Spiro compound and organic electroluminescent device

Abstract

The invention belongs to the technical field of organic electroluminescence, and discloses a spiro compound and an organic electroluminescence device. The structural general formula of the spiro compound is as shown in formula (1): # imgabs0 # and # imgabs1 #, wherein ring A is selected from substituted or unsubstituted benzene ring or naphthalene ring; x is independently selected from C (R2) 2, O, S, NR3; x1, X2 and X3 are respectively and independently selected from N or CR3, and at least one of X1, X2 and X3 is N. The spiro compound is applied to a luminescent device and has the advantages of low driving voltage, high luminous efficiency, long service life of the device and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of organic electroluminescence, and particularly relates to a spiro compound and an organic electroluminescent device. Background Art

[0002] At present, organic electroluminescent devices (OLEDs), as a new generation of display technology, have received more and more attention in both display and lighting technology, and have a wide range of application prospects. However, compared with market application requirements, the performance of OLED devices such as luminous efficiency, driving voltage, and service life still needs to be further improved.

[0003] The basic structure of an OLED device 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 electrodes 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 generating the light emission of the OLED. However, organic functional materials are the core components of light-emitting devices, and the thermal stability, photochemical stability, electrochemical stability, quantum yield, film formation stability, crystallinity, color saturation, etc. of the materials are the main factors affecting the performance of the device.

[0004] Patent document 1 (CN111433190A) records 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 light-emitting devices, and the efficiency of the device needs to be improved. Patent document 2 (KR1020180022190A) describes Such triazine electron transport / hole transport materials, the device performance using such materials as the main material needs to be further improved, especially the device efficiency and life; Patent document 3 (KR1020220042658A) records Dimethylfluorene-linked triazine materials with similar structures, the efficiency and life of devices using such structural materials also need to be improved; Patent document 4 (CN115304586A) records This type of benzocycloalkyl spiro ring structure connects N heterocyclic materials, and the device efficiency and life of this type of material also need to be improved. The above compounds are used as electron transport layer materials in light-emitting devices, and they have strong planarity, high sublimation temperature, poor material stability, and the luminous efficiency, life and other performance of the device need to be further improved. Summary of the invention

[0005] The present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention provides a spiro compound and an organic electroluminescent device.

[0006] A first aspect of the present application provides a spiro compound.

[0007] In some embodiments, a spirocyclic compound has a general structural formula as shown in formula (1):

[0008]

[0009] wherein ring A is selected from a substituted or unsubstituted benzene ring or a naphthalene ring;

[0010] X is independently selected from C(R2)2, O, S, NR3;

[0011] X1, X2, and X3 are independently selected from N or CR3, and at least one of X1, X2, and X3 is N;

[0012] R1, R2, and R3 are each independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C5-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphino, or C6-C60 arylamine;

[0013] L is selected from a single bond, a substituted or unsubstituted aryl group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaryl group having 6 to 30 ring atoms;

[0014] a is an integer from 0 to 6,

[0015] wherein Ar1 and Ar2 are independently selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C2-C60 heteroaryl;

[0016] The heteroatoms in the heteroaryl, heteroalkyl or heterocycloalkyl are independently selected from at least one heteroatom of O, S, N, Se, Si and Ge;

[0017] The substitutions in Ar1 and Ar2 are substituted by deuterium, F, Cl, Br, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkyl substituted amine, C6-C12 aryl, cyano, isocyano or phosphino, and the number of substitutions of each substituent group is independently selected from one of single substitution to the maximum number of substitutions.

[0018] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0019] The spiro compound of the present invention has a compound in which a cycloalkyl spiro ring is connected to an N heterocycle. The spiro compound of the present invention has the advantages of low driving voltage, high luminous efficiency, long device life, etc., and can be used as a hole blocking layer material and an electron transport layer material in an OLED light-emitting device. At the same time, it has a low melting point, and as a molten material, it is beneficial to improve the evaporation stability of the material. The compound is used as a hole blocking layer material and an electron transport layer material, and has the possibility of being applied to LED, OLED, and AMOLED industries. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 Compound A70 of the present application 1 H NMR spectrum;

[0021] Figure 2 This is a schematic structural diagram of an organic electroluminescent device of the present application. DETAILED DESCRIPTION

[0022] In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the following embodiments are listed for illustration. It should be pointed out that the following embodiments do not limit the protection scope of the present invention.

[0023] 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.

[0024] 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.

[0025] The raw materials and solvents involved in the synthesis of the spirocyclic compounds in this application were purchased from suppliers familiar to those skilled in the art such as Alfa and Acros.

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

[0027] In the present specification, the "carbon number a to b" in the expression "substituted or unsubstituted X group having a to b carbon atoms" refers to the carbon number when the X group is unsubstituted, and does not include the carbon number of the substituent when the X group is substituted.

[0028] Specific examples of the alkyl group include linear or branched alkyl groups, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl and its isomers, n-hexyl and its isomers, n-heptyl and its isomers, n-octyl and its isomers, n-nonyl and its isomers, n-decyl and its isomers, etc., preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl, and more preferably propyl, isopropyl, isobutyl, sec-butyl and tert-butyl.

[0029] Specific examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-norbornyl, 2-norbornyl and the like, and cyclopentyl and cyclohexyl are preferred.

[0030] Specific examples of the alkenyl group include vinyl, propenyl, allyl, 1-butadienyl, 2-butadienyl, 1-hexatrienyl, 2-hexatrienyl, and 3-hexatrienyl, and propenyl and allyl are preferred.

[0031] Specific examples of heteroalkyl groups include straight-chain or branched alkyl and cycloalkyl groups containing atoms other than carbon and hydrogen, such as mercaptomethylmethane, methoxymethane, ethoxymethane, tert-butoxymethane, N,N-dimethylmethane, butylene oxide, cyclopentyl, and hexyl oxide, preferably methoxymethane and cyclopentyl.

[0032] The aryl group and the heteroaryl group each independently include a monocyclic or polycyclic structure, wherein a plurality of rings in the polycyclic structure are connected to each other via a single bond or fused to each other.

[0033] Specific examples of the aryl group include phenyl, naphthyl, anthracenyl, phenanthrenyl, naphthyl, pyrenyl, perylene, The invention may be substituted with any of the following: 1) a benzo[c]phenanthrenyl group, 2) a benzo[g]chrysene group, 3) a fluorenyl group, 4) a spirobifluorenyl group, 5) a benzofluorenyl group, 6) a dibenzofluorenyl group, 7) a biphenyl group, 8) a terphenyl group, 9) a quaterphenyl group or 10) a fluoranthene group.

[0034] Specific examples of heteroaryl groups include pyrrolyl, pyrrolopyrrolyl, furopyrrolyl, thienopyrrolyl, pyridinyl, pyrazolyl, pyrimidinyl, pyrazinyl, triazinyl, pyridazinyl, phenazinyl, phenothiazinyl, phenoxazinyl, indolyl, isoindolyl, imidazolyl, benzimidazolyl, triazolyl, tetrazolyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, furofuranyl, azadibenzofuranyl, thienofuranyl, diazadibenzofuranyl, benzo[B]naphtho[1,2

[0063] the following may be used: 1-D] furanyl, quinolyl, isoquinolyl, quinoxalinyl, quinazolinyl, quinazolinonyl, carbazolyl, azacarbazolyl, diazacarbazolyl, phenanthridinyl, primary pyridinyl, acridinyl, dihydroacridinyl, phenanthrolinyl, oxazolinyl, oxazolyl, oxadiazolyl, benzisoxazolyl, thiazolyl, benzothiazolyl, benzisothiazolyl, pyrroloimidazolyl, furazanyl, thienyl, benzothienyl, dibenzothienyl, azadibenzothienyl, diazadibenzothienyl, thienothiphenyl or o-naphthyridinyl.

[0035] In some embodiments, a spirocyclic compound has a general structural formula as shown in formula (1):

[0036]

[0037] wherein ring A is selected from a substituted or unsubstituted benzene ring or a naphthalene ring;

[0038] X is independently selected from C(R2)2, O, S, NR3;

[0039] X1, X2, and X3 are independently selected from N or CR3, and at least one of X1, X2, and X3 is N;

[0040] R1, R2, and R3 are each independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C5-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphino, or C6-C60 arylamine;

[0041] L is selected from a single bond, a substituted or unsubstituted aryl group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaryl group having 6 to 60 ring atoms;

[0042] a is an integer from 0 to 6,

[0043] wherein Ar1 and Ar2 are independently selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C2-C60 heteroaryl;

[0044] The heteroatoms in the heteroaryl, heteroalkyl or heterocycloalkyl are independently selected from at least one heteroatom of O, S, N, Se, Si and Ge;

[0045] The substitutions in Ar1 and Ar2 are substituted by deuterium, F, Cl, Br, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkyl substituted amine, C6-C12 aryl, cyano, isocyano or phosphino, and the number of substitutions of each substituent group is independently selected from one of single substitution to the maximum number of substitutions.

[0046] In some embodiments of the present application, R1 is a substituent on each ring, each independently selected from deuterium, halogen, cyano, nitro, C1-C30 alkyl, C1-C30 heteroalkyl, C2-C20 alkenyl, C2-C30 alkynyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, C6-C40 aryl, C5-C40 heteroaryl, C1-C30 alkoxy, C6-C40 aryloxy, C3-C40 alkylsilyl, C6-C40 arylsilyl, C1-C30 alkylboryl, C6-C40 arylboryl, C6-C40 arylphosphinyl or C6-C40 arylamine.

[0047] In some embodiments of the present application, the C6-C60 aryl phosphino group includes a C6-C60 monoaryl phosphino group or a C6-C60 diaryl phosphino group.

[0048] In some embodiments of the present application, R1 is a substituent on each ring, each independently selected from deuterium, halogen, cyano, nitro, C1-C20 alkyl, C1-C20 heteroalkyl, C2-C10 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C30 aryl, C5-C30 heteroaryl, C1-C20 alkoxy, C6-C30 aryloxy, C3-C30 alkylsilyl, C6-C30 arylsilyl, C1-C20 alkylboryl, C6-C30 arylboryl, C6-C30 arylphosphinyl or C6-C30 arylamine.

[0049] In some embodiments of the present application, R2 and R3 are independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C20 alkyl, C1-C20 heteroalkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C30 aryl, C5-C30 heteroaryl, C1-C30 alkoxy, C6-C30 aryloxy, C3-C20 alkylsilyl, C6-C30 arylsilyl, C1-C20 alkylboryl, C6-C30 arylboryl, C6-C30 arylphosphinyl or C6-C30 arylamine.

[0050] In some embodiments of the present application, R2 and R3 are independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C10 alkyl, C1-C10 heteroalkyl, C2-C10 alkenyl, C2-C10 alkynyl, C3-C10 cycloalkyl, C3-C10 heterocycloalkyl, C6-C30 aryl, C5-C30 heteroaryl, C1-C30 alkoxy, C6-C30 aryloxy, C3-C20 alkylsilyl, C6-C30 arylsilyl, C1-C20 alkylboryl, C6-C30 arylboryl, C6-C30 arylphosphinyl or C6-C30 arylamine.

[0051] In some embodiments of the present application, L is selected from a single bond, a substituted or unsubstituted aryl group having 6-30 ring atoms, or a substituted or unsubstituted heteroaryl group having 6-30 ring atoms.

[0052] In some embodiments of the present application, a is an integer of 0-3.

[0053] In some embodiments of the present application, Ar1 and Ar2 are independently selected from substituted or unsubstituted C6-C30 aryl groups, and substituted or unsubstituted C2-C30 heteroaryl groups.

[0054] In some embodiments of the present application, the structure represented by formula (1) is selected from the structures represented by any one of the following formulas (B-1) to (B-9):

[0055]

[0056] Wherein, X, X1, X2, X3, L, Ar1, Ar2, a, R1 are the same as those in formula (1);

[0057] R4 is selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C5-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphinyl or C6-C60 arylamine.

[0058] In some embodiments of the present application, L is selected from a single bond and a structure shown in any one of the following formulas C-1 to C-18;

[0059]

[0060]

[0061] Wherein, R is a substituent, and each R is independently selected from deuterium, halogen, cyano, nitro, C1-C20 alkyl, C1-C20 heteroalkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C30 aryl, C5-C30 heteroaryl, C1-C20 alkoxy, C6-C30 aryloxy, C3-C20 alkylsilyl, C6-C30 arylsilyl, C1-C20 alkylboryl, C6-C30 arylboryl, C6-C30 arylphosphino or C6-C30 arylamine;

[0062] m is selected from integers of 0-4.

[0063] In some embodiments of the present application, X1, X2, and X3 contain at least two Ns, and further, X1, X2, and X3 all contain Ns.

[0064] In some embodiments of the present application, R3 is selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C20 alkyl, C1-C20 heteroalkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C30 aryl, C5-C30 heteroaryl, C1-C20 alkoxy, C6-C30 aryloxy, C3-C20 alkylsilyl, C6-C30 arylsilyl, C1-C20 alkylboryl, C6-C30 arylboryl, C6-C30 arylphosphino or C6-C30 arylamine.

[0065] In some embodiments of the present application, Ar1 and Ar2 are each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted The invention may be a substituted or unsubstituted carbazolyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted fluoranthene, a substituted or unsubstituted benzoxazolyl, a substituted or unsubstituted benzimidazolyl, a substituted or unsubstituted benzotriazolyl, a substituted or unsubstituted triphenylene radical, or a combination of at least two of these groups.

[0066] In some embodiments of the present application, formula (1) contains at least one deuterium atom.

[0067] In some embodiments of the present application, the formula (1) is one of the following structural formulas, or one of the structures in which hydrogen is partially or completely replaced by deuterium or fluorine in the following structural formulas:

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082] In some embodiments of the present application, 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 organic layers comprises a spiro compound represented by formula (1).

[0083] In some embodiments of the present application, the organic layer includes at least one of a light-emitting layer, a hole blocking layer, and an electron transport layer.

[0084] In some embodiments of the present application, the spiro compound represented by formula (1) is used as a hole blocking layer material or an electron transport layer material.

[0085] The following embodiments are only for facilitating the understanding of the technical invention and should not be regarded as specific limitations of the present invention.

[0086] Synthesis of Compound A7

[0087] The synthetic route of compound A7 is as follows:

[0088]

[0089] Synthesis of Compound A7-3

[0090] Compound A7-1 (10.00 g, 25.82 mmol), compound A7-2 (4.44 g, 28.40 mmol), tetrakis(triphenylphosphine)palladium (Pd(PP3)4, 0.60 g, 0.52 mmol), potassium carbonate (8.92 g, 64.55 mmol), tetrahydrofuran (THF, 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 75°C, and the reaction was carried out for 4 hours. The reaction was monitored by TLC (thin layer chromatography) (by volume ratio, ethyl acetate: n-hexane = 1:15 as the developing solvent). When compound A7-1 was completely consumed, the heating was stopped;

[0091] After the reaction was completed, a large amount of solid was precipitated, which was directly filtered to obtain 20 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 10 g of white solid. Toluene (200 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 A7-3 (8.37 g, mass purity: 99.71%, yield: 77.38%), and the mass spectrum result was: 419.12 (M+H).

[0092] Synthesis of Compound A7-6

[0093] Compound A7-4 (30.00 g, 150.68 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 (nBuLi) n-hexane solution (78.36 mL, 195.89 mmol, concentration 2.5 mol / L) was added dropwise. 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 for 1 hour. Finally, compound A7-5 (58.56 g, 226.03 mmol) was slowly added dropwise. The addition was completed in 10 minutes, and the temperature was maintained at -78 ° C for 1.5 hours. Monitoring by TLC (ethyl acetate: n-hexane = 1:20 as the developing solvent), compound A7-4 was completely consumed.

[0094] Deionized water (100 mL) was added dropwise to the system to quench the reaction. After warming to room temperature, the mixture 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. The sample was mixed with silica gel on a chromatography column and dry-coated. Purification was performed by silica gel column chromatography (200-300 mesh silica gel, ethyl acetate: n-hexane = 1:30 as eluent by volume). After elution, the mixture was concentrated under reduced pressure at 65°C for 1.5 hours to obtain a white solid as compound A7-6 (21.34 g, mass purity: 99.41%, yield: 37.34%). The mass spectrometry result was: 379.06 (M+H)

[0095] Synthesis of Compound A7-7

[0096] Compound A7-6 (21.00 g, 55.37 mmol) and dichloromethane (370 mL) were added into a 1000 mL three-necked round-bottom flask, and then the system was cooled to 0°C, and trifluoromethanesulfonic acid (TfOH, 16.62 g, 110.73 mmol) was added dropwise. The addition was completed over 15 minutes, and the temperature was maintained with stirring for 30 minutes. The reaction was monitored by TLC (ethyl acetate: n-hexane = 1:30 as the developing solvent), and compound A7-6 was completely consumed.

[0097] Deionized water was added dropwise to the system to quench the reaction (100 mL). The liquids were separated, and the sample was mixed with silica gel and dry-loaded onto the chromatography column. Purification was performed by silica gel column chromatography (200-300 mesh silica gel, ethyl acetate:n-hexane = 1:50 as eluent). After elution, the mixture was concentrated under reduced pressure at 65 °C for 2 hours to obtain a white solid compound A7-7 (10.74 g, mass purity: 99.75%, yield: 53.69%). The mass spectrum result was: 361.05 (M+H).

[0098] Synthesis of Compound A7-9

[0099] Compound A7-7 (10.50 g, 29.06 mmol), compound A7-8 (8.12 g, 31.97 mmol), 1,1-bis(diphenylphosphine)dichloropalladium iron (Pd(dppf)Cl2, 0.43 g, 0.58 mmol), potassium acetate (KOAc, 7.13 g, 72.66 mol), and 1,4-dioxane (1,4-Dioxane, 350 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 80 ° C for 4 hours. The reaction was monitored by TLC (ethyl acetate: n-hexane = 1:15 as the developing solvent). Compound A7-7 was completely consumed.

[0100] The temperature was lowered to 60°C, and the solvent was removed by concentration under reduced pressure. Ethyl acetate (500 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, ethyl acetate:n-hexane=1:15 as eluent). After elution, the mixture was concentrated under reduced pressure at 70°C for 1 hour to obtain a white solid as compound A7-9 (8.89 g, mass purity: 99.35%, yield: 74.91%), and the mass spectrum result was: 409.23 (M+H).

[0101] Synthesis of Compound A7

[0102] Compound A7-9 (8.00 g, 19.59 mmol), compound A7-3 (8.21 g, 19.59 mmol), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) (Pd(aMphos)Cl2, 0.28 g, 0.39 mmol), potassium carbonate (6.77 g, 48.98 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 6 hours. The reaction was monitored by TLC (ethyl acetate: n-hexane = 1:20 as the developing solvent). When compound A7-9 was completely consumed, the heating was stopped.

[0103] After the reaction, a large amount of solid was precipitated, which was directly filtered to obtain 13g of solid. Xylene (350mL) 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. 10g 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 temperature 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 A7 (9.04g, mass purity: 99.95%, yield: 69.40%). 9.04g of crude compound A7 was purified by sublimation to obtain sublimation pure compound A7 (7.23g, mass purity: 99.98%, yield: 79.97%), and the mass spectrum result was: 665.29 (M+H).

[0104] The NMR characterization results of compound A7 are: 1 H NMR(400MHz, CDCl3)δ8.39–8.31(m,2H),8.23(s,1H),8.17(t,J=2.9Hz,1H), 8.09(d,J=15.0Hz,1H),8.06–8.01(m,2H),7.98–7.87(m,4H),7.78(dd,J=15. 0,2.9Hz,1H),7.74–7.66(m,2H),7.65–7.44(m,10H),7.41–7.18(m,2H),6.9 6-6.76(m,4H),3.12(t,J=12.0Hz,2H),2.60-2.32(m,2H),1.90–1.61(m,2H).

[0105] Synthesis of Compound A36

[0106] The synthetic route of compound A36 is as follows:

[0107]

[0108] Synthesis of Compound A36-2

[0109] Referring to the synthesis and purification method of compound A7-9, it is only necessary to change the corresponding raw materials to obtain the target compound A36-2 (8.71 g, mass purity: 99.16%, yield: 74.07%), and the mass spectrum result is: 315.12 (M+H).

[0110] Synthesis of Compound A36-4

[0111] Referring to the synthesis and purification method of compound A7-3, it is only necessary to change the corresponding raw materials to obtain the target compound A36-4 (7.82 g, mass purity: 99.74%, yield: 68.93%), and the mass spectrum result is: 420.12 (M+H).

[0112] Synthesis of Compound A36

[0113] Referring to the synthesis and purification method of compound A7, only the corresponding raw materials need to be changed to obtain the target compound A36 (8.16 g, mass purity: 99.93%, yield: 71.49%). 8.16 g of crude compound A36 was purified by sublimation to obtain sublimation pure compound A36 (5.49 g, mass purity: 99.93%, yield: 67.28%), and the mass spectrum result was: 666.28 (M+H).

[0114] The NMR characterization results of compound A36 are: 1 H NMR (400MHz, CDCl3) δ8.44(d,J=2.9Hz,1H),8.41–8.31(m,4H),8.15(d,J=15.0Hz,1H),8.11–8.02(m,2H),7.94–7.87(m,2H),7.83-7.74(m,3H),7. 57–7.30(m,11H),7.24(t,J=14.8,3.2Hz,1H),6.97–6.87(m,2H),6.86–6 .76(m,2H),3.02(t,J=12.0Hz,2H),2.55–2.28(m,2H),1.89–1.60(m,2H).

[0115] Synthesis of Compound A38

[0116] The synthetic route of compound A38 is as follows:

[0117]

[0118] Synthesis of Compound A38-2

[0119] Referring to the synthesis and purification method of compound A7-6, it is only necessary to change the corresponding raw materials to obtain the target compound A38-2 (16.83 g, mass purity: 99.46%, yield: 29.45%), and the mass spectrum result is: 379.06 (M+H).

[0120] Synthesis of compound A38-3

[0121] Referring to the synthesis and purification method of compound A7-7, it is only necessary to change the corresponding raw materials to obtain the target compound A38-3 (7.94 g, mass purity: 99.39%, yield: 50.52%), and the mass spectrum result is: 361.05 (M+H).

[0122] Synthesis of Compound A38-4

[0123] Referring to the synthesis and purification method of compound A7-9, it is only necessary to change the corresponding raw materials to obtain the target compound A38-4 (6.72 g, mass purity: 99.24%, yield: 75.26%), and the mass spectrum result is: 409.23 (M+H).

[0124] Synthesis of Compound A38

[0125] Referring to the synthesis and purification method of compound A7, only the corresponding raw materials need to be changed to obtain the target compound A38 (7.03 g, mass purity: 99.95%, yield: 66.34%). 7.03 g of crude compound A38 was purified by sublimation to obtain sublimation pure compound A38 (4.96 g, mass purity: 99.94%, yield: 70.55%), and the mass spectrum result was: 666.28 (M+H).

[0126] The NMR characterization results of compound A38 are: 1 H NMR (400MHz, CDCl3) δ8.42–8.31(m,4H),8.19–8.12(m,1H),8.09–8.03(m,2H), 8.00(dd,J=14.8,3.1Hz,1H),7.90(dd,J=14.7,3.2Hz,1H),7.82–7.75(m,2H),7 .68(dd,J=14.9,3.2Hz,1H),7.58–7.30(m,12H),7.24(t,J=14.8,3.3Hz,1H),6 .97–6.77(m,4H),2.71(t,J=11.8Hz,2H),2.62-2.25(m,2H),1.91–1.59(m,2H).

[0127] Synthesis of Compound A66

[0128] The synthetic route of compound A66 is as follows:

[0129]

[0130] Synthesis of Compound A66-2

[0131] Referring to the synthesis and purification method of compound A7-3, it is only necessary to change the corresponding raw materials to obtain the target compound A66-2 (12.27 g, mass purity: 99.56%, yield: 75.64%), and the mass spectrum result is: 420.12 (M+H).

[0132] Synthesis of Compound A66

[0133] Referring to the synthesis and purification method of compound A7, only the corresponding raw materials need to be changed to obtain the target compound A66 (7.34 g, mass purity: 99.96%, yield: 66.75%). 7.34 g of crude compound A66 was purified by sublimation to obtain sublimation pure compound A66 (4.69 g, mass purity: 99.95%, yield: 63.96%), and the mass spectrum result was: 666.28 (M+H).

[0134] The NMR characterization results of compound A66 are: 1 H NMR(400MHz, CDCl3)δ8.41–8.31(m,6H),8.09(d,J=15.0Hz,1H),8.07–8.00(m,2 H),7.90(dd,J=14.7,3.2Hz,1H),7.78(dd,J=15.0,2.9Hz,1H),7.75–7.66(m,2H ),7.64–7.46(m,10H),7.39-7.30(m,1H),7.28-7.20(m,1H),6.95–6.87(m,2H), 6.86–6.77(m,2H),3.02(t,J=12.0Hz,2H),2.58–2.30(m,2H),1.89–1.61(m,2H).

[0135] Synthesis of compound A70

[0136] The synthetic route of compound A70 is as follows:

[0137]

[0138] Synthesis of Compound A70-2

[0139] Referring to the synthesis and purification method of compound A7-3, it is only necessary to change the corresponding raw materials to obtain the target compound A70-2 (12.27 g, mass purity: 99.56%, yield: 75.64%), and the mass spectrum result is: 420.12 (M+H).

[0140] Synthesis of Compound A70-4

[0141] Referring to the synthesis and purification method of compound A7-6, it is only necessary to change the corresponding raw materials to obtain the target compound A70-4 (17.83 g, mass purity: 99.31%, yield: 31.34%), and the mass spectrum result is: 381.04 (M+H).

[0142] Synthesis of Compound A70-5

[0143] Referring to the synthesis and purification method of compound A7-7, it is only necessary to change the corresponding raw materials to obtain the target compound A70-5 (10.36 g, mass purity: 99.64%, yield: 62.14%), and the mass spectrum result is: 363.03 (M+H).

[0144] Synthesis of Compound A70-6

[0145] Referring to the synthesis and purification method of compound A7-9, it is only necessary to change the corresponding raw materials to obtain the target compound A70-6 (8.12 g, mass purity: 99.42%, yield: 71.89%), and the mass spectrum result is: 411.21 (M+H).

[0146] Synthesis of compound A70

[0147] Referring to the synthesis and purification method of compound A7, only the corresponding raw materials need to be changed to obtain the target compound A70 (8.38 g, mass purity: 99.92%, yield: 64.36%). 8.38 g of crude compound A70 was purified by sublimation to obtain sublimation pure compound A70 (5.02 g, mass purity: 99.95%, yield: 59.90%), and the mass spectrum result was: 668.26 (M+H).

[0148] The NMR characterization results of compound A70 are: 1 H NMR(400MHz, CDCl3)δ9.00(s,1H),8.87–8.70(m,5H),7.92–7.81(m,4H),7.76–7.51(m,12H),7.41(t,J=7.3Hz,1H),7.36-7.27(m,2H ),7.10(dd,J=11.1,4.1Hz,1H),6.98(d,J=8.2Hz,1H),6.65(t,J=7.4Hz,1H),6.41(d,J=7.8Hz,1H),4.64(s,2H),2.42-2.26(m,2H).

[0149] Figure 1 Compound A70 of the present application 1 H NMR spectrum, where “f1 (ppm)” represents the chemical shift.

[0150] Synthesis of compound A109

[0151] The synthetic route of compound A109 is as follows:

[0152]

[0153] Synthesis of Compound A109-2

[0154] Referring to the synthesis and purification method of compound A7-3, it is only necessary to change the corresponding raw materials to obtain the target compound A109-2 (11.26 g, mass purity: 99.49%, yield: 74.93%), and the mass spectrum result is: 402.05 (M+H).

[0155] Synthesis of Compound A109-4

[0156] Referring to the synthesis and purification method of compound A7-3, it is only necessary to change the corresponding raw materials to obtain the target compound A109-4 (9.12 g, mass purity: 99.52%, yield: 73.18%), and the mass spectrum result is: 448.15 (M+H).

[0157] Synthesis of Compound A109-6

[0158] Referring to the synthesis and purification method of compound A7-6, it is only necessary to change the corresponding raw materials to obtain the target compound A109-6 (16.09 g, mass purity: 99.57%, yield: 29.31%), and the mass spectrum result is: 397.02 (M+H).

[0159] Synthesis of Compound A109-7

[0160] Referring to the synthesis and purification method of compound A7-7, it is only necessary to change the corresponding raw materials to obtain the target compound A109-7 (7.46 g, mass purity: 99.45%, yield: 48.83%), and the mass spectrum result is: 379.01 (M+H).

[0161] Synthesis of Compound A109-8

[0162] Referring to the synthesis and purification method of compound A7-9, it is only necessary to change the corresponding raw materials to obtain the target compound A109-8 (5.97 g, mass purity: 99.61%, yield: 75.87%), and the mass spectrum result is: 427.18 (M+H).

[0163] Synthesis of compound A109

[0164] Referring to the synthesis and purification method of compound A7, only the corresponding raw materials need to be changed to obtain the target compound A109 (6.43 g, mass purity: 99.97%, yield: 70.02%). 6.43 g of crude compound A109 was purified by sublimation to obtain sublimation pure compound A109 (4.29 g, mass purity: 99.94%, yield: 66.71%), and the mass spectrum result was: 712.27 (M+H).

[0165] The NMR characterization results of compound A109 are: 1 H NMR (400MHz, CDCl3) δ8.42–8.31(m,4H),8.09(d,J=15.0Hz,1H),8.02(d,J=2.9H z,1H),7.97(d,J=2.7Hz,1H),7.95–7.82(m,4H),7.78(dd,J=15.0,2.9Hz,1H),7. 64–7.56(m,3H),7.54–7.45(m,6H),7.39–7.30(m,2H),7.28-7.18(m,2H),7.17-7 .00(m,2H),3.60(t,J=11.1Hz,2H),3.15-2.85(m,2H),2.58(s,3H),2.23(s,3H).

[0166] Synthesis of compound A152

[0167] The synthetic route of compound A152 is as follows:

[0168]

[0169] Synthesis of Compound A152-2

[0170] Referring to the synthesis and purification method of compound A7-3, it is only necessary to change the corresponding raw materials to obtain the target compound A152-2 (12.27 g, mass purity: 99.39%, yield: 71.41%), and the mass spectrum result is: 460.15 (M+H).

[0171] Synthesis of Compound A152

[0172] Referring to the synthesis and purification method of compound A7, only the corresponding raw materials need to be changed to obtain the target compound A152 (10.94 g, mass purity: 99.94%, yield: 59.41%). 10.94 g of crude compound A152 was purified by sublimation to obtain sublimation pure compound A152 (6.72, mass purity: 99.95%, yield: 61.42%), and the mass spectrum result was: 706.31 (M+H).

[0173] The NMR characterization results of compound A152 are: 1 H NMR (400MHz, CDCl3) δ8.42–8.31(m,4H),8.24(d,J=2.9Hz,1H),8.09(d,J=15.0Hz,3H),8.00( dd,J=11.2,2.9Hz,2H),7.90(dd,J=14.7,3.2Hz,1H),7.78(dd,J=15.0,2.9Hz,3H),7.59(dd, J=14.7,3.3Hz,1H),7.55–7.46(m,6H),7.39-7.30(m,1H),7.24(t,J=14.9,3.3Hz,1H),6.98– 6.76(m,4H),3.08(t,J=12.0Hz,2H),2.60-2.29(m,2H),1.89-1.70(m,2H),1.70-1.67(m,6H).

[0174] Synthesis of Compound A167

[0175] The synthetic route of compound A167 is as follows:

[0176]

[0177] Synthesis of Compound A167-2

[0178] Referring to the synthesis and purification method of compound A7-9, it is only necessary to change the corresponding raw materials to obtain the target compound A167-2 (8.64 g, mass purity: 99.39%, yield: 73.47%), and the mass spectrum result is: 315.12 (M+H).

[0179] Synthesis of Compound A167-4

[0180] Referring to the synthesis and purification method of compound A7-3, it is only necessary to change the corresponding raw materials to obtain the target compound A167-4 (8.37 g, mass purity: 99.71%, yield: 65.92%), and the mass spectrum result is: 470.13 (M+H).

[0181] Synthesis of Compound A167-6

[0182] Referring to the synthesis and purification method of compound A7-6, it is only necessary to change the corresponding raw materials to obtain the target compound A167-6 (14.73 g, mass purity: 99.36%, yield: 25.89%), and the mass spectrum result is: 381.04 (M+H).

[0183] Synthesis of Compound A167-7

[0184] Referring to the synthesis and purification method of compound A7-7, it is only necessary to change the corresponding raw materials to obtain the target compound A167-7 (7.15 g, mass purity: 99.73%, yield: 53.60%), and the mass spectrum result is: 363.03 (M+H).

[0185] Synthesis of Compound A167-8

[0186] Referring to the synthesis and purification method of compound A7-9, it is only necessary to change the corresponding raw materials to obtain the target compound A167-8 (5.77 g, mass purity: 99.67%, yield: 72.97%), and the mass spectrum result is: 411.21 (M+H).

[0187] Synthesis of Compound A167

[0188] Referring to the synthesis and purification method of compound A7, only the corresponding raw materials need to be changed to obtain the target compound A167 (6.76 g, mass purity: 99.97%, yield: 70.25%). 6.76 g of crude compound A167 was purified by sublimation to obtain sublimation pure compound A167 (4.07 g, mass purity: 99.96%, yield: 60.21%), and the mass spectrum result was: 718.28 (M+H).

[0189] The NMR characterization results of compound A167 are as follows: 1 H NMR(400MHz, CDCl3)δ9.09(t,J=3.0Hz,1H),8.53–8.45(m,2H),8.42–8.30(m,2H),8.20–8.11(m,2H),8.11–7.96(m,3H),7.90(dd,J= 14.7,3.2Hz,1H),7.83–7.74(m,3H),7.66–7.30(m,12H),7.28-7.20(m,2H),7.02–6.78(m,3H),4.32–4.15(m,2H),2.87-2.54(m,2H).

[0190] Synthesis of Compound A199

[0191] The synthetic route of compound A199 is as follows:

[0192]

[0193] Synthesis of Compound A199-3

[0194] Compound A199-1 (30.00 g, 177.28 mmol), compound A199-2 (18.31 g, 212.73 mmol), cuprous iodide (1.69 g, 8.86 mmol), trifluoromethanesulfonic acid (26.60 g, 177.28 mmol), trifluoromethanesulfonic anhydride (50.01 g, 177.26 mmol), 1,2-dichloroethane (300 mL) were added into a 1000 mL three-necked round-bottom flask, the oil temperature was raised to 120 ° C, the reaction was carried out for 24 hours, and TLC monitoring (ethyl acetate: n-hexane = 1:50 as the developing solvent) was performed. When compound A199-1 was completely consumed, the heating was stopped.

[0195] Deionized water was added dropwise to the system to quench the reaction (100 mL), the liquids were separated, the sample was mixed with silica gel on the chromatography column and dry loaded, and purified by silica gel column chromatography (200-300 mesh silica gel, ethyl acetate: n-hexane = 1:50 as eluent), after elution, the mixture was concentrated under reduced pressure at 50 ° C for 2 hours to obtain a white solid compound A199-3 (13.72 g, mass purity: 99.38%, yield: 34.66%), and the mass spectrum result was: 224.10 (M+H)

[0196] Synthesis of Compound A199-5

[0197] Referring to the synthesis and purification method of compound A7-6, it is only necessary to change the corresponding raw materials to obtain the target compound A199-5 (11.78 g, mass purity: 99.59%, yield: 47.30%), and the mass spectrum result is: 412.14 (M+H).

[0198] Synthesis of Compound A199-6

[0199] Referring to the synthesis and purification method of compound A7-7, it is only necessary to change the corresponding raw materials to obtain the target compound A199-6 (6.34 g, mass purity: 99.64%, yield: 57.65%), and the mass spectrum result is: 394.13 (M+H).

[0200] Synthesis of Compound A199-7

[0201] Referring to the synthesis and purification method of compound A7-9, it is only necessary to change the corresponding raw materials to obtain the target compound A199-7 (5.61 g, mass purity: 99.33%, yield: 75.87%), and the mass spectrum result is: 486.25 (M+H).

[0202] Synthesis of compound A199

[0203] Referring to the synthesis and purification method of compound A7, only the corresponding raw materials need to be changed to obtain the target compound A199 (5.37 g, mass purity: 99.95%, yield: 63.81%). 5.37 g of compound A199 (3.67 g, mass purity: 99.97%, yield: 68.34%), the mass spectrum result is: 743.31 (M+H).

[0204] The NMR characterization results of compound A199 are as follows: 1 H NMR (400MHz, CDCl3) δ8.46(d,J=2.9Hz,1H),8.41–8.30(m,5H),8.15(d,J=15.0Hz,1H),8.06(dd,J=15.0,2.9Hz,1H),7.90(dd,J=14.7,3.2Hz,1H),7. 83–7.75(m,2H),7.71-7.65(m,2H),7.58–7.29(m,15H),7.29–7.14(m,4H) ,7.10–7.01(m,1H),6.97-6.89(m,1H),3.7-3.47(m,2H),2.82-2.5(m,2H).

[0205] Synthesis of Compound A246

[0206] The synthetic route of compound A246 is as follows:

[0207]

[0208] Synthesis of Compound A246-2

[0209] Referring to the synthesis and purification method of compound A7-6, it is only necessary to change the corresponding raw materials to obtain the target compound A246-2 (15.70 g, mass purity: 99.46%, yield: 36.40%), and the mass spectrum result is: 429.08 (M+H).

[0210] Synthesis of Compound A246-3

[0211] Referring to the synthesis and purification method of compound A7-7, it is only necessary to change the corresponding raw materials to obtain the target compound A246-3 (8.37 g, mass purity: 99.31%, yield: 58.24%), and the mass spectrum result is: 411.07 (M+H).

[0212] Synthesis of Compound A246-4

[0213] Referring to the synthesis and purification method of compound A7-9, it is only necessary to change the corresponding raw materials to obtain the target compound A246-4 (6.82 g, mass purity: 99.52%, yield: 76.50%), and the mass spectrum result is: 459.24 (M+H).

[0214] Synthesis of Compound A246

[0215] Referring to the synthesis and purification method of compound A5, only the corresponding raw materials need to be changed to obtain the target compound A246 (7.18 g, mass purity: 99.95%, yield: 70.73%). 7.18 g of crude compound A246 was purified by sublimation to obtain sublimation pure compound A246 (4.37 g, mass purity: 99.95%, yield: 60.86%), and the mass spectrum result was: 716.31 (M+H).

[0216] The NMR characterization results of compound A246 are: 1 H NMR (400MHz, CDCl3) δ8.95–8.85(m,1H),8.47–8.30(m,7H),8.16(d,J=2.9Hz,1 H),8.04(t,J=2.9Hz,1H),7.97(dd,J=14.9,3.0Hz,1H),7.85–7.77(m,1H),7.7 4-7.57(m,6H),7.54–7.45(m,6H),7.37–7.24(m,2H),7.09(d,J=15.0Hz,1H),6 .98–6.76(m,4H),3.10(t,J=12.0Hz,2H),2.63-2.32(m,2H),1.90–1.61(m,2H).

[0217] Synthesis of Compound A266

[0218] The synthetic route of compound A266 is as follows:

[0219]

[0220] Synthesis of Compound A266-2

[0221] Referring to the synthesis and purification method of compound A7-3, it is only necessary to change the corresponding raw materials to obtain the target compound A266-2 (14.36 g, mass purity: 99.47%, yield: 75.27%), and the mass spectrum result is: 402.05 (M+H).

[0222] Synthesis of Compound A266-3

[0223] Referring to the synthesis and purification method of compound A7-3, it is only necessary to change the corresponding raw materials to obtain the target compound A266-3 (10.71 g, mass purity: 99.59%, yield: 62.18%), and the mass spectrum result is: 434.13 (M+H).

[0224] Synthesis of Compound A266

[0225] Referring to the synthesis and purification method of compound A7, only the corresponding raw materials need to be changed to obtain the target compound A266 (6.49 g, mass purity: 99.93%, yield: 68.97%). 6.49 g of crude compound A266 was purified by sublimation to obtain sublimation pure compound A266 (3.97 g, mass purity: 99.95%, yield: 61.17%), and the mass spectrum result was: 730.31 (M+H).

[0226] The NMR characterization results of compound A266 are: 1 H NMR (400MHz, CDCl3) δ8.93–8.85(m,1H),8.62(dd,J=14.9,3.0Hz,1H),8.43(d,J=15.0Hz,1H),8.40–8 .31(m,4H),8.21(d,J=2.9Hz,1H),8.16(d,J=2.9Hz,1H),8.04(t,J=2.9Hz,1H),7.97(dd,J=14.9,3.0 Hz,1H),7.84–7.77(m,1H),7.75–7.57(m,5H),7.55–7.45(m,6H),7.37–7.24(m,2H),7.09(d,J=15.0H z,1H),6.97–6.77(m,4H),3.13(t,J=12.0Hz,2H),2.61–2.33(m,2H),2.23(s,3H),1.90–1.62(m,2H).

[0227] Synthesis of Compound A284

[0228] The synthetic route of compound A284 is as follows:

[0229]

[0230] Synthesis of Compound A284-2

[0231] Referring to the synthesis and purification method of compound A7-6, it is only necessary to change the corresponding raw materials to obtain the target compound A284-2 (11.73 g, mass purity: 99.58%, yield: 36.45%), and the mass spectrum result is: 431.06 (M+H).

[0232] Synthesis of Compound A284-3

[0233] Referring to the synthesis and purification method of compound A7-7, it is only necessary to change the corresponding raw materials to obtain the target compound A284-3 (6.36 g, mass purity: 99.31%, yield: 57.71%), and the mass spectrum result is: 413.05 (M+H).

[0234] Synthesis of Compound A284-4

[0235] Referring to the synthesis and purification method of compound A7-3, it is only necessary to change the corresponding raw materials to obtain the target compound A284-4 (4.98 g, mass purity: 99.79%, yield: 77.10%), and the mass spectrum result is: 445.13 (M+H).

[0236] Synthesis of Compound A284-5

[0237] Referring to the synthesis and purification method of compound A7-9, it is only necessary to change the corresponding raw materials to obtain the target compound A284-5 (4.51 g, mass purity: 99.64%, yield: 76.34%), and the mass spectrum result is: 537.25 (M+H).

[0238] Synthesis of Compound A284-7

[0239] Referring to the synthesis and purification method of compound A7-3, it is only necessary to change the corresponding raw materials to obtain the target compound A284-7 (6.04 g, mass purity: 99.43%, yield: 76.51%), and the mass spectrum result is: 421.99 (M+H).

[0240] Synthesis of Compound A284-8

[0241] Referring to the synthesis and purification method of compound A7-9, it is only necessary to change the corresponding raw materials to obtain the target compound A284-8 (4.83 g, mass purity: 99.65%, yield: 72.43%), and the mass spectrum result is: 470.17 (M+H).

[0242] Synthesis of Compound A284-10

[0243] Referring to the synthesis and purification method of compound A7-3, it is only necessary to change the corresponding raw materials to obtain the target compound A284-10 (3.15 g, mass purity: 99.49%, yield: 78.13%), and the mass spectrum result is: 421.11 (M+H).

[0244] Synthesis of Compound A284

[0245] Referring to the synthesis and purification method of compound A7, only the corresponding raw materials need to be changed to obtain the target compound A284 (4.01 g, mass purity: 99.92%, yield: 70.77%). 4.01 g of crude compound A284 was purified by sublimation to obtain sublimation pure compound A284 (2.37 g, mass purity: 99.95%, yield: 59.10%), and the mass spectrum result was: 795.30 (M+H).

[0246] The NMR characterization results of compound A284 are as follows: 1 H NMR(400MHz, CDCl3)δ8.93–8.86(m,1H),8.66(d,J=2.9Hz,1H),8.42–8.31(m,5H),8.22 (t,J=2.9Hz,1H),8.15(d,J=15.0Hz,1H),8.06(dd,J=15.0,2.9Hz,1H),7.97(dd,J=14.8 ,3.1Hz,1H),7.85–7.78(m,1H),7.75–7.55(m,6H),7.54–7.45(m,6H),7.43–7.21(m,4H ),7.17–7.05(m,2H),7.00–6.80(m,4H),4.32(t,J=10.0,2.9Hz,2H),3.05-2.55(m,2H).

[0247] Synthesis of Compound A343

[0248] The synthetic route of compound A343 is as follows:

[0249]

[0250] Synthesis of Compound A343-2

[0251] Referring to the synthesis and purification method of compound A7-3, it is only necessary to change the corresponding raw materials to obtain the target compound A343-2 (11.36 g, mass purity: 99.46%, yield: 71.95%), and the mass spectrum result is: 421.99 (M+H).

[0252] Synthesis of Compound A343-4

[0253] Referring to the synthesis and purification method of compound A7-3, it is only necessary to change the corresponding raw materials to obtain the target compound A343-4 (8.33 g, mass purity: 99.51%, yield: 68.11%), and the mass spectrum result is: 470.13 (M+H).

[0254] Synthesis of Compound A343-6

[0255] Referring to the synthesis and purification method of compound A7-6, it is only necessary to change the corresponding raw materials to obtain the target compound A343-6 (14.27 g, mass purity: 99.36%, yield: 33.08%), and the mass spectrum result is: 429.08 (M+H).

[0256] Synthesis of Compound A343-7

[0257] Referring to the synthesis and purification method of compound A7-7, it is only necessary to change the corresponding raw materials to obtain the target compound A343-7 (6.82 g, mass purity: 99.78%, yield: 50.85%), and the mass spectrum result is: 411.07 (M+H).

[0258] Synthesis of Compound A343-8

[0259] Referring to the synthesis and purification method of compound A7-9, it is only necessary to change the corresponding raw materials to obtain the target compound A343-8 (5.46, mass purity: 99.24%, yield: 75.38%), and the mass spectrum result is: 459.24 (M+H).

[0260] Synthesis of Compound A343

[0261] Referring to the synthesis and purification method of compound A7, only the corresponding raw materials need to be changed to obtain the target compound A343 (5.54 g, mass purity: 99.96%, yield: 66.31%). 5.54 g of crude compound A343 was purified by sublimation to obtain sublimation pure compound A343 (3.76 g, mass purity: 99.96%, yield: 68.01%), and the mass spectrum result was: 766.31 (M+H).

[0262] The NMR characterization results of compound A343 are: 1 H NMR (400MHz, CDCl3) δ8.41–8.31(m,5H),8.24(d,J=2.9Hz,1H),8.20–7.96(m,8 H),7.84-7.76(m,2H),7.73(d,J=14.3Hz,1H),7.64–7.54(m,4H),7.54–7.48(m, 6H),7.48–7.43(m,1H),7.42–7.36(m,1H),6.96–6.77(m,4H),2.83(dd,J=16.8, 6.9Hz,2H),2.80–2.70(m,1H),2.43(t,J=24.9,11.6Hz,1H),1.89–1.62(m,2H).

[0263] Synthesis of Compound A372

[0264] The synthetic route of compound A372 is as follows:

[0265]

[0266] Synthesis of Compound A372-3

[0267] Referring to the synthesis and purification method of compound A7-3, it is only necessary to change the corresponding raw materials to obtain the target compound A372-3 (9.62 g, mass purity: 99.72%, yield: 71.60%), and the mass spectrum result is: 586.16 (M+H).

[0268] Synthesis of compound A372

[0269] Referring to the synthesis and purification method of compound A7, only the corresponding raw materials need to be changed to obtain the target compound A372 (7.16 g, mass purity: 99.90%, yield: 70.80%). 7.16 g of crude compound A372 was purified by sublimation to obtain sublimation pure compound A372 (5.17 g, mass purity: 99.95%, yield: 72.21%), and the mass spectrum result was: 882.34 (M+H).

[0270] The NMR characterization results of compound A372 are: 1 H NMR (400MHz, CDCl3) δ9.23(t,J=2.9Hz,1H),8.82(t,J=3.0Hz,1H),8.47–8.31(m,4H),8.18(d,J=3.0Hz,1H),8.05–7.94(m,4H),7.84-7.78(m,1 H),7.74–7.66(m,3H),7.66–7.26(m,18H),6.95–6.87(m,2H),6.85–6.7 7(m,2H),3.14(t,J=12.0Hz,2H),2.64–2.18(m,2H),1.90–1.61(m,2H).

[0271] Synthesis of compound A390

[0272] The synthetic route of compound A390 is as follows:

[0273]

[0274] Synthesis of Compound A390-2

[0275] Referring to the synthesis and purification method of compound A7-3, it is only necessary to change the corresponding raw materials to obtain the target compound A390-2 (9.72 g, mass purity: 99.44%, yield: 75.28%), and the mass spectrum result is: 398.10 (M+H).

[0276] Synthesis of Compound A390-3

[0277] Referring to the synthesis and purification method of compound A7-3, it is only necessary to change the corresponding raw materials to obtain the target compound A390-3 (8.14 g, mass purity: 99.67%, yield: 69.74%), and the mass spectrum result is: 430.18 (M+H).

[0278] Synthesis of compound A390

[0279] Referring to the synthesis and purification method of compound A7, only the corresponding raw materials need to be changed to obtain the target compound A390 (6.59 g, mass purity: 99.94%, yield: 65.38%). 6.59 g of crude compound A390 was purified by sublimation to obtain sublimation pure compound A390 (4.11 g, mass purity: 99.96%, yield: 62.36%), and the mass spectrum result was: 676.35 (M+H).

[0280] The NMR characterization results of compound A390 are: 1 H NMR (400MHz, CDCl3) δ8.41-8.35(m,1H),8.32(t,J=3.0Hz,1H),8.09(d,J=15.0Hz,1H ),8.06–8.00(m,2H),7.90(dd,J=14.7,3.2Hz,1H),7.78(dd,J=15.0,2.9Hz,1H),7.74 –7.66(m,2H),7.64–7.53(m,4H),7.39-7.30(m,1H),7.28-7.20(m,1H),6.97–6.87(m, 2H),6.86–6.77(m,2H),3.02(t,J=12.0Hz,2H),2.59-2.27(m,2H),1.90–1.61(m,2H).

[0281] Synthesis of compound A402

[0282] The synthetic route of compound A402 is as follows:

[0283]

[0284] Synthesis of Compound A402-2

[0285] Compound A402-1 (50.00 g, 192.97 mmol), platinum dioxide (4.38 g, 19.30 mmol) and heavy water (500 ml) were added to a 1000 ml pressure reactor, and the vacuum argon gas was replaced three times. The temperature was raised to 250° C. and the reaction was carried out for 20 hours.

[0286] Cool to room temperature, add dichloromethane (300 ml), wash three times with deionized water (100 ml * 3), separate, mix with silica gel and dry-load onto column, purify by silica gel column chromatography (200-300 mesh silica gel, n-hexane: dichloromethane = 5:1 as eluent), after elution, concentrate under reduced pressure at 60°C for 1 hour to obtain the target compound A402-2 (30.19 g, purity: 99.30%, yield: 58.78%). Mass spectrum: 266.01 (M+H).

[0287] Synthesis of Compound A402-3

[0288] Referring to the synthesis and purification method of compound A7-6, it is only necessary to change the corresponding raw materials to obtain the target compound A343-3 (35.45 g, purity: 99.28%, yield: 35.45%), mass spectrum: 386.11 (M+H).

[0289] Synthesis of Compound A402-4

[0290] Referring to the synthesis and purification method of compound A7-7, it is only necessary to change the corresponding raw materials to obtain the target compound A402-4 (7.62 g, purity: 99.62%, yield: 59.21%), mass spectrum: 368.10 (M+H).

[0291] Synthesis of Compound A402-5

[0292] Referring to the synthesis and purification method of compound A7-9, it is only necessary to change the corresponding raw materials to obtain the target compound A402-5 (6.45 g, purity: 99.30%, yield: 76.24%), mass spectrum: 416.27 (M+H).

[0293] Synthesis of compound A402

[0294] Referring to the synthesis and purification method of compound A7, only the corresponding raw materials need to be changed to obtain the target compound A402 (7.21 g, purity: 99.90%, yield: 74.18%). 7.21 g of crude compound A402 was purified by sublimation to obtain sublimation pure compound A402 (5.41 g, purity: 99.96%, yield: 75.03%), and the mass spectrum result was: 673.33 (M+H).

[0295] The NMR characterization results of compound A402 are:1 H NMR (400MHz, CDCl3) δ8.42–8.32(m,6H),8.18(t,J=3.0Hz,1H),7.75–7.66(m,2H),7.64–7.58(m,3H),7.54–7. 46(m,6H),6.96–6.87(m,2H),6.86–6.77(m,2H),3.02(t,J=12.0Hz,2H),2.58–2.30(m,2H),1.89-1.64(m,2H).

[0296] Synthesis of Compound A414

[0297] The synthetic route of compound A414 is as follows:

[0298]

[0299] Synthesis of Compound A414-3

[0300] Referring to the synthesis and purification method of compound A7-3, it is only necessary to change the corresponding raw materials to obtain the target compound A414-3 (9.64 g, mass purity: 99.50%, yield: 74.82%), and the mass spectrum result is: 271.98 (M+H).

[0301] Synthesis of Compound A414-4

[0302] Referring to the synthesis and purification method of compound A7-9, it is only necessary to change the corresponding raw materials to obtain the target compound A414-4 (8.17 g, mass purity: 99.22%, yield: 77.41%), and the mass spectrum result is: 320.16 (M+H).

[0303] Synthesis of Compound A414-5

[0304] Referring to the synthesis and purification method of compound A7-3, it is only necessary to change the corresponding raw materials to obtain the target compound A414-5 (7.35 g, mass purity: 99.76%, yield: 69.11%), and the mass spectrum result is: 425.15 (M+H).

[0305] Synthesis of Compound A414-7

[0306] Referring to the synthesis and purification method of compound A7-6, it is only necessary to change the corresponding raw materials to obtain the target compound A414-7 (13.88 g, mass purity: 99.45%, yield: 36.43%), and the mass spectrum result is: 379.06 (M+H).

[0307] Synthesis of Compound A414-8

[0308] Referring to the synthesis and purification method of compound A7-7, it is only necessary to change the corresponding raw materials to obtain the target compound A414-8 (6.92 g, mass purity: 99.63%, yield: 53.82%), and the mass spectrum result is: 361.05 (M+H).

[0309] Synthesis of Compound A414-9

[0310] Referring to the synthesis and purification method of compound A7-9, it is only necessary to change the corresponding raw materials to obtain the target compound A414-9 (5.11 g, mass purity: 99.37%, yield: 69.55%), and the mass spectrum result is: 409.23 (M+H).

[0311] Synthesis of Compound A414

[0312] Referring to the synthesis and purification method of compound A7, only the corresponding raw materials need to be changed to obtain the target compound A414 (5.24 g, mass purity: 99.97%, yield: 63.79%). 5.24 g of crude compound A414 was purified by sublimation to obtain sublimation pure compound A414 (3.11 g, mass purity: 99.97%, yield: 59.35%), and the mass spectrum result was: 671.31 (M+H).

[0313] The NMR characterization results of compound A414 are as follows: 1 H NMR(400MHz, CDCl3) δ8.46(d,J=2.9Hz,1H),8.41–8.33(m,4H),8.32(t,J=4.7Hz,1H),8.15(d,J=15.0Hz, 1H),8.06(dd,J=15.0,2.9Hz,1H),7.90(dd,J=14.7,3.2Hz,1H),7.68(dd,J=15.0,2.9Hz,1H),7.60(dd,J= 14.7,3.3Hz,1H),7.55–7.46(m,6H),7.41(d,J=15.0Hz,1H),7.38-7.30(m,1H),7.28-7.19(m,1H),6.95–6.87(m,2H),6.86–6.77(m,2H),3.05(t,J=12.0Hz,2H),2.57–2.30(m,2H),1.89–1.61(m,2H). Synthesis of compound A418

[0314] The synthetic route of compound A418 is as follows:

[0315]

[0316] Synthesis of Compound A418-3

[0317] Referring to the synthesis and purification method of compound A7-3, it is only necessary to change the corresponding raw materials to obtain the target compound A418-3 (13.47 g, purity: 99.56%, yield: 70.61%), mass spectrum: 316.97 (M+H).

[0318] Synthesis of Compound A418-5

[0319] Referring to the synthesis and purification method of compound A7-6, it is only necessary to change the corresponding raw materials to obtain the target compound A418-5 (8.73 g, purity: 99.23%, yield: 51.65%), mass spectrum: 413.16 (M+H).

[0320] Synthesis of Compound A418-6

[0321] Referring to the synthesis and purification method of compound A7-7, it is only necessary to change the corresponding raw materials to obtain the target compound A418-6 (5.20 g, purity: 99.49%, yield: 63.97%), mass spectrum: 395.15 (M+H).

[0322] Synthesis of Compound A418-7

[0323] Referring to the synthesis and purification method of compound A7-9, it is only necessary to change the corresponding raw materials to obtain the target compound A418-7 (4.81 g, purity: 99.15%, yield: 78.10%), mass spectrum: 487.27 (M+H).

[0324] Synthesis of Compound A418

[0325] Referring to the synthesis and purification method of compound A7, only the corresponding raw materials need to be changed to obtain the target compound A418 (4.18 g, purity: 99.92%, yield: 70.39%). 4.18 g of crude compound A418 was purified by sublimation to obtain sublimation pure compound A418 (2.86 g, purity: 99.92%, yield: 68.42%), mass spectrum: 602.33 (M+H).

[0326] The NMR characterization results of compound A418 are as follows: 1H NMR (400MHz, CDCl3) δ8.93–8.86(m,1H),8.40(dd,J=25.6,9.0Hz,2H),7.97(dd,J=14.9,3.0Hz,1H),7.86–7.78(m,1H),7.64(dd,J=15.0,3.1Hz,1H),7 .35–7.26(m,2H),7.09(d,J=15.0Hz,1H),6.95–6.87(m,2H),6.86–6.78(m, 2H),2.66-2.36(m,2H),1.91-1.78(m,1H),1.64-1.53(m,1H),0.91(s,6H).

[0327] Synthesis of Compound A446

[0328] The synthetic route of compound A446 is as follows:

[0329]

[0330] Synthesis of Compound A446-3

[0331] Add magnesium chips (1.71g, 70.50mmol) to a 500ml three-necked round-bottom flask, dissolve compound A446-1 (28.53g, 119.30mmol) in tetrahydrofuran (250ml) and add to a 500ml constant pressure dropping funnel; replace the entire device with nitrogen three times, drop the organic phase into the three-necked round-bottom flask, heat to 60 degrees, and control the dropping speed (dropping is completed within 1 hour). After the dropwise addition is completed, continue to maintain 60 degrees for 2 hours, cool to room temperature, and set aside the Grignard reagent.

[0332] Compound A446-2 (10.00 g, 54.23 mmol) was added to a 1000 ml three-necked round-bottom flask, dissolved with tetrahydrofuran (200 ml), and the Grignard reagent was added to a 500 ml constant pressure dropping funnel. After the entire device was replaced with nitrogen three times, the temperature was lowered to about -5-0 degrees, and the Grignard reagent was added dropwise (maintaining the temperature for 1 hour). After the addition was completed, the temperature was naturally raised to room temperature, and then heated to 50 degrees for 2 hours, and then cooled to room temperature, and 5%-10% hydrochloric acid (100 ml) was added to quench.

[0333] After the reaction was quenched, tetrahydrofuran was spin-dried, toluene (400 ml) was added, it was passed through diatomaceous earth (10 g), and it was rinsed with toluene (200 ml) and then dried. The organic phase was washed with deionized water until neutral, dried with anhydrous magnesium sulfate for 0.5 h, and then n-hexane (150 ml) was added, passed through silica gel (60 g, 200-300 mesh chromatography column silica gel), and rinsed with toluene: n-hexane = 4:1 as the developing agent, about 200 ml. The organic phase was concentrated to about 20 ml, 150 ml of n-hexane was added, stirred at room temperature for 1 hour, filtered, and vacuum dried for 3 hours to obtain a light yellow solid as compound A446-3 (16.42 g, purity: 99.01%, yield: 70.09%), mass spectrum: 432.21 (M+H).

[0334] Synthesis of Compound A446-4

[0335] Referring to the synthesis and purification method of compound A7-3, it is only necessary to change the corresponding raw materials to obtain the target compound A446-4 (9.38 g, purity: 99.72%, yield: 69.36%), mass spectrum: 584.28 (M+H).

[0336] Synthesis of Compound A446

[0337] Referring to the synthesis and purification method of compound A7, only the corresponding raw materials need to be changed to obtain the target compound A446 (7.30 g, purity: 99.95%, yield: 72.44%). 7.30 g of crude compound A446 was purified by sublimation to obtain sublimation pure compound A446 (4.67 g, purity: 99.97%, yield: 63.96%), and the mass spectrum result was: 837.48 (M+H).

[0338] The NMR characterization results of compound A446 are: 1 H NMR (400MHz, CDCl3) δ8.61–8.54(m,4H),8.40-8.35(m,1H),8.32(t,J=3.0Hz, 1H),8.02(t,J=2.9Hz,1H),7.74–7.66(m,2H),7.64–7.54(m,7H),6.96–6.87(m ,2H),6.86–6.78(m,2H),3.09(t,J=12.0Hz,2H),2.64(dd,J=42.8,21.4Hz,2H) ,2.55–2.26(m,2H),2.21–1.99(m,4H),1.88–1.61(m,6H),1.58–1.32(m,12H).

[0339] Application example: Fabrication of organic electroluminescent devices

[0340] As attached Figure 2 As shown, an organic electroluminescent device includes a stacked glass substrate 1, an anode 2, a hole injection layer 3, a first hole transport layer 4 (HTL1), a second hole transport layer 5 (HTL2), a light-emitting layer 6, a hole blocking layer 7 (HBL), an electron transport layer 8 (ETL), and a cathode 9.

[0341] A glass substrate 1 having an ITO transparent electrode (anode 2) on its surface is provided, wherein the thickness of the ITO transparent electrode is 100 nm;

[0342] The glass substrate 1 was ultrasonically cleaned in ethanol for 10 minutes, then dried at 150° C., and then treated with N2 plasma for 30 minutes;

[0343] Compound HATCN is evaporated on the surface of one side of the ITO transparent electrode (anode 2) to form a hole injection layer 3, and the thickness of the hole injection layer 3 is 5 nm;

[0344] Compound HTM1 is evaporated on the surface of one side of the hole injection layer 3 to form a first hole transport layer 4, and the thickness of the first hole transport layer 4 is 60 nm;

[0345] Compound HTM2 is evaporated on the surface of one side of the first hole transport layer 4 to form a second hole transport layer 5, and the thickness of the second hole transport layer 5 is 10 nm;

[0346] The host material and the guest material are co-evaporated on the surface of one side of the second hole transport layer 5 to form a light-emitting layer 6, wherein the weight ratio of the host material to the guest material is 98%:2%; the thickness of the light-emitting layer is 25nm;

[0347] HBL material is evaporated on the surface of one side of the light-emitting layer 6 to form a hole blocking layer 7, and the thickness of the hole blocking layer 7 is 5 nm; the HBL material is the spiro compound of the present application or the comparative compound;

[0348] An electron transport material is evaporated on the surface of one side of the hole blocking layer 7 to form an electron transport layer 8, the thickness of the electron transport layer is 350 nm, and the electron transport material is a mixture of the compound ETL, the spirocyclic compound of the present application or the comparative compound and LiQ, and the weight ratio of the compound ETL, the spirocyclic compound of the present application or the comparative compound to LiQ is 1:1;

[0349] Metal Mg and Ag are co-evaporated on the surface of one side of the electron transport layer 8 to form a cathode 9 composed of a magnesium-silver alloy material. The thickness of the cathode 9 is 100 nm, and the weight ratio of Mg to Ag is 1:9.

[0350]

[0351] Effect evaluation:

[0352] The above-mentioned organic electroluminescent device was tested for device performance, and the spirocyclic compound prepared in the present application and the comparative compound 1-4 were used as hole blocking layer material and electron transport layer material for comparison, respectively. A constant current power supply (Keithley 2400) was used to flow a fixed current density through the light-emitting element, and the luminescence spectrum was tested using a spectroscopic radiation system (CS2000). At the same time, at 10 mA / cm 2 The IVL (current-voltage-luminance) performance of the device was measured at 50 mA / cm 2 The life of the LT95 device was tested under the following conditions. The results are shown in Table 1 below (the examples in Table 1 are the spiro compounds of the present invention, and the comparative examples are the comparative compounds).

[0353] Table 1

[0354]

[0355]

[0356] As can be seen from Table 1, the spirocyclic compounds of the present application are applied to organic electroluminescent devices as hole blocking layer materials and electron transport layer materials, and show more superior performance in driving voltage, luminous efficiency and device life compared with comparative compounds 1-4.

[0357] The above results show that the spiro compound of the present application has the advantages of high luminous efficiency, low voltage, long life, etc., and can be used in organic light-emitting devices. In particular, as hole blocking layer materials and electron transport layer materials, it has the potential to be applied to the AMOLED industry.

Claims

1. A spiro compound, characterized in that Its general structural formula is shown in formula (1): wherein ring A is selected from a substituted or unsubstituted benzene ring or a naphthalene ring; X is independently selected from C(R2)2, O, S, NR3; X1, X2, and X3 are independently selected from N or CR3, and at least one of X1, X2, and X3 is N; R1, R2, and R3 are each independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C5-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphino, or C6-C60 arylamine; L is selected from a single bond, a substituted or unsubstituted aryl group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaryl group having 6 to 60 ring atoms; a is an integer from 0 to 6, wherein Ar1 and Ar2 are independently selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C2-C60 heteroaryl; The heteroatoms in the heteroaryl, heteroalkyl or heterocycloalkyl are independently selected from at least one heteroatom of O, S, N, Se, Si and Ge; The substitutions in Ar1 and Ar2 are independently substituted by deuterium, F, Cl, Br, C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 alkyl substituted amine, C6-C12 aryl, cyano, isocyano or phosphino, and the number of substitutions of each substituent group is independently selected from one of single substitution to maximum number substitution.

2. The spiro compound according to claim 1, characterized in that L is selected from a single bond, a substituted or unsubstituted aryl group having 6-30 ring atoms, or a substituted or unsubstituted heteroaryl group having 6-30 ring atoms; and / or a is an integer of 0-3; and / or Ar1 and Ar2 are independently selected from a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C2-C30 heteroaryl group.

3. The spiro compound according to claim 1, characterized in that R1 is a ring substituent, each independently selected from deuterium, halogen, cyano, nitro, C1-C20 alkyl, C1-C20 heteroalkyl, C2-C10 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C30 aryl, C5-C30 heteroaryl, C1-C20 alkoxy, C6-C30 aryloxy, C3-C30 alkylsilyl, C6-C30 arylsilyl, C1-C20 alkylboryl, C6-C30 arylboryl, C6-C30 arylphosphino or C6-C30 arylamine; And / or, R2 and R3 are each independently selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C20 alkyl, C1-C20 heteroalkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C30 aryl, C5-C30 heteroaryl, C1-C30 alkoxy, C6-C30 aryloxy, C3-C20 alkylsilyl, C6-C30 arylsilyl, C1-C20 alkylboryl, C6-C30 arylboryl, C6-C30 arylphosphino or C6-C30 arylamine.

4. The spiro compound according to claim 1, characterized in that The structure represented by the formula (1) is selected from the structures represented by any one of the following formulas (B-1) to (B-9): Wherein, X, X1, X2, X3, L, Ar1, Ar2, a, and R1 are the same as those in formula (1); R4 is selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C40 alkyl, C1-C40 heteroalkyl, C2-C40 alkenyl, C2-C40 alkynyl, C3-C40 cycloalkyl, C3-C40 heterocycloalkyl, C6-C60 aryl, C5-C60 heteroaryl, C1-C40 alkoxy, C6-C60 aryloxy, C3-C40 alkylsilyl, C6-C60 arylsilyl, C1-C40 alkylboryl, C6-C60 arylboryl, C6-C60 arylphosphinyl or C6-C60 arylamine.

5. The spiro compound according to claim 1, characterized in that L is selected from a single bond and a structure represented by any one of the following formulas C-1 to C-18; Wherein, R is a substituent, and each R is independently selected from deuterium, halogen, cyano, nitro, C1-C20 alkyl, C1-C20 heteroalkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C30 aryl, C5-C30 heteroaryl, C1-C20 alkoxy, C6-C30 aryloxy, C3-C20 alkylsilyl, C6-C30 arylsilyl, C1-C20 alkylboryl, C6-C30 arylboryl, C6-C30 arylphosphino or C6-C30 arylamine; m is selected from integers of 0-4.

6. The spiro compound according to claim 1, characterized in that X1, X2 and X3 contain at least two N; and / or R3 is selected from hydrogen, deuterium, halogen, cyano, nitro, C1-C20 alkyl, C1-C20 heteroalkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 cycloalkyl, C3-C20 heterocycloalkyl, C6-C30 aryl, C5-C30 heteroaryl, C1-C20 alkoxy, C6-C30 aryloxy, C3-C20 alkylsilyl, C6-C30 arylsilyl, C1-C20 alkylboryl, C6-C30 arylboryl, C6-C30 arylphosphino or C6-C30 arylamine.

7. The spiro compound according to claim 1, characterized in that Ar1 and Ar2 are each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted The formula (1) may be a substituted or unsubstituted carbazolyl, a substituted or unsubstituted pyridyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted fluoranthene, a substituted or unsubstituted benzoxazolyl, a substituted or unsubstituted benzimidazolyl, a substituted or unsubstituted benzotriazolyl, a substituted or unsubstituted triphenylene radical, or a combination of at least two of these groups; and / or, the formula (1) contains at least one deuterium atom.

8. The spiro compound according to claim 1, characterized in that The formula (1) is one of the following structural formulas, or one of the following structural formulas in which hydrogen is partially or completely replaced by deuterium or fluorine:

9. 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 layer of the organic layers comprises the spiro compound according to any one of claims 1 to 8.

10. The organic electroluminescent device according to claim 9, characterized in that: The organic layer includes at least one of a light-emitting layer, a hole blocking layer, and an electron transport layer.

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