H, m), 8.31 ~ 8.35 (1H, d), 8.54 ~ 8.66 (3H, m).

[0246] Example 16: Synthesis of compound 2-28:

[0247]

[0248] Synthesis of compound 2-28: In a 500 ml three-necked flask, under nitrogen protection, intermediate A-c (44 mmol), 11-phenyl-11,12-dihydroindolo[2,3-a]carbazole (44 mmol), activated copper powder (88 mmol), 18-crown-6 (8.8 mmol), potassium carbonate (110 mmol) and o-dichlorobenzene (150 ml) were added successively, heated and stirred, and the temperature was raised to reflux for 58 h. The reaction solution was cooled to room temperature, 200 ml of toluene was added, filtered, and the filtrate was rotary evaporated under reduced pressure. Column chromatography was performed with petroleum ether / ethyl acetate as eluent to obtain compound 2-28 (yield: 75%) as a light yellow solid.

[0249] Mass: C45H26N4O, calculated: 638.21, found: 638.20. 1H-NMR (400 MHz, CDC13) (ppm) δ = 7.06 ~ 7.19 (5H, m), 7.47 ~ 7.68 (14H, m) 7.76 ~ 7.84 (2H, m), 7.92 ~ 8.03 (2H, m), 8.53 ~ 8.57 (2H, m), 8.60 ~ 8.64 (1H, m).

[0250] Example 17: Synthesis of compound 2-31:

[0251]

[0252] Synthesis of intermediate 2-31-1: The synthesis method was the same as that of intermediate 1-1-1, and intermediate 2-31-1 was obtained (yield: 89%).

[0253] Synthesis of compound 2-31: The synthesis method was the same as that of compound 1-1, and compound 2-31 was obtained (yield: 84%).

[0254] Mass: C39H23N3O, calculated: 549.18, found: 549.21. 1H-NMR (400MHz, CDC13) (ppm) δ = 7.07-7.24 (4H, m), 7.35-7.44 (1H, m) 7.50-7.72 (6H, m), 7.76-7.85 (3H, m), 7.88-8.04 (6H, m), 8.16-8.23 (1H, m), 8.52-8.57 (1H, m), 8.59-8.64 (1H, m).

[0255] Device Example 1

[0256] The glass plate coated with ITO transparent conductive layer was treated with ultrasonic in commercial cleaning agent, rinsed in deionized water, treated with ultrasonic in acetone: ethanol mixed solvent (volume ratio 1:1) to remove oil, baked in clean environment until water was completely removed, cleaned with ultraviolet light and ozone, and the surface was bombarded with low-energy cation beam;

[0257] The glass substrate with anode above was placed in a vacuum chamber, vacuumed to 1 x 10 -5 Pa, HAT-CN was vacuumed evaporated on the anode layer as a hole injection layer, the evaporation rate was 0.1 nm / s, and the total film thickness was 1 nm; then NPB was evaporated as a hole transport layer, the evaporation rate was 0.1 nm / s, and the thickness was 60 nm;

[0258] TCTA was vacuumed evaporated on the hole transport layer as an electron blocking layer of the device, the evaporation rate was 0.1 nm / s, and the total film thickness was 10 nm;

[0259] The light-emitting layer of the device was vacuumed evaporated on the electron blocking layer, the light-emitting layer included host material and guest material, the evaporation rate of the host material DIC-TRZ was 0.1 nm / s, the evaporation rate of the guest material Ir(ppy)3 was set at 10% proportion, and the total film thickness was 30 nm;

[0260] The electron transport layer of the device was vacuumed evaporated on the light-emitting layer, the evaporation rate of compound 1-1 was 0.1 nm / s, and the total film thickness was 30 nm;

[0261] LiF with a thickness of 0.5 nm was vacuumed evaporated on the electron transport layer (ETL) as an electron injection layer, and Al layer with a thickness of 150 nm was vacuumed evaporated as the cathode of the device.

[0262] The molecular structure is as follows:

[0263]

[0264] Device Examples 2-14

[0265] An organic electroluminescent device of Device Example 2 to 14 was produced in a similar manner to Device Example 1, except that the compound 1-1 in Device Example 1 was replaced with the compound shown in Table 5.

[0266] Device Comparative Examples 1 to 3

[0267] An organic electroluminescent device of Device Comparative Examples 1 to 3 was produced in a similar manner to Device Example 1, except that the compound 1-1 in Device Example 1 was replaced with the following compounds Ref-1, Ref-2 and Ref-3, respectively.

[0268]

[0269] Test Example 1

[0270] At a luminance of 10,000 cd / m 2 The driving voltage and current efficiency of the organic electroluminescent device obtained in Device Example 2 to 14 were measured, and the results are shown in Table 5.

[0271] Table 5

[0272]

[0273]

[0274] The above results show that the organic compound of the present application has a lower driving voltage and higher device luminous efficiency when used as an electron transport material in an organic electroluminescent device, compared to the comparative examples.

[0275] Device Example 15

[0276] A glass plate coated with an ITO transparent conductive layer was treated with ultrasonic waves in a commercial cleaning agent, rinsed in deionized water, treated with ultrasonic waves in an acetone: ethanol mixed solvent (volume ratio 1:1) to remove oil, baked in a clean environment until water was completely removed, washed with ultraviolet light and ozone, and the surface was bombarded with a low-energy cation beam;

[0277] The above glass substrate with an anode was placed in a vacuum chamber, vacuumed to 1 x 10 -5 Pa, HAT-CN was vacuum deposited as a hole injection layer on the anode layer film at a deposition rate of 0.1 nm / s, and the total film thickness was 1 nm; then the hole transport layer NPB was deposited at a deposition rate of 0.1 nm / s, and the thickness was 60 nm;

[0278] The electron blocking layer compound 2-3 of the device was vacuum deposited on the hole transport layer at a deposition rate of 0.1 nm / s, and the total film thickness was 10 nm;

[0279] A light-emitting layer of the device is vacuum deposited on the electron blocking layer, and the light-emitting layer comprises a host material and a guest material. The host material DIC-TRZ is deposited at a rate of 0.1 nm / s, and the guest material Ir(ppy)3 is deposited at a rate of 10% of the host material, and the total film thickness is 30 nm.

[0280] An electron transport layer of the device is vacuum deposited on the light-emitting layer, and the ET-1 is deposited at a rate of 0.1 nm / s, and the total film thickness is 30 nm.

[0281] A LiF layer with a thickness of 0.5 nm is vacuum deposited on the electron transport layer (ETL) as an electron injection layer, and an Al layer with a thickness of 150 nm is used as the cathode of the device.

[0282]

[0283] Device Examples 16-19

[0284] The organic electroluminescent devices of Device Examples 16-19 are prepared by a method similar to that of Device Example 15, except that the compound 2-3 in Device Example 15 is replaced by the compounds shown in Table 6.

[0285] Device Example 20

[0286] The organic electroluminescent device of Device Example 20 is prepared by a method similar to that of Device Example 15, except that the compound 2-3 and ET-1 in Device Example 15 are replaced by compound 2-28 and compound 1-64, respectively.

[0287] Device Comparative Examples 4-5

[0288] The organic electroluminescent devices of Device Comparative Examples 4-5 are prepared by a method similar to that of Device Example 15, except that the compound 2-3 in Device Example 15 is replaced by the following compounds Ref-4 and Ref-5, respectively.

[0289]

[0290] Test Example 2

[0291] The driving voltage and current efficiency of the organic electroluminescent devices shown in Table 6 are measured at a luminance of 10000 cd / m2, and the results are shown in Table 6. 2

[0292] Table 6

[0293] Device Example No. Electron blocking material Electron transport material Driving voltage (V) Current efficiency (cd / A) Example 15 Compound 2-3 ET-1 4.35 68.0 Example 16 Compound 2-9 ET-1 4.42 67.2 Example 17 Compound 2-17 ET-1 4.44 67.6 Example 18 Compound 2-28 ET-1 4.37 68.4 Example 19 Compound 2-31 ET-1 4.38 66.7 Example 20 Compound 2-28 Compound 1-64 4.35 70.3 Comparative Example 4 Compound Ref-4 ET-1 4.57 62.3 Comparative Example 5 Compound Ref-5 ET-1 4.55 61.5

[0294] ​The above results show that, compared with the comparative examples, the organic compound of the present application has lower driving voltage and higher device luminous efficiency when used as an electron blocking material in an organic electroluminescent device.

[0295] The above describes the preferred embodiments of the present application in detail, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application and belong to the protection scope of the present application.

Claims

1. An organic compound, characterized in that, The compound is any one of the following compounds: 。 2. An organic compound, characterized in that, The compound is any one of the following compounds: 。 3. The use of the organic compound according to claim 1 or 2 in organic electroluminescent devices.

4. An organic electroluminescent device containing one or more organic compounds as described in claim 1, characterized in that, The organic compound is present in the electron transport layer of the organic electroluminescent device.

5. An organic electroluminescent device containing one or more organic compounds as described in claim 2, characterized in that, The organic compound is present in the electron blocking layer of the organic electroluminescent device.

6. The organic electroluminescent device according to claim 4 or 5, wherein, The organic electroluminescent device includes an anode, a hole injection layer, a hole transport layer, an optional electron blocking layer, a light-emitting layer, an optional hole blocking layer, an electron transport layer, an electron injection layer, a cathode, and a capping layer, which are stacked sequentially.

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