An organic compound, application thereof, and an organic electroluminescence device

Abstract

The application relates to the field of organic electroluminescence devices, discloses an organic compound and application and an organic electroluminescence device, the compound has a structure shown in formula (1). The organic compound has a lower driving voltage and higher device light-emitting efficiency when the organic compound is used as a red light host material in the organic electroluminescence device.

Description

Technical Field

[0001] The present invention relates to the field of organic electroluminescent devices, in particular to an organic compound, application of the compound in an organic electroluminescent device and an organic electroluminescent device containing the compound. Technical Background

[0002] The luminescent materials used in organic electroluminescent devices (OLEDs) are generally organometallic complexes that exhibit phosphorescence. The radiative transition of triplet excitons in most organic molecules is forbidden, which is not conducive to the luminescence of the device. However, the spin-orbit coupling effect of noble metal atoms allows the radiative transition from the originally spin-forbidden excited triplet state to the ground state to be locally allowed, effectively utilizing singlet and triplet excitons. Theoretically, the internal quantum efficiency can reach 100%, and the intersystem crossing probability from the singlet excited state to the triplet excited state is increased, resulting in efficient phosphorescence, which can achieve up to four times the energy efficiency and power efficiency. The characteristics of phosphorescent OLEDs are not only determined by the triplet emitter used. Other materials used, such as the host material, are also particularly important. Therefore, improvements to the host material can also lead to significant improvements in OLED characteristics.

[0003] According to existing technologies, many different material classes can be used as hosts for phosphorescent emitters, including carbazole derivatives, dibenzofuran derivatives, and triazine derivatives. However, phosphorescent host materials still need improvement, particularly in terms of device efficiency and operating voltage. Therefore, the development of high-performance red-emitting hosts is of paramount importance. Summary of the Invention

[0004] The purpose of the present invention is to overcome the problems of high driving voltage and low luminous efficiency of organic electroluminescent devices.

[0005] To achieve the above problem, the first aspect of the present invention provides an organic compound having a structure shown in formula (1),

[0006] The compound has the structure shown in formula (1):

[0007]

[0008] In formula (1),

[0009] Ring Z is of formula (2) and is bonded to formula (1) via a dotted line;

[0010] X is O, S, N(R9) or C(R 10 )2;

[0011] L is present or absent, and when present, it is C with or without heteroatoms. 6-30 Aromatic groups;

[0012] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 each independently selected from H, D, C 1-10 alkyl, C 1-10 alkoxy, C 6-30 aromatic group with or without heteroatom(s); or 6-30 aromatic group with or without heteroatom(s).

[0013] Ar is a substituted or unsubstituted group provided by the structure of formula (A);

[0014]

[0015] X1, X2, X3, X4, X5, X6are each independently selected from C and N;

[0016] R 11 , R 12 , R 13 , and R 14 are each independently selected from nothing or each independently selected from C 6-30 aromatic group with or without heteroatom(s); or

[0017] R 11 , R 12 , and R 13 any two of which are adjacent are cyclized to form a benzene ring or cyclized to form a C 6-30 aromatic group with or without heteroatom(s); the remaining one is nothing or a C 6-30 aromatic group with or without heteroatom(s); and R 14 is nothing or a C 6-30 aromatic group with or without heteroatom(s);

[0018] any bondable position of the structure of formula (A) is connected to the parent structure, or any bondable position of the structure of formula (A) is connected to the parent structure through L;

[0019] The second aspect of the present application provides the use of the organic compound of the first aspect in an organic electroluminescence device.

[0020] The third aspect of the present application provides an organic electroluminescence device containing one or more than two of the organic compounds of the first aspect, which exist in at least one of the electron transport layer, the light-emitting layer, and the hole blocking layer of the organic electroluminescence device.

[0021] Preferably, the organic compound is present in the light-emitting layer of the organic electroluminescence device.

[0022] The organic compound of the present application has a lower driving voltage and higher device light-emitting efficiency when used as a red light host material in an organic electroluminescence device.

[0023] The present application has at least the following specific advantages:

[0024] 1. The compound of the present application can balance the electrons and holes in the device, thereby obtaining a wider carrier recombination region, and thus improving the light-emitting efficiency and brightness;

[0025] 2. The fused ring compound provided by the present application can well adjust the HOMO and LUMO energy level range, so that the energy level matching degree with the adjacent material layer is high, the hole and electron injection barrier can be reduced, thereby reducing the driving voltage and improving the light-emitting efficiency.

[0026] 3. The compound provided by the present application has a high triplet energy level, which can limit the reverse flow of triplet energy from the phosphorescent guest to the host, and can limit the triplet exciton in the light-emitting layer, thereby improving the light-emitting efficiency and brightness. DETAILED DESCRIPTION

[0027] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The ranges or values should be construed to be approximations that allow for significant figures to account for slightly different measurements over time. For numeric values, the endpoints between the various ranges, the endpoints between the various ranges and the individual point values, and the individual point values can be combined with one another to form one or more new numeric ranges, which should be considered as being specifically disclosed herein.

[0028] As described previously, the present application provides an organic compound in one aspect, which has a structure represented by formula (1):

[0029]

[0030] In formula (1),

[0031] Ring Z is formula (2) and is bonded to formula (1) by a dashed line;

[0032] X is O, S, N(R9) or C(R 10 )2;

[0033] L is present or absent, and when present, is a C 6-30 aromatic group with or without heteroatoms;

[0034] R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 are each independently selected from H, D, C1-10 Alkyl, C 1-10 Alkoxy, C with or without heteroatoms 6-30 Any of the aromatic groups; or cyclized to form a C containing or not containing heteroatoms 6-30 aromatic groups.

[0035] Ar is a substituted or unsubstituted group provided by the structure represented by formula (A);

[0036]

[0037] X1, X2, X3, X4, X5, and X6 are each independently selected from C and N;

[0038] R 11 、R 12 、R 13 and R 14 are each independently selected from C 6-30 an aromatic group; or

[0039] R 11 、R 12 and R 13 Any two adjacent rings in the ring form a benzene ring or a C ring containing or not containing heteroatoms. 6-30 The remaining one is absent or is a C containing or not containing heteroatoms 6-30 an aromatic group; and R 14 There is no C or it contains or does not contain heteroatoms 6-30 Aromatic groups;

[0040] Any bonding position in the structure represented by formula (A) is connected to the parent core structure, or any bonding position in the structure represented by formula (A) is connected to the parent core structure through L;

[0041] According to a preferred embodiment, the compound represented by formula (1) is represented by any one of the following formulas (3) and (4);

[0042]

[0043] In formula (3) and formula (4),

[0044] X, L, Ar and R1 to R8 are the same as defined above.

[0045] According to a preferred embodiment, Ar is selected from the group consisting of nothing or any one of a substituent of formula (Q1), a substituent of formula (Q2), a substituent of formula (Q3), a substituent of formula (Q4), a substituent of formula (Q5), a substituent of formula (Q6), a substituent of formula (Q7), a substituent of formula (Q8),

[0046]

[0047] In formula (Q1), formula (Q2), formula (Q3), formula (Q4), formula (Q5), formula (Q6), formula (Q7), formula (Q8),

[0048] at least one of Y1, Y2 and Y3 is N, and optionally the remaining one is C;

[0049] R 21 and R 22 are each independently selected from a C 6-20 aromatic group with or without heteroatoms;

[0050] Preferably, R 21 and R 22 are each independently selected from a phenyl group, a biphenyl group, a naphthyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a 9,9-dimethylfluorenyl group, a pyridyl group, a pyrimidyl group, a phenyl-substituted naphthyl group, a naphthyl-substituted phenyl group;

[0051] R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 and R 30 are each independently selected from a C 6-20 aromatic group with or without heteroatoms;

[0052] Preferably, R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 and R 30 are each independently selected from H, a phenyl group, a naphthyl group, a C 1-6 alkyl group, a 9,9-dimethylfluorenyl group, a dibenzothiophenyl group, a dibenzofuranyl group, a phenyl-substituted naphthyl group, a naphthyl-substituted phenyl group, a benzothianaphthyl group.

[0053] According to a preferred embodiment, the optional L is selected from a C6-20 an aromatic group of formula

[0054] Preferably, L, if present, is a linking group selected from the group consisting of structures of benzene, naphthalene, anthracene, phenanthrene, biphenyl, dibenzothiophene, dibenzofuran, 9,9-dimethylfluorene, quinoline, isoquinoline, phenyl-substituted naphthyl;

[0055] According to one preferred embodiment, R1, R2, R3, R4, R5, R6, R7, R8, R9and R 10 are each independently selected from the group consisting of H, D, C 1-6 alkyl, C 1-6 alkoxy, C 6-20 aromatic group with or without heteroatoms;

[0056] Preferably, R1, R2, R3, R4, R5, R6, R7, R8are each independently selected from the group consisting of H;

[0057] R9and R 10 are each independently selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, methoxy, ethoxy, n-propoxy, i-propoxy, phenyl, naphthyl, anthryl, phenanthryl, biphenyl.

[0058] The present application does not particularly limit the specific method for preparing the aforementioned compounds, and a person 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 a person 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 a person skilled in the art should not understand it as a limitation of the present application.

[0059] 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.

[0060] According to one preferred embodiment, the present application provides an organic electroluminescent device, comprising: a first electrode; a second electrode disposed opposite to the first electrode; and one or more organic material layers disposed between the first electrode and the second electrode, wherein the one or more organic material layers comprise at least one of the aforementioned compounds of the present application.

[0061] One of the first electrode and the second electrode of the present application is an anode, and the other is a cathode.

[0062] According to a preferred embodiment of the present application, the organic electroluminescent device of the present application comprises a hole injection layer, a hole transport layer, a light-emitting layer, an electron blocking layer, an electron injection layer, etc. as the organic material layer.

[0063] As described above, the third aspect of the present application provides an organic electroluminescent device containing one or more than two kinds of the organic compound of the first aspect, the organic compound being present in at least one of the electron transport layer, the light-emitting layer and the hole blocking layer of the organic electroluminescent device;

[0064] Preferably, the organic compound is present in the light-emitting layer of the organic electroluminescent device.

[0065] Preferably, the organic compound is present in the light-emitting layer of the organic electroluminescent device as a red light-emitting host material.

[0066] The inventors of the present application have found that the compound of the present application, when used as a red light-emitting host material in the light-emitting layer of an organic electroluminescent device, can significantly reduce the driving voltage of the organic electroluminescent device and improve the light-emitting efficiency.

[0067] Preferably, the organic electroluminescent device comprises 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, which are sequentially stacked.

[0068] The organic electroluminescent device of the present application is preferably coated with one layer or multiple layers by means of a sublimation method. In this case, the compound provided by the present application is applied by vapor deposition at an initial pressure of less than 10 -3 Pa, preferably less than 10 -6 Pa.

[0069] The organic electroluminescent device of the present application is also preferably coated with one layer or multiple layers by means of an organic vapor phase deposition method or by means of carrier gas sublimation. In this case, the compound is applied at a pressure of 10 -6 Pa to 100 Pa. A particular example of this method is the organic vapor jet printing method, in which the compound provided by the present application is applied directly through a nozzle and forms the device structure.

[0070] The organic electroluminescent device of the present application preferably forms a layer or a multi-layer structure by spin coating or by means of any printing method, such as screen printing, flexographic printing, inkjet printing, offset printing, more preferably photoinitiated thermal imaging or inkjet printing, by formulating the compound of the present application into a solution. In general, when a plurality of layers are formed by this method, layer-to-layer damage occurs, i.e. when a layer is formed and another layer is formed using a solution, the solvent in the solution damages the already formed layer, which is not conducive to the formation of an organic electroluminescent device. However, the compound of the present application can be cross-linked upon heating or UV exposure, thereby maintaining the integrity of the layer without being damaged. The compound of the present application can be additionally applied from a solution and fixed in the corresponding layer by subsequent cross-linking or immobilization in the polymer network.

[0071] The organic electroluminescent device of the present application can be manufactured as a hybrid system by solution application of one or more layers and by vapor deposition of one or more other layers.

[0072] According to some embodiments of the present application, the anode material forming the anode, in general, 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, a metal, such as vanadium, chromium, copper, and gold, or other alloys, a metal oxide, such as zinc oxide, indium oxide, indium tin oxide, indium zinc oxide, and tin dioxide, a combination of a metal and an oxide, such as zinc oxide: aluminum, but is not limited thereto.

[0073] 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 forming 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.

[0074] According to some embodiments of the present application, the material forming the hole transport layer is a material capable of receiving holes from the anode or hole injection layer, moving the holes to the light emitting layer, and having a high mobility with respect to holes.

[0075] According to some embodiments of the present application, the hole injection material and 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 is not limited thereto.

[0076] 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:

[0077]

[0078] 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.

[0079] 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.

[0080] 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.

[0081] 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 emission.

[0082] According to some embodiments of the present application, the material forming the electron blocking layer includes, but is not limited to, an aromatic amine derivative (e.g., NPB), a spirobifluorene amine (e.g., SpMA2), wherein some electron blocking materials and hole injection materials and hole transport materials have similar structures.

[0083] According to some embodiments of the present application, 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 electrons, and is preferably a material having good quantum efficiency for fluorescence or phosphorescence.

[0084] According to some embodiments of the present application, the light-emitting layer can include a host material and a guest material.

[0085] According to some embodiments of the present application, the host material is selected from the compounds described in the present application.

[0086] 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, but is not limited to, derivatives of perylene, derivatives of anthracene, derivatives of fluorene, derivatives of stilbenyl aromatic, derivatives of arylamine, derivatives of organosilicon, derivatives of organoboron, derivatives of carbazole-triazine, derivatives of acridine, derivatives containing ketone, derivatives of sulfone group, derivatives of cyano, and derivatives of xanthene.

[0088] In some preferred embodiments of the present application, the derivatives of sulfone group have the general formula as shown below:

[0089]

[0090] The derivatives containing ketone have the general formula as shown below:

[0091]

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

[0093] According to some embodiments of the present application, the material of the hole-blocking layer can also preferably be a compound having the following 1st and / or 2nd conditions:

[0094] 1st: having a deeper HOMO energy level (a larger absolute value), which aims to reduce the number of holes leaving the light-emitting layer, thereby increasing the recombination probability of electrons and holes in the light-emitting layer.

[0095] 2nd: having a larger triplet energy, which aims to reduce the number of excitons leaving the light-emitting layer, thereby increasing the efficiency of exciton conversion luminescence.

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

[0097] The electron transport layer is a layer that receives electrons from the electron injection layer and transports the electrons to the light emitting layer, and as an electron transport material, a material capable of receiving electrons from the cathode, moving the electrons to the light emitting layer, and having a high mobility for the electrons is suitable. The electron transport material includes, for example, an Al complex of 8-hydroxyquinoline; a complex including Alq3; an organic radical compound; a hydroxyflavone-metal complex; and the like, but is not limited thereto.

[0098] 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 ability to transport electrons, having an effect of injecting electrons from the cathode, having an excellent effect of injecting electrons to the light emitting layer or light emitting material, preventing excitons generated in the light emitting layer from moving to the hole injection layer, and further having an excellent film formation ability. The electron injection layer material includes, for example, LiF, CsF, Cs2CO3, LiQ, but is not limited thereto.

[0099] According to some embodiments of the present application, the cathode material is generally preferably a material having a small work function, which can smoothly inject 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.

[0100] The present application will be described in detail below by way of examples. In the following examples, each of the various raw materials used is a general commercially available product unless otherwise specified.

[0101] The present application will be described in detail below by way of examples. In the following examples, each of the various raw materials used is a general commercially available product unless otherwise specified. Unless otherwise specified, the room temperature described below means 25±1°C.

[0102] Synthesis of Intermediate A:

[0103]

[0104] Synthesis of Intermediate A-1: Under nitrogen protection, 0.05 mol of the reactant imidazo[1,2-a]pyridin-3-ol, 0.052 mol of the reactant 2-fluoroaniline, 0.11 mol of sodium tert-butoxide, 0.5 mmol of Pd2(dba)3, and 0.5 mmol of tri-tert-butylphosphine were added to 150 mL of toluene, the mixture was stirred, heated to 110°C, and refluxed for 12 hours. The reaction was complete; it was naturally cooled to room temperature, filtered, the filtrate was rotary evaporated under reduced pressure until no fraction was obtained, and it was passed through a neutral silica gel column to obtain Intermediate A-1 (yield: 79%).

[0105] Synthesis of intermediate A: 0.03 mol of intermediate A-1, 0.3 mmol of Pd2(dba)3, 0.6 mmol of 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl and 0.07 mol of cesium carbonate were dissolved in 280 ml of anhydrous xylene under argon protection to form a suspension, which was refluxed for 10 hours. The reaction mixture was refined by column chromatography to obtain intermediate A (yield: 60%).

[0106] Mass spectrum: C13H9N3O, Theoretical value: 223.07, Found: 223.10. Elemental analysis: Theoretical value: C: 69.95%, H: 4.06%, N: 18.82%, Found: C: 69.96%, H: 4.05%, N: 18.81%.

[0107] Synthesis of intermediate B:

[0108]

[0109] Synthesis of intermediate B-1: 0.02 mol of 2-bromo-3-chloro-1H-imidazo[1,2-A]pyridine, 0.022 mol of 2-aminobenzenethiol, 0.05 mol of sodium tert-butoxide, 0.2 mmol of Pd2(dba)3 and 0.2 mmol of tri-tert-butylphosphine were added to 150 ml of toluene under nitrogen protection, and the mixture was stirred and heated to 110°C, and refluxed for 12 hours until the reaction was complete. It was naturally cooled to room temperature, filtered, and the filtrate was rotary evaporated under reduced pressure until no fraction was obtained. It was passed through a neutral silica gel column to obtain intermediate B-1 (yield: 83%).

[0110] Synthesis of intermediate B: 0.05 mol of intermediate B-1 was dissolved in 100 ml of toluene solvent, and 0.05 mol of iodobenzene, 0.06 mol of sodium tert-butoxide, 0.5 mmol of tri-tert-butylphosphine, and 0.5 mmol of tris(dibenzylideneacetone)dipalladium were sequentially added under nitrogen protection, and the mixture was stirred and heated to reflux. After 2 hours, the reaction was detected to be complete, the reaction liquid was rotary evaporated under reduced pressure, and column chromatography was performed to obtain intermediate B (yield: 74%).

[0111] Mass spectrum: C13H9N3S, Theoretical value: 239.05, Found: 239.06. Elemental analysis: Theoretical value: C: 65.25%, H: 3.79%, N: 17.56%, Found: C: 65.24%, H: 3.78%, N: 17.55%.

[0112] Synthesis of intermediate D:

[0113]

[0114] Synthesis of intermediate D-1 : The same as the synthesis of intermediate B-1, the reactants 2-bromo-3-chloro-1 H-imidazo[1,2-A]pyridine and 2- aminobenzenethiol were replaced by 2-bromoimidazo[1,2-A]pyridine and 2-(2- aminophenyl)propan-2-ol to obtain intermediate D-1 (yield: 79%).

[0115] Synthesis of intermediate D: Under nitrogen protection, 0.01 mol of intermediate D-1 was weighed, dissolved with a mixture of concentrated H3PO4 and water with a volume ratio of 1 :(2.0) containing 0.05 mol of phosphoric acid as the solvent, and reacted at room temperature for 6 hours until the reaction was complete; neutralized to pH = 7 with an aqueous NaOH solution, extracted with dichloromethane, separated into layers, filtered the organic phase, and the filtrate was rotary evaporated under reduced pressure until no fraction was obtained, and then passed through a neutral silica gel column to obtain intermediate D (yield: 73%).

[0116] Mass spectrum: C16H15N3, Theoretical value: 249.13, Found: 249.15. Elemental analysis: Theoretical value: C: 77.08%, H: 6.06%, N: 16.85%, Found: C: 77.10%, H: 6.05%, N: 16.84%.

[0117] Synthesis of intermediate E:

[0118]

[0119] Synthesis of intermediate E-1 : The same as the synthesis of intermediate B-1, the reactants 2-bromo-3-chloro-1 H-imidazo[1,2-A]pyridine and 2- aminobenzenethiol were replaced by 2-bromoimidazo[1,2-A]pyridine-3-amine and 1 -iodo-2-nitrobenzene to obtain intermediate E-1 (yield: 80%).

[0120] Synthesis of intermediate E: A 500 mL two-necked round-bottom flask was taken and fitted with a stirrer and an upper reflux tube, dried, and then filled with nitrogen, 0.01 mmol of intermediate E-1, 0.01 mmol of triphenylphosphine, and 100 mL of 1,2-dichlorobenzene were added, and then heated at 180°C for 12 hours. After the reaction was completed, the reaction system was cooled to room temperature, concentrated, and the crude product was purified by chromatography (ethyl acetate / hexane, 1 / 10) to obtain intermediate E (yield: 50%).

[0121] Mass spectrum: C13H10N4, Theoretical value: 222.09, Found: 222.10. Elemental analysis: Theoretical value: C: 70.26%, H: 4.54%, N: 25.21%, Found: C: 70.25%, H: 4.55% N: 25.20%.

[0122] Synthesis of intermediate F:

[0123]

[0124] Synthesis of intermediate F-1 : same as the synthesis of intermediate A-1, changing the reactants to 2-fluoro-3-nitroimidazo[1,2-a]pyridine and phenol, reaction gave intermediate F-1 (yield: 69%)

[0125] Synthesis of intermediate F: same as the synthesis of intermediate E, changing the reactant to intermediate F-1, reaction gave intermediate F (yield: 67%).

[0126] Mass: C13H9N3O, Theoretical value: 223.07, Found: 223.08. Elemental analysis: Theoretical value: C: 69.95%, H: 4.06%, N: 18.82%, Found: C: 69.94%, H: 4.07%, N: 18.83%.

[0127] Synthesis of intermediate G:

[0128]

[0129] Synthesis of intermediate G-1 : same as the synthesis of intermediate B, changing the reactants to 2-bromoimidazo[1,2-a]pyridine and 2-aminothiophenol, reaction gave intermediate G-1 (yield: 67%).

[0130] Synthesis of intermediate G: same as the synthesis of intermediate A, changing the reactant to intermediate G-1, reaction gave intermediate G (yield: 66%).

[0131] Mass: C13H9N3S, Theoretical value: 239.05, Found: 239.06. Elemental analysis: Theoretical value: C: 65.25%, H: 3.79%, N: 17.56%, Found: C: 65.23%, H: 3.77%, N: 17.55%.

[0132] Synthesis of intermediate H:

[0133]

[0134] Synthesis of intermediate H-1 : same as the synthesis of intermediate B-1, changing the reactants 2-bromo-3-chloro-1 H-imidazo[1,2-A]pyridine and 2- aminothiophenol to 3-chloroimidazo[1,2-a]pyridine and 2-(2- aminophenyl)propan-2-ol, reaction gave intermediate H-1 (yield: 62%).

[0135] Synthesis of intermediate H: same as the synthesis of intermediate D, changing the reactant to intermediate H-1, reaction gave intermediate H (yield: 67%).

[0136] Mass: C16H15N3, Theoretical value: 249.13, Found: 249.14. Elemental analysis: Theoretical value: C: 77.08%, H: 6.06%, N: 16.85%, Found: C: 77.09%, H: 6.07%, N: 16.83%.

[0137] Preparation Example 1: Synthesis of compound 1-3

[0138]

[0139] Synthesis of compound 1-3: Into a 250 ml two-necked flask, 0.05 mol of reactant A, 5 mmol of 4,6-bis(diphenyl-4-yl)-2-chloropyrimidine, 0.025 mmol of palladium acetate, 0.028 mmol of tri-tert-butylphosphine, 7.5 mmol of sodium tert-butoxide, 15 ml of toluene were added, respectively, under nitrogen protection, and the mixture was reacted at 80°C for 2 hours. Water was added to the reaction system, which was extracted with dichloromethane. The obtained extract was dried with magnesium sulfate, filtered, and rotary evaporated. The crude product was purified by chromatography (ethyl acetate / n-hexane, 1 / 10) to obtain compound 1-3 (yield: 81%).

[0140] Mass: C41H27N5O2, Theoretical value: 605.22, Found: 605.23.1H-NMR (400MHz, CDCl3) (ppm) δ = 6.70-6.78 (1H, m), 6.81-6.90 (3H, m), 6.97-7.05 (1H, m), 7.17-7.25 (1H, m), 7.37-7.54 (7H, m), 7.72-7.78 (4H, m), 7.82-7.89 (5H, m), 8.26-8.33 (4H, m), 8.45-8.51 (1H, m).

[0141] Preparation Example 2: Synthesis of compound 1-14

[0142]

[0143] Synthesis of intermediate 1-14-1 : under nitrogen protection, 0.05 mol of 4-bromo-2-chloro-6-phenylpyrimidine, 0.05 mol of 9,9-dimethyl-9H-fluoren-2-ylboronic acid, 0.1 mol of potassium carbonate, 0.5 mmol of Pd(PPh3)Cl2 and 0.5 mmol of triphenylphosphine were added into a 200 mL three-necked flask, then 180 mL of a mixed solution of toluene, ethanol and water in a volume ratio of 1:1:1 was added, heated to reflux for 24 hours, the reaction was observed by TLC until the reaction was completed, naturally cooled to room temperature, filtered, and the filtrate was rotary evaporated to no fraction. The obtained material was purified by silica gel column (a mixed solvent of V dichloromethane: V petroleum ether = 1:5 as eluent) to obtain intermediate 1-14-1 (yield: 81%).

[0144] Synthesis of intermediate 1-14-2: under nitrogen protection, 0.01 mol of intermediate 1-14-1 was dissolved in 45 mL of tetrahydrofuran, cooled to -78°C, and a solution containing 0.02 mol of n-butyllithium in cyclohexane was slowly added dropwise. After the addition was completed, it was stirred for 30 minutes; a solution containing 0.035 mol of trimethyl borate in tetrahydrofuran was slowly added dropwise, and after the addition was completed, it was slowly warmed to room temperature and incubated for 10 hours; after the reaction was completed, it was cooled to 0°C, and distilled water was slowly added dropwise. After no gas was generated, it was stirred for 1 hour, and then warmed to room temperature; the reaction liquid was extracted with 150 mL of ethyl acetate, and the extract was washed with 150 mL of saturated brine three times, finally dried over anhydrous magnesium sulfate, and the solution was distilled under reduced pressure. The obtained solid was recrystallized with 400 mL of a mixed solution of V toluene: V ethanol = 3:1 to obtain intermediate 1-14-2 (yield: 73%).

[0145] Synthesis of intermediate 1-14-3: the same as the synthesis method of intermediate 1-14-1, the reactants 4-bromo-2-chloro-6-phenylpyrimidine and 9,9-dimethyl-9H-fluoren-2-ylboronic acid were replaced by intermediate 1-14-2 and 4,4'-dichlorobiphenyl, and the reaction obtained intermediate 1-14-3 (yield: 71%).

[0146] Synthesis of compound 1-14: the same as the synthesis method of compound 1-3, the reactant 4,6-bis(diphenyl-4-yl)-2-chloropyrimidine was replaced by 2-(diphenyl-3-yl)-4-(4-bromophenyl)-6-phenyl-1,3,5-triazine, and the reaction obtained compound 1-38 (yield: 78%).

[0147] Mass: C50H35N5O, Theoretical value: 721.28, Found: 721.30.1H-NMR (400 MHz, CDCI3) (ppm) δ = 1.67 ~ 1.71 (6H, s), 6.70 ~ 6.77 (1H, m), 6.81 ~ 6.90 (3H, m), 6.98 ~ 7.05 (1H, m), 7.18 ~ 7.28 (4H, m), 7.31 ~ 7.39 (3H, m), 7.45 ~ 7.62 (7H, m), 7.76 ~ 7.80 (1H, s), 7.88 ~ 7.98 (5H, m), 8.07 ~ 8.13 (2H, m), 8.22 ~ 8.24 (1H, s), 8.46 ~ 8.50 (1H, m).

[0148] Preparation Example 3: Synthesis of Compound 1-38

[0149]

[0150] Synthesis of Compound 1-38: The same as the synthesis method of Compound 1-3, the reactant 4,6-bis(diphenyl-4-yl)-2-chloropyrimidine was replaced by 2-(diphenyl-3-yl)-4-(4-bromophenyl)-6-phenyl-1,3,5-triazine, the reaction resulted in Compound 1-38 (yield: 78%).

[0151] Mass: C40H26N6O, Theoretical value: 606.22, Found: 606.21.1H-NMR (400 MHz, CDCI3) (ppm) δ = 6.70 ~ 6.77 (1H, m), 6.81 ~ 6.90 (3H, m), 6.97 ~ 7.05 (1H, m), 7.17 ~ 7.25 (1H, m), 7.34 ~ 7.56 (9H, m), 7.58 ~ 7.64 (1H, m), 7.66 ~ 7.78 (3H, m), 7.98 ~ 8.04 (2H, m), 8.31 ~ 8.41 (4H, m), 8.45 ~ 8.51 (1H, m).

[0152] Preparation Example 4: Synthesis of Compound 1-81

[0153]

[0154] Synthesis of Intermediate 1-81-1: The same as the synthesis method of Intermediate 1-14-1, the reactants 4-bromo-2-chloro-6-phenylpyrimidine and 9,9-dimethyl-9H-fluoren-2-ylboronic acid were replaced by diphenyl-2-ylboronic acid and 2-bromo-4-(4-chlorophenyl)quinazoline, the reaction resulted in Intermediate 1-81-1 (yield: 73%).

[0155] Synthesis of compound 1-81: The same reaction as the synthesis of compound 1-3, using 4,6-bis(diphenyl-4-yl)-2-chloropyrimidine instead of intermediate 1-18-1, gave compound 1-81 (yield: 77%).

[0156] Mass: C39H25N5O, 579.21 (theoretical), 579.20 (found).1H-NMR (400MHz, CDCI3) (ppm) δ = 6.70-6.78 (1H, m), 6.81-6.90 (3H, m), 6.97-7.05 (1H, m), 7.17-7.25 (1H, m), 7.33-7.64 (9H, m), 7.70-7.84 (5H, m), 7.92-8.02 (3H, m), 8.10-8.16 (1H, m), 8.45-8.51 (1H, m).

[0157] Preparation Example 5: Synthesis of compound 1-115

[0158]

[0159] Synthesis of intermediate 1-115-1: The same reaction as the synthesis of intermediate 1-14-1, using 4-bromo-2-chloro-6-phenylpyrimidine and 9,9-dimethyl-9H-fluoren-2-ylboronic acid instead of 3,4'-dichlorobiphenyl and 4,6-diphenylpyrimidin-2-ylboronic acid, gave intermediate 1-115-1 (yield: 75%).

[0160] Synthesis of compound 1-115: The same reaction as the synthesis of compound 1-3, using 4,6-bis(diphenyl-4-yl)-2-chloropyrimidine and intermediate A instead of intermediate 1-18-1 and intermediate B, gave compound 1-115 (yield: 74%).

[0161] Mass: C41H27N5S, 621.20 (theoretical), 621.19 (found).1H-NMR (400MHz, CDCI3) (ppm) δ = 6.82-6.97 (2H, m), 6.99-7.11 (2H, m), 7.17-7.25 (1H, m), 7.30-7.40 (3H, m), 7.44-7.64 (10H, m), 7.66-7.74 (1H, m), 7.90-7.98 (4H, m), 8.22-8.28 (2H, m), 8.35-8.41 (1H, m), 8.45-8.51 (1H, m).

[0162] Preparation Example 6: Synthesis of compound 1-184

[0163]

[0164] Synthesis of intermediate 1-184-1: The same synthesis method as intermediate 1-14-1 was used, except that the reactants 4-bromo-2-chloro-6-phenylpyrimidine and 9,9-dimethyl-9H-fluoren-2-ylboronic acid were replaced with 4-chloronaphthalene-1-ylboronic acid and 2-bromo-4-phenylquinazoline to obtain intermediate 1-184-1 (yield: 79%).

[0165] Synthesis of compound 1-184: The same synthesis method as compound 1-3 was used, except that the reactants 4,6-di(biphenyl-4-yl)-2-chloropyrimidine and intermediate A were replaced with intermediate 1-184-1 and intermediate B, and the reaction gave compound 1-184 (yield: 77%).

[0166] Mass spectrum: C37H23N5S, theoretical value: 569.17, found value: 569.18. 1H-NMR (400 MHz, CDCl3) (ppm) δ = 6.82~6.97 (2H, m), 6.99~7.11 (2H, m), 7.17~7.25 (1H, m), 7.30~7.35 (1H, m), 7.40~7.58 (5H, m), 7.61~7.69 (2H, m), 7.74~7.83 (5H, m), 7.98~8.03 (1H, m), 8.10~8.16 (1H, m), 8.19~8.25 (1H, m), 8.45~8.51 (1H, m), 8.94~9.00 (1H, m).

[0167] Preparation Example 7: Synthesis of Compound 1-223

[0168]

[0169] Synthesis of intermediate 1-223-1: The same method as the synthesis of intermediate 1-14-2 was used, except that the reactant intermediate 1-14-1 was replaced with 2-chloro-4-(naphthalen-1-yl)-6-phenyl-1,3,5-triazine, and the intermediate 1-223-1 was obtained by reaction (yield: 83%).

[0170] Synthesis of intermediate 1-223-2: The same synthesis method as intermediate 1-14-1 was used, except that the reactants 4-bromo-2-chloro-6-phenylpyrimidine and 9,9-dimethyl-9H-fluoren-2-ylboronic acid were replaced with intermediate 1-223-1 and 1,4-dichloronaphthalene to obtain intermediate 1-223-2 (yield: 71%).

[0171] Synthesis of compound 1-223: The same synthesis method as compound 1-3 was used, except that the reactants 4,6-di(biphenyl-4-yl)-2-chloropyrimidine and intermediate A were replaced with intermediate 1-223-2 and intermediate D, and the reaction gave compound 1-223 (yield: 75%).

[0172] Mass: C45H32N6, Theoretical value: 656.27, Found: 656.30.1H-NMR (400 MHz, CDCI3) (ppm) δ = 1.73 ~ 1.77 (6H, s), 6.83 ~ 6.87 (1H, m), 6.92 ~ 6.96 (1H, m), 7.15 ~ 7.23 (4H, m), 7.42 ~ 7.53 (8H, m), 7.76 ~ 7.79 (2H, m), 7.81 ~ 7.86 (2H, m), 7.93 ~ 7.95 (1H, m), 7.98 ~ 8.02 (1H, m), 8.21 ~ 8.23 (1H, m), 8.34 ~ 8.38 (2H, m), 8.46 ~ 8.48 (1H, m), 8.95 ~ 8.99 (2H, s).

[0173] Preparation Example 8: Synthesis of Compound 1-246

[0174]

[0175] Synthesis of intermediate 1-246-1: The same as the synthesis of intermediate 1-14-1, the reactants 4-bromo-2-chloro-6-phenylpyrimidine and 9,9-dimethyl-9H-fluoren-2-ylboronic acid were replaced by intermediate 1-223-1 and p-dichlorobenzene, and the reaction resulted in intermediate 1-246-1 (yield: 77%).

[0176] Synthesis of compound 1-246: The same as the synthesis of compound 1-3, the reactants 4,6-bis(diphenyl-4-yl)-2-chloropyrimidine and intermediate A were replaced by intermediate 1-246-1 and intermediate D, and the reaction resulted in compound 1-246 (yield: 73%).

[0177] Mass: C40H29N5, Theoretical value: 579.24, Found: 579.25.1H-NMR (400 MHz, CDCI3) (ppm) δ = 1.73 ~ 1.77 (6H, s), 6.81 ~ 6.89 (1H, m), 6.90 ~ 6.98 (1H, m), 7.15 ~ 7.25 (4H, m), 7.34 ~ 7.40 (2H, m), 7.43 ~ 7.58 (4H, m), 7.76 ~ 7.89 (4H, m), 7.91 ~ 7.96 (1H, m), 7.97 ~ 8.04 (3H, m), 8.11 ~ 8.15 (1H, m), 8.45 ~ 8.49 (1H, m), 8.93 ~ 9.01 (1H, m).

[0178] Preparation Example 9: Synthesis of compound 1-294

[0179]

[0180] Synthesis of intermediate 1-294-1: The same as the synthetic method of compound 1-3, the reactants 4,6-bis(diphenyl-4-yl)-2-chloropyrimidine and intermediate A were replaced with intermediate E-1 and 1-chlorobenzene, and the reaction yielded compound 1-294-1 (yield: 67%).

[0181] Synthesis of intermediate 1-294-2: Take 500 ml two-necked round-bottom flask, put in a stirring rod and connect a reflux tube, dry and fill with nitrogen, then add 0.01 mmol of intermediate 1-294-1, 0.01 mmol of triphenylphosphine, 100 ml of 1,2-dichlorobenzene, and then heat at 180°C for 12 hours. After the reaction is completed, cool to room temperature, concentrate the reaction system, and purify the crude product by chromatography (ethyl acetate / hexane, 1 / 10) to obtain intermediate 1-249-2 (yield: 54%).

[0182] Synthesis of intermediate 1-294-3: The same as the synthetic method of intermediate 1-14-1, the reactants 4-bromo-2-chloro-6-phenylpyrimidine and 9,9-dimethyl-9H-fluoren-2-ylboronic acid were replaced with 4-(naphthalen-1-yl)phenylboronic acid and 4-bromo-2-(4-chlorophenyl)quinazoline, and the reaction yielded intermediate 1-294-3 (yield: 77%).

[0183] Synthesis of compound 1-294: The same as the synthetic method of compound 1-3, the reactants 4,6-bis(diphenyl-4-yl)-2-chloropyrimidine and intermediate A were replaced with intermediate 1-294-3 and intermediate 1-294-2, and the reaction yielded compound 1-294 (yield: 61%).

[0184] Mass: C49H32N6, Theoretical value: 704.27, Found: 704.30.1H-NMR (400MHz, CDCl3) (ppm) δ = 6.82~6.90 (1H, m), 6.91~7.04 (3H, m), 7.05~7.19 (4H, m), 7.20~7.29 (5H, m), 7.30~7.44 (4H, m), 7.47~7.59 (2H, m), 7.73~7.84 (3H, m), 7.86~7.92 (1H, m), 7.97~8.06 (3H, m), 8.10~8.16 (1H, m), 8.26~8.33 (2H, m), 8.45~9.54 (2H, m), 8.91~8.98 (1H, m).

[0185] Preparation Example 10: Synthesis of compound 2-15

[0186]

[0187] Synthesis of intermediate 2-15-1: The same as the synthetic method of intermediate 1-14-2, using intermediate 1-14-1 with 2-chloro-4,6-di(naphthalen-1-yl)-1,3,5-triazine as the reactant, to give intermediate 2-15-1 (yield: 81%).

[0188] Synthesis of intermediate 2-15-2: The same as the synthetic method of intermediate 1-14-1, using 4-bromo-2-chloro-6-phenylpyrimidine and 9,9-dimethyl-9H-fluoren-2-ylboronic acid with intermediate 2-15-1 and 3,3'-dichlorobiphenyl as the reactants, to give intermediate 2-15-2 (yield: 73%).

[0189] Synthesis of compound 2-15: The same as the synthetic method of compound 1-3, using 4,6-di(biphenyl-4-yl)-2-chloropyrimidine and intermediate 2-15-2 with intermediate F as the reactants, to give compound 2-15 (yield: 64%).

[0190] Mass: C48H30N6O, Theoretical value: 706.25, Found: 706.26.1H-NMR (400MHz, CDCI3) (ppm) δ = 6.70-6.78 (1H, m), 6.81-6.90 (3H, m), 6.97-7.05 (1H, m), 7.14-7.29 (4H, m), 7.43-7.53 (5H, m), 7.54-7.64 (2H, m), 7.66-7.74 (1H, m), 7.78-7.89 (4H, m), 7.91-8.04 (4H, m), 8.35-8.41 (2H, m), 8.45-8.51 (1H, m), 8.93-9.01 (2H, m).

[0191] Preparation Example 11: Synthesis of compound 2-24

[0192]

[0193] Synthesis of intermediate 2-24-1: The same as the synthetic method of intermediate 1-14-1, using 4-bromo-2-chloro-6-phenylpyrimidine and 9,9-dimethyl-9H-fluoren-2-ylboronic acid with 2,3-dibromoquinoxaline and 9,9-dimethyl-9H-fluoren-4-ylboronic acid as the reactants, to give intermediate 2-24-1 (yield: 69%).

[0194] Synthesis of intermediate 2-24-2: The same as the synthetic method of intermediate 1-14-1, using 4-bromo-2-chloro-6-phenylpyrimidine and 9,9-dimethyl-9H-fluoren-2-ylboronic acid with intermediate 2-24-1 and 4-chloronaphthalen-1-ylboronic acid as the reactants, to give intermediate 2-24-2 (yield: 72%).

[0195] Synthesis of compound 2-24: the same as the synthesis of compound 1-3, using the reactant 4,6-bis(diphenyl-4-yl)-2-chloropyrimidine and intermediate A replaced by intermediate 2-24-2 and intermediate F, the reaction resulted in compound 2-24 (yield: 61%).

[0196] Mass: C46H31N5O, calc'd: 669.25, found: 669.21.1H-NMR (400MHz, CDCI3) (ppm) δ = 1.71 ~ 1.67 (6H, s), 6.72 ~ 6.76 (1H, m), 6.83 ~ 6.88 (3H, m), 6.99 ~ 7.03 (1H, m), 7.19 ~ 7.26 (2H, m), 7.32 ~ 7.36 (1H, m), 7.42 ~ 7.55 (5H, m), 7.65 ~ 7.69 (2H, m), 7.78 ~ 7.82 (3H, m), 7.89 ~ 7.96 (2H, m), 8.21 ~ 8.23 (1H, m), 8.32 ~ 8.36 (2H, d), 8.47 ~ 8.49 (1H, m), 8.96 ~ 8.98 (1H, m).

[0197] Preparation 12: Synthesis of compound 2-34

[0198]

[0199] Synthesis of intermediate 2-34-1: the same as the synthesis of intermediate 1-14-1, using the reactants 4-bromo-2-chloro-6-phenylpyrimidine and 9,9-dimethyl-9H-fluoren-2-ylboronic acid replaced by 2,3-dibromoquinoxaline and diphenyl-2-ylboronic acid, the reaction resulted in intermediate 2-34-1 (yield: 67%).

[0200] Synthesis of intermediate 2-34-2: the same as the synthesis of intermediate 1-14-1, using the reactants 4-bromo-2-chloro-6-phenylpyrimidine and 9,9-dimethyl-9H-fluoren-2-ylboronic acid replaced by intermediate 2-34-1 and 4-chloronaphthalen-1-ylboronic acid, the reaction resulted in intermediate 2-24-2 (yield: 75%).

[0201] Synthesis of compound 2-34: the same as the synthesis of compound 1-3, using the reactant 4,6-bis(diphenyl-4-yl)-2-chloropyrimidine and intermediate A replaced by intermediate 2-34-2 and intermediate F, the reaction resulted in compound 2-34 (yield: 66%).

[0202] Mass: C43H27N5O, Calculated: 629.22, Found: 629.21.1H-NMR (400 MHz, CDCI3) (ppm) δ = 6.70 ~ 6.78 (1H, m), 6.81 ~ 6.90 (3H, m), 6.97 ~ 7.05 (1H, m), 7.17 ~ 7.26 (1H, m), 7.36 ~ 7.55 (6H, m), 7.59 ~ 7.75 (4H, m), 7.75 ~ 7.85 (5H, m), 7.97 ~ 8.03 (1H, m), 8.19 ~ 8.25 (1H, m), 8.31 ~ 8.37 (1H, d), 8.45 ~ 8.55 (2H, m), 8.94 ~ 9.00 (1H, m).

[0203] Preparation Example 13: Synthesis of compound 2-53

[0204]

[0205] Synthesis of intermediate 2-53-1: The same as the synthesis method of intermediate 1-14-1, the reactants 4-bromo-2-chloro-6-phenylpyrimidine and 9,9-dimethyl-9H-fluoren-2-ylboronic acid were replaced by 4,6-dibromo-2-chloropyrimidine and two equivalents of naphthalen-1-ylboronic acid, and the reaction resulted in intermediate 2-53-1 (yield: 62%).

[0206] Synthesis of intermediate 2-53-2: The same as the synthesis method of intermediate 1-14-2, the reactant intermediate 1-14-1 was replaced by intermediate 2-53-1, and the reaction resulted in intermediate 2-53-2 (yield: 81%).

[0207] Synthesis of intermediate 2-53-3: The same as the synthesis method of intermediate 1-14-1, the reactants 4-bromo-2-chloro-6-phenylpyrimidine and 9,9-dimethyl-9H-fluoren-2-ylboronic acid were replaced by intermediate 2-53-2 and 4,4'-dichlorobiphenyl, and the reaction resulted in intermediate 2-53-3 (yield: 65%).

[0208] Synthesis of compound 2-53: The same as the synthesis method of compound 1-3, the reactants 4,6-bis(biphenyl-4-yl)-2-chloropyrimidine and intermediate A were replaced by intermediate 2-53-3 and intermediate G, and the reaction resulted in compound 2-53 (yield: 69%).

[0209] Mass: C49H31N5S, 721.23, 721.25. 1H-NMR (400MHz, CDC13) (ppm) δ = 6.82-6.97 (2H, m), 6.99-7.11 (2H, m), 7.17-7.28 (3H, m), 7.30-7.40 (3H, m), 7.43-7.58 (7H, m), 7.78-7.89 (4H, m), 7.91-8.05 (6H, m), 8.21-8.25 (1H, m), 8.45-8.51 (1H, m), 8.93-9.01 (2H, m).

[0210] Preparation Example 14: Synthesis of compound 2-62

[0211]

[0212] Synthesis of intermediate 2-62-1: The same as the synthesis of intermediate 1-14-2, the reactant intermediate 1-14-1 was replaced by 2,4-bis(diphenyl-4-yl)-6-chloro-1,3,5-triazine, the reaction resulted in intermediate 2-62-1 (yield: 61%).

[0213] Synthesis of intermediate 2-62-2: The same as the synthesis of intermediate 1-14-1, the reactants 4-bromo-2-chloro-6-phenylpyrimidine and 9,9-dimethyl-9H-fluoren-2-ylboronic acid were replaced by intermediate 2-62-1 and 1-bromo-4-chlorodibenzo[b,d]thiophene, the reaction resulted in intermediate 2-62-2 (yield: 71%).

[0214] Synthesis of compound 2-62: The same as the synthesis of compound 1-3, the reactants 4,6-bis(diphenyl-4-yl)-2-chloropyrimidine and intermediate A were replaced by intermediate 2-62-2 and intermediate G, the reaction resulted in compound 2-62 (yield: 64%).

[0215] Mass: C52H32N6S2, 804.21, 804.20. 1H-NMR (400MHz, CDC13) (ppm) δ = 6.82-6.97 (2H, m), 6.99-7.11 (2H, m), 7.17-7.35 (8H, m), 7.36-7.66 (9H, m), 7.71-7.78 (4H, m), 7.83-7.89 (1H, m), 7.93-7.99 (4H, m), 8.42-8.51 (2H, m).

[0216] Preparation Example 15: Synthesis of compound 2-81

[0217]

[0218] Synthesis of intermediate 2-81-1: The same synthesis method as intermediate 1-14-2 was used, except that the reactant intermediate 1-14-1 was replaced with 2-chloro-4-(9,9-dimethyl-9H-fluoren-2-yl)-6-phenyl-1,3,5-triazine to obtain intermediate 2-81-1 (yield: 57%).

[0219] Synthesis of intermediate 2-81-2: The same synthesis method as intermediate 1-14-1 was used, except that the reactants 4-bromo-2-chloro-6-phenylpyrimidine and 9,9-dimethyl-9H-fluoren-2-ylboronic acid were replaced with intermediate 2-81-1 and 1-bromo-4-chloronaphthalene to obtain intermediate 2-81-2 (yield: 68%).

[0220] Synthesis of compound 2-81: The same synthesis method as compound 1-3 was used, except that the reactants 4,6-di(biphenyl-4-yl)-2-chloropyrimidine and intermediate A were replaced with intermediate 2-81-2 and intermediate H, and the reaction gave compound 2-81 (yield: 61%).

[0221] Mass spectrum: C50H38N6, theoretical value: 722.32, found value: 722.30. 1H-NMR (400MHz, CDCl3) (ppm) δ = 1.67 ~ 1.70 (6H, a), 1.74 ~ 1.77 (6H, s), 6.82 ~ 6.97 (2H, m), 7.15 ~ 7.28 (5H, m), 7.31 ~ 7.41 (1H, m), 7 .43~7.54(6H,m), 7.58~7.62(1H,m), 7.74~7.81(3H,m), 7.88~7.92(1H,m), 8.07~8.1 1(1H,d), 8.20~8.27(2H,m), 8.32~8.40(2H,m), 8.46~8.50(1H,m), 8.95~8.99(1H,m).

[0222] Preparation Example 16: Synthesis of Compound 2-101

[0223]

[0224] Synthesis of intermediate 2-101-1: The same synthesis method as compound 1-3 was used, except that the reactants 4,6-di(biphenyl-4-yl)-2-chloropyrimidine and intermediate A were replaced with intermediate E-1 and 4-(4-chlorophenyl)-2-phenylquinazoline to obtain compound 2-101-1 (yield: 57%).

[0225] Synthesis of intermediate 2-101-2: the same as the synthesis of intermediate 1-294-2, using intermediate 2-101-1 instead of intermediate 1-294-1 as the reactant, to give intermediate 2-101-2 (yield: 59%).

[0226] Synthesis of compound 2-101: the same as the synthesis of compound 1-3, using intermediate 2-101-2 and 1-chloronaphthalene instead of 4,6-di(biphenyl-4-yl)-2-chloropyrimidine and intermediate A as the reactants, to give compound 2-101 (yield: 55%).

[0227] Mass (m / z): C43H28N6, calculated: 628.24, found: 628.25.1H-NMR (400MHz, CDCl3) (ppm) δ = 6.81-6.99 (3H, m), 7.10-7.25 (3H, m), 7.33-7.67 (12H, m), 7.70-7.87 (4H, m), 8.09-8.17 (2H, m), 8.19-8.25 (1H, m), 8.30-8.40 (2H, m), 8.45-8.51 (1H, m).

[0228] Device Example 1

[0229] The glass plate coated with ITO transparent conductive layer was subjected to ultrasonic treatment, washed in deionized water, ultrasonically degreased in a mixed solvent of acetone: ethanol (volume ratio 1:1), baked to completely remove moisture in a clean environment, cleaned with ultraviolet light and ozone, and the surface was bombarded with low-energy cation beams;

[0230] The glass substrate with anode mentioned above was placed in a vacuum chamber, vacuumed to 1x10 -4 Pa, HAT-CN was vacuum deposited on the anode layer film as a hole injection layer, the deposition rate was 0.1 nm / s, and the total film thickness was 5 nm; then NPB was deposited as a hole transport layer, the deposition rate was 0.1 nm / s, and the thickness was 60 nm; TCTA was vacuum deposited on the hole transport layer as an electron blocking layer, the deposition rate was 0.1 nm / s, and the thickness was 10 nm; the light-emitting layer of the device was vacuum deposited on the hole transport layer, the light-emitting layer included a host material and a guest material, a multi-source co-deposition method was used, the deposition rate of the host material compound 1-3 was 0.1 nm / s, and the deposition rate of the guest material (piq)2Ir(acac) was set to 5% of the deposition rate of the host material, and the total film thickness was 30 nm;

[0231] A hole blocking layer TPBi was vacuum evaporated on the light emitting layer, the evaporation rate was 0.1 nm / s, and the thickness was 5 nm; then an electron transport layer was evaporated, the evaporation rate of ET-1 and ET-2 was adjusted to 0.1 nm / s by multi-source co-evaporation, and the total film thickness was 30 nm;

[0232] A LiF layer with a thickness of 1 nm was vacuum evaporated on the electron transport layer (ETL) as an electron injection layer, and an Al layer with a thickness of 150 nm was evaporated as the cathode of the device.

[0233] The molecular structure involved is as follows:

[0234]

[0235] Device Example 2 to Device Example 16

[0236] The organic electroluminescent devices of Device Example 2 to Device Example 16 were prepared by a method similar to that of Device Example 1, except that the compound 1-3 in Device Example 1 was replaced by the compound in Table 1, respectively.

[0237] Device Comparative Example 1

[0238] The organic electroluminescent device of Device Comparative Example 1 was prepared by a method similar to that of Device Example 1, except that the compound 1-3 in Device Example 1 was replaced by CBP, respectively.

[0239]

[0240] Test Example 1

[0241] The driving voltage and current efficiency of the organic electroluminescent devices prepared in Device Example 1 to Device Example 16 and Device Comparative Example 1 were measured at a luminance of 2000 cd / m 2

[0242] Table 1

[0243] Red host material Driving voltage (V) Efficiency (cd / A) Luminance (cd / m 2 )]]> Device example 1 1-3 4.12 11.9 2000 Device example 2 1-14 4.14 11.7 2000 Device example 3 1-38 4.09 12.2 2000 Device example 4 1-81 4.16 11.5 2000 Device example 5 1-115 4.13 11.8 2000 Device example 6 1-184 4.20 11.4 2000 Device example 7 1-223 4.10 12.1 2000 Device example 8 1-246 4.15 11.6 2000 Device example 9 1-294 4.11 12.0 2000 Device example 10 2-15 3.87 10.3 2000 Device example 11 2-24 3.82 9.7 2000 Device example 12 2-34 3.85 9.8 2000 Device example 13 2-53 3.92 10.0 2000 Device example 14 2-62 3.89 10.2 2000 Device example 15 2-81 3.86 10.1 2000 Device example 16 2-101 3.80 10.9 2000 Device comparative example 1 CBP 4.97 7.8 2000

[0244] As can be seen from the experimental results shown in Table 1, when the compound of the present application is used as a red light host material of an organic electroluminescent device, it has a lower driving voltage and a higher luminous efficiency compared with the prior art.

[0245] The above describes 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 fall within the protection scope of the present application.​

Claims

1. An organic compound, characterized in that The compound has the structure shown in formula (1): In formula (1), Ring Z is of formula (2) and is bonded to formula (1) via a dotted line; X is O, S, N(R9) or C(R 10 )2; L is present or absent. When L is present, L is a linking group provided by any one structure selected from benzene, naphthalene, anthracene, phenanthrene, biphenyl, dibenzothiophene, dibenzofuran, 9,9-dimethylfluorene, and phenyl-substituted naphthyl; R1, R2, R3, R4, R5, R6, R7, R8, R 10 Each independently selected from H, C 1-10 Alkyl, C 1-10 Any one of the alkoxy groups; R9 is selected from C 6-30 Aromatic groups; Ar is selected from any one of the structures represented by formula (Q1), formula (Q2), formula (Q3), and formula (Q5), In formula (Q1), formula (Q2), formula (Q3), and formula (Q5), At least one of Y1, Y2 and Y3 is N, and optionally the remaining one is C; R 21 and R 22 Each independently selected from C containing or not containing heteroatoms 6-20 Aromatic groups; R 23 、R 24 、R 27 Each independently selected from C containing or not containing heteroatoms 6-20 aromatic groups.

2. The organic compound according to claim 1, characterized in that The compound represented by the formula (1) is represented by any one of the following formulas (3) and (4); In formula (3) and formula (4), X, L, Ar, and R1 to R8 are as defined in claim 1.

3. The organic compound according to claim 1 or 2, characterized in that R 21 and R 22 Each is independently selected from phenyl, biphenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl, 9,9-dimethylfluorenyl, pyridyl, pyrimidinyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl; R 23 、R 24 、R 27 Each is independently selected from phenyl, naphthyl, 9,9-dimethylfluorenyl, dibenzothienyl, dibenzofuranyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, and benzothieno-naphthyl.

4. The organic compound according to claim 1 or 2, characterized in that R1, R2, R3, R4, R5, R6, R7, R8 and R 10 Each independently selected from H, C 1-6 Alkyl, C 1-6 Any one of the alkoxy groups; R9 is selected from C 6-20 aromatic groups.

5. The organic compound according to claim 1 or 2, characterized in that R1, R2, R3, R4, R5, R6, R7, and R8 are each independently selected from H; R9 is selected from any one of phenyl, naphthyl, anthracenyl, phenanthrenyl, and biphenyl; R 10 Any one selected from methyl, ethyl, n-propyl, isopropyl, methoxy, ethoxy, n-propoxy and isopropoxy.

6. An organic compound, characterized in that The compound is any one of the following compounds:

7. Use of the organic compound according to any one of claims 1 to 6 in an organic electroluminescent device.

8. An organic electroluminescent device, characterized in that: An organic compound containing one or more organic compounds according to any one of claims 1 to 6, wherein the organic compound is present in at least one of the electron transport layer, the light emitting layer and the hole blocking layer of the organic electroluminescent device.

9. The organic electroluminescent device according to claim 8, characterized in that: The organic compound is present in the light-emitting layer of the organic electroluminescent device.

10. The organic electroluminescent device according to claim 9, characterized in that: The organic compound serves as a red light host material and exists in the light-emitting layer of the organic electroluminescent device.

11. The organic electroluminescent device according to any one of claims 8 to 10, characterized in that: The organic electroluminescent device comprises 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 covering layer which are stacked in sequence.

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