Heterocyclic compound and organic electroluminescent device

Abstract

The application belongs to the technical field of light-emitting materials, and discloses a heterocyclic compound and an organic electroluminescent device. The heterocyclic compound has a structural general formula as shown in formula (1): formula (1). The heterocyclic compound has the advantages of low driving voltage, high luminous efficiency, long device life and the like, and can be used as an electron transport material, a hole blocking layer material and an N-type charge generation layer material in an OLED light-emitting device.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of light-emitting materials, and particularly relates to a heterocyclic compound and an organic electroluminescent device. BACKGROUND

[0002] At present, an organic electroluminescent device (OLED) as a new generation of display technology has obtained more and more attention in display and lighting technology, and has a very wide application prospect. However, compared with the market application requirements, the performance of the OLED such as the luminous efficiency, the driving voltage and the service life still needs to be improved.

[0003] Generally, the basic structure of the OLED is a sandwich structure in which various different functional organic functional material thin films are sandwiched between metal electrodes, just like a sandwich structure. Under the driving of the current, holes and electrons are injected from the cathode and the anode respectively, the holes and the electrons are combined in the light-emitting layer after moving a distance, and are released in the form of light or heat, so that the OLED emits light. However, the organic functional material is the core component of the OLED, and the thermal stability, the photochemical stability, the electrochemical stability, the quantum yield, the film-forming stability, the crystallinity and the color saturation of the material are all main factors affecting the performance of the device.

[0004] Patent document 1 (CN113840822A) describes An electron transport compound connected with a triazine ring and a tripyridine ring, which can be used as an electron transport material in a light-emitting device, and the device efficiency needs to be improved; patent document 2 (WO2014010824A1) describes A naphthalene-attached double-triazine electron transport / hole blocking material, and the device performance needs to be further improved, especially the service life still cannot meet the application requirements; patent document 3 (CN114057660A) describes A double-triazine material connected with a steric phenyl group, and the device efficiency and the service life of this structure also need to be improved.

[0005] Therefore, it is urgent to provide a new organic light-emitting material which helps to improve the performance of the light-emitting device. SUMMARY

[0006] The present application aims to at least solve one of the technical problems existing in the prior art. To this end, the present application provides a heterocyclic compound and an organic electroluminescent device.

[0007] The first aspect of the present application provides a heterocyclic compound.

[0008] In some embodiments, a heterocyclic compound has a structure general formula as shown in formula (1):

[0009] Formula (1),

[0010] wherein ring A is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted phenanthrene ring, or a substituted or unsubstituted annular structure represented by formula (1-1): formula (1-1);

[0011] wherein ring B, ring C are independently selected from a benzene ring or a naphthalene ring, and X is CRaRb, O, S, or Se; Ra, Rb are independently selected from hydrogen, C1-C30 alkyl, C1-C30 heteroalkyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C3-C30 alkylsilyl, or C6-C30 arylsilyl;

[0012] X1-X6 are independently selected from N or CR1, and at least one of X1-X3 is N, and at least one of X4-X6 is N;

[0013] L1, L2 are independently selected from a substituted C6-C60 arylene or a substituted C5-C60 heteroarylene, and at least one of the substituents in L1, L2 contains deuterium;

[0014] R1 is selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboron, C6-C60 arylboron, C6-C60 arylphosphine, or C6-C60 arylamine;

[0015] Ar1, Ar2, Ar3, Ar4 are independently selected from a substituted or unsubstituted C6-C30 aryl, a substituted or unsubstituted C3-C30 heteroaryl, a substituted or unsubstituted C9-C30 cycloalkyl and aryl;

[0016] the substituents in Ar1, Ar2, Ar3, Ar4 are at least one of deuterium, halogen, cyano, isocyano, phosphine, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl-substituted amine, C1-C6 hydrocarbon-substituted or unsubstituted C6-C30 aryl, C1-C6 hydrocarbon-substituted or unsubstituted C3-C30 heteroaryl, wherein the number of substitutions is from mono-substitution to the maximum number of substitutions;

[0017] The substituents in the ring A are substituted with at least one selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboron, C6-C60 arylboron, C6-C60 arylphosphine, or C6-C60 arylamine, wherein the number of substitutions is from monosubstitution to the maximum number of substitutions;

[0018] The heteroatoms in the heteroarylene, heteroalkyl, heterocycloalkyl, and heteroaryl are independently selected from at least one of O, S, N, Se, Si, and Ge.

[0019] The beneficial effects of the present application relative to the prior art are as follows:

[0020] The heterocyclic compound has the advantages of low driving voltage, high luminous efficiency, long device lifetime, etc., and can be used as an electron transport material, a hole blocking layer material, and an N-type charge generation layer material in an OLED light-emitting device. At the same time, the heterocyclic compound has a relatively low melting point, which is beneficial to improving the evaporation stability of the material as a fused material. The heterocyclic compound as an electron transport material, a hole blocking layer material, and an N-type charge generation layer material has a prospect of application in the LED, OLED, and AMOLED industries. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 FIG. 1 is a structural schematic diagram of an organic electroluminescent device 1 according to an embodiment of the present application;

[0022] Figure 2 FIG. 2 is a structural schematic diagram of an organic electroluminescent device 2 according to an embodiment of the present application. DETAILED DESCRIPTION

[0023] In order to make those skilled in the art more clearly understand the technical solutions described in the present application, the following examples are given for illustration. It should be pointed out that the following examples do not constitute a limitation on the scope of protection required by the present application.

[0024] The raw materials, reagents, or devices used in the following examples, unless otherwise specified, can be obtained from conventional commercial channels or can be obtained by existing known methods.

[0025] In some embodiments, a heterocyclic compound has a general structure as shown in formula (1):

[0026] Formula (1),

[0027] wherein ring A is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted phenanthrene ring, or a substituted or unsubstituted annular structure represented by formula (1-1): formula (1-1);

[0028] wherein ring B, ring C are independently selected from a benzene ring or a naphthalene ring, X is CRaRb, O, S or Se, * represents the connection site of ring A with L1, L2; Ra, Rb are independently selected from hydrogen, C1-C30 alkyl, C1-C30 heteroalkyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C3-C30 alkylsilyl or C6-C30 arylsilyl;

[0029] X1-X6 are independently selected from N or CR1, and at least one of X1-X3 is N, and at least one of X4-X6 is N;

[0030] L1, L2 are independently selected from a substituted C6-C60 arylene group or a substituted C5-C60 heteroarylene group, and at least one of the substituents in L1, L2 contains deuterium;

[0031] R1 is selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboron, C6-C60 arylboron, C6-C60 arylphosphine or C6-C60 arylamine;

[0032] Ar1, Ar2, Ar3, Ar4 are independently selected from a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, a substituted or unsubstituted C9-C30 cycloalkyl group and aryl group;

[0033] the substitution in Ar1, Ar2, Ar3, Ar4 is at least one of deuterium, halogen, cyano, isocyano, phosphine, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl-substituted amine, C1-C6 hydrocarbon-substituted or unsubstituted C6-C30 aryl, C1-C6 hydrocarbon-substituted or unsubstituted C3-C30 heteroaryl, wherein the number of substitutions is from mono-substitution to the maximum number of substitutions;

[0034] substituted with at least one selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboronyl, C6-C60 arylboronyl, C6-C60 arylphosphino, or C6-C60 arylamino, wherein the number of substitutions ranges from mono-substitution to the maximum number of substitutions;

[0035] the heteroatoms in the heteroalkyl, heterocycloalkyl, heteroaryl, and heteroarylene groups are independently selected from at least one of O, S, N, Se, Si, and Ge.

[0036] In some embodiments, the ring structure of Formula (1-1) is selected from a dibenzofuran ring, a fluorene ring, or a naphthobenzofuran ring.

[0037] In some embodiments, the ring structure of Formula (1) is selected from any one of the following structures:

[0038] ;

[0039] wherein X is CRaRb, O, S, or Se;

[0040] * indicates the connection site of the ring A with L1, L2 in Formula (1);

[0041] Raand Rbare each independently selected from hydrogen, C1-C20 alkyl, C1-C20 heteroalkyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C20 aryl, C3-C20 heteroaryl, C3-C20 alkylsilyl, or C6-C20 arylsilyl;

[0042] R2and R3are each independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C3-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboronyl, C6-C60 arylboronyl, C6-C60 arylphosphino, or C6-C60 arylamino;

[0043] a, b each represent an integer from 0 to 4, when a takes an integer from 2 to 4, each R2 is the same or different; when b takes an integer from 2 to 4, each R3 is the same or different.

[0044] In some embodiments, the C6-C60 aryl phosphine group is selected from a C6-C60 monoaryl phosphine group or a C6-C60 diaryl phosphine group.

[0045] In some embodiments, Ra, Rb are each independently selected from hydrogen, C1-C6 alkyl, C1-C6 heteroalkyl, C3-C12 cycloalkyl, C3-C12 heterocycloalkyl, C6-C20 aryl, C3-C20 heteroaryl.

[0046] In some embodiments, R2, R3 are each independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C30 alkyl, C1-C30 heteroalkyl, C2-C30 alkenyl, C2-C30 alkynyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, C6-C40 aryl, C3-C40 heteroaryl, C1-C30 alkoxy, C6-C40 aryloxy, C3-C30 alkylsilyl, C6-C40 arylsilyl, C1-C30 alkylboron, C6-C40 arylboron, C6-C40 aryl phosphine group, or C6-C40 aryl amine group.

[0047] In some embodiments, the ring A structure of formula (1) is selected from one of the following structures:

[0048]

[0049] ; wherein R2, R3 are each independently selected from hydrogen, deuterium, halogen, cyano, C1-C20 alkyl, C3-C20 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl;

[0050] a, b each represent an integer from 0 to 4, when a takes an integer from 2 to 4, each R2 is the same or different; when b takes an integer from 2 to 4, each R3 is the same or different.

[0051] In some embodiments, the substituents of L1, L2 satisfy one of the following conditions:

[0052] (1) the substituents in L1, L2 are deuterium;

[0053] (2) the substituents in L1, L2 are deuterium-containing substituents;

[0054] (3) the substituents in L1, L2 comprise at least one deuterium, and further comprise at least one of halogen, cyano, isocyano, phosphino, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl-substituted amine, C1-C6 hydrocarbyl-substituted or unsubstituted C6-C30 aryl, C1-C6 hydrocarbyl-substituted or unsubstituted C3-C30 heteroaryl.

[0055] In some embodiments, L1, L2 are each independently selected from the group consisting of C6-C40 arylene substituted with substituents, and C5-C40 heteroarylene substituted with substituents, and at least one of the substituents in L1, L2 comprises deuterium.

[0056] In some embodiments, L1, L2 are each independently selected from the group consisting of C6-C30 arylene substituted with substituents, and C5-C30 heteroarylene substituted with substituents, and at least one of the substituents in L1, L2 comprises deuterium.

[0057] In some embodiments, L1, L2 are each independently selected from the group consisting of C6-C20 arylene substituted with substituents, and C5-C20 heteroarylene substituted with substituents, and at least one of the substituents in L1, L2 comprises deuterium.

[0058] In some embodiments, the substituents in L1, L2 are at least one of deuterium, deuterium-substituted C1-C6 alkyl, the number of substituents is from three to the maximum number of substitutions, and the number of deuterium substitutions in the deuterium-substituted C1-C6 alkyl is from one to the maximum number of substitutions.

[0059] In some embodiments, L1 and L2 are the same structure.

[0060] In some embodiments, L1, L2 are each independently selected from the group consisting of deuterated phenylene, deuterated biphenylene, deuterated naphthylene, and deuterated pyridylene, the number of deuterium substitutions is from one to the maximum number of substitutions.

[0061] In some embodiments, at least two of X1-X3 comprise N, and at least two of X4-X6 comprise N.

[0062] In some embodiments, X1-X6 are each N.

[0063] In some embodiments, R1is selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C20alkyl, C1-C20heteroalkyl, C2-C20alkenyl, C2-C20alkynyl, C3-C20cycloalkyl, C3-C20heterocycloalkyl, C6-C30aryl, C3-C30heteroaryl, C1-C20alkoxy, C6-C30aryloxy, C3-C20alkylsilyl, C6-C30arylsilyl, C1-C20alkylboron, C6-C30arylboron, C6-C30arylphosphine, or C6-C30arylamine.

[0064] In some embodiments, R1is selected from hydrogen, deuterium, halogen, cyano, C1-C6alkyl, C1-C6heteroalkyl, C3-C12cycloalkyl, C3-C12heterocycloalkyl, C6-C20aryl, C3-C20heteroaryl.

[0065] In some embodiments, Ar1, Ar2, Ar3, Ar4are each independently selected from substituted or unsubstituted C6-C20aryl, substituted or unsubstituted C3-C20heteroaryl, substituted or unsubstituted C9-C20cycloalkyl and aryl.

[0066] In some embodiments, the substitution in Ar1, Ar2, Ar3, Ar4is at least one of deuterium, halogen, cyano, C1-C6alkyl, C3-C16cycloalkyl, C1-C6hydrocarbyl substituted or unsubstituted C6-C20aryl, C1-C6hydrocarbyl substituted or unsubstituted C3-C20heteroaryl, wherein the number of substitutions is from monosubstitution to the maximum number of substitutions.

[0067] In some embodiments, Ar1, Ar2, Ar3, Ar4 are independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted chrysenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted pyridinyl, substituted or unsubstituted pyrimidinyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted benzotriazolyl, substituted or unsubstituted benzophenanthryl, substituted or unsubstituted benzopyridinyl, substituted or unsubstituted cyclohexenylbenzene, wherein the substitution in Ar1, Ar2, Ar3, Ar4 is at least one of deuterium, fluorine, cyano, C1-C6 alkyl, C3-C16 cycloalkyl, C6-C12 aryl unsubstituted or substituted with C1-C6 alkyl, C3-C12 heteroaryl unsubstituted or substituted with C1-C6 alkyl, wherein the number of substitution is mono-substitution to the maximum number of substitution.

[0068] In some embodiments, Ar1 and Ar3 have the same structure, and Ar2 and Ar4 have the same structure.

[0069] In some embodiments, the ring A contains at least one deuterium atom.

[0070] In some embodiments, the heterocyclic compound represented by formula (1) satisfies at least one of the following conditions:

[0071] (1) X1-X3, X4-X6 are independently selected from one of the following structural formulae:

[0072] ;

[0073] (2) the six-membered ring of X1-X3 and the six-membered ring of X4-X6 have the same structure;

[0074] (3) L1, L2 are independently selected from one of the following structural formulae:

[0075] ;

[0076] (4) L1 and L2 have the same structural formula;

[0077] (5) ring A is selected from one of the following structural formulae:

[0078] ;

[0079] (6) Ar1-Ar4are each independently selected from one of the following structural formulas:

[0080] ;

[0081] (7) Ar1and Ar3are the same structural formula, and Ar2and Ar4are the same structural formula;

[0082] (8) the following two groups of ring A in formula (1) are the same structural formula;

[0083] , .

[0084] In some embodiments, the heterocyclic compound represented by formula (1) is selected from one of the following structural formulas, or one of the following structural formulas in which hydrogen is partially or completely replaced by deuterium or fluorine:

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095] .

[0096] A second aspect of the present application provides an organic electroluminescent device.

[0097] Specifically, an organic electroluminescent device comprising the above-mentioned heterocyclic compound.

[0098] In some embodiments, an organic electroluminescent device comprises: an anode, a cathode, and an organic layer between the anode and the cathode.

[0099] The organic layer comprises a light-emitting layer, and further comprises at least one of an electron-transporting layer, a hole-blocking layer, and an N-type charge-generation layer.

[0100] The material of at least one of the electron-transporting layer, the hole-blocking layer, or the N-type charge-generation layer contains the above-mentioned heterocyclic compound. For example, in some embodiments, the organic layer comprises an electron-transporting layer, and the material of the electron-transporting layer contains the above-mentioned heterocyclic compound. Alternatively, the organic layer comprises a hole-blocking layer, and the material of the hole-blocking layer contains the above-mentioned heterocyclic compound. Alternatively, the organic layer comprises an N-type charge-generation layer, and the material of the N-type charge-generation layer contains the above-mentioned heterocyclic compound.

[0101] A third aspect of the present application provides use of the above-mentioned compound in the field of semiconductors.

[0102] Specifically, use of the above-mentioned heterocyclic compound in the preparation of a semiconductor device.

[0103] In some embodiments, the semiconductor device comprises an optoelectronic device.

[0104] Definitions

[0105] Unless otherwise defined, scientific and technical terms used in this disclosure have the meanings commonly understood by one of ordinary skill in the art, although it is intended to be more fully described herein. In some cases, terms with commonly understood meanings are defined herein for clarity. It will be apparent to those skilled in the art that the present application can be practiced without resorting to the details of the following definitions.

[0106] It should be noted that in the present specification, the expression "substituted or unsubstituted X group having a-b carbons" means the number of carbons in the case where the X group is not substituted, and does not include the number of carbons in the substituents when the X group is substituted.

[0107] The maximum number of substitutions refers to the maximum number of hydrogen atoms contained in the group when the group is substituted with a substituent other than hydrogen.

[0108] An alkyl group is a straight-chain or branched saturated hydrocarbon group, and the number of carbon atoms can be 1 to 60, 1 to 40, 1 to 30, 1 to 20, 1 to 12, 1 to 6, or 1 to 3. Non-limiting examples of alkyl groups include methyl, ethyl, propyl, butyl, heptyl, decyl, and the like.

[0109] Cycloalkyl is an alkyl group in a cyclic structure, which can include monocyclic, polycyclic, and spiroalkyl groups. For example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl, and the like.

[0110] As an alkenyl group, for example, vinyl, propenyl, allyl, 1-butyldienyl, 2-butyldienyl, 1-hexatrienyl, 2-hexatrienyl, 3-hexatrienyl, and the like.

[0111] Heteroalkyl refers to an alkyl group in which at least one carbon atom is replaced by a non-carbon atom, but does not include cases in which a carbon atom is replaced by a non-carbon atom as a connecting site (e.g., alkoxy, alkylsilyl). For example, mercaptomethylmethane, methoxymethylmethane, ethoxymethylmethane, t-butoxymethylmethane, N,N-dimethylmethane, epoxybutane, epoxy pentane, epoxyhexane, and the like, with methoxymethylmethane and epoxy pentane being preferred.

[0112] Aryl refers to a monovalent group derived from an aromatic ring compound by removing one hydrogen atom, and can be a monocyclic aryl group or a polycyclic aryl group. In the polycyclic aryl group, at least one ring is an aromatic ring system. In the polycyclic aryl group, the plurality of rings can be connected to each other via a single bond or can be fused to each other. For example, the aryl group is selected from phenyl, naphthyl, anthryl, phenanthryl, tetracenyl, pyrenyl, perylenyl, chrysenyl, acenaphthyl, benzopyrenyl, benzo[c]phenanthryl, benzo[g]phenanthryl, fluorenyl, spirobifluorenyl, benzofluorenyl, dibenzofluorenyl, biphenyl, terphenyl, quaterphenyl, or fluoranthenyl.

[0113] Heteroaryl refers to a monovalent group of a heterocyclic aromatic system in which at least one carbon atom is replaced by a non-carbon atom selected from O, S, N, Se, Si, or Ge, on the basis of an aryl group, but does not include cases in which the aryl group is replaced by a non-carbon atom as a connecting site (e.g., aryloxy, arylsilyl, arylamine). For example, pyrrolyl, pyrrolopyrrolyl, furopyrrolyl, thienopyrrolyl, pyridyl, pyrazolyl, pyrimidinyl, pyrazinyl, pyridazinyl, phenoxazinyl, phenothiazinyl, phenoxazinyl, indolyl, isoindolyl, imidazolyl, benzimidazolyl, triazolyl, tetrazolyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, furopuropyrrolyl, azadibenzofuranyl, thienofuranyl, diazadibenzofuranyl, benzo[B]naphtho[1,2-D]furanyl, quinolyl, isoquinolyl, quinoxalyl, quinazolyl, quinazolinonyl, carbazolyl, azacarbazolyl, diazacarbazolyl, phenanthridinyl, berberinyl, acridinyl, dihydroacridinyl, phenanthrolinyl, oxazolinyl, oxazolyl, oxadiazolyl, benzisoxazolyl, thiazolyl, benzothiazolyl, benzisothiazolyl, pyrroloimidazolyl, furazanyl, thienyl, benzothienyl, dibenzothienyl, azadibenzothienyl, diazadibenzothienyl, thienothienyl, or o-diazanaphthalenyl.

[0114] Ar is aryl, HeteroAr is heteroaryl, Arylene is arylene, HeteroArylene is heteroarylene, respectively corresponding to the same structure of the bivalent radical of aryl, heteroaryl.

[0115] The following examples are only for the convenience of understanding the technical invention, and should not be regarded as specific limitations of the present application.

[0116] The raw materials and solvents involved in the synthesis of the compounds in the present application are purchased from Alfa, Acros and other suppliers well known to those skilled in the art.

[0117] The following compound Ax is a simple name of the heterocyclic compound Ax. For example, compound A4 is a simple name of the heterocyclic compound.

[0118] The synthetic route of compound A4 is as follows:

[0119] ;

[0120] Synthesis of compound A4-3:

[0121] Compound A4-1 (15.00 g, 47.12 mmol), compound A4-2 (5.79 g, 47.12 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4, 0.55 g, 0.47 mmol), potassium carbonate (16.28 g, 117.80 mmol), tetrahydrofuran (THF, 350 mL), deionized water (125 mL) were added into a 1000 mL three-necked round-bottom flask, replaced with vacuum nitrogen three times, then the system was heated to 60°C for 3 hours, TLC (thin layer chromatography, ethyl acetate: n-hexane = 1:20 as developing agent, 1:20 as volume ratio) was used to monitor the reaction, and compound A4-1 was consumed completely.

[0122] After cooling to room temperature, part of the solvent was removed by concentration under reduced pressure, ethyl acetate (200 mL) was added, washed with deionized water three times (100 mL*3), separated, and the silica gel sample was mixed and dried for column chromatography. Silica gel column chromatography purification (200-300 mesh silica gel, ethyl acetate: n-hexane = 1:20 as eluent, 1:20 as volume ratio) was carried out. After elution, 60°C reduced pressure concentration for 1 hour obtained white solid as compound A4-3 (9.32 g, mass purity: 99.42%, yield: 73.39%), mass spectrum result: 268.94 (M+H).

[0123] Synthesis of compound A4-5:

[0124] Compound A4-3 (9.00 g, 33.39 mmol), compound A4-4 (4.07 g, 33.39 mmol), tetrakis(triphenylphosphine)palladium (0.39 g, 0.33 mmol), potassium carbonate (11.54 g, 83.48 mmol), tetrahydrofuran (225 mL), deionized water (75 mL) were added into a 500 mL three-necked round-bottom flask, replaced with vacuum nitrogen for three times, then the system was heated to 75 °C for 3 hours, TLC (ethyl acetate: n-hexane = 1:15 as developing agent) was used to monitor the reaction, compound A4-3 was consumed completely;

[0125] The system was cooled to room temperature, and part of the solvent was removed by concentration under reduced pressure. Ethyl acetate (200 mL) was added, and deionized water was used for washing three times (100 mL*3). The mixture was separated, and the silica gel was used for column chromatography. The silica gel column chromatography purification was carried out (200-300 mesh silica gel, ethyl acetate: n-hexane = 1:15 as eluent). After elution, the white solid of compound A4-5 (6.27 g, mass purity: 99.36 %, yield: 70.40 %) was obtained by concentration under reduced pressure at 60 °C for 1 hour. The mass spectrometry result was 267.06 (M+H).

[0126] Synthesis of compound A4-8:

[0127] Compound A4-6 (15.00 g, 76.74 mmol), compound A4-7 (21.43 g, 84.41 mmol), 1,1-bis(diphenylphosphino)ferrocene palladium dichloride (Pd(dppf)Cl2, 0.56 g, 0.77 mmol), potassium acetate (KOAc, 18.83 g, 191.84 mmol), 1,4-dioxane (350 mL) were added into a 500 mL three-necked round-bottom flask, replaced with vacuum nitrogen for three times, then the system was heated to 100 °C for 4 hours, TLC (ethyl acetate: n-hexane = 1:30 as developing agent) was used to monitor the reaction, compound A4-6 was consumed completely;

[0128] The system was cooled to room temperature, and the solvent was removed by concentration under reduced pressure. Ethyl acetate (300 mL) was added, and deionized water was used for washing three times (100 mL*3). The mixture was separated, and the silica gel was used for column chromatography. The silica gel column chromatography purification was carried out (200-300 mesh silica gel, ethyl acetate: n-hexane = 1:30 as eluent). After elution, the oil of compound A4-8 (9.74 g, mass purity: 99.38 %, yield: 79.13 %) was obtained by concentration under reduced pressure at 50 °C for 1 hour. The mass spectrometry result was 161.04 (M+H).

[0129] Synthesis of compound A4-10:

[0130] Compound A4-8 (9.35 g, 58.29 mmol), compound A4-9 (5.50 g, 23.31 mmol), 1,1- bis(diphenylphosphino)ferrocene palladium dichloride (0.18 g, 0.17 mmol), potassium carbonate (8.06 g, 58.29 mmol), toluene (Tol, 250 mL), ethanol (EtOH, 50 mL), deionized water (50 mL) were added into a 500 mL three-necked round-bottom flask, replaced with vacuum nitrogen for three times, then the system was heated to 70 °C for 16 hours, TLC (dichloromethane: n-hexane = 1:10 as developing agent) was used to monitor the reaction, compound A4-9 was consumed completely;

[0131] The system was cooled to 60 °C, the solvent was removed by concentration under reduced pressure, ethyl acetate (300 mL) was added, washed with deionized water for three times (100 mL*3), separated, and then the silica gel dry column method was used for column chromatography purification (200-300 mesh silica gel, dichloromethane: n-hexane = 1:10 as eluent), after elution, the white solid was obtained by concentration under reduced pressure at 60 °C for 1 hour, which was compound A4-10 (4.60 g, mass purity: 99.63%, yield: 64.22%), and the mass spectrometry result was 307.08 (M+H).

[0132] Synthesis of compound A4-11:

[0133] Compound A4-10 (4.50 g, 14.65 mmol), compound A4-7 (7.81 g, 30.76 mmol), tris(dibenzylideneacetone)dipalladium (Pd2(dba)3, 0.14 g, 0.15 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropyl biphenyl (X-Phos, 0.14 g, 0.29 mmol), potassium acetate (3.59 g, 36.62 mmol), 1,4-dioxane (1,4-Dioxane, 200 mL) were added into a 500 mL three-necked round-bottom flask, replaced with vacuum nitrogen for three times, then the system was heated to 100 °C for 4 hours, TLC (ethyl acetate: n-hexane = 1:15 as developing agent) was used to monitor the reaction, compound A4-10 was consumed completely;

[0134] The system was cooled to 60 °C, the solvent was removed by concentration under reduced pressure, ethyl acetate (200 mL) was added, washed with deionized water for three times (100 mL*3), separated, and then the silica gel dry column method was used for column chromatography purification (200-300 mesh silica gel, ethyl acetate: n-hexane = 1:15 as eluent), after elution, the white solid was obtained by concentration under reduced pressure at 60 °C for 1 hour, which was compound A4-11 (5.31 g, mass purity: 99.49%, yield: 73.95%), and the mass spectrometry result was 491.33 (M+H).

[0135] Synthesis of compound A4:

[0136] Compound A4-11 (5.00 g, 10.20 mmol), compound A4-5 (5.71 g, 21.42 mmol), dichlorobis-(4-dimethylaminophenyl) palladium (Pd(aMphos)Cl2, 0.72 g, 0.10 mmol), potassium carbonate (3.52 g, 25.50 mmol), 1,4-dioxane (350 mL), deionized water (50 mL) were added into a 500 mL three-necked round-bottom flask, replaced with vacuum nitrogen three times, then the system was heated to 80 °C for 6 hours, TLC (dichloromethane: n-hexane = 1:5 as developing agent) was used to monitor the reaction, compound A4-11 was consumed completely;

[0137] The temperature was lowered to 60 °C, and the solvent was removed by concentration under reduced pressure. Ethyl acetate (300 mL) was added, and deionized water was washed three times (100 mL*3). The liquid was separated, and the silica gel was mixed and dried. The silica gel column chromatography purification was performed (200-300 mesh silica gel, dichloromethane: n-hexane = 1:5 as eluent). After elution, the white solid was obtained by concentration under reduced pressure at 60 °C for 1 hour. The sublimation purification was performed on the 5.04 g of compound A4 crude product to obtain sublimation compound A4 (3.14 g, mass purity: 99.95%, yield: 62.30%). The mass spectrometry result was 699.33 (M+H).

[0138] The compound A4 nuclear magnetic characterization result was: 1 H NMR (400 MHz, CDCl3) δ 8.79 – 8.72 (m, 4H),8.70 (d, J = 2.9 Hz, 2H), 8.38 (d, J = 2.9 Hz, 2H), 8.32 – 8.25 (m, 8H), 7.96(dd, J = 11.1, 6.9 Hz, 2H), 7.63 – 7.44 (m, 8H).

[0139] Compounds A15, A28, A29, A31, A71, A98, A111, A130, A149, A175, A178, A210, A234, A252, A319, A346, A416, A423, A441, A460, A464, and A470 were prepared by a similar method to the synthesis of compound A4, except that different raw materials were used, i.e., compound A4-6, compound A4-9, and A4-5 in the synthesis of compound A4 were replaced with other raw materials.

[0140] In the synthesis of A15, A28, A29, A31, A71, A98, A111, A130, the starting material A4-6 in the synthesis of compound A4 is replaced in turn by the following structural formula:

[0141] , , , , , , , .

[0142] The starting material A4-9 is replaced in turn by the following structural formula:

[0143] , , , , , , , .

[0144] The starting material A4-5 is replaced in turn by the following structural formula:

[0145] , , , , , , , .

[0146] In the synthesis of A149, A175, A178, A210, A234, A252, A319, A346, the starting material A4-6 in the synthesis of compound A4 is replaced in turn by the following structural formula:

[0147] , , , , , , , .

[0148] The starting material A4-9 is replaced in turn by the following structural formula:

[0149] , , , , , , , .

[0150] Raw material A4-5 is replaced by the following structural formula in turn:

[0151] , , , , , , , .

[0152] In the synthesis of A416, A423, A441, A460, A464, A470, the raw material A4-6 in the synthesis of compound A4 is replaced by the following structural formula in turn:

[0153] , , , , , .

[0154] Raw material A4-9 is replaced by the following structural formula in turn:

[0155] , , , , , ,

[0156] Raw material A4-5 is replaced by the following structural formula in turn:

[0157] , , , , , .

[0158] Among them, the CAS numbers of the following raw materials A4-5 are 3842-55-5, 29509-91-9, 2511017-74-4, 2417550-95-7, 1342819-12-8, 1472062-94-4, 1883265-32-4, 149817-62-9, 1300115-09-6, 1689576-03-1

[0159] , , , , , , , , , .

[0160] A4, A15, A28, A29, A31, A71, A98, A111, A130, A149, A175, A178, A210, A234, A252, A319, A346, A416, A423, A441, A460, A464, A470 correspond to the structural formula in turn:

[0161] , .

[0162] A15 yield is 70.11%; mass spectrum result (M+H) is 854.07; nuclear magnetic resonance characterization result is 1 H NMR (400 MHz, CDCl3) δ 8.41 – 8.32 (m, 6H), 8.17 (t, J = 3.0 Hz, 2H), 7.96 (dd, J = 11.1, 6.9Hz, 2H), 7.79 – 7.66 (m, 6H), 7.64 – 7.57 (m, 4H), 7.54 – 7.45 (m, 10H), 7.42(d, J = 14.5 Hz, 2H).

[0163] A28 yield is 65.24%; mass spectrum result (M+H) is 726.88; nuclear magnetic resonance characterization result is 1 H NMR (400 MHz, CDCl3) δ 8.40 – 8.32 (m, 8H), 8.22 (d, J = 2.9 Hz, 1H), 8.14 (d, J = 14.9 Hz, 1H), 8.01 (dd, J= 15.0, 2.9 Hz, 1H), 7.54 – 7.46 (m, 12H)。

[0164] A29 yield was 70.52%; mass spectrometry result (M+H) was 777.35; nuclear magnetic resonance characterization result was 1 H NMR (400 MHz, CDCl3) δ 8.39 – 8.33 (m, 8H), 8.26 (d, J = 3.1 Hz, 1H), 8.15 (d, J = 15.0 Hz, 1H), 7.78-7.72 (m, 2H), 7.54 – 7.45 (m, 14H), 7.45 – 7.39 (m, 1H), 7.35 (dd, J = 15.0, 2.9 Hz, 1H).

[0165] A31 yield was 63.84%; mass spectrometry result (M+H) was 719.31; nuclear magnetic resonance characterization result was 1 H NMR (400 MHz, CDCl3) δ 8.40 – 8.32 (m, 8H), 7.94 (dd, J = 15.0, 9.9 Hz, 1H), 7.71 (dd, J = 16.0, 3.0 Hz, 1H), 7.54 – 7.46 (m, 12H), 7.41 (dd, J = 16.0, 14.9, Hz, 1H).

[0166] A71 yield was 68.17%; mass spectrometry result (M+H) was 751.93; nuclear magnetic resonance characterization result was 1 H NMR (400 MHz, CDCl3) δ 8.43 (dd, J = 14.9, 3.0 Hz, 2H), 8.40 – 8.31 (m, 8H), 7.87 – 7.80 (m, 2H), 7.69 – 7.60 (m, 2H), 7.55 – 7.46 (m, 12H).

[0167] A98 yield was 72.26%; mass spectrometry result (M+H) was 749.96; nuclear magnetic resonance characterization result was 1H NMR (400 MHz, CDCl3) δ 8.91 (dd, J = 14.5, 3.5 Hz, 1H), 8.38 – 8.29 (m, 4H), 8.21 (s, 2H), 8.02 (dd, J = 15.0, 2.9 Hz, 1H), 7.97 – 7.88 (m, 5H), 7.59 – 7.45 (m, 12H), 7.45 – 7.30 (m, 3H).

[0168] The yield of A111 was 76.32%; the mass spectrometry result (M+H) was 584.77; the nuclear magnetic resonance characterization result was 1 H NMR (400 MHz, CDCl3) δ 8.93 (dd, J = 14.5, 3.6 Hz, 1H), 8.42 – 8.31 (m, 8H), 8.03 (dd, J =15.0, 2.9 Hz, 1H), 7.94 (s, 1H), 7.54 – 7.41 (m, 14H), 7.35 (s, 1H).

[0169] The yield of A130 was 69.42%, and the mass spectrometry result (M+H) was 751.93; the nuclear magnetic resonance characterization result was 1 H NMR (400 MHz, CDCl3) δ 8.98 (s, 2H), 8.39 – 8.32 (m, 8H), 7.54 – 7.46 (m, 12H), 7.33 (s, 2H), 7.27 (d, J = 18.0 Hz, 2H).

[0170] The yield of A149 was 78.47%; the mass spectrometry result (M+H) was 852.05; the nuclear magnetic resonance characterization result was 1 H NMR (400 MHz, CDCl3) δ 9.09 (t, J = 3.0 Hz, 2H), 8.49 (dd, J = 15.0, 3.0 Hz, 2H), 8.40 – 8.32(m, 4H), 8.20 – 8.13 (m, 2H), 8.11 – 7.97 (m, 6H), 7.66 – 7.55 (m, 4H), 7.55– 7.46 (m, 8H), 7.43 – 7.35 (m, 2H).

[0171] The yield of A175 was 72.33%; the mass spectrometry result (M+H) was 932.1; the nuclear magnetic resonance characterization result was1 H NMR (400 MHz, CDCl3) δ 8.51 (dd, J = 13.1, 4.8 Hz, 1H), 8.40 - 8.32 (m, 4H), 8.07 (d, J = 15.0 Hz, 1H), 8.00 - 7.93 (m, 4H), 7.83 - 7.72 (m, 6H), 7.54 - 7.45 (m, 10H), 7.45 - 7.36 (m, 3H), 7.29 - 7.21 (m, 4H), 6.79 (s, 1H).

[0172] A178 yield 67.25%; mass spectrum result (M+H) 903.40; NMR characterization result 1 H NMR (400 MHz, CDCl3) δ 8.51 (dd, J = 13.1, 4.8 Hz, 1H), 8.40 - 8.32 (m, 4H), 8.07 (d, J = 15.0 Hz, 1H), 8.00 - 7.93 (m, 4H), 7.83 - 7.72 (m, 6H), 7.54 - 7.45 (m, 10H), 7.45 - 7.36 (m, 3H), 7.29 - 7.21 (m, 4H), 6.79 (s, 1H).

[0173] A210 yield 74.56%; mass spectrum result (M+H) 801.99; NMR characterization result 1 H NMR (400 MHz, CDCl3) δ 9.08 (dd, J = 14.5, 3.4 Hz, 2H), 8.40 - 8.32 (m, 8H), 8.17 (dd, J = 14.5, 3.4 Hz, 2H), 7.74-7.67 (m, 2H), 7.66 - 7.58 (m, 2H), 7.54 - 7.46 (m, 12H).

[0174] A234 yield 68.86%; mass spectrum result (M+H) 801.99; NMR characterization result 1H NMR (400 MHz, CDC13) δ 9.11 (d, J = 15.0 Hz, 2H), 8.43 (dd, J = 15.0, 2.9 Hz, 2H), 8.40 - 8.30 (m, 8H), 7.92 (t, J = 1.6 Hz, 2H), 7.70-7.66 (m, 2H), 7.54 - 7.46 (m, 12H).

[0175] A252 yield 75.62%; mass spectrum result (M+H) 791.96; NMR characterization result 1 H NMR (400 MHz, CDC13) δ 8.38 - 8.31 (m, 8H), 8.10 (d, J = 2.8 Hz, 1H), 7.67 (s, 1H), 7.64 -7.53 (m, 3H), 7.52 - 7.45 (m, 13H).

[0176] A319 yield 73.81%; mass spectrum result (M+H) 904.17; NMR characterization result 1 H NMR (400 MHz, CDC13) δ 8.53 - 8.45 (m, 4H), 8.41 - 8.32 (m, 4H), 7.98 (dd, J = 14.5, 3.4Hz, 1H), 7.86 - 7.76 (m, 2H), 7.57 - 7.46 (m, 7H), 7.41 - 7.35 (m, 5H), 7.35- 7.27 (m, 1H), 1.33 (s, 18H).

[0177] A346 yield 76.77%; mass spectrum result (M+H) 854.02; NMR characterization result 1 H NMR (400 MHz, CDC13) δ 8.41 - 8.32 (m, 4H), 8.08-8.02 (m, 1H), 7.92 - 7.89 (m, 1H), 7.81 -7.71 (m, 4H), 7.68 (d, J = 2.0 Hz, 2H), 7.55 - 7.39 (m, 9H), 7.36 - 7.26 (m, 2H), 7.25 - 7.15 (m, 1H), 1.69 (s, 6H).

[0178] A416 yield 66.35%; mass spectrum result (M+H) 701.87; NMR characterization result 1H NMR (400 MHz, CDC13) δ 9.18 (dd, J = 14.9, 3.0 Hz, 4H), 9.14 (s, 4H), 8.55 (dd, J = 15.0, 2.9 Hz, 4H), 7.78-7.70 (m, 4H), 7.28 - 7.18 (m, 8H).

[0179] A423 yield 72.62%; mass spectrometry result (M+H) 751.93; nuclear magnetic resonance characterization result 1 H NMR (400 MHz, CDC13) δ 9.18 (dd, J = 14.9, 3.0 Hz, 4H), 9.14 (s, 4H), 8.58-8.50 (m, 5H), 8.24 (d, J = 2.9 Hz, 1H), 8.14 (dd, J = 15.0, 2.8 Hz, 1H), 7.88 - 7.82 (m, 1H), 7.81 - 7.69 (m, 5H), 7.35 (dd, J = 15.0, 2.9 Hz, 1H), 7.28-7.20 (m, 4H).

[0180] A441 yield 71.34%; mass spectrometry result (M+H) 705.9; nuclear magnetic resonance characterization result 1 H NMR (400 MHz, CDC13) δ 8.41 - 8.32 (m, 8H), 7.54 - 7.45 (m, 12H).

[0181] A460 yield 74.40%; mass spectrometry result (M+H) 778.09.

[0182] A464 yield 75.93%; mass spectrometry result (M+H) 806.02; nuclear magnetic resonance characterization result 1 H NMR (400 MHz, CDC13) δ 8.40 - 8.33 (m, 8H), 7.96 (dd, J = 11.1, 6.9 Hz, 2H), 7.60 (dd, J = 11.0, 6.9 Hz, 2H), 7.53 - 7.48 (m, 12H).

[0183] A470 yield 76.92%; mass spectrometry result (M+H) 912.18; nuclear magnetic resonance characterization result 1H NMR (400 MHz, CDC13) δ 8.41 - 8.30 (m, 8H), 8.08 - 8.02 (m, 2H), 7.55 - 7.46 (m, 14H), 7.41 (s, 2H).

[0184] The synthetic route of compound A389 is as follows:

[0185] ;

[0186] Synthesis of compound A389-3:

[0187] Compound A389-1 (10.00 g, 27.95 mmol), compound A389-2 (4.48 g, 27.95 mmol), tetrakis(triphenylphosphine)palladium (0.32 g, 0.28 mmol), sodium hydroxide (2.79 g, 69.87 mmol), tetrahydrofuran (300 mL), deionized water (100 mL) were added into a 500 mL three-necked round-bottom flask, replaced with vacuum nitrogen for three times, then the system was heated to 75°C for 4 hours, and the reaction was monitored by TLC (ethyl acetate: n-hexane = 1:15 as developing agent). Compound A389-1 was consumed completely.

[0188] After the reaction was completed, a large amount of solid was precipitated, which was directly suction filtered to obtain 12 g of solid. Tetrahydrofuran (500 mL) was added to dissolve and clarify, and silica gel (60 g, 200-300 mesh chromatographic silica gel) was filtered once. The filtrate was combined and concentrated at 50°C for 1 hour to obtain 10 g of white solid. Toluene (90 mL) was added, and the oil was heated to 105°C to dissolve and clarify. The temperature was naturally lowered to room temperature, and stirring was performed at 1 hour. Filtration was performed, and the white solid was obtained by vacuum drying at 70°C for 3 hours. The white solid was compound A389-3 (9.15 g, mass purity: 99.37%, yield: 74.76%), and the mass spectrometry result was 438.12 (M+H).

[0189] Synthesis of compound A389-4:

[0190] Compound A389-3 (9.00 g, 20.55 mmol), compound A4-7 (5.22 g, 20.55 mmol), tris(dibenzylideneacetone)dipalladium (0.19 g, 0.21 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropyl biphenyl (0.20 g, 0.41 mmol), potassium acetate (5.04 g, 51.38 mmol), 1,4-dioxane (350 mL) were added into a 500 mL three-necked round-bottom flask, replaced with vacuum nitrogen for three times, then the system was heated to 100°C for 4 hours, and the reaction was monitored by TLC (ethyl acetate: n-hexane = 1:15 as developing agent). Compound A389-3 was consumed completely.

[0191] The reaction solution was cooled to room temperature, and part of the solvent was removed by concentration under reduced pressure. Ethyl acetate (200 mL) was added, and the mixture was washed with deionized water three times (100 mL*3). The mixture was separated, and the silica gel was dried and columned. The silica gel column was purified (200-300 mesh silica gel, ethyl acetate: n-hexane = 1:15 as eluent). After elution, the white solid was obtained by concentration under reduced pressure at 60°C for 1 hour. The mass of the compound A389-4 was 8.24 g (mass purity: 99.29 %, yield: 75.73 %), and the mass spectrum result was 530.25 (M+H).

[0192] Synthesis of compound A389-6:

[0193] The synthesis and purification method of compound A389-3 was referred to, and only the corresponding raw materials were changed. The target compound A389-6 was obtained (9.37 g, mass purity: 99.50 %, yield: 72.12 %), and the mass spectrum result was 348.11 (M+H).

[0194] Synthesis of compound A389-7:

[0195] The synthesis and purification method of compound A389-4 was referred to, and only the corresponding raw materials were changed. The target compound A389-7 was obtained (8.24 g, mass purity: 99.39 %, yield: 75.73 %), and the mass spectrum result was 440.24 (M+H).

[0196] Synthesis of compound A389-9:

[0197] Compound A389-7 (9.00 g, 20.48 mmol), compound A389-8 (6.30 g, 20.48 mmol), 1,1'-bis(diphenylphosphino)ferrocene palladium dichloride (0.15 g, 0.20 mmol), potassium carbonate (7.08 g, 51.21 mmol), toluene (250 mL), ethanol (50 mL), and deionized water (50 mL) were added to a 500 mL three-necked round-bottom flask. The system was replaced with vacuum nitrogen three times, and then heated to 75°C for 6 hours. The reaction was monitored by TLC (ethyl acetate: n-hexane = 1:15 as developing agent). Compound A389-7 was consumed.

[0198] After the reaction was completed, a large amount of solid was precipitated, which was directly suction filtered to obtain 10 g of solid. Tetrahydrofuran (300 mL) was added to dissolve the solid, which was then filtered once through silica gel (60 g, 200-300 mesh chromatographic column silica gel). The filtrate was combined and concentrated at 50°C for 1 hour to obtain 8 g of white solid. Toluene (60 mL) was added, and the oil was heated to 105°C to dissolve the solid, which was then naturally cooled to room temperature and stirred for 1 hour. The mixture was suction filtered, and the filter cake was dried at 70°C under vacuum for 3 hours to obtain white solid compound A389-9 (7.68 g, mass purity: 99.54%, yield: 69.42%). The mass spectrometry result was 540.21 (M+H).

[0199] Synthesis of compound A389

[0200] Compound A389-9 (7.00 g, 12.96 mmol), compound A389-4 (6.86 g, 12.96 mmol), dichlorobis-(4-dimethylaminophenyl) palladium (0.10 g, 0.13 mmol), potassium carbonate (4.48 g, 32.40 mmol), 1,4-dioxane (250 mL), and deionized water (50 mL) were added to a 500 mL three-necked round-bottom flask, which was replaced with nitrogen three times, and then the system was heated to 80°C for reaction for 4 hours. TLC (dichloromethane: n-hexane = 1:3 as developing agent) was used to monitor the reaction, and compound A389-9 was completely consumed.

[0201] After the reaction was completed, a large amount of solid was precipitated, which was directly suction filtered to obtain 10 g of solid. Tetrahydrofuran (300 mL) was added to dissolve the solid, which was then filtered once through silica gel (60 g, 200-300 mesh chromatographic column silica gel). The filtrate was combined and concentrated at 50°C for 1 hour to obtain 8 g of white solid. Toluene (60 mL) was added, and the oil was heated to 105°C to dissolve the solid, which was then naturally cooled to room temperature and stirred for 1 hour. The mixture was suction filtered, and the filter cake was dried at 70°C under vacuum for 3 hours to obtain white solid compound A389-9 (7.68 g, mass purity: 99.54%, yield: 69.42%). The mass spectrometry result was 540.21 (M+H).

[0202] The nuclear magnetic resonance characterization result of compound A389 was as follows: 1H NMR (400 MHz, CDCl3) δ 8.39 – 8.31 (m,7H), 8.09 (d, J = 14.9 Hz, 1H), 7.98 (dd, J = 14.6, 3.4 Hz, 1H), 7.88 (d, J =3.0 Hz, 1H), 7.81 – 7.70 (m, 4H), 7.59 – 7.52 (m, 2H), 7.52 – 7.45 (m, 9H),7.44 – 7.26 (m, 3H), 1.69 (s, 6H)。

[0203] Compounds A490, A492 were prepared by a similar synthetic method of compound A389, except that the starting materials used were different, i.e. the starting material A389-1, starting material A389-5, starting material A389-8 in the synthesis of compound A389 were replaced by other starting materials, respectively.

[0204] In the synthesis of A490, A492, the starting material A389-1 in the synthesis of compound A389 was replaced by

[0205] , the starting material A389-5 was replaced by , the starting material A389-8 was replaced by , respectively.

[0206] The structural formula of A490, A492 is:

[0207] .

[0208] The yield of A490 was 68.35%, the corresponding mass spectrum result (M+H) was 749.96, and the corresponding nuclear magnetic resonance result was 1 HNMR (400 MHz, CDCl3) δ 8.89 (dd, J = 15.0, 3.1 Hz, 2H), 8.37 (dd, J = 15.0, 2.9 Hz, 4H), 8.23 (s, 2H), 7.97 – 7.91 (m, 6H), 7.70 (t, J = 15.0 Hz, 2H), 7.55(dd, J = 3.2, 1.4 Hz, 4H), 7.54 – 7.45 (m, 8H)。

[0209] The yield corresponding to A492 is 70.49%, the mass spectrum result (M+H) corresponding to which is 700.89, and the nuclear magnetic resonance result corresponding to which is δ 9.18 (dd, J = 14.9, 3.0 Hz, 2H), 9.14 (s, 2H), 8.55 (dd, J = 15.0, 2.9 Hz, 2H), 8.39-8.32 (m, 2H), 8.23 (s, 1H), 8.10 (t, J = 3.0 Hz, 1H), 7.97-7.91 (m, 2H), 7.79-7.66 (m, 3H), 7.64-7.58 (m, 2H), 7.58-7.45 (m, 6H), 7.27-7.19 (m, 2H).

[0210] Application Example: Preparation of an Organic Electroluminescent Device

[0211] As shown in the accompanying drawings, an organic electroluminescent device 1 comprises a glass substrate 1, an anode 2, a hole injection layer 3, a first hole transport layer 4 (HTL1), a second hole transport layer 5 (HTL2), a light-emitting layer 6, a hole blocking layer 7 (HBL), an electron transport layer 8 (ETL), and a cathode 9, which are arranged in layers. Figure 1 A preparation method of an organic electroluminescent device 1 comprises the following steps:

[0212] A glass substrate 1 having an ITO transparent electrode (anode 2) on the surface is provided, and the thickness of the anode is 100 nm.

[0213] A compound HATCN is evaporated on the surface of the anode 2 to form a hole injection layer 3, and the thickness of the hole injection layer 3 is 5 nm.

[0214] A compound HTM1 is evaporated on the surface of the hole injection layer 3 to form a first hole transport layer 4 (HTL1), and the thickness of the first hole transport layer 4 is 60 nm.

[0215] A compound HTM2 is evaporated on the surface of the first hole transport layer 4 to form a second hole transport layer 5 (HTL2), and the thickness of the second hole transport layer 5 is 10 nm.

[0216] A host material and a guest material (the weight ratio of the host material to the guest material is 97%:3%) are co-evaporated on the surface of the second hole transport layer 5 to form a light-emitting layer 6, and the thickness of the light-emitting layer 6 is 25 nm.

[0217] A hole blocking material is evaporated on the surface of the light-emitting layer 6 to form a hole blocking layer 7 (HBL), and the thickness of the hole blocking layer 7 is 5 nm.

[0218] A hole blocking material is evaporated on the surface of the light-emitting layer 6 to form a hole blocking layer 7 (HBL), and the thickness of the hole blocking layer 7 is 5 nm.

[0219] An electron transport material was evaporated on the surface of the hole blocking layer 7 to form an electron transport layer 8 (ETL) with a thickness of 350 nm;

[0220] A metal Mg / Ag (Mg and Ag in a weight ratio of 1:9) was evaporated on the surface of the electron transport layer 8 to form a cathode 9 with a thickness of 100 nm, thereby obtaining the organic electroluminescent device 1.

[0221] The hole blocking material is the heterocyclic compound or the comparative compound of the present application, and the electron transport material is the electron transport material ETL or the heterocyclic compound LiQ (in a weight ratio of 1:1) of the present application.

[0222] The structural formulas of HATCN, HTM1, HTM2, the host material (BH), the guest material (BD), ETL, LiQ, and the comparative compounds 1-3 are as follows:

[0223] .

[0224] Evaluation:

[0225] The organic electroluminescent device 1 was subjected to device performance testing, and the heterocyclic compound and the comparative compounds 1-3 prepared in the present application were used as the hole blocking material and the electron transport material for comparison. A constant current power supply (Keithley 2400) was used, a fixed current density was used to flow through the light-emitting element, and a spectroradiometer (CS 2000) was used to test the luminescence spectrum. At the same time, the IVL (current-voltage-luminance) performance of the device was determined at 10 mA / cm 2 The results are shown in Table 1 below (in Table 1, the examples use the heterocyclic compound of the present application, and the comparative examples use the comparative compounds).

[0226] Table 1

[0227]

[0228] From the data comparison in Table 1 above, it can be seen that the heterocyclic compound of the present application used as the hole blocking layer material and the electron transport layer material in the organic electroluminescent device 1 exhibits more superior performance in driving voltage, luminous efficiency, and device lifetime compared to the comparative compounds 1-3.

[0229] As Figure 2As shown, it is a structural schematic diagram of the organic electroluminescent device 2, including glass substrate 01, anode 02, hole injection layer 03, first hole transport layer 04, first electron blocking layer 05, first light emitting layer 06, first electron transport layer 07, N-type charge generation layer 08, P-type charge generation layer 09, second hole transport layer 10, second electron blocking layer 11, second light emitting layer 12, second electron transport layer 13, electron injection layer 14, cathode 15, which are sequentially stacked.

[0230] The method for manufacturing the organic electroluminescent device 2, comprising the following steps:

[0231] Providing a glass substrate 01 with an ITO transparent electrode (anode 02) on the surface, the thickness of the anode is 1000 nm;

[0232] Evaporating compound HATCN on the surface of the anode 02 to form a hole injection layer 03, the thickness is 20 nm;

[0233] Evaporating HTM1 on the surface of the hole injection layer 03 to form a first hole transport layer 04, the thickness is 10 nm;

[0234] Evaporating HTM2 on the surface of the first hole transport layer 04 to form a first electron blocking layer 05, the thickness is 5 nm;

[0235] Co-evaporating host material (BH) and guest material (BD) on the surface of the first electron blocking layer 05 to form a first light emitting layer 06, wherein the weight ratio of the host material (BH) and the guest material (BD) is 97:3, and the thickness of the first light emitting layer 06 is 20 nm;

[0236] Co-evaporating ETL and LiQ on the surface of the first light emitting layer 06 to form a first electron transport layer 07, wherein the weight ratio of ETL and LiQ is 1:1, and the thickness of the first electron transport layer 07 is 35 nm;

[0237] Co-evaporating heterocyclic compound and Yb on the surface of the first electron transport layer 07 to form an N-type charge generation layer 08 (denoted as N-CGL layer), the type of heterocyclic compound in the N-CGL layer of each embodiment and comparative example is shown in Table 2, and the weight ratio of the heterocyclic compound and Yb is 95:5, and the thickness of the N-type charge generation layer 08 is 100 nm;

[0238] Evaporating HATCN on the surface of the N-type charge generation layer 08 to form a P-type charge generation layer 09, the thickness is 10 nm;

[0239] Evaporating HTM1 on the surface of the P-type charge generation layer 09 to form a second hole transport layer 10, the thickness is 10 nm;

[0240] A second electron blocking layer 11 is formed by evaporating HTM2 on the surface of the second hole transport layer 10, and the thickness of the second electron blocking layer 11 is 5 nm;

[0241] A second light emitting layer 12 is formed by co-evaporating a host material (BH) and a guest material (BD) on the surface of the second electron blocking layer 11, wherein the weight ratio of the host material (BH) and the guest material (BD) is 97:3, and the thickness of the second light emitting layer 12 is 20 nm;

[0242] A second electron transport layer 13 is formed by co-evaporating ETL and LiQ on the surface of the second light emitting layer 12, wherein the weight ratio of ETL and LiQ is 1:1, and the thickness of the second electron transport layer 13 is 35 nm;

[0243] An electron injection layer 14 is formed by evaporating Yb on the surface of the second electron transport layer 13, and the thickness of the electron injection layer 14 is 1 nm;

[0244] A cathode 15 is formed by evaporating Ag on the surface of the electron injection layer 14, and the thickness of the cathode 15 is 1000 nm, thereby obtaining an organic electroluminescent device 2.

[0245] Evaluation:

[0246] The prepared organic electroluminescent device 2 is subjected to device performance test. A constant current power supply (Keithley 2400) is used to flow a fixed current density through the light emitting element, and a spectroradiometric luminance meter (CS 2000) is used to test the light emitting spectrum. At the same time, the IVL (current-voltage-luminance) performance of the device is determined at 10 mA / cm 2 The LT95 device lifetime is tested at 1000 nits, and the test results are shown in Table 2 (in Table 2, the examples use the heterocyclic compounds of the present application, and the comparative examples use the comparative compounds).

[0247] Table 2

[0248]

[0249] As can be seen from Table 2, the N-CGL layer prepared by using the heterocyclic compound of the present application has a significantly reduced device operating voltage when used in a tandem organic electroluminescent device, effectively reducing the power consumption of the device. At the same time, the current efficiency and the device lifetime are significantly improved. The heterocyclic compound as an N-type charge generation layer material is suitable for OLED light emitting devices, and has the potential to be applied in the AMOLED industry.

[0250] The above results show that the heterocyclic compound has high luminous efficiency, low voltage, long life and the like, and can be used in an organic light-emitting device. In particular, as a hole blocking layer material, an electron transport layer material, an N-type charge generation layer material, the heterocyclic compound has the possibility of application in the AMOLED industry.

Claims

1. A heterocyclic compound, characterized by, A structure general formula is as shown in formula (1): Formula (1), Wherein, ring A is selected from any one of the following structures: ； Wherein, X is CRaRb, O, S or Se; * indicates the connection site of ring A and L1, L2 in formula (1); Ra, Rb are independently selected from hydrogen or methyl; R2, R3 are independently selected from hydrogen, deuterium, halogen, cyano or C1-C6 alkyl; a, b are both integers from 0 to 4, when a is an integer from 2 to 4, each R2 is the same or different; when b is an integer from 2 to 4, each R3 is the same or different; X1-X6 are independently selected from N or CH, and at least one of X1-X3 is N, and at least one of X4-X6 is N; L1, L2 are independently selected from per-deuterated C6-C20 arylene; Ar1, Ar2, Ar3, Ar4 are independently selected from one of the following structural formulas: 。 2. The heterocyclic compound according to claim 1, characterized by The ring A structure shown in formula (1) is selected from one of the following structures: ； Wherein, R2, R3 are independently selected from hydrogen, deuterium, halogen, cyano or C1-C6 alkyl; a, b are both integers from 0 to 4, when a is an integer from 2 to 4, each R2 is the same or different; when b is an integer from 2 to 4, each R3 is the same or different.

3. The heterocyclic compound according to claim 1, characterized by L1, L2 are independently selected from per-deuterated phenylene, per-deuterated biphenylene or per-deuterated naphthylene; and / or, in ring A the structure is selected from a dibenzofuran ring, a fluorene ring, or a naphthobenzofuran ring.

4. The heterocyclic compound according to claim 1, characterized by At least two of X1-X3 are N, and at least two of X4-X6 are N.

5. The heterocyclic compound according to any one of claims 1 to 2, characterized by X1-X6 are all N; Or, the ring A contains at least one deuterium atom.

6. The heterocyclic compound according to claim 1, characterized by The heterocyclic compound represented by formula (1) satisfies at least one of the following conditions: (1) the six-membered rings of X1-X3 and X4-X6 are independently selected from one of the following structural formulas: ； (2) the six-membered rings of X1-X3 and X4-X6 are the same structure; (3) L1 and L2 are independently selected from one of the following structural formulas: ； (4) L1 and L2 are the same structure; (5) ring A is selected from one of the following structural formulas: ； (6) Ar1 and Ar3 are the same structure, and Ar2 and Ar4 are the same structure; (7) the following two groups of ring A in formula (1) are the same structure 、 。 7. An organic electroluminescent device, characterized by The heterocyclic compound of any one of claims 1-6.

8. The organic electroluminescent device according to claim 7, characterized in that Including: An anode, a cathode and an organic layer between the anode and the cathode; The organic layer includes a light-emitting layer, and further includes at least one of an electron transport layer, a hole blocking layer and an N-type charge generation layer; The material of at least one of the electron transport layer, the hole blocking layer or the N-type charge generation layer contains the heterocyclic compound of any one of claims 1-6.

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