Boron-nitrogen compound and organic electroluminescent device using same

Abstract

The invention relates to the technical field of organic photoelectric materials, in particular to a boron-nitrogen compound and an organic electroluminescent device using the compound. According to the invention, a large steric hindrance group containing pyrene substituted amido is introduced into a main ring structure containing furan or thiophene, so that the planar configuration of the main ring structure is distorted, and the distance between molecules is increased by introducing other substituent groups, so that the adverse effect of a concentration quenching effect on efficiency is weakened. When the boron-nitrogen compound disclosed by the invention is used as a luminescent material in an OLED (Organic Light Emitting Diode) device, especially as a blue light doping material, the device can show excellent performance and stability, the starting voltage can be reduced, the luminous efficiency can be improved, and the service life of the device can be prolonged. It is worthy of noting that the boron-nitrogen compound serves as a doping material and is combined with a specific main body material to prepare an OLED device, more excellent device performance is achieved, the requirement of current panel manufacturing enterprises for high-performance materials can be met, and good commercialized application prospects are achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of organic optoelectronic materials, and particularly relates to a boron nitride compound and an organic light-emitting device using the compound. Background Art

[0002] With the development of multimedia technology and the improvement of information requirements, the requirements for the performance of panel displays are getting higher and higher. Among them, OLED has a series of advantages such as self-luminous, low-voltage DC drive, all-solid-state, wide viewing angle, rich colors, etc., and has attracted wide attention due to its potential applications in new-generation displays and lighting technologies, and has a very broad application prospect. An organic light-emitting device is a self-luminous device. The mechanism of OLED luminescence is that under the action of an external electric field, electrons and holes are respectively injected from the positive and negative electrodes, migrate, recombine and decay in the organic material to generate light. The typical structure of OLED includes one or several functional layers such as a cathode layer, an anode layer, an electron injection layer, an electron transport layer, a hole blocking layer, a hole transport layer, a hole injection layer, and an organic light-emitting layer.

[0003] Although the research progress of organic light-emitting materials is very rapid at present, there are still many problems to be solved, such as the improvement of external quantum efficiency (EQE), the design and synthesis of new materials with higher color purity, the design and synthesis of new materials with high-efficiency electron transport / hole blocking, etc. For organic light-emitting devices, the luminescence quantum efficiency of the device is a comprehensive reflection of various factors and is also an important index to measure the quality of the device. In the host material of an organic light-emitting device, in addition to the triplet energy level being higher than that of the guest material to prevent the reverse transfer of the energy released by exciton transition, more importantly, it has good hole migration performance. However, materials with both high triplet energy levels and good hole mobilities are still lacking in the host material. Therefore, how to design new host materials with better performance has always been an urgent problem for those skilled in the art. Summary of the Invention

[0004] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide a boron nitride compound and its application. The present invention improves the hole mobility through a specific compound, maximizes the hole transport and luminescence effects. Preparing the compound into a device has good luminous efficiency and high commercial application prospects.

[0005] To achieve the above technical purpose, the technical solution of the present invention is as follows:

[0006] The present invention provides a boron nitride compound, and the boron nitride compound has a general formula structure as shown in Formula I:

[0007]

[0008] In Formula I, m is an integer between 0 and 9, and n is an integer between 0 and 5;

[0009] R 1 and R 2 are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 heterocycloalkyl, substituted or unsubstituted C3-C10 cycloalkenyl, substituted or unsubstituted C3-C10 heterocycloalkenyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C60 aryl;

[0010] When m>1, multiple Rs 1 are each independent, the same or different from each other, and the substitution positions of multiple Rs 1 are different;

[0011] When n>1, multiple Rs 2 are each independent, the same or different from each other, and the substitution positions of multiple Rs 2 are different;

[0012] L is selected from a single bond, substituted or unsubstituted C6-C60 arylene,

[0013] The Q group is selected from any one of the structures shown in Formulas II-1 to II-12:

[0014]

[0015] wherein X is O or S;

[0016] Multiple rs are the same or different from each other, and are each independently selected from integers between 0 and 5;

[0017] R 3 and R 5 -R 8 are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 heterocycloalkyl, substituted or unsubstituted C3-C10 cycloalkenyl, substituted or unsubstituted C3-C10 heterocycloalkenyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C60 aryl;

[0018] When multiple Rs 3 are present, multiple Rs 3 are each independent, the same or different from each other, and the substitution positions of multiple Rs 3 are different;

[0019] When multiple Rs 5 are present, multiple Rs5 Each is independent, the same as or different from one another, and the substitution positions of multiple Rs 5 are different;

[0020] When multiple Rs 6 are present, multiple Rs 6 each is independent, the same as or different from one another, and the substitution positions of multiple Rs 6 are different;

[0021] When multiple Rs 7 are present, multiple Rs 7 each is independent, the same as or different from one another, and the substitution positions of multiple Rs 7 are different;

[0022] When multiple Rs 8 are present, multiple Rs 3 each is independent, the same as or different from one another, and the substitution positions of multiple Rs 8 are different;

[0023] When the "substituted or unsubstituted" is substituted, the substituents are each independently selected from deuterium, halogen, cyano, silyl, C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C6-C30 aryl, C3-C30 heteroaryl,

[0024] In the said heteroarylene, heterocycloalkyl, heterocycloalkenyl, heteroaryl, the heteroatoms are each independently at least one of N, O, S, Si, P.

[0025] Preferably, the said R 3 and R 5 -R 8Each independently selected from the following groups: hydrogen, deuterium, halogen, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted n-propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted isobutyl, substituted or unsubstituted sec-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted perylenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted furyl, substituted or unsubstituted thienyl, substituted or unsubstituted indenyl, substituted or unsubstituted indolyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted carbolinyl, substituted or unsubstituted 9,9-dimethylfluorene, substituted or unsubstituted 9,9-diphenylfluorene, substituted or unsubstituted spirobifluorene, substituted or unsubstituted phenanthrolinyl, substituted or unsubstituted benzoquinolinyl, substituted or unsubstituted benzoisoquinolinyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted benzopyrazolyl, substituted or unsubstituted phthalazinyl.

[0026] Preferably, the said R 3 , R 5 -R 8 Each independently selected from hydrogen, deuterium, tert-butyl, phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, fluoranthenyl, pyrenyl, perylenyl, triphenylenyl and a combination of two or more of the above groups.

[0027] More preferably, the said R 3 , R 5 -R 8Each independently selected from hydrogen, deuterium, isopropyl, tert-butyl, phenyl, biphenyl, phenyl substituted with tert-butyl and / or deuterium, biphenyl substituted with tert-butyl and / or deuterium, phenyl substituted with isopropyl and / or deuterium, biphenyl substituted with isopropyl and / or deuterium, wherein the tert-butyl may be deuterated tert-butyl and the isopropyl may be deuterated isopropyl.

[0028] Specifically, isopropyl (tert-butyl) and deuterated aryl groups (phenyl, biphenyl, etc.) include the case where there are two substituents on the aromatic ring at the same time, or the case where isopropyl (tert-butyl) is deuterated on the aromatic ring substituted with isopropyl (tert-butyl).

[0029] Preferably, the boron nitride compound is selected from any one of the following chemical structures:

[0030]

[0031]

[0032]

[0033]

[0034] Furthermore, the present invention also provides an application of the boron nitride compound having the structure shown in formula (I) above in electronic devices.

[0035] Furthermore, the electronic devices include organic light-emitting diodes (OLEDs), organic integrated circuits (O-ICs), organic field-effect transistors (O-FETs), organic thin-film transistors (O-TFTs), organic light-emitting transistors (O-LETs), organic solar cells (O-SCs), organic optical detectors, organic photoreceptors, organic field quenching devices (O-FQDs), light-emitting electrochemical cells (LECs), and organic laser diodes (O-lasers). The boron nitride compound having the structure shown in formula (I) is used as a light-emitting layer material in electronic devices.

[0036] The present invention also provides an organic light-emitting device, which includes: a substrate layer; a first electrode on the substrate; an organic light-emitting functional layer on the first electrode; a second electrode on the organic light-emitting functional layer; the organic light-emitting functional layer includes a light-emitting layer; and the light-emitting layer includes the boron nitride compound having the structure shown in formula (I) above.

[0037] Preferably, the light-emitting layer further contains a host material, and the host material can be selected from an anthracene compound having the structure shown in the following formula II or formula III:

[0038]

[0039] In Formula II and Formula III, L1 is a single bond, a substituted or unsubstituted C6-C60 aryl group;

[0040] Ar1 is selected from hydrogen, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C6-C60 heteroaryl group;

[0041] R9 is selected from hydrogen, deuterium, a substituted or unsubstituted C6-C60 aryl group.

[0042] Furthermore, L1 is a single bond, a phenylene group, a deuterated phenylene group, a naphthylene group, a deuterated naphthylene group;

[0043] Ar1 is selected from hydrogen, a phenyl group, a biphenyl group, a deuterated phenyl group, a naphthyl group, a deuterated naphthyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, a dimethylfluorenyl group, a diphenylfluorenyl group, a spirobifluorenyl group;

[0044] R9 is selected from hydrogen, deuterium, a phenyl group, a naphthyl group, a biphenyl group, a deuterated phenyl group, a deuterated naphthyl group, a deuterated biphenyl group.

[0045] Furthermore, L1 is selected from any one of the following chemical structures:

[0046]

[0047] Furthermore, the anthracene compounds are selected from any one of the following chemical structures:

[0048]

[0049] The present invention also provides a composition, and the composition contains a boron nitride compound having the structure shown in Formula (I) above. Preferably, the composition further contains an anthracene compound having the structure shown in Formula (II) above.

[0050] The present invention also provides a preparation, and the preparation contains a boron nitride compound having the structure shown in Formula (I) above or the composition described above and at least one solvent.

[0051] There is no particular limitation on the solvent, and unsaturated hydrocarbon solvents well-known to those skilled in the art such as toluene, xylene, mesitylene, tetralin, decalin, dicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, etc., halogenated saturated hydrocarbon solvents such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, etc., halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, etc., ether solvents such as tetrahydrofuran, tetrahydropyran, etc., and ester solvents such as alkyl benzoate can be used.

[0052] The present invention also provides a display or lighting device, which comprises one or more of the above-mentioned organic electroluminescent devices.

[0053] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0054] In the main ring structure containing furan or thiophene of the present invention, a sterically hindered group containing a pyrene-substituted amino group is introduced to distort its planar configuration, and the distance between molecules is increased by introducing other substituents, thereby weakening the adverse effect of concentration quenching on efficiency. The compound provided by the present invention has a good wavelength range, the comparative energy level difference (HOMO-LUMO) increases, and the wavelength of PL moves in the deep blue direction, solving the problem of red shift of the wavelength with the increase of molecular weight. When the boron nitride compound of the present invention is used as a light-emitting material in an OLED device, especially as a blue light doping material, the device can exhibit excellent performance and stability, can reduce the driving voltage, improve the light-emitting efficiency and extend the service life of the device. Especially when the boron nitride compound of the present invention is used as a doping material and an anthracene compound as a host material to jointly prepare an OLED device, it has more excellent device performance, can meet the requirements of current panel manufacturing enterprises for high-performance materials, and has good commercial application prospects. Description of the Drawings

[0055] Figure 1 It is a schematic diagram of the device structure of an organic electroluminescent element according to an embodiment of the present invention, wherein, a first electrode layer 1, a hole injection layer 2, a hole transport layer 3, a light-emitting auxiliary layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7 and a second electrode layer 8. Detailed Embodiments

[0056] The content of the present invention will be described in detail below. The description of the constituent elements recorded below is sometimes based on representative embodiments or specific examples of the present invention, but the present invention is not limited to such embodiments or specific examples.

[0057] As used in the present invention, the term "halogen group" may include fluorine, chlorine, bromine or iodine.

[0058] As used in the present invention, the term "C1-C10 alkyl" refers to a monovalent substituent derived from a straight-chain or branched-chain saturated hydrocarbon having 1 to 10 carbon atoms, and examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl and hexyl.

[0059] As used in the present invention, the term "C3-C10 cycloalkyl" refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 10 carbon atoms. Examples of such cycloalkyls include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, etc.

[0060] As used in the present invention, the term "C2-C10 heterocycloalkyl" refers to a monovalent substituent derived from a monocyclic or polycyclic group having 2 to 10 carbon atoms and containing at least one heteroatom in the ring, said heteroatom being selected from O, S, N, P, Si.

[0061] As used in the present invention, the term "alkoxy" refers to a straight-chain, branched-chain or cyclic chain. The number of carbon atoms in the alkoxy is not particularly limited herein, but the alkoxy preferably has 1 to 10 carbon atoms. Specific examples thereof include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, benzyloxy.

[0062] As used in the present invention, the term "cycloalkenyl" refers to an unsaturated carbocyclic ring and does not have aromaticity.

[0063] As used in the present invention, the term "heterocycloalkenyl" refers to an unsaturated heterocyclic ring and does not have aromaticity.

[0064] As used in the present invention, the term "C6-C60 aryl" refers to a monovalent substituent derived from an aromatic hydrocarbon having a single ring or a combination of two or more rings and having 6 to 60 carbon atoms. Further, such aryl may have a form in which two or more of the rings are simply attached to each other laterally or fused to each other. Examples of such aryls include, but are not limited to, phenyl, biphenyl, naphthyl, phenanthryl, anthryl, pyrenyl, triphenylenyl, fluoranthenyl, dimethyl 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirobifluorenyl, etc.

[0065] As used in the present invention, the term "arylene" refers to a divalent aryl derived by removing one hydrogen atom from "aryl", for example, phenyl becomes phenylene by removing one hydrogen atom, and naphthyl becomes naphthylene by removing one hydrogen atom.

[0066] As used in the present invention, the term "heteroaryl having 3 to 60 carbon atoms" refers to a monovalent substituent derived from a monocyclic or polycyclic aromatic hydrocarbon having 3 to 60 carbon atoms. In this connection, at least one carbon, preferably 1 - 3 carbons in the ring, is replaced by a heteroatom such as N, O, S, P, B or Si. In addition, such heteroaryl can have a form in which two or more rings are simply side - linked to each other or fused to each other or fused to an aryl group. Examples of such heteroaryl include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, indolizinyl, indolyl, indolopyridyl, purinyl, phenanthrolinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, thiazolyl, imidazolyl, oxazolyl, furyl, thienyl, benzofuryl, benzothienyl, benzothiazolyl, benzimidazolyl, benzoxazolyl, carbazolyl, dibenzofuryl, dibenzothienyl, etc., and the present invention is not limited thereto.

[0067] As used in the present invention, the term "heteroarylene" refers to a divalent heteroaryl derived by removing one hydrogen atom from "heteroaryl", for example, pyridyl becomes pyridylene after removing one hydrogen atom.

[0068] As used in the present invention, the term "silyl" refers to a trisubstituted silyl, such as trimethylsilyl, triphenylsilyl, etc.

[0069] As used in the present invention, in the expression "Z group having X - Y carbon atoms" or "Z group of C(X - Y)", "having X - Y carbon atoms" means the number of carbon atoms of the Z group when it is unsubstituted, excluding the carbon atoms of the substituents when it is substituted. For example, an aryl group having 6 to 60 carbon atoms means that when unsubstituted, the number of carbon atoms in the aryl group is any integer from 6 to 60, that is, when unsubstituted, the number of carbon atoms can be 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20... 60.

[0070] As used in the present invention, the term "substituted" means that a hydrogen atom in a compound is replaced by another substituent. The position where substitution occurs can be the position where the hydrogen atom is replaced. That is, this position is not limited to a specific position, as long as the hydrogen at this position can be replaced by a substituent, and the substitution can be deuteration. For example, carbazolyl, as long as not otherwise specified in this specification, includes any of the following groups, but is not limited thereto,

[0071]

[0072] represents the substitution position. "Unsubstituted" means retaining a hydrogen atom, and in this case, the hydrogen atom includes protium, deuterium, and tritium.

[0073] When there are two or more substituents, the two or more substituents may be the same or different.

[0074] As used herein, the term "quinoline" includes

[0075] As used herein, the term "terphenyl" includes

[0076] As used herein, the term "benzoquinoline" includes

[0077] As used herein, a hydrogen atom includes protium, deuterium, and tritium. The compounds described in the present invention may contain deuterium atoms of natural origin, or deuterium atoms may be introduced by deuterating a part or all of the starting compounds. If deuterium atoms are introduced from the starting materials, the deuteration rate may be 100%, or less than 100%, or less than 95%, or less than 90%, or less than 80%, and the deuteration rate may also be 1% or more, or 5% or more, or 10% or more. If the deuteration rate is not 100%, it represents a mixture of deuterated compounds and non-deuterated compounds, or a mixture of fully deuterated compounds and incompletely deuterated compounds, or a mixture of fully deuterated compounds, non-deuterated compounds, and incompletely deuterated compounds.

[0078] As used herein, terms such as the first, the second, A, B, etc. are used. The above terms are only used to distinguish the components and do not limit the nature or order of the components corresponding to the terms.

[0079] The compounds disclosed herein may exhibit desired properties and have emission and / or absorption spectra that can be adjusted by selecting appropriate ligands. On the other hand, the present invention may exclude any one or more of the compounds, structures, or parts thereof specifically described herein.

[0080] The compounds of the present invention can be prepared using a variety of methods, including but not limited to those described in the examples provided herein.

[0081] It should be noted that the above general description and the following detailed description are only exemplary and explanatory and are not restrictive. The present application can be more easily understood by referring to the following specific embodiments and the examples included therein.

[0082] Before disclosing and describing the compounds, devices, and / or methods of the present invention, it should be understood that they are not limited to specific synthetic methods (otherwise indicated) or specific reagents (otherwise indicated), as these can of course vary. It should also be understood that the terms used in this invention are for the purpose of describing specific aspects only and are not intended to be limiting. Although any methods and materials similar or equivalent to those described in this invention can be used in this practice or test, exemplary methods and materials are described below. Synthetic Examples All starting materials and solvents are commercially available unless otherwise specified, and the solvents are used directly without further treatment.

[0083] The substrate described in this invention can be any substrate used in typical organic optoelectronic devices. It can be a glass or transparent plastic substrate, or a substrate of an opaque material such as silicon or stainless steel, or a flexible PI film. Different substrates have different mechanical strengths, thermal stabilities, transparencies, surface smoothness, and water resistances, and are used in different directions according to their properties. As the materials for the hole injection layer, hole transport layer, and electron injection layer, any material can be selected from the related materials known for OLED devices, and this invention does not specifically limit them.

[0084] Example 1: Preparation of Compounds 1-4

[0085]

[0086] Step1. In a reaction vessel under nitrogen, add 2,5-dibromo-1,3-difluorobenzene (13.6 g, 50 mmol), phenol (4.7 g, 50 mmol), potassium carbonate (8.3 g, 55 mmol), and N-methylpyrrolidone (225 mL), stir and reflux for 9 hours, cool to room temperature, separate the organic layer with chloroform and water, and distill the organic layer. Redissolve it in chloroform, wash twice with water, separate the organic layer, add anhydrous magnesium sulfate, stir, filter, and distill the residue under reduced pressure. The concentrated compound is obtained by silica gel column chromatography to give 1-1-1 (6.9 g, yield = 40%).

[0087] LC-MS(APCI): 344.34(M+H + )。

[0088] Step 2. Add 1-1-1 (17.3 g, 50 mmol), 1-1-2 (6.8 g, 51 mmol), potassium carbonate (8.3 g, 60 mmol) and N-methylpyrrolidone (225 mL) to the reaction vessel under nitrogen. Stir and reflux for 9 hours, cool to room temperature, separate the organic layer with chloroform and water, and distill the organic layer. Redissolve it in chloroform, wash twice with water, separate the organic layer, add anhydrous magnesium sulfate, stir and filter, and distill the residue under reduced pressure. The concentrated compound is obtained by silica gel column chromatography to give 1-1-3 (12.7 g, yield = 55%).

[0089] LC-MS (APCI): 458.85 (M+H + )。

[0090] Step 3. Dissolve the intermediate 1-1-3 (13.8 g, 30 mmol) in 300 mL of tert-butylbenzene and cool to 0 °C. Add tert-butyllithium (1.7 M, 45 mmol), and stir at 60 °C for 2 hours. Then cool the reaction mixture to 0 °C, add boron tribromide (4.3 mL, 45 mmol), and stir at room temperature for 0.5 hour. Cool the reaction mixture to 0 °C again, add N,N-diisopropylethylamine (7.8 mL, 45 mmol), and stir at 60 °C for 2 hours. After the reaction is completed, cool to room temperature, separate the organic layer with chloroform and water, and distill the organic layer. Redissolve it in chloroform, wash twice with water, separate the organic layer, add anhydrous magnesium sulfate, stir and filter, and distill the residue under reduced pressure. The concentrated compound is obtained by silica gel column chromatography to give 1-1-4 (8.2 g, yield = 70%).

[0091] LC-MS (APCI): 388.87 (M+H + )。

[0092] Step 4. Dissolve 1-1-5 (4.9 g, 12 mmol) in 1,3-dimethyl-2-imidazolidinone (200 mL) under nitrogen, slowly add sodium hydride (60% oily, 0.86 g), and stir for 30 minutes. Add 1-1-4 (4.7 g, 12 mmol), and stir at 110 °C for 6 hours. Cool the reaction solution, wash with water, remove the palladium catalyst by passing through diatomaceous earth, evaporate to dryness, recrystallize with dichloromethane / petroleum ether to obtain a solid, and then wash with a mixed solvent of toluene / ethyl acetate at 45 °C for 2 h, filter by suction to obtain 1-1-1 (3.0 g, yield 35%).

[0093] LC-MS (APCI): 714.58 (M+H + )。

[0094] Example 2: Preparation of Compound 1-9

[0095]

[0096] Step 1. A suspension of zirconium tetrachloride (41.5 g, 178.6 mmol) in DCM (200 ml) was added to tert-butyl methyl ether (15.7 g, 178.6 mmol) at 0 °C. After stirring for 30 minutes at 0 °C, 1-bromopyrene (50.0 g, 178.6 mmol) in DCM was placed therein. The mixture was stirred at 60 °C for 8 hours, cooled with saturated aqueous sodium bicarbonate solution, and then DCM was added. The organic layer was separated, dried over magnesium sulfate, and evaporated in vacuo to obtain a residue, which was purified by silica gel column chromatography with n-hexane / ethyl acetate (20:1 to 4:1) to obtain 2 (15.5 g, yield 31%).

[0097] LC-MS (APCI): 337.24 (M+H + )。

[0098] Step 2. Under nitrogen atmosphere, 2 (15.5 g, 46.12 mmol) and 3-aminophenol (5.12 g, 47.00 mmol) were separately placed in a 250 mL three-necked flask, and then sodium tert-butoxide (11.5 g, 120 mmol) and toluene (150 mL) were added. After stirring well, the air in the flask was displaced with nitrogen. The catalyst [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium (225 mg, 0.4 mmol) and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (246 mg, 0.6 mmol) were heated to 100 °C and reacted for 12 h. After cooling to room temperature, the reaction solution was poured into saturated ammonium chloride aqueous solution, extracted with ethyl acetate, the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated to obtain a brown oily substance, which was purified by silica gel column chromatography to obtain 4 (13.5 g, yield 87%).

[0099] LC-MS (APCI): 366.56 (M+H + )。

[0100] Step 3. Under nitrogen atmosphere, 4 (15.5 g, 36.96 mmol) and 1-bromo-4-tert-butylbenzene (7.84 g, 36.96 mmol) were separately placed into a 250 mL three-necked flask, and then sodium tert-butoxide (11.5 g, 120 mmol) and toluene (150 mL) were added. After stirring well, the air in the flask was displaced with nitrogen. The catalyst [1,1'-bis(diphenylphosphino)ferrocene] dichloropalladium (225 mg, 0.4 mmol) and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (246 mg, 0.6 mmol) were heated to 100 °C and reacted for 12 h. After cooling to room temperature, the reaction solution was poured into a saturated ammonium chloride aqueous solution, extracted with ethyl acetate, the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, filtered and concentrated to obtain a brown oily substance, which was purified by silica gel column chromatography to obtain 1-9-0 (11.7 g, yield 87%).

[0101] LC-MS (APCI): 500.72 (M+H + )

[0102] Step 4. Under nitrogen atmosphere, a dichloromethane solution containing 9.00 g of 2-bromo-1-(5-bromo-2-hydroxyphenyl)ethanone was cooled to 0 °C, 4.7 g of triethylamine was added dropwise, and the reaction system was heated to 25 °C and stirred for reaction. After 6 h, the reaction progress was monitored by gas phase. After the reaction was completed, 30 mL of water was added to the reaction system for quenching, and then 40 mL of brine was added for washing. After washing, the dichloromethane phase was separated from the aqueous phase. The dichloromethane phase was rotary evaporated at 40 °C until the solvent was completely evaporated to obtain a crude product of 5-bromobenzofuranone. The crude product was reconstituted with 80 mL of ethyl acetate, washed with 40 mL of brine, the organic and aqueous phases were separated, and the organic phase was concentrated to 25% of the original volume by rotary evaporation at 40 °C. After rotary evaporation, 20 mL of petroleum ether was added for recrystallization, the solid was collected by filtration, and the solid was dried with an oil pump to obtain pure 5-bromobenzofuranone (7.47 g, 83.6%).

[0103] LC-MS (APCI): 212.96 (M+H + )

[0104] Step 5. Under nitrogen atmosphere, a tetrahydrofuran solution of 7: 7.47 g of 5-bromobenzofuranone was cooled to 0 °C, 5.00 g of sodium hydroxide solution was added dropwise, and the reaction system was heated to 25 °C and stirred for reaction. After the reaction was completed, compound 8 (7.00 g, 90%) was obtained after post-treatment and purification.

[0105] LC-MS (APCI): 212.96 (M+H + )

[0106] Step6. Under nitrogen atmosphere, dissolve 8 (6.00 g, 28.30 mmol), phenylboronic acid (3.43 g, 28.40 mmol), 60 mg (0.21 mmol) of Pd(OAc) 2 , 30 ml (42.45 mmol) of potassium carbonate (K 2 CO 3 ) aqueous solution, 263 mg (0.84 mmol) of tris(ortho-tolyl)phosphine (P(o-tolyl)3), and 20 ml of 1,2-dimethoxyethane (dimethoxyethane) in a mixture, and stir at 80 °C for 9 hours. After the reaction is completed, the extracted solid is filtered and recovered. Then it is dissolved in toluene and filtered through Celite and alumina. The filtrate is washed with water and saturated salt solution, and dried over magnesium sulfate. After natural filtration, the filtrate is concentrated to obtain 5.1 g of the target substance 1-9-2, with a yield of 85%.

[0107] LC-MS(APCI): 211.35 (M+H + ).

[0108]

[0109] Step7. Dissolve 1-9-0 (5.29 g, 12 mmol) in 1,3-dimethyl-2-imidazolidinone (200 mL) under nitrogen atmosphere, slowly add sodium hydride (60% oily, 0.86 g), and stir for 30 minutes. After adding 2,5-dibromo-1,3-difluorobenzene (3.26 g, 12 mmol), stir at 110 °C for 6 hours. Cool the reaction solution, wash with water, filter through Celite to remove the palladium catalyst, evaporate to dryness, recrystallize with dichloromethane / petroleum ether to obtain a solid, and then wash with a mixed solvent of toluene / ethyl acetate at 45 °C for 2 h, filter by suction to obtain 1-9-1 (4.04 g, yield 45%).

[0110] LC-MS(APCI): 748.55 (M+H + ).

[0111] Step8. Dissolve 1-9-2 (2.52 g, 12 mmol) in 1,3-dimethyl-2-imidazolidinone (200 mL) under nitrogen atmosphere, slowly add sodium hydride (60% oily, 0.86 g), and stir for 30 minutes. After adding 1-9-1 (9.00 g, 12 mmol), stir at 110 °C for 6 hours. Cool the reaction solution, wash with water, filter through Celite to remove the palladium catalyst, evaporate to dryness, recrystallize with dichloromethane / petroleum ether to obtain a solid, and then wash with a mixed solvent of toluene / ethyl acetate at 45 °C for 2 h, filter by suction to obtain 1-9-3 (5.64 g, yield 50%).

[0112] LC-MS(APCI): 938.88 (M+H +)。

[0113] Step9. Under nitrogen atmosphere, compound 1-9-3 (10.24 g, 10.9 mmol) and 1-9-4 (2.14 g, 12.0 mmol) were added to tetrahydrofuran (300 mL), and the mixture was stirred and refluxed. Then, potassium carbonate (6.0 g, 43.5 mmol) was dissolved in 54 mL of water, and after sufficient stirring, tetrakis(triphenylphosphine)palladium(0) (0.55 g, 0.5 mmol) was added. After reacting for 12 hours, the mixture was cooled to room temperature, and the organic layer and the aqueous layer were separated. The organic layer was distilled. It was redissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The remaining solution was distilled under reduced pressure. The concentrated compound was obtained by silica gel column chromatography to give 1-9-5 (9.09 g, yield 84%).

[0114] LC-MS (APCI): 999.47 (M+H + )。

[0115] Step10. Intermediate 1-12-5 (40.2 g, 35.0 mmol) was dissolved in 300 mL of tert-butylbenzene and cooled to 0 °C. tert-Butyllithium (31.5 mL, 53.6 mmol) was added, and the mixture was stirred at 60 °C for 2 hours. Then the reaction mixture was cooled to 0 °C, boron tribromide (5.2 mL, 53.6 mmol) was added, and the mixture was stirred at room temperature for 0.5 hour. The reaction mixture was cooled to 0 °C again, N,N-diisopropylethylamine (9.3 mL, 53.6 mmol) was added, and the mixture was stirred at 60 °C for 2 hours. After the reaction was completed, the mixture was cooled to room temperature, and the organic layer was separated with chloroform and water. The organic layer was distilled. It was redissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, and then filtered. The remaining solution was distilled under reduced pressure. The concentrated compound was obtained by silica gel column chromatography to give 1-9 to give 1-9 (10.33 g, yield 32%).

[0116] LC-MS (APCI): 922.32 (M+H + )。

[0117] Example 3: Preparation of Compound 1-7

[0118]

[0119] Referring to the synthesis method of compound 1-1 in Example 1, compound 1-7 was synthesized to obtain compound 1-7. The synthesis methods of 1-7-0 and 1-7-2 refer to those of 1-9-0 and 1-9-2 in Example 2.

[0120] LC-MS (APCI): 942.58 (M+H + )。

[0121] Example 4: Preparation of Compound 1-13

[0122]

[0123] Referring to the synthetic route of Compound 1-9-0 in Example 2, 3-chloroaniline was used instead of 3-((6-(tert-butyl)pyren-1-yl)amino)phenol to synthesize Compound N-(4-(tert-butyl)phenyl)-3-chloroaniline.

[0124] LC-MS(APCI): 260.11(M+H + )

[0125]

[0126] Step1. Under a nitrogen atmosphere, in a 500 ml round-bottom flask, Compound 5-bromo-1-benzofuran (10 g, 51.2 mmol) and Compound phenylboronic acid (6.25 g, 51.2 mmol) were completely dissolved in 150 mL of xylene, then potassium carbonate (10.6 g, 76.8 mmol) was added. After adding bis(tri-tert-butylphosphine)palladium(0) (0.17 g, 0.33 mmol), the mixture was heated and stirred for 3 hours. The temperature was lowered to room temperature, filtered, and the base was removed. Then the xylene was concentrated under reduced pressure and recrystallized with 250 mL of ethyl acetate to produce Compound 5-phenyl-1-benzofuran (7.80 g, yield: 78%).

[0127] LC-MS(APCI): 195.64(M+H+)

[0128] Step2. A solution of 5-phenyl-1-benzofuran (7.80 g, 40.2 mmol) in tetrahydrofuran (80 mL) was cooled to 5 °C, and then NBS (8.60 g, 48.2 mmol) was slowly added. The reaction solution was reacted at room temperature overnight, then poured into a sodium thiosulfate solution and extracted with ethyl acetate (80 mL x 3). The combined organic phases were dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (eluted with petroleum ether) to obtain the compound: 3-bromo-5-phenylbenzofuran (5.54 g, yield 71%).

[0129] LC-MS(APCI): 272.35(M+H + )

[0130] Step 3. Add 3-bromo-5-phenylbenzofuran (5.0 g, 18.4 mmol) and 4-tert-butylaniline (2.75 g, 18.4 mmol) into a three-necked flask, add xylene (70 mL), add sodium tert-butoxide (2.65 g, 27.6 mmol), after adding bis(tri-tert-butylphosphine)palladium(0) (0.17 g, 0.33 mmol), displace with nitrogen twice, heat and stir for 3 hours. After the reaction is terminated, cool the obtained product to room temperature and wash with water. The organic layer is dried over anhydrous magnesium sulfate, and then filtered and concentrated. It can be purified by column chromatography or distillation to obtain 1-13-2 (3.2 g, yield 65%).

[0131] LC-MS(APCI): 342.72(M+H + )

[0132]

[0133] Refer to the synthesis method of compound 1-9 in Example 2. Use aniline instead of 3-aminophenol, and use the above-synthesized product N-(4-(tert-butyl)phenyl)-3-chloroaniline instead of 1-bromo-4-(tert-butyl)benzene to synthesize compound 1-13-0; replace compound 1-9-2 in Example 2 with compound 1-13-2. Except for this, synthesize compound 1-13 (9.4 g, yield 43%) by the same method as in Example 2.

[0134] LC-MS(APCI): 1128.25(M+H + )

[0135] Example 5: Preparation of Compound 1-16

[0136]

[0137] The synthesis of compound 1-16-0-3 refers to the synthesis method of compound 1-9-5 in Example 2, only replacing compound 1-9-3 with 1-16-0-1 and 1-9-1 with 1-16-0-2. (35.7 g, yield 83%).

[0138] LC-MS(APCI): 256.45(M+H + )

[0139] Synthesis of compound 1-16-0-4: Dissolve 1-16-0-3 (10 g, 39.1 mmol) in 50 mL of ethanol, add iron powder (1 g, 17.8 mmol), dropwise add 10 mL of hydrochloric acid, heat and react, then add ammonia water to adjust the pH value to alkaline, extract and distill to obtain compound 1-16-0-4 (7.4 g, yield 84%).

[0140] LC-MS (APCI): 226.56 (M+H + )

[0141]

[0142] The synthesis of 1-16-0-5 refers to the synthesis method of compound 4 in Reference Example 2, except that compound 3 is replaced with 1-16-0-9. (10.4 g, yield 71%).

[0143] LC-MS (APCI): 406.64 (M+H + )

[0144] The synthesis of 1-16-0-7 refers to the synthesis of compound 1-1 in Reference Example 1, except that compound 1-1-4 is replaced with 1-16-0-6 and 1-1-5 is replaced with 1-16-0-5. (12.1 g, yield 73%).

[0145] LC-MS (APCI): 533.78 (M+H + )

[0146] The synthesis of 1-16-0 refers to the synthesis of compound 1-1 in Reference Example 1, except that 1-1-4 is replaced with 1-16-0-7 and 1-1-5 is replaced with 1-16-0-8. (13.2 g, yield 64%).

[0147] LC-MS (APCI): 706.56 (M+H + )

[0148]

[0149] Compound 1-16 was synthesized by referring to the synthesis method of compound 1-13 in Reference Example 4, and compound 1-16 was obtained (8.6 g, yield 31%).

[0150] LC-MS (APCI): 1184.56 (M+H + )

[0151] Example 6: Preparation of Compound 1-20

[0152] The synthesis of compound 1-20-2 refers to the synthesis of compound 1-13-2-1 in Reference Example 4, except that the raw material 3-chlorobenzofuran is replaced with 3-bromo-5-(tert-butyl)benzo[b]thiophene.

[0153] The synthesis method of compound 1-20-0 is the same as that of compound 1-16-0.

[0154]

[0155] Compound 1-20 was synthesized according to the synthesis method of compound 1-13 in Example 4, and compound 1-20 (8.7 g, 35%) was obtained.

[0156] LC-MS (APCI): 1180.24 (M+H + )

[0157] Example 7: Preparation of Compound 1-26

[0158]

[0159] 3-Bromobenzothiophene (21.3 g, 0.1 mol), p-bromoaniline (0.017 g, 0.1 mol), tris(dibenzylideneacetone)dipalladium(0) (1.73 g, 3 mmol), and sodium tert-butoxide (28.8 g, 0.3 mol) were weighed and successively added to a 1000 mL three-necked flask. About 450 mL of anhydrous toluene was added. After pumping and purging with nitrogen three times, the temperature was raised to 100 °C and the reaction was carried out for 4 hours. After the raw materials reacted sufficiently, water was added for dilution, and the mixture was extracted with ethyl acetate. The excess solvent was removed by vacuum distillation. The crude product was heated with hydrochloric acid / ethyl acetate (volume ratio 1:10), and compound C was obtained by suction filtration.

[0160]

[0161] Compound 1-26 was synthesized according to the synthesis method of compound 1-13 in Example 4, and compound 1-26 (10.6 g, 42%) was obtained. The synthesis method of 1-26-2 was referred to the synthesis of compound 1-9-0, and compound C was used instead of compound 4 in Example 2.

[0162] LC-MS (APCI): 1124.37 (M+H + )

[0163] Example 8: Preparation of Compound 1-27

[0164]

[0165] (1) Under nitrogen atmosphere, 5-bromobenzo[b]thiophene (13.6 g, 64.17 mmol), bis(pinacolato)diboron (16.3 g, 64.17 mmol), potassium carbonate (13.3 g, 96.26 mmol) and tetrahydrofuran (225 mL) were added to the reaction vessel, stirred and refluxed for 9 hours, cooled to room temperature, and the organic layer was separated with chloroform and water. The organic layer was distilled. It was redissolved in chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added and stirred, then filtered, and the residual liquid was distilled under reduced pressure. The concentrated compound was obtained by silica gel column chromatography as A-1-1 (11.0 g, 80%).

[0166] (2) A-1-1 (10 g, 38.46 mmol) was mixed with chloroform (75 mL) and acetic acid (75 mL), and NBS (16.6 g, 93.268 mmol) was gradually added at 0 °C. The mixture was stirred for 4 hours and then stirred at room temperature for 48 hours. After the reaction was completed, the reaction mass was diluted with chloroform (200 mL), and the resulting mixture was washed successively with saturated solutions of sodium thiosulfate (200 mL), sodium carbonate (200 mL), and brine (150 mL). The extracted organic layer was then dried over sodium sulfate, filtered, and evaporated under reduced pressure. The resulting red liquid was filtered through a silica gel pad and eluted with n-hexane to obtain B (8.00 g).

[0167]

[0168] Compound 1-27 (8.9 g, 39%) was synthesized by referring to the synthesis method of compound 1-9 in Example 2;

[0169] Among them, the synthesis method of 1-27-2 was referred to the synthesis of compound 1-9-0 in Example 2, and compound A-B was used instead of compound 4 in Example 2; the synthesis method of compound A-B was referred to the above steps and the synthesis of 1-13-5 in Example 4.

[0170] LC-MS (APCI): 1200.65 (M+H + )

[0171] Example 9: Preparation of Compound 1-38

[0172]

[0173] 1-20 (30.16 g, 25.5 mmol) was dissolved in DMSO-d6 (64.4 g, 765 mmol), and sodium 2-methylpropane-2-olate (1.225 g, 12.75 mmol) was added. The reaction mixture was degreased, immersed in an oil bath, and stirred overnight at 70 °C. After that, the reaction mixture was cooled, and extracted three times with ethyl acetate, 50 ml of ethyl acetate each time. The extracts were collected, dried over sodium sulfate, filtered, and evaporated. Column chromatography was used for extraction, and purification was carried out from dichloromethane / carbon black to obtain compound 1-38 (30.91 g, 95%).

[0174] LC-MS (APCI): 1235.81 (M+H + )

[0175] Example 10: Preparation of Compound 1-48

[0176]

[0177]

[0178] Compound 1-48 was prepared by referring to the synthesis methods of compounds 1-9 in Example 2 and the synthesis methods of compounds 1-13 in Example 4, and Compound 1-48 was obtained. (12.4 g, yield 87%)

[0179] LC-MS (APCI): 941.58 (M+H + )

[0180] Example 11: Preparation of Compound 1-50

[0181]

[0182] Under a nitrogen atmosphere, in a 500 ml round-bottom flask, Compound 1-16-0-5 (7.1 g, 17.4 mmol) and 3-chlorophenol (2.2 g, 17 mmol) were completely dissolved in 150 mL of xylene, then NaOtBu (2.49 g, 23.69 mmol) was added. After adding bis(tri-tert-butylphosphine)palladium(0) (0.17 g, 0.33 mmol), the mixture was heated and stirred for 3 hours. The temperature was lowered to room temperature, and the base was removed by filtration. Then the xylene was concentrated under reduced pressure and recrystallized from 250 mL of ethyl acetate to produce Compound 1-50-1 (6.1 g, yield: 70%).

[0183] LC-MS (APCI): 498.14 (M+H + )

[0184]

[0185] Compound 1-48 was prepared by referring to the synthesis methods of compounds 1-9 in Example 2 and the synthesis methods of compounds 1-13 in Example 4, and Compound 1-48 was obtained. (12.4 g, yield 90%)

[0186] LC-MS (APCI): 993.74 (M+H + )

[0187] Example 12: Preparation of Compound 2-1

[0188]

[0189] Step1. Put benzene (D6) (10 g, 119 mmol) and phthalic anhydride (21.2 g, 143 mmol) into a flask and dissolve them with dichloromethane (200 mL). After adding aluminum trichloride (19 g, 143 mmol) several times at 0 °C, stir the reactants at room temperature. After the reaction is completed, add 2 mL of distilled water to the reaction system, stir for 30 minutes, and filter the generated solid. Wash the solid with n-hexane to obtain o-benzoylbenzoic acid (D5) (23 g, yield = 85%).

[0190] LC-MS(APCI): 310.35(M+H + )。

[0191]

[0192] Step2. Add o-benzoylbenzoic acid (D5) (20 g, 90 mmol) and polyphosphoric acid (50 mL) to a flask. Heat the reaction solution to 140 °C and stir for 2 hours, then cool it to below 50 °C and slowly add distilled water. Filter the generated solid, wash and dry it with a small amount of methanol to obtain anthracene-9,10-dione (D4) (16.6 g, yield = 81%).

[0193] LC-MS(APCI): 290.14(M+H + )。

[0194]

[0195] Step3. Put 2-bromoanthraquinone (D4) (17.5 g, 60 mmol) and phenylboronic acid (13.76 g, 80 mmol) into a flask and dissolve them with toluene (150 mL). Subsequently, add Pd(PPh3) 4 (0.46 g, 0.4 mmol) and potassium carbonate (2 mol / L solution 60 mL) respectively, and heat and stir for 12 hours. After the reaction is completed, extract the reaction solution with dichloromethane and obtain 2-phenylanthraquinone (D4) (13.84 g, yield = 80%) by column chromatography

[0196] LC-MS(APCI): 289.41(M+H + )。

[0197]

[0198] Step4. Put 2-phenylanthraquinone (D4) (8.65 g, 30 mmol) into a flask and dissolve it with MeOH (100 mL). Add NaBH 4(4.56 g, 120 mmol), was stirred at room temperature for 17 hours. After the reaction was completed, the reaction solution was added to distilled water (200 mL), and the resulting solid was filtered and washed several times with distilled water. The solid was then placed back into the flask, and hydrochloric acid (1.5 mol / L, 100 mL) was added, followed by heating and stirring for 12 hours. The resulting solid was filtered, washed several times with distilled water, and dried to obtain 2-phenylanthracene-9(10H)-quinone (D4) (5.76 g, yield = 70%).

[0199] LC-MS (APCI): 275.33 (M+H + )。

[0200]

[0201] Step5. 2-Phenylanthracene-9(10H)-quinone (D4) (10.97 g, 40 mmol) was placed into a flask and dissolved in isopropanol (200 mL). Sodium borohydride (5.92 g, 160 mmol) was added in portions at 0 °C, and the mixture was stirred at room temperature for 17 hours. After the reaction was completed, the reaction solution was added to 200 mL of distilled water, and the resulting solid was filtered and washed several times with distilled water. The solid was obtained as 2-phenylanthracene (D4) (8.89 g, yield = 86%) by column chromatography.

[0202] LC-MS (APCI): 259.24 (M+H + )。

[0203]

[0204] Step6. 2-Phenylanthracene (D4) (15.50 g, 60 mmol) and N-bromosuccinimide (11.9 g, 70 mmol) were placed into a flask, dissolved in N,N-dimethylformamide (150 mL), and stirred for 2 hours. After the reaction was completed, the reaction mixture was poured into distilled water (150 mL). The resulting solid was filtered, washed with hexane, and dried to obtain 2-phenyl-9-bromoanthracene (D4) (15.6 g, yield = 88%).

[0205] LC-MS (APCI): 337.52 (M+H + )。

[0206]

[0207] Step 7. Put 2-phenyl-9-bromoanthracene (D4) (20.24 g, 60 moL) and phenylboronic acid (13.76 g, 80 moL) into a flask, and dissolve them in toluene (150 mL). Subsequently, add Pd(PPh3)4 (0.46 g, 0.4 mmol) and potassium carbonate (2 mol / L solution 60 mL) respectively, and heat and stir for 12 hours. After the reaction is completed, extract the reaction solution with dichloromethane, and obtain 2,9-diphenylanthracene (D4) (17.06 g, yield: 85.0%) by column chromatography.

[0208] LC-MS (APCI): 335.15 (M+H + )。

[0209]

[0210] Step 8. Put 2,9-diphenylanthracene (D4) (16.72 g, 50 moL) and N,N-dimethylformamide (10.2 g, 60 moL) into a flask, dissolve them in N,N-dimethylformamide (150 mL) and stir for 2 hours. After the reaction is completed, put the reaction solution into distilled water (200 mL), filter the generated solid, wash and dry it with n-hexane to obtain 9-bromo-2,10-diphenylanthracene (D4) (18.39 g, yield: 89%).

[0211] LC-MS (APCI): 413.74 (M+H + )。

[0212]

[0213] Step 9. Under nitrogen conditions, add compound 9-bromo-2,10-diphenylanthracene (D4) (4.51 g, 10.9 mmol) and 7-boronic acid-naphtho[2,1-d]benzofuran (2.9 g, 11.0 mmol) to tetrahydrofuran (300 mL), stir and reflux. Then dissolve potassium carbonate (6.0 g, 43.5 mmol) in 54 mL of water, fully stir and then add tetrakis(triphenylphosphine)palladium (0.55 g, 0.5 mmol). After reacting for 12 hours, cool to room temperature, separate the organic layer and the water layer, and distill the organic layer. Redissolve it in chloroform, wash it twice with water, separate the organic layer, add anhydrous magnesium sulfate, stir and filter, and distill the remaining liquid under reduced pressure. The concentrated compound is obtained by silica gel column chromatography to get 2-1 (4.24 g, yield 70%).

[0214] LC-MS (APCI): 551.71 (M+H + )。

[0215] Example 13: Preparation of Compound 2-2

[0216] Using 3-biphenylboronic acid instead of phenylboronic acid, compound 2-2 (11.4 g, yield 78%) was prepared by the same method as in Example 12 except for this.

[0217] LC-MS (APCI): 626.75 (M+H + )

[0218] Example 14: Preparation of compound 2-3

[0219] Using 3-(2-naphthyl)phenylboronic acid instead of phenylboronic acid, compound 2-3 (14.4 g, yield 84%) was prepared by the same method as in Example 12 except for this.

[0220] LC-MS (APCI): 676.25 (M+H + )

[0221] Example 15: Preparation of compound 2-5

[0222] Using phenyl-D5-boronic acid instead of phenylboronic acid, compound 2-5 (10.4 g, yield 69%) was prepared by the same method as in Example 12 except for this.

[0223] LC-MS (APCI): 556.72 (M+H + )

[0224] Example 16: Preparation of compound 2-7

[0225]

[0226] (3-Bromophenyl-2,4,5,6-d4)boronic acid (10 g, 48 mmol) and 2-naphthaleneboronic acid (8.4 g, 48 mmol) were placed in a flask and dissolved in toluene (100 mL). Subsequently, Pd(PPh 3 )(0.46 g, 0.4 mmol) and potassium carbonate (2 mol / L solution 60 mL) were added respectively, and the mixture was heated and stirred for 12 hours. After the reaction was completed, the reaction solution was extracted with dichloromethane, and (3-(naphthalen-2-yl)phenyl-2,4,5,6-d4)boronic acid (9.85 g, yield: 80%) was obtained by column chromatography. 4 (0.46 g, 0.4 mmol) and potassium carbonate (2 mol / L solution 60 mL) were added respectively, and the mixture was heated and stirred for 12 hours. After the reaction was completed, the reaction solution was extracted with dichloromethane, and (3-(naphthalen-2-yl)phenyl-2,4,5,6-d4)boronic acid (9.85 g, yield: 80%) was obtained by column chromatography.

[0227] LC-MS (APCI): 253.65 (M+H + )

[0228] Compound 2-7 was prepared by the same method as in Example 12, except that (3-(naphthalen-2-yl)phenyl-2,4,5,6-d4)boronic acid synthesized above was used instead of benzeneboronic acid. (6.4 g, yield 87%)

[0229] LC-MS (APCI): 681.44 (M+H + )

[0230] Example 17: Preparation of Compound 2-9

[0231] Compound 2-9 was prepared by the same method as in Example 12, except that 1-naphthaleneboronic acid was used instead of benzeneboronic acid. (9.4 g, yield 67%)

[0232] LC-MS (APCI): 601.47 (M+H + )

[0233] Example 18: Preparation of Compound 2-12

[0234] Compound 2-12 was prepared by the same method as in Example 12, except that 2-phenyl-6-naphthaleneboronic acid was used instead of benzeneboronic acid. (11.6 g, yield 75%)

[0235] LC-MS (APCI): 677.57 (M+H + )

[0236] Example 19: Preparation of Compound 2-13

[0237] Compound 2-13 was prepared by the same method as in Example 12, except that (naphthalen-1-yl-D7)boronic acid was used instead of benzeneboronic acid. (9.7 g, yield 78%)

[0238] LC-MS (APCI): 608.72 (M+H + )

[0239] Example 20: Preparation of Compound 2-24

[0240] Compound 2-24 was prepared by the same method as in Example 12, except that dibenzofuran-1-boronic acid was used instead of 7-borono-naphtho[2,1-d]benzofuran, and (3-(naphthalen-2-yl)phenyl-2,4,5,6-d4)boronic acid in Example 16 was used instead of benzeneboronic acid. (12.4 g, yield 89%)

[0241] LC-MS (APCI): 631.55 (M+H + )

[0242] Device Preparation Example:

[0243] This embodiment provides an organic electroluminescent device, as Figure 1 shown, including a first electrode layer 1, a hole injection layer 2, a hole transport layer 3, a light-emitting auxiliary layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a second electrode layer 8.

[0244] In the present invention, a hole injection material is evaporated on the surface or anode of an ITO glass with a light-emitting area of 2 mm × 2 mm to form a hole injection layer (HIL) with a thickness of 5 - 100 nm and a hole transport layer (HTL) with a thickness of 5 - 200 nm; secondly, on the above-mentioned hole transport layer, BP is vacuum deposited with a thickness of 5 - 20 nm to form a light-emitting auxiliary layer; subsequently, a light-emitting layer (EML) with a thickness of 10 - 100 nm (which may contain the compound described in the present invention) is formed on BP, an electron transport layer (ETL) with a thickness of 20 - 200 nm, an electron injection layer with a thickness of 0.1 - 10 nm, and a cathode with a thickness of 50 - 200 nm are formed; if necessary, an electron blocking layer (EBL) is added between the HTL and EML layers to fabricate an OLED device. And the OLED is tested by standard methods. The device materials involved in the present invention can be obtained by known synthesis methods unless otherwise specified.

[0245] Comparative Example 1:

[0246] The structure of Comparative Example 1 of the device provided by the present invention is specifically: ITO / HTL: HAT-CN (10 nm, 97:3) / HT (120 nm) / BP (10 nm) / Compound 2-1: BD-1 (97:3 v / v%) (30 nm) / ET and Liq (35 nm, 1:1) / LiF (0.2 nm) / Al (150 nm).

[0247] The structural formulas of the materials involved are as follows:

[0248]

[0249] Specifically, the test conditions for efficiency are: the device efficiency is tested at a current density of 15 mA / cm 2 , taking the efficiency of Comparative Example 1 as 100%, the efficiency of other device embodiments relative to Comparative Example 1 is obtained.

[0250] The test conditions for lifespan are: a voltage is applied to the obtained organic electroluminescent element so that the current density reaches 30 mA / cm 2 , and the time until the luminance becomes 95% of the initial luminance (LT95 (unit: hours)) is measured. Taking the time until the initial luminance of Comparative Example 1 becomes 95% as 100%, the lifespan of other device embodiments relative to Comparative Example 1 is obtained.

[0251] Device Embodiment:

[0252] Device Examples 1 - 11 were prepared respectively using a structure similar to that of Comparative Example 1, with the only difference being that BD-1 in Comparative Example 1 was replaced with Compound 1-1, 1-9, 1-7, 1-13, 1-16, 1-20, 1-26, 1-27, 1-38, 1-48, and 1-50 respectively. The testing method for the light-emitting characteristics of each of the above-prepared device examples was the same as that of Comparative Example 1, and the specific data are shown in Table 1.

[0253] Table 1. Table of Electroluminescent Characteristics of Organic Light-Emitting Devices

[0254] Device Host material Doping material Efficiency (%) Lifetime (%) Comparative Example 1 2-1 BD-1 100 100 Device Example 1 2-1 1-1 105 115 Device Example 2 2-1 1-9 115 116 Device Example 3 2-1 1-7 107 112 Device Example 4 2-1 1-13 117 120 Device Example 5 2-1 1-16 112 119 Device Example 6 2-1 1-20 114 115 Device Example 7 2-1 1-26 108 118 Device Example 8 2-1 1-27 109 118 Device Example 9 2-1 1-38 118 112 Device Example 10 2-1 1-48 111 116 Device Example 11 2-1 1-50 110 119

[0255] As can be seen from Table 1, compared with Comparative Example 1, Device Examples 1 - 11 prepared in this application showed good performance improvements in both efficiency and device lifetime.

[0256] Device Examples 12 - 18 and Comparative Examples 2 - 4 were prepared respectively using a structure similar to that of Comparative Example 1, with the only difference being that the light-emitting layer materials in Comparative Example 1 were replaced with the materials in Table 2, and the ratio of the host material to the doping material was the same as that in Comparative Example 1. The testing method for the light-emitting characteristics of each of the above-prepared device examples and comparative examples was the same as that of Comparative Example 1, and the specific data are shown in Table 2.

[0257] Table 2. Table of Electroluminescent Characteristics of Organic Light-Emitting Devices with Combined Materials

[0258]

[0259]

[0260] As can be seen from Table 2, when other host materials were used, the devices prepared with the boron nitride compounds provided by the present invention showed a slight decrease in efficiency and lifetime, but still had a relatively high improvement compared with Comparative Example 2, indicating that the boron nitride compounds provided by the present invention have excellent light-emitting characteristics, and after applying them together with specific host materials to organic electroluminescent devices, the performance of the devices has achieved an unexpected improvement. It is an organic light-emitting functional material with good performance and is expected to be commercially promoted and applied.

[0261] Although the present invention has been described in conjunction with the embodiments, the present invention is not limited to the above embodiments. It should be understood that, under the guidance of the inventive concept of the present invention, those skilled in the art can make various modifications and improvements, and the appended claims define the scope of the present invention. Obviously, the above embodiments are merely examples given for clear illustration and are not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or variations can be made based on the above description. It is not necessary and impossible to enumerate all the implementation manners here. And the obvious changes or variations derived therefrom still fall within the protection scope of the present invention.

Claims

1. A boron nitride compound, characterized in that, the boron nitride compound has a general formula structure as shown in Formula I: In Formula I, m is an integer between 0 and 9, and n is an integer between 0 and 5; R 1 、R 2 each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 heterocycloalkyl, substituted or unsubstituted C3-C10 cycloalkenyl, substituted or unsubstituted C3-C10 heterocycloalkenyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C60 aryl; When m > 1, multiple Rs 1 are each independent, identical to or different from one another, and the substitution positions of the multiple Rs 1 are different; When n > 1, multiple Rs 2 are each independently the same as or different from one another, and the substitution positions of the multiple Rs 2 are different; L is selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, the Q group is selected from any one of the structures shown in Formula II-1 to Formula II-12: wherein, X is O or S; multiple r's are the same or different from each other, and each independently is selected from an integer between 0 and 5; R 3 ,R 5 -R 8 each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 heterocycloalkyl, substituted or unsubstituted C3-C10 cycloalkenyl, substituted or unsubstituted C3-C10 heterocycloalkenyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C60 aryl; Multiple Rs 3 When present, multiple Rs 3 are each independently the same as or different from one another, and the substitution positions of multiple Rs 3 are different; Multiple Rs 5 When present, multiple Rs 5 are each independently the same as or different from one another, and the substitution positions of multiple Rs 5 are different; Multiple Rs 6 When present, multiple Rs 6 are each independently the same as or different from one another, and the substitution positions of multiple Rs 6 are different; Multiple Rs 7 When present, multiple Rs 7 are each independently the same as or different from one another, and the substitution positions of multiple Rs 7 are different; Multiple Rs 8 When present, multiple Rs 8 are each independently the same as or different from one another, and the substitution positions of multiple Rs 8 are different; the substituents in the "substituted or unsubstituted" are each independently selected from deuterium, halogen, cyano group, silyl group, C1-C10 alkyl group, C3-C10 cycloalkyl group, C1-C10 alkoxy group, C6-C30 aryl group, C3-C30 heteroaryl group, the heteroatoms in the heteroarylene group, heterocycloalkyl group, heterocycloalkenyl group, and heteroaryl group are each independently at least one of N, O, S, Si, and P.

2. The boron nitride compound according to claim 1, characterized in that, Said R 3 , R 5 -R 8 are each independently selected from the following groups: hydrogen, deuterium, halogen, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted n-propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted isobutyl, substituted or unsubstituted sec-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted perylenyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted quinolinyl, substituted or unsubstituted isoquinolinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted furyl, substituted or unsubstituted thienyl, substituted or unsubstituted indenyl, substituted or unsubstituted indolyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted carbolinyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted phenanthrolinyl, substituted or unsubstituted benzoquinolinyl, substituted or unsubstituted benzoisoquinolinyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted benzopyrazolyl, substituted or unsubstituted phthalazinyl.

3. The boron nitride compound according to claim 1, characterized in that, The described R 3 , R 5 -R 8 are each independently selected from hydrogen, deuterium, tert-butyl, phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, fluoranthenyl, pyrenyl, perylenyl, triphenylenyl, and combinations of two or more of the above groups.

4. The boron nitride compound according to claim 1, characterized in that, the boron nitride compound is selected from any one of the following chemical structures:

5. An organic electroluminescent device, characterized in that, the organic electroluminescent device includes: a substrate layer; a first electrode, which is on the substrate; an organic light-emitting functional layer, which is on the first electrode; a second electrode, which is on the organic light-emitting functional layer; the organic light-emitting functional layer includes a light-emitting layer; the light-emitting layer includes the boron nitride compound according to any one of claims 1-4.

6. The organic electroluminescent device according to claim 5, characterized in that, the light-emitting layer further contains a host material, and the host material includes an anthracene compound, and the anthracene compound has a structure as shown in Formula II or III below: In Formula II and Formula III, L 1 is a single bond, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Ar 1 selected from hydrogen, a substituted or unsubstituted C6-C60 aryl group, or a substituted or unsubstituted C6-C60 heteroaryl group; R 9 selected from hydrogen, deuterium, substituted or unsubstituted C6-C60 aryl groups.

7. The organic electroluminescent device according to claim 6, characterized in that, L 1 is a single bond, phenylene, deuterated phenylene, naphthylene, deuterated naphthylene; Ar 1 selected from hydrogen, phenyl, biphenyl, deuterated phenyl, naphthyl, deuterated naphthyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl; R 9 Selected from hydrogen, deuterium, phenyl, naphthyl, biphenyl, deuterated phenyl, deuterated naphthyl, deuterated biphenyl.

8. The organic electroluminescent device according to claim 6, characterized in that, The said L 1 Selected from any one of the chemical structures shown below:

9. The organic electroluminescent device according to claim 6, characterized in that, the anthracene compound is selected from any one of the following chemical structures:

10. A display or lighting device, characterized in that, the device includes the organic electroluminescent device according to any one of claims 5-9.

Images