Compound and organic electroluminescent device

Abstract

The invention belongs to the technical field of organic compounds, and particularly relates to a compound and an organic electroluminescent device. The structure of the compound is shown as a formula (I): # imgabs0 #. The compound has the advantages of high luminous efficiency, low driving voltage, long service life and the like.

Description

Technical Field

[0001] The present application belongs to the technical field of organic compounds, and in particular relates to a compound and an organic electroluminescent device. Background Art

[0002] Organic light-emitting diodes (OLEDs), a new generation of display technology, have outstanding effects in display and lighting technology, and therefore have received increasing attention. However, compared with market application requirements, the performance of OLEDs, such as luminous efficiency, driving voltage, and service life, still needs to be further improved.

[0003] Generally speaking, the basic structure of OLED is a thin film of organic functional materials with various functions sandwiched between metal electrodes, like a sandwich structure. Driven by electric current, holes and electrons are injected from the positive and negative poles respectively. After moving a certain distance, the holes and electrons are recombined in the light-emitting layer and released in the form of light or heat, thus producing the OLED's luminous effect. However, organic functional materials are the core components of organic electroluminescent devices. The thermal stability, photochemical stability, electrochemical stability, quantum yield, film formation stability, crystallinity, color saturation, etc. of the materials are all factors that affect the performance of the device.

[0004] Patent document 1 (CN115043785A) discloses This type of aliphatic condensed benzene compounds can be used as electron transport materials in organic electroluminescent devices. The device voltage is relatively high, and the efficiency and life span need to be further improved. Patent document 2 (CN111433190A) discloses Compounds in which cyclohexylfluorene is bonded to a triazine ring via a linker can be used as a host material and an electron transport material in an organic electroluminescent device, and the efficiency of the device needs to be improved. Patent document 3 (CN110615759A) discloses Compounds in which adamantyl fluorene is bonded to a triazine ring via a linker are used as electron transport layer materials in organic electroluminescent devices, but their luminous efficiency, life span and other performances need to be further improved. Patent document 4 (CN114763341A) discloses Compounds in which a norbornyl fluorenyl group is bonded to a nitrogen heterocycle via a linker are used as electron transport layer materials in organic electroluminescent devices. The material stability, luminous efficiency, life span and other performances need to be further improved. Patent document 5 (KR1020210156912A) discloses Compounds in which benzoheterocyclic and fluorenyl groups are bonded to nitrogen heterocycles via linkers are used as electron transport layer materials in organic electroluminescent devices. They have strong planarity, high sublimation temperature, and poor material stability. At the same time, the luminous efficiency, life span and other performance of the device need to be further improved.

[0005] Therefore, there is an urgent need to provide a new organic compound or organic electroluminescent device to solve the problems of OLED light emitting efficiency, life span or driving voltage. Summary of the invention

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

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

[0008] In some embodiments, a compound has a general structural formula as shown in formula (I):

[0009]

[0010] Wherein, X1, X2, X3, and X4 are independently selected from N or CH, and at least one is N, and adjacent X1-X4 are not N at the same time;

[0011] L is selected from a single bond, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 6 to 30 ring atoms;

[0012] Ar1, Ar2, Ar3 are independently selected from a substituted or unsubstituted aromatic group having 5-60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5-60 ring atoms, a substituted or unsubstituted aryloxy group having 5-60 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5-60 ring atoms, or a combination of these systems, which can form a monocyclic or polycyclic aliphatic or aromatic ring system with the ring bonded to the group;

[0013] 4 R are each independently selected from substituted or unsubstituted C1-C30 alkyl;

[0014] The substitution of L and R is substituted by at least one of deuterium, halogen, cyano, isocyano, trifluoromethyl, C1-C6 alkyl, C1-C6 haloalkyl, C3-C16 cycloalkyl, C6-C30 aryl, and triphenylsilyl, wherein the number of substitutions is from a single substitution to a maximum number of substitutions;

[0015] The heteroatoms in the heteroaromatic group, heteroaromatic group or heteroaryloxy group are independently selected from at least one of P, O, S, N, Se, Si and Ge.

[0016] Compared with the prior art, the beneficial effects of this application are as follows:

[0017] (1) The present invention introduces an aliphatic condensed ring as a steric hindering group into the molecule to obtain a compound represented by formula (1), which is applied to an organic electroluminescent device to obtain a high-performance organic electroluminescent device.

[0018] (2) The compound represented by formula (1) of the present invention has the advantages of good film-forming property, high luminous efficiency, low driving voltage, long life, etc., and can be used in organic electroluminescent devices. In particular, as hole blocking layer materials and electron transport layer materials, it has the potential to be applied to the AMOLED industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 Schematic diagram of the structure of the organic electroluminescent device in the embodiment of the present application. DETAILED DESCRIPTION

[0020] In order to make the technical solution described in this application more clearly understood by those skilled in the art, the following examples are listed for illustration. It should be noted that the following examples do not limit the scope of protection claimed in this application.

[0021] In the description of the present application, it should be understood that the orientation or positional relationship indicated by the terms "upper" and "lower" and the like is based on the orientation or positional relationship shown in the accompanying drawings, and is only for the convenience of describing the present application and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as a limitation on the present application. In addition, the terms "first" and "second" are used for descriptive purposes only, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the said features.

[0022] Unless otherwise specified, the raw materials, reagents or devices used in the following examples can be obtained from conventional commercial sources or by existing known methods.

[0023] The raw materials and solvents involved in the synthesis of the compounds of the present application were purchased from suppliers well known to those skilled in the art, such as Alfa and Acros.

[0024] In the present application, aromatic group, aromatic series and aromatic ring system have the same meaning and can be interchanged.

[0025] In the present application, heteroaromatic group, heteroaromatic series and heteroaromatic ring system have the same meaning and can be interchanged.

[0026] In the present application, "substituted" means that a hydrogen atom in a substituted group is replaced by a substituent.

[0027] In the present application, the "number of ring atoms" refers to the number of atoms constituting the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound) obtained by bonding atoms to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring atoms. The same is true for the "number of ring atoms" described below unless otherwise specified. For example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, and the number of ring atoms of a thienyl group is 5.

[0028] In the present application, an aromatic ring system or aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including monocyclic groups and polycyclic ring systems. A heteroaromatic ring system or heteroaromatic group refers to a hydrocarbon group (containing heteroatoms) containing at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. The heteroatoms can be selected from Si, N, P, O, S and / or Ge, and are particularly preferably selected from Si, N, P, O and / or S. These polycyclic rings can have two or more rings, in which two carbon atoms are shared by two adjacent rings, i.e., condensed rings. At least one of these polycyclic ring species is aromatic or heteroaromatic. For the purpose of the present application, an aromatic group or heteroaromatic group includes not only a system of aromatic or heteroaromatic groups, but also, wherein multiple aromatic or heteroaromatic groups can also be interrupted by short non-aromatic units (<10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamines, diaryl ethers, etc. are also considered aromatic groups for the purposes of this application.

[0029] Specific examples of aromatic groups include benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, or derivatives thereof.

[0030] Specific examples of heteroaromatic groups include furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furanopyrrole, furanofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-naphthylidene, quinoxaline, phenanthridine, primary pyridine, quinazoline, quinazolinone, or derivatives of the above groups.

[0031] In the present application, "alkyl" refers to a straight or branched saturated hydrocarbon group. Specifically, the number of carbon atoms can be 1 to 60, 1 to 40, 1 to 30, 1 to 20, 1 to 12, 1 to 6, or 1 to 3. Non-limiting examples of alkyl include methyl, ethyl, propyl, butyl, heptyl, decyl, etc. Each group includes various isomers, such as butyl includes isomers such as n-butyl, isobutyl, sec-butyl, tert-butyl, etc.

[0032] In the present application, cycloalkyl refers to a non-aromatic carbonyl ring consisting of at least 2 carbon atoms, which may include monocyclic, polycyclic and spiroalkyl. Non-limiting examples of cycloalkyl include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicyclo[3.1.1]heptyl, spiro[4.5]decyl, spiro[5.5]undecyl, adamantyl, norbornyl.

[0033] In the present application, alkoxy refers to a group having -O-alkyl, that is, an alkyl group as defined above is attached to a given group or a given structural formula via an oxygen atom. Non-limiting examples of alkoxy include: methoxy, ethoxy and tert-butoxy.

[0034] In some embodiments, a compound has a general structural formula as shown in formula (I):

[0035]

[0036] Wherein, X1, X2, X3, and X4 are independently selected from N or CH, and at least one is N, and adjacent X1-X4 are not N at the same time;

[0037] L is selected from a single bond, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 6 to 30 ring atoms;

[0038] Ar1, Ar2, Ar3 are independently selected from a substituted or unsubstituted aromatic group having 5-60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5-60 ring atoms, a substituted or unsubstituted aryloxy group having 5-60 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5-60 ring atoms, or a combination of these systems, which can form a monocyclic or polycyclic aliphatic or aromatic ring system with the ring bonded to the group;

[0039] 4 R are each independently selected from substituted or unsubstituted C1-C30 alkyl;

[0040] The substitution in L and R is substituted by at least one of deuterium, halogen, cyano, isocyano, trifluoromethyl, C1-C6 alkyl, C1-C6 haloalkyl, C3-C16 cycloalkyl, C6-C30 aryl, and triphenylsilyl, wherein the number of substitutions ranges from single substitution to the maximum number of substitutions;

[0041] The heteroatoms in the heteroaromatic group, heteroaromatic group or heteroaryloxy group are independently selected from at least one of P, O, S, N, Se, Si and Ge.

[0042] In some embodiments, the substitution range of Ar1, Ar2, Ar3 is the same as the range of R1-R6.

[0043] When Ar1, Ar2, and Ar3 are defined above, "the combination of these systems" means that multiple groups are combined to form Ar1, Ar2, and Ar3, for example, an aromatic group with 5-60 ring atoms and a heteroaromatic group with 5-60 ring atoms can form Ar1. "It can form a monocyclic or polycyclic aliphatic or aromatic ring system with the ring bonded to the group" means that Ar1, Ar2, and Ar3 can form a monocyclic or polycyclic ring. In addition, the group in Ar3 can also form a ring with the benzene ring to which Ar3 is connected.

[0044] In some embodiments, X1, X2, X3, and X4 are independently selected from N or CH, and at least one is N, and adjacent X1-X4 are not N at the same time.

[0045] In some embodiments, X1 may be N, and X2, X3, and X4 may be CH.

[0046] In some embodiments, X2 may be N, and X1, X3, and X4 may be CH.

[0047] In some embodiments, X3 may be N, and X1, X2, and X4 may be CH.

[0048] In some embodiments, X4 may be N, and X1, X2, and X3 may be CH.

[0049] In some embodiments, X1 and X3 may be N, and X2 and X4 may be CH.

[0050] In some embodiments, X1 and X4 may be N, and X2 and X3 may be CH.

[0051] In some embodiments, X2 and X4 may be N, and X1 and X3 may be CH.

[0052] In some embodiments, the compound represented by formula (1) is selected from one of the following structures of formula (2-1) to formula (2-7):

[0053]

[0054] In some embodiments, Ar1, Ar2, and Ar3 are independently selected from a substituted or unsubstituted aromatic group having 5-40 ring atoms, a substituted or unsubstituted heteroaromatic group having 5-40 ring atoms, a substituted or unsubstituted aryloxy group having 5-40 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5-40 ring atoms, or a combination of these systems, which can form a monocyclic or polycyclic aliphatic or aromatic ring system with the ring bonded to the group.

[0055] In some embodiments, the substitution in L refers to substitution by at least one of fluorine, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl or phenyl.

[0056] In some embodiments, the substitutions in Ar1-Ar3 are independently selected from at least one of fluorine, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl, trifluoromethyl, triphenylsilyl, cyclohexyl, adamantyl, phenyl or biphenyl.

[0057] In some embodiments, the substitutions in the four Rs are independently selected from at least one of fluorine, cyano, C1-C4 alkyl, phenyl, trifluoromethyl, triphenylsilyl, cyclohexyl, adamantyl or biphenyl.

[0058] In some embodiments, the four Rs are each independently selected from substituted or unsubstituted C1-C20 alkyl groups.

[0059] In some embodiments, the four Rs are each independently selected from substituted or unsubstituted C1-C10 alkyl groups.

[0060] In some embodiments, the four Rs are each independently selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, or tert-butyl.

[0061] In some embodiments, the four Rs may be the same or different, for example, all may be methyl.

[0062] In some embodiments, L is selected from a single bond, phenylene, or naphthylene.

[0063] In some embodiments, the substitution in L refers to substitution by at least one of deuterium, halogen, cyano, C1-C4 alkyl, C1-C3 haloalkyl, phenyl, naphthyl, fluorenyl, spirofluorenyl or C3-C10 cycloalkyl.

[0064] In some embodiments, the substitution in L refers to substitution by fluorine, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl or phenyl.

[0065] In some embodiments, L is selected from a single bond, or one of the groups shown in the following formulae A-1 to A-18, or one of the groups selected from any combination of the groups shown in formulae A-1 to A-18:

[0066]

[0067]

[0068] The groups in formula A-1 to A-18 may be optionally substituted by 0, 1, 2 or 3 groups selected from D, F, Cl, Br, cyano, C1-C4 alkyl, C1-C3 haloalkyl, phenyl, naphthyl, fluorenyl, spirofluorenyl and C3-C10 cycloalkyl.

[0069] In some embodiments, Ar1-Ar3 are independently selected from a substituted or unsubstituted aromatic group having 5-40 ring atoms, a substituted or unsubstituted heteroaromatic group having 5-40 ring atoms, a substituted or unsubstituted aryloxy group having 5-40 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5-40 ring atoms, and one or more of the groups are each other and / or the ring bonded to the group to form a polycyclic aliphatic or aromatic ring system.

[0070] In some embodiments, Ar1-Ar3 are independently selected from a substituted or unsubstituted aromatic group having 5-30 ring atoms, a substituted or unsubstituted heteroaromatic group having 5-30 ring atoms, a substituted or unsubstituted aryloxy group having 5-30 ring atoms, or a substituted or unsubstituted heteroaryloxy group having 5-30 ring atoms.

[0071] In some embodiments, Ar1-Ar3 are independently selected from a deuterated or undeuterated aromatic group having 5-20 ring atoms, a deuterated or undeuterated heteroaromatic group having 5-20 ring atoms, a deuterated or undeuterated aryloxy group having 5-20 ring atoms, or a deuterated or undeuterated heteroaryloxy group having 5-20 ring atoms, or a combination of these systems, wherein one or more groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or the ring bonded to the group.

[0072] In some embodiments, Ar1-Ar3 are independently selected from a deuterated or undeuterated aromatic group having 5-15 ring atoms, a deuterated or undeuterated heteroaromatic group having 5-15 ring atoms, a deuterated or undeuterated aryloxy group having 5-15 ring atoms, or a deuterated or undeuterated heteroaryloxy group having 5-15 ring atoms, or a combination of these systems, wherein one or more groups can form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and / or the ring bonded to the group.

[0073] In some embodiments, the aromatic group is selected from benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, or derivatives thereof.

[0074] In some embodiments, the heteroaromatic group is selected from furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-naphthyridine, quinoxaline, phenanthridine, primary idine, quinazoline, quinazolinone, or derivatives thereof.

[0075] In some embodiments, Ar1-Ar3 in formula (1) are independently selected from any one of the following structures (the connectable site in W or V is connected to formula (1)):

[0076]

[0077] W is selected from N or CR1;

[0078] V is selected from any one of O, S, S=O, SO2, NR2, CR3R4 or SiR5R6;

[0079] Each occurrence of R1-R6 is independently selected from hydrogen, D, straight-chain alkyl having 1 to 10 C atoms, straight-chain alkoxy having 1 to 10 C atoms, straight-chain thioalkoxy having 1 to 20 C atoms, branched-chain alkyl or cyclic alkyl having 3 to 10 C atoms, branched-chain alkoxy or cyclic alkoxy having 3 to 10 C atoms, branched-chain thioalkoxy or cyclic thioalkoxy having 3 to 10 C atoms, silyl, keto having 1 to 10 C atoms, alkoxy having 2 to 10 C atoms, Oxycarbonyl, aryloxycarbonyl having 7 to 10 C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, a substituted or unsubstituted aromatic group having 5 to 10 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms, an aryloxy group having 5 to 10 ring atoms, a heteroaryloxy group having 5 to 10 ring atoms, or a combination of these groups; R1-R6 may form a ring;

[0080] The substitution of R1-R6 is by at least one of deuterium, halogen, cyano, isocyano, trifluoromethyl, C1-C3 alkyl, C1-C3 haloalkyl, C3-C5 cycloalkyl, C6-C10 aryl, triphenylsilyl, wherein the number of substitutions is from a single substitution to a maximum number of substitutions.

[0081] In some embodiments, R1-R6 are independently selected from hydrogen, D, a straight chain alkyl group having 1 to 10 C atoms, a branched chain alkyl group having 3 to 10 C atoms, a cycloalkyl group having 3 to 10 C atoms, Cl, Br, F, cyano or phenyl.

[0082] In some embodiments, Ar1-Ar3 in Formula (1) or Formula (2-1)-Formula (2-7) are independently selected from one of the following groups:

[0083]

[0084] The meaning of Ra is the same as R1;

[0085] s is any integer selected from 0-5.

[0086] In some embodiments, Ar1-Ar3 are the same as or different from each other and are each independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted thienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzothioxadienyl, substituted or unsubstituted dibenzodioxinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted benzocarbazolyl, or substituted or unsubstituted indolocarbazolyl, substituted or unsubstituted pyrene, substituted or unsubstituted furanyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted thienyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted benzocarbazolyl.

[0087] In some embodiments, the substituents in Ar1-Ar3 are independently selected from fluorine, cyano, methyl, ethyl, n-propyl, isopropyl, tert-butyl, trifluoromethyl, triphenylsilyl, cyclohexyl, adamantyl, phenyl or biphenyl.

[0088] In some embodiments, Ar1-Ar3 are independently selected from the following groups or a combination of the following groups:

[0089]

[0090]

[0091] In some embodiments, a portion of the H of the compound according to formula (1) is deuterated, for example, more than 10% of the H is deuterated, more than 20% of the H is deuterated, more than 30% of the H is deuterated, or more than 40% of the H is deuterated.

[0092] In some embodiments, the compound represented by formula (1) is selected from one of the following structural formulas:

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102] A second aspect of the present application provides an organic electroluminescent device.

[0103] There are many forms of organic electroluminescent devices, and the organic electroluminescent devices are divided into upright structures and inverted structures. The organic electroluminescent device of the upright structure includes a substrate, an anode, a light-emitting structure, and a cathode stacked from bottom to top, and the light-emitting structure includes the compound shown in formula (1). The organic electroluminescent device of the inverted structure may include a substrate, a cathode, a light-emitting structure, and an anode stacked from bottom to top, and the light-emitting structure includes the compound shown in formula (1).

[0104] In some embodiments, an organic electroluminescent device comprises an anode, a cathode, and one or more organic layers between the anode and the cathode, wherein at least one of the one or more organic layers comprises a compound represented by formula (1).

[0105] In some embodiments, the compound represented by formula (1) is used as a component of a light-emitting layer, a hole blocking layer or an electron transporting layer.

[0106] In some embodiments, the one or more organic layers are functional layers, and the functional layers are selected from at least one of a hole injection layer (HIL), a hole transport layer (HTL), an emitting layer (EmL), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL);

[0107] The electron transport layer comprises a compound represented by formula (1).

[0108] In some embodiments, an organic electroluminescent device includes an anode, a hole injection layer, a first hole transport layer, a second hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a cathode stacked in sequence; the electron transport layer is composed of a compound represented by formula (1).

[0109] A display or lighting element comprises the above organic electroluminescent device.

[0110] The preparation of specific compounds was carried out as follows.

[0111] Synthesis of compound 1:

[0112]

[0113] Synthesis of compound 1-3:

[0114] Compound 1-1 (20.00 g, 74.71 mmol), compound 1-2 (17.58 g, 74.71 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4, 0.86 g, 0.75 mmol), sodium hydroxide (7.47 g, 186.77 mmol), tetrahydrofuran (THF, 450 mL), and deionized water (150 mL) were added to a 1000 mL three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. The oil temperature was raised to 75 ° C. and reacted for 6 hours. TLC monitoring (thin layer chromatography, ethyl acetate: n-hexane = 1:15 as the developing solvent) was used up. When compound 1-1 was completely consumed, heating was stopped.

[0115] After the reaction was completed, a large amount of solid was precipitated, which was directly filtered to obtain 31 g of solid. Dichloromethane (600 mL) was added to dissolve and clarify. Silica gel (60 g, 200-300 mesh chromatography column silica gel) was filtered once, and the filtrates were combined and concentrated at 65°C for 1 hour to obtain 25 g of white solid. Toluene (340 mL) was added, and the oil temperature was raised to 105°C to dissolve and clarify. The temperature was naturally cooled to room temperature and stirred for 1 hour, filtered, and dried in vacuo at 70°C for 3 hours to obtain a white solid as compound 1-3 (22.51 g, mass purity: 99.43%, yield: 71.28%), and the mass spectrum result was: 421.83 (M+H).

[0116] Synthesis of compound 1-5:

[0117] Compound 1-3 (22.00 g, 52.05 mmol), compound 1-4 (10.31 g, 52.05 mmol), tetrakis(triphenylphosphine)palladium (0.60 g, 0.52 mmol), potassium carbonate (17.98 g, 130.11 mmol), toluene (Toluene, 360 mL), ethanol (EtOH, 120 mL), and deionized water (120 mL) were added to a 2000 mL three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. The oil temperature was raised to 65 ° C. and the reaction was carried out for 3 hours. TLC monitoring (ethyl acetate: n-hexane = 1:20 as the developing solvent in a volume ratio) was used up. When compound 1-3 was completely consumed, heating was stopped.

[0118] After the reaction was completed, a large amount of solid was precipitated, which was directly filtered to obtain 26 g of solid. Dichloromethane (700 mL) was added to dissolve and clarify. Silica gel (50 g, 200-300 mesh chromatography column silica gel) was filtered once, and the filtrates were combined and concentrated at 65°C to obtain 21 g of white solid. Tetrahydrofuran (600 mL) was added, and the oil temperature was raised to 65°C to dissolve and clarify. Methanol (300 mL) was then added, and the temperature was naturally cooled to room temperature and stirred for 2 hours. A large amount of solid was precipitated, which was filtered and dried in vacuo at 70°C for 2 hours to obtain a white solid as compound 1-5 (18.71 g, mass purity: 99.73%, yield: 72.48%), and the mass spectrum result was: 496.15 (M+H).

[0119] Synthesis of compound 1-7:

[0120] Compound 1-6 (40.00 g, 149.70 mmol) and dry tetrahydrofuran (400 mL) were added to a 1000 mL three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. Then the system was cooled to -78 ° C, and then n-butyl lithium (n-BuLi) n-hexane solution (65.87 mL, 164.67 mmol, concentration 2.5 mol / L) was added dropwise, and the temperature in the system was controlled not to be higher than -70 ° C. The addition was completed in 20 minutes, and the temperature was maintained at -78 ° C and stirred for 1 hour. Finally, triethyl borate (B (OEt) 3, 32.78 g, 224.55 mmol) was slowly added dropwise, and the addition was completed in 10 minutes; the temperature was naturally raised to room temperature and stirred for 2 hours, and TLC monitoring (according to the volume ratio of ethyl acetate: n-hexane = 1:20 as the developing solvent) showed that compound 1-6 was completely consumed.

[0121] Deionized water (100 mL) was added dropwise to the system to quench the reaction. After warming to room temperature, the liquid was directly separated. The aqueous phase was extracted twice with ethyl acetate (200 mL*2). The organic phases were combined and concentrated under reduced pressure at 65°C for 1 hour to obtain a light yellow solid. Ethyl acetate (20 mL) and n-hexane (200 mL) were added at room temperature and heated to 60°C for slurrying for 2 hours. The mixture was cooled to room temperature and filtered. The mixture was vacuum dried at 70°C for 2 hours to obtain a white solid, which was compound 1-7 (20.17 g, mass purity: 99.13%, yield: 58.06%). The mass spectrometry result was: 233.16 (M+H)

[0122] Synthesis of compound 1-9:

[0123] Compound 1-7 (20.00 g, 86.16 mmol), compound 1-8 (16.58 g, 86.16 mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (Pd(dppf)Cl2, 0.63 g, 0.86 mmol), potassium carbonate (29.77 g, 215.40 mmol), tetrahydrofuran (375 mL), and deionized water (125 mL) were added to a 1000 mL three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. Then, the system was heated to 75 ° C for 4 hours, and the reaction was monitored by TLC (ethyl acetate: n-hexane = 1:20 by volume as the developing solvent). Compound 1-8 was completely consumed.

[0124] After the reaction was completed, a large amount of solid was precipitated, which was directly filtered to obtain 26 g of solid. Tetrahydrofuran (500 mL) was added to dissolve and clarify. Silica gel (60 g, 200-300 mesh chromatography column silica gel) was filtered once, and the filtrates were combined and concentrated at 50°C for 1 hour to obtain 23 g of white solid. Toluene (90 mL) was added, and the oil temperature was raised to 105°C to dissolve and clarify. The mixture was naturally cooled to room temperature and stirred for 1 hour, filtered, and dried in vacuo at 70°C for 3 hours to obtain a white solid as compound 1-9 (18.41 g, mass purity: 99.31%, yield: 71.26%), and the mass spectrum result was: 300.16 (M+H).

[0125] Synthesis of compound 1-11:

[0126] Compound 1-9 (18.00 g, 60.03 mmol), compound 1-10 (15.24 g, 60.03 mmol), tris(dibenzylideneacetone)dipalladium (Pd2(dba)3, 0.55 g, 0.60 mmol), 2-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (X-Phos, 0.57 g, 1.20 mmol), potassium acetate (14.73 g, 150.08 mmol), 1,4-dioxane (1,4-Dioxane, 300 mL) were added to a 1000 mL three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. Then, the system was heated to 100 ° C for 2 hours, and the reaction was monitored by TLC (ethyl acetate: n-hexane = 1:20 by volume as the developing solvent). Compound 1-9 was completely consumed.

[0127] The temperature was lowered to 60°C, and the solvent was removed by concentration under reduced pressure. Ethyl acetate (700 mL) was added, and the mixture was washed three times with deionized water (300 mL*3). The mixture was separated, and the sample was mixed with silica gel and dry-loaded onto a column. Purification was performed by silica gel column chromatography (200-300 mesh silica gel, and the eluent was ethyl acetate: n-hexane = 1:30 by volume). After elution, the mixture was concentrated under reduced pressure at 70°C for 2 hours to obtain a white solid as compound 1-11 (17.85 g, mass purity: 99.06%, yield: 75.98%), and the mass spectrum result was: 392.26 (M+H).

[0128] Synthesis of compound 1:

[0129] Compound 1-5 (18.00 g, 36.29 mmol), compound 1-11 (14.20 g, 36.29 mmol), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) (Pd(aMphos)Cl2, 0.26 g, 0.36 mmol), potassium carbonate (12.54 g, 90.73 mmol), 1,4-dioxane (225 mL), and deionized water (75 mL) were added to a 500 mL three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. The oil temperature was raised to 80 ° C. and the reaction was carried out for 3 hours. TLC monitoring (ethyl acetate: n-hexane = 1:20 as the developing solvent) was used up. When compound 1-5 was completely consumed, heating was stopped.

[0130] After the reaction was completed, a large amount of solid was precipitated, which was directly filtered to obtain 23g of solid. Xylene (360mL) was added and heated to 130°C to dissolve and clarify. Silica gel (20g, 200-300 mesh chromatography column silica gel) was filtered once, and the filtrate was cooled to room temperature and stirred for 2 hours. 21.5g of white solid was obtained by suction filtration. Xylene (240mL) was added, and the oil temperature was raised to 130°C to dissolve and clarify. The mixture was naturally cooled to room temperature and stirred for 2 hours. The filter cake was vacuum dried at 90°C for 3 hours to obtain a white solid compound 1 (19.21g, mass purity: 99.92%, yield: 73.02%). 19.21 grams of crude compound 1 was purified by sublimation to obtain sublimation pure compound 1 (12.29g, mass purity: 99.95%, yield: 63.99%), and the mass spectrum result was: 725.31 (M+H).

[0131] The NMR characterization results of compound 1 are: 1 H NMR (400MHz, CDCl3) δ8.47(dd,J=15.0,3.1Hz,1H),8.44(t,J=2.9Hz,1H),8.40(t,J=3.0Hz,1H),8.39–8.31(m,4H),8.07(t,J=3.0Hz,1H),7.97( dd,J=15.0,2.9Hz,1H),7.79–7.72(m,2H),7.63(d,J=2.9Hz,1H),7.54–7 .32(m,10H),7.25(s,4H),7.19–7.07(m,2H),1.76(m,4H),0.96(s,12H).

[0132] Synthesis of compound 2:

[0133]

[0134] Synthesis of compound 2-2:

[0135] Referring to the synthesis and purification method of compound 1-5, it is only necessary to change the corresponding raw materials to obtain the target compound 2-2 (15.23 g, mass purity: 99.61%, yield: 71.25%), and the mass spectrum result is: 520.11 (M+H).

[0136] Synthesis of compound 2:

[0137] Referring to the synthesis and purification method of compound 1, only the corresponding raw materials need to be changed to obtain the target compound 2 (16.32 g, mass purity: 99.92%, yield: 75.54%). 16.32 g of crude compound 2 was purified by sublimation to obtain sublimation pure compound 2 (10.97 g, mass purity: 99.94%, yield: 67.23%), and the mass spectrum result was: 749.36 (M+H).

[0138] The NMR characterization results of compound 2 are: 1 H NMR (400MHz, CDCl3) δ9.08 (dd, J=14.3, 3.6Hz, 1H), 8.84 (dd, J=14.2, 3.7Hz, 1H), 8.50–8.42(m,3H),8.41–8.31(m,4H),8.27(dd,J=14.2,3.7Hz,1H),8.23(d,J=3. 1Hz,1H),8.16(t,J=3.0Hz,1H),7.98–7.87(m,2H),7.75–7.58(m,4H),7.56(d,J= 3.0Hz, 1H), 7.54–7.45 (m, 7H), 7.13 (d, J = 20.0Hz, 2H), 1.71 (m, 4H), 0.91 (s, 12H).

[0139] Synthesis of compound 3:

[0140]

[0141] Synthesis of compound 3-2:

[0142] Referring to the synthesis and purification method of compound 1-3, it is only necessary to change the corresponding raw materials to obtain the target compound 3-2 (19.15 g, mass purity: 99.46%, yield: 69.94%), and the mass spectrum result is: 574.03 (M+H).

[0143] Synthesis of compound 3-4:

[0144] Referring to the synthesis and purification method of compound 1-5, it is only necessary to change the corresponding raw materials to obtain the target compound 3-4 (14.61 g, mass purity: 99.72%, yield: 77.27%), and the mass spectrum result is: 572.18 (M+H).

[0145] Synthesis of compound 3-10:

[0146] Referring to the synthesis and purification method of compound 1-11, it is only necessary to change the corresponding raw materials to obtain the target compound 3-10 (4.09 g, mass purity: 98.91%, yield: 69.55%), and the mass spectrum result is: 315.24 (M+H).

[0147] Synthesis of compound 3:

[0148] Referring to the synthesis and purification method of compound 1, only the corresponding raw materials need to be changed to obtain the target compound 3 (7.03 g, mass purity: 99.90%, yield: 71.73%). 7.03 grams of crude compound 3 was purified by sublimation to obtain sublimation pure compound 3 (4.61 g, mass purity: 99.90%, yield: 65.57%), and the mass spectrum result was: 801.38 (M+H).

[0149] The NMR characterization results of compound 3 are as follows: 1 H NMR (400MHz, CDCl3) δ8.47(dd,J=15.0,2.9Hz,1H),8.38(dd,J=3.0,1.7Hz,2H),8.20(t,J=3.0Hz,1H),8.01–7.89(m,5H),7. 80–7.67(m,7H),7.55–7.35(m,9H),7.28–7.21(m,4H),7.13(m,2H),7.02(dd,J=15.0,3.3Hz,1H),1.67(m,4H),0.93(s,12H).

[0150] Synthesis of compound 4:

[0151]

[0152] Synthesis of compound 4-2:

[0153] Compound 4-1 (8.0 g, 41.79 mmol), compound 1-11 (16.35 g, 41.79 mmol), [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (0.31 g, 0.42 mmol), sodium carbonate (11.07 g, 104.46 mmol), tetrahydrofuran (375 mL), and deionized water (125 mL) were added to a 1000 mL three-necked round-bottom flask, and the vacuum nitrogen was replaced three times. Then, the system was heated to 60 ° C for 4 hours. The reaction was monitored by TLC (ethyl acetate: n-hexane = 1:15 as the developing solvent). Compound 4-1 was completely consumed.

[0154] After the reaction was completed, a large amount of solid was precipitated, which was directly filtered to obtain 16 g of solid. Tetrahydrofuran (500 mL) was added to dissolve and clarify. Silica gel (60 g, 200-300 mesh chromatography column silica gel) was filtered once, and the filtrates were combined and concentrated at 50°C for 1 hour to obtain 15 g of white solid. Toluene (50 mL) was added, and the oil temperature was raised to 105°C to dissolve and clarify. The temperature was naturally cooled to room temperature and stirred for 1 hour, filtered, and dried in vacuo at 70°C for 3 hours to obtain a white solid as compound 4-2 (11.34 g, mass purity: 99.53%, yield: 72.19%), and the mass spectrum result was: 376.17 (M+H).

[0155] Synthesis of compound 4-3:

[0156] Referring to the synthesis and purification method of compound 1-11, it is only necessary to change the corresponding raw materials to obtain the target compound 4-3 (10.98 g, mass purity: 99.02%, yield: 80.28%), and the mass spectrum result is: 468.29 (M+H).

[0157] Synthesis of compound 4-5:

[0158] Referring to the synthesis and purification method of compound 1-5, it is only necessary to change the corresponding raw materials to obtain the target compound 4-5 (11.34 g, mass purity: 99.42%, yield: 76.10%), and the mass spectrum result is: 420.11 (M+H).

[0159] Synthesis of compound 4:

[0160] Referring to the synthesis and purification method of compound 1, only the corresponding raw materials need to be changed to obtain the target compound 4 (12.56 g, mass purity: 99.93%, yield: 80.84%). 12.56 grams of crude compound 4 was purified by sublimation to obtain sublimation pure compound 4 (8.03 g, mass purity: 99.95%, yield: 63.96%), and the mass spectrum result was: 725.32 (M+H).

[0161] The NMR characterization results of compound 4 are as follows: 1 H NMR(400MHz, CDCl3)δ8.47(dd,J=7.5,1.4Hz,1H),8.44–8.40(m,2H),8.39–8.3 3(m,4H),8.20(t,J=1.5Hz,1H),7.92(dd,J=7.5,1.4Hz,1H),7.75(dd,J=7.5,1. 2Hz,2H),7.59(d,J=1.4Hz,1H),7.54–7.46(m,8H),7.44–7.38(m,1H),7.30(dd ,J=7.5,1.4Hz,1H),7.25(s,4H),7.18–7.09(m,2H),1.77(m,4H),0.93(s,12H).

[0162] Synthesis of compound 5:

[0163]

[0164] Synthesis of compound 5-2:

[0165] Referring to the synthesis and purification method of compound 1-9, it is only necessary to change the corresponding raw materials to obtain the target compound 5-2 (9.85 g, mass purity: 99.73%, yield: 76.26%), and the mass spectrum result is: 300.14 (M+H).

[0166] Synthesis of compound 5-3:

[0167] Referring to the synthesis and purification method of compound 1-11, it is only necessary to change the corresponding raw materials to obtain the target compound 5-3 (9.12 g, mass purity: 99.62%, yield: 76.99%), and the mass spectrum result is: 588.27 (M+H).

[0168] Synthesis of compound 5:

[0169] Referring to the synthesis and purification method of compound 1, only the corresponding raw materials need to be changed to obtain the target compound 5 (8.23 g, mass purity: 99.95%, yield: 74.11%). 8.23 ​​grams of crude compound 5 was purified by sublimation to obtain sublimation pure compound 5 (5.13 g, mass purity: 99.95%, yield: 62.37%), and the mass spectrum result was: 725.32 (M+H).

[0170] The NMR characterization results of compound 5 are as follows: 1 H NMR (400MHz, CDCl3) δ8.68(t,J=3.0Hz,1H),8.47(dd,J=15.0,3.1Hz,1H),8.42–8.31(m,5H),8.28(t,J=3.0Hz,1H),7.90(dd, J=14.9,3.0Hz,1H),7.79–7.70(m,2H),7.56–7.36(m,10H),7.28–7.21(m,5H),7.20–7.07(m,2H),1.70(m,4H),0.93(s,12H).

[0171] Synthesis of compound 6:

[0172]

[0173] Synthesis of compound 6-2:

[0174] Referring to the synthesis and purification method of compound 1-5, it is only necessary to change the corresponding raw materials to obtain the target compound 6-2 (14.17 g, mass purity: 99.49%, yield: 75.24%), and the mass spectrum result is: 510.13 (M+H).

[0175] Synthesis of compound 6-3:

[0176] Referring to the synthesis and purification method of compound 1-11, it is only necessary to change the corresponding raw materials to obtain the target compound 6-3 (13.46 g, mass purity: 99.23%, yield: 81.52%), and the mass spectrum result is: 602.25 (M+H).

[0177] Synthesis of compound 6:

[0178] Referring to the synthesis and purification method of compound 1, only the corresponding raw materials need to be changed to obtain the target compound 6 (9.13 g, mass purity: 99.92%, yield: 74.32%). 9.13 grams of crude compound 6 was sublimated and purified to obtain sublimation pure compound 6 (6.09 g, mass purity: 99.96%, yield: 66.70%), and the mass spectrum result was: 739.33 (M+H).

[0179] The NMR characterization results of compound 6 are: 1 H NMR (400MHz, CDCl3) δ8.68(t,J=3.0Hz,1H),8.51–8.43(m,2H),8.42–8.30(m,5H),8.05–7.95(m,2H),7.90(dd,J=15.0, 3.1Hz,1H),7.78(d,J=15.0Hz,1H),7.60–7.45(m,9H),7.44–7.23(m,3H),7.20–7.08(m,2H),1.73(m,4H),0.91(s,12H).

[0180] Synthesis of compound 7:

[0181]

[0182] Synthesis of compound 7-2:

[0183] Referring to the synthesis and purification method of compound 1-9, it is only necessary to change the corresponding raw materials to obtain the target compound 7-2 (14.31 g, mass purity: 99.52%, yield: 74.25%), and the mass spectrum result is: 300.12 (M+H).

[0184] Synthesis of compound 7-3:

[0185] Referring to the synthesis and purification method of compound 1-11, it is only necessary to change the corresponding raw materials to obtain the target compound 7-3 (12.84 g, mass purity: 99.05%, yield: 70.27%), and the mass spectrum result is: 392.26 (M+H).

[0186] Synthesis of compound 7-5:

[0187] Referring to the synthesis and purification method of compound 1-5, it is only necessary to change the corresponding raw materials to obtain the target compound 7-5 (12.53 g, mass purity: 99.62%, yield: 71.19%), and the mass spectrum result is: 496.15 (M+H).

[0188] Synthesis of compound 7:

[0189] Referring to the synthesis and purification method of compound 1, only the corresponding raw materials need to be changed to obtain the target compound 7 (13.86 g, mass purity: 99.93%, yield: 75.86%). 13.86 grams of crude compound 7 was purified by sublimation to obtain sublimation pure compound 7 (8.92 g, mass purity: 99.95%, yield: 64.35%), and the mass spectrum result was: 725.35 (M+H).

[0190] The NMR characterization results of compound 7 are: 1 H NMR(400MHz, CDCl3)δ9.43(d,J=0.6Hz,1H),9.07(d,J=15.0Hz,1H),8.42–8.30(m,5H),8.24–8.17(m,2H),8.02–7.91(m,2H),7.89–7 .73(m,3H),7.66–7.55(m,2H),7.55–7.36(m,10H),7.29(dd,J=14.9,3.0Hz,1H),7.11(d,J=15.0Hz,1H),1.75(m,4H),0.91(s,12H).

[0191] Synthesis of compound 8:

[0192]

[0193] Synthesis of compound 8:

[0194] Referring to the synthesis and purification method of compound 1, only the corresponding raw materials need to be changed to obtain the target compound 8 (11.09 g, mass purity: 99.94%, yield: 72.51%). 11.09 grams of crude compound 8 was purified by sublimation to obtain sublimation pure compound 8 (6.47 g, mass purity: 99.94%, yield: 58.34%), and the mass spectrum result was: 801.38 (M+H).

[0195] The NMR characterization results of compound 8 are: 1H NMR (400MHz, CDCl3) δ9.43(d,J=0.6Hz,1H),9.07(d,J=15.0Hz,1H),8.38(d,J=2.9Hz,1H),8.27(d,J=3.1Hz,1H),8.22(d,J=3.1Hz,1H),8.02 –7.92(m,4H),7.84(d,J=15.0Hz,1H),7.80–7.70(m,6H),7.48(m,10H) ,7.31–7.21(m,5H),7.11(d,J=15.0Hz,1H),1.70(m,4H),0.94(s,12H).

[0196] Synthesis of compound 9:

[0197]

[0198] Synthesis of compound 9-2:

[0199] Referring to the synthesis and purification method of compound 1-9, it is only necessary to change the corresponding raw materials to obtain the target compound 9-2 (7.21 g, mass purity: 99.62%, yield: 68.43%), and the mass spectrum result is: 301.13 (M+H).

[0200] Synthesis of compound 9-3:

[0201] Referring to the synthesis and purification method of compound 1-11, it is only necessary to change the corresponding raw materials to obtain the target compound 9-3 (6.13 g, mass purity: 99.14%, yield: 67.14%), and the mass spectrum result is: 393.26 (M+H).

[0202] Synthesis of compound 9-5:

[0203] Referring to the synthesis and purification method of compound 1-5, it is only necessary to change the corresponding raw materials to obtain the target compound 9-5 (8.47 g, mass purity: 99.71%, yield: 76.50%), and the mass spectrum result is: 520.17 (M+H).

[0204] Synthesis of compound 9:

[0205] Referring to the synthesis and purification method of compound 1, only the corresponding raw materials need to be changed to obtain the target compound 9 (8.52 g, mass purity: 99.94%, yield: 73.85%). 8.52 g of crude compound 9 was purified by sublimation to obtain sublimation pure compound 9 (5.05, mass purity: 99.95%, yield: 59.28%), and the mass spectrum result was: 750.37 (M+H).

[0206] The NMR characterization results of compound 9 are as follows: 1 H NMR(400MHz, CDCl3) δ9.36(d,J=0.6Hz,1H),9.11(d,J=14.9Hz,1H),8.70(dd, J=14.1,3.8Hz,1H),8.50–8.41(m,5H),8.40–8.32(m,4H),8.10(t,J=3.0Hz,1 H),7.97–7.87(m,2H),7.80–7.70(m,1H),7.64(m,2H),7.55–7.45(m,7H),7.2 2(dd,J=15.0,2.9Hz,1H),7.11(d,J=15.0Hz,1H),1.76(m,4H),0.96(s,12H).

[0207] Synthesis of compound 10:

[0208]

[0209] Synthesis of compound 10-2:

[0210] Referring to the synthesis and purification method of compound 1-9, only the corresponding raw materials need to be changed to obtain the target compound 10-2 (5.13 g, mass purity: 99.63%, yield: 72.15%), and the mass spectrum result is: 301.03 (M+H).

[0211] Synthesis of compound 10-4:

[0212] Referring to the synthesis and purification method of compound 1-3, it is only necessary to change the corresponding raw materials to obtain the target compound 10-4 (11.03 g, mass purity: 99.82%, yield: 76.96%), and the mass spectrum result is: 512.04 (M+H).

[0213] Synthesis of compound 10-5:

[0214] Referring to the synthesis and purification method of compound 1-5, it is only necessary to change the corresponding raw materials to obtain the target compound 10-5 (8.56 g, mass purity: 99.51%, yield: 78.25%), and the mass spectrum result is: 510.12 (M+H).

[0215] Synthesis of compound 10-6:

[0216] Referring to the synthesis and purification method of compound 1-11, only the corresponding raw materials need to be changed to obtain the target compound 10-6 (7.69 g, mass purity: 99.12%, yield: 76.71%), and the mass spectrum result is: 602.21 (M+H)

[0217] Synthesis of compound 10:

[0218] Referring to the synthesis and purification method of compound 1, only the corresponding raw materials need to be changed to obtain the target compound 10 (7.13 g, mass purity: 99.92%, yield: 77.28%). 7.13 grams of crude compound 10 was sublimated and purified to obtain sublimation pure compound 10 (4.39 g, mass purity: 99.94%, yield: 61.56%), and the mass spectrum result was: 740.45 (M+H).

[0219] The NMR characterization results of compound 10 are: 1 H NMR (400MHz, CDCl3) δ9.36 (s, 1H), 8.55–8.46 (m, 2H), 8.41 (dd, J = 4.7, 3.1Hz, 2H), 8.38–8.33 (m, 2H) ,8.05(t,J=1.4Hz,1H),7.98(dd,J=7.4,1.5Hz,1H),7.75(dd,J=7.5,1.2Hz,2H),7.69(d,J=7.5Hz,1 H),7.63(dd,J=7.5,1.4Hz,1H),7.54(dd,J=7.5,1.4Hz,1H),7.50(m,6H),7.44–7.36(m,2H),7.32(d d, J=7.5, 1.4Hz, 1H), 7.25 (dd, J=7.5, 1.4Hz, 1H), 7.11 (d, J=7.5Hz, 1H), 1.68 (m, 4H), 0.96 (s, 12H).

[0220] The compound of the present application is used to prepare an organic electroluminescent device.

[0221] Figure 1 Schematic diagram of the structure of the organic electroluminescent device in the embodiment of the present application. Figure 1 1 represents a glass substrate, 2 represents an anode, 3 represents a hole injection layer, 4 represents a first hole transport layer, 5 represents a second hole transport layer, 6 represents a light emitting layer, 7 represents a hole blocking layer, 8 represents an electron transport layer, 9 represents an electron injection layer, and 10 represents a cathode.

[0222] An organic electroluminescent device with a positive structure is a specific embodiment. First, a 50mm*50mm*1.0mm glass substrate with an ITO (100nm) transparent electrode (anode) is ultrasonically cleaned in ethanol for 10 minutes, then dried at 150°C and treated with N2 Plasma (plasma treatment) for 30 minutes, and the treated glass substrate is mounted on a substrate support of a vacuum evaporation device. First, the compound HATCN is evaporated on the surface of the side with the transparent electrode line in a manner of covering the transparent electrode to form a film with a thickness of 5nm (hole injection layer); then, a layer of HTM1 is evaporated to form a film with a thickness of 60nm (first hole transport layer); then, a layer of HTM2 is evaporated on the HTM1 film to form a film with a thickness of 10nm (second hole transport layer); then, the main material and the doping material are evaporated on the HTM2 film layer in a co-evaporation mode to obtain a light-emitting layer, wherein the light-emitting layer has a film thickness of 20nm, and the mass ratio of the main material to the doping material is 97%:3%. HBL (5 nm) is evaporated on the light-emitting layer as a hole blocking layer material to obtain a hole blocking layer; then an electron transport layer material is evaporated on the hole blocking layer (the electron transport layer material is composed of the compound of the present invention or the comparative compound and Liq in a mass ratio of 5:5) to obtain an electron transport layer, wherein the thickness of the electron transport layer is 30 nm; then LiF (1 nm) is evaporated on the electron transport layer as an electron injection material to obtain an electron injection layer; then Al (100 nm) is evaporated to form a cathode.

[0223] The material structure used in the above-mentioned organic electroluminescent device is as follows:

[0224]

[0225] The above organic electroluminescent device was subjected to device performance testing. In each embodiment and comparative example, a constant current power supply (Keithley 2400) was used to flow a fixed current density through the light-emitting element, and a spectroradiometer (CS2000) was used to test the luminous spectrum. At the same time, 10 mA / cm 2 The driving voltage and current efficiency under the test 20mA / cm 2 The brightness decay time (LT 90 All data are based on Comparative Example 1 (the driving voltage, current efficiency, LT 90 The life value is expressed as a percentage, which is based on the driving voltage, current efficiency, LT 90 life as a basis for measuring the driving voltage, current efficiency, LT 90 Lifespan. Using the driving voltage of Example 1 as 98%, current efficiency as 105%, and LT 90Taking the life span of 105% as an example, it means that the driving voltage of the organic electroluminescent device of Example 1 under the same test conditions is only 98% of that of the comparative example 1, and the current efficiency is 105% of that of the comparative example 1. 90 The lifespan is 105% of that of comparative example 1). The results are shown in Table 1 below.

[0226] Table 1

[0227]

[0228]

[0229] From the data in Table 1, it can be seen that the compounds of the present invention are used as components of the electron transport layer in organic electroluminescent devices, and show more superior performance in terms of driving voltage, luminous efficiency and device life compared with the comparative compounds.

[0230] The above results show that the device prepared by the compound of the present invention has the advantages of low driving voltage, long life, high luminous efficiency, etc., and can be used in organic electroluminescent devices. In particular, as an electron transport material, it has the potential to be applied to the AMOLED industry.

Claims

1. A compound, characterized in that Its general structural formula is shown in formula (I): Wherein, X1, X2, X3, and X4 are independently selected from N or CH, and at least one is N, and adjacent X1-X4 are not N at the same time; L is selected from a single bond, a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaromatic group having 6 to 30 ring atoms; Ar1, Ar2, Ar3 are independently selected from a substituted or unsubstituted aromatic group having 5-60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5-60 ring atoms, a substituted or unsubstituted aryloxy group having 5-60 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5-60 ring atoms, or a combination of these systems, which can form a monocyclic or polycyclic aliphatic or aromatic ring system with the ring bonded to the group; 4 R are each independently selected from substituted or unsubstituted C1-C30 alkyl; The substitution of L and R is substituted by at least one of deuterium, halogen, cyano, isocyano, trifluoromethyl, C1-C6 alkyl, C1-C6 haloalkyl, C3-C16 cycloalkyl, C6-C30 aryl, and triphenylsilyl, wherein the number of substitutions is from a single substitution to a maximum number of substitutions; The heteroatoms in the heteroaromatic group, heteroaromatic group or heteroaryloxy group are independently selected from at least one of P, O, S, N, Se, Si and Ge.

2. The compound according to claim 1, characterized in that The compound represented by formula (1) is selected from one of the following structures of formula (2-1) to formula (2-7):

3. The compound according to claim 1, characterized in that The substitution in L refers to substitution with at least one of deuterium, halogen, cyano, C1-C4 alkyl, C1-C3 haloalkyl, phenyl, naphthyl, fluorenyl, spirofluorenyl or C3-C10 cycloalkyl; and / or, the substitution in the four Rs are independently selected from at least one of fluorine, cyano, C1-C4 alkyl, trifluoromethyl, triphenylsilyl, cyclohexyl, adamantyl, phenyl or biphenyl.

4. The compound according to claim 1, characterized in that L is selected from a single bond, or one of the groups shown in the following formulas A-1 to A-18, or one of the groups selected from any combination of the groups shown in formulas A-1 to A-18: The groups in formula A-1 to A-18 may be optionally substituted by 0, 1, 2 or 3 groups selected from D, F, Cl, Br, cyano, C1-C4 alkyl, C1-C3 haloalkyl, phenyl, naphthyl, fluorenyl, spirofluorenyl and C3-C10 cycloalkyl.

5. The compound according to claim 1, characterized in that In formula (1), Ar1-Ar3 are independently selected from any one of the following structures: W is selected from N or CR1; V is selected from any one of O, S, S=O, SO2, NR2, CR3R4 or SiR5R6; Each occurrence of R1-R6 is independently selected from hydrogen, D, straight-chain alkyl having 1 to 10 C atoms, straight-chain alkoxy having 1 to 10 C atoms, straight-chain thioalkoxy having 1 to 10 C atoms, branched-chain alkyl or cyclic alkyl having 3 to 10 C atoms, branched-chain alkoxy or cyclic alkoxy having 3 to 10 C atoms, branched-chain thioalkoxy or cyclic thioalkoxy having 3 to 10 C atoms, silyl, keto having 1 to 10 C atoms, alkoxy having 2 to 10 C atoms, Oxycarbonyl, aryloxycarbonyl having 7 to 10 C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, isothiocyanate, hydroxyl, nitro, CF3, Cl, Br, F, a substituted or unsubstituted aromatic group having 5 to 10 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms, an aryloxy group having 5 to 10 ring atoms, a heteroaryloxy group having 5 to 10 ring atoms, or a combination of these groups; R1-R6 may form a ring; The substitution of R1-R6 is by at least one of deuterium, halogen, cyano, isocyano, trifluoromethyl, C1-C3 alkyl, C1-C3 haloalkyl, C3-C5 cycloalkyl, C6-C10 aryl, triphenylsilyl, wherein the number of substitutions is from a single substitution to a maximum number of substitutions.

6. The compound according to claim 5, characterized in that Ar1-Ar3 in formula (1) or formula (2-1) to formula (2-7) are independently selected from one of the following groups: Ra and V have the same meanings as R1 in claim 5; s is any integer selected from 0-5.

7. The compound according to claim 1, characterized in that Ar1-Ar3 are the same as or different from each other and are each independently substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted thienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted dibenzothioxadienyl, substituted or unsubstituted dibenzodioxadienyl, substituted or unsubstituted quinolyl, substituted or unsubstituted benzocarbazolyl, or substituted or unsubstituted indolocarbazolyl, substituted or unsubstituted pyrene, substituted or unsubstituted furanyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted thienyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted benzocarbazolyl.

8. The compound according to claim 5 or 6, characterized in that The Ar1-Ar3 are independently selected from the following groups or a combination of the following groups:

9. The compound according to claim 1, characterized in that The compound represented by formula (1) is selected from one of the following structural formulas:

10. An organic electroluminescent device, characterized in that: The invention comprises an anode, a cathode and one or more organic layers between the anode and the cathode, wherein at least one of the one or more organic layers comprises a compound represented by formula (1) according to any one of claims 1 to 9.

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