Spiro compound and organic light-emitting device

Abstract

The invention discloses a spiro compound and an organic light-emitting device. The structural general formula of the spiro compound is shown in the specification, in the formula, A ring is selected from substituted or unsubstituted benzene ring and substituted or unsubstituted naphthalene ring. The compound has the advantages of high optical and electrical stability, low driving voltage, high luminous efficiency, long device service life and the like, can be used as a luminous layer, a hole blocking layer or an electron transport layer, and is applied to OLED (Organic Light Emitting Diode) luminescent devices.

Description

TECHNICAL FIELD

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

[0002] In today's era of rapid technological development, display and lighting technology, as a key field of information dissemination and visual presentation, is constantly driving innovation and change in related industries. Among them, organic light-emitting devices (OLED) stand out as a new generation of display technology with their self-luminous, high contrast, wide viewing angle, fast response speed, and flexible display, and many other unique advantages, which have attracted more and more attention in the field of display and lighting, and have shown a very broad application prospect, and are expected to become the mainstream technology of future display and lighting market.

[0003] However, although the OLED technology has developed rapidly, compared with the growing application demand of the market, the current OLED device still needs to be further improved in terms of key performance such as luminous efficiency, driving voltage, and service life. Organic functional materials, as the core component of OLED light-emitting devices, their performance characteristics play a decisive role in the overall performance of the device. Specifically, thermal stability determines the performance retention ability of the material in a high temperature environment, and good thermal stability can ensure that the device works stably under different temperature conditions, avoiding the performance degradation or even failure of the material due to temperature rise; photochemical stability is related to the anti-degradation ability of the material under light conditions, and stable photochemical properties help to maintain the luminous intensity and color purity of the device, and prolong the service life of the device; electrochemical stability affects the stability of the material under the action of electric field, and high electrochemical stability can reduce the oxidation-reduction reaction of the material in the electric field and reduce the damage to the electrode and the material layer; quantum yield reflects the efficiency of the material converting electrical energy into light energy, and higher quantum yield means higher luminous efficiency; film forming stability determines the uniformity and compactness of the material in the process of forming a thin film, and good film forming stability helps to improve the performance consistency and reliability of the device; crystallinity has an important influence on the electron transport performance and light-emitting performance of the material, and appropriate crystallinity can optimize the electron transport channel of the material and improve the luminous efficiency of the device; color saturation is directly related to the display color quality of the device, and high color saturation can present more vivid and realistic colors to meet the user's demand for high-quality display.

[0004] In order to improve the performance of OLED devices, researchers have been constantly exploring and developing new organic functional materials. Patent document KR1020150129282A discloses a spirofluorene-attached bistriazine electron transport material (SBT) having a structure in which a spirofluorene is connected to a bistriazine. ), which to some extent solves the problem of insufficient electrochemical stability of organic functional materials, reduces the redox reaction of the material in the electric field by improving the electrochemical stability of the material, and thus to some extent realizes the effect of improving the service life of the OLED device. It should be pointed out that the material still has a large optimization space in terms of driving voltage and light and electrical stability. Lower light and electrical stability can lead to gradual performance degradation of the material under long-term light or electric field, affecting the luminous efficiency and service life of the device; and higher driving voltage will increase the energy consumption of the device, aggravate the electrochemical damage of the electrode and material layer, and is not conducive to the long-term stable operation of the device.

[0005] Therefore, it is of great significance to develop new functional materials with excellent comprehensive performance, especially organic functional materials that can improve electrochemical stability and electrical conductivity while effectively reducing driving voltage and improving light and electrical stability, for further improving the performance of OLED devices and promoting the wide application of OLED technology in the fields of display and lighting. 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 spiro compound and an organic light-emitting device.

[0007] In some embodiments, a spiro compound has the following structure: Formula (1) In formula (1), the A ring is selected from a substituted or unsubstituted benzene ring, or a substituted or unsubstituted naphthalene ring; X is selected from a single bond, O or S; * indicates a connection site in L1; X1, X2, X3are each independently selected from N or CR4, and at least one is N; L1is selected from any one of the following structures shown in formula (A-1) to formula (A-11):

[0008] ; In formula (A-1) to formula (A-11) indicates a connection site of L1; R1, R2are each independently selected from a substituted or unsubstituted C1-C40alkyl, a substituted or unsubstituted C1-C40heteroalkyl, a substituted or unsubstituted C3-C40alkylsilyl, a substituted or unsubstituted C6-C60arylsilyl, a substituted or unsubstituted C3-C40cycloalkyl, or a substituted or unsubstituted C3-C40heterocycloalkyl; R3, R4, R5, R6are each independently selected from hydrogen, deuterium, halogen, cyano, isocyano, nitro, substituted or unsubstituted C1-C40alkyl, substituted or unsubstituted C1-C40heteroalkyl, C2-C40alkenyl, C2-C40alkynyl, substituted or unsubstituted C3-C40cycloalkyl, substituted or unsubstituted C3-C40heterocycloalkyl, substituted or unsubstituted C6-C60aryl, substituted or unsubstituted C2-C60heteroaryl, substituted or unsubstituted C1-C40alkoxy, substituted or unsubstituted C6-C60aryloxy, substituted or unsubstituted C1-C40alkylsilyl, substituted or unsubstituted C6-C60arylsilyl, substituted or unsubstituted C1-C40alkylboron, substituted or unsubstituted C6-C60arylboron, substituted or unsubstituted C6-C60arylphosphine, or substituted or unsubstituted C6-C60arylamide; a, b, f, g are each independently selected from an integer from 0 to 4; c, e are selected from an integer from 0 to 3; d is selected from an integer from 0 to 5; Ar1, Ar2are independently selected from substituted or unsubstituted C6-C30aryl, substituted or unsubstituted C2-C30heteroaryl; the substituents in the ring A, Ar1, Ar2, R1-R6 are each independently selected from at least one of deuterium, halogen, cyano, isocyano, phosphine, C1-C6alkyl, C3-C16cycloalkyl, C1-C6alkyl substituted amide, C1-C6hydrocarbon substituted or unsubstituted C6-C30aryl, C1-C6hydrocarbon substituted or unsubstituted C3-C30heteroaryl, wherein the number of substitutions is from monosubstitution to the maximum number of substitutions; the heteroatoms in the heteroaryl, heteroalkyl and heterocycloalkyl are independently selected from at least one of O, S, N, Se, Si and Ge.

[0009] Compared with the prior art, the application has the following advantages: The spiro compound of the application has excellent light and electrical stability, significantly reduced driving voltage, significantly improved luminous efficiency, and significantly prolonged device life. These significantly excellent characteristics enable the spiro compound to be used as an electron transport material or a hole blocking layer material, and to be widely used in OLED light emitting devices. In addition, the spiro compound has a low melting point and can be used as a melt type material, which helps to improve the stability of material evaporation and provides convenience for industrial production. Due to the above characteristics, the spiro compound as a hole blocking layer material or an electron transport layer material has application potential in the OLED industry and feasibility in the application of AMOLED industry, and provides a new material selection for technical innovation and industrial upgrading in the related field. DETAILED DESCRIPTION

[0010] In order to make the skilled in the art more clearly understand the technical solutions described in the present application, the following examples are listed for illustration. It should be noted that the following examples do not constitute a limitation on the scope of protection required by the present application.

[0011] The raw materials, reagents or devices used in the following examples, if not specifically stated, can be obtained from conventional commercial channels, or can be obtained by existing known methods.

[0012] The first aspect of the present application provides a spiro compound.

[0013] A spiro compound, the structure of which is shown in the following formula: Formula (1) In formula (1), A ring is selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring; X is selected from a single bond, O or S; * indicates the connection site in L1; X1, X2, X3are each independently selected from N or CR4, and at least one is N; L1is selected from any one of the structures shown in the following formula (A-1) to formula (A-11):

[0014] ; In formula (A-1) to formula (A-11) indicates the connection site of L1; R1, R2are each independently selected from a substituted or unsubstituted C1-C40alkyl, a substituted or unsubstituted C1-C40heteroalkyl, a substituted or unsubstituted C3-C40alkylsilyl, a substituted or unsubstituted C6-C60arylsilyl, a substituted or unsubstituted C3-C40cycloalkyl, or a substituted or unsubstituted C3-C40heterocycloalkyl; R3, R4, R5, R6are each independently selected from hydrogen, deuterium, halogen, cyano, isocyano, nitro, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C3-C40 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C2-C60 heteroaryl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C3-C40 alkylsilyl, substituted or unsubstituted C6-C60 arylsilyl, substituted or unsubstituted C1-C40 alkylboron, substituted or unsubstituted C6-C60 arylboron, substituted or unsubstituted C6-C60 arylphosphine, or substituted or unsubstituted C6-C60 arylamine; a, b, f, g are each independently selected from an integer from 0 to 4; c, e are selected from an integer from 0 to 3; d is selected from an integer from 0 to 5; Ar1, Ar2are independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl; the substituents in the ring A, Ar1, Ar2, R1-R6 are each independently selected from 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; the heteroatoms in the heteroaryl, heteroalkyl and heterocycloalkyl are independently selected from at least one of O, S, N, Se, Si and Ge.

[0015] In some embodiments, the heteroatoms in the heteroaryl, heteroalkyl and heterocycloalkyl are O, S, N or Si.

[0016] In some embodiments, the Ar1, Ar2are not substituted or unsubstituted dibenzofuranyl.

[0017] In some embodiments, the structure represented by formula (1) is selected from the structures represented by formula (B-1) to formula (B-8): ; wherein the substitution position of R0in formula (B-3) to (B-8) is any position on the naphthalene ring; R0is independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, isocyano, phosphino, C1-C6alkyl, C3-C16cycloalkyl, C1-C6alkyl substituted amine, C1-C6hydrocarbyl substituted or unsubstituted C6-C30aryl, C1-C6hydrocarbyl substituted or unsubstituted C3-C30heteroaryl, n is an integer selected from 0-4, and m is an integer selected from 0-6. In some embodiments, the structure of Formula (1) is selected from the group consisting of structures of Formulae (B-1-1) to (B-8-1): .

[0018] In some embodiments, the structure of Formula (1) is selected from the group consisting of structures of Formulae (B-9) to (B-16): .

[0019] In some embodiments, R1, R2are each independently selected from the group consisting of substituted or unsubstituted C1-C20alkyl, substituted or unsubstituted C1-C20heteroalkyl, substituted or unsubstituted C3-C20alkylsilyl, substituted or unsubstituted C6-C30arylsilyl, substituted or unsubstituted C3-C20cycloalkyl, or substituted or unsubstituted C3-C20heterocycloalkyl.

[0020] In some embodiments, R1, R2are each independently selected from the group consisting of substituted or unsubstituted C1-C10alkyl, substituted or unsubstituted C1-C10heteroalkyl, substituted or unsubstituted C3-C10alkylsilyl, substituted or unsubstituted C6-C20arylsilyl, substituted or unsubstituted C3-C10cycloalkyl, or substituted or unsubstituted C3-C10heterocycloalkyl.

[0021] In some embodiments, R1, R2are each independently selected from the group consisting of methyl, ethyl, propyl, butyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted epoxypentyl, substituted or unsubstituted epoxycyclohexyl, substituted or unsubstituted norbornyl, or substituted or unsubstituted trimethylsilyl.

[0022] In some embodiments, R1and R2are each independently selected from at least one of t-butyl, cyclopentyl, cyclohexyl, adamantyl, epoxypentyl, deuterated cyclohexyl, or trimethylsilyl.

[0023] In some embodiments, R1and R2are structurally identical.

[0024] In some embodiments, R3, R4, R5, R6are each independently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C20alkyl, substituted or unsubstituted C1-C20heteroalkyl, C2-C20alkenyl, C2-C20alkynyl, substituted or unsubstituted C3-C20cycloalkyl, substituted or unsubstituted C3-C20heterocycloalkyl, substituted or unsubstituted C6-C30aryl, substituted or unsubstituted C2-C36heteroaryl, substituted or unsubstituted C1-C20alkoxy, substituted or unsubstituted C6-C30aryloxy, substituted or unsubstituted C3-C20alkylsilyl, substituted or unsubstituted C6-C30arylsilyl, substituted or unsubstituted C1-C30alkylboron, substituted or unsubstituted C6-C30arylboron, substituted or unsubstituted C6-C30arylphosphine, or substituted or unsubstituted C6-C30arylamine.

[0025] In some embodiments, R3, R4, R5, R6are each independently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C10alkyl, substituted or unsubstituted C1-C10heteroalkyl, C2-C10alkenyl, C2-C10alkynyl, substituted or unsubstituted C3-C10cycloalkyl, substituted or unsubstituted C3-C10heterocycloalkyl, substituted or unsubstituted C6-C20aryl, substituted or unsubstituted C2-C20heteroaryl, substituted or unsubstituted C1-C10alkoxy, substituted or unsubstituted C6-C20aryloxy, substituted or unsubstituted C3-C10alkylsilyl, substituted or unsubstituted C6-C20arylsilyl, substituted or unsubstituted C1-C20alkylboron, substituted or unsubstituted C6-C20arylboron, substituted or unsubstituted C6-C20arylphosphine, or substituted or unsubstituted C6-C20arylamine.

[0026] In some embodiments, R3, R4, R5, R6are each independently selected from deuterium, cyano, substituted or unsubstituted C1-C10alkyl, substituted or unsubstituted C1-C10heteroalkyl, substituted or unsubstituted C3-C10cycloalkyl, substituted or unsubstituted C3-C10heterocycloalkyl, substituted or unsubstituted C6-C20aryl, or substituted or unsubstituted C2-C20heteroaryl.

[0027] In some embodiments, R3-R6are each independently selected from deuterium, substituted or unsubstituted C6-C12aryl.

[0028] In some embodiments, R3-R6are each independently selected from deuterium, phenyl, cyano-substituted phenyl, deuterium-substituted phenyl, biphenyl.

[0029] In some embodiments, the substituents in R1-R6 are independently selected from at least one of deuterium, halogen, cyano, isocyano, phosphino, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl substituted amine, C1-C6 hydrocarbyl substituted or unsubstituted C6-C20 aryl, C1-C6 hydrocarbyl substituted or unsubstituted C3-C20 heteroaryl, in a number ranging from monosubstitution to the maximum number of substitutions.

[0030] In some embodiments, the substituents in ring A, Ar1, Ar2, and each R0 are independently selected from deuterium, halogen, cyano, isocyano, phosphino, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl substituted amine, C1-C6 hydrocarbyl substituted or unsubstituted C6-C12 aryl, C1-C6 hydrocarbyl substituted or unsubstituted C3-C12 heteroaryl.

[0031] In some embodiments, R0 can also be hydrogen. It is understood that when a-f, m, n are 0, it means no corresponding substituent, and the structure to which the substituent is attached is by default H.

[0032] In some embodiments, the substituents in Ar1, Ar2 are in a number ranging from monosubstitution to the maximum number of substitutions.

[0033] In some embodiments, the substituents in ring A, Ar1, Ar2, and each R0 are independently selected from deuterium, halogen, cyano, isocyano, phosphino, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl substituted amine, C1-C6 hydrocarbyl substituted or unsubstituted C6-C12 aryl, C1-C6 hydrocarbyl substituted or unsubstituted C3-C12 heteroaryl.

[0034] In some embodiments, Ar1, Ar2 are independently selected from substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C2-C20 heteroaryl.

[0035] In some embodiments, Ar1 and Ar2 are independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, 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 carbazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted naphthoxazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted benzotriazolyl, substituted or unsubstituted benzophenanthryl, or a combination of at least two of the foregoing.

[0036] In some embodiments, the groups in which at least two of Ar1 and Ar2 are bonded may be substituted or unsubstituted pyridine-substituted phenyl, substituted or unsubstituted phenyl-substituted naphthyl, or substituted or unsubstituted naphthyl-substituted phenyl.

[0037] In some embodiments, Ar1 and Ar2 are independently selected from phenyl, anthracene, or 9,9-dimethylfluorenyl.

[0038] In some implementations, Ar1 and Ar2 are substituted with deuterium, F, cyano, or isocyano.

[0039] In some implementations, there are two Ns in X1-X3.

[0040] In some implementations, X1-X3 are all N.

[0041] In some implementations, formula (1) contains at least one deuterium atom.

[0042] In some embodiments, the compound has one of the following structural formulas: , , , , , , , , , , , , , , , , , , , , , , 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 .

[0043] The second aspect of the present application provides the use of the above-mentioned spiro compound.

[0044] Specifically, the second aspect of the present application provides the use of the above-mentioned spiro compound in the field of semiconductors.

[0045] Specifically, an organic light-emitting device comprises the above-mentioned spiro compound.

[0046] In some embodiments, an organic light-emitting device (OLED) comprises a cathode and an anode, the cathode and the anode being oppositely arranged, and an organic layer being arranged between the cathode and the anode, the organic layer comprising the above-mentioned spiro compound.

[0047] In some embodiments, the organic layer includes at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. The light emitting layer, the hole blocking layer, or the electron transport layer in the organic layer includes the spiro compound.

[0048] In some embodiments, the organic layer includes a light emitting layer including the hetero-spiro compound; or, the organic layer includes a light emitting layer, and further includes a hole blocking layer or an electron transport layer disposed between the light emitting layer and the cathode, the hole blocking layer or the electron transport layer including the spiro compound.

[0049] In some embodiments, the device includes the spiro compound in the hole blocking layer and / or the electron transport layer.

[0050] In some embodiments, the device includes the spiro compound as a hole blocking layer material.

[0051] In some embodiments, the device includes the spiro compound as one of the electron transport layer materials.

[0052] Definitions Unless otherwise defined, all scientific and technical terms used in this disclosure have the meanings that are commonly understood by one of ordinary skill in the art. However, for better understanding of the present application, the definitions of some terms are provided below. When the definitions of the terms provided in the present application are inconsistent with the meanings commonly understood by one of ordinary skill in the art, the definitions and explanations of the terms provided in the present application shall prevail.

[0053] It should be noted that in the present specification, “*” and indicates the connection site with other groups.

[0054] The “carbon number a~b” in the expression “R group having a carbon number a~b which is substituted or unsubstituted” indicates the carbon number of the R group in the case of being unsubstituted, and does not include the carbon number of the substituent when the R group is substituted.

[0055] The “substitution” in “substituted or unsubstituted” means that one or more hydrogen atoms are replaced with other atoms or functional groups (i.e., substituents), and unless otherwise limited by the definition, also includes replacement of one or more hydrogen atoms with a group formed by the connection of two or more of the above substituents.

[0056] The “maximum number of substitutions” refers to the maximum number of hydrogen atoms contained in the group when the substituents other than hydrogen are present.

[0057] "Combination of at least two" means that at least two defined groups are connected by a single bond or fused. For example, phenyl and phenyl are fused to form naphthyl, or phenyl and phenyl are connected by a single bond to form biphenyl. It should be understood that the combination of groups is subject to the defined carbon number range.

[0058] "An integer of 0-5" can be any one of 0, 1, 2, 3, 4, or 5, or a range consisting of any two of them. The same applies to "an integer of 0-4" and "an integer of 0-3".

[0059] The term "halogen" means fluorine, chlorine, bromine, or iodine.

[0060] The term "alkyl" means a straight-chain or branched saturated hydrocarbon group. The number of carbon atoms can be C1-C40, C1-C30, C1-C20, C1-C12, C1-C10, C1-C6, or C1-C4. Non-limiting examples include methyl, ethyl, propyl, butyl, heptyl, and decyl, etc. Each group includes various isomers, such as butyl includes n-butyl, isobutyl, sec-butyl, t-butyl, and the like.

[0061] The term "alkenyl" means a hydrocarbon containing at least one unsaturated carbon-carbon double bond. The number of carbon atoms can be C2-C40, C2-C30, C2-C20, C2-C12, C2-C10, C2-C6, or C2-C4. Non-limiting examples include ethenyl, propenyl, allyl, butadienyl, hexatrienyl, and the like.

[0062] The term "alkynyl" means a hydrocarbon containing at least one unsaturated carbon-carbon triple bond. The number of carbon atoms can be C2-C40, C2-C30, C2-C20, C2-C12, C2-C10, C2-C6, or C2-C4. Non-limiting examples include ethynyl and propynyl, and the like.

[0063] The term "cycloalkyl" means an alkyl group with a cyclic structure, which can include monocyclic, polycyclic, and spiroalkyl groups. The number of carbon atoms can be C3-C40, C3-C30, C3-C20, C3-C12, C3-C10, or C3-C6. Non-limiting examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, and 2-norbornyl, and the like.

[0064] The term "heteroalkyl" refers to at least one carbon atom being replaced by a non-carbon atom or a group containing a non-carbon atom on the basis of alkyl, which non-carbon atom can be selected from at least one of O, S, N, Se, Si, and Ge, but excluding the case that the carbon atom connected to the main structure is replaced by a non-carbon atom (e.g. alkoxyl, alkylsilyl). The number of carbon atoms can be C1-C40, C1-C30, C1-C20, C1-C12, C1-C10, C1-C6, or C1-C4. Non-limiting examples of heteroalkyl include mercaptomethylmethyl, methoxymethylmethyl, ethoxymethylmethyl, t-butoxymethylmethyl, N,N-dimethylmethyl, epoxybutyl, epoxy pentyl, or epoxyhexyl, etc. In some embodiments of the present application, the heteroalkyl is methoxymethyl or epoxy pentyl.

[0065] The term "heterocycloalkyl" refers to at least one carbon atom being replaced by a non-carbon atom on the basis of cycloalkyl, which non-carbon atom can be selected from at least one of O, S, N, Se, Si, and Ge. The number of carbon atoms of heterocycloalkyl can be C3-C40, C3-C30, C3-C20, C3-C12, C3-C10, or C3-C6. Non-limiting examples of heterocycloalkyl include: epoxybutyl, epoxy pentyl, and epoxyhexyl.

[0066] The term "aryl" refers to an aromatic hydrocarbon group derived by removing a hydrogen atom from an aromatic ring compound, which can be monocyclic aryl or polycyclic aryl. At least one ring in polycyclic aryl is an aromatic ring system. Multiple rings in polycyclic aryl can be connected to each other via a single bond or can be fused to each other, for example, a phenyl group and a phenyl group are fused to form a naphthyl group, or a phenyl group and a phenyl group are connected by a single bond to form a biphenyl group. The number of carbon atoms can be C6-C60, C6-C30, C6-C20, C6-C12, or C6-C10. Non-limiting examples include phenyl, naphthyl, anthryl, phenanthryl, tetracene, pyrenyl, perylenyl, acenaphthyl, benzopyrenyl, benzophenanthryl, benzo[g]indacenyl, fluorenyl, spirobifluorenyl, benzofluorenyl, dibenzofluorenyl, biphenyl, terphenyl, quaterphenyl, and fluoranthene, etc. Benzophenanthryl includes 1,2 benzophenanthrene, 3,4-benzophenanthrene, 9,10-benzophenanthrene, etc.

[0067] The term "heteroaryl" refers to at least one carbon atom of an aryl group is replaced by a non-carbon atom, which can be a monocyclic heteroaryl or a polycyclic heteroaryl. The multiple rings in a polycyclic heteroaryl group can be connected to each other via single bonds or can be fused to each other, wherein at least one ring has at least one carbon atom replaced by a non-carbon atom, for example, phenyl and carbazolyl are fused to form benzocarbazolyl, or phenyl and carbazolyl are connected by a single bond to form phenyl-substituted carbazolyl or carbazolyl-substituted phenyl. The non-carbon atom can be selected from a monovalent group of a heterocyclic aromatic system of O, S, N, Se, Si, or Ge, but excluding the case where aryl is connected by a non-carbon atom as a linking point (e.g., aryloxy, arylsilyl, arylamine group). The number of carbon atoms can be C3-C30, C3-C20, C3-C12, C3-C10, or C3-C6. Non-limiting examples include pyrrolyl, pyrrolopyrrolyl, furopyrrolyl, thienopyrrolyl, pyridyl, pyrazolyl, pyrimidinyl, pyrazinyl, pyridazinyl, phenoxazinyl, phenothiazinyl, phenoxazinyl, indolyl, isoindolyl, indolazolyl, imidazolyl, benzimidazolyl, triazolyl, tetrazolyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, furopyrrolyl, azadibenzofuranyl, thienofuranyl, diazadibenzofuranyl, benzo[B]naphtho[1,2-D]furanyl, quinolyl, isoquinolyl, quinoxalyl, quinazolyl, quinazolinonyl, carbazolyl, azacarbazolyl, diazacarbazolyl, phenanthridinyl, perimidinyl, acridinyl, dihydroacridinyl, phenanthrolinyl, oxazolinyl, oxazolyl, oxadiazolyl, benzisoxazolyl, thiazolyl, benzothiazolyl, benzisothiazolyl, pyrroloimidazolyl, furazanyl, thienyl, benzothienyl, dibenzothienyl, azadibenzothienyl, diazadibenzothienyl, thienothienyl, and phthalazinyl, and the like.

[0068] In the terms "alkylsilyl", "arylsilyl", the number of alkyl or aryl groups can be 1 to 3; in the terms "alkylboron group", "alkylamine group", "arylboron group", "arylphosphine group", "arylamine group", the number of alkyl or aryl groups can be 1 or 2; the defined number of carbons refers to the total number of carbons of the group.

[0069] The terms "alkoxy", "aryloxy" refer to a group having the structure "-O-alkyl", "-O-aryl", respectively, i.e., an alkyl or aryl group as defined above connected to the parent structure via an oxygen atom. Examples of "alkoxy" groups include methoxy, ethoxy, and tert-butoxy (-O-C(CH3)3 or Examples of aryloxy groups include phenoxy, naphthoxy, or biphenylyloxy.

[0070] The term "arylalkyl" refers to an alkyl group substituted with an aryl group, wherein "aryl" and "alkyl" are defined as previously described. The number of carbon atoms in an arylalkyl group can be C7-C30, C7-20, C7-12, or C7-10. Non-limiting examples include: benzyl, phenethyl, phenylpropyl, tolylmethyl, and p-tolylmethyl, among others.

[0071] The term "hydrocarbyl" includes both aromatic and aliphatic hydrocarbyl groups, wherein aliphatic hydrocarbyl groups include alkyl, alkenyl, or alkynyl groups.

[0072] In the present specification, "room temperature" refers to 25±5°C, and in the present application, specifically 25°C.

[0073] As used herein, the term "and / or" means that the listed items are individually present or combined. In fact, the term means that "at least one" or "one or more" of the listed items is used or present.

[0074] The following examples are merely for the convenience of understanding the technical invention, and should not be regarded as specific limitations of the present application.

[0075] The raw materials and solvents involved in the synthesis of the compounds in the present application are purchased from suppliers well known to those skilled in the art, such as Alfa, Acros, etc.

[0076] Synthesis of compound A7 ; Synthesis of compound A7-3 Compound A7-1 (15.00 g, 43.44 mmol, CAS: 70728-89-1), dry tetrahydrofuran (200 ml) were added into a 500 ml three-necked round-bottom flask, replaced with vacuum nitrogen three times, then the system was cooled to -78°C, then n-butyllithium in n-hexane solution (22.59 ml, 56.47 mmol, concentration 2.5 mol / L) was added dropwise, the temperature in the system was controlled not to be higher than -70°C, and the dropwise addition was completed in 20 minutes. The system was stirred at -78°C for 0.5 hours. Finally, compound A7-2 (11.25 g, 43.44 mmol, CAS: 3096-56-8) was slowly added dropwise, and the addition was completed in 10 minutes. The system was continuously stirred at 78°C for 1.5 hours, and TLC monitoring (dichloromethane:n-hexane = 1:5 as developing agent) showed that compound A7-1 was consumed completely. Deionized water (100 ml) was added dropwise to quench the reaction, and the system was directly separated after being warmed to room temperature. The aqueous phase was extracted twice with dichloromethane (100 ml*2), and the combined organic phase was concentrated under reduced pressure at 65°C for 1 hour to obtain a light yellow solid. The sample was mixed and dried, and was subjected to silica gel column chromatography (200 Deionized water (100 ml) was added dropwise to quench the reaction, and the system was directly separated after being warmed to room temperature. The aqueous phase was extracted twice with dichloromethane (100 ml*2), and the combined organic phase was concentrated under reduced pressure at 65°C for 1 hour to obtain a light yellow solid. The sample was mixed and dried, and was subjected to silica gel column chromatography (200 300 mesh silica gel, dichloromethane: n-hexane = 1:10 as eluent, after elution, concentrated at 65°C under reduced pressure to obtain white solid compound A7-3 (16.18g, purity: 99.25%, yield: 70.88%), mass spectrum: 525.17 (M+H) Synthesis of compound A7-4 Compound A7-3 (16.00g,30.45mmol), concentrated hydrochloric acid (16ml, 36%), acetic acid (200ml) were added into a 500ml three-necked round-bottom flask, then the system was cooled to 70°C, and the reaction was carried out for 1h, and the reaction was monitored by TLC (dichloromethane: n-hexane = 1:5 as developing agent), and compound A7-3 was consumed.

[0077] Methanol (100ml) was added to the system, and a large amount of solid was precipitated, and the mixture was filtered, and the sample was mixed with silica gel, and dried, and column chromatography was carried out (200-300 mesh silica gel, dichloromethane: n-hexane = 1:10 as eluent), and after elution, the solvent was removed by concentration at 65°C under reduced pressure to obtain white solid compound A7-3 (16.18g, purity: 99.25%, yield: 70.88%). 300 mesh silica gel, dichloromethane: n-hexane = 1:5 as eluent, after elution, concentrated at 65°C under reduced pressure to obtain white solid compound A7-4 (10.67g, purity: 99.44%, yield: 69.05%), mass spectrum: 507.16 (M+H) Synthesis of compound A7-6 Compound A7-4 (10.50g, 20.69mmol), compound A7-5 (5.25g, 20.69mmol), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (0.15g, 0.21mmol), potassium acetate (5.08g, 51.72mmol), 1,4-dioxane (250ml) were added into a 500ml three-necked round-bottom flask, and the system was replaced with nitrogen three times, then the system was heated to 100°C, and the reaction was carried out for 2h, and the reaction was monitored by TLC (ethyl acetate: n-hexane = 1:5 as developing agent), and compound A7-4 was consumed.

[0078] The system was cooled to 60°C, and the solvent was removed by concentration under reduced pressure, and dichloromethane (150ml) was added, and the mixture was washed with deionized water three times (50ml*3), and the mixture was separated, and the sample was mixed with silica gel, and dried, and column chromatography was carried out (200-300 mesh silica gel, ethyl acetate: n-hexane = 1:10 as eluent), and after elution, the solvent was removed by concentration at 60°C under reduced pressure for 1h to obtain white solid compound A7-6 (8.31g, purity: 99.30%, yield: 72.43%), mass spectrum: 555.34 (M+H).

[0079] Synthesis of compound A7 Compound A7-6 (8.00 g, 14.43 mmol), compound A7-7 (6.06 g, 14.43 mmol, CAS: 2425605-06-5), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (0.11 g, 0.14 mmol), potassium carbonate (4.98 g, 36.06 mmol), 1,4-dioxane (250 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, and compound A7-6 was consumed completely.

[0080] After the reaction was completed, it was cooled to room temperature, dichloromethane (80 ml*3) and deionized water (50 ml) were added for extraction, and the organic phase was rotary dried (60 °C) to obtain a light yellow solid. The silica gel was mixed and column chromatography was performed. After elution, 60 °C reduced pressure concentration was performed for 1 hour to obtain white solid as compound A7 (8.23 g, purity: 99.94%, yield: 70.26%). After sublimation purification of 8.23 g of compound A7 crude product, sublimation compound A7 (6.82, purity: 99.95%, yield: 82.86%) was obtained, mass spectrum: 812.39 (M+H).

[0081] 1 H NMR (400 MHz, CDCl3) δ 8.73 – 8.66 (m, 5H), 8.56 (d, J = 1.5 Hz,1H), 7.82 (d, J = 7.5 Hz, 1H), 7.69 (dd, J = 7.9, 4.3 Hz, 3H), 7.60 (t, J =7.2 Hz, 2H), 7.56 – 7.50 (m, 5H), 7.40 – 7.34 (m, 3H), 7.17 – 7.06 (m, 7H),6.83 (s, 1H), 6.74 (d, J = 7.3 Hz, 3H), 1.21 (s, 18H). Synthesis of intermediate A18-2 ; Synthesis of intermediate A18-2 Compound A18-1 (15.00 g, 50.24 mmol, CAS: 1625-89-4) was added to a 500 mL three-necked flask, dichloromethane (150 ml) was added, stirred, cooled to -15-8 ℃, then iodine (0.64 g, 2.51 mmol) was added, and stirred for about 1 h, then liquid bromine (9.63 g, 60.29 mmol) was dissolved in dichloromethane (100 ml), slowly added dropwise into the reaction system, then incubated at -15-8 ℃ for 5 h, TLC (n-hexane as developing agent) was used to monitor the reaction, and compound A18-1 was consumed completely.

[0082] About 100 mL of saturated sodium thiosulfate solution was added dropwise to quench the reaction until the reaction system turned colorless or light yellow, and then about 100 mL of saturated NaHCO3 solution was added to adjust the pH of the system to weak alkaline, and then the temperature was raised to room temperature and stirred for 1 h, then extracted and separated, the aqueous phase was extracted with dichloromethane (100 ml*2), and the organic phase was rotary evaporated (60 ℃) to obtain a light yellow solid. Silica gel was mixed, column chromatography was performed, and the silica gel column was purified (200-300 mesh silica gel, n-hexane as eluent), then after elution, 60 ℃ reduced pressure concentration was performed for 1 h to obtain compound A18-2 (15.02 g, purity: 99.02%, yield: 79.20%), mass spectrum: 377.07 (M+H).

[0083] Synthesis of intermediate A90-7

[0084] Synthesis of intermediate A90-2 Referring to the synthesis and purification method of compound A7-6, only the corresponding raw materials were changed to obtain target compound A90-2 (17.39 g, purity: 99.22%, yield: 73.54%), mass spectrum: 306.16 (M+H).

[0085] Synthesis of intermediate A90-4 Compound A90-2 (17.00 g, 55.70 mmol), compound A90-3 (17.68 g, 55.70 mmol, CAS: 535934-25-9), tetrakis(triphenylphosphine)palladium (0.64 g, 0.56 mmol), potassium carbonate (19.25 g, 139.26 mmol), toluene (250 ml), ethanol (50 ml), and water (50 ml) were added to a 500 ml single-necked round-bottomed flask, and the system was replaced with vacuum nitrogen three times, then the system was heated to 60 ℃ for 5 h, TLC (ethyl acetate:n-hexane=1:10 as developing agent) was used to monitor the reaction, and compound A90-2 was consumed completely.

[0086] The temperature was lowered to 60°C, and the solvent was removed by concentration under reduced pressure. Dichloromethane (200 ml) was added, and deionized water was used to wash three times (50 ml*3). The extraction was separated, and silica gel was mixed. The sample was dried and columned. Silica gel column chromatography purification was performed (200-300 mesh silica gel, dichloromethane: n-hexane = 1:5 as eluent). After elution, white solid compound A90-7 (10.39 g, purity: 99.51%, yield: 69.09%) was obtained by concentration under reduced pressure at 60°C for 1 hour. Mass spectrum: 521.15 (M+H).

[0087] Synthesis of intermediate A90-5 Referring to the synthesis and purification method of compound A7-6, only the corresponding raw materials need to be changed to obtain the target compound A90-5 (12.15 g, purity: 99.30%, yield: 76.96%). Mass spectrum: 416.15 (M+H).

[0088] Synthesis of intermediate A90-7 Compound A90-5 (12.00 g, 28.87 mmol), compound A90-6 (7.73 g, 28.87 mmol, CAS: 3842-55-5), tetrakis(triphenylphosphine)palladium (0.33 g, 0.29 mmol), sodium hydroxide (2.89 g, 72.16 mmol), tetrahydrofuran (250 ml), water (50 ml) were added to a 500 ml three-necked round-bottom flask, and the system was replaced with nitrogen three times. Then the system was heated to 75°C for 8 hours. TLC (dichloromethane:n-hexane = 1:5 as developing agent) was used to monitor the reaction. Compound A90-5 was consumed.

[0089] The temperature was lowered to 60°C, and the solvent was removed by concentration under reduced pressure. Dichloromethane (200 ml) was added, and deionized water was used to wash three times (50 ml*3). The extraction was separated, and silica gel was mixed. The sample was dried and columned. Silica gel column chromatography purification was performed (200-300 mesh silica gel, dichloromethane: n-hexane = 1:5 as eluent). After elution, white solid compound A90-7 (10.39 g, purity: 99.51%, yield: 69.09%) was obtained by concentration under reduced pressure at 60°C for 1 hour. Mass spectrum: 521.15 (M+H).

[0090] Synthesis of intermediates A99-5 and A99-7 ; Synthesis of intermediate A99-3 Compound A99-1 (20.00 g, 64.10 mmol), compound A99-2 (17.58 g, 157.05 mmol, CAS: 850036-28-1), dichlorobis-(4-dimethylaminophenyl) palladium (0.46 g, 0.64 mmol), potassium carbonate (22.15 g, 160.25 mmol), tetrahydrofuran (250 ml), water (50 ml) were added into a 500 ml three-necked round bottom flask, replaced with nitrogen three times, then the system was heated to 60 °C for 6 hours, TLC (n-hexane as developing agent) was used to monitor the reaction, compound A99-1 was consumed completely.

[0091] After cooling to room temperature, deionized water (300 ml) and methanol (500 ml) were added, stirred at room temperature for 1 h, then suction filtered, the solid was washed with methanol and water, to obtain brown-yellow solid A99-3 (16.92 g, yield: 92.16%), mass spectrum: 287.17 (M+H). The obtained solid was directly used in the next step without purification.

[0092] Synthesis of intermediate A99-4 Compound A99-3 (16.50 g, 57.61 mmol) was added into a 500 ml single-necked flask, THF (300 ml) was added, then Pd / C (2.50 g, 10%) was added, stirred, replaced with hydrogen four times, stirred at room temperature (intermediate replaced with hydrogen balloon three times), reacted for 12 hours. When all the white solid was dissolved, the raw material was consumed, and the reaction was stopped.

[0093] After the reaction was completed, n-hexane (200 ml) was added, stirred for about 0.5 h, then passed through a short silica gel column (about 80 g, 200-300 mesh), the silica gel was washed with n-hexane until the filtrate had no obvious fluorescence, the filtrate was collected and rotary evaporated to obtain a light yellow solid, toluene (50 ml) was added to the solid, heated to about 75 °C to dissolve, then the heating was turned off, cooled to about 65 °C, methanol (150 ml) was added dropwise, cooled to room temperature, stirred for about 1.5 h, suction filtered, washed with methanol to obtain a white solid. Ethyl acetate (80 ml) was added to the obtained solid, heated to reflux to dissolve, then the heating was turned off, cooled to about 60 °C, methanol (150 ml) was added dropwise, cooled to room temperature, stirred overnight, suction filtered, washed with methanol to obtain a white solid, rotary evaporated to obtain solid compound A99-4 (13.84 g, purity: 99.87%, yield: 82.71%), mass spectrum: 291.20 (M+H).

[0094] Synthesis of intermediate A99-5 The target compound A90-5 (14.47 g, purity: 99.01%, yield: 84.29%) was obtained according to the synthetic and purification methods of compound A90-7 by changing the corresponding raw materials, mass spectrum: 369.11 (M+H).

[0095] Synthesis of intermediate A99-7 The target compound A99-7 (11.31 g, purity: 99.60%, yield: 70.36%) was obtained according to the synthetic and purification methods of compound A90-7 by changing the corresponding raw materials, mass spectrum: 496.15 (M+H).

[0096] Synthesis of intermediate A143-4

[0097] Synthesis of intermediate A143-4 The target compound A143-4 (11.49 g, purity: 99.57%, yield: 80.26%) was obtained according to the synthetic and purification methods of compounds A99-3, A99-4, A99-5 by changing the corresponding raw materials, mass spectrum: 397.15 (M+H).

[0098] Synthesis of intermediate A215-4

[0099] Synthesis of intermediate A215-2 The target compound A215-2 (12.86 g, purity: 99.09%, yield: 73.81%) was obtained according to the synthetic and purification methods of compound A7-6 by changing the corresponding raw materials, mass spectrum: 339.24 (M+H). A215-1 CAS: 2245-43-4.

[0100] Synthesis of intermediate A215-3 The target compound A215-3 (10.75 g, purity: 99.57%, yield: 68.84%) was obtained according to the synthetic and purification methods of compound A90-4 by changing the corresponding raw materials, mass spectrum: 423.30 (M+H).

[0101] Synthesis of intermediate A215-4 The target compound A215-4 (10.21 g, purity: 99.31%, yield: 81.94%) was obtained according to the synthetic and purification methods of compound A18-2 by changing the corresponding raw materials, mass spectrum: 501.21 (M+H).

[0102] Synthesis of intermediate A270-4

[0103] Synthesis of intermediate A270-4 The synthesis and purification of compound A99-3, A99-4, A99-5 were carried out by referring to the above-mentioned method, only the corresponding raw materials were changed, the target compound A270-4 (12.92g, purity: 99.72%, yield: 76.80%) was obtained, mass spectrum: 401.10 (M+H). Among them, A270-1 CAS: 1002127-60-7.

[0104] Synthesis of intermediate A278-3

[0105] Synthesis of intermediate A278-3 The synthesis and purification of compound A90-7 were carried out by referring to the above-mentioned method, only the corresponding raw materials were changed, the target compound A278-3 (11.80g, purity: 99.54%, yield: 72.36%) was obtained, mass spectrum: 520.15 (M+H). Among them, A278-1 CAS: 1821147-80-1, A278-2 CAS: 1186403-21-3.

[0106] Synthesis of intermediate A321-3

[0107] The synthesis and purification of compound A90-7 were carried out by referring to the above-mentioned method, only the corresponding raw materials were changed, the target compound A321-3 (10.52g, purity: 99.36%, yield: 68.52%) was obtained, mass spectrum: 535.19 (M+H). Among them, A321-1 CAS: 1292291-85-0, A321-2 CAS: 2641692-27-3.

[0108] Synthesis of intermediate A345-4

[0109] Synthesis of intermediate A345-3 The synthesis and purification of compound A90-4 were carried out by referring to the above-mentioned method, only the corresponding raw materials were changed, the target compound A345-3 (114.87g, purity: 99.40%, yield: 74.95%) was obtained, mass spectrum: 419.01 (M+H). Among them, A345-1 CAS: 535934-25-9, A345-2 CAS: 1310405-29-8.

[0110] Synthesis of intermediate A345-4 The synthesis and purification method of compound A7-6 was referred to, only the corresponding raw material was changed, the target compound A345-4 (11.64 g, purity: 99.19%, yield: 72.18%) was obtained, mass spectrum: 467.19 (M+H).

[0111] Synthesis of intermediate A345-5 The synthesis and purification method of compound A90-7 was referred to, only the corresponding raw material was changed, the target compound A345-5 (9.85 g, purity: 99.63%, yield: 69.89%) was obtained, mass spectrum: 572.18 (M+H). Synthesis of intermediate A396-3

[0112] Synthesis of intermediate A396-2 The synthesis and purification method of compound A7-6 was referred to, only the corresponding raw material was changed, the target compound A396-2 (113.02 g, purity: 99.10%, yield: 74.02%) was obtained, mass spectrum: 320.16 (M+H). A396-1 CAS: 2765536-77-2.

[0113] Synthesis of intermediate A396-3 The synthesis and purification method of compound A90-7 was referred to, only the corresponding raw material was changed, the target compound A396-3 (11.96 g, purity: 99.47%, yield: 69.20%) was obtained, mass spectrum: 425.15 (M+H).

[0114] Synthesis of intermediate A401-3 ; Synthesis of intermediate A401-2 The synthesis and purification method of compound A7-6 was referred to, only the corresponding raw material was changed, the target compound A401-2 (13.25 g, purity: 99.20%, yield: 75.29%) was obtained, mass spectrum: 319.15 (M+H). A401-1 CAS: 2813363-07-2.

[0115] Synthesis of intermediate A401-3 The synthesis and purification method of compound A90-7 was referred to, only the corresponding raw material was changed, the target compound A401-3 (12.27 g, purity: 99.46%, yield: 70.94%) was obtained, mass spectrum: 424.14 (M+H).

[0116] Synthesis of intermediate A411-2

[0117] Synthesis of intermediate A411-1 Compound A143-3 (15.00 g, 47.10 mmol), sodium hydroxide (3.77 g, 94.19 mmol), DMSO-d6 (150 ml) were added into a 500 mL Schlenk reaction tube, replaced with nitrogen for three times, then sealed, heated to 110°C for 22 h.

[0118] After cooling to room temperature, the system was placed in an ice water bath and stirred, deionized water (50 ml) and methanol (100 ml) were added, stirred for about 3 h, suction filtered, the solid was washed with deionized water (50 ml*2), then washed with methanol (50 ml) twice, to obtain a white solid, the obtained solid was added to toluene (80 ml), heated to about 100°C to dissolve, then cooled to about 60°C, methanol (160 ml) was added dropwise, then cooled to room temperature, stirred for 2 h. Suction filtered, the solid was washed with methanol to obtain white solid compound A411-1 (14.16 g, purity: 99.89%, yield: 93.81%), mass spectrum: 321.25 (M+H).

[0119] Synthesis of intermediate A411-2 Referring to the synthesis and purification method of compound A18-2, only the corresponding starting material needs to be changed, to obtain the target compound A411-2 (15.06 g, purity: 99.13%, yield: 86.32%), mass spectrum: 399.16 (M+H).

[0120] In combination with the above intermediates, compounds A18, A50, A69, A90, A99, A111, A118, A130, A143, A174, A215, A270, A278, A311, A321, A345, A375, A396, A401, A411 were prepared by the similar synthesis method of compound A7, except that different starting materials were used, and the starting materials used are shown in Table 1.

[0121] Table 1

[0122]

[0123] Synthesis of compound A0

[0124] Synthesis of compound A0-3 Compound A0-1 (10.00 g, 37.35 mmol), compound A0-2 (8.79 g, 37.35 mmol), tetrakis(triphenylphosphine)palladium (0.43 g, 0.37 mmol), sodium hydroxide (3.73 g, 93.38 mmol), tetrahydrofuran (225 mL), deionized water (75 mL) were added into a 500 mL three-necked round-bottom flask, replaced with vacuum nitrogen 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, and compound A0-1 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 washed three times (50 mL*3). The liquid was separated, and the silica gel was mixed and dried. The sample was column-purified by silica gel column chromatography (200-300 mesh silica gel, ethyl acetate: n-hexane = 1:20 as eluent). After elution, the white solid was obtained by concentration under reduced pressure at 60 °C for 1 hour, and the white solid was compound A0-3 (11.62 g, purity: 99.53%, yield: 73.59%). Mass spectrum: 422.00 (M+H).

[0126] Synthesis of compound A0-5 Referring to the synthesis and purification method of compound A0-3, only the corresponding raw materials need to be changed, and the target compound A0-5 (9.07 g, purity: 99.48%, yield: 70.27%) is obtained. Mass spectrum: 496.15 (M+H).

[0127] Synthesis of compound A0 Referring to the synthesis and purification method of compound A0-3, only the corresponding raw materials need to be changed, and the target compound A0 (9.53 g, purity: 99.97%, yield: 71.67%) is obtained. After sublimation purification of 9.53 g of crude compound A0, sublimation compound A0 (6.09 g, purity: 99.99%, yield: 63.90%) is obtained. Mass spectrum: 776.30 (M+H).

[0128] 1H NMR (400 MHz, CDC13) δ 8.66 (t, J = 2.2 Hz, 1H), 8.44 - 8.37 (m, 5H), 8.00 - 7.96 (m, 2H), 7.84 (dd, J = 6.3, 1.6 Hz, 3H), 7.74 (dd, J = 7.8, 2.3 Hz, 1H), 7.60 - 7.56 (m, 2H), 7.55 - 7.44 (m, 12H), 7.41 - 7.30 (m, 8H), 6.90 (dd, J = 6.9, 1.4 Hz, 1H), 6.76 - 6.73 (m, 2H). Synthesis of intermediate A433-3

[0129] Synthesis of intermediate A433-3 Compound A433-1 (15.00 g, 28.65 mmol, CAS: 1609484-52-7), compound A433-2 (7.28 g, 28.65 mmol), 1,1-bis(diphenylphosphino)ferrocene palladium dichloride (0.21 g, 0.29 mmol), potassium acetate (7.03 g, 71.63 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 80 °C for 4 hours, TLC (n-hexane: ethyl acetate = 10: 1 as developing agent) was used to monitor the reaction, compound A433-1 was consumed completely.

[0130] The system was cooled to 60 °C, and the solvent was removed by concentration under reduced pressure. Ethyl acetate (300 mL) was added, and the mixture was washed with deionized water three times (100 mL*3). The organic phase was separated, and silica gel was added. The mixture was dried and columned. Silica gel column chromatography purification was performed (200-300 mesh silica gel, n-hexane: ethyl acetate = 10: 1 as eluent). After elution, the white solid was obtained by concentration under reduced pressure at 60 °C for 1 hour. The white solid was compound A433-3 (12.64 g, purity: 99.40%, yield: 77.32%), and the mass spectrum was 571.33 (M+H).

[0131] Synthesis of intermediate A434-5

[0132] Synthesis of compound A434-3 Compound A434-1 (20.00 g, 62.97 mmol, CAS: 2378552-11-3), dry tetrahydrofuran (400 mL) were added into a 1000 mL three-necked round-bottom flask, replaced with vacuum nitrogen for three times, then the system was cooled to -78 °C, then n-butyllithium solution in n-hexane (32.74 mL, 81.86 mmol, concentration 2.5 mol / L) was added dropwise, the temperature in the system was controlled not higher than -70 °C, and the dropwise addition was completed in 20 minutes. The system was stirred at -78 °C for 1 hour. Finally, compound A434-2 (20.26 g, 69.27 mmol) was added dropwise slowly, and the addition was completed in 10 minutes. The system was continuously stirred at -78 °C for 1.5 hours, and TLC (ethyl acetate: n-hexane = 1:10 as developing agent) was used for monitoring. Compound A434-1 was consumed completely. Deionized water (100 mL) was added dropwise to quench the reaction, and the system was directly separated after being warmed to room temperature. The water phase was extracted twice with ethyl acetate (200 mL x 2), and the combined organic phase was concentrated under reduced pressure at 65 °C for 1 hour to obtain a light yellow solid. The sample was mixed with silica gel, and dry column was used for column chromatography purification (200 300 mesh silica gel, ethyl acetate: n-hexane = 1:10 (v / v) as eluent). After elution, the white solid compound A434-3 (20.46 g, purity: 99.52 %, yield: 61.17 %) was obtained by concentrating under reduced pressure at 65 °C for 1 hour. Mass spectrum: 531.24 (M+H).

[0133] Synthesis of compound A434-4 Compound A434-3 (20.00 g, 37.66 mmol), acetic acid (200 mL), hydrochloric acid (20 mL) were added into a 500 mL three-necked round-bottom flask, and then the system was heated to 45 °C and stirred for 18 hours. TLC (ethyl acetate: n-hexane = 1:10 as developing agent) was used for monitoring the reaction. Compound A434-3 was consumed completely.

[0134] Ethyl acetate (300 mL) was added to the system, and the system was separated. The sample was mixed with silica gel, and dry column was used for column chromatography purification (200 300 mesh silica gel, ethyl acetate: n-hexane = 1:10 as eluent). After elution, the white solid compound A434-4 (13.47 g, purity: 99.60 %, yield: 69.71 %) was obtained by concentrating under reduced pressure at 65 °C for 2 hours. Mass spectrum: 513.23 (M+H).

[0135] Synthesis of intermediate A434-5 ​Referring to the synthesis and purification method of compound A433-3, only the corresponding starting material needs to be changed, and the target compound A434-5 (11.84 g, purity: 99.48%, yield: 77.29%) is obtained. Mass spectrum: 605.35 (M+H). In combination with the above intermediates, compounds A431, A433, A434, A436, A438 are prepared by the method of similar compound A0, except that different starting materials are used, and the starting materials used are shown in Table 2.

[0136] Table 2

[0137] Application example: preparation of an organic light-emitting device The spiro compound prepared in the above examples is applied to an organic light-emitting device, which comprises a glass substrate, an anode, a hole injection layer, a first hole transport layer (HTL1), a second hole transport layer (HTL2), a light-emitting layer, a hole blocking layer (HBL), an electron transport layer (ETL), and a cathode which are arranged in layers. Specifically, the preparation method of the organic light-emitting device is as follows: Take a glass substrate with an ITO transparent electrode (anode) on the surface, wherein the anode thickness is 100 nm; ultrasonically clean the glass substrate in ethanol for 10 minutes, then dry at 150°C, and then treat with N2Plasma (plasma) for 30 minutes; evaporate compound HATCN on the surface of the anode side to form a hole injection layer, wherein the hole injection layer thickness is 5 nm; evaporate compound HTM1 on the surface of the hole injection layer side to form a first hole transport layer, wherein the first hole transport layer thickness is 60 nm; evaporate compound HTM2 on the surface of the first hole transport layer side to form a second hole transport layer, and the second hole transport layer thickness is 10 nm; co-evaporate the host material and the guest material on the surface of the second hole transport layer side to form a light-emitting layer, wherein the weight ratio of the host material and the guest material is 97%:3%; the light-emitting layer thickness is 25 nm; evaporate HBL material on the surface of the light-emitting layer side to form a hole blocking layer, wherein the hole blocking layer thickness is 5 nm; the HBL material is a spiro compound or a comparative compound of the present application, and the specific material is shown in Table 3; evaporate an electron transport material on the surface of the hole blocking layer side to form an electron transport layer, wherein the electron transport layer thickness is 350 nm, and the electron transport material is compound ETL or a mixture of a spiro compound (or a comparative compound) of the present application and LiQ with a weight ratio of 1:1 in the mixture, and the specific material combination is shown in Table 3; co-evaporate metals Mg and Ag on the surface of the electron transport layer side to form a cathode composed of a magnesium-silver alloy material, wherein the cathode thickness is 100 nm, and the weight ratio of Mg to Ag is 1:9.

[0138] wherein the structures of HAT-CN, HTM1, HTM2, host material (BH), guest material (BD), ETL, LiQ and comparative compounds 1-4 are as follows:

[0139] .

[0140] Evaluation: The above organic light-emitting device was subjected to device performance test, and the spiro compound prepared in the application and the comparative compound were respectively used as a hole blocking layer material and an electron transport layer 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 (CS2000) 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 and the LT95 device lifetime was tested at 1000 nits. The results are shown in Table 3 below.

[0141] Table 3

[0142] The compound of the application adopts a non-planar rigid spiro ring as a core structure, has a high electron mobility, is conducive to the balance of electron and hole transport, and can fine-tune the energy level through a specific connection mode of the connecting group, so that the electron injection energy barrier is low, which is conducive to improving the device performance. According to the comparison of the test results, the compound of the application used as a hole blocking layer material and an electron transport layer material in an organic light-emitting device shows more superior performance in driving voltage, luminous efficiency and device lifetime compared with the comparative compound.

[0143] The above results show that the compound of the application has good light, electrical and thermal stability, high luminous efficiency, low voltage, long service life and other advantages, and can be used in an organic light-emitting device. Especially as a hole blocking layer material and an electron transport layer material, it has the possibility of application in the AMOLED industry.

[0144] In addition, since it is impossible to enumerate all the compounds of the application, within the scope of the application claimed, especially the compounds with the structural formula specifically given in the application have high light, electrical and thermal stability, low sublimation temperature, low driving voltage, high luminous efficiency, long device lifetime and other advantages.

Claims

1. A spiro compound, characterized by: The structure of the spiro compound is shown in the following formula: Formula (1) In formula (1), A ring is selected from substituted or unsubstituted benzene ring, substituted or unsubstituted naphthalene ring; X is selected from single bond, O or S; * indicates the connection site in L1; X1, X2, X3 are independently selected from N or CR4, and at least one is N; L1 is selected from any one of the structures shown in the following formula (A-1) to formula (A-11): ； in formulae (A-1) to (A-11) represents the linking site of L1; R1, R2 are each independently selected from substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C1-C40 heteroalkyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C6-C60 aryl silyl group, substituted or unsubstituted C3-C40 cycloalkyl or substituted or unsubstituted C3-C40 heterocycloalkyl; R3, R4, R5, R6 are each independently selected from hydrogen, deuterium, halogen, cyano, isocyano, nitro, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C3-C40 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C2-C60 heteroaryl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C3-C40 alkyl silyl group, substituted or unsubstituted C6-C60 aryl silyl group, substituted or unsubstituted C1-C40 alkyl boron group, substituted or unsubstituted C6-C60 aryl boron group, substituted or unsubstituted C6-C60 aryl phosphine group or substituted or unsubstituted C6-C60 aryl amine group; a, b, f, g are each independently selected from an integer from 0 to 4; c, e are selected from an integer from 0 to 3; d is selected from an integer from 0 to 5; Ar1, Ar2 are independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl; The substitution in the ring A, Ar1, Ar2, R1-R6 is each independently selected from at least one of deuterium, halogen, cyano, isocyano, phosphine group, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl substituted amine group, C1-C6 hydrocarbon group substituted or unsubstituted C6-C30 aryl, C1-C6 hydrocarbon group substituted or unsubstituted C3-C30 heteroaryl, wherein the number of substitutions is mono-substitution to the maximum number of substitutions; The heteroatoms in the heteroaryl, heteroalkyl and heterocycloalkyl are independently selected from at least one of O, S, N, Se, Si and Ge.

2. The spiro compound according to claim 1, characterized by: The structure shown in formula (1) is selected from the structures shown in the following formula (B-1) to formula (B-8): ； In formula (B-3) to (B-8), the substitution position of R0 is any position on the naphthalene ring; R0is independently selected from hydrogen, deuterium, halogen, cyano, isocyano, phosphino, C1-C6alkyl, C3-C16cycloalkyl, C1-C6alkyl substituted amine, C1-C6hydrocarbyl substituted or unsubstituted C6-C30aryl, C1-C6hydrocarbyl substituted or unsubstituted C3-C30heteroaryl, n is selected from an integer from 0 to 4, and m is selected from an integer from 0 to 6.

3. The spiro compound according to any one of claims 1 to 2, characterized in that: The structure of formula (1) is selected from the group consisting of the structures of formula (B-9) to formula (B-16): 。 4. The spiro compound according to any one of claims 1 to 2, characterized in that: R1, R2are each independently selected from substituted or unsubstituted C1-C20alkyl, substituted or unsubstituted C1-C20heteroalkyl, substituted or unsubstituted C3-C20alkylsilyl, substituted or unsubstituted C6-C30arylsilyl, substituted or unsubstituted C3-C20cycloalkyl, or substituted or unsubstituted C3-C20heterocycloalkyl; and / or, R3, R4, R5, R6are each independently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C20alkyl, substituted or unsubstituted C1-C20heteroalkyl, C2-C20alkenyl, C2-C20alkynyl, substituted or unsubstituted C3-C20cycloalkyl, substituted or unsubstituted C3-C20heterocycloalkyl, substituted or unsubstituted C6-C30aryl, substituted or unsubstituted C2-C36heteroaryl, substituted or unsubstituted C1-C20alkoxy, substituted or unsubstituted C6-C30aryloxy, substituted or unsubstituted C3-C20alkylsilyl, substituted or unsubstituted C6-C30arylsilyl, substituted or unsubstituted C1-C30alkylboron, substituted or unsubstituted C6-C30arylboron, substituted or unsubstituted C6-C30arylphosphine, or substituted or unsubstituted C6-C30arylamine; and / or, the substitution in R1-R6is independently selected from substitution by at least one of deuterium, halogen, cyano, or C1-C6alkyl, with substitution number being mono-substitution to the maximum number of substitution.

5. The spiro compound according to any one of claims 1 to 2, characterized in that: Ar1, Ar2are independently selected from substituted or unsubstituted C6-C20aryl, substituted or unsubstituted C2-C20heteroaryl; and / or, X1-X3are all N. R0is independently selected from hydrogen, deuterium, halogen, cyano, isocyano, phosphino, C1-C6alkyl, C3-C16cycloalkyl, C1-C6alkyl substituted amine, C1-C6hydrocarbyl substituted or unsubstituted C6-C30aryl, C1-C6hydrocarbyl substituted or unsubstituted C3-C30heteroaryl, n is selected from an integer from 0 to 4, and m is selected from an integer from 0 to 6.

6. The spiro compound according to any one of claims 1 to 2, characterized in that: Ar1and Ar2are independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, 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 carbazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted naphthoxazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted benzotriazolyl, substituted or unsubstituted benzophenanthryl, or a combination of at least two of the foregoing; and / or, the substitution in Ar1and Ar2is deuterium, F, cyano, or isocyano.

7. The spiro compound according to any one of claims 1 to 2, characterized in that: R1, R2are each independently selected from methyl, ethyl, propyl, butyl, substituted or unsubstituted cyclopentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted cyclopentyloxy, substituted or unsubstituted cyclohexyloxy, substituted or unsubstituted norbornyl, or substituted or unsubstituted trimethylsilyl; and / or, R3-R6are each independently selected from deuterium, substituted or unsubstituted C6-C12 aryl; and / or, at least one deuterium atom is contained in formula (1).

8. The spiro compound according to any one of claims 1 to 2, characterized by: The compound is one of the following structural formulae: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 。 9. An organic light emitting device, characterized by: The organic layer comprises a light-emitting layer, and the light-emitting layer comprises the heterospirocyclic compound; or the organic layer comprises a light-emitting layer and a hole-blocking layer or an electron-transporting layer disposed between the light-emitting layer and the cathode, and the hole-blocking layer or the electron-transporting layer comprises the spiro compound.

10. The organic light emitting device of claim 9, wherein: The organic layer comprises a light-emitting layer, and the light-emitting layer comprises the heterospirocyclic compound; or the organic layer comprises a light-emitting layer and a hole-blocking layer or an electron-transporting layer disposed between the light-emitting layer and the cathode, and the hole-blocking layer or the electron-transporting layer comprises the spiro compound.

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