Organoboron compound as well as preparation method and application thereof

Abstract

The invention relates to the technical field of organic light-emitting materials, in particular to an organoboron compound and a preparation method and application thereof. The organic boron compound has a structure as shown in a formula I or a formula II. The organic boron compound provided by the invention not only can be used for assembling an OLED device by an evaporation process, but also can be used for a light-emitting layer of the OLED device by a solution processing process to prepare the OLED device with high efficiency and long service life. The problems that an existing multiple resonance type blue light TADF material is low in efficiency and too high in doping concentration, and consequently spectrum red shift and emission peak widening are caused are solved or at least partially solved.

Description

Technical Field

[0001] The present invention relates to the technical field of organic light-emitting materials, and particularly relates to an organic boron compound, a preparation method thereof, and an application thereof. Background Art

[0002] Organic light-emitting devices (OLEDs) have the characteristics of rich colors, thin thickness, wide viewing angles, fast response, and the ability to fabricate flexible devices, and are considered to be the most promising next-generation flat panel display and solid-state lighting technologies. Generally speaking, an OLED is composed of an ITO anode, a hole injection layer (TIL), a hole transport layer (HTL), a light-emitting layer (EL), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), and a cathode. Excitons are formed by the combination of holes and electrons injected from the positive and negative electrodes on the organic thin film. When the excitons return from the excited state to the stable ground state, energy is released in the form of light, thereby emitting light. After nearly three decades of development, OLED technology has currently been mass-produced in many panel factories and has also been fully promoted in terminal display and lighting devices. However, traditional OLEDs show relatively low color purity and face strong challenges from other new color gamut standards such as quantum dots and perovskites, such as BT.2020. Therefore, developing OLEDs with sharp emission spectra having a narrow full width at half maximum (FWHM) is one of the fundamental problems in current OLED display technology.

[0003] Thermally activated delayed fluorescence (TADF) materials are a new generation of organic light-emitting materials following traditional fluorescent and phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (ΔEST), and utilize the thermally activated reverse intersystem crossing (RISC) process to transfer triplet excitons to singlet excitons to emit fluorescence, thereby realizing the full utilization of singlet and triplet excitons and achieving an internal quantum efficiency of 100%.

[0004] Currently, red and green light-emitting materials have been iterated to the latest generation of mature TADF materials, and both the efficiency and stability basically meet the requirements of current various scenario applications. However, due to the high corresponding energy of blue light materials, there is still a certain gap between their efficiency and color purity and commercial applications. Multiple resonance type TADF blue light materials can increase the RISC rate by regulating the triplet energy level and reducing the singlet-triplet energy gap (ΔEST), but most of these molecular design strategies are accompanied by a red shift of the emission. Summary of the Invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide an organic boron compound, a preparation method thereof, and an application thereof.

[0006] The present invention provides an organic boron compound having a structure shown in Formula I or Formula II:

[0007]

[0008] Wherein, X is hydrogen or deuterium;

[0009] n is any integer from 1 to 5;

[0010] R1, R2, R3, R4, R5, and R6 are each independently selected from H, D, F, Cl, Br, I, -OH, -SH, -NH2, nitro, cyano, substituted or unsubstituted C1-C30 linear or branched hydrocarbon groups, substituted or unsubstituted C3-C30 cycloalkyl groups, substituted or unsubstituted C6-C60 aromatic groups, substituted or unsubstituted C3-C60 heteroaromatic groups, -NR7R8; the heteroatoms in the heteroaromatic groups are selected from one or more of Si, Ge, N, P, O, S, and Se;

[0011] R7 and R8 are independently selected from substituted or unsubstituted C1-C30 linear or branched hydrocarbon groups, substituted or unsubstituted C6-C60 aromatic groups, substituted or unsubstituted C3-C60 heteroaromatic groups;

[0012] m is any integer from 1 to 10;

[0013] Ar1, Ar2, and Ar3 are independently selected from substituted or unsubstituted C6-C30 aromatic groups, substituted or unsubstituted C3-C30 heteroaromatic groups; the heteroatoms in the heteroaromatic groups are selected from one or more of Si, Ge, N, P, O, S, and Se;

[0014] Q is selected from H, D, substituted or unsubstituted C1-C30 linear or branched hydrocarbon groups, substituted or unsubstituted C3-C30 cycloalkyl groups, substituted or unsubstituted C1-C30 alkoxy groups, substituted or unsubstituted C1-C30 alkylthio groups, substituted or unsubstituted C6-C60 aromatic groups, substituted or unsubstituted C3-C60 heteroaromatic groups; the heteroatoms in the heteroaromatic groups are selected from one or more of Si, Ge, N, P, O, S, and Se.

[0015] The present invention provides a method for preparing the above-mentioned organoboron compound, comprising the following steps:

[0016] S1. The intermediate represented by M1 and the intermediate represented by M2 or M3 undergo a C-N coupling reaction to form the intermediate represented by M4 or M5;

[0017] S2. The intermediate represented by M4, the intermediate represented by M5, and the intermediate represented by M6 undergo a C-N coupling reaction to form the intermediate represented by M8;

[0018] Or the intermediate represented by M4 and the intermediate represented by formula M7 undergo a C-N coupling reaction to form the intermediate represented by M9;

[0019] The intermediate shown in S3 and M8 reacts with BBr₃ to form the organoboron compound shown in Formula I;

[0020] The intermediate shown in M9 reacts with BBr₃ to form the organoboron compound shown in Formula II;

[0021]

[0022] Wherein, X, Q, Ar₁, Ar₂, Ar₃, R₁, R₂, R₃, R₄, R₅, R₆, n, and m are defined as described above;

[0023] Y is hydrogen or a halogen.

[0024] The present invention provides the application of the above organoboron compound as an organic electroluminescent material.

[0025] The present invention provides an organic electroluminescent device, comprising an anode, a cathode, and an organic thin film layer located between the anode and the cathode; the organic thin film layer comprises the aforementioned organoboron compound.

[0026] Compared with the prior art, the organoboron compound provided by the present invention has a resonance structure composed of one boron atom and two nitrogen atoms as the molecular backbone, and uses methyl-substituted benzene as a spacer group to form a symmetric structure or an asymmetric structure respectively. The role of methyl-substituted benzene is to regulate the position and distribution of the HOMO and LUMO energy levels, and then regulate the emission color and achieve deep blue light emission. At the same time, the steric hindrance of the methyl group increases the dihedral angle with the planar molecular backbone to inhibit self-aggregation and improve the luminescence efficiency. This type of organoboron compound can be used not only for evaporating and depositing processes to assemble OLED devices, but also for the light-emitting layer of solution-processed OLED devices to prepare OLED devices with high efficiency and long life.

[0027] The present invention solves or at least partially solves the problems of low efficiency of existing multiple resonance type blue light TADF materials, spectral red shift and broadening of emission peaks caused by too high doping concentration. Detailed Embodiments

[0028] The present invention provides an organoboron compound having the structure shown in Formula I or Formula II:

[0029]

[0030] Wherein, X is hydrogen or deuterium;

[0031] n is any integer from 1 to 5;

[0032] R1, R2, R3, R4, R5, and R6 are each independently selected from H, D, F, Cl, Br, I, -OH, -SH, -NH2, nitro, cyano, a substituted or unsubstituted C1-C30 straight-chain or branched-chain hydrocarbon group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C3-C60 heteroaromatic group, -NR7R8; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S, and Se;

[0033] R7 and R8 are each independently selected from a substituted or unsubstituted C1-C30 straight-chain or branched-chain hydrocarbon group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C3-C60 heteroaromatic group;

[0034] m is any integer from 1 to 10;

[0035] Ar1, Ar2, and Ar3 are each independently selected from a substituted or unsubstituted C6-C30 aromatic group, a substituted or unsubstituted C3-C30 heteroaromatic group; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S, and Se;

[0036] Q is selected from H, D, a substituted or unsubstituted C1-C30 straight-chain or branched-chain hydrocarbon group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C1-C30 alkylthio group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C3-C60 heteroaromatic group; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S, and Se.

[0037] In some specific embodiments of the present invention, n is 1, 2, 3, 4, or 5, or a range value with any of the above values as the upper or lower limit.

[0038] n represents the number of -CX3 substituents on the benzene ring. When n is not 1, the -CX3 substituents may be the same or different.

[0039] In some specific embodiments of the present invention, R1, R2, R3, R4, R5, and R6 are each independently selected from H, D, F, Cl, Br, I, -OH, -SH, -NH2, nitro, cyano, a substituted or unsubstituted C1-C10 straight-chain or branched-chain hydrocarbon group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C14 aromatic group, a substituted or unsubstituted C3-C14 heteroaromatic group, -NR7R8; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S, and Se.

[0040] In some specific embodiments of the present invention, each of R1, R2, R3, R4, R5, and R6 is independently selected from H, D, F, Cl, Br, I, -OH, -SH, -NH2, nitro group, cyano group, substituted or unsubstituted C1-C6 linear or branched hydrocarbon group, substituted or unsubstituted C3-C6 cycloalkyl group, substituted or unsubstituted C6-C14 aromatic group, substituted or unsubstituted C3-C14 heteroaromatic group, -NR7R8; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S, and Se.

[0041] In some specific embodiments of the present invention, R7 and R8 are independently selected from substituted or unsubstituted C1-C10 linear or branched hydrocarbon groups, substituted or unsubstituted C6-C10 aromatic groups, and substituted or unsubstituted C3-C10 heteroaromatic groups.

[0042] In some specific embodiments of the present invention, R7 and R8 are independently selected from substituted or unsubstituted C1-C6 linear or branched hydrocarbon groups, substituted or unsubstituted C6-C10 aromatic groups, and substituted or unsubstituted C3-C10 heteroaromatic groups.

[0043] In the present invention, the hydrocarbon group includes saturated and / or unsaturated hydrocarbon groups, including but not limited to alkyl groups, alkenes, and alkynes, preferably alkyl groups.

[0044] In some specific embodiments of the present invention, -NR7R8 is selected from N,N-dimethylamino, N,N-diphenylamino, or N-methyl-N-phenylamino.

[0045] In the present invention, the substitution is by a primary substituent.

[0046] The primary substituent is preferably one or more of D, F, Cl, Br, I, -OH, -SH, -NH2, nitro group, cyano group, substituted or unsubstituted C1-C30 linear or branched alkyl groups, substituted or unsubstituted C6-C60 aromatic groups, and substituted or unsubstituted C3-C60 heteroaromatic groups.

[0047] In some specific embodiments of the present invention, the primary substituent is preferably one or more of D, F, Cl, Br, I, -OH, -SH, -NH2, nitro group, cyano group, substituted or unsubstituted C1-C10 linear or branched alkyl groups, substituted or unsubstituted C6-C14 aromatic groups, and substituted or unsubstituted C3-C14 heteroaromatic groups.

[0048] In some specific embodiments of the present invention, the primary substituent is preferably one or more of D, F, Cl, Br, I, -OH, -SH, -NH2, nitro group, cyano group, substituted or unsubstituted C1-C6 linear or branched alkyl group, substituted or unsubstituted C6-C10 aromatic group, and substituted or unsubstituted C3-C13 heteroaromatic group.

[0049] In some specific embodiments of the present invention, the primary substituent is preferably one or more of D, F, Cl, Br, I, -OH, -SH, -NH2, nitro group, cyano group, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, phenyl, thiophenyl, furyl, pyrrolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl or carbazolyl which may be substituted or unsubstituted.

[0050] Preferably, the primary substituent may be optionally substituted with one or more of D, F, Cl, Br, I, -OH, -SH, -NH2, nitro group, cyano group, C1-C30 linear or branched hydrocarbon group, phenyl, carbazolyl.

[0051] In some specific embodiments of the present invention, the primary substituent may be optionally substituted with one or more of D, F, Cl, Br, I, -OH, -SH, -NH2, nitro group, cyano group, C1-C10 linear or branched hydrocarbon group, phenyl, carbazolyl.

[0052] In some specific embodiments of the present invention, the primary substituent may be optionally substituted with one or more of D, F, Cl, Br, I, -OH, -SH, -NH2, nitro group, cyano group, C1-C6 linear or branched hydrocarbon group, phenyl, carbazolyl.

[0053] The hydrocarbon group includes saturated and / or unsaturated hydrocarbon groups, including but not limited to alkyl, alkene, alkyne groups, and is preferably an alkyl group.

[0054] In some specific embodiments of the present invention, R1, R2, R3, R4, R5, R6 are each independently selected from H, D, F, Cl, Br, I, -OH, -SH, -NH2, nitro group, cyano group, or selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, phenyl, N,N-dimethylamino, N,N-diphenylamino, N-methyl-N-phenylamino, carbazolyl or the following groups which may be unsubstituted or substituted with a primary substituent:

[0055]

[0056] wherein, L a 、L b 、L cEach independently selected from a single bond, H, D, a substituted or unsubstituted linear or branched C1-C30 hydrocarbon group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C3-C60 heteroaromatic group; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S, and Se.

[0057] In some specific embodiments of the present invention, the L a , L b , L c Each independently selected from a single bond, H, D, a substituted or unsubstituted linear or branched C1-C10 hydrocarbon group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C6-C14 aromatic group, a substituted or unsubstituted C3-C14 heteroaromatic group; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S, and Se.

[0058] The hydrocarbon group includes saturated and / or unsaturated hydrocarbon groups, including but not limited to alkyl, alkene, and alkyne groups, preferably alkyl groups.

[0059] In some specific embodiments of the present invention, the L a , L b , L c Each independently selected from a single bond, H, D, a substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl or phenyl, thiophenyl, furyl, pyrrolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl or carbazolyl.

[0060] The above groups:

[0061]

[0062] Can be connected to the parent nucleus through any carbon atom or through an N atom. When connected to the parent nucleus through an N atom, the L a Is a connecting bond.

[0063] It should be noted that the L b , L c Can also be a connecting bond, indicating that the carbon atoms to which L b , L c Are directly connected to the parent nucleus.

[0064] The definition of the above primary substituents is the same as described above and will not be elaborated here.

[0065] The m is the number of the substituents R1, R2 or R6 of Ar1, Ar2, Ar3, and the number of m is determined according to the number of carbon atoms in Ar1, Ar2, Ar3, preferably any integer from 1 to 10. In some specific embodiments of the present invention, the m is 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, or a range value with any of the above values as the upper or lower limit.

[0066] When m is not 1, it means that there are multiple substituents on Ar1, Ar2 and / or Ar3, and the multiple substituents can be the same or different.

[0067] In some specific embodiments of the present invention, Ar1, Ar2, Ar3 are independently selected from:

[0068] a) phenyl;

[0069] b) a five- or six-membered monocyclic heteroaromatic group; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S and Se;

[0070] c) a condensed aryl group formed by condensing 2 to 4 of a); specifically, it can be 2, 3 or 4 of a) condensed; in some embodiments, specifically, it can be naphthyl, anthryl or phenanthryl;

[0071] d) a condensed heteroaromatic group formed by condensing a) and b); the total number of a) and b) is preferably 2 to 4, specifically, it can be 2, 3 or 4;

[0072] e) a condensed heteroaromatic group formed by condensing 2 to 4 of b); specifically, it can be 2, 3 or 4 of b) condensed.

[0073] The b) is preferably: pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl or any of the following structures:

[0074]

[0075] The definition of L a , L b is the same as that described above.

[0076] It should be noted that L a and / or L b can also be a connecting bond, indicating that the carbon atoms connected by L a , L b are directly connected to the parent nucleus.

[0077] In some specific embodiments of the present invention, Ar1, Ar2, Ar3 are independently selected from any of the following structures:

[0078]

[0079] L a 、L b 、L c are each independently selected from a single bond, H, D, a substituted or unsubstituted C1-C30 linear or branched hydrocarbon group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C3-C60 heteroaromatic group; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S, and Se.

[0080] The definition of the aforesaid L a 、L b 、L c is the same as described above and will not be elaborated here.

[0081] When Ar1 and Ar2 are selected from the above structures, they are fused to the parent nucleus through any two adjacent carbon atoms.

[0082] When Ar3 is selected from the above structures, it is connected to the parent nucleus through any carbon atom, nitrogen atom, or Si atom.

[0083] When connected to the parent nucleus through an N atom or an Si atom, the aforesaid L a and / or L b represents a connecting bond.

[0084] It should be noted that in the above structure 12, L a and / or L b can represent a connecting bond. In this case, structure 12 is connected to the parent nucleus through the carbon atoms at the connection positions of L a 、L b .

[0085] Examples are as follows:

[0086]

[0087] * represents the connection position.

[0088] In the above structure 17, L b and / or L c can represent a connecting bond. In this case, structure 17 is connected to the parent nucleus through the carbon atoms at the connection positions of L b 、L c .

[0089] Examples are as follows:

[0090]

[0091] * represents the connection position.

[0092] In some specific embodiments of the present invention, Q is selected from H, D, a substituted or unsubstituted straight-chain or branched C1-C10 hydrocarbon group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C1-C10 alkylthio group, a substituted or unsubstituted C6-C20 aromatic group, a substituted or unsubstituted C3-C20 heteroaromatic group; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S, and Se.

[0093] In some specific embodiments of the present invention, Q is selected from H, D, a substituted or unsubstituted straight-chain or branched C1-C6 hydrocarbon group, a substituted or unsubstituted C3-C6 cycloalkyl group, a substituted or unsubstituted C1-C6 alkoxy group, a substituted or unsubstituted C1-C6 alkylthio group, a substituted or unsubstituted C6-C14 aromatic group, a substituted or unsubstituted C3-C14 heteroaromatic group; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S, and Se.

[0094] In some specific embodiments of the present invention, Q is independently selected from:

[0095] a) hydrogen or deuterium:

[0096] b) phenyl;

[0097] c) a five- or six-membered monocyclic heteroaromatic group; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S, and Se;

[0098] d) a condensed aryl group formed by the fusion of 2-4 b); specifically, it can be the fusion of 2, 3, or 4 b); in some embodiments, it can specifically be naphthyl, anthracenyl, or phenanthryl;

[0099] e) a fused heteroaromatic group formed by the fusion of a) and b); the total number of a) and b) is preferably 2-4, specifically 2, 3, or 4;

[0100] f) a fused heteroaromatic group formed by the fusion of 2-4 b); specifically, it can be the fusion of 2, 3, or 4 b);

[0101] g) -NR7R8; the definition of -NR7R8 is the same as described above. In some embodiments, it can be N,N-dimethylamino, N,N-diphenylamino;

[0102] h) a group formed by connecting 2-3 phenyl groups through single bonds, including but not limited to biphenyl, terphenyl, etc.;

[0103] i) a phenyl group substituted by one or more of c), d), e), f), and / or g);

[0104] j) a group formed by the fusion of a carbazolyl group with a benzofuranyl, benzothiophenyl or benzopyrrolyl group;

[0105] Preferably, the c) is: pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, oxazolyl or any of the following structures:

[0106]

[0107] The said L a and L b are defined as described above.

[0108] It should be noted that the said L a and / or L b can also be a connecting bond, indicating that the carbon atoms connected by L a and L b are directly connected to the parent nucleus.

[0109] Preferably, the said Q can be further substituted by one or more of C1-C6 alkyl, phenyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl.

[0110] In some specific embodiments of the present invention, the said Q has any of the following structures:

[0111]

[0112] L c and L d each independently selected from a single bond, H, D, a substituted or unsubstituted C1-C30 straight-chain or branched-chain hydrocarbon group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C3-C60 heteroaromatic group; the heteroatoms in the said heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S and Se.

[0113] Wherein, * represents the connection position.

[0114] L c and L d are defined as described above and will not be elaborated here.

[0115] It should be noted that the said L c and / or L d can be a single bond, indicating that the C atom, N atom or Si atom connected by the said Q through L c and L d is connected to the parent nucleus.

[0116] In some specific embodiments of the present invention, the organoboron compound has any one of the following structures:

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124]

[0125]

[0126]

[0127] The present invention provides a method for preparing the above organoboron compound, comprising the following steps:

[0128] S1. The intermediate represented by M1 and the intermediate represented by M2 or M3 undergo a C-N coupling reaction to form the intermediate represented by M4 or M5;

[0129] S2. The intermediate represented by M4, the intermediate represented by M5 and the intermediate represented by M6 undergo a C-N coupling reaction to form the intermediate represented by M8;

[0130] Or the intermediate represented by M4 and the intermediate represented by formula M7 undergo a C-N coupling reaction to form the intermediate represented by M9;

[0131] S3. The intermediate represented by M8 reacts with BBr3 to form the organoboron compound represented by formula I;

[0132] The intermediate represented by M9 reacts with BBr3 to form the organoboron compound represented by formula II;

[0133]

[0134] Wherein, X, Q, Ar1, Ar2, Ar3, R1, R2, R3, R4, R5, R6, n, m are defined as described above;

[0135] Y is hydrogen or halogen.

[0136] In some embodiments, the halogen is Br, Cl or I.

[0137] In some embodiments, step S1 is specifically as follows:

[0138] Under an inert atmosphere, the intermediate M1 is mixed with the intermediate M2 or M3, a catalyst, a ligand, a base and an organic solvent, and then heated to react for a certain period of time to obtain the intermediate represented by formula M4 or M5.

[0139] The reaction is preferably carried out under the action of a catalyst, a ligand and a base. The catalyst is preferably tris(dibenzylideneacetone)dipalladium (Pd2dba3) or palladium acetate (Pd(OAc)2); the base is preferably cesium carbonate, potassium tert-butoxide or sodium tert-butoxide; the ligand is preferably (±)-2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl (BINAP), tri-tert-butylphosphine tetrafluoroborate (t-Bu3PHBF4), tri(o-methylphenyl)phosphine (o-Tol3P) or 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (Sphos); the organic solvent of the reaction is preferably one or more of dioxane, toluene or xylene. The molar ratio of the catalyst to compound M1 is preferably (0.01-0.1):1. The reaction is preferably carried out under a protective atmosphere. The present invention does not particularly limit the type of protective gas used to provide the protective atmosphere; any conventional protective gas in the art, such as nitrogen, helium, or argon, can be used. The reaction temperature is preferably 90-120°C, and the reaction time is preferably 4-48 hours. After the above reaction, the intermediate compound represented by Formula M4 or Formula M5 is produced in the system.

[0140] In some embodiments, step S2 is specifically as follows:

[0141] Under an inert atmosphere, intermediates M4 and M5 are mixed with M6, a catalyst, a ligand, a base and an organic solvent, or M4 is mixed with M7, a catalyst, a ligand, a base and an organic solvent, and then reacted to obtain an intermediate compound represented by formula M8 or formula M9.

[0142] The reaction is preferably carried out under the action of a catalyst, a ligand and a base. The catalyst is preferably tris(dibenzylideneacetone)dipalladium (Pd2dba3) or palladium acetate (Pd(OAc)2); the base is preferably cesium carbonate, potassium tert-butoxide or sodium tert-butoxide; the ligand is preferably (±)-2,2'-bis-(diphenylphosphino)-1,1'-binaphthyl (BINAP), tri-tert-butylphosphine tetrafluoroborate (t-Bu3PHBF4), tri(o-methylphenyl)phosphine (o-Tol3P) or 2-dicyclohexylphosphine-2',6'-dimethoxybiphenyl (Sphos); the organic solvent is preferably one or more of dioxane, toluene or xylene. The molar ratio of the catalyst to compound M1 is preferably (0.01-0.1):1. The reaction is preferably carried out under a protective atmosphere. The present invention does not particularly limit the type of protective gas used to provide the protective atmosphere; any conventional protective gas in the art, such as nitrogen, helium, or argon, can be used. The reaction temperature is preferably 90-120°C, and the reaction time is preferably 4-48 hours. After the above reaction, the intermediate compound represented by Formula M8 or Formula M9 is produced in the system.

[0143] In some embodiments, step S3 is specifically as follows:

[0144] When Y is H, the cyclization is preferably carried out directly under the action of BBr3.

[0145] Specifically, under an argon atmosphere, the intermediate represented by formula M8 or formula M9 is added to a thick-walled reaction bottle, and then the solvent is injected, the air is fully ventilated, and BBr3 is added. After high-temperature reaction for a certain period of time, the organic boron compound represented by formula (I) or formula (II) is obtained.

[0146] The reaction is preferably carried out in an organic solvent. The organic solvent is preferably one or more of xylene, trimethylbenzene, chlorobenzene, or o-dichlorobenzene. The ratio of the organic solvent to the intermediate represented by Formula M8 or Formula M9 is preferably (2-50) mL: (0.1-10) mol. The organic solvent is preferably a dry organic solvent. The reaction temperature is preferably 180-240° C., and the reaction time is preferably 24-48 hours.

[0147] When Y is a halogen (Cl, Br or I), it is preferred to form a lithium salt under the action of butyl lithium and then undergo a cyclization reaction with BBr3.

[0148] Specifically, first mix the intermediate represented by Formula M8 or Formula M9 with an organic solvent, then add n-butyllithium dropwise at the first temperature. After the addition is completed, add BBr3 dropwise at the second temperature. After the addition is completed, stir and mix at the third temperature. Then, at the fourth temperature, add an organic amine base dropwise. After the addition is completed, raise the temperature to the reaction temperature for the reaction. Among them, the first temperature is preferably a low temperature below 0 °C, specifically -5 to -78 °C. The second temperature is preferably -5 to -78 °C, preferably the same as the first temperature. The third temperature is preferably room temperature, specifically 20 to 40 °C. The time for stirring and mixing is preferably 0.5 to 6 h. The fourth temperature is preferably lower than the third temperature, that is, after the stirring and mixing, the temperature is lowered, and then the organic amine base is added dropwise; specifically, the fourth temperature is -78 to 0 °C. After all the materials are added, raise the temperature to the above reaction temperature for the reaction. After the reaction, an organic boron compound represented by Formula (I) or Formula (II) is generated in the system.

[0149] The above reaction is preferably carried out under the action of n-butyllithium. The n-butyllithium is preferably n-BuLi (n-butyllithium) and tert-BuLi (tert-butyllithium). The molar ratio of the n-butyllithium to the intermediate represented by Formula M8 or Formula M9 is preferably (1 to 5):1.

[0150] The reaction is preferably carried out in an organic solvent. The organic solvent is preferably one or more of o-xylene, m-xylene, p-xylene, isopropylbenzene, and tert-butylbenzene. The dosage ratio of the organic solvent to the intermediate represented by Formula M8 or Formula M9 is preferably (50 to 500) mL:(0.1 to 10) mol. The organic solvent is preferably a dry organic solvent. The molar ratio of BBr3 (boron tribromide) to the intermediate represented by Formula M8 or Formula M9 is preferably (1 to 10):1. The reaction is preferably carried out in the presence of an organic amine base to neutralize the acid during the reaction. The organic amine base is preferably N,N-diisopropylethylamine and / or triethylamine. The molar ratio of the organic amine base to the intermediate represented by Formula M8 or Formula M9 is preferably (1 to 10):1. The reaction is preferably carried out under a protective atmosphere. The present invention has no particular limitation on the type of protective gas providing the protective atmosphere, and it can be a conventional protective gas in the art, such as nitrogen, helium, or argon, etc. The temperature of the reaction is preferably 90 to 200 °C; the time of the reaction is preferably 8 to 48 h. After the above reaction, an organic boron compound represented by Formula (I) or Formula (II) is generated in the system.

[0151] The present invention provides the application of the above organic boron compound as an organic electroluminescent material.

[0152] Preferably, the organic boron compound is used as a blue light emitting material in the organic electroluminescent material.

[0153] The present invention provides an organic electroluminescent device, comprising an anode, a cathode, and an organic thin film layer located between the anode and the cathode; the organic thin film layer comprises the above-mentioned organic boron compound.

[0154] The present invention has no particular limitation on the structure of the organic electroluminescent device, and a conventional organic electroluminescent device well-known to those skilled in the art can be used. Those skilled in the art can make selections and adjustments according to application scenarios, quality requirements, and product requirements. The structure of the organic electroluminescent device of the present invention preferably comprises: a substrate; an anode disposed on the substrate; an organic thin film layer disposed on the anode; and a cathode disposed on the organic thin film layer.

[0155] The thickness of the substrate is preferably 0.3 to 0.7 mm, more preferably 0.4 to 0.6 mm; the present invention has no special limitation on the selection of the substrate, and a substrate of a conventional organic electroluminescent device well-known to those skilled in the art can be used. Those skilled in the art can make selections and adjustments according to application scenarios, quality requirements, and product requirements. In the present invention, the substrate is preferably glass or plastic.

[0156] According to the present invention, the anode is preferably a material easy for hole injection, more preferably a conductive metal or a conductive metal oxide, and still more preferably indium tin oxide.

[0157] The organic thin film layer can be one layer or multiple layers, and at least one layer is a light-emitting layer; the light-emitting layer comprises the above-mentioned organic boron compound; preferably, the light-emitting layer is directly composed of the organic boron compound provided by the present invention.

[0158] The cathode is preferably a metal, including but not limited to calcium, magnesium, barium, aluminum, and silver, and preferably aluminum.

[0159] To improve the performance and efficiency of the device, the organic thin film layer between the anode and the light-emitting layer preferably further includes one or more of a hole injection layer, a hole transport layer, and an electron blocking layer. The organic thin film layer between the light-emitting layer and the cathode preferably further includes one or more of a hole blocking layer, an electron injection layer, and an electron transport layer. The present invention does not particularly limit the materials and thicknesses of the hole injection layer, the hole transport layer, the electron blocking layer, the organic electroluminescent layer, the hole blocking layer, the electron injection layer, and the electron transport layer, and they can be selected and adjusted according to the materials and thicknesses well-known to those skilled in the art. The present invention does not particularly limit the preparation processes of the electrode, the hole injection layer, the hole transport layer, the electron blocking layer, the hole blocking layer, the electron injection layer, and the electron transport layer, and preferably vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing, and stereolithography processes are used for preparation. The present invention does not particularly limit the preparation process of the organic electroluminescent layer, and preferably solution spin coating, solution blade coating, inkjet printing, offset printing, and stereolithography processes are used for preparation.

[0160] The present invention does not particularly limit the preparation method of the organic electroluminescent device, and it can be carried out according to the following method: forming an anode on the substrate; forming one or more organic thin film layers on the anode, which includes a light-emitting layer; forming a cathode on the organic thin film layer.

[0161] The light-emitting layer includes one or more of the above-mentioned organic boron compounds.

[0162] The present invention does not particularly limit the structure and materials of the organic electroluminescent device in the above preparation method, as well as the corresponding preferred principles, and they can correspond to the materials and structures, and the corresponding preferred principles in the foregoing organic electroluminescent device, and will not be elaborated herein one by one.

[0163] The present invention first forms an anode on the substrate. The present invention does not particularly limit the formation method of the anode, and it can be carried out according to the method well-known to those skilled in the art. Then, an organic thin film layer below the light-emitting layer, a light-emitting layer, and an organic thin film layer above the light-emitting layer are formed on the anode. The present invention does not particularly limit the formation methods of the organic thin film layers below and above the light-emitting layer, and they can be formed by vacuum evaporation, solution spin coating, solution blade coating, inkjet printing, offset printing, or stereolithography. The present invention does not particularly limit the formation method of the light-emitting layer, and it can be formed by solution spin coating, solution blade coating, inkjet printing, offset printing, or stereolithography. After the above-mentioned organic layers are formed, a cathode is prepared on its surface. The present invention does not particularly limit the formation method of the cathode, and preferably it is a method well-known to those skilled in the art, including but not limited to vacuum evaporation.

[0164] To further illustrate the present invention, it will be described in detail below in conjunction with embodiments. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the invention.

[0165] For all raw materials of the present invention, there is no particular limitation on their sources, and they can be purchased on the market or prepared by conventional methods well-known to those skilled in the art.

[0166] Example 1

[0167] The chemical structure and synthetic route of 1-2 are as follows:

[0168]

[0169] Under an argon atmosphere, 3,5-dimethylbromobenzene (1.85 g, 10 mmol), p-tert-butylaniline (1.8 g, 12 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), t-BuONa (2.9 g, 30 mmol) were added to a 250 mL three-necked flask, and then 50 mL of toluene was injected, and the reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 1-2a (2.2 g, yield: 88%) was obtained. Elemental analysis: theoretical value C, 86.08; H, 4.53; N, 7.87; measured value C, 86.02; H, 4.56; N, 7.88. MALDI-TOF MS (m / z): theoretical value 253.2; experimental value 253.2 (M + )

[0170] Under an argon atmosphere, 1-2a (1.88 g, 4 mmol), 2-chloro-1,3-dibromobenzene (1.2 g, 4.8 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), t-BuONa (0.39 g, 4 mmol) were added to a 100 mL three-necked flask, and then 50 mL of toluene was injected, and the reaction was carried out at 110 °C for 18 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 1-2b (1.96 g, yield: 80%) was obtained. Elemental analysis: theoretical value C, 81.99; H, 7.70; N, 4.55 measured value C, 81.99; H, 7.70; N, 4.55. MALDI-TOF (m / z): theoretical value 614.3; experimental value 614.3 (M + )

[0171] Under an argon atmosphere, 1-2b (1.2 g, 2 mmol) and dry tert-butylbenzene (15 mL) were weighed in a 250 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -30 °C, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (0.8 g, 8 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 100 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the filtered organic phase. The product 1-2 (1.14 g, yield: 60%) was obtained by column separation. Elemental analysis: theoretical values C, 85.70; H, 7.7; N, 4.76; measured values C, 85.75; H, 7.64; N, 4.79. MALDI-TOF MS (m / z): theoretical value 558.3; experimental value 558.3 (M + )。

[0172] Example 2

[0173] The chemical structures and synthetic routes of 1-19 are as follows:

[0174]

[0175] Under an argon atmosphere, 5-bromo-2-iodo-m-xylene (6.2 g, 20 mmol), phenylboronic acid (2.44 g, 20 mmol), Pd(PPh3)4 (462 mg, 0.2 mmol), and K2CO3 (8.34 g, 60 mmol) were added to a 250 mL three-necked flask. Then, 60 mL of dioxane and 30 mL of deoxygenated water were injected, and the reaction was carried out at 80 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the compound 1-19a (3.9 g, yield: 75%) was obtained by column separation and solvent removal. Elemental analysis: theoretical values C, 64.39; H, 5.02; measured values C, 64.36; H, 5.05;. GC-MS (m / z): theoretical value 260.0; experimental value 260.0 (M + )。

[0176] Under an argon atmosphere, 1-19a (2.6 g, 10 mmol), p-tert-butylaniline (1.62 g, 12 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), and t-BuONa (2.9 g, 30 mmol) were added to a 100 mL three-necked flask, and then 50 mL of toluene was injected. The reaction was carried out at 110 °C for 18 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 1-19b (2.97 g, yield: 90%) was obtained. Elemental analysis: theoretical values C, 87.49; H, 8.26; N, 4.25; measured values C, 87.49; H, 8.26; N, 4.27. GC-MS (m / z): theoretical value 329.5; experimental value 329.5 (M + ).

[0177] Under an argon atmosphere, 1-19b (1.97 g, 6 mmol), 2-chloro-1,3-dibromobenzene (0.67 g, 2.5 mmol), Pd2(dba)3 (110 mg, 0.12 mmol), t-Bu3PHBF4 (129 mg, 0.48 mmol), and t-BuONa (1.72 g, 18 mmol) were added to a 100 mL three-necked flask, and then 60 mL of toluene was injected. The reaction was carried out at 110 °C for 18 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 1-19c (1.53 g, yield: 80%) was obtained. Elemental analysis: theoretical values C, 84.51; H, 7.22; N, 3.65; measured values C, 84.52; H, 7.23; N, 3.64. MALDI-TOF MS (m / z): theoretical value 766.4; experimental value 766.4 (M + ).

[0178] Under an argon atmosphere, 1-19c (2.29 g, 3 mmol) and dry tert-butylbenzene (25 mL) were weighed in a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (4.6 mL, 1.3 M, 6 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -40 °C, boron tribromide (1.65 g, 6.6 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 100 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent of the filtered organic phase was removed. The product 1-19 (0.72 g, yield: 30%) was obtained by column separation. Elemental analysis: theoretical values C, 87.55; H, 7.21; N, 3.78; measured values C, 87.56; H, 7.22; N, 3.76. MALDI-TOF MS (m / z): theoretical value 740.4; experimental value 740.4 (M + ).

[0179] Example 3

[0180] The chemical structure and synthetic route of 1-46 are as follows:

[0181]

[0182] Under an argon atmosphere, 3,5-dimethyl-4-bromoiodobenzene (3.1 g, 10 mmol), 9-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]carbazole (4.1 g, 11 mmol), Pd(PPh3)4 (231 mg, 0.2 mmol), and K2CO3 (4.2 g, 30 mmol) were added to a 100 mL three-necked flask. Then, 30 mL of dioxane and 15 mL of water were injected, and the reaction was carried out at 85 °C for 16 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, the solvent was removed under reduced pressure, and the compound 1-46a (3.18 g, yield: 75%) was obtained by column separation and desolvation. Elemental analysis: theoretical values C, 73.25; H, 4.73; N, 3.29; measured values C, 73.27; H, 4.75; N, 3.30. MALDI-TOF MS (m / z): theoretical value 425.1; experimental value 425.1 (M + ).

[0183] Under an argon atmosphere, 1-46a (3 g, 7 mmol), p-toluidine (1.25 g, 8.4 mmol), Pd2(dba)3 (128 mg, 0.14 mmol), BINAP (348 mg, 0.56 mmol), and t-BuONa (2.0 g, 21 mmol) were added to a 100 mL three-necked flask. Then, 100 mL of toluene was injected, and the reaction was carried out at 110 °C for 24 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 1-46b (2.53 g, yield: 80%) was obtained. Elemental analysis: theoretical values: C, 87.41; H, 6.93; N, 5.66; measured values: C, 87.43; H, 6.95; N, 5.64. MALDI-TOFMS (m / z): theoretical value 452.6; experimental value 452.6 (M + )

[0184] Under an argon atmosphere, 1-46b (5.4 g, 12 mmol), 3,5-dibromotoluene (1.23 g, 5 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (2.88 g, 6 mmol) were added to a 100 mL three-necked flask. Then, 100 mL of toluene was injected, and the reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 1-46c (3.74 g, yield: 75%) was obtained. Elemental analysis: theoretical values: C, 88.27; H, 6.09; N, 5.64; measured values: C, 87.89; H, 6.42; N, 5.6C, 88.27; H, 6.09; N, 5.64 9. MALDI-TOF MS (m / z): theoretical value 992.4; experimental value 992.4 (M + )

[0185] Under an argon atmosphere, 1-46c (1 g, 1 mmol) was added to a 120 m thick-walled reaction flask. Then, 15 mL of o-dichlorobenzene was injected, and after sufficient gas exchange, BBr3 (1 g, 4 mmol) was added, and the reaction was carried out at 230 °C for 24 hours. After cooling to room temperature, the reaction mixture was placed in an ice-water bath. After cooling, methanol was slowly added dropwise to quench the reaction, and the solvent was removed under reduced pressure. The residue was subjected to column separation and solvent removal to obtain compound 1-46 (0.61 g, yield: 60%). Elemental analysis: theoretical values: C, 87.58; H, 5.74; N, 5.60; measured values: C, 87.58; H, 5.74; N, 5.60. MALDI-TOF MS (m / z): theoretical value 1000.4; experimental value 1000.4 (M + )

[0186] Example 4

[0187] The chemical structure and synthetic route of 1-48 are as follows:

[0188]

[0189] In a 100 mL three-necked flask under an argon atmosphere, 2-methyl-4-bromoiodobenzene (2.95 g, 10 mmol), 9-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]carbazole (4.1 g, 11 mmol), Pd(PPh3)4 (231 mg, 0.2 mmol), and K2CO3 (4.2 g, 30 mmol) were added. Then, 30 mL of dioxane and 15 mL of water were injected, and the reaction was carried out at 85 °C for 16 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, the solvent was removed under reduced pressure, and compound 1-48a (3.18 g, yield: 75%) was obtained through column separation and desolvation. Elemental analysis: theoretical value C, 28.32; H, 2.04; measured value C, 28.32; H, 2.04;. MALDI-TOF MS (m / z): theoretical value 411.0; experimental value 411.0 (M + )

[0190] Under an argon atmosphere, 1-48a (2.87 g, 7 mmol), p-tert-butylaniline (1.25 g, 8.4 mmol), Pd2(dba)3 (128 mg, 0.14 mmol), BINAP (348 mg, 0.56 mmol), and t-BuONa (2.0 g, 21 mmol) were added to a 100 mL three-necked flask. Then, 100 mL of toluene was injected, and the reaction was carried out at 110 °C for 24 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and compound 1-48b (2.82 g, yield: 84%) was obtained through column separation and desolvation. Elemental analysis: theoretical value: C, 87.46; H, 6.71; N, 5.83 measured value: C, 87.46; H, 6.72; N, 5.84. MALDI-TOF MS (m / z): theoretical value 480.2; experimental value 480.2 (M + )

[0191] Under an argon atmosphere, 3,5-dimethylbromobenzene (0.25 g, 1 mmol), 1-48b (2.3 g, 2.4 mmol), Pd2(dba)3 (19 mg, 0.02 mmol), t-Bu3PHBF4 (23.2 mg, 0.08 mmol), and t-BuONa (0.39 g, 4 mmol) were added to a 100 mL three-necked flask. Then, 30 mL of toluene was injected, and the reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 50 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 1-48c (0.89 g, yield: 85%) was obtained. Elemental analysis: theoretical values C, 88.13; H, 6.53; N, 5.34; measured values C, 88.13; H, 6.53; N, 5.34. MALDI-TOF MS (m / z): theoretical value 1048.5; experimental value 1048.5 (M + ).

[0192] Under an argon atmosphere, 1-48c (1 g, 1 mmol) was added to a 120 m thick-walled reaction flask. Then, 15 mL of o-dichlorobenzene was injected, and after sufficient gas replacement, BBr3 (1 g, 4 mmol) was added, and the reaction was carried out at 200 °C for 24 hours. After cooling to room temperature, it was placed in an ice-water bath. After cooling, methanol was slowly added dropwise to quench the reaction, and the solvent was removed under reduced pressure. The residue was separated by column chromatography and the solvent was removed to obtain compound 1-48 (0.51 g, yield: 51%). Elemental analysis: theoretical values C, 87.48; H, 6.20; N, 5.30; measured values C, 87.48; H, 6.20; N, 5.31. MALDI-TOF MS (m / z): theoretical value 1056.5; experimental value 1056.5 (M + ).

[0193] Example 5

[0194] The chemical structure and synthesis route of 1-89 are as follows:

[0195]

[0196] In a 100 mL three-necked flask under an argon atmosphere, 2,6-dimethyl-4-bromoiodobenzene (3.1 g, 10 mmol), 3-pyridineboronic acid (1.35 g, 11 mmol), Pd(PPh3)4 (231 mg, 0.2 mmol), and K2CO3 (4.2 g, 30 mmol) were added. Then, 30 mL of dioxane and 15 mL of water were injected, and the reaction was carried out at 85 °C for 16 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, the solvent was removed under reduced pressure, and compound 1-89a (2 g, yield: 77%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 59.56; H, 4.61; N, 5.34; measured values C, 59.56; H, 4.61; N, 5.34. MALDI-TOF MS (m / z): theoretical value 261.0; experimental value 261.0 (M + ).

[0197] Under an argon atmosphere, 1-89a (1.8 g, 7 mmol), p-tert-butylaniline (1.25 g, 8.4 mmol), Pd2(dba)3 (128 mg, 0.14 mmol), BINAP (348 mg, 0.56 mmol), and t-BuONa (2.0 g, 21 mmol) were added to a 100 mL three-necked flask. Then, 100 mL of toluene was injected, and the reaction was carried out at 110 °C for 24 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and compound 1-89b (2.1 g, yield: 90%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values: C, 83.59; H, 7.93; N, 8.48 measured values C, 83.59; H, 7.93; N, 8.48. MALDI-TOF MS (m / z): theoretical value 330.2; experimental value 330.2 (M + ).

[0198] Under an argon atmosphere, 1-89b (1.98 g, 6 mmol), 2-chloro-1,3-dibromobenzene (0.67 g, 2.5 mmol), Pd2(dba)3 (110 mg, 0.12 mmol), t-Bu3PHBF4 (129 mg, 0.48 mmol), and t-BuONa (1.72 g, 18 mmol) were added to a 100 mL three-necked flask. Then, 60 mL of toluene was injected, and the reaction was carried out at 110 °C for 18 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed several times with deionized water. The organic phase was separated, and after column separation and solvent removal, compound 1-89c (3.0 g, yield: 80%) was obtained. Elemental analysis: theoretical values C, 81.17; H, 6.94; N, 7.28; measured values C, 81.18; H, 6.95; N, 7.29. MALDI-TOF MS (m / z): theoretical value 768.4; experimental value 768.4 (M + ).

[0199] Under an argon atmosphere, 1-89c (1.53 g, 2 mmol) and dry tert-butylbenzene (30 mL) were weighed into a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -40 °C, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, the solvent of the filtered organic phase was removed, and the product 1-89 (0.89 g, yield: 60%) was obtained by column separation. Elemental analysis: theoretical values C, 84.08; H, 6.92; N, 7.54; measured values C, 84.08; H, 6.92; N, 7.54. MALDI-TOF MS (m / z): theoretical value 742.4; experimental value 742.4 (M + ).

[0200] Example 6

[0201] The chemical structure and synthetic route of 1-97 are as follows:

[0202]

[0203] In a 100 mL three-necked flask under an argon atmosphere, 2,6-dimethyl-4-bromoiodobenzene (3.1 g, 10 mmol), 2,4-diphenyl-6-pinacolato-1,3,5-triazine (3.94 g, 11 mmol), Pd(PPh3)4 (231 mg, 0.2 mmol), and K2CO3 (4.2 g, 30 mmol) were added. Then, 30 mL of dioxane and 15 mL of water were injected, and the reaction was carried out at 85 °C for 16 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, the solvent was removed under reduced pressure, and compound 1-97a (2.9 g, yield: 70%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 66.36; H, 4.36; N, 10.09; measured values C, 66.36; H, 4.36; N, 10.09. MALDI-TOF MS (m / z): theoretical value 415.0; experimental value 415.0 (M + ).

[0204] Under an argon atmosphere, 1-97a (2.9 g, 7 mmol), p-tert-butylaniline (1.25 g, 8.4 mmol), Pd2(dba)3 (128 mg, 0.14 mmol), BINAP (348 mg, 0.56 mmol), and t-BuONa (2.0 g, 21 mmol) were added to a 100 mL three-necked flask. Then, 100 mL of toluene was injected, and the reaction was carried out at 110 °C for 24 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and 1-97b (2.26 g, yield: 90%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values: C, 81.78; H, 6.66; N, 11.56; measured values C, 81.78; H, 6.66; N, 11.56. MALDI-TOF MS (m / z): theoretical value 484.2; experimental value 484.2 (M + ).

[0205] Under an argon atmosphere, 1-97b (2.9 g, 6 mmol), 2-chloro-1,3-dibromobenzene (0.67 g, 2.5 mmol), Pd2(dba)3 (110 mg, 0.12 mmol), t-Bu3PHBF4 (129 mg, 0.48 mmol), and t-BuONa (1.72 g, 18 mmol) were added to a 100 mL three-necked flask. Then, 60 mL of toluene was injected, and the reaction was carried out at 110 °C for 18 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 1-97c (4.3 g, yield: 80%) was obtained. Elemental analysis: theoretical values C, 80.24; H, 6.08; N, 10.40; measured values C, 80.24; H, 6.08; N, 10.41. MALDI-TOF MS (m / z): theoretical value 1076.5; experimental value 1076.5 (M + ).

[0206] Under an argon atmosphere, 1-97c (2.1 g, 2 mmol) and dry tert-butylbenzene (30 mL) were weighed into a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -40 °C, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, the solvent of the filtered organic phase was removed, and the product 1-97 (0.84 g, yield: 40%) was obtained by column separation. Elemental analysis: theoretical values C, 82.27; H, 6.04; N, 10.66; measured values C, 82.27; H, 6.04; N, 10.66. MALDI-TOF MS (m / z): theoretical value 1050.5; experimental value 1050.5 (M + ).

[0207] Example 7

[0208] The chemical structure and synthetic route of 1-103 are as follows:

[0209]

[0210] In a 100 mL three-necked flask under an argon atmosphere, 2-trideuteriomethyl-4-bromoiodobenzene (3.0 g, 10 mmol), 9-(4-phenyl-6-pinacolato-1,3,5-triazin-2-yl)-9H-carbazole (4.48 g, 11 mmol), Pd(PPh3)4 (231 mg, 0.2 mmol), and K2CO3 (4.2 g, 30 mmol) were added. Then, 30 mL of THF and 15 mL of water were injected, and the reaction was carried out at 70 °C for 24 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, the solvent was removed under reduced pressure, and compound 1-103a (3.69 g, yield: 75%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 68.02; H, 4.48; N, 11.33; measured values C, 68.03; H, 4.48; N, 11.34. MALDI-TOF (m / z): theoretical value 493.1; experimental value 493.1 (M + ).

[0211] Under an argon atmosphere, 1-103a (3.45 g, 7 mmol), p-tert-butylaniline (1.25 g, 8.4 mmol), Pd2(dba)3 (128 mg, 0.14 mmol), BINAP (348 mg, 0.56 mmol), and t-BuONa (2.0 g, 21 mmol) were added to a 100 mL three-necked flask. Then, 100 mL of toluene was injected, and the reaction was carried out at 110 °C for 24 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and compound 1-103b (3.31 g, yield: 90%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 81.11; H, 6.45; N, 12.45; measured values C, 81.11; H, 6.45; N, 12.45. MALDI-TOF (m / z): theoretical value 526.2; experimental value 526.2 (M + ).

[0212] Under an argon atmosphere, 1-103b (2.63 g, 6 mmol), 2-chloro-1,3-dibromobenzene (0.67 g, 2.5 mmol), Pd2(dba)3 (110 mg, 0.12 mmol), t-Bu3PHBF4 (129 mg, 0.48 mmol), and t-BuONa (1.72 g, 18 mmol) were added to a 100 mL three-necked flask. Then, 60 mL of toluene was injected, and the reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 1-103c (2.8 g, yield: 80%) was obtained. Elemental analysis: theoretical values C, 79.81; H, 5.96; N, 11.35; measured values C, 79.81; H, 5.96; N, 11.35. MALDI-TOF MS (m / z): theoretical value 1232.5; experimental value 1232.5 (M + ).

[0213] Under an argon atmosphere, 1-103c (2.4 g, 2 mmol) and dry tert-butylbenzene (30 mL) were weighed into a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -40 °C, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, and the solvent of the filtered organic phase was removed. The product 1-103 (0.71 g, yield: 35%) was obtained by column separation. Elemental analysis: theoretical values C, 81.58; H, 5.93; N, 11.60; measured values C, 81.58; H, 5.93; N, 11.60. MALDI-TOF (m / z): theoretical value 1026.5; experimental value 1026.5 (M + ).

[0214] Example 8

[0215] The chemical structure and synthetic route of 1-106 are as follows:

[0216]

[0217] 1.84 g (10 mmol) of o - aminodiphenylamine and 1.97 g (10 mmol) of 4 - bromo - 2,5 - dimethylbenzaldehyde were added to a 250 mL single - necked flask. 90 mL of DMF and 10 mL of water were added, and the mixture was heated to 80 °C and reacted overnight. The solvent was removed under reduced pressure, and the product 1 - 106a (3.2 g, yield: 85%) was obtained by column chromatography. Elemental analysis: theoretical values C, 66.85; H, 4.54; N, 7.43; measured values C, 66.86; H, 4.55; N, 7.45. MALDI - TOF (m / z): theoretical value 376.0, experimental value 376.0 (M + )

[0218] Under an argon atmosphere, 1 - 106a (4.52 g, 10 mmol), p - tert - butylaniline (1.8 g, 12 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), t - BuONa (2.9 g, 30 mmol) were added to a 100 mL three - necked flask, and then 50 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. The temperature was lowered to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the compound 1 - 106b (3.6 g, yield: 80%) was obtained by column chromatography and solvent removal. Elemental analysis: theoretical values C, 83.56; H, 7.01; N, 9.43; measured values C, 83.53; H, 7.01; N, 9.44. MALDI - TOF MS (m / z)): theoretical value 445.2; experimental value 445.2 (M+).

[0219] Under an argon atmosphere, 1 - 106b (2.67 g, 6 mmol), 2 - chloro - 1,3 - dibromobenzene (0.67 g, 2.5 mmol), Pd2(dba)3 (110 mg, 0.12 mmol), t - Bu3PHBF4 (129 mg, 0.48 mmol), t - BuONa (1.72 g, 18 mmol) were added to a 100 mL three - necked flask, and then 60 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. The temperature was lowered to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the compound 1 - 106c (1.53 g, yield: 80%) was obtained by column chromatography and solvent removal. Elemental analysis: theoretical values C, 81.70; H, 6.35; N, 8.41; measured values C, 81.71; H, 6.36; N, 8.42. MALDI - TOF MS (m / z): theoretical value 998.4; experimental value 998.4 (M + )

[0220] Under an argon atmosphere, 1-106c (2.0 g, 2 mmol) and dry tert-butylbenzene (30 mL) were weighed in a 100 mL two-necked reaction flask. tert-Butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise at -30 °C. After the addition, the mixture was stirred at room temperature for 2 hours. Then, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system at -40 °C. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent of the filtered organic phase was removed. The product 1-106 (1.2 g, yield: 60%) was obtained by column chromatography. Elemental analysis: theoretical values C, 83.93; H, 6.32; N, 8.64; measured values C, 83.93; H, 6.32; N, 8.64. MALDI-TOF (m / z): theoretical value 972.5; experimental value 972.5 (M + )。

[0221] Example 9

[0222] The chemical structure and synthetic route of 1-107 are as follows:

[0223]

[0224] o-Aminodiphenylamine (1.84 g, 10 mmol) and 4-bromo-2-methylbenzaldehyde (1.97 g, 10 mmol) were added to a 250 mL single-necked flask. 90 mL of DMF and 10 mL of water were added, and the mixture was heated to 80 °C and reacted overnight. The solvent was removed under reduced pressure, and the product 1-107a (3.25 g, yield: 90%) was obtained by column chromatography. Elemental analysis: theoretical values C, 66.13; H, 4.16; N, 7.71; measured values C, 66.13; H, 4.16; N, 7.71. MALDI-TOF MS (m / z): theoretical value 362.0; experimental value 362.0 (M + )。

[0225] Under an argon atmosphere, 1-107a (3.62 g, 10 mmol), p-tert-butylaniline (1.8 g, 12 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), and t-BuONa (2.9 g, 30 mmol) were added to a 100 mL three-necked flask, and then 50 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 1-107b (3.79 g, yield: 88%) was obtained. Elemental analysis: theoretical values C, 87.41; H, 8.51; N, 4.08; measured values C, 87.41; H, 8.51; N, 4.08. MALDI-TOF MS (m / z)): theoretical value 431.2; experimental value 431.2 (M + ).

[0226] Under an argon atmosphere, 2-chloro-1,3-dibromobenzene (2.2 g, 8 mmol), 1-107b (3.44 g, 8 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), and t-BuONa (2.32 g, 24 mmol) were added to a 100 mL three-necked flask, and then 30 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 1-107c (3.46 g, yield: 70%) was obtained. Elemental analysis: theoretical values C, 69.63; H, 5.03; N, 6.77; measured values C, 69.65; H, 5.03; N, 6.73. MALDI-TOF MS (m / z): theoretical value 619.1; experimental value 619.1 (M + ).

[0227] Under an argon atmosphere, 1-107a (3.62 g, 10 mmol), p-tert-butylbenzidine (2.7 g, 12 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), and t-BuONa (2.9 g, 30 mmol) were added to a 100 mL three-necked flask, and then 50 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 1-107d (4.3 g, yield: 85%) was obtained. Elemental analysis: theoretical values C, 85.17; H, 6.55; N, 8.28; measured values C, 85.17; H, 6.56; N, 8.24. MALDI-TOF MS (m / z): theoretical value 507.2; experimental value 507.2 (M + ).

[0228] Under an argon atmosphere, 1-107c (3.09 g, 5 mmol), 1-107d (3.04 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (1.44 g, 15 mmol) were added to a 100 mL three-necked flask, and then 50 mL of toluene was injected. The reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 1-107e (3.78 g, yield: 90%) was obtained. Elemental analysis: theoretical values:: C, 82.54; H, 6.06; N, 8.02; measured values:: C, 82.55; H, 6.06; N, 8.03. MALDI-TOF MS (m / z): theoretical value 1046.4; experimental value 1046.4 (M + ).

[0229] Under an argon atmosphere, 1-107e (2.08 g, 2 mmol) and dry tert-butylbenzene (25 mL) were weighed in a 100 mL two-necked reaction flask. tert-Butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise at -30 °C. After the addition, the mixture was stirred at room temperature for 2 hours. Then, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system at -40 °C. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the filtered organic phase. The product 1-107 (0.65 g, yield: 32%) was obtained by column separation. Elemental analysis: theoretical values C, 84.69; H, 6.02; N, 8.23; measured values C, 84.69; H, 6.02; N, 8.23. MALDI-TOF MS (m / z): theoretical value 1020.5; experimental value 1020.5 (M + ).

[0230] Example 10

[0231] The chemical structure and synthetic route of 1-108 are as follows:

[0232]

[0233] Under an argon atmosphere, 9,9'-(5-pinacolato-1,3-phenylene)bis(9H-carbazole) (5.3 g, 10 mmol), 5-bromo-2-iodo-1,3-dimethylbenzene (3.1 g, 10 mmol), Pd(PPh3)4 (231 mg, 0.1 mmol), and K2CO3 (4.17 g, 30 mmol) were added to a 250 mL three-necked flask. Then, 50 mL of dioxane and 15 mL of deoxygenated water were injected, and the reaction was carried out at 80 °C for 20 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the compound 1-108a (2.8 g, yield: 80%) was obtained by column separation and solvent removal. Elemental analysis: theoretical values C, 77.16; H, 4.60; N, 4.74; measured values C, 77.15; H, 4.62; N, 4.76. GC-MS (m / z): theoretical value 590.1; experimental value 590.1 (M + ).

[0234] Under an argon atmosphere, 1-108a (5.9 g, 10 mmol), p-tert-butylaniline (1.62 g, 12 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), t-BuONa (2.9 g, 30 mmol) were added to a 250 mL three-necked flask, and then 80 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 1-108b (5.9 g, yield: 90%) was obtained. Elemental analysis: theoretical values: C, 87.37; H, 6.26; N, 6.37; measured values: C, 87.37; H, 6.24; N, 6.34. GC-MS (m / z): theoretical value 659.3; experimental value 659.3 (M + ).

[0235] Under an argon atmosphere, 1-108b (3.3 g, 5 mmol), 2-chloro-1,3-dibromobenzene (1.62 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), t-BuONa (1.44 g, 15 mmol) were added to a 100 mL three-necked flask, and then 60 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 1-108c (5.7 g, yield: 80%) was obtained. Elemental analysis: theoretical values C, 85.78; H, 5.86; N, 5.88; measured values C, 85.76; H, 5.84; N, 5.88. MALDI-TOF MS (m / z): theoretical value 1426.6; experimental value 1426.6 (M + ).

[0236] Under an argon atmosphere, 1-108b (2.8 g, 2 mmol) and dry tert-butylbenzene (30 mL) were weighed in a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -40 °C, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent of the filtered organic phase was removed. The product 1-108 (1.2 g, yield: 44%) was obtained by column separation. Elemental analysis: theoretical values C, 87.41; H, 5.83; N, 6.00; measured values C, 87.42; H, 5.85; N, 6.01. MALDI-TOF (m / z): theoretical value 1440.6; experimental value 1440.6 (M + ).

[0237] Example 11

[0238] The chemical structure and synthetic route of 1-109 are as follows:

[0239]

[0240] Under an argon atmosphere, 9,9'-(5-pinacolato-1,3-phenylene)bis(9H-carbazole) (5.3 g, 10 mmol), 3,5-dimethyl-4-bromoiodobenzene (3.1 g, 10 mmol), Pd(PPh3)4 (231 mg, 0.1 mmol), and K2CO3 (4.17 g, 30 mmol) were added to a 250 mL three-necked flask. Then, 50 mL of dioxane and 15 mL of deoxygenated water were injected, and the reaction was carried out at 80 °C for 20 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the compound 1-109a (2.8 g, yield: 80%) was obtained by column separation and solvent removal. Elemental analysis: theoretical values C, 77.16; H, 4.60; N, 4.74; measured values C, 77.15; H, 4.62; N, 4.76. GC-MS (m / z): theoretical value 590.1; experimental value 590.1 (M + ).

[0241] Under an argon atmosphere, 1-109a (5.9 g, 10 mmol), p-toluidine (1.28 g, 12 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), and t-BuONa (2.9 g, 30 mmol) were added to a 250 mL three-necked flask, and then 80 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 1-109b (5.3 g, yield: 86%) was obtained. Elemental analysis: theoretical values: C, 87.49; H, 5.71; N, 6.80; measured values: C, 87.49; H, 5.71; N, 6.80. GC-MS (m / z): theoretical value 617.2; experimental value 617.2 (M + ).

[0242] Under an argon atmosphere, 1-109b (7.4 g, 12 mmol), 3,5-dibromotoluene (1.23 g, 5 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (1.44 g, 15 mmol) were added to a 100 mL three-necked flask, and then 60 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 1-109c (4.6 g, yield: 70%) was obtained. Elemental analysis: theoretical values C, 88.02; H, 5.64; N, 6.35; measured values C, 88.02; H, 5.64; N, 6.35. MALDI-TOF MS (m / z): theoretical value 1322.6; experimental value 1322.6 (M + ).

[0243] Under an argon atmosphere, 1-109c (1.3 g, 1 mmol) was added to a 120 m thick-walled reaction flask, and then 15 mL of o-dichlorobenzene was injected. After sufficient gas exchange, BBr3 (1 g, 4 mmol) was added, and the reaction was carried out at 200 °C for 24 hours. After cooling to room temperature, it was placed in an ice-water bath. After cooling, methanol was slowly added dropwise to quench the reaction, and the solvent was removed under reduced pressure. The residue was separated by column chromatography and the solvent was removed to obtain compound 1-109 (0.66 g, yield: 50%). Elemental analysis: theoretical values C, 87.50; H, 5.38; N, 6.31; measured values C, 87.50; H, 5.38; N, 6.31. MALDI-TOF MS (m / z): theoretical value 1331.4; experimental value 1331.4 (M+).

[0244] Example 12

[0245] The chemical structure and synthetic route of 2-2 are as follows:

[0246]

[0247] Under an argon atmosphere, 2,4,6-trimethylbromobenzene (1.98 g, 10 mmol), p-tert-butylaniline (1.62 g, 12 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), and t-BuONa (2.9 g, 30 mmol) were added to a 100 mL three-necked flask, and then 50 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and compound 2-2a (2.32 g, yield: 87%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 85.34; H, 9.42; N, 5.24; measured values C, 85.31; H, 9.45; N, 5.27. GC-MS (m / z): theoretical value 267.2; experimental value 267.2 (M + ).

[0248] Under an argon atmosphere, 2-chloro-1,3-dibromobenzene (2.7 g, 10 mmol), 2-2a (2.67 g, 10 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), and t-BuONa (3.9 g, 40 mmol) were added to a 100 mL three-necked flask, and then 70 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and compound 2-2b (2.95 g, yield: 65%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 66.32; H, 6.21; N, 2.97; measured values C, 66.30; H, 6.25; N, 2.90. MALDI-TOF MS (m / z): theoretical value 455.1; experimental value 455.1 (M + ).

[0249] Under an argon atmosphere, 2-2b (2.28 g, 5 mmol), 2a (1.53 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (1.44 g, 15 mmol) were added to a 100 mL three-necked flask, and then 60 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 2-2c (2.2 g, yield: 70%) was obtained. Elemental analysis: theoretical value C, 82.07; H, 7.85; N, 4.45; measured value C, 82.01; H, 7.89; N, 4.42. MALDI-TOF MS (m / z): theoretical value 628.3; experimental value 628.3 (M + ).

[0250] Under an argon atmosphere, 2-2c (2.05 g, 3 mmol) and dry tert-butylbenzene (25 mL) were weighed into a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (4.6 mL, 1.3 M, 6 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -30 °C, boron tribromide (1.65 g, 6.6 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 100 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, and the solvent of the filtered organic phase was removed. The product 2-2 (0.72 g, yield: 40%) was obtained by column separation. Elemental analysis: theoretical value C, 85.70; H, 7.86; N, 4.65; measured value C, 85.64; H, 7.83; N, 4.61. MALDI-TOF (m / z): theoretical value 602.3; experimental value 659.3 (M + ).

[0251] Example 13

[0252] The chemical structure and synthetic route of 2-5 are as follows:

[0253]

[0254] Under an argon atmosphere, pentamethylbromobenzene (2.27 g, 10 mmol), p-tert-butylaniline (1.62 g, 12 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), and t-BuONa (2.9 g, 30 mmol) were added to a 250 mL three-necked flask, and then 50 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 2-5a (2.51 g, yield: 85%) was obtained. Elemental analysis: theoretical values C, 85.37; H, 9.89; N, 4.74; measured values C, 87.45; H, 8.23; N, 4.21. GC-MS (m / z): theoretical value 295.2; experimental value 295.2 (M + ).

[0255] Under an argon atmosphere, 1a (1.47 g, 5 mmol), 2-5a (2.8 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (1.44 g, 15 mmol) were added to a 100 mL three-necked flask, and then 60 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 2-5b (2.74 g, yield: 80%) was obtained. Elemental analysis: theoretical values C, 82.36; H, 8.38; N, 4.09; measured values C, 82.31; H, 8.39; N, 4.10. MALDI-TOF MS (m / z): theoretical value 685.4; experimental value 685.4 (M + ).

[0256] Under an argon atmosphere, 2-5b (2.05 g, 3 mmol) and dry tert-butylbenzene (20 mL) were weighed in a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (4.6 mL, 1.3 M, 6 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -30 °C, boron tribromide (1.65 g, 6.6 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 100 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent was removed from the filtered organic phase. The product 2-5 (1.22 g, yield: 62%) was obtained by column chromatography. Elemental analysis: theoretical values C, 85.69; H, 8.42; N, 4.25; measured values C, 85.65; H, 8.45; N, 4.23. MALDI-TOF MS (m / z): theoretical value 659.4; experimental value 659.4 (M + )。

[0257] Example 14

[0258] The chemical structure and synthetic route of 2-6 are as follows:

[0259]

[0260] Under an argon atmosphere, 2-chloro-1,3-dibromobenzene (2.7 g, 10 mmol), 4,4'-(di-tert-butylphenyl)amine (2.8 g, 10 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), SPhos (232 mg, 0.8 mmol), and t-BuONa (3.9 g, 40 mmol) were added to a 100 mL three-necked flask. Then, 50 mL of toluene was injected, and the reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the compound 2-6a (2.8 g, yield: 60%) was obtained by column chromatography and solvent removal. Elemental analysis: theoretical values C, 66.32; H, 6.21; N, 2.97; measured values C, 66.30; H, 6.25; N, 2.90. MALDI-TOF MS (m / z): theoretical value 470.1; experimental value 470.1 (M + )。

[0261] Under an argon atmosphere, 2-bromo-1,3-bis(trideuteriomethyl)benzene (1.9 g, 10 mmol), p-tert-butylaniline (1.8 g, 12 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), t-BuONa (2.9 g, 30 mmol) were added to a 100 mL three-necked flask, and then 50 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 2-6b (2.34 g, yield: 90%) was obtained. Elemental analysis: theoretical values C, 86.08; H, 4.53; N, 7.87; measured values C, 86.02; H, 4.56; N, 7.88. MALDI-TOF MS (m / z)): theoretical value 259.2; experimental value 259.2 (M+).

[0262] Under an argon atmosphere, 2-6a (1.88 g, 4 mmol), 2-6b (1.2 g, 4.8 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), t-BuONa (0.39 g, 4 mmol) were added to a 100 mL three-necked flask, and then 50 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 2-6c (2.2 g, yield: 85%) was obtained. Elemental analysis: theoretical values C, 81.38; H, 8.85; N, 4.31; measured values C, 81.31; H, 8.89; N, 4.35. MALDI-TOF MS (m / z): theoretical value 648.4; experimental value 648.4 (M + )

[0263] Under an argon atmosphere, 2-6c (1.9 g, 3 mmol) and dry tert-butylbenzene (20 mL) were weighed in a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (4.6 mL, 1.3 M, 6 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -30 °C, boron tribromide (1.65 g, 6.6 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 100 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent of the filtered organic phase was removed. The product 2-6 (1.14 g, yield: 60%) was obtained by column separation. Elemental analysis: theoretical value C, 84.86; H, 8.90; N, 4.50; measured value C, 84.82; H, 8.94; N, 4.44. MALDI-TOF MS (m / z): theoretical value 622.4; experimental value 622.4 (M + )。

[0264] Example 15

[0265] The chemical structure and synthetic route of 2-7 are as follows:

[0266]

[0267] Under an argon atmosphere, 2-bromo-1,4-bis(trideuteriomethyl)benzene (1.9 g, 10 mmol), p-tert-butylaniline (1.8 g, 12 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), and t-BuONa (2.9 g, 30 mmol) were added to a 250 mL three-necked flask. Then, 50 mL of toluene was injected, and the reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the compound 2-7a (2.13 g, yield: 82%) was obtained by column separation and solvent removal. Elemental analysis: theoretical value C, 83.34; H, 11.26; N, 5.40; measured value C, 83.36; H, 11.29; N, 5.44. GC-MS (m / z): theoretical value 259.25; experimental value 259.2 (M + )。

[0268] Under an argon atmosphere, 2-6a (1.88 g, 4 mmol), 2-7a (1.2 g, 4.8 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (1.2 g, 12 mmol) were added to a 100 mL three-necked flask, and then 50 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 2-7b (2.0 g, yield: 79%) was obtained. Elemental analysis: theoretical values C, 81.38; H, 8.85; N, 4.31; measured values C, 81.31; H, 8.89; N, 4.35. MALDI-TOF MS (m / z): theoretical value 648.4; experimental value 648.4 (M + ).

[0269] Under an argon atmosphere, 2-7b (1.9 g, 3 mmol) and dry tert-butylbenzene (20 mL) were weighed into a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (4.6 mL, 1.3 M, 6 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -30 °C, boron tribromide (1.65 g, 6.6 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 100 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, and the solvent of the filtered organic phase was removed. The product 2-7 (0.75 g, yield: 40%) was obtained by column separation. Elemental analysis: theoretical values C, 84.86; H, 8.90; N, 4.50; measured values C, 84.82; H, 8.94; N, 4.44. MALDI-TOF MS (m / z): theoretical value 622.4; experimental value 622.4 (M + ).

[0270] Example 16

[0271] The chemical structure and synthetic route of 2-8 are as follows:

[0272]

[0273] Under an argon atmosphere, 4-bromo-4'-propyl-1,1'-biphenyl (2.7 g, 10 mmol), 2,4,6-trimethylaniline (1.62 g, 12 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), t-BuONa (2.9 g, 30 mmol) were added to a 250 mL three-necked flask, and then 50 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 2-8a (2.96 g, yield: 90%) was obtained. Elemental analysis: theoretical value C, 87.49; H, 8.26; N, 4.25; measured value C, 87.45; H, 8.23; N, 4.21. GC-MS (m / z): theoretical value 329.2; experimental value 329.2 (M + ).

[0274] Under an argon atmosphere, 2-6a (1.64 g, 5 mmol), 2-8a (2.8 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), t-BuONa (1.44 g, 15 mmol) were added to a 100 mL three-necked flask, and then 60 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 2-8b (2.7 g, yield: 75%) was obtained. Elemental analysis: theoretical value C, 83.47; H, 7.71; N, 3.8; measured value C, 83.43; H, 7.74; N, 3.82. MALDI-TOF MS (m / z): theoretical value 718.4; experimental value 718.4 (M + ).

[0275] Under an argon atmosphere, 2-8b (2.15 g, 3 mmol) and dry tert-butylbenzene (20 mL) were weighed in a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (4.6 mL, 1.3 M, 6 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -30 °C, boron tribromide (1.65 g, 6.6 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 100 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent of the filtered organic phase was removed. The product 2-8 (1.25 g, yield: 60%) was obtained by column separation. Elemental analysis: theoretical values C, 86.68; H, 7.71; N, 4.04; measured values C, 86.63; H, 7.74; N, 4.03. MALDI-TOF (m / z): theoretical value 692.4; experimental value 692.4 (M + )。

[0276] Example 17

[0277] The chemical structure and synthetic route of 2-9 are as follows:

[0278]

[0279] Under an argon atmosphere, 4-bromo-4'-propyl-1,1'-biphenyl (2.7 g, 10 mmol), p-tert-butylaniline (1.8 g, 12 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), and t-BuONa (2.9 g, 30 mmol) were added to a 100 mL three-necked flask. Then, 50 mL of toluene was injected, and the reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and compound 2-9a (3.09 g, yield: 90%) was obtained by column separation and solvent removal. Elemental analysis: theoretical values C, 87.41; H, 8.51; N, 4.08; measured values C, 87.41; H, 8.51; N, 4.08. MALDI-TOF MS (m / z)): theoretical value 343.2; experimental value 343.2 (M + )。

[0280] Under an argon atmosphere, 2-chloro-1,3-dibromobenzene (2.7 g, 10 mmol), 2-9a (3.43 g, 10 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), and t-BuONa (2.9 g, 30 mmol) were added to a 100 mL three-necked flask. Then, 30 mL of toluene was injected, and the reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 2-9b (3.2 g, yield: 60%) was obtained. Elemental analysis: theoretical values C, 69.86; H, 5.86; N, 2.63; measured values C, 69.86; H, 5.86; N, 2.63. MALDI-TOF MS (m / z): theoretical value 531.1; experimental value 531.1 (M + ).

[0281] Under an argon atmosphere, p-propylbenzidine (2.53 g, 12 mmol), 1-19a (2.6 g, 10 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), and t-BuONa (2.9 g, 30 mmol) were added to a 100 mL three-necked flask. Then, 50 mL of toluene was injected, and the reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 2-9c (3.54 g, yield: 90%) was obtained. Elemental analysis: theoretical values C, 88.96; H, 7.47; N, 3.58; measured values C, 88.96; H, 7.47; N, 3.58. MALDI-TOF MS (m / z)): theoretical value 391.2; experimental value 391.2 (M+).

[0282] Under an argon atmosphere, 2-9b (2.66 g, 5 mmol), 2-9c (2.34 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (1.44 g, 15 mmol) were added to a 100 mL three-necked flask, and then 50 mL of toluene was injected. The reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 2-9d (3.78 g, yield: 90%) was obtained. Elemental analysis: theoretical values: C, 85.43; H, 7.05; N, 3.32; measured values: C, 85.43; H, 7.05; N, 3.32. MALDI-TOF MS (m / z): theoretical value 842.4; experimental value 842.4 (M + ).

[0283] Under an argon atmosphere, 2-9d (1.68 g, 2 mmol) and dry tert-butylbenzene (25 mL) were weighed into a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -40 °C, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. After cooling to 0 °C again, N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, the solvent of the filtered organic phase was removed, and the product 2-9 (0.49 g, yield: 30%) was obtained by column separation. Elemental analysis: theoretical values: C, 88.21; H, 7.03; N, 3.43; measured values: C, 88.21; H, 7.04; N, 3.43. MALDI-TOF MS (m / z): theoretical value 816.4; experimental value 816.4 (M + ).

[0284] Example 18

[0285] The chemical structure and synthetic route of 2-26 are as follows:

[0286]

[0287] In a 100 mL three-necked flask under an argon atmosphere, 2-methyl-4-bromoiodobenzene (2.95 g, 10 mmol), 3,5-diphenylphenylboronic acid pinacol ester (3.9 g, 11 mmol), Pd(PPh3)4 (231 mg, 0.2 mmol), and K2CO3 (4.2 g, 30 mmol) were added. Then, 30 mL of dioxane and 15 mL of water were injected, and the reaction was carried out at 85 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, the solvent was removed under reduced pressure, and compound 2-26a (3.13 g, yield: 78%) was obtained through column separation and solvent removal. Elemental analysis: theoretical value C, 75.19; H, 4.80;; measured value C, 75.19; H, 4.81;;. MALDI-TOF (m / z): theoretical value 398.0; experimental value 398.0 (M + )

[0288] Under an argon atmosphere, in a 100 mL three-necked flask, 2-26a (1.99 g, 5 mmol), p-tert-butylaniline (0.89 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), BINAP (124 mg, 0.2 mmol), and t-BuONa (1.5 g, 15 mmol) were added. Then, 30 mL of toluene was injected, and the reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and compound 2-26b (2.1 g, yield: 90%) was obtained through column separation and solvent removal. Elemental analysis: theoretical value C, 89.89; H, 7.11; N, 3.00; measured value C, 89.89; H, 7.11; N, 3.00. GC-MS (m / z): theoretical value 467.2; experimental value 467.2 (M + )

[0289] Under an argon atmosphere, in a 100 mL three-necked flask, 2-26b (2.35 g, 5 mmol), 1a (2.08 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.39 g, 4 mmol) were added. Then, 150 mL of toluene was injected, and the reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and compound 2-26c (3.4 g, yield: 80%) was obtained through column separation and solvent removal. Elemental analysis: theoretical value C, 85.43; H, 7.17; N, 3.27; measured value C, 85.43; H, 7.17; N, 3.28. MALDI-TOF MS (m / z): theoretical value 856.4; experimental value 856.4 (M+ )。

[0290] Under an argon atmosphere, 2-26c (1.71 g, 2 mmol) and dry tert-butylbenzene (30 mL) were weighed in a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -40 °C, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent of the filtered organic phase was removed. The product 2-26 (0.66 g, yield: 40%) was obtained by column chromatography. Elemental analysis: theoretical value C, 88.17; H, 7.16; N, 3.37; measured value C, 88.17; H, 7.16; N, 3.37. MALDI-TOF (m / z): theoretical value 830.4; experimental value 830.4 (M + )。

[0291] Example 19

[0292] The chemical structure and synthetic route of 2-28 are as follows:

[0293]

[0294] Under an argon atmosphere, 4-chloro-3,5-dibromotoluene (2.8 g, 10 mmol), p-tert-butylaniline (2.8 g, 10 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), SPhos (232 mg, 0.8 mmol), and t-BuONa (3.9 g, 40 mmol) were added to a 100 mL three-necked flask. Then, 50 mL of toluene was injected, and the reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the compound 2-28a (2.9 g, yield: 60%) was obtained by column chromatography and solvent removal. Elemental analysis: theoretical value C, 66.88; H, 6.44; N, 2.89; measured value C, 66.88; H, 6.44; N, 2.89. MALDI-TOF MS (m / z): theoretical value 483.1; experimental value 483.1 (M + )。

[0295] In a 100 mL three-necked flask under an argon atmosphere, 3-methyl-4-bromoiodobenzene (2.95 g, 10 mmol), 3,5-diphenylphenylboronic acid pinacol ester (3.9 g, 11 mmol), Pd(PPh3)4 (231 mg, 0.2 mmol), and K2CO3 (4.2 g, 30 mmol) were added. Then, 30 mL of dioxane and 15 mL of water were injected, and the reaction was carried out at 85 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, the solvent was removed under reduced pressure, and compound 2-28b (2.78 g, yield: 70%) was obtained through column separation and solvent removal. Elemental analysis: Theoretical values C, 75.19; H, 4.80;; Measured values C, 75.19; H, 4.81;;. MALDI-TOF MS (m / z): Theoretical value 398.0; Experimental value 398.0 (M + )。

[0296] Under an argon atmosphere, 2-28b (2 g, 5 mmol), p-tert-butylaniline (0.89 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), BINAP (124 mg, 0.2 mmol), and t-BuONa (1.5 g, 15 mmol) were added to a 100 mL three-necked flask. Then, 30 mL of toluene was injected, and the reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and compound 2-28c (2.1 g, yield: 90%) was obtained through column separation and solvent removal. Elemental analysis: Theoretical values C, 89.89; H, 7.11; N, 3.00; Measured values C, 89.89; H, 7.11; N, 3.00. GC-MS (m / z): Theoretical value 467.2; Experimental value 467.2 (M + )。

[0297] Under an argon atmosphere, 2-28a (2.41 g, 5 mmol), 2-28c (2.8 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (1.44 g, 15 mmol) were added to a 100 mL three-necked flask. Then, 50 mL of toluene was injected, and the reaction was carried out at 90 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and compound 2-28d (3.48 g, yield: 80%) was obtained through column separation and solvent removal. Elemental analysis: Theoretical values C, 85.43; H, 7.29; N, 3.21; Measured values C, 85.42; H, 7.29; N, 3.22. MALDI-TOF MS (m / z): Theoretical value 870.4; Experimental value 870.4 (M+ )

[0298] Under an argon atmosphere, 2-28d (1.74 g, 2 mmol) and dry tert-butylbenzene (30 mL) were weighed in a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -40 °C, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction, and the organic phase was separated. Anhydrous sodium sulfate was added for drying. The solvent of the filtered organic phase was removed, and the product 2-28 (0.58 g, yield: 35%) was obtained by column separation. Elemental analysis: theoretical value C, 88.13; H, 7.28; N, 3.32; measured value C, 88.13; H, 7.28; N, 3.32. MALDI-TOF MS (m / z): theoretical value 844.4; experimental value 844.4 (M + )

[0299] Example 20

[0300] The chemical structure and synthetic route of 2-34 are as follows:

[0301]

[0302] Under an argon atmosphere, 3-methyl-4-bromoiodobenzene (2.95 g, 10 mmol), 2,6-diphenylphenylboronic acid (3.0 g, 11 mmol), Pd(PPh3)4 (231 mg, 0.2 mmol), and K2CO3 (4.2 g, 30 mmol) were added to a 100 mL three-necked flask. Then, 30 mL of dioxane and 15 mL of water were injected, and the reaction was carried out at 85 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, the solvent was removed under reduced pressure, and the compound 2-34a (3.38 g, yield: 85%) was obtained by column separation and solvent removal. Elemental analysis: theoretical value C, 75.19; H, 4.80;; measured value C, 75.19; H, 4.81;. MALDI-TOF (m / z): theoretical value 398.0; experimental value 398.0 (M + )

[0303] Under an argon atmosphere, 2-34a (2 g, 7 mmol), p-tert-butylaniline (0.89 g, 8.4 mmol), Pd2(dba)3 (128 mg, 0.14 mmol), BINAP (174 mg, 0.28 mmol), and t-BuONa (2.0 g, 21 mmol) were added to a 100 mL three-necked flask, and then 50 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 2-34b (2.94 g, yield: 90%) was obtained. Elemental analysis: theoretical values C, 89.89; H, 7.11; N, 3.00; measured values C, 89.89; H, 7.11; N, 3.00. GC-MS (m / z): theoretical value 467.2; experimental value 467.2 (M + ).

[0304] Under an argon atmosphere, 2-6a (2.34 g, 5 mmol), 2-34b (2.8 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (1.44 g, 15 mmol) were added to a 100 mL three-necked flask, and then 50 mL of toluene was injected. The reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 2-34c (3.5 g, yield: 82%) was obtained. Elemental analysis: theoretical values: C, 85.43; H, 7.17; N, 3.27; measured values: C, 85.44; H, 7.17; N, 3.25. MALDI-TOF MS (m / z): theoretical value 856.4; experimental value 856.4 (M + ).

[0305] Under an argon atmosphere, 2-34c (1.71 g, 2 mmol) and dry tert-butylbenzene (25 mL) were weighed in a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -40 °C, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent of the filtered organic phase was removed. The product 2-34 (0.63 g, yield: 38%) was obtained by column separation. Elemental analysis: theoretical value C, 88.17; H, 7.16; N, 3.37; measured value C, 88.17; H, 7.16; N, 3.37. MALDI-TOF (m / z): theoretical value 830.4; experimental value 830.4 (M + ).

[0306] Example 21

[0307] The chemical structure and synthetic route of 2-48 are as follows:

[0308]

[0309] Under an argon atmosphere, 1,3-bis(trideuteriomethyl)-5-bromobenzene (1.9 g, 10 mmol), p-tert-butylaniline (1.8 g, 12 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), and t-BuONa (2.9 g, 30 mmol) were added to a 100 mL three-necked flask. Then, 50 mL of toluene was injected, and the reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the compound 2-48a (2.33 g, yield: 90%) was obtained by column separation and solvent removal. Elemental analysis: theoretical value C, 83.34; H, 11.26; N, 5.40; measured value C, 83.35; H, 11.27; N, 5.41. MALDI-TOF MS (m / z)): theoretical value 259.2; experimental value 259.2 (M+).

[0310] Under an argon atmosphere, 2-chloro-1,3-dibromobenzene (1.35 g, 5 mmol), 2-48a (1.3 g, 5 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), SPhos (126 mg, 0.4 mmol), and t-BuONa (1.95 g, 20 mmol) were added to a 100 mL three-necked flask, and then 30 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 2-48b (1.32 g, yield: 60%) was obtained. Elemental analysis: theoretical values C, 64.22; H, 6.96; N, 3.12; measured values C, 64.24; H, 6.98; N, 3.13. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS (m / z)): theoretical value 447.1; experimental value 447.1 (M + ).

[0311] Under an argon atmosphere, 9,9'-(5-bromo-1,3-phenylene)bis(9H-carbazole) (4.87 g, 10 mmol), p-tert-butylaniline (1.5 g, 10 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), and t-BuONa (2.9 g, 30 mmol) were added to a 100 mL three-necked flask, and then 50 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 2-48c (4.9 g, yield: 89%) was obtained. Elemental analysis: theoretical values: C, 86.45; H, 5.99; N, 7.56; measured values: C, 86.45; H, 5.99; N, 7.56. GC-MS (m / z): theoretical value 555.2; experimental value 555.2 (M + ).

[0312] Under an argon atmosphere, 2-48c (2.77 g, 5 mmol), 2-48b (1.55 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (1.44 g, 15 mmol) were added to a 100 mL three-necked flask. Then, 60 mL of toluene was injected, and the reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 2-48d (3.68 g, yield: 80%) was obtained. Elemental analysis: theoretical values C, 83.22; H, 6.87; N, 6.07; measured values C, 83.23; H, 6.89; N, 6.04. MALDI-TOF (m / z): theoretical value 922.4; experimental value 922.4 (M + ).

[0313] Under an argon atmosphere, 2-48d (1.84 g, 2 mmol) and dry tert-butylbenzene (30 mL) were weighed into a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -40 °C, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, the solvent of the filtered organic phase was removed, and the product 2-48 (0.54 g, yield: 30%) was obtained by column separation. Elemental analysis: theoretical values C, 85.70; H, 6.85; N, 6.25; measured values C, 85.72; H, 6.83; N, 6.24. MALDI-TOF (m / z): theoretical value 896.5; experimental value 896.5.5 (M + ).

[0314] Example 22

[0315] The chemical structure and synthetic route of 2-50 are as follows:

[0316]

[0317] Under an argon atmosphere, 1-46a (3 g, 7 mmol), p-tert-butylaniline (1.25 g, 8.4 mmol), Pd2(dba)3 (128 mg, 0.14 mmol), BINAP (348 mg, 0.56 mmol), and t-BuONa (2.0 g, 21 mmol) were added to a 100 mL three-necked flask, and then 100 mL of toluene was injected. The reaction was carried out at 110 °C for 24 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and compound 2-50a (2.78 g, yield: 80%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values: C, 87.41; H, 6.93; N, 5.66; measured values: C, 87.43; H, 6.95; N, 5.64. MALDI-TOF (m / z): theoretical value 494.2; experimental value 494.2 (M + ).

[0318] Under an argon atmosphere, 2-6a (2.35 g, 5 mmol), 2-50a (2.96 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (0.39 g, 4 mmol) were added to a 100 mL three-necked flask, and then 150 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and compound 2-50b (3.3 g, yield: 75%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values: C, 84.18; H, 7.06; N, 4.75; measured values: C, 84.19; H, 7.09; N, 4.75. Matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOF (m / z)): theoretical value 884.4; experimental value 884.4 (M + ).

[0319] Under an argon atmosphere, 2-50b (1.76 g, 2 mmol) and dry tert-butylbenzene (30 mL) were weighed in a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -40 °C, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent of the filtered organic phase was removed. The product 2-50 (0.86 g, yield: 50%) was obtained by column chromatography. Elemental analysis: theoretical value C, 86.79; H, 7.05; N, 4.90; measured value C, 86.79; H, 7.04; N, 4.91. MALDI-TOF (m / z): theoretical value 857.5; experimental value 857.5 (M + ).

[0320] Example 23

[0321] The chemical structure and synthetic route of 2-51 are as follows:

[0322]

[0323] Under an argon atmosphere, 3,5-dibromotoluene (2.47 g, 10 mmol), 4,4'-(dimethylphenyl)amine (1.97 g, 10 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), and t-BuONa (2.9 g, 30 mmol) were added to a 100 mL three-necked flask. Then, 50 mL of toluene was injected, and then 50 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the compound 2-51a (2.0 g, yield: 55%) was obtained by column chromatography and solvent removal. Elemental analysis: theoretical value C, 68.86; H, 5.50; N, 3.82; measured value C, 68.86; H, 5.51; N, 3.83. MALDI-TOF MS (m / z): theoretical value 365.0; experimental value 365.0 (M + ).

[0324] Under an argon atmosphere, 2-51a (1.8 g, 5 mmol), 1-46b (2.7 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (1.44 g, 15 mmol) were added to a 100 mL three-necked flask. Then, 100 mL of toluene was injected, and the reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water multiple times. The organic phase was separated, and after column chromatography and solvent removal, compound 2-51b (2.76 g, yield: 75%) was obtained. Elemental analysis: theoretical values C, 87.89; H, 6.42; N, 5.69; measured values C, 87.89; H, 6.42; N, 5.69. MALDI-TOF MS (m / z): theoretical value 737.3; experimental value 737.3 (M + ).

[0325] Under an argon atmosphere, 2-51b (0.73 g, 1 mmol) was added to a 120 m thick-walled reaction flask. Then, 15 mL of o-dichlorobenzene was injected, and after sufficient gas exchange, BBr3 (1 g, 4 mmol) was added. The reaction was carried out at 200 °C for 24 hours. After cooling to room temperature, the reaction mixture was placed in an ice-water bath. After cooling, methanol was slowly added dropwise to quench the reaction, and the solvent was removed under reduced pressure. The residue was subjected to column chromatography and solvent removal to obtain compound 2-51 (0.29 g, yield: 40%). Elemental analysis: theoretical values C, 86.97; H, 5.95; N, 5.63 measured values C, 86.97; H, 5.95; N, 5.63. MALDI-TOF MS (m / z): theoretical value 745.3; experimental value 745.3 (M+).

[0326] Example 24

[0327] The chemical structure and synthetic route of 2-82 are as follows:

[0328]

[0329] In a 100 mL three-necked flask under an argon atmosphere, 2,6-dimethyl-4-bromoiodobenzene (3.1 g, 10 mmol), 2-pyridylboronic acid (1.35 g, 11 mmol), Pd(PPh3)4 (231 mg, 0.2 mmol), and K2CO3 (4.2 g, 30 mmol) were added. Then, 30 mL of dioxane and 15 mL of water were injected, and the reaction was carried out at 85 °C for 16 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, the solvent was removed under reduced pressure, and compound 2-82a (1.95 g, yield: 75%) was obtained through column separation and solvent removal. Elemental analysis: C, 59.56; H, 4.61; Br, 30.48; N, 5.34. MALDI-TOF MS (m / z): theoretical value 261.0; experimental value 261.0 (M + ).

[0330] Under an argon atmosphere, in a 100 mL three-necked flask, 2-82a (1.8 g, 7 mmol), p-tert-butylaniline (1.25 g, 8.4 mmol), Pd2(dba)3 (128 mg, 0.14 mmol), BINAP (348 mg, 0.56 mmol), and t-BuONa (2.0 g, 21 mmol) were added. Then, 100 mL of toluene was injected, and the reaction was carried out at 110 °C for 24 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and the polycyclic compound 2-82b (1.84 g, yield: 80%) was obtained through column separation and solvent removal. Elemental analysis: theoretical value: C, 83.59; H, 7.93; N, 8.48 measured value C, 83.59; H, 7.93; N, 8.48. MALDI-TOF (m / z): theoretical value 330.2; experimental value 330.2 (M + ).

[0331] Under an argon atmosphere, in a 100 mL three-necked flask, 1a (2.35 g, 5 mmol), 23b (1.98 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (1.44 g, 15 mmol) were added. Then, 100 mL of toluene was injected, and the reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and compound 2-82c (2.87 g, yield: 80%) was obtained through column separation and solvent removal. Elemental analysis: theoretical value C, 81.69; H, 7.56; N, 5.83; measured value C, 81.69; H, 7.56; N, 5.83. MALDI-TOF MS (m / z): theoretical value 719.4; experimental value 719.4 (M+ )

[0332] Under an argon atmosphere, 2-82c (1.43 g, 2 mmol) and dry tert-butylbenzene (25 mL) were weighed in a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -40 °C, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent of the filtered organic phase was removed. The product 2-82 (0.69 g, yield: 50%) was obtained by column chromatography. Elemental analysis: theoretical values C, 84.63; H, 7.10; N, 6.93; C, 84.83; H, 7.56; N, 6.06; measured values C, 84.83; H, 7.56; N, 6.06. MALDI-TOF (m / z): theoretical value 693.4; experimental value 693.4 (M + )。

[0333] Example 25

[0334] The chemical structure and synthetic route of 2-87 are as follows:

[0335]

[0336] Under an argon atmosphere, 9,9'-(5-pinacol ester-1,3-phenylene)bis(9H-carbazole) (5.3 g, 10 mmol), 2,5-dibromo-1,4-dimethylbenzene (2.6 g, 10 mmol), Pd(PPh3)4 (231 mg, 0.1 mmol), and K2CO3 (4.17 g, 30 mmol) were added to a 250 mL three-necked flask. Then, 50 mL of dioxane and 15 mL of deoxygenated water were injected, and the reaction was carried out at 100 °C for 20 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the compound 2-87a (2.95 g, yield: 50%) was obtained by column chromatography and solvent removal. Elemental analysis: theoretical values C, 77.16; H, 4.60; N, 4.74; measured values C, 77.15; H, 4.62; N, 4.76. GC-MS (m / z): theoretical value 590.1; experimental value 590.1 (M + )。

[0337] Under an argon atmosphere, 2-87a (2.95 g, 5 mmol), p-tert-butylaniline (1.62 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), BINAP (124 mg, 0.1 mmol), and t-BuONa (1.45 g, 15 mmol) were added to a 250 mL three-necked flask, and then 50 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 2-87b (2.64 g, yield: 80%) was obtained. Elemental analysis: theoretical values: C, 87.37; H, 6.26; N, 6.37; measured values: C, 87.37; H, 6.24; N, 6.34. GC-MS (m / z): theoretical value 659.3; experimental value 659.3 (M + ).

[0338] Under an argon atmosphere, 2-87b (3.3 g, 5 mmol), 2-6a (2.7 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (1.44 g, 15 mmol) were added to a 100 mL three-necked flask, and then 60 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 2-87c (6.0 g, yield: 85%) was obtained. Elemental analysis: theoretical values C, 84.66; H, 6.62; N, 5.34; measured values C, 84.65; H, 6.63; N, 5.34. MALDI-TOF MS (m / z): theoretical value 1048.5; experimental value 1048.5 (M + ).

[0339] Under an argon atmosphere, 2-87c (2.1 g, 2 mmol) and dry tert-butylbenzene (30 mL) were weighed in a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -40 °C, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent of the filtered organic phase was removed. The product 2-87 (1.2 g, yield: 44%) was obtained by column separation. Elemental analysis: theoretical values C, 86.87; H, 6.60; N, 5.48; measured values C, 86.87; H, 6.60; N, 5.48. MALDI-TOF MS (m / z): theoretical value 1022.5; experimental value 1022.5 (M + ).

[0340] Example 26

[0341] The chemical structure and synthetic route of 2-91 are as follows:

[0342]

[0343] o-Aminodiphenylamine (1.84 g, 10 mmol) and 4-bromo-2,5-dimethylbenzaldehyde (1.97 g, 10 mmol) were added to a 250 mL single-necked flask. 90 mL of DMF and 10 mL of water were added, and the mixture was heated to 80 °C and reacted overnight. The solvent was removed under reduced pressure, and the product 2-91a (3.38 g, yield: 90%) was obtained by column separation. Elemental analysis: theoretical values C, 66.85; H, 4.54; N, 7.43; measured values C, 66.86; H, 4.55; N, 7.45. MALDI-TOF MS (m / z): theoretical value 376.0, experimental value 376.0 (M + ).

[0344] Under an argon atmosphere, 2-91a (4.52 g, 10 mmol), p-tert-butylaniline (1.8 g, 12 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), and t-BuONa (2.9 g, 30 mmol) were added to a 100 mL three-necked flask, and then 50 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 2-91b (3.6 g, yield: 80%) was obtained. Elemental analysis: theoretical values C, 83.56; H, 7.01; N, 9.43; measured values C, 83.56; H, 7.01; N, 9.43. MALDI-TOF MS (m / z): theoretical value 445.2; experimental value 445.2 (M+).

[0345] Under an argon atmosphere, 2-6a (2.35 g, 5 mmol), 2-91b (2.67 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (1.44 g, 15 mmol) were added to a 100 mL three-necked flask, and then 100 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 2-91c (3.12 g, yield: 75%) was obtained. Elemental analysis: theoretical values C, 81.93; H, 7.12; N, 6.71; measured values C, 81.94; H, 7.13; N, 6.72. MALDI-TOF MS (m / z): theoretical value 834.4; experimental value 834.4 (M+)

[0346] Under an argon atmosphere, 2-91c (1.67 g, 2 mmol) and dry tert-butylbenzene (30 mL) were weighed in a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -40 °C, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent of the filtered organic phase was removed. The product 2-91 (0.81 g, yield: 50%) was obtained by column chromatography. Elemental analysis: theoretical value C, 84.63; H, 7.10; N, 6.93; measured value C, 84.64; H, 7.11; N, 6.94. MALDI-TOF MS (m / z): theoretical value 808.4; experimental value 808.4 (M + ).

[0347] Example 27

[0348] The chemical structure and synthetic route of 2-92 are as follows:

[0349]

[0350] o-Phenylenediamine (1.84 g, 10 mmol) and 5-bromo-2-methylbenzaldehyde (1.97 g, 10 mmol) were added to a 250 mL single-necked flask. 90 mL of DMF and 10 mL of water were added, and the mixture was heated to 80 °C and reacted overnight. The solvent was removed under reduced pressure, and the product 2-92a (3.25 g, yield: 90%) was obtained by column chromatography. Elemental analysis: theoretical value C, 66.13; H, 4.16; N, 7.71; measured value C, 66.13; H, 4.16; N, 7.71. MALDI-TOF MS (m / z): theoretical value 362.0; experimental value 362.0 (M + ).

[0351] Under an argon atmosphere, 2-92a (3.62 g, 10 mmol), p-tert-butylaniline (1.8 g, 12 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), and t-BuONa (2.9 g, 30 mmol) were added to a 100 mL three-necked flask, and then 50 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 2-92b (3.66 g, yield: 85%) was obtained. Elemental analysis: theoretical values C, 87.41; H, 8.51; N, 4.08; measured values C, 87.41; H, 8.51; N, 4.08. MALDI-TOF MS (m / z): theoretical value 431.2; experimental value 431.2 (M+).

[0352] Under an argon atmosphere, 2-6a (2.35 g, 5 mmol), 2-92b (2.58 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (1.44 g, 15 mmol) were added to a 100 mL three-necked flask, and then 50 mL of toluene was injected. The reaction was carried out at 110 °C for 12 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 2-92c (3.69 g, yield: 90%) was obtained. Elemental analysis: theoretical values C, 81.87; H, 6.99; N, 6.82; measured values C, 81.87; H, 6.99; N, 6.82. MALDI-TOF MS (m / z): theoretical value 820.4; experimental value 820.4 (M + )

[0353] Under an argon atmosphere, 2-92c (1.64 g, 2 mmol) and dry tert-butylbenzene (25 mL) were weighed in a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -40 °C, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent of the filtered organic phase was removed. The product 2-92 (0.71 g, yield: 45%) was obtained by column chromatography. Elemental analysis: theoretical values C, 84.62; H, 6.97; N, 7.05; measured values C, 84.62; H, 6.97; N, 7.06. MALDI-TOF MS (m / z): theoretical value 794.4; experimental value 794.4 (M + )

[0354] Example 28

[0355] The chemical structure and synthetic route of 2-100 are as follows:

[0356]

[0357] Under an argon atmosphere, 2-48c (6.66 g, 12 mmol), 1-107c (6.19 g, 10 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), t-Bu3PHBF4 (232 mg, 0.8 mmol), and t-BuONa (2.88 g, 30 mmol) were added to a 100 mL three-necked flask. Then, 100 mL of toluene was injected, and the reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the compound 2-100a (7.66 g, yield: 70%) was obtained by column chromatography and solvent removal. Elemental analysis: theoretical values C, 83.30; H, 5.80; N, 7.67; measured values C, 83.30; H, 5.80; N, 7.67. MALDI-TOF MS (m / z): theoretical value 1094.4; experimental value 1094.4 (M + )

[0358] Under an argon atmosphere, 2-100a (2.2 g, 2 mmol) and dry tert-butylbenzene (30 mL) were weighed in a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -40 °C, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, dried over anhydrous sodium sulfate, and the solvent of the filtered organic phase was removed. The product 2-100 (1.17 g, yield: 55%) was obtained by column chromatography. Elemental analysis: theoretical values C, 85.38; H, 5.75; N, 7.86; measured values C, 85.38; H, 5.75; N, 7.86. MALDI-TOF MS (m / z): theoretical value 1068.5; experimental value 1068.5 (M + )。

[0359] Example 29

[0360] The chemical structure and synthetic route of 2-102 are as follows:

[0361]

[0362] Under an argon atmosphere, 2-chloro-1,3-dibromobenzene (2.67 g, 10 mmol), 2-48c (5.55 g, 10 mmol), Pd2(dba)3 (184 mg, 0.2 mmol), BINAP (248 mg, 0.4 mmol), and t-BuONa (2.88 g, 30 mmol) were added to a 100 mL three-necked flask. Then, 50 mL of toluene was injected, and the reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and the compound 2-102a (4.46 g, yield: 60%) was obtained by column chromatography and solvent removal. Elemental analysis: theoretical values C, 74.15; H, 4.73; N, 5.64; measured values C, 74.15; H, 4.74; N, 5.65. MALDI-TOF MS (m / z): theoretical value 743.1; experimental value 743.1 (M + )。

[0363] Under an argon atmosphere, 2-102a (3.7 g, 5 mmol), 2-92b (2.6 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (1.44 g, 15 mmol) were added to a 100 mL three-necked flask, and then 100 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 2-102b (7.66 g, yield: 70%) was obtained. Elemental analysis: theoretical values C, 83.30; H, 5.80; N, 7.67; measured values C, 83.31; H, 5.81; N, 7.647. MALDI-TOF MS (m / z): theoretical value 1094.4; experimental value 1094.4 (M + ).

[0364] Under an argon atmosphere, 2-102b (2.2 g, 2 mmol) and dry tert-butylbenzene (30 mL) were weighed into a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -40 °C, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. It was cooled to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, the solvent of the filtered organic phase was removed, and the product 2-102 (1.2 g, yield: 57%) was obtained by column separation. Elemental analysis: theoretical values C, 85.38; H, 5.75; N, 7.86; measured values C, 85.35; H, 5.74; N, 7.83. MALDI-TOF MS (m / z): theoretical value 1068.5; experimental value 1068.5 (M + ).

[0365] Example 30

[0366] The chemical structure and synthetic route of 2-106 are as follows:

[0367]

[0368] In a 100 mL three-necked flask under an argon atmosphere, 3,5-dimethyl-4-bromoiodobenzene (3.1 g, 10 mmol), 2,4-diphenyl-6-pinacolato-1,3,5-triazine (3.94 g, 11 mmol), Pd(PPh3)4 (231 mg, 0.2 mmol), and K2CO3 (4.2 g, 30 mmol) were added. Then, 30 mL of dioxane and 15 mL of water were injected, and the reaction was carried out at 85 °C for 16 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, the solvent was removed under reduced pressure, and compound 2-106a (3.32 g, yield: 80%) was obtained through column separation and desolvation. Elemental analysis: theoretical values C, 66.36; H, 4.36; N, 10.09; measured values C, 66.36; H, 4.36; N, 10.09. MALDI-TOF MS (m / z): theoretical value 415.0; experimental value 415.0 (M + ).

[0369] Under an argon atmosphere, in a 100 mL three-necked flask, 2-106a (2.9 g, 7 mmol), p-tert-butylaniline (1.25 g, 8.4 mmol), Pd2(dba)3 (128 mg, 0.14 mmol), BINAP (348 mg, 0.56 mmol), and t-BuONa (2.0 g, 21 mmol) were added. Then, 100 mL of toluene was injected, and the reaction was carried out at 110 °C for 24 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and compound 2-106b (4.25 g, yield: 88%) was obtained through column separation and desolvation. Elemental analysis: theoretical values: C, 81.78; H, 6.66; N, 11.56 measured values C, 81.78; H, 6.66; N, 11.56. MALDI-TOF MS (m / z): theoretical value 484.2; experimental value 484.2 (M + ).

[0370] Under an argon atmosphere, 2-6a (2.35 g, 5 mmol), 2-106b (2.42 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (1.44 g, 15 mmol) were added to a 100 mL three-necked flask, and then 100 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 2-106c (3.7 g, yield: 85%) was obtained. Elemental analysis: theoretical values C, 81.02; H, 6.92; N, 8.01; measured values C, 81.02; H, 6.92; N, 8.01. MALDI-TOF MS (m / z): theoretical value 873.4; experimental value 873.4 (M + )

[0371] Under an argon atmosphere, 2-106c (1.74 g, 2 mmol) and dry tert-butylbenzene (30 mL) were weighed into a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -40 °C, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. It was cooled to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, and the solvent of the filtered organic phase was removed. The product 2-106 (0.68 g, yield: 40%) was obtained by column separation. Elemental analysis: theoretical values C, 83.57; H, 6.89; N, 8.26; measured values C, 83.57; H, 6.89; N, 8.26. MALDI-TOF MS (m / z): theoretical value 847.4; experimental value 847.4 (M + )

[0372] Example 31

[0373] The chemical structure and synthetic route of 2-107 are as follows:

[0374]

[0375] In a 100 mL three-necked flask under an argon atmosphere, 3-methyl-5-bromoiodobenzene (2.9 g, 10 mmol), 2,4-diphenyl-6-pinacolato-1,3,5-triazine (3.94 g, 11 mmol), Pd(PPh3)4 (231 mg, 0.2 mmol), and K2CO3 (4.2 g, 30 mmol) were added. Then, 30 mL of dioxane and 15 mL of water were injected, and the reaction was carried out at 85 °C for 16 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, the solvent was removed under reduced pressure, and compound 2-107a (3.32 g, yield: 80%) was obtained through column separation and desolvation. Elemental analysis: theoretical values C, 65.68; H, 4.01; Br, 19.86; N, 10.45; measured values C, 65.68; H, 4.01; Br, 19.86; N, 10.45. MALDI-TOF MS (m / z): theoretical value 401.0; experimental value 401.0 (M + ).

[0376] Under an argon atmosphere, 2-107a (2.8 g, 7 mmol), p-tert-butylaniline (1.25 g, 8.4 mmol), Pd2(dba)3 (128 mg, 0.14 mmol), BINAP (348 mg, 0.56 mmol), and t-BuONa (2.0 g, 21 mmol) were added to a 100 mL three-necked flask. Then, 100 mL of toluene was injected, and the reaction was carried out at 110 °C for 24 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and compound 2-107b (2.95 g, yield: 90%) was obtained through column separation and desolvation. Elemental analysis: theoretical values: C, 81.67; H, 6.43; N, 11.91; measured values C, 81.64; H, 6.42; N, 11.92. MALDI-TOF MS (m / z): theoretical value 470.2; experimental value 470.2 (M + ).

[0377] Under an argon atmosphere, 2-6a (2.35 g, 5 mmol), 2-107b (2.82 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (1.44 g, 15 mmol) were added to a 100 mL three-necked flask, and then 100 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 2-107c (3.43 g, yield: 80%) was obtained. Elemental analysis: theoretical values C, 80.95; H, 6.79; N, 8.14; measured values C, 80.95; H, 6.79; N, 8.14. MALDI-TOF MS (m / z): theoretical value 859.4; experimental value 859.4 (M + )

[0378] Under an argon atmosphere, 2-107c (1.72 g, 2 mmol) and dry tert-butylbenzene (30 mL) were weighed into a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise. After the addition, it was stirred at room temperature for 2 hours. Then, at -40 °C, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. It was cooled to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, the organic phase obtained by filtration was removed of the solvent, and the product 2-107 (0.58 g, yield: 35%) was obtained by column separation. Elemental analysis: theoretical values C, 83.54; H, 6.77; N, 8.40; measured values C, 83.54; H, 6.77; N, 8.40. MALDI-TOF MS (m / z): theoretical value 833.4; experimental value 833.4 (M + )

[0379] Example 32

[0380] The chemical structure and synthetic route of 2-111 are as follows:

[0381]

[0382] In a 100 mL three-necked flask under an argon atmosphere, 2-methyl-4-bromoiodobenzene (2.9 g, 10 mmol), 2,4-diphenyl-6-pinacolato-1,3,5-triazine (3.94 g, 11 mmol), Pd(PPh3)4 (231 mg, 0.2 mmol), and K2CO3 (4.2 g, 30 mmol) were added. Then, 30 mL of dioxane and 15 mL of water were injected, and the reaction was carried out at 85 °C for 16 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, the solvent was removed under reduced pressure, and compound 2-111a (3.4 g, yield: 85%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 65.68; H, 4.01; Br, 19.86; N, 10.45; measured values C, 65.68; H, 4.01; Br, 19.86; N, 10.45. MALDI-TOF MS (m / z): theoretical value 401.0; experimental value 401.0 (M + ).

[0383] Under an argon atmosphere, 2-111a (2.8 g, 7 mmol) and p-tert-butylaniline (1.25 g, 8.4 mmol) were added to a 100 mL three-necked flask, followed by Pd2(dba)3 (128 mg, 0.14 mmol), BINAP (348 mg, 0.56 mmol), and t-BuONa (2.0 g, 21 mmol). Then, 100 mL of toluene was injected, and the reaction was carried out at 110 °C for 24 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and the mixture was washed with deionized water several times. The organic phase was separated, and compound 2-111b (2.9 g, yield: 88%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values: C, 81.67; H, 6.43; N, 11.91; measured values C, 81.64; H, 6.42; N, 11.92. MALDI-TOF MS (m / z): theoretical value 470.2; experimental value 470.2 (M + ).

[0384] Under an argon atmosphere, 2-102a (3.7 g, 5 mmol), 2-111b (2.82 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (1.44 g, 15 mmol) were added to a 100 mL three-necked flask. Then, 100 mL of toluene was injected, and the reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water multiple times. The organic phase was separated, and after column separation and solvent removal, compound 2-111c (3.9 g, yield: 70%) was obtained. Elemental analysis: theoretical values C, 82.55; H, 5.68; N, 8.64; measured values C, 82.55; H, 5.68; N, 8.64. MALDI-TOF MS (m / z): theoretical value 1133.4; experimental value 1133.4 (M + ).

[0385] Under an argon atmosphere, 2-111c (2.2 g, 2 mmol) and dry tert-butylbenzene (30 mL) were weighed into a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -40 °C, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, and the solvent of the filtered organic phase was removed. The product 2-111 (0.66 g, yield: 30%) was obtained by column separation. Elemental analysis: theoretical values C, 83.54; H, 6.77; N, 8.40; measured values C, 83.54; H, 6.77; N, 8.40. MALDI-TOF MS (m / z): theoretical value 1107.5; experimental value 1107.5 (M + ).

[0386] Example 33

[0387] The chemical structure and synthetic route of 2-115 are as follows:

[0388]

[0389] In a 100 mL three-necked flask under an argon atmosphere, 5-bromo-2-iodo-m-xylene (3.1 g, 10 mmol), 9-(4-phenyl-6-pinacolato-1,3,5-triazin-2-yl)-9H-carbazole (4.48 g, 11 mmol), Pd(PPh3)4 (231 mg, 0.2 mmol), and K2CO3 (4.2 g, 30 mmol) were added. Then, 30 mL of THF and 15 mL of water were injected, and the reaction was carried out at 70 °C for 24 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, the solvent was removed under reduced pressure, and compound 2-115a (3.78 g, yield: 75%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values C, 68.92; H, 4.19; N, 11.09; measured values C, 68.92; H, 4.19; N, 11.09. MALDI-TOF MS (m / z): theoretical value 504.0; experimental value 504.0 (M + ).

[0390] Under an argon atmosphere, 2-115a (2.5 g, 7 mmol), p-tert-butylaniline (1.25 g, 8.4 mmol), Pd2(dba)3 (128 mg, 0.14 mmol), BINAP (348 mg, 0.56 mmol), and t-BuONa (2.0 g, 21 mmol) were added to a 100 mL three-necked flask. Then, 100 mL of toluene was injected, and the reaction was carried out at 110 °C for 24 hours. After cooling to room temperature, deionized water and 100 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and compound 2-115b (3.6 g, yield: 90%) was obtained through column separation and solvent removal. Elemental analysis: theoretical values: C, 81.64; H, 6.15; N, 12.21 measured values C, 81.64; H, 6.15; N, 12.21. MALDI-TOF MS (m / z): theoretical value 573.2; experimental value 573.2 (M + ).

[0391] Under an argon atmosphere, 2-6a (2.35 g, 5 mmol), 2-115b (2.87 g, 6 mmol), Pd2(dba)3 (92 mg, 0.1 mmol), t-Bu3PHBF4 (116 mg, 0.4 mmol), and t-BuONa (1.44 g, 15 mmol) were added to a 100 mL three-necked flask, and then 100 mL of toluene was injected. The reaction was carried out at 110 °C for 20 hours. After cooling to room temperature, deionized water and 200 mL of dichloromethane were added for extraction, and it was washed with deionized water several times. The organic phase was separated, and after column separation and solvent removal, compound 2-115c (4.0 g, yield: 85%) was obtained. Elemental analysis: theoretical values C, 81.01; H, 6.59; N, 8.72; measured values C, 81.02; H, 6.59; N, 8.73. MALDI-TOF MS (m / z): theoretical value 962.4; experimental value 962.4 (M + ).

[0392] Under an argon atmosphere, 2-115c (1.92 g, 2 mmol) and dry tert-butylbenzene (30 mL) were weighed into a 100 mL two-necked reaction flask. At -30 °C, tert-butyllithium solution (3.1 mL, 1.3 M, 4 mmol) was added dropwise. After the addition, the mixture was stirred at room temperature for 2 hours. Then, at -40 °C, boron tribromide (1.1 g, 4.4 mmol) was added dropwise to the system. After the addition, the temperature was raised to 60 °C and stirred for 1 hour. The temperature was lowered to 0 °C again, and N,N-diisopropylethylamine (1.2 g, 12 mmol) was added dropwise to the reaction system. After the addition, the temperature was raised to 160 °C and reacted for 16 hours. After the reaction was cooled to room temperature, dichloromethane and water were added for extraction. The organic phase was separated, anhydrous sodium sulfate was added for drying, the solvent of the filtered organic phase was removed, and the product 2-115 (0.75 g, yield: 40%) was obtained by column separation. Elemental analysis: theoretical values C, 83.32; H, 6.56; N, 8.97 measured values C, 83.32; H, 6.56; N, 8.97. MALDI-TOF MS (m / z): theoretical value 936.5; experimental value 936.5 (M + ).

[0393] The photophysical properties of the organoboron compounds prepared in Examples 1 to 33 of the present invention were detected. See Table 1, which shows the photophysical properties of the organoboron compounds prepared in the examples of the present invention

[0394] Table 1 Photophysical properties of the organoboron fused-ring compounds prepared in the examples of the present invention

[0395]

[0396] Note: ΔE in the table STΔE is the energy difference between the singlet energy level and the triplet energy level. The fluorescence spectrum and the onset value difference of the phosphorescence spectrum were measured by making a test sample film by doping the compound in mCP at a concentration of 1.5 wt.%. The test instrument is HORIBA FluoroMax spectrofluorometer (Japan); the delayed fluorescence lifetime was obtained by doping the compound in polystyrene at a concentration of 1 wt% to make a test sample and measuring it with a time-resolved fluorescence spectrometer. The test instrument is Edinburgh fluorescence spectrometer (FLS-980, UK).

[0397] As can be seen from Table 1, the polycyclic compounds in the examples provided by the present invention have a small ΔE ST (≤0.2 eV), showing a thermally activated delayed fluorescence effect, and its delayed fluorescence lifetime is 8 - 25 μs, so it is beneficial to utilize triplet excitons and improve the device efficiency.

[0398] Device Examples

[0399] As a device example, the present invention provides a device structure: ITO / BCFCN (70 nm) / EBL (5 nm) / EML (30 nm) / HBL (5 nm) / ANT-BIZ: 50 wt% Liq (30 nm) / Liq (1 nm) / Al (150 nm), where the emitting layer (EML) includes a host material BBK-523 and the organic boron compound of the present invention (the optimized mass ratio of the organic boron compound to BBK-523 is 2:98). BCFCN and ANT-BIZ are used as the hole injection layer and the electron injection layer respectively, EBL is the electron blocking layer, and HBL is the hole blocking layer. The process of preparing the device by vacuum evaporation for the organic light-emitting layer is as follows: On indium tin oxide loaded on a glass substrate, HT21, EBL, EML (the invented light-emitting compound and BBK-523 in a mass ratio of 2:98), HBL, ANT-BIZ:Liq, and Liq / Al cathode are sequentially deposited under a vacuum of 4×10 -4 Pa to obtain an organic electroluminescent device. The structural formulas of BCFCN, ANT-BIZ, BBK-523, EBL, Liq, and HBL are shown in the following figures:

[0400]

[0401] Example 34

[0402] Taking 1-2 in Example 1 as the implementation object, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, and preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0403] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with 1-2 provided by the present invention.

[0404] Example 35

[0405] Taking 1-19 in Example 2 as the implementation object, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0406] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with 1-19 provided by the present invention.

[0407] Example 36

[0408] Taking 1-46 in Example 3 as the implementation object, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0409] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with 1-46 provided by the present invention.

[0410] Example 37

[0411] Taking 1-48 in Example 4 as the implementation object, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0412] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with 1-48 provided by the present invention.

[0413] Example 38

[0414] Taking 1-89 in Example 5 as the implementation object, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0415] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with 1-89 provided by the present invention.

[0416] Example 39

[0417] Taking 1-97 in Example 6 as the implementation object, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0418] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with 1-97 provided by the present invention.

[0419] Example 40

[0420] Taking 1-103 in Example 7 as the object of implementation, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0421] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with 1-103 provided by the present invention.

[0422] Example 41

[0423] Taking 1-106 in Example 8 as the object of implementation, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0424] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with 1-106 provided by the present invention.

[0425] Example 42

[0426] Taking 1-107 in Example 9 as the object of implementation, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0427] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with 1-107 provided by the present invention.

[0428] Example 43

[0429] [[ID=३३]]Taking 1-108 in Example 10 as the object of implementation, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0430] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with 1-108 provided by the present invention.

[0431] Example 44

[0432] Taking 1-109 in Example 11 as the object of implementation, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0433] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with 1-109 provided by the present invention.

[0434] Example 45

[0435] Taking 2-2 in Example 12 as the object of implementation, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0436] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with 2-2 provided by the present invention.

[0437] Example 46

[0438] Taking 2-5 in Example 13 as the object of implementation, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0439] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with 2-5 provided by the present invention.

[0440] Example 47

[0441] Taking 2-6 in Example 14 as the object of implementation, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0442] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with 2-6 provided by the present invention.

[0443] Example 48

[0444] Taking 2-8 in Example 15 as the object of implementation, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0445] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with 2-8 provided by the present invention.

[0446] Example 49

[0447] Taking 2-8 in Example 16 as the object of implementation, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0448] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with 2-8 provided by the present invention.

[0449] Example 50

[0450] Taking 2-9 in Example 17 as the object of implementation, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, and preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0451] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with 2-9 provided by the present invention.

[0452] Example 51

[0453] Taking 2-26 in Example 18 as the object of implementation, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, and preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0454] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with 2-26 provided by the present invention.

[0455] Example 52

[0456] Taking 2-28 in Example 19 as the object of implementation, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, and preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0457] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with 2-28 provided by the present invention.

[0458] Example 52

[0459] Taking 2-34 in Example 20 as the object of implementation, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, and preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0460] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with 2-34 provided by the present invention.

[0461] Example 54

[0462] Taking 2-48 in Example 21 as the object of implementation, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, and preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0463] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with 2-48 provided by the present invention.

[0464] Example 55

[0465] Taking 2-50 in Example 22 as the object of implementation, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0466] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with 2-50 provided by the present invention.

[0467] Example 56

[0468] Taking 2-51 in Example 23 as the object of implementation, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0469] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with 2-51 provided by the present invention.

[0470] Example 57

[0471] Taking 2-82 in Example 24 as the object of implementation, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0472] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with 2-82 provided by the present invention.

[0473] Example 58

[0474] Taking 2-87 in Example 25 as the object of implementation, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0475] Referring to Table 2, Table 2 provides the performance parameters of the electroluminescent devices prepared with 2-87 provided by the present invention.

[0476] Example 59

[0477] Taking 2-91 in Example 26 as the object of implementation, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0478] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with 2-91 provided by the present invention.

[0479] Example 60

[0480] Taking 2-92 in Example 27 as the object of implementation, it is mixed with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, and an organic electroluminescent device is prepared using the device structure, and the obtained device is tested.

[0481] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with 2-92 provided by the present invention.

[0482] Example 61

[0483] Taking 2-100 in Example 28 as the object of implementation, it is mixed with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, and an organic electroluminescent device is prepared using the device structure, and the obtained device is tested.

[0484] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with 2-100 provided by the present invention.

[0485] Example 62

[0486] Taking 2-102 in Example 29 as the object of implementation, it is mixed with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, and an organic electroluminescent device is prepared using the device structure, and the obtained device is tested.

[0487] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with 2-102 provided by the present invention.

[0488] Example 63

[0489] Taking 2-106 in Example 30 as the object of implementation, it is mixed with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, and an organic electroluminescent device is prepared using the device structure, and the obtained device is tested.

[0490] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with 2-106 provided by the present invention.

[0491] Example 64

[0492] Taking 2-107 in Example 31 as the object of implementation, it is mixed with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, and an organic electroluminescent device is prepared using the device structure, and the obtained device is tested.

[0493] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with 2-107 provided by the present invention.

[0494] Example 65

[0495] Taking 2-111 in Example 32 as the object, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0496] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with 2-111 provided by the present invention.

[0497] Example 66

[0498] Taking 2-115 in Example 33 as the object, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device.

[0499] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with 2-115 provided by the present invention.

[0500] Comparative Example 1

[0501] Taking the reference compound tDABNA as the object, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device. The structural formula of M-tDABNA is shown in the following figure:

[0502]

[0503] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the reference compound tDABNA.

[0504] Comparative Example 2

[0505] Taking the reference compound M-tDABNA as the object, mixing it with BBK-523 (mass ratio 2:98) as the organic light-emitting layer, preparing an organic electroluminescent device using the device structure, and testing the obtained device. The structural formula of M-tDABNA is shown in the following figure:

[0506]

[0507] Refer to Table 2, which provides the performance parameters of the electroluminescent devices prepared with the reference compound M-tDABNA.

[0508] Table 2 Performance parameters of the electroluminescent devices prepared with the compounds provided in the examples of the present invention

[0509]

[0510]

[0511] Note: The turn-on voltage in the table is the driving voltage of the device when the brightness is 1 cd m -2 ; The maximum external quantum efficiency is obtained according to the calculation method described in the literature (Jpn. J. Appl. Phys. 2001, 40, L783) based on the current-voltage curve and electroluminescence spectrum of the device; The full width at half maximum is the peak width at half of the peak height of the electroluminescence spectrum at room temperature, that is, a straight line parallel to the peak bottom is drawn through the midpoint of the peak height, and the distance between the two intersection points of this straight line and both sides of the peak.

[0512] As can be seen from Table 2, compared with the results of Comparative Example 1, the electroluminescent devices prepared from the organic boron compounds provided by the present invention all have a narrow electroluminescent spectrum and a high external quantum efficiency. The maximum external quantum efficiency of the device prepared from the organic boron fused-ring compound provided by the present invention reaches 9.2%, which is higher than the device efficiencies of the comparative compounds tDABNA and M-tDABNA (7.4% and 7.6%); The full width at half maximum of its electroluminescent spectrum is minimized to 19 nm, which is smaller than the full width at half maximum of the comparative compounds tDABNA and M-tDABNA (26 and 27 nm).

[0513] The description of the above embodiments is only used to help understand the method and its core idea of the present invention. It should be noted that for those of ordinary skill in the art of this technology, without departing from the principle of the present invention, several improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims

1. An organoboron compound having a structure represented by Formula I or Formula II: Among them, X is hydrogen or deuterium; n is any integer from 1 to 5; R1, R2, R3, R4, R5, R6 are each independently selected from H, D, F, Cl, Br, I, -OH, -SH, -NH2, nitro group, cyano group, substituted or unsubstituted C1-C30 linear or branched hydrocarbon group, substituted or unsubstituted C3-C30 cycloalkyl group, substituted or unsubstituted C6-C60 aromatic group, substituted or unsubstituted C3-C60 heteroaromatic group, -NR7R8; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S and Se; R7 and R8 are independently selected from substituted or unsubstituted C1-C30 linear or branched hydrocarbon group, substituted or unsubstituted C6-C60 aromatic group, substituted or unsubstituted C3-C60 heteroaromatic group; m is any integer from 1 to 10; Ar1, Ar2, Ar3 are independently selected from substituted or unsubstituted C6-C30 aromatic group, substituted or unsubstituted C3-C30 heteroaromatic group; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S and Se; Q is selected from H, D, substituted or unsubstituted C1-C30 linear or branched hydrocarbon group, substituted or unsubstituted C3-C30 cycloalkyl group, substituted or unsubstituted C1-C30 alkoxy group, substituted or unsubstituted C1-C30 alkylthio group, substituted or unsubstituted C6-C60 aromatic group, substituted or unsubstituted C3-C60 heteroaromatic group; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S and Se.

2. The organic boron compound according to claim 1, wherein R1, R2, R3, R4, R5, R6 are each independently selected from H, D, F, Cl, Br, I, -OH, -SH, -NH2, nitro group, cyano group, substituted or unsubstituted C1-C10 linear or branched hydrocarbon group, substituted or unsubstituted C3-C6 cycloalkyl group, substituted or unsubstituted C6-C14 aromatic group, substituted or unsubstituted C3-C14 heteroaromatic group, -NR7R8; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S and Se; R7 and R8 are independently selected from substituted or unsubstituted C1-C10 linear or branched hydrocarbon group, substituted or unsubstituted C6-C10 aromatic group, substituted or unsubstituted C3-C10 heteroaromatic group; The substitution is by a primary substituent; The primary substituent is selected from one or more of D, F, Cl, Br, I, -OH, -SH, -NH2, nitro group, cyano group, substituted or unsubstituted C1-C30 linear or branched alkyl group, substituted or unsubstituted C6-C60 aromatic group, substituted or unsubstituted C3-C60 heteroaromatic group; The primary substituent may optionally be substituted by one or more of D, F, Cl, Br, I, -OH, -SH, -NH2, nitro group, cyano group, a linear or branched hydrocarbon group having 1 to 30 carbon atoms, phenyl group, or carbazolyl group.

3. The organoboron compound according to claim 2, wherein Each of R1, R2, R3, R4, R5, and R6 is independently selected from H, D, F, Cl, Br, I, -OH, -SH, -NH2, nitro group, cyano group, or is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, phenyl, N,N-dimethylamino, N,N-diphenylamino, N-methyl-N-phenylamino, carbazolyl group, or the following groups, which are unsubstituted or substituted by a primary substituent: L a 、L b 、L c are each independently selected from H, D, a substituted or unsubstituted linear or branched C1-C30 hydrocarbon group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C3-C60 heteroaromatic group; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S, and Se.

4. The organic boron compound according to claim 3, wherein The said L a , L b , L c are each independently selected from H, D, substituted or unsubstituted methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, phenyl, thienyl, furyl, pyrrolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl or carbazolyl; The primary substituent is selected from D, F, Cl, Br, I, -OH, -SH, -NH2, nitro group, cyano group, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-pentyl, isopentyl, n-hexyl, phenyl, thienyl, furyl, pyrrolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, or carbazolyl group; The primary substituent may optionally be substituted by one or more of D, F, Cl, Br, I, -OH, -SH, -NH2, nitro group, cyano group, a linear or branched hydrocarbon group having 1 to 6 carbon atoms, phenyl group, or carbazolyl group.

5. The organoboron compound according to claim 1, characterized in that, Ar1, Ar2, and Ar3 are independently selected from any one of the following structures: L a 、L b 、L c Each is independently selected from H, D, a substituted or unsubstituted linear or branched C1-C30 hydrocarbon group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C3-C60 heteroaromatic group; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S, and Se.

6. The organoboron compound according to claim 1, characterized in that, Q has any one of the following structures: L c and L d are each independently selected from H, D, a substituted or unsubstituted linear or branched C1-C30 hydrocarbon group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C6-C60 aromatic group, a substituted or unsubstituted C3-C60 heteroaromatic group; the heteroatoms in the heteroaromatic group are selected from one or more of Si, Ge, N, P, O, S, and Se.

7. The organoboron compound according to claim 1, wherein Has any one of the following structures:

8. A method for preparing the organoboron compound according to any one of claims 1 to 7, comprising the following steps: S1. The intermediate represented by M1 and the intermediate represented by M2 or M3 undergo a C-N coupling reaction to form the intermediate represented by M4 or M5; S2. The intermediate represented by M4, the intermediate represented by M5, and the intermediate represented by M6 undergo a C-N coupling reaction to form the intermediate represented by M8; Or the intermediate represented by M4 and the intermediate represented by formula M7 undergo a C-N coupling reaction to form the intermediate represented by M9; S3. The intermediate represented by M8 reacts with BBr3 to form the organoboron compound represented by formula I; The intermediate represented by M9 reacts with BBr3 to form the organoboron compound represented by formula II; Wherein, X, Q, Ar1, Ar2, Ar3, R1, R2, R3, R4, R5, R6, n, and m are defined as in any one of claims 1 to 7; Y is hydrogen or a halogen.

9. Use of the organoboron compound according to any one of claims 1 to 7 as an organic electroluminescent material.

10. An organic electroluminescent device, comprising an anode, a cathode, and an organic thin film layer located between the anode and the cathode; the organic thin film layer comprises the organoboron compound according to any one of claims 1 to 7.

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