Organic compound based on anthracene structure and preparation method and application thereof

Abstract

The invention belongs to the technical field of semiconductors, and particularly relates to an organic compound based on an anthracene structure and a preparation method and application thereof. According to the organic compound based on the anthracene structure, anthracene is used as a framework, the HOMO energy level is adjusted through modification of other aromatic groups, the structure stereoscopicity is effectively improved, the molecular overall steric hindrance is large, rotation is not prone to occurring, the glass transition temperature, molecular thermal stability and carrier mobility are high, the HOMO energy level is appropriate, meanwhile, the high singlet energy level is achieved, and the organic compound can be applied to the field of organic light emitting devices. A suitable triplet state energy level (T1) and good reversible oxidation-reduction characteristics are provided. The organic compound can be used as a host material, has a good triplet state-triplet state coupling effect, can utilize triplet state exciton luminescence, and significantly improves the luminous efficiency and prolongs the service life of an OLED device.

Description

Technical Field

[0001] The present invention belongs to the field of semiconductor technology, and in particular relates to an organic compound based on anthracene structure and a preparation method and application thereof. Background Art

[0002] At present, organic electroluminescent (OLED: Organic Light Emission Diodes) devices have been used in products such as smart phones and tablets, and may be used in large-size products such as TVs in the future. However, the performance of existing OLED devices still cannot meet actual needs. For example, the performance such as luminous efficiency and service life needs to be improved. The OLED optoelectronic functional materials used in OLED devices are divided into two categories: charge injection transport materials and luminescent materials. Among them, charge injection transport materials are further divided into four categories: electron injection transport materials, electron blocking materials, hole injection transport materials and hole blocking materials. The luminescent materials are further divided into two categories: main luminescent materials and doped materials. High-performance OLED light-emitting devices naturally require OLED optoelectronic functional materials to have good optoelectronic properties.

[0003] OLED optoelectronic functional materials include more than two film layers, and the optoelectronic functional materials used in OLED devices include at least hole injection materials, hole transport materials, luminescent materials and electron transport materials, with a wide variety of material types and combinations. In addition, for the combination of OLED devices with different structures, the optoelectronic functional materials used have strong selectivity, and the performance of the same material in devices with different structures varies, or even completely different. Therefore, in view of the industrial application requirements of OLED devices, as well as the different functional film layers and optoelectronic characteristics of OLED devices, it is necessary to use suitable and high-performance OLED functional materials or material combinations to achieve the comprehensive characteristics of high efficiency, long life and low voltage of the device.

[0004] As far as the current industry demand for OLED display lighting is concerned, the performance of OLED materials is far from enough. For example, the luminous efficiency is low and the lifespan is short, which lags behind the requirements of panel manufacturers. Summary of the invention

[0005] The purpose of the present invention is to provide an organic compound based on anthracene structure and a preparation method and application thereof. The organic compound based on anthracene structure provided by the present invention can significantly improve the luminous efficiency and service life of OLED devices.

[0006] In order to achieve the above object, the present invention provides the following technical solutions:

[0007] The present invention provides an anthracene-based organic compound, the structure of which is shown in Formula X:

[0008]

[0009] In formula X, Ar1 and Ar2 are independently C6 to C 30 Aryl, substituted C6~C 30 Aryl, C5~C 30 Heteroaryl or substituted C5~C 30 Heteroaryl; n is 0, 1 or 2; R1 is a deuterium atom, C6~C 30 Aryl, substituted C6~C 30 One or more of aryl, amino and substituted amino (the above R1 site drawing method indicates that R1 is located at any substitutable site on the anthracene ring); R2 is a hydrogen atom, a deuterium atom, a C6-C 30 Aryl, substituted C6~C 30 Aryl, a structure represented by formula Y or a structure represented by formula Z (* represents a connection site);

[0010]

[0011] Formula Y or Formula Z is connected to Formula X by a C1-C2 bond, a C2-C3 bond or a C3-C4 bond; wherein X in Formula Z is O, S or N-Ar3, and Ar3 is C6-C 30 Aryl, substituted C6~C 30 Aryl, C5~C 30 Heteroaryl or substituted C5~C 30 Heteroaryl.

[0012] Preferably, among Ar1, Ar2 and Ar3, the C6 to C 30 The aryl group includes phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, phenanthrenyl or pyrenyl; the substituted C6~C 30 The aryl group includes substituted phenyl, substituted biphenyl, substituted naphthyl, substituted 9,9-dimethylfluorenyl, substituted phenanthrenyl or substituted pyrenyl; the substituted C6-C 30 The substituents of the aromatic group include deuterium atoms, methoxy groups, cyano groups, halogen atoms, C1-C 20 Alkyl, C3~C 20 Cycloalkyl, C6~C 30 Aryl or 5-30 membered heteroaryl containing heteroatoms; the C5-C 30 The heteroaryl group includes dibenzofuranyl, dibenzothiophenyl, carbazolyl, pyridyl, pyrimidinyl or isoquinolyl; the substituted C5~C 30 The heteroaryl group includes a substituted dibenzofuranyl group, a substituted dibenzothiophenyl group, a substituted carbazolyl group, a substituted pyridyl group, a substituted pyrimidyl group or a substituted isoquinolyl group; the substituted C5-C 30 Substituents for the heteroaryl group include deuterium atoms, methoxy groups, cyano groups, halogen atoms, C1-C 20 Alkyl, C3~C20 Cycloalkyl, C6~C 30 Aryl or 5-30 membered heteroaryl containing heteroatoms.

[0013] Preferably, in R1, the C6 to C 30 The aryl group includes phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, spirofluorenyl, anthracenyl, phenanthrenyl or pyrenyl; the substituted C6-C 30 The aryl group includes substituted phenyl, substituted biphenyl, substituted naphthyl, substituted 9,9-dimethylfluorenyl, substituted spirofluorenyl, substituted anthracenyl, substituted phenanthrenyl or substituted pyrenyl; the substituted C6-C 30 The substituents of the aryl group include deuterium atoms, cyano groups, methoxy groups, halogen atoms, C1-C5 alkyl groups, C6-C 30 One or more of an aryl group and a 5- to 30-membered heterocyclic group; the substituent of the substituted amino group includes a deuterium atom, a cyano group, a methoxy group, a halogen atom, a C1-C5 alkyl group, a C6-C 30 One or more of an aryl group and a 5- to 30-membered heterocyclic group.

[0014] Preferably, in R2, the C6 to C 30 The aryl group includes phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, phenanthrenyl or pyrenyl; the substituted C6~C 30 The aryl group includes substituted phenyl, substituted biphenyl, substituted naphthyl, substituted 9,9-dimethylfluorenyl, substituted phenanthrenyl or substituted pyrenyl; the substituted C6-C 30 The substituents of the aromatic group include deuterium atoms, methoxy groups, cyano groups, halogen atoms, C1-C 20 Alkyl, C3~C 20 Cycloalkyl, C6~C 30 Aryl or 5-30 membered heteroaryl containing heteroatoms.

[0015] Preferably, the anthracene-based organic compound is one of Formula 1 to Formula 238.

[0016] The present invention also provides a method for preparing the anthracene-based organic compound described in the above scheme, comprising the following steps:

[0017] (1) Compound A, compound B, a palladium catalyst, a base and a solvent are mixed to perform a first Suzuki cross-coupling reaction to obtain a compound C, the structure of which is shown in Formula C:

[0018]

[0019] The structure of the compound A is shown in formula A:

[0020]

[0021] In formula A, V is chlorine, bromine or iodine;

[0022] The structure of the compound B is shown in Formula B:

[0023]

[0024] (2) Compound C is mixed with compound D, a good solvent, a palladium catalyst, a base and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl to carry out a second Suzuki cross-coupling reaction to obtain compound E, the structure of which is shown in Formula E:

[0025]

[0026] n and R1 in Formula A, Formula C and Formula E are the same as n and R1 in Formula X;

[0027] The structure of the compound D is shown in Formula D:

[0028]

[0029] Ar1 in Formula D and Formula E is the same as Ar1 in Formula X, and W in Formula D is chlorine, bromine or iodine;

[0030] (3) Mixing the compound E and the compound F, a composite solvent, a palladium catalyst, a base and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl to perform a third Suzuki cross-coupling reaction to obtain the anthracene-based organic compound; the structure of the compound F is shown in Formula F:

[0031]

[0032] In formula F, Ar2 and R2 are the same as Ar2 and R2 in formula X, and G is chlorine, bromine or iodine;

[0033] There is no requirement for the chronological order of step (2) and step (3).

[0034] Preferably, the second Suzuki cross-coupling reaction is carried out in a protective atmosphere and microwave conditions; the temperature of the second Suzuki cross-coupling reaction is 80-120° C., and the insulation time is 3-24 h.

[0035] The present invention also provides the use of the organic compound based on anthracene structure described in the above scheme or the organic compound based on anthracene structure obtained by the preparation method described in the above scheme in an organic electroluminescent device.

[0036] The present invention also provides an organic electroluminescent device, comprising one or more functional layers, wherein the functional layers contain the organic compound based on anthracene structure described in the above scheme or the organic compound based on anthracene structure obtained by the preparation method described in the above scheme.

[0037] The present invention also provides the application of the organic electroluminescent device described in the above solution in the field of lighting or display elements.

[0038] The present invention provides an organic compound based on anthracene structure. The organic compound based on anthracene structure provided by the present invention uses anthracene as a skeleton, and adjusts the HOMO energy level through the modification of other aromatic groups, effectively improves the stereoscopic structure, has large overall steric hindrance of the molecule, is not easy to rotate, has a high glass transition temperature, molecular thermal stability and carrier mobility, has a suitable HOMO energy level, and has a high singlet energy level, a suitable triplet energy level (T1), and good reversible redox characteristics. The organic compound of the present invention can be used as a main material, has a good triplet-triplet coupling effect, can utilize triplet excitons to emit light, and significantly improves the luminous efficiency and service life of OLED devices.

[0039] The present invention also provides a method for preparing the organic compound based on anthracene structure described in the above scheme. The preparation method provided by the present invention has simple steps, convenient operation, high feasibility, and is suitable for large-scale production.

[0040] The present invention also provides the application of the organic compound based on anthracene structure described in the above scheme in an organic electroluminescent device. The organic compound based on anthracene structure provided by the present invention is used in OLED devices, which can effectively improve the luminous efficiency and service life of OLED devices, and the current efficiency, power efficiency and external quantum efficiency are greatly improved, the application effect is good, and the industrialization prospect is broad.

[0041] The present invention also provides an organic electroluminescent device, comprising one or more functional layers, wherein the functional layers contain the organic compound based on anthracene structure described in the above scheme or the organic compound based on anthracene structure obtained by the preparation method described in the above scheme. The organic electroluminescent device provided by the present invention has high luminous efficiency, long service life, and broad industrialization prospects.

[0042] The present invention also provides the application of the organic electroluminescent device described in the above solution in the field of lighting or display elements. The organic electroluminescent device provided by the present invention is suitable for use in lighting or display elements, and has good effects. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0044] Figure 1 The process flow chart of the preparation method of the organic compound based on anthracene structure of the present invention;

[0045] Figure 2 is a process flow chart of the preparation method of compound F-1;

[0046] Figure 3 is a process flow chart of the preparation method of compound F-2;

[0047] Figure 4 is a process flow chart of the preparation method of compound F-3;

[0048] Figure 5 is a process flow chart of the preparation method of compound F-4;

[0049] Figure 6 is a process flow chart of the preparation method of compound F-5;

[0050] Figure 7 is a process flow chart of the preparation method of compound F-6;

[0051] Figure 8 is a process flow chart of the preparation method of compound F-7;

[0052] Fig. 9 is a process flow chart of the preparation method of compound F-8;

[0053] Fig.10 is a process flow chart of the preparation method of compound D-1;

[0054] Fig.11 A schematic diagram of the structure of an organic electroluminescent device prepared in an application example of the present invention;

[0055] Figure numerals: 1-substrate layer, 2-anode layer, 3-hole injection layer, 4-hole transport layer, 5-electron blocking layer, 6-light-emitting layer, 7-electron transport layer, 8-electron injection layer, 9-cathode layer, 10-light extraction layer. DETAILED DESCRIPTION

[0056] The present invention provides an anthracene-based organic compound, the structure of which is shown in Formula X:

[0057]

[0058] In formula X, Ar1 and Ar2 are independently C6 to C 30 Aryl, substituted C6~C 30 Aryl, C5~C 30 Heteroaryl or substituted C5~C 30 Heteroaryl; n is 0, 1 or 2; R1 is a deuterium atom, C6~C 30 Aryl, substituted C6~C 30 One or more of aryl, amino and substituted amino (the above R1 site drawing method indicates that R1 is located at any substitutable site on the anthracene ring); R2 is a hydrogen atom, a deuterium atom, a C6-C 30 Aryl, substituted C6~C 30 Aryl, a structure represented by formula Y or a structure represented by formula Z (* represents a connection site);

[0059]

[0060] Formula Y or Formula Z is connected to Formula X by a C1-C2 bond, a C2-C3 bond or a C3-C4 bond; wherein X in Formula Z is O, S or N-Ar3, and Ar3 is C6-C 30 Aryl, substituted C6~C 30 Aryl, C5~C 30 Heteroaryl or substituted C5~C 30 Heteroaryl.

[0061] In the present invention, among Ar1 and Ar2, the C6 to C 30 The aryl group preferably includes a phenyl group, a biphenyl group, a naphthyl group, a 9,9-dimethylfluorenyl group, a phenanthryl group or a pyrenyl group.

[0062] In the present invention, among Ar1 and Ar2, the substituted C6 to C 30 The aryl group preferably includes a substituted phenyl group, a substituted biphenyl group, a substituted naphthyl group, a substituted 9,9-dimethylfluorenyl group, a substituted phenanthrenyl group or a substituted pyrenyl group.

[0063] In the present invention, among Ar1 and Ar2, the substituted C6 to C 30 The substituents of the aryl group preferably include a deuterium atom, a methoxy group, a cyano group, a halogen atom, a C1-C 20 Alkyl, C3~C 20 Cycloalkyl, C6~C 30 aryl or 5-30 membered heteroaryl containing heteroatoms; the halogen atom is preferably a fluorine atom; the C1-C 20 The alkyl group preferably includes one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl and n-hexyl; the C3-C 20The cycloalkyl group preferably includes one or more of cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane and cyclodecane; the C6-C 30 The aryl group preferably includes phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, spirofluorenyl, anthracenyl, phenanthryl or pyrene; the biphenyl group is preferably dibiphenyl; the heteroatoms in the 5- to 30-membered heteroaryl group containing heteroatoms preferably include one or more of oxygen atoms, sulfur atoms and nitrogen atoms, and the number of heteroatoms is preferably more than 1. The 5- to 30-membered heteroaryl group preferably includes one or more of naphthyridinyl, furanyl, dibenzofuranyl, carbazolyl and pyridyl.

[0064] In the present invention, among Ar1 and Ar2, the C5 to C 30 The heteroaryl group preferably includes a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, a pyridyl group, a pyrimidinyl group or an isoquinolinyl group.

[0065] In the present invention, among Ar1 and Ar2, the substituted C5 to C 30 The heteroaryl group preferably includes a substituted dibenzofuranyl group, a substituted dibenzothiophenyl group, a substituted carbazolyl group, a substituted pyridyl group, a substituted pyrimidinyl group or a substituted isoquinolinyl group.

[0066] In the present invention, among Ar1 and Ar2, the substituted C5 to C 30 The substituents of the heteroaryl group preferably include a deuterium atom, a methoxy group, a cyano group, a halogen atom, a C1-C 20 Alkyl, C3~C 20 Cycloalkyl, C6~C 30 aryl or 5-30 membered heteroaryl containing heteroatoms; the halogen atom is preferably a fluorine atom; the C1-C 20 The alkyl group preferably includes one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl and n-hexyl; the C3-C 20 The cycloalkyl group preferably includes one or more of cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane and cyclodecane; the C6-C 30 The aryl group preferably includes phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, spirofluorenyl, anthracenyl, phenanthryl or pyrene; the biphenyl group is preferably dibiphenyl; the heteroatoms in the 5- to 30-membered heteroaryl group containing heteroatoms preferably include one or more of oxygen atoms, sulfur atoms and nitrogen atoms, and the number of heteroatoms is preferably more than 1. The 5- to 30-membered heteroaryl group preferably includes one or more of naphthyridinyl, furanyl, dibenzofuranyl, carbazolyl and pyridyl.

[0067] In the present invention, Ar1 and Ar2 are independently more preferably:

[0068] In the present invention, in R1, the C6 to C 30 The aryl group preferably includes phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, spirofluorenyl, anthracenyl, phenanthrenyl or pyrenyl; the biphenyl group is preferably dibiphenyl.

[0069] In the present invention, in R1, the substituted C6 to C 30 The aryl group preferably includes a substituted phenyl group, a substituted biphenyl group, a substituted naphthyl group, a substituted 9,9-dimethylfluorenyl group, a substituted spirofluorenyl group, a substituted anthracenyl group, a substituted phenanthrenyl group or a substituted pyrenyl group; the substituted biphenyl group is preferably a substituted dibiphenyl group.

[0070] In the present invention, in R1, the substituted C6 to C 30 The substituents of the aryl group preferably include a deuterium atom, a cyano group, a methoxy group, a halogen atom, a C1-C5 alkyl group, a C6-C 30 The halogen atom is preferably a fluorine atom; the C1-C5 alkyl group preferably includes one or more of a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group and a pentyl group; the C6-C 30 The aryl group preferably includes one or more of phenyl, naphthyl and biphenyl; the biphenyl group preferably includes one or more of diphenyl and terphenyl; the 5-30 membered heterocyclic group preferably includes one or more of naphthyridinyl, furyl, dibenzofuranyl, carbazolyl and pyridyl.

[0071] In the present invention, the substituent of the substituted amino group in R1 preferably includes a deuterium atom, a cyano group, a methoxy group, a halogen atom, a C1-C5 alkyl group, a C6-C 30 The halogen atom is preferably a fluorine atom; the C1-C5 alkyl group preferably includes one or more of a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group and a pentyl group; the C6-C 30 The aryl group preferably includes one or more of phenyl, naphthyl and biphenyl; the biphenyl group preferably includes one or more of diphenyl and terphenyl; the 5-30 membered heterocyclic group preferably includes one or more of naphthyridinyl, furyl, dibenzofuranyl, carbazolyl and pyridyl.

[0072] In the present invention, R1 is more preferably: a hydrogen atom,

[0073] In the present invention, in R2, the C6 to C 30 The aryl group preferably includes a phenyl group, a biphenyl group, a naphthyl group, a 9,9-dimethylfluorenyl group, a phenanthryl group or a pyrenyl group.

[0074] In the present invention, in R2, the substituted C6 to C 30 The aryl group preferably includes a substituted phenyl group, a substituted biphenyl group, a substituted naphthyl group, a substituted 9,9-dimethylfluorenyl group, a substituted phenanthrenyl group or a substituted pyrenyl group.

[0075] In the present invention, in R2, the substituted C6 to C 30 The substituents of the aryl group preferably include a deuterium atom, a methoxy group, a cyano group, a halogen atom, a C1-C 20 Alkyl, C3~C 20 Cycloalkyl, C6~C 30 aryl or 5-30 membered heteroaryl containing heteroatoms; the halogen atom preferably includes one or more of fluorine, chlorine, bromine and iodine; the C1-C 20 The alkyl group preferably includes one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl and n-hexyl; the C3-C 20 The cycloalkyl group preferably includes one or more of cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane and cyclodecane; the C6-C 30 The aryl group preferably includes phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, spirofluorenyl, anthracenyl, phenanthryl or pyrene; the biphenyl group is preferably dibiphenyl; the heteroatoms in the 5- to 30-membered heteroaryl group containing heteroatoms preferably include one or more of oxygen atoms, sulfur atoms and nitrogen atoms, and the number of heteroatoms is preferably more than 1. The 5- to 30-membered heteroaryl group preferably includes one or more of naphthyridinyl, furanyl, dibenzofuranyl, carbazolyl and pyridyl.

[0076] In the present invention, the R2 is more preferably:

[0077]

[0078] In the present invention, Ar3 in Formula Z, the C6~C 30 The aryl group preferably includes a phenyl group, a biphenyl group, a naphthyl group, a 9,9-dimethylfluorenyl group, a phenanthryl group or a pyrenyl group.

[0079] In the present invention, Ar3 in Formula Z, the substituted C6~C 30 The aryl group preferably includes a substituted phenyl group, a substituted biphenyl group, a substituted naphthyl group, a substituted 9,9-dimethylfluorenyl group, a substituted phenanthrenyl group or a substituted pyrenyl group.

[0080] In the present invention, Ar3 in Formula Z, the substituted C6~C 30 The substituents of the aryl group preferably include a deuterium atom, a methoxy group, a cyano group, a halogen atom, a C1-C 20 Alkyl, C3~C 20 Cycloalkyl, C6~C 30aryl or 5-30 membered heteroaryl containing heteroatoms; the halogen atom preferably includes one or more of fluorine, chlorine, bromine and iodine; the C1-C 20 The alkyl group preferably includes one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl and n-hexyl; the C3-C 20 The cycloalkyl group preferably includes one or more of cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane and cyclodecane; the C6-C 30 The aryl group preferably includes phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, spirofluorenyl, anthracenyl, phenanthryl or pyrene; the biphenyl group is preferably dibiphenyl; the heteroatoms in the 5- to 30-membered heteroaryl group containing heteroatoms preferably include one or more of oxygen atoms, sulfur atoms and nitrogen atoms, and the number of heteroatoms is preferably more than 1. The 5- to 30-membered heteroaryl group preferably includes one or more of naphthyridinyl, furanyl, dibenzofuranyl, carbazolyl and pyridyl.

[0081] In the present invention, Ar3 in Formula Z, the C5 to C 30 The heteroaryl group preferably includes a dibenzofuranyl group, a dibenzothiophenyl group, a carbazolyl group, a pyridyl group, a pyrimidinyl group or an isoquinolinyl group.

[0082] In the present invention, Ar3 in Formula Z, the substituted C5~C 30 The heteroaryl group preferably includes a substituted dibenzofuranyl group, a substituted dibenzothiophenyl group, a substituted carbazolyl group, a substituted pyridyl group, a substituted pyrimidinyl group or a substituted isoquinolinyl group.

[0083] In the present invention, Ar3 in Formula Z, the substituted C5~C 30 The substituents of the heteroaryl group preferably include a deuterium atom, a methoxy group, a cyano group, a halogen atom, a C1-C 20 Alkyl, C3~C 20 Cycloalkyl, C6~C 30 aryl or 5-30 membered heteroaryl containing heteroatoms; the halogen atom preferably includes one or more of fluorine, chlorine, bromine and iodine; the C1-C 20 The alkyl group preferably includes one or more of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl and n-hexyl; the C3-C 20 The cycloalkyl group preferably includes one or more of cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane and cyclodecane; the C6-C 30The aryl group preferably includes phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, spirofluorenyl, anthracenyl, phenanthryl or pyrene; the biphenyl group is preferably dibiphenyl; the heteroatoms in the 5- to 30-membered heteroaryl group containing heteroatoms preferably include one or more of oxygen atoms, sulfur atoms and nitrogen atoms, and the number of heteroatoms is preferably more than 1. The 5- to 30-membered heteroaryl group preferably includes one or more of naphthyridinyl, furanyl, dibenzofuranyl, carbazolyl and pyridyl.

[0084] In the present invention, the structure represented by formula Z is more preferably:

[0085]

[0086] In a specific embodiment of the present invention, the organic compound based on anthracene structure is preferably one of Formula 1 to Formula 238:

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093] The present invention also provides a method for preparing the anthracene-based organic compound described in the above scheme, comprising the following steps:

[0094] (1) Compound A, compound B, a palladium catalyst, a base and a solvent are mixed to perform a first Suzuki cross-coupling reaction to obtain a compound C, the structure of which is shown in Formula C:

[0095]

[0096] The structure of the compound A is shown in formula A:

[0097]

[0098] In formula A, V is chlorine, bromine or iodine;

[0099] The structure of the compound B is shown in Formula B:

[0100]

[0101] (2) Compound C is mixed with compound D, a good solvent, a palladium catalyst, a base and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl to carry out a second Suzuki cross-coupling reaction to obtain compound E, the structure of which is shown in Formula E:

[0102]

[0103] n and R1 in Formula A, Formula C and Formula E are the same as n and R1 in Formula X;

[0104] The structure of the compound D is shown in Formula D:

[0105]

[0106] Ar1 in Formula D and Formula E is the same as Ar1 in Formula X, and W in Formula D is chlorine, bromine or iodine;

[0107] (3) Mixing the compound E and the compound F, a composite solvent, a palladium catalyst, a base and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl to perform a third Suzuki cross-coupling reaction to obtain the anthracene-based organic compound; the structure of the compound F is shown in Formula F:

[0108]

[0109] In formula F, Ar2 and R2 are the same as Ar2 and R2 in formula X, and G is chlorine, bromine or iodine;

[0110] There is no requirement for the time sequence of steps (2) and (3).

[0111] In the present invention, compound A, compound B, a palladium catalyst (referred to as the first palladium catalyst), a base (referred to as the first base) and a solvent (referred to as the first solvent) are mixed to carry out a first Suzuki cross-coupling reaction to obtain compound C. In the present invention, the first palladium catalyst is preferably Pd(dppf)Cl2.

[0112] In the present invention, the first base preferably includes one or more of potassium acetate, sodium carbonate, cesium carbonate, potassium carbonate and sodium tert-butoxide.

[0113] In the present invention, the first solvent preferably includes one or more of 1,4-dioxane, toluene and xylene.

[0114] In the present invention, the molar ratio of compound A to compound B is preferably 10-12:10-12, more preferably 10-11:11-12, and further preferably 10.0:12.0.

[0115] In the present invention, the molar ratio of the compound A to the first palladium catalyst is preferably 1-1.2:0.02-0.04, more preferably 1-1.1:0.02-0.03, and further preferably 1:0.02.

[0116] In the present invention, the molar ratio of the compound A to the first base is preferably 1-1.2:2-5, more preferably 1-1.1:3-4, and further preferably 1:3.

[0117] In the present invention, the mass volume ratio of the compound A to the first solvent is preferably (100-600) mg:(1-2) mL, more preferably (200-500) mg:(1-1.5) mL, and further preferably 300 mg:1 mL.

[0118] In the present invention, the first Suzuki cross-coupling reaction is preferably carried out in a protective atmosphere; the protective atmosphere is preferably nitrogen; the temperature of the first Suzuki cross-coupling reaction is preferably 80 to 150°C, more preferably 110 to 140°C, further preferably 130°C, and the insulation time is preferably 3 to 24h, more preferably 3 to 12h, further preferably 5h.

[0119] In the present invention, the first Suzuki cross-coupling reaction preferably further comprises purifying the obtained reaction product; the purification is preferably silica gel column chromatography.

[0120] In the present invention, the compound C is preferably compound C-1; the structure of the compound C-1 is shown in formula C-1:

[0121]

[0122] After obtaining compound C, the present invention mixes compound C with compound D, a good solvent, a palladium catalyst (referred to as the second palladium catalyst), a base (referred to as the second base) and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (Xphos) to perform a second Suzuki cross-coupling reaction to obtain compound E. In the present invention, the second palladium catalyst is preferably Pd(OAc)2; the type of the second base is preferably the same as that of the first base, which will not be repeated here.

[0123] In the present invention, the molar ratio of compound C to compound D is preferably 1 to 3:1, more preferably 1.4 to 2.5:1, further preferably 1.8 to 2.2:1, and further preferably 2:1.

[0124] In the present invention, the compound D preferably includes one or more of compound D-1 (structure as shown in formula D-1), compound D-2 (structure as shown in formula D-2), compound D-3 (structure as shown in formula D-3), compound D-4 (structure as shown in formula D-4), compound D-5 (structure as shown in formula D-5), compound D-6 (structure as shown in formula D-6), compound D-7 (structure as shown in formula D-7), compound D-8 (structure as shown in formula D-8), compound D-9 (structure as shown in formula D-9), compound D-10 (structure as shown in formula D-10), compound D-11 (structure as shown in formula D-11), compound D-12 (structure as shown in formula D-12) and compound D-13 (structure as shown in formula D-13), and the specific structural formulas are shown in Table 1.

[0125] In the present invention, the preparation method of the compound D-1 preferably comprises the following steps: Compound N-1 is mixed with compound M, a mixed solvent, Pd(OAc)2, Cs2CO3 and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl to carry out a fifth Suzuki cross-coupling reaction to obtain compound D-1 (process flow as shown in Fig.10 shown).

[0126] In the present invention, the structure of the compound N-1 is shown in Formula N-1:

[0127]

[0128] In the present invention, the structure of the compound M is shown in Formula M:

[0129]

[0130] In the present invention, the preparation method of the compound M comprises the following steps: mixing compound P, compound O, Pd(dppf)Cl2, potassium acetate and 1,4-dioxane to carry out a sixth Suzuki cross-coupling reaction to obtain compound M.

[0131] In the present invention, the structure of the compound P is shown in Formula P:

[0132]

[0133] In the present invention, the structure of the compound O is shown in Formula O:

[0134]

[0135] In the present invention, the molar ratio of the compound P to the compound O is preferably 10-12:10-12, more preferably 10-11:11-12, and further preferably 10:12.

[0136] In the present invention, the molar ratio of the compound P to Pd(dppf)Cl2 is preferably 1-2:0.01-0.05, more preferably 1-1.5:0.01-0.03, and further preferably 1:0.02.

[0137] In the present invention, the molar ratio of the compound P to potassium acetate is preferably 1-1.2:2-5, more preferably 1:3.

[0138] In the present invention, the ratio of the total mass of the compound P and the compound O to the volume of 1,4-dioxane is preferably (100-1000) mg:1 mL, and more preferably (300-600) mg:1 mL.

[0139] In the present invention, the sixth Suzuki cross-coupling reaction is preferably carried out in a protective atmosphere; the protective atmosphere is preferably nitrogen; the temperature of the sixth Suzuki cross-coupling reaction is preferably 80-150°C, more preferably 130°C, and the insulation time is preferably 3-24h, more preferably 5h.

[0140] In the present invention, the sixth Suzuki cross-coupling reaction preferably further comprises purifying the obtained product; the purification is preferably silica gel column chromatography.

[0141] In the present invention, the molar ratio of the compound N-1 to the compound M is preferably 10-12:7-8, and more preferably 11.11:7.40.

[0142] In the present invention, the molar ratio of the compound N-1 to Pd(OAc)2 is preferably 10-12:0.01-0.10, more preferably 11-12:0.01-0.02, and further preferably 11.11:0.012.

[0143] In the present invention, the molar ratio of the compound N-1 to Cs2CO3 is preferably 1-1.2:2-5, more preferably 1-1.1:2-4, and further preferably 1:3.

[0144] In the present invention, the molar ratio of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl to Pd(OAc)2 is preferably 1-1.2:1-5, more preferably 1:2.

[0145] In the present invention, the mass volume ratio of the compound N-1 to the mixed solvent is preferably (100-600) mg: (1-2) mL, more preferably (200-500) mg: (1-1.5) mL, and further preferably 300 mg: 1 mL.

[0146] In the present invention, the mixed solvent preferably includes benzene homologues, alcohol and water; the benzene homologues are preferably toluene; the alcohol is preferably ethanol; the water is preferably deionized water; the concentration of the benzene homologues in the mixed solvent is preferably 100-600 mg / mL, more preferably 300-500 mg / mL; the volume ratio of the alcohol to water is preferably 1:1.

[0147] In the present invention, the fifth Suzuki cross-coupling reaction is preferably carried out under a protective atmosphere and microwave conditions; the protective atmosphere is preferably nitrogen; the temperature of the fifth Suzuki cross-coupling reaction is preferably 80 to 150°C, more preferably 110 to 140°C, further preferably 120°C, and the insulation time is preferably 3 to 24h, more preferably 3 to 12h, further preferably 3h.

[0148] In the present invention, the fifth Suzuki cross-coupling reaction preferably further comprises extracting the obtained reaction product, drying the organic layer and purifying the obtained reaction product in sequence.

[0149] In the present invention, the extraction agent is preferably dichloromethane.

[0150] In the present invention, the reagent used for drying the organic layer is preferably anhydrous MgSO4.

[0151] In the present invention, the purification is preferably performed by column chromatography.

[0152] In the present invention, the preparation method of the compound D-2 to the compound D-13 is the same as the preparation method of the compound D-1, except that the compound N-1 is replaced by the compound N-2 to the compound N-13 in sequence, and the structural formulas of the compound N and the compound D are shown in Table 1:

[0153] Table 1 Structural formulas of compounds N-2 to N-13 and compounds D-2 to D-13

[0154]

[0155]

[0156] In the present invention, the molar ratio of the compound C to the second palladium catalyst is preferably 100:0.1-0.3, more preferably 100:0.15-0.25, and further preferably 100:0.2.

[0157] In the present invention, the molar ratio of the compound C to the second base is preferably 1:0.5-3, more preferably 1:1-2.5, further preferably 1:1.5-2, and further preferably 1:1.8.

[0158] In the present invention, the molar ratio of the compound C to 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl is preferably 1:1-4, more preferably 1:2-3, and further preferably 1:2.5.

[0159] In the present invention, the mass volume ratio of the compound C to the good solvent is preferably (100-600) mg:(1-2) mL, more preferably (200-500) mg:(1-1.5) mL, and further preferably 300 mg:1 mL.

[0160] In the present invention, the good solvent preferably includes benzene homologues, alcohol and water; the benzene homologues are preferably toluene; the alcohol is preferably ethanol; the water is preferably deionized water; the volume ratio of the benzene homologues to the alcohol is preferably 3:1; the volume ratio of the benzene homologues to water is preferably 3:1.

[0161] In the present invention, the second Suzuki cross-coupling reaction is preferably carried out in a protective atmosphere and microwave conditions; the protective atmosphere is preferably nitrogen; the temperature of the second Suzuki cross-coupling reaction is preferably 80 to 120°C, more preferably 90 to 110°C, further preferably 95 to 105°C, further preferably 100°C, and the insulation time is preferably 3 to 24h, more preferably 5 to 20h, further preferably 8 to 15h, further preferably 10 to 12h. The present invention confirms that the reaction is complete by sampling a point plate.

[0162] In the present invention, the second Suzuki cross-coupling reaction preferably further includes a first post-treatment; the first post-treatment preferably includes: extracting the obtained reaction product in sequence to obtain an organic layer, drying and purifying the organic layer.

[0163] In the present invention, the extraction agent is preferably dichloromethane.

[0164] In the present invention, the organic layer drying agent is preferably anhydrous magnesium sulfate (anhydrous MgSO4).

[0165] In the present invention, the purification is preferably performed by silica gel column chromatography; the eluent of the silica gel column chromatography is preferably a mixed solvent of dichloromethane and ethyl acetate.

[0166] After obtaining compound E, the present invention mixes compound E and compound F, a composite solvent, a palladium catalyst (referred to as the third palladium catalyst), a base (referred to as the third base) and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (Xphos) to perform a third Suzuki cross-coupling reaction to obtain the organic compound based on anthracene structure. In the present invention, the third palladium catalyst is preferably Pd(OAc)2; the type of the third base is preferably the same as the first base.

[0167] In the present invention, the molar ratio of compound E to compound F is preferably 1 to 3:1, more preferably 1.5 to 2.5:1, and further preferably 2:1.

[0168] In the present invention, the compound F is preferably one or more of compound F-1 (structure such as formula F-1), compound F-2 (structure such as formula F-2), compound F-3 (structure such as formula F-3), compound F-4 (structure such as formula F-4), compound F-5 (structure such as formula F-5), compound F-6 (structure such as formula F-6), compound F-7 (structure such as formula F-7) and compound F-8 (structure such as formula F-8);

[0169]

[0170] In the present invention, the preparation method of the compound F-1 preferably comprises the following steps:

[0171] (1) mixing o-bromobenzaldehyde, compound L-1, Pd(dppf)Cl2, N,N-dimethylformamide, potassium carbonate and water to carry out a fourth Suzuki cross-coupling reaction to obtain intermediate K-1;

[0172] (2) mixing the intermediate K-1 with anhydrous tetrahydrofuran and phenylmagnesium chloride to carry out a nucleophilic addition reaction to obtain an intermediate J-1;

[0173] (3) mixing the intermediate J-1 with an ion exchange resin and toluene and refluxing to carry out a cyclization reaction to obtain the intermediate I-1;

[0174] (4) The intermediate I-1 is mixed with carbon tetrachloride to carry out a halogenation reaction to obtain compound F-1.

[0175] In the present invention, o-bromobenzaldehyde, compound L-1, Pd(dppf)Cl2, N,N-dimethylformamide (DMF), potassium carbonate and water are mixed to perform a fourth Suzuki cross-coupling reaction to obtain an intermediate K-1. In the present invention, the structure of the compound L-1 is shown in formula L-1:

[0176]

[0177] In the present invention, the molar ratio of o-bromobenzaldehyde to compound L-1 is preferably 1:1 to 1.1, more preferably 1:1.02 to 1.08, and further preferably 1:1.04 to 1.06.

[0178] In the present invention, the molar ratio of o-bromobenzaldehyde to Pd(dppf)Cl2 is preferably 34.9:0.177.

[0179] In the present invention, the mass volume ratio of o-bromobenzaldehyde to N,N-dimethylformamide is preferably 6.45 g:60 mL.

[0180] In the present invention, the molar ratio of o-bromobenzaldehyde to potassium carbonate is preferably 34.9:72.4.

[0181] In the present invention, the volume ratio of potassium carbonate to water is preferably 1:3.

[0182] In the present invention, the fourth Suzuki cross-coupling reaction is preferably carried out under a protective atmosphere and stirring conditions; the protective atmosphere is preferably nitrogen; the temperature of the fourth Suzuki cross-coupling reaction is preferably 60 to 90° C., more preferably 80° C., and the insulation time is preferably 2 to 12 h, more preferably 3 to 5 h.

[0183] In the present invention, the fourth Suzuki cross-coupling reaction preferably further comprises extracting, purifying by column chromatography, rotary evaporating and drying the obtained product in sequence.

[0184] After obtaining the intermediate K-1, the present invention mixes the intermediate K-1 with anhydrous tetrahydrofuran and phenylmagnesium chloride (referred to as the first mixing) to perform a nucleophilic addition reaction to obtain the intermediate J-1. In the present invention, the mass volume ratio of the intermediate K-1 to anhydrous tetrahydrofuran is preferably (5-15) g: (50-100) mL, more preferably (8-10) g: (60-70) mL, and further preferably 9.37 g: 68 mL.

[0185] In the present invention, the mass ratio of the intermediate K-1 to phenylmagnesium chloride is preferably 5-15:5-10, more preferably 8-10:6-8, and further preferably 9.37:7.39.

[0186] In the present invention, the first mixing is preferably carried out in a protective atmosphere; the protective atmosphere is preferably nitrogen; the first mixing is preferably: premixing the intermediate K-1 and anhydrous tetrahydrofuran to obtain a premixed liquid, cooling the premixed liquid to -30°C and then dropping a phenylmagnesium chloride tetrahydrofuran solution.

[0187] In the present invention, the concentration of the phenylmagnesium chloride tetrahydrofuran solution is preferably 1 to 5 mol / L, more preferably 3 mol / L.

[0188] In the present invention, the nucleophilic addition reaction is preferably carried out in a protective atmosphere; the protective atmosphere is preferably nitrogen; the nucleophilic addition reaction preferably includes a first reaction stage and a second reaction stage carried out in sequence; the temperature of the first reaction stage is preferably -5 to 0°C, more preferably -4 to -1°C, further preferably -3 to -2°C, and the insulation time is preferably 0.5 to 24h, more preferably 1h; the temperature of the second reaction stage is preferably room temperature, and the reaction time is preferably 1min to 24h, more preferably 5min to 5h.

[0189] In the present invention, the nucleophilic addition reaction preferably further includes a third post-treatment of the obtained reaction product; the third post-treatment preferably comprises: adjusting the pH value of the obtained reaction product to neutral, terminating the reaction, extracting, washing the organic phase, drying, removing the desiccant, removing the solvent from the filtrate, crystallizing and purifying.

[0190] In the present invention, the step of adjusting the pH value to neutral is preferably: adding hydrochloric acid to the reaction solution; the concentration of the hydrochloric acid is preferably 0.5 to 1.5 mol / L, more preferably 1 mol / L.

[0191] In the present invention, the extractant for the extraction is preferably ethyl acetate.

[0192] In the present invention, the organic phase is preferably washed with water and then with saturated brine in sequence.

[0193] In the present invention, the drying agent is preferably anhydrous magnesium sulfate.

[0194] In the present invention, the desiccant removal is preferably performed by filtration.

[0195] In the present invention, the desolventizing of the filtrate is preferably performed by rotary evaporation and filtration in sequence.

[0196] In the present invention, the crystallization is preferably performed by adding n-hexane to the filtrate after the solvent is removed to precipitate colorless crystals.

[0197] In the present invention, the purification is preferably performed by silica gel column chromatography.

[0198] After obtaining the intermediate J-1, the present invention mixes the intermediate J-1 with an ion exchange resin and toluene and refluxes to perform a cyclization reaction to obtain the intermediate I-1. In the present invention, the mass ratio of the intermediate J-1 to the ion exchange resin is preferably 6 to 10:0.1 to 1, more preferably 7 to 9:0.3 to 0.4, and further preferably 8.48:0.36.

[0199] In the present invention, the ion exchange resin is preferably Amberlyst 15 ion exchange resin.

[0200] In the present invention, the mass volume ratio of the intermediate J-1 to toluene is preferably (5-15) g:(50-150) mL, more preferably (7-10) g:(90-120) mL, and further preferably 8.48 g:100 mL.

[0201] In the present invention, the temperature of the cyclization reaction is preferably 80 to 125° C., more preferably 90 to 110° C., and the insulation time is preferably 1 to 12 h, more preferably 4 h.

[0202] In the present invention, after the cyclization reaction, the obtained reaction product is preferably subjected to a fourth post-treatment; the fourth post-treatment is preferably: removing the catalyst, removing the solvent from the filtrate and purifying the obtained reaction product in sequence.

[0203] In the present invention, the catalyst removal is preferably performed by filtration; the filtrate solvent removal is preferably performed by rotary evaporation; and the purification is preferably performed by silica gel column chromatography.

[0204] After obtaining the intermediate I-1, the present invention mixes the intermediate I-1 with carbon tetrachloride (referred to as the second mixing) for halogenation reaction to obtain compound F-1. In the present invention, the molar volume ratio of the intermediate I-1 to carbon tetrachloride is preferably 4mmol:15mL.

[0205] In the present invention, the temperature of the halogenation reaction is preferably 240-260°C, more preferably 250°C, the pressure is preferably 6-8MPa, more preferably 7MPa, and the insulation time is preferably 2-12h, more preferably 7h; the halogenation reaction is preferably carried out in nitrogen.

[0206] In the present invention, after the halogenation reaction, the fifth post-treatment of the obtained reaction product is preferably further included; the fifth post-treatment is preferably: cooling, washing, drying and purifying the obtained reaction product in sequence.

[0207] In the present invention, the final temperature of the cooling is preferably room temperature; and the purification is preferably chromatography column purification.

[0208] In the present invention, the preparation method of the compounds F-2 to F-8 is the same as the preparation method of the compound F-1, except that the raw material compound L-1 is replaced by the compounds L-2 to L-8. The corresponding process flow is as follows: Figure 2 to Figure 9 shown.

[0209] In the present invention, the molar ratio of the compound E to the third palladium catalyst is preferably 100:0.1-0.3, more preferably 100:0.15-0.25, and further preferably 100:0.2.

[0210] In the present invention, the molar ratio of the compound E to the third base is preferably 1:0.5-3, more preferably 1:1-2.5, and further preferably 1:1.5-2.

[0211] In the present invention, the molar ratio of the compound E to 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl is preferably 1:1-4, more preferably 1:1.5-3.5, and further preferably 1:2-3.

[0212] In the present invention, the mass volume ratio of the compound E to the complex solvent is preferably (100-600) mg:(1-2) mL, more preferably (200-500) mg:(1-1.5) mL, and further preferably 300 mg:1 mL.

[0213] In the present invention, the composite solvent preferably includes benzene homologues, alcohol and water; the benzene homologues are preferably toluene; the alcohol is preferably ethanol; the water is preferably deionized water; the volume ratio of the benzene homologues to the alcohol is preferably 3:1; the volume ratio of the benzene homologues to water is preferably 3:1.

[0214] In the present invention, the third Suzuki cross-coupling reaction is preferably carried out in a protective atmosphere and microwave conditions; the protective atmosphere is preferably nitrogen; the temperature of the third Suzuki cross-coupling reaction is preferably 80 to 120°C, more preferably 85 to 115°C, further preferably 90 to 110°C, further preferably 95 to 105°C, and the insulation time is preferably 3 to 24h, more preferably 6 to 20h, further preferably 10 to 16h, further preferably 12 to 14h. The present invention confirms that the reaction is complete by sampling a point plate.

[0215] In the present invention, the third Suzuki cross-coupling reaction preferably further includes a second post-treatment; the second post-treatment preferably includes: extracting the obtained reaction product in sequence to obtain an organic layer, drying and purifying the organic layer.

[0216] In the present invention, the extraction agent is preferably dichloromethane.

[0217] In the present invention, the organic layer drying agent is preferably anhydrous magnesium sulfate (anhydrous MgSO4).

[0218] In the present invention, the purification is preferably silica gel column chromatography; the eluent of the silica gel column chromatography is preferably a mixed solvent of a non-polar solvent and a polar solvent; the non-polar solvent preferably includes one or more of n-heptane, n-hexane and petroleum ether; the polar solvent preferably includes one or more of dichloromethane and ethyl acetate; the volume ratio of the non-polar solvent to the polar solvent is preferably 5-15:1-5, more preferably 7-12:2-4, and further preferably 8-10:2-3.

[0219] The present invention provides a method for preparing anthracene-based organic compounds, the process flow is as follows Figure 1 In the present invention, compound A and compound B are subjected to a first Suzuki cross-coupling reaction to obtain compound C, and then compound C and compound D are subjected to a second Suzuki cross-coupling reaction to obtain compound E, and then compound E and compound F are subjected to a third Suzuki cross-coupling reaction to obtain an organic compound based on anthracene structure.

[0220] The present invention also provides the use of the organic compound based on anthracene structure described in the above scheme or the organic compound based on anthracene structure obtained by the preparation method described in the above scheme in an organic electroluminescent device.

[0221] The present invention also provides an organic electroluminescent device, comprising one or more functional layers, wherein the functional layers contain the organic compound based on anthracene structure described in the above scheme or the organic compound based on anthracene structure obtained by the preparation method described in the above scheme.

[0222] In the present invention, the functional layer is preferably a light-emitting layer.

[0223] The present invention also provides the application of the organic electroluminescent device described in the above solution in the field of lighting or display elements.

[0224] In order to further illustrate the present invention, the scheme of the present invention is described in detail below in conjunction with the accompanying drawings and embodiments, but they should not be understood as limiting the protection scope of the present invention.

[0225] In the specific embodiments of the present invention, unless otherwise specified, all raw materials are purchased from Yantai Wanrun Fine Chemicals Co., Ltd.

[0226] Example

[0227] 1. Synthesis of Compound C-1

[0228]

[0229] Pass nitrogen, add 10.0 mol of compound A-1, 12.0 mol of compound B, 0.3 g of Pd(dppf)Cl2 and 30.0 mmol of potassium acetate into 100 mL of 1,4-dioxane, react at 130°C for 5 h, and then separate and purify the reaction product by silica gel column chromatography to obtain intermediate C-1;

[0230] 2. Synthesis of Compound 7

[0231]

[0232] (1) In a 250 mL three-necked flask, nitrogen was introduced, 5 mol of compound C-1 and 7.40 mol of compound D-1 were weighed, dissolved in a toluene / water / ethanol mixed solvent with a volume ratio of 3:1:1, and then 0.012 mol of Pd(OAc)2, 7.21 mmol of Cs2CO3 and 14.42 mmol of Xphos were added, and microwave reaction was carried out at 120°C for 3 h under nitrogen protection; after the reaction, the organic layer was extracted with dichloromethane, dried with anhydrous MgSO4, and then separated and purified by column chromatography to obtain compound E-1;

[0233] (2) Weigh 5 mol of compound E-1 and 7.40 mol of compound F-1, dissolve them in a mixed solution of toluene / water / ethanol with a volume ratio of 3:1:1, then add 0.012 mol of Pd(OAc)2, 7.21 mmol of Cs2CO3 and 14.42 mmol of Xphos, and react at 120°C for 3 h in a nitrogen atmosphere; after the reaction, extract with dichloromethane to obtain an organic layer, dry it with anhydrous MgSO4, and then separate and purify it by column chromatography to obtain compound 7.

[0234] Examples 2 to 18 adopt the same preparation method as Example 1, except that: the corresponding intermediates D and intermediates F are used to replace the compound D-1 and compound F-1 of Example 1, respectively, to obtain compound 11, compound 17, compound 46, compound 54, compound 58, compound 62, compound 65, compound 79, compound 89, compound 96, compound 103, compound 126, compound 11, compound 163, compound 179, compound 194 and compound 226, respectively. The specific raw materials are shown in Table 2:

[0235] Table 2 Structural formula of raw materials and products of Examples 1 to 18

[0236]

[0237]

[0238]

[0239]

[0240] Test Case

[0241] The anthracene-based organic compounds prepared in Examples 1 to 18 were structurally characterized, and the results are shown in Table 3:

[0242] Table 3 Structural characterization of anthracene-based organic compounds prepared in Examples 1 to 18

[0243]

[0244]

[0245]

[0246] It can be seen from Table 3 that the present invention successfully prepared various organic compounds based on anthracene structures.

[0247] Application Examples

[0248] The preparation methods of the devices in Application Examples 1 to 18 and Application Comparative Examples 1 to 3 are exactly the same, and the same substrate materials and electrode materials are used. The film thickness of the electrode materials remains the same. The specific preparation steps are as follows:

[0249] (a) The substrate layer 1 is transparent glass, and Ag is vacuum-deposited on the surface of the substrate layer 1 with a thickness of 100 nm to serve as the anode layer 2;

[0250] (b) On the anode layer 2, HAT-CN is vacuum-deposited to a thickness of 10 nm as the hole injection layer 3;

[0251] (c) On the hole injection layer 3, HT-1 was vacuum-deposited to a thickness of 140 nm as the hole transport layer 4;

[0252] (d) On the hole transport layer 4, EB-1 is vacuum evaporated to a thickness of 30 nm as the electron blocking layer 5;

[0253] (e) On the electron blocking layer 5, a light-emitting layer 6 is evaporated, wherein the compound D-1 is used as the main material, the compound BD-1 is used as the doping material, the mass ratio of the compound D-1 to the compound BD-1 is 90:10, and the thickness is 40 nm;

[0254] (f) On the light-emitting layer 6, the compound ET-1 and the compound Liq are vacuum-deposited in a mass ratio of 1:1 to a thickness of 40 nm to serve as the electron transport layer 7;

[0255] (g) On the electron transport layer 7, LiF is vacuum evaporated to a thickness of 1 nm to serve as the electron injection layer 8;

[0256] (h) On the electron injection layer 8, a Mg-Ag layer with a mass ratio of 1:9 and a thickness of 15 nm is vacuum-deposited as the cathode layer 9;

[0257] (i) Alq3 was vacuum-deposited on the cathode layer 9 to a thickness of 70 nm as the light extraction layer 10 to obtain an electroluminescent device (structure as shown in FIG. Fig.11 The current efficiency and life of the device were measured, and the results are shown in Table 4.

[0258] The structures of the compounds used in the above application examples are as follows:

[0259]

[0260]

[0261] Table 4 Organic electroluminescent devices prepared by using Examples 1 to 18 and Comparative Examples 1 to 3

[0262]

[0263]

[0264] The performance of the organic electroluminescent devices prepared in Examples 1 to 18 and Comparative Examples 1 to 3 was tested, and the results are shown in Table 5:

[0265] Table 5 Test data of the devices of application examples 1 to 18 and application comparative examples 1 to 3

[0266]

[0267]

[0268] Note: The current efficiency is tested using the IVL (current-voltage-luminance) test system, and the current density during the test is 10mA / cm 2 .

[0269] It can be seen from Table 5 that the anthracene-based organic compound provided by the present invention is used as one of the main bodies of the light-emitting layer, and the device efficiency and device life are significantly improved compared with the application of Comparative Examples 1 to 3.

[0270] It can be seen from the above embodiments that the anthracene-based organic compound provided by the present invention can significantly improve the luminous efficiency and service life of OLED devices.

[0271] Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.

Claims

1. An organic compound based on anthracene structure, It is characterized in that The structure is shown in formula X: In formula X, Ar 1 and Ar 2 Independently for C 6 ~C 30 Aryl, substituted C 6 ~C 30 Aryl, C 5 ~C 30 Heteroaryl or substituted C 5 ~C 30 heteroaryl; n is 0, 1 or 2; R 1 is a deuterium atom, C 6 ~C 30 Aryl, substituted C 6 ~C 30 One or more of aryl, amino and substituted amino; R 2 for hydrogen atoms, deuterium atoms, C 6 ~C 30 Aryl, substituted C 6 ~C 30 Aryl, a structure represented by formula Y or a structure represented by formula Z; Formula Y or Formula Z is connected to Formula X by a C1-C2 bond, a C2-C3 bond or a C3-C4 bond; wherein X in Formula Z is O, S or N-Ar 3 ,Ar 3 C 6 ~C 30 Aryl, substituted C 6 ~C 30 Aryl, C 5 ~C 30 Heteroaryl or substituted C 5 ~C 30 Heteroaryl.

2. The anthracene-based organic compound according to claim 1, It is characterized in that Ar 1 ,Ar 2 and Ar 3 In the C 6 ~C 30 The aryl group includes phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, phenanthrenyl or pyrenyl; the substituted C 6 ~C 30 The aryl group includes a substituted phenyl group, a substituted biphenyl group, a substituted naphthyl group, a substituted 9,9-dimethylfluorenyl group, a substituted phenanthrenyl group or a substituted pyrenyl group; 6 ~C 30 Substituents for the aromatic group include deuterium atoms, methoxy groups, cyano groups, halogen atoms, C 1 ~C 20 Alkyl, C 3 ~C 20 Cycloalkyl, C 6 ~C 30 Aryl or 5-30 membered heteroaryl containing heteroatoms; said C 5 ~C 30 The heteroaryl group includes dibenzofuranyl, dibenzothiophenyl, carbazolyl, pyridyl, pyrimidinyl or isoquinolyl; the substituted C 5 ~C 30 The heteroaryl group includes a substituted dibenzofuranyl group, a substituted dibenzothiophenyl group, a substituted carbazolyl group, a substituted pyridyl group, a substituted pyrimidinyl group or a substituted isoquinolinyl group; the substituted C 5 ~C 30 Substituents for the heteroaryl group include deuterium atoms, methoxy groups, cyano groups, halogen atoms, C 1 ~C 20 Alkyl, C 3 ~C 20 Cycloalkyl, C 6 ~C 30 Aryl or 5-30 membered heteroaryl containing heteroatoms.

3. The anthracene-based organic compound according to claim 1 or 2, It is characterized in that R 1 In the C 6 ~C 30 The aryl group includes phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, spirofluorenyl, anthracenyl, phenanthrenyl or pyrenyl; the substituted C 6 ~C 30 The aryl group includes a substituted phenyl group, a substituted biphenyl group, a substituted naphthyl group, a substituted 9,9-dimethylfluorenyl group, a substituted spirofluorenyl group, a substituted anthracenyl group, a substituted phenanthrenyl group or a substituted pyrenyl group; the substituted C 6 ~C 30 Substituents for the aromatic group include deuterium atoms, cyano groups, methoxy groups, halogen atoms, C 1 ~C 5 Alkyl, C 6 ~C 30 One or more of an aryl group and a 5- to 30-membered heterocyclic group; the substituent of the substituted amino group includes a deuterium atom, a cyano group, a methoxy group, a halogen atom, a C 1 ~C 5 Alkyl, C 6 ~C 30 One or more of an aryl group and a 5- to 30-membered heterocyclic group.

4. The anthracene-based organic compound according to claim 1 or 2, It is characterized in that R 2 In the C 6 ~C 30 The aryl group includes phenyl, biphenyl, naphthyl, 9,9-dimethylfluorenyl, phenanthrenyl or pyrenyl; the substituted C 6 ~C 30 The aryl group includes a substituted phenyl group, a substituted biphenyl group, a substituted naphthyl group, a substituted 9,9-dimethylfluorenyl group, a substituted phenanthrenyl group or a substituted pyrenyl group; 6 ~C 30 Substituents for the aromatic group include deuterium atoms, methoxy groups, cyano groups, halogen atoms, C 1 ~C 20 Alkyl, C 3 ~C 20 Cycloalkyl, C 6 ~C 30 Aryl or 5-30 membered heteroaryl containing heteroatoms.

5. The anthracene-based organic compound according to claim 1, It is characterized in that The anthracene-based organic compound is one of Formula 1 to Formula 238:

6. The method for preparing an anthracene-based organic compound according to any one of claims 1 to 5, It is characterized in that The following steps are involved: (1) Compound A, compound B, a palladium catalyst, a base and a solvent are mixed to perform a first Suzuki cross-coupling reaction to obtain a compound C, the structure of which is shown in Formula C: The structure of the compound A is shown in formula A: In formula A, V is chlorine, bromine or iodine; The structure of the compound B is shown in Formula B: (2) Compound C is mixed with compound D, a good solvent, a palladium catalyst, a base and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl to carry out a second Suzuki cross-coupling reaction to obtain compound E, the structure of which is shown in Formula E: In formula A, formula C and formula E, n and R 1 With formula X n and R 1 same; The structure of the compound D is shown in Formula D: Ar in Formula D and Formula E 1 With Ar in formula X 1 The same, in formula D, W is chlorine, bromine or iodine; (3) Mixing the compound E and the compound F, a composite solvent, a palladium catalyst, a base and 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl to perform a third Suzuki cross-coupling reaction to obtain the anthracene-based organic compound; the structure of the compound F is shown in Formula F: Ar in Formula F 2 and R 2 With Ar in formula X 2 and R 2 Same, G is chlorine, bromine or iodine; There is no requirement for the chronological order of step (2) and step (3).

7. The preparation method according to claim 6, It is characterized in that The second Suzuki cross-coupling reaction is carried out in a protective atmosphere and microwave conditions; the temperature of the second Suzuki cross-coupling reaction is 80-120° C., and the insulation time is 3-24 hours.

8. Use of the organic compound based on anthracene structure according to any one of claims 1 to 5 or the organic compound based on anthracene structure obtained by the preparation method according to any one of claims 6 to 7 in an organic electroluminescent device.

9. An organic electroluminescent device, It is characterized in that The invention comprises one or more functional layers, wherein the functional layers contain the organic compound based on anthracene structure according to any one of claims 1 to 5 or the organic compound based on anthracene structure obtained by the preparation method according to any one of claims 6 to 7.

10. Use of the organic electroluminescent device according to claim 9 in the field of lighting or display elements.

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