Spirocyclic compound and organic electroluminescent device

Abstract

The application belongs to the technical field of organic electroluminescence, and discloses a spiro compound and an organic electroluminescent device. The structural general formula of the spiro compound is shown in formula (1). The spiro compound is applied to a light-emitting device, and has the advantages of low driving voltage, high light-emitting efficiency, long device life and the like.

Description

TECHNICAL FIELD

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

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

[0003] The basic structure of a general OLED device is a sandwich structure with various different functional organic functional material films sandwiched between metal electrodes. Under the driving of current, holes and electrons are injected from the cathode and anode respectively, and then recombine in the light-emitting layer after moving a distance, and are released in the form of light or heat, thereby generating the light emission of the OLED. However, the organic functional material is the core component of the light-emitting device, and the thermal stability, photochemical stability, electrochemical stability, quantum yield, film-forming stability, crystallinity and color saturation of the material are all main factors affecting the performance of the device.

[0004] Patent document 1 (CN111433190A) describes spirofluorene bonded to a triazine ring, these compounds can be used as electron / hole transport materials for light-emitting devices, and the device efficiency needs to be improved; patent document 2 (CN117777035A) describes a class of naphthospirofluorene triazine electron transport / hole transport materials, the device performance of this class of materials as electron / hole transport materials also needs to be further improved, especially the device efficiency and service life; patent document 3 (KR1020220042658A) describes a similar structure of oxaspirofluorene connecting triazine materials, the device efficiency and service life of this structure also need to be improved; patent document 4 (CN110234632A) describes a class of dimethyl spiro ring structure connecting triazine ring electron transport materials, the device voltage, luminous efficiency, service life and other performance of this class of materials still need to be further improved. SUMMARY

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

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

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

[0008]

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

[0010] X is independently selected from C(R1)2, O, S, or NR2;

[0011] n is independently selected from 0 or an integer from 1 to 6, when n = 0, no ring is formed, and m is 1, 2, or 3, Rx is hydrogen or deuterium; when n > 1, a ring is formed; when n > 2, each X is the same or different, and only one X is selected from O, S, or NR2;

[0012] X1, X2, X3are each independently selected from N or CR3, and at least one is N;

[0013] L in formula (1) is selected from any one of the following structures shown in formula (A-1) to formula (A-6):

[0014]

[0015]

[0016] wherein * indicates the site connected to formula (1);

[0017] R1, R2, R3are each independently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C1-C40 heteroalkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C3-C40 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C3-C40 alkylsilyl, substituted or unsubstituted C6-C60 arylsilyl, substituted or unsubstituted C1-C40 alkylboron, substituted or unsubstituted C6-C60 arylboron, substituted or unsubstituted C6-C60 arylphosphine, or substituted or unsubstituted C6-C60 arylamine;

[0018] wherein Ar1, Ar2, Ar3are independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl;

[0019] The substituent is at least one of deuterium, halogen, cyano, isocyano, phosphino, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl-substituted amine, C1-C6 hydrocarbon-substituted or unsubstituted C6-C30 aryl, C1-C6 hydrocarbon-substituted or unsubstituted C3-C30 heteroaryl, wherein the number of substitutions is from monosubstitution to the maximum number of substitutions;

[0020] The heteroatom in the heteroaryl, heteroalkyl or heterocycloalkyl is independently selected from at least one of O, S, N, Se, Si, Ge.

[0021] The beneficial effects of the present application relative to the prior art are as follows:

[0022] The spiro compound has a compound in which a spirofluorene is connected with an electron-withdrawing group such as pyrimidine, triazine and the like. The spiro compound has low driving voltage, high luminous efficiency, long device life and the like, and can be used as a hole blocking layer material in an OLED light-emitting device. At the same time, the spiro compound has a low melting point, and as a melt type material, is advantageous for improving the evaporation stability of the material. The compound can be used as a hole blocking layer material and an electron transport layer material, and has the possibility of being applied to the LED, OLED and AMOLED industries. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 A11 is a compound of the present application 1 H NMR spectrum;

[0024] Figure 2 A structure diagram of an organic electroluminescent device of the present application. DETAILED DESCRIPTION

[0025] In order to make those skilled in the art more clearly understand the technical solutions of the present application, the following examples are given for illustration. It should be pointed out that the following examples do not constitute a limitation on the scope of protection required by the present application.

[0026] In the description of the present application, it should be understood that the terms "upper", "lower" and the like indicate the orientation or positional relationship shown in the drawings, and are only for the purpose of facilitating the description of the present application and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation on the present application. In addition, the terms "first", "second" are only for the purpose of description, and cannot be understood as indicating or implying relative importance or implicitly indicating the number of the technical features indicated. Therefore, the features limited by "first", "second" can explicitly or implicitly include one or more of the features.

[0027] The starting materials, reagents or the like used in the following examples are commercially available unless otherwise specified, or can be obtained by known methods.

[0028] The starting materials and solvents used in the synthesis of the spiro compounds of the present application were purchased from Alfa, Acros and other suppliers well known to those skilled in the art.

[0029] In the present application, "substituted" means that a hydrogen atom in a substituent is replaced with a substituent.

[0030] Note that, in the present specification, "carbon number a to b" in the expression "substituted or unsubstituted X group having a carbon number of a to b" means the carbon number in the case where the X group is unsubstituted, and does not include the carbon number of the substituent when the X group is substituted.

[0031] As a specific example of the heteroalkyl group, there are straight-chain or branched-chain alkyl groups, cycloalkyl groups, and the like, which are composed of atoms other than carbon and hydrogen, such as mercaptomethylmethane group, methoxymethylmethane group, ethoxymethylmethane group, t-butoxymethylmethane group, N,N-dimethylmethane group, epoxybutane group, epoxy pentane group, epoxyhexane group, and the like, and methoxymethylmethane group and epoxy pentane group are preferable.

[0032] As a specific example of the aryl group, there are aromatic hydrocarbon groups derived from aromatic ring compounds by removing one hydrogen atom, and can be monocyclic aryl groups or polycyclic aryl groups. At least one ring in the polycyclic aryl group is an aromatic ring system. The plurality of rings in the polycyclic aryl group can be connected to each other via a single bond or can be fused to each other. The number of carbon atoms in the aryl group can be 6 to 60, 6 to 40, 6 to 30, 6 to 20, 6 to 12, or 6 to 10. For example, when the polycyclic aryl group contains a fused ring structure, it can be specifically formed by fusing a C3-C30 aliphatic ring (a saturated or unsaturated aliphatic ring containing 3 to 30 ring skeleton carbon atoms) and a C3-C30 aromatic ring (an aromatic ring containing 3 to 30 ring skeleton carbon atoms), more specifically, a C3-C20 aliphatic ring and a C6-C30 aromatic ring. The aryl group is selected from, for example, phenyl, naphthyl, anthryl, phenanthryl, tetracenyl, pyrenyl, perylenyl, acenaphthyl, benzopyrenyl, benzo[c]phenanthryl, benzo[g]chrysenyl, fluorenyl, spirobifluorenyl, benzofluorenyl, dibenzofluorenyl, biphenyl, terphenyl, quaterphenyl, or fluoranthenyl.

[0033] ​As specific examples of heteroaryl groups, for example, pyrrolyl, pyrrolopyrrolyl, furopyrrolyl, thienopyrrolyl, pyridyl, pyrazolyl, pyrimidinyl, pyrazinyl, pyridazinyl, phenoxazinyl, phenothiazinyl, phenoxazinyl, indolyl, isoindolyl, imidazolyl, benzimidazolyl, triazolyl, tetrazolyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, furopuropyrrolyl, azadibenzofuranyl, thienofuranyl, diazadibenzofuranyl, benzo[B]naphtho[1,2-D]furanyl, quinolyl, isoquinolyl, quinoxalyl, quinazolinyl, quinazolinonyl, carbazolyl, azacarbazolyl, diazacarbazolyl, phenanthridinyl, perimidinyl, acridinyl, dihydroacridinyl, phenanthrolinyl, oxazolinyl, oxazolyl, oxadiazolyl, benzisoxazolyl, thiazolyl, benzothiazolyl, benzisothiazolyl, pyrroloimidazolyl, furazanyl, thienyl, benzothienyl, dibenzothienyl, azadibenzothienyl, diazadibenzothienyl, thienothienyl, or o-diazanaphthalenyl.

[0034] In some embodiments, a spiro compound has a general structure according to Formula (1):

[0035]

[0036] wherein ring A is selected from a substituted or unsubstituted phenyl ring or a substituted or unsubstituted naphthalene ring;

[0037] X is independently selected from C(R1)2, O, S, or NR2;

[0038] n is independently selected from 0 or an integer from 1 to 6, when n = 0, no ring is formed, and m is 1, 2, or 3, Rx is hydrogen or deuterium; when n > 1, a ring is formed; when n > 2, each X is the same or different, and only one X is selected from O, S, or NR2;

[0039] X1, X2, X3are each independently selected from N or CR3, and at least one is N;

[0040] L in Formula (1) is selected from any one of the structures according to Formula (A-1) to Formula (A-6):

[0041]

[0042]

[0043] wherein * indicates the site connected to Formula (1);

[0044] R1, R2, R3are each independently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C40alkyl, substituted or unsubstituted C1-C40heteroalkyl, substituted or unsubstituted C2-C40alkenyl, substituted or unsubstituted C2-C40alkynyl, substituted or unsubstituted C3-C40cycloalkyl, substituted or unsubstituted C3-C40heterocycloalkyl, substituted or unsubstituted C6-C60aryl, substituted or unsubstituted C5-C60heteroaryl, substituted or unsubstituted C1-C40alkoxy, substituted or unsubstituted C6-C60aryloxy, substituted or unsubstituted C3-C40alkylsilyl, substituted or unsubstituted C6-C60arylsilyl, substituted or unsubstituted C1-C40alkylboron, substituted or unsubstituted C6-C60arylboron, substituted or unsubstituted C6-C60arylphosphine, or substituted or unsubstituted C6-C60arylamide;

[0045] wherein Ar1, Ar2, Ar3are independently selected from substituted or unsubstituted C6-C30aryl, substituted or unsubstituted C2-C30heteroaryl;

[0046] substituted with at least one of deuterium, halogen, cyano, isocyano, phosphine, C1-C6alkyl, C3-C16cycloalkyl, C1-C6alkyl substituted amine, C1-C6hydrocarbyl substituted or unsubstituted C6-C30aryl, C1-C6hydrocarbyl substituted or unsubstituted C3-C30heteroaryl, wherein the number of substitutions is mono-substitution to the maximum number of substitutions;

[0047] the heteroatoms in the heteroaryl, heteroalkyl, or heterocycloalkyl are independently selected from at least one of O, S, N, Se, Si, Ge.

[0048] In some embodiments of the present application, the substituted or unsubstituted C6-C60arylphosphine includes a substituted or unsubstituted C6-C60monarylphosphine or a substituted or unsubstituted C6-C60diarylphosphine.

[0049] In some embodiments of the application, R1, R2, R3 are each independently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 heteroalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C5-C40 heteroaryl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C40 aryloxy, substituted or unsubstituted C3-C20 alkylsilyl, substituted or unsubstituted C6-C40 arylsilyl, substituted or unsubstituted C1-C20 alkylboron, substituted or unsubstituted C6-C40 arylboron, substituted or unsubstituted C6-C40 arylphosphine, or substituted or unsubstituted C6-C40 arylamine.

[0050] In some embodiments of the application, Ar1, Ar2, Ar3 are independently selected from substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C2-C20 heteroaryl.

[0051] In some embodiments of the application, the substitution is at least one of deuterium, halogen, cyano, isocyano, phosphine, C1-C6 alkyl, C3-C12 cycloalkyl, C1-C6 alkyl substituted amine, C1-C6 hydrocarbyl substituted or unsubstituted C6-C20 aryl, C1-C6 hydrocarbyl substituted or unsubstituted C3-C20 heteroaryl, wherein the number of substitutions is mono-substitution to the maximum number of substitutions.

[0052] In some embodiments of the application, at least two of X1-X3 contain N, and R3 is selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 heteroalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C5-C30 heteroaryl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C20 alkylsilyl, substituted or unsubstituted C6-C30 arylsilyl, substituted or unsubstituted C1-C20 alkylboron, substituted or unsubstituted C6-C30 arylboron, substituted or unsubstituted C6-C30 arylphosphine, or substituted or unsubstituted C6-C30 arylamine.

[0053] In some embodiments of the present application, the structure represented by Formula (1) is selected from any one of the structures represented by Formulas (B-1) to (B-9) below:

[0054]

[0055]

[0056] wherein X, X1-X3, L, Ar1, Ar2, n are consistent with the foregoing;

[0057] In some embodiments of the present application, (B-1) to (B-9) in the are selected from any one of the structures represented by Formulas (C-1) to (C-8) below:

[0058]

[0059] In some embodiments of the present application, at least two of X1-X3 are N. All of X1-X3 can also be N.

[0060] In some embodiments of the present application, all of X1-X3 are N, and n is 0.

[0061] In some embodiments of the present application, R3 is selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 heteroalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C5-C30 heteroaryl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C20 alkylsilyl, substituted or unsubstituted C6-C30 arylsilyl, substituted or unsubstituted C1-C20 alkylboron, substituted or unsubstituted C6-C30 arylboron, substituted or unsubstituted C6-C30 arylphosphine, or substituted or unsubstituted C6-C30 arylamine.

[0062] In some embodiments of the present application, Ar1, Ar2, Ar3 are each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted benzotriazolyl, substituted or unsubstituted benzophenanthryl, or a combination of at least two of the above.

[0063] In some embodiments of the present application, the formula (1) contains at least one deuterium atom.

[0064] In some embodiments of the present application, the spiro compound of formula (1) is one of the following structural formulae, or a structure in which the hydrogen in one of the following structural formulae is partially or completely replaced by deuterium or fluorine:

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079] 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, at least one of the organic layers comprising a spiro compound of formula (1).

[0080] In some embodiments of the present application, the organic layer comprises at least one of an emitting layer, a hole blocking layer, and an electron transport layer, and the spiro compound is a material in the emitting layer, the hole blocking layer, or the electron transport layer.

[0081] In some embodiments of the present application, the spiro compound shown in formula (1) is used as a hole blocking layer material or an electron transport layer material.

[0082] The following examples are only for the convenience of understanding the technical invention, and should not be regarded as a specific limitation of the present application.

[0083] The raw materials and solvents involved in the synthesis of the spiro compound in the present application are purchased from Alfa, Acros and other suppliers well known to those skilled in the art.

[0084] Synthesis of compound A5

[0085] The synthesis route of compound A5 is as follows:

[0086]

[0087] Synthesis of compound A5-3

[0088] Compound A5-1 (15.00 g, 56.06 mmol), compound A5-2 (17.08 g, 67.28 mmol), 1,1-bis(diphenylphosphino)ferrocene palladium dichloride (Pd(dppf)Cl2, 0.41 g, 0.56 mmol), potassium acetate (KOAc, 13.76 g, 140.16 mol), 1,4-dioxane (1,4-Dioxane, 350 mL) were added into a 1000 mL three-necked round-bottom flask, replaced with vacuum nitrogen three times, then the system was heated to 80°C for 4 hours, TLC (thin layer chromatography, ethyl acetate: n-hexane = 1:15 by volume ratio as developing agent) was used to monitor the reaction, and compound A5-1 was consumed.

[0089] 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 with deionized water three times (300 mL*3), and then separated. The silica gel was used for sample mixing and drying, and then column chromatography was performed (200-300 mesh silica gel, ethyl acetate: n-hexane = 1:15 by volume ratio as eluent). After elution, the white solid was obtained by concentration under reduced pressure at 70°C for 1 hour, and the mass was 13.16 g (mass purity: 99.27%, yield: 74.61%), and the mass spectrum result was 315.12 (M+H).

[0090] Synthesis of compound A5-5

[0091] Compound A5-3 (13.00 g, 41.32 mmol), compound A5-4 (14.17 g, 41.32 mmol), tetrakis(triphenylphosphine)palladium (Pd(PPh3)4, 0.48 g, 0.41 mmol), sodium hydroxide (4.13 g, 103.30 mmol), tetrahydrofuran (THF, 450 mL), deionized water (150 mL) were added into a 1000 mL three-necked round-bottom flask, which was replaced with nitrogen for three times, and then the oil temperature was raised to 75 °C. The reaction was carried out for 4 h, and TLC monitoring (ethyl acetate: n-hexane = 1:15 as developing agent) showed that compound A5-1 was consumed completely.

[0092] After the reaction was completed, a large amount of solid was precipitated, which was directly suction filtered to obtain 20 g of solid. Dichloromethane (600 mL) was added to dissolve the solid, which was then clarified and filtered through silica gel (60 g, 200-300 mesh chromatographic column silica gel). The filtrate was combined and concentrated at 65 °C for 1 h to obtain 15 g of white solid. Toluene (340 mL) was added, and the oil temperature was raised to 105 °C to dissolve the solid, which was then clarified. The temperature was naturally lowered to room temperature, and the mixture was stirred for 1 h. The mixture was suction filtered, and the white solid was dried at 70 °C under vacuum for 3 h to obtain compound A5-5 (14.25 g, mass purity: 99.52%, yield: 69.67%) as a white solid. The mass spectrometry result was: 495.16 (M+H).

[0093] Synthesis of compound A5-8

[0094] Compound A5-7 (20.00 g, 74.75 mmol), dry tetrahydrofuran (400 mL) were added into a 1000 mL three-necked round-bottom flask, which was replaced with nitrogen for three times. Then the system was cooled to -78 °C, and then n-butyllithium (nBuLi) in n-hexane solution (38.87 mL, 97.18 mmol, concentration 2.5 mol / L) was added dropwise, and the internal temperature of the system was controlled to be not higher than -70 °C. The addition was completed in 20 min, and the stirring was continued at -78 °C for 1 h. Finally, compound A5-6 (23.26 g, 104.65 mmol) was slowly added dropwise, and the addition was completed in 10 min. The stirring was continued at -78 °C for 1.5 h, and TLC monitoring (ethyl acetate: n-hexane = 1:20 as developing agent) showed that compound A5-7 was consumed completely.

[0095] The reaction was quenched by adding deionized water (100 mL) dropwise to the system. After being warmed to room temperature, the mixture was directly separated. The aqueous phase was extracted twice with ethyl acetate (200 mL*2). The combined organic phase was concentrated under reduced pressure at 65°C for 1 hour to obtain a light yellow solid. The sample was mixed and dried, and then column chromatography was performed on silica gel (200-300 mesh silica gel, ethyl acetate:n-hexane = 1:30 as eluent). After elution, the white solid obtained by concentrating under reduced pressure at 65°C for 1.5 hours was compound A5-8 (15.74 g, mass purity: 99.77%, yield: 51.24%). The mass spectrometry result was 411.14 (M+H).

[0096] Synthesis of compound A5-9

[0097] Compound A5-8 (15.50 g, 37.72 mmol) and dichloromethane (DCM, 370 mL) were added to a 1000 mL three-necked round-bottom flask. Then the system was cooled to 0°C, and trifluoromethyl sulfonic acid (TfOH, 11.32 g, 75.44 mmol) was added dropwise. The dropwise addition was completed in 15 minutes. The system was stirred at the temperature for 30 minutes. TLC (ethyl acetate:n-hexane = 1:30 as developing agent) was used to monitor the reaction. Compound A5-8 was consumed completely.

[0098] Deionized water (100 mL) was added dropwise to the system to quench the reaction. The mixture was separated, and column chromatography was performed on silica gel (200-300 mesh silica gel, ethyl acetate:n-hexane = 1:50 as eluent). After elution, the white solid obtained by concentrating under reduced pressure at 65°C for 2 hours was compound A5-9 (12.06 g, mass purity: 99.90%, yield: 81.37%). The mass spectrometry result was 393.13 (M+H).

[0099] Synthesis of compound A5-10

[0100] Compound A5-9 (12.00 g, 30.54 mmol), compound A5-2 (9.31 g, 36.65 mmol), tris(dibenzylideneacetone)dipalladium (Pd2(dba)3, 0.28 g, 0.31 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropyl biphenyl (X-Phos, 0.29 g, 0.61 mmol), potassium acetate (7.49 g, 76.35 mmol), and 1,4-dioxane (300 mL) were added to a 1000 mL three-necked round-bottom flask. The system was replaced with nitrogen three times, and then the system was heated to 100°C for 2 hours. TLC (ethyl acetate:n-hexane = 1:20 as developing agent) was used to monitor the reaction. Compound 1-9 was consumed completely.

[0101] 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 with deionized water three times (300 mL*3). The mixture was separated, and the silica gel was used for column chromatography. The silica gel column chromatography was performed (200-300 mesh silica gel, ethyl acetate: n-hexane = 1:30 as eluent). After elution, the white solid was obtained by concentration under reduced pressure at 70°C for 2 hours. The mass spectrometry result was 485.26 (M+H).

[0102] Synthesis of compound A5

[0103] Compound A5-10 (10.00 g, 20.64 mmol), compound A5-5 (10.22 g, 20.64 mmol), dichlorobis-(4-dimethylaminophenyl) palladium (II) (Pd(aMphos)Cl2, 0.15 g, 0.21 mmol), potassium carbonate (7.13 g, 51.61 mmol), 1,4-dioxane (225 mL), deionized water (75 mL) were added into a 500 mL three-necked round-bottom flask, and the flask was replaced with nitrogen three times under vacuum. The oil temperature was raised to 80°C, and the reaction was performed for 6 hours. TLC monitoring (ethyl acetate: n-hexane = 1:20 as developing agent) showed that compound A5-10 was consumed completely, and the heating was stopped.

[0104] A large amount of solid was precipitated after the reaction was completed. The solid was directly filtered to obtain 15 g of solid. Xylene (350 mL) was added, and the mixture was heated to 130°C to dissolve and clarify. The mixture was filtered once through silica gel (20 g, 200-300 mesh column chromatography silica gel). The filtrate was cooled to room temperature and stirred for 2 hours. The mixture was filtered, and the filter cake was dried at 90°C under vacuum for 3 hours to obtain white solid compound A5 (12.16 g, mass purity: 99.95%, yield: 72.10%). The 12.16 g of crude compound A5 was purified by sublimation to obtain sublimed compound A5 (10.46 g, mass purity: 99.98%, yield: 86.02%). The mass spectrometry result was 817.35 (M+H).

[0105] The nuclear magnetic resonance characterization result of compound A5 was as follows: 1H NMR (400 MHz, CDC13) δ 8.40 (dd, J = 7.7, 5.1 Hz, 4H), 8.30 (d, J = 15.0 Hz, 2H), 8.23 (s, 1H), 8.16 (s, 1H), 8.08 (d, J = 15.0 Hz, 1H), 7.94 (d, J = 2.9 Hz, 1H), 7.87 (s, 1H), 7.85 (d, J = 15.0 Hz, 2H), 7.82 - 7.72 (m, 4H), 7.68 (dd, J = 15.0, 2.9 Hz, 1H), 7.61 - 7.56 (m, 1H), 7.54 - 7.36 (m, 13H), 7.26 - 7.21 (m, 2H), 7.15 (dd, J = 11.1, 6.9 Hz, 4H), 1.69 (s, 6H).

[0106] Synthesis of compound A11

[0107] The synthetic route of compound A11 is as follows:

[0108]

[0109] Synthesis of compound A11-2

[0110] Referring to the synthesis and purification method of compound A5-5, only the corresponding raw materials need to be changed to obtain the target compound A11-2 (10.09 g, mass purity: 99.75%, yield: 75.61%). The mass spectrum result is: 420.12 (M+H).

[0111] Synthesis of compound A11

[0112] Referring to the synthesis and purification method of compound A5, only the corresponding raw materials need to be changed to obtain the target compound A11 (13.04 g, mass purity: 99.93%, yield: 73.80%). After sublimation purification of 13.04 g of crude compound A11, sublimation purified compound A11 (11.32 g, mass purity: 99.93%, yield: 86.81%) is obtained. The mass spectrum result is: 742.31 (M+H).

[0113] The nuclear magnetic resonance characterization result of compound A11 is as follows: 1H NMR (400 MHz, CDC13) δ 8.72 (dd, J = 18.4, 5.3 Hz, 6H), 7.81 (dd, J = 7.6, 3.6 Hz, 2H), 7.61 - 7.51 (m, 9H), 7.36 (dd, J = 18.6, 7.7 Hz, 2H), 7.21 - 7.12 (m, 3H), 7.04 (d, J = 6.8 Hz, 2H), 7.01 - 6.92 (m, 3H), 6.86 (t, J = 7.0 Hz, 3H), 6.56 (s, 1H), 6.27 (d, J = 7.3 Hz, 2H), 1.87 (s, 3H), 1.73 (s, 3H).

[0114] Figure 1 Compound A11 is 1 H NMR spectrum, wherein "f1 (ppm)" represents chemical shift.

[0115] Synthesis of compound A23

[0116] The synthetic route of compound A23 is as follows:

[0117]

[0118] Synthesis of compound A23-3

[0119] Compound A23-1 (15.00 g, 47.27 mmol), compound A23-2 (9.76 g, 56.72 mmol), tetrakis(triphenylphosphine)palladium (0.55 g, 0.47 mmol), potassium carbonate (16.33 g, 118.17 mmol), tetrahydrofuran (225 mL), deionized water (75 mL) were added into a 500 mL three-necked round-bottom flask, vacuum nitrogen replacement for three times, the oil temperature was raised to 60°C, and the reaction was carried out for 4 hours. TLC monitoring (ethyl acetate: n-hexane = 1:20 as developing agent), compound A23-1 was consumed, and the heating was stopped.

[0120] The reaction solution was cooled to room temperature, concentrated under reduced pressure to remove the solvent, ethyl acetate (500 mL) was added, washed with deionized water three times (300 mL*3), separated, and the silica gel sample was dried and columned. Silica gel column chromatography purification (200-300 mesh silica gel, ethyl acetate: n-hexane = 1:30 as eluent) was carried out. After elution, 70°C reduced pressure concentration for 2 hours to obtain white solid compound A23-3 (11.09 g, mass purity: 99.34%, yield: 73.87%), and the mass spectrum result was: 316.97 (M+H).

[0121] Synthesis of compound A23-4

[0122] The synthesis and purification method of compound A5-3 were referred to, only the corresponding raw materials were changed, and the target compound A23-4 (9.42 g, mass purity: 99.20%, yield: 74.58%) was obtained. The mass spectrum result was 365.14 (M+H).

[0123] Synthesis of compound A23-5

[0124] The synthesis and purification method of compound A5-5 were referred to, only the corresponding raw materials were changed, and the target compound A23-5 (8.31 g, mass purity: 99.79%, yield: 71.65%) was obtained. The mass spectrum result was 470.13 (M+H).

[0125] Synthesis of compound A23

[0126] The synthesis and purification method of compound A5 were referred to, only the corresponding raw materials were changed, and the target compound A23 (9.16 g, mass purity: 99.95%, yield: 67.94%) was obtained. After sublimation purification of 9.16 g of crude compound A23, sublimation compound A23 (7.21 g, mass purity: 99.94%, yield: 78.71%) was obtained. The mass spectrum result was 792.33 (M+H).

[0127] The nuclear magnetic resonance characterization result of compound A23 was as follows: 1 H NMR (400 MHz, CDCl3) δ 8.52 (d, J = 2.8 Hz, 1H), 8.41-8.31 (m, 4H), 8.15 (d, J = 15.0 Hz, 1H), 8.12-8.02 (m, 4H), 7.99 (dd, J = 15.0, 2.9 Hz, 1H), 7.94-7.85 (m, 2H), 7.68 (dd, J = 15.1, 2.9 Hz, 1H), 7.62 (dd, J = 14.4, 4.0 Hz, 1H), 7.59-7.29 (m, 14H), 7.27-7.21 (m, 2H), 7.19-7.09 (m, 4H), 1.65 (s, 6H).

[0128] Synthesis of compound A48

[0129] The synthesis route of the synthesis of compound A48 was as follows:

[0130]

[0131] Synthesis of compound A48-3

[0132] Referring to the synthesis and purification method of compound A5-5, only the corresponding raw materials need to be changed, and the target compound A48-3 (12.39 g, mass purity: 99.38%, yield: 72.90%) is obtained. The mass spectrum result is: 267.95 (M+H).

[0133] Synthesis of compound A48-4

[0134] Referring to the synthesis and purification method of compound A5-3, only the corresponding raw materials need to be changed, and the target compound A48-4 (10.29 g, mass purity: 99.24%, yield: 72.96%) is obtained. The mass spectrum result is: 316.12 (M+H).

[0135] Synthesis of compound A48-5

[0136] Referring to the synthesis and purification method of compound A5-5, only the corresponding raw materials need to be changed, and the target compound A48-5 (9.15 g, mass purity: 99.57%, yield: 68.61%) is obtained. The mass spectrum result is: 421.11 (M+H).

[0137] Synthesis of compound A48

[0138] Referring to the synthesis and purification method of compound A5, only the corresponding raw materials need to be changed, and the target compound A48 (10.38 g, mass purity: 99.92%, mass purity: 99.24%, yield: 65.34%) is obtained. After sublimation purification of 10.38 g of crude compound A48, sublimation compound A48 (8.57 g, mass purity: 99.93%, yield: 82.56%) is obtained. The mass spectrum result is: 743.31 (M+H).

[0139] The nuclear magnetic resonance characterization result of compound A48 is: 1 H NMR (400 MHz, CDC13) δ 8.44-8.30 (m, 6H), 8.15 (d, J = 15.0 Hz, 1H), 8.08 (d, J = 15.0 Hz, 1H), 7.98 (d, J = 2.9 Hz, 1H), 7.93-7.85 (m, 1H), 7.68 (dd, J = 15.0, 2.9 Hz, 1H), 7.64-7.57 (m, 1H), 7.54-7.40 (m, 10H), 7.39-7.32 (m, 2H), 7.27-7.21 (m, 2H), 7.19-7.10 (m, 5H), 6.95-6.85 (m, 1H), 1.67 (s, 6H).

[0140] Synthesis of compound A62

[0141] The synthetic route of compound A62 is as follows:

[0142]

[0143]

[0144] Synthesis of compound A62-2

[0145] Referring to the synthesis and purification method of compound A23-3, only the corresponding raw materials need to be changed to obtain the target compound A62-2 (8.04 g, mass purity: 99.23%, yield: 71.34%), and the mass spectrum result is: 356.96 (M+H).

[0146] Synthesis of compound A62-3

[0147] Referring to the synthesis and purification method of compound A5-3, only the corresponding raw materials need to be changed to obtain the target compound A62-3 (5.97 g, mass purity: 99.17%, yield: 65.94%), and the mass spectrum result is: 405.14 (M+H).

[0148] Synthesis of compound A62-4

[0149] Referring to the synthesis and purification method of compound A5-5, only the corresponding raw materials need to be changed to obtain the target compound A62-4 (5.73 g, mass purity: 99.75%, yield: 77.07%), and the mass spectrum result is: 510.13 (M+H).

[0150] Synthesis of compound A62-6

[0151] Referring to the synthesis and purification method of compound A5-8, only the corresponding raw materials need to be changed to obtain the target compound A62-6 (9.87 g, mass purity: 99.62%, yield: 53.39%), and the mass spectrum result is: 411.14 (M+H).

[0152] Synthesis of compound A62-7

[0153] Referring to the synthesis and purification method of compound A5-9, only the corresponding raw materials need to be changed to obtain the target compound A62-7 (6.72 g, mass purity: 99.86%, yield: 73.98%), and the mass spectrum result is: 393.13 (M+H).

[0154] Synthesis of compound A62-8

[0155] Referring to the synthesis and purification method of compound A5-3, only the corresponding raw materials need to be changed, and the target compound A62-8 (5.72 g, mass purity: 99.51%, yield: 71.38%) is obtained. The mass spectrum result is: 485.26 (M+H).

[0156] Synthesis of compound A62

[0157] Referring to the synthesis and purification method of compound A5, only the corresponding raw materials need to be changed, and the target compound A62 (6.13 g, mass purity: 99.94%, yield: 71.38%) is obtained. After sublimation purification of 6.13 g of crude compound A62, sublimation purified compound A62 (4.17 g, mass purity: 99.94%, yield: 68.03%) is obtained. The mass spectrum result is: 832.33 (M+H).

[0158] The nuclear magnetic resonance characterization result of compound A62 is: 1 H NMR (400 MHz, CDCl3) δ 8.43-8.31 (m, 5H), 8.15 (d, J = 15.0 Hz, 1H), 8.06 (dd, J = 15.0, 2.9 Hz, 1H), 7.98 (dd, J = 14.6, 3.4 Hz, 1H), 7.93-7.86 (m, 1H), 7.78 (d, J = 15.0 Hz, 1H), 7.68 (dd, J = 14.9, 3.0 Hz, 1H), 7.60-7.46 (m, 8H), 7.46-7.29 (m, 7H), 7.29-7.19 (m, 4H), 7.19-7.11 (m, 4H), 5.85 (dd, J = 15.0, 3.1 Hz, 1H), 1.68 (s, 6H).

[0159] Synthesis of compound A102

[0160] The synthesis route of compound A102 is as follows:

[0161]

[0162] Synthesis of compound A102-2

[0163] Referring to the synthesis and purification method of compound A5-3, only the corresponding raw materials need to be changed, and the target compound A102-2 (8.36 g, mass purity: 99.16%, yield: 71.63%) is obtained. The mass spectrum result is: 329.14 (M+H).

[0164] Synthesis of compound A102-3

[0165] The synthesis and purification method of compound A5-5 were referred to, only the corresponding raw materials were changed, the target compound A102-3 (8.71 g, mass purity: 99.43%, yield: 70.29%) was obtained, and the mass spectrum result was 509.17 (M+H).

[0166] Synthesis of compound A102-5

[0167] The synthesis and purification method of compound A5-8 were referred to, only the corresponding raw materials were changed, the target compound A102-5 (14.38 g, mass purity: 99.29%, yield: 55.63%) was obtained, and the mass spectrum result was 449.02 (M+H).

[0168] Synthesis of compound A102-6

[0169] The synthesis and purification method of compound A5-9 were referred to, only the corresponding raw materials were changed, the target compound A102-6 (9.75 g, mass purity: 99.64%, yield: 72.56%) was obtained, and the mass spectrum result was 431.01 (M+H).

[0170] Synthesis of compound A102-8

[0171] The synthesis and purification method of compound A5-8 were referred to, only the corresponding raw materials were changed, the target compound A102-8 (5.58 g, mass purity: 99.28%, yield: 58.03%) was obtained, and the mass spectrum result was 437.16 (M+H).

[0172] Synthesis of compound A102-9

[0173] The synthesis and purification method of compound A5-9 were referred to, only the corresponding raw materials were changed, the target compound A102-9 (3.94 g, mass purity: 99.67%, yield: 74.72%) was obtained, and the mass spectrum result was 419.15 (M+H).

[0174] Synthesis of compound A102-10

[0175] The synthesis and purification method of compound A5-3 were referred to, only the corresponding raw materials were changed, the target compound A102-10 (3.51 g, mass purity: 99.34%, yield: 73.86%) was obtained, and the mass spectrum result was 511.27 (M+H).

[0176] Synthesis of compound A102

[0177] Referring to the synthesis and purification method of compound A5, only the corresponding raw materials need to be changed, and the target compound A102 (3.86 g, mass purity: 99.94%, yield: 63.68%) can be obtained. After sublimation purification of 3.86 g of compound A102 crude product, sublimation compound A102 (2.71, mass purity: 99.95%, yield: 70.21%) was obtained, and the mass spectrum result was: 857.38 (M+H).

[0178] The nuclear magnetic characterization result of compound A102 is: 1 H NMR (400 MHz, CDC13) δ 8.44-8.25 (m, 6H), 8.23 (s, 1H), 8.15 (d, J = 15.0 Hz, 1H), 8.08 (d, J = 15.0 Hz, 1H), 7.92-7.80 (m, 4H), 7.79-7.72 (m, 2H), 7.68 (dd, J = 15.0, 2.9 Hz, 1H), 7.62-7.54 (m, 2H), 7.54-7.36 (m, 8H), 7.28-7.20 (m, 2H), 7.20-7.10 (m, 8H), 5.47-5.38 (m, 1H), 2.41-2.34 (m, 4H), 2.34 (s, 3H), 1.55-1.47 (m, 4H).

[0179] Synthesis of compound A118

[0180] The synthesis route of compound A118 is as follows:

[0181]

[0182] Synthesis of compound A118-2

[0183] Referring to the synthesis and purification method of compound A5-3, only the corresponding raw materials need to be changed, and the target compound A118-2 (7.84 g, mass purity: 99.15%, yield: 66.67%) can be obtained, and the mass spectrum result is: 315.12 (M+H).

[0184] Synthesis of compound A118-3

[0185] Referring to the synthesis and purification method of compound A5-5, only the corresponding raw materials need to be changed, and the target compound A118-3 (7.62 g, mass purity: 99.71%, yield: 76.12%) can be obtained, and the mass spectrum result is: 420.12 (M+H).

[0186] Synthesis of compound A118-5

[0187] The synthesis and purification method of compound A5-8 were referred to, only the corresponding raw materials were changed, to obtain the target compound A118-5 (9.15 g, mass purity: 99.52%, yield: 58.41%), and the mass spectrum result was 451.18 (M+H).

[0188] Synthesis of compound A118-6

[0189] The synthesis and purification method of compound A5-9 were referred to, only the corresponding raw materials were changed, to obtain the target compound A118-6 (6.16 g, mass purity: 99.72%, yield: 71.29%), and the mass spectrum result was 433.16 (M+H).

[0190] Synthesis of compound A118-7

[0191] The synthesis and purification method of compound A5-3 were referred to, only the corresponding raw materials were changed, to obtain the target compound A118-7 (5.24 g, mass purity: 99.40%, yield: 72.09%), and the mass spectrum result was 525.29 (M+H).

[0192] Synthesis of compound A118

[0193] The synthesis and purification method of compound A5 were referred to, only the corresponding raw materials were changed, to obtain the target compound A118 (5.06 g, mass purity: 99.93%, yield: 67.81%). After sublimation purification of 5.06 g of crude compound A118, sublimation purified compound A118 (3.57 g, mass purity: 99.96%, yield: 70.55%) was obtained, and the mass spectrum result was 782.35 (M+H).

[0194] The nuclear magnetic characterization result of compound A118 was as follows: 1 H NMR (400 MHz, CDCI3) δ 8.41-8.31 (m, 4H), 8.20 (d, J = 3.1 Hz, 1H), 8.15 (d, J = 15.0 Hz, 1H), 8.08 (d, J = 15.0 Hz, 1H), 7.97 (d, J = 3.1 Hz, 1H), 7.92-7.86 (m, 1H), 7.82-7.75 (m, 2H), 7.73-7.63 (m, 3H), 7.55-7.39 (m, 11H), 7.35 (dd, J = 15.0, 2.9 Hz, 1H), 7.27-7.21 (m, 2H), 7.15 (dd, J = 11.1, 6.9 Hz, 4H), 5.73 (s, 1H), 2.34-2.26 (m, 4H), 1.61-1.53 (m, 6H).

[0195] Synthesis of compound A137

[0196] The synthesis route of compound A137 is as follows:

[0197]

[0198] Synthesis of compound A137-2

[0199] Referring to the synthesis and purification method of compound A5-3, only the corresponding raw materials need to be changed to obtain the target compound A137-2 (8.19 g, mass purity: 99.09%, yield: 69.65%), and the mass spectrum result is: 315.12 (M+H).

[0200] Synthesis of compound A137-3

[0201] Referring to the synthesis and purification method of compound A5-5, only the corresponding raw materials need to be changed to obtain the target compound A137-3 (7.86 g, mass purity: 99.34%, yield: 73.61%), and the mass spectrum result is: 420.12 (M+H).

[0202] Synthesis of compound A137-5

[0203] Referring to the synthesis and purification method of compound A5-8, only the corresponding raw materials need to be changed to obtain the target compound A137-5 (13.04 g, mass purity: 99.59%, yield: 58.76%), and the mass spectrum result is: 479.21 (M+H).

[0204] Synthesis of compound A137-6

[0205] Referring to the synthesis and purification method of compound A5-9, only the corresponding raw materials need to be changed to obtain the target compound A137-6 (8.80 g, mass purity: 99.65%, yield: 70.34%), and the mass spectrum result is: 461.20 (M+H).

[0206] Synthesis of compound A137-7

[0207] Referring to the synthesis and purification method of compound A5-3, only the corresponding raw materials need to be changed to obtain the target compound A137-7 (7.16 g, mass purity: 99.33%, yield: 70.28%), and the mass spectrum result is: 553.32 (M+H).

[0208] Synthesis of compound A137

[0209] Referring to the synthesis and purification method of compound A5, only the corresponding raw materials need to be changed, and the target compound A137 (6.74 g, mass purity: 99.97%, yield: 65.68%) can be obtained. After sublimation purification of 6.74 g of compound A137 crude product, sublimation purified compound A137 (4.93 g, mass purity: 99.97%, yield: 73.14%) was obtained, and the mass spectrum result was: 810.38 (M+H).

[0210] The nuclear magnetic characterization result of compound A137 is: 1 H NMR (400 MHz, CDC13) δ 8.39-8.33 (m, 5H), 8.15 (d, J = 7.4 Hz, 1H), 8.10-8.03 (m, 3H), 7.89 (d, J = 9.0 Hz, 1H), 7.82-7.75 (m, 4H), 7.68 (dd, J = 7.5, 1.4 Hz, 1H), 7.56-7.43 (m, 10H), 7.41 (d, J = 7.2 Hz, 1H), 7.27-7.20 (m, 2H), 7.15 (dd, J = 5.5, 3.4 Hz, 4H), 5.75 (d, J = 9.1 Hz, 1H), 2.32 (t, J = 6.0 Hz, 4H), 1.50 (t, J = 6.0 Hz, 4H), 0.87 (s, 6H).

[0211] Synthesis of compound A153

[0212] The synthesis route of compound A153 is as follows:

[0213]

[0214] Synthesis of compound A153-3

[0215] Referring to the synthesis and purification method of compound A23-3, only the corresponding raw materials need to be changed, and the target compound A153-3 (10.64 g, mass purity: 99.31%, yield: 74.36%) can be obtained, and the mass spectrum result is: 316.97 (M+H).

[0216] Synthesis of compound A153-4

[0217] Referring to the synthesis and purification method of compound A5-8, only the corresponding raw materials need to be changed, and the target compound A153-4 (8.36 g, mass purity: 99.52%, yield: 54.85%) can be obtained, and the mass spectrum result is: 461.16 (M+H).

[0218] Synthesis of compound A153-5

[0219] Referring to the synthesis and purification method of compound A5-9, only the corresponding raw materials need to be changed, and the target compound A153-5 (5.71 g, mass purity: 99.46%, yield: 71.08%) is obtained. The mass spectrum result is: 443.15 (M+H).

[0220] Synthesis of compound A153-6

[0221] Referring to the synthesis and purification method of compound A5-3, only the corresponding raw materials need to be changed, and the target compound A153-6 (4.75 g, mass purity: 99.33%, yield: 71.58%) is obtained. The mass spectrum result is: 535.27 (M+H).

[0222] Synthesis of compound A153

[0223] Referring to the synthesis and purification method of compound A5, only the corresponding raw materials need to be changed, and the target compound A153 (4.81 g, mass purity: 99.95%, yield: 72.14%) is obtained. After sublimation purification of 4.81 g of crude compound A153, sublimation purified compound A153 (3.05 g, mass purity: 99.95%, yield: 63.41%) is obtained. The mass spectrum result is: 792.33 (M+H).

[0224] The nuclear magnetic resonance characterization result of compound A153 is: 1 H NMR (400 MHz, CDCl3) δ 8.90 (dd, J = 7.1, 1.8 Hz, 1H), 8.42 (d, J = 7.5 Hz, 1H), 8.39 (d, J = 1.5 Hz, 1H), 8.38-8.33 (m, 4H), 8.15 (d, J = 7.4 Hz, 1H), 8.06 (dd, J = 7.5, 1.4 Hz, 1H), 7.99 (d, J = 1.4 Hz, 1H), 7.87 (dd, J = 7.5, 1.4 Hz, 1H), 7.81-7.76 (m, 3H), 7.67 (dd, J = 5.5, 3.4 Hz, 2H), 7.60 (dd, J = 7.5, 1.4 Hz, 1H), 7.52-7.48 (m, 6H), 7.48-7.45 (m, 5H), 7.39 (m, 5H), 7.34-7.25 (m, 2H), 7.18-7.13 (m, 4H), 7.09 (d, J = 7.5 Hz, 1H), 1.65 (s, 6H).

[0225] 7.39 (m, 5H), 7.34-7.25 (m, 2H), 7.18-7.13 (m, 4H), 7.09 (d, J = 7.5 Hz, 1H), 1.65 (s, 6H).

[0226] Synthesis of compound A169

[0227] The synthesis route of compound A169 is as follows:

[0228]

[0229] Synthesis of compound A169-2

[0230] Refer to the synthesis and purification method of compound A23-3, only need to change the corresponding raw material, the target compound A169-2 (14.36g, mass purity: 99.47%, yield: 75.27%) is obtained, and the mass spectrum result is: 316.97 (M+H). TBAB is tetrabutylammonium bromide.

[0231] Synthesis of compound A169-3

[0232] Refer to the synthesis and purification method of compound A5-8, only need to change the corresponding raw material, the target compound A169-3 (13.70g, mass purity: 99.39%, yield: 62.18%) is obtained, and the mass spectrum result is: 499.04 (M+H).

[0233] Synthesis of compound A169-4

[0234] Refer to the synthesis and purification method of compound A5-9, only need to change the corresponding raw material, the target compound A169-4 (9.82g, mass purity: 99.63%, yield: 75.46%) is obtained, and the mass spectrum result is: 481.03 (M+H).

[0235] Synthesis of compound A169-5

[0236] Refer to the synthesis and purification method of compound A5-8, only need to change the corresponding raw material, the target compound A169-5 (6.04g, mass purity: 99.46%, yield: 59.26%) is obtained, and the mass spectrum result is: 501.19 (M+H).

[0237] Synthesis of compound A169-6

[0238] Refer to the synthesis and purification method of compound A5-9, only need to change the corresponding raw material, the target compound A169-6 (4.15g, mass purity: 99.73%, yield: 71.75%) is obtained, and the mass spectrum result is: 483.18 (M+H).

[0239] Synthesis of compound A169-7

[0240] Refer to the synthesis and purification method of compound A5-3, only need to change the corresponding raw material, the target compound A169-7 (3.55g, mass purity: 99.22%, yield: 74.61%) is obtained, and the mass spectrum result is: 575.30 (M+H).

[0241] Synthesis of compound A169-9

[0242] The synthesis and purification method of compound A5-5 was referred to, only the corresponding raw materials were changed, and the target compound A169-9 (3.74 g, mass purity: 99.82%, yield: 73.17%) was obtained. The mass spectrum result was 536.18 (M+H).

[0243] Synthesis of compound A169

[0244] The synthesis and purification method of compound A5 was referred to, only the corresponding raw materials were changed, and the target compound A169 (3.66 g, mass purity: 99.93%, yield: 68.97%) was obtained. After sublimation purification of 3.66 g of crude compound A169, sublimation purified compound A169 (2.35 g, mass purity: 99.95%, yield: 64.20%) was obtained. The mass spectrum result was 948.42 (M+H).

[0245] The nuclear magnetic characterization result of compound A169 is as follows: 1 H NMR (400 MHz, CDC13) δ 8.94-8.87 (m, 1H), 8.50 (d, J = 2.9 Hz, 1H), 8.41-8.31 (m, 2H), 8.24 (d, J = 2.9 Hz, 1H), 8.15 (d, J = 15.0 Hz, 1H), 8.12-8.02 (m, 2H), 7.94-7.84 (m, 2H), 7.83-7.74 (m, 4H), 7.70 (dd, J = 11.1, 6.9 Hz, 2H), 7.63-7.57 (m, 2H), 7.56-7.39 (m, 9H), 7.39-7.22 (m, 4H), 7.22-7.06 (m, 5H), 6.16 (dd, J = 15.0, 2.9 Hz, 1H), 2.35-2.22 (m, 4H), 1.69 (s, 6H), 1.63-1.50 (m, 6H).

[0246] Synthesis of compound A201

[0247] The synthesis route of compound A201 is as follows:

[0248]

[0249] Synthesis of compound A201-2

[0250] The synthesis and purification method of compound A5-5 was referred to, only the corresponding raw materials were changed, and the target compound A201-2 (7.24 g, mass purity: 99.58%, yield: 74.78%) was obtained. The mass spectrum result was 469.16 (M+H).

[0251] Synthesis of compound A201-3

[0252] Referring to the synthesis and purification method of compound A5-3, only the corresponding raw materials need to be changed, and the target compound A201-3 (5.93 g, mass purity: 99.31%, yield: 70.88%) is obtained. The mass spectrum result is: 561.29 (M+H).

[0253] Synthesis of compound A201

[0254] Referring to the synthesis and purification method of compound A5, only the corresponding raw materials need to be changed, and the target compound A201 (6.07 g, mass purity: 99.97%, yield: 75.62%) is obtained. After sublimation purification of 6.07 g of crude compound A201, sublimation compound A201 (4.16 g, mass purity: 99.97%, yield: 68.53%) is obtained. The mass spectrum result is: 818.35 (M+H).

[0255] The nuclear magnetic resonance characterization result of compound A201 is: 1 H NMR (400 MHz, CDCl3) δ 9.27 (t, J = 2.9 Hz, 1H), 8.46 (d, J = 2.9 Hz, 1H), 8.43-8.29 (m, 4H), 8.15 (d, J = 15.0 Hz, 1H), 8.11-8.03 (m, 2H), 8.00 (d, J = 2.9 Hz, 1H), 7.92-7.85 (m, 1H), 7.83-7.76 (m, 2H), 7.75-7.58 (m, 6H), 7.55-7.39 (m, 11H), 7.27-7.21 (m, 2H), 7.18-7.11 (m, 4H), 5.50-5.40 (m, 1H), 1.69 (s, 6H).

[0256] Synthesis of compound A210

[0257] The synthesis route of compound A210 is as follows:

[0258]

[0259] Synthesis of compound A210-3

[0260] Referring to the synthesis and purification method of compound A23-3, only the corresponding raw materials need to be changed, and the target compound A210-3 (6.52 g, mass purity: 99.62%, yield: 77.05%) is obtained. The mass spectrum result is: 267.95 (M+H).

[0261] Synthesis of compound A210-4

[0262] Referring to the synthesis and purification method of compound A5-5, only the corresponding raw materials need to be changed, and the target compound A210-4 (8.67 g, mass purity: 99.53%, yield: 65.59%) is obtained. The mass spectrum result is: 546.19 (M+H).

[0263] Synthesis of compound A210-5

[0264] Referring to the synthesis and purification method of compound A5-3, only the corresponding raw materials need to be changed, and the target compound A210-5 (7.35 g, mass purity: 99.20%, yield: 74.06%) is obtained. The mass spectrum result is: 638.32 (M+H).

[0265] Synthesis of compound A210

[0266] Referring to the synthesis and purification method of compound A5, only the corresponding raw materials need to be changed, and the target compound A210 (5.86 g, mass purity: 99.92%, yield: 65.17%) is obtained. After sublimation purification of 5.86 g of crude compound A210, sublimation purified compound A210 (3.62 g, mass purity: 99.95%, yield: 61.77%) is obtained. The mass spectrum result is: 819.34 (M+H).

[0267] The nuclear magnetic resonance characterization result of compound A210 is: 1 H NMR (400 MHz, CDC13) δ 8.74-8.66 (m, 1H), 8.41-8.30 (m, 5H), 8.26 (d, J = 2.9 Hz, 1H), 8.15 (d, J = 15.0 Hz, 1H), 8.08 (d, J = 15.0 Hz, 1H), 8.01-7.85 (m, 4H), 7.71-7.58 (m, 3H), 7.55-7.41 (m, 10H), 7.35 (dd, J = 15.0, 2.9 Hz, 1H), 7.29-

[0268] 7.21 (m, 4H), 7.19-7.10 (m, 4H), 5.48-5.43 (m, 1H), 1.69 (s, 6H).

[0269] Synthesis of compound A234

[0270] The synthesis route of compound A234 is as follows:

[0271]

[0272] Synthesis of compound A234-1

[0273] Referring to the synthesis and purification method of compound A5-5, only the corresponding raw materials need to be changed, and the target compound A234-1 (14.35 g, mass purity: 99.37%, yield: 70.43%) is obtained. The mass spectrum result is: 545.21 (M+H).

[0274] Synthesis of compound A234-2

[0275] Referring to the synthesis and purification method of compound A5-3, only the corresponding raw materials need to be changed, and the target compound A234-2 (11.12 g, mass purity: 99.24%, yield: 68.01%) is obtained. The mass spectrum result is: 637.32 (M+H).

[0276] Synthesis of compound A234-4

[0277] Referring to the synthesis and purification method of compound A5-5, only the corresponding raw materials need to be changed, and the target compound A234-4 (7.32 g, mass purity: 99.49%, yield: 61.09%) is obtained. The mass spectrum result is: 460.15 (M+H).

[0278] Synthesis of compound A234

[0279] Referring to the synthesis and purification method of compound A5, only the corresponding raw materials need to be changed, and the target compound A234 (9.96 g, mass purity: 99.95%, yield: 70.06%) is obtained. After sublimation purification of 9.96 g of crude compound A234, sublimation purified compound A234 (6.29 g, mass purity: 99.96%, yield: 63.15%) is obtained. The mass spectrum result is: 934.41 (M+H).

[0280] The nuclear magnetic resonance characterization result of compound A234 is: 1 H NMR (400 MHz, CDC13) δ 8.93 (d, J = 2.9 Hz, 1H), 8.39 - 8.33 (m, 3H), 8.15 (d, J = 15.0 Hz, 1H), 8.09 (dd, J = 15.0, 4.9 Hz, 2H), 7.99 - 7.93 (m, 2H), 7.93 - 7.86 (m, 2H), 7.83 - 7.72 (m, 6H), 7.68 (dd, J = 14.9, 3.0 Hz, 1H), 7.54 - 7.39 (m, 8H), 7.39 - 7.31 (m, 2H), 7.29 - 7.13 (m, 10H), 5.39 - 5.34 (m, 1H), 1.69 (s, 12H).

[0281] Synthesis of compound A269

[0282] The synthetic route of compound A269 is as follows:

[0283]

[0284] Synthesis of compound A269-2

[0285] Referring to the synthesis and purification method of compound A5-8, only the corresponding raw materials need to be changed to obtain the target compound A269-2 (10.32 g, mass purity: 99.46%, yield: 59.05%), and the mass spectrum result is: 503.21 (M+H).

[0286] Synthesis of compound A269-3

[0287] Referring to the synthesis and purification method of compound A5-9, only the corresponding raw materials need to be changed to obtain the target compound A269-3 (7.34 g, mass purity: 99.34%, yield: 76.13%), and the mass spectrum result is: 485.20 (M+H).

[0288] Synthesis of compound A269-4

[0289] Referring to the synthesis and purification method of compound A5-3, only the corresponding raw materials need to be changed to obtain the target compound A269-4 (6.09 g, mass purity: 99.16%, yield: 73.09%), and the mass spectrum result is: 577.32 (M+H).

[0290] Synthesis of compound A269-5

[0291] Referring to the synthesis and purification method of compound A5-5, only the corresponding raw materials need to be changed to obtain the target compound A269-5 (4.37 g, mass purity: 99.49%, yield: 74.83%), and the mass spectrum result is: 561.23 (M+H). Toluene represents toluene.

[0292] Synthesis of compound A269-6

[0293] Referring to the synthesis and purification method of compound A5-3, only the corresponding raw materials need to be changed to obtain the target compound A269-6 (3.47 g, mass purity: 99.78%, yield: 74.59%), and the mass spectrum result is: 653.35 (M+H).

[0294] Synthesis of compound A269

[0295] Referring to the synthesis and purification method of compound A5, only the corresponding raw materials need to be changed, and the target compound A269 (3.29 g, mass purity: 99.96%, yield: 69.37%) can be obtained. After sublimation purification of 3.29 g of compound A269 crude product, sublimation purified compound A269 (2.21 g, mass purity: 99.96%, yield: 67.20%) was obtained, and the mass spectrum result was: 910.41 (M+H).

[0296] The nuclear magnetic characterization result of compound A269 is: 1 H NMR (400 MHz, CDCl3) δ 8.47 (d, J = 2.9 Hz, 1H), 8.36 (dd, J = 9.8, 8.3 Hz, 4H), 8.23 (s, 1H), 8.14 (s, 1H), 8.08 (d, J = 14.9 Hz, 2H), 7.93-7.86 (m, 1H), 7.77 (t, J = 3.1 Hz, 3H), 7.74-7.57 (m, 4H), 7.54-7.36 (m, 11H), 7.28-7.19 (m, 2H), 7.15 (dd, J = 11.0, 7.0 Hz, 4H), 6.98 (dd, J = 11.1, 7.1 Hz, 2H), 5.85-5.74 (m, 1H), 2.46 (t, J = 7.2 Hz, 2H), 2.21 (s, 2H), 1.72 (t, J = 7.3 Hz, 5H), 1.07 (t, J = 7.3 Hz, 5H).

[0297] Synthesis of compound A295

[0298] The synthesis route of compound A295 is as follows:

[0299]

[0300] Synthesis of compound A295-1

[0301] Referring to the synthesis and purification method of compound A5-5, only the corresponding raw materials need to be changed, and the target compound A295-1 (9.62 g, mass purity: 99.72%, yield: 71.60%) can be obtained, and the mass spectrum result is: 595.21 (M+H).

[0302] Synthesis of compound A295-2

[0303] Referring to the synthesis and purification method of compound A5-3, only the corresponding raw materials need to be changed, and the target compound A295-2 (8.04 g, mass purity: 99.26%, yield: 73.35%) can be obtained, and the mass spectrum result is: 687.34 (M+H).

[0304] Synthesis of compound A295

[0305] The synthesis and purification method of compound A5 were referred to, only the corresponding raw materials were changed, and the target compound A295 (7.16 g, mass purity: 99.90%, yield: 70.80%) was obtained. After sublimation purification of 5.84 g of compound A295, sublimation purified compound A295 (5.04 g, mass purity: 99.95%, yield: 70.39%) was obtained, and the mass spectrum result was: 868.36 (M+H).

[0306] The nuclear magnetic characterization result of compound A295 was: 1 H NMR (400 MHz, CDCl3) δ 9.03 (d, J = 3.1 Hz, 1H), 8.95-8.86 (m, 1H), 8.46-8.31 (m, 6H), 8.18-8.12 (m, 2H), 7.92-7.83 (m, 3H), 7.83-7.75 (m, 3H), 7.70 (t, J = 14.8 Hz, 1H), 7.64-7.57 (m, 2H), 7.54-7.39 (m, 11H), 7.39-7.23 (m, 4H), 7.20-7.05 (m, 5H), 1.64 (s, 6H).

[0307] Synthesis of compound A346

[0308] The synthesis route of compound A346 is as follows:

[0309]

[0310] Synthesis of compound A346-2

[0311] The synthesis and purification method of compound A23-3 were referred to, only the corresponding raw materials were changed, and the target compound A346-2 (9.68 g, mass purity: 99.45%, yield: 75.13%) was obtained, and the mass spectrum result was: 271.98 (M+H).

[0312] Synthesis of compound A346-3

[0313] The synthesis and purification method of compound A5-3 were referred to, only the corresponding raw materials were changed, and the target compound A346-3 (8.07 g, mass purity: 99.41%, yield: 72.44%) was obtained, and the mass spectrum result was: 320.16 (M+H).

[0314] Synthesis of compound A346-4

[0315] The synthesis and purification method of compound A5-5 were referred to, only the corresponding raw materials were changed, and the target compound A346-4 (7.58 g, mass purity: 99.76%, yield: 71.27%) was obtained. The mass spectrum result was 425.15 (M+H).

[0316] Synthesis of compound A346

[0317] The synthesis and purification method of compound A5 were referred to, only the corresponding raw materials were changed, and the target compound A346 (8.62 g, mass purity: 99.94%, yield: 65.38%) was obtained. After sublimation purification of 8.62 g of compound A346 crude product, sublimation compound A346 (6.72 g, mass purity: 99.96%, yield: 77.95%) was obtained. The mass spectrum result was 747.35 (M+H).

[0318] The nuclear magnetic resonance characterization result of compound A346 was as follows: 1 H NMR (400 MHz, CDCl3) δ 8.40-8.32 (m, 5H), 8.15 (d, J = 15.0 Hz, 1H), 8.11-8.03 (m, 2H), 7.92-7.86 (m, 2H), 7.68 (dd, J = 15.0, 2.9 Hz, 1H), 7.59-7.54 (m, 1H), 7.54-7.40 (m, 8H), 7.40-7.33 (m, 2H), 7.27-7.21 (m, 2H), 7.19-7.11 (m, 4H), 1.69 (s, 6H).

[0319] Synthesis of compound A380

[0320] The synthesis route of compound A380 was as follows:

[0321]

[0322] Synthesis of compound A380-2

[0323] The synthesis and purification method of compound A23-3 were referred to, only the corresponding raw materials were changed, and the target compound A380-2 (9.86 g, mass purity: 99.34%, yield: 76.53%) was obtained. The mass spectrum result was 271.98 (M+H).

[0324] Synthesis of compound A380-3

[0325] The synthesis and purification method of compound A5-3 were referred to, only the corresponding raw materials were changed, and the target compound A380-3 (8.34 g, mass purity: 99.50%, yield: 72.57%) was obtained. The mass spectrum result was 320.16 (M+H).

[0326] Synthesis of compound A380-5

[0327] According to the synthesis and purification method of compound A5-5, only the corresponding raw materials need to be changed to obtain the target compound A380-5 (9.08 g, mass purity: 99.76%, yield: 67.02%), and the mass spectrum result is: 577.21 (M+H).

[0328] Synthesis of compound A380-7

[0329] According to the synthesis and purification method of compound A5-8, only the corresponding raw materials need to be changed to obtain the target compound A380-7 (21.73 g, mass purity: 99.45%, yield: 56.76%), and the mass spectrum result is: 499.04 (M+H).

[0330] Synthesis of compound A380-8

[0331] According to the synthesis and purification method of compound A5-9, only the corresponding raw materials need to be changed to obtain the target compound A380-8 (14.49 g, mass purity: 99.63%, yield: 69.92%), and the mass spectrum result is: 481.03 (M+H).

[0332] Synthesis of compound A380-9

[0333] According to the synthesis and purification method of compound A5-8, only the corresponding raw materials need to be changed to obtain the target compound A380-9 (8.92 g, mass purity: 99.37%, yield: 61.07%), and the mass spectrum result is: 501.19 (M+H).

[0334] Synthesis of compound A380-10

[0335] According to the synthesis and purification method of compound A5-9, only the corresponding raw materials need to be changed to obtain the target compound A380-10 (6.51 g, mass purity: 99.82%, yield: 74.56%), and the mass spectrum result is: 483.18 (M+H).

[0336] Synthesis of compound A380-11

[0337] According to the synthesis and purification method of compound A5-3, only the corresponding raw materials need to be changed to obtain the target compound A380-11 (5.07 g, mass purity: 99.79%, yield: 71.04%), and the mass spectrum result is: 575.30 (M+H).

[0338] Synthesis of compound A380

[0339] Referring to the synthesis and purification method of compound A5, only the corresponding raw materials need to be changed to obtain the target compound A380 (6.19 g, mass purity: 99.97%, yield: 71.92%). After sublimation purification of 6.19 g of crude compound A380, sublimation purified compound A380 (4.76 g, mass purity: 99.97%, yield: 76.89%) was obtained, and the mass spectrum result was: 989.46 (M+H).

[0340] The nuclear magnetic characterization result of compound A380 is: 1 H NMR (400 MHz, CDC13) δ 8.42 (d, J = 15.0 Hz, 1H), 8.20 - 8.12 (m, 3H), 8.02 - 7.92 (m, 5H), 7.90 - 7.79 (m, 3H), 7.78 - 7.71 (m, 4H), 7.62 - 7.32 (m, 12H), 7.28 - 7.22 (m, 4H), 7.19 - 7.11 (m, 4H), 7.08 - 6.99 (m, 2H), 2.33 - 2.17 (m, 4H), 1.64 - 1.49 (m, 6H).

[0341] 1.49 (m, 6H).

[0342] Synthesis of compound A391

[0343] The synthesis route of compound A391 is as follows:

[0344]

[0345] Synthesis of compound A391-2

[0346] Referring to the synthesis and purification method of compound A23-3, only the corresponding raw materials need to be changed to obtain the target compound A391-2 (13.59 g, mass purity: 99.46%, yield: 78.31%), and the mass spectrum result was: 342.98 (M+H).

[0347] Synthesis of compound A391-3

[0348] Referring to the synthesis and purification method of compound A5-3, only the corresponding raw materials need to be changed to obtain the target compound A391-3 (11.49 g, mass purity: 99.45%, yield: 74.86%), and the mass spectrum result was: 391.16 (M+H).

[0349] Synthesis of compound A391-5

[0350] The synthesis and purification method of compound A5-5 were referred to, only the corresponding raw materials were changed, the target compound A391-5 (10.14 g, mass purity: 99.84%, yield: 71.17%) was obtained, and the mass spectrum result was 506.21 (M+H).

[0351] Synthesis of compound A391-7

[0352] The synthesis and purification method of compound A5-8 were referred to, only the corresponding raw materials were changed, the target compound A391-7 (18.07 g, mass purity: 99.50%, yield: 52.45%) was obtained, and the mass spectrum result was 449.02 (M+H).

[0353] Synthesis of compound A391-8

[0354] The synthesis and purification method of compound A5-9 were referred to, only the corresponding raw materials were changed, the target compound A391-8 (12.19 g, mass purity: 99.36%, yield: 70.51%) was obtained, and the mass spectrum result was 431.01 (M+H).

[0355] Synthesis of compound A391-10

[0356] The synthesis and purification method of compound A5-8 were referred to, only the corresponding raw materials were changed, the target compound A391-10 (7.61 g, mass purity: 99.75%, yield: 60.45%) was obtained, and the mass spectrum result was 453.15 (M+H).

[0357] Synthesis of compound A391-11

[0358] The synthesis and purification method of compound A5-9 were referred to, only the corresponding raw materials were changed, the target compound A391-11 (5.16 g, mass purity: 99.63%, yield: 71.65%) was obtained, and the mass spectrum result was 435.14 (M+H).

[0359] Synthesis of compound A391-12

[0360] The synthesis and purification method of compound A5-3 were referred to, only the corresponding raw materials were changed, the target compound A391-12 (4.62 g, mass purity: 99.57%, yield: 76.34%) was obtained, and the mass spectrum result was 527.27 (M+H).

[0361] Synthesis of compound A391

[0362] The synthesis and purification method of compound A5 were referred to, only the corresponding raw materials were changed, and the target compound A391 (5.37 g, mass purity: 99.91%, yield: 72.19%) was obtained. After sublimation purification of 5.37 g of compound A391 crude product, sublimation purified compound A391 (3.26 g, mass purity: 99.96%, yield: 60.70%) was obtained, and the mass spectrum result was: 870.42 (M+H).

[0363] The nuclear magnetic characterization result of compound A391 was: 1 H NMR (400 MHz, CDC13) δ 8.47 (d, J = 2.9 Hz, 1H), 8.15 (d, J = 15.0 Hz, 1H), 8.06 (dd, J = 15.0, 2.9 Hz, 1H), 7.93 - 7.83 (m, 3H), 7.79 - 7.71 (m, 2H), 7.70 - 7.63 (m, 2H), 7.54 - 7.36 (m, 5H), 7.29 - 7.20 (m, 6H), 7.20 - 7.11 (m, 4H), 5.73 - 5.65 (m, 1H), 5.41 - 5.32 (m, 1H), 3.72 (t, J = 21.0 Hz, 4H), 2.45 (t, J = 21.0 Hz, 4H).

[0364] Synthesis of compound A396

[0365] The synthesis route of compound A396 is as follows:

[0366]

[0367] Synthesis of compound A396-2

[0368] The synthesis and purification method of compound A5-5 were referred to, only the corresponding raw materials were changed, and the target compound A396-2 (9.76 g, mass purity: 99.60%, yield: 73.47%) was obtained, and the mass spectrum result was: 418.13 (M+H).

[0369] Synthesis of compound A396-4

[0370] The synthesis and purification method of compound A5-8 were referred to, only the corresponding raw materials were changed, and the target compound A396-4 (9.47 g, mass purity: 99.59%, yield: 58.12%) was obtained, and the mass spectrum result was: 469.13 (M+H).

[0371] Synthesis of compound A396-5

[0372] The synthesis and purification method of compound A5-9 were referred to, only the corresponding raw materials were changed, and the target compound A396-5 (6.15 g, mass purity: 99.48%, yield: 71.06%) was obtained. The mass spectrum result was 451.12 (M+H).

[0373] Synthesis of compound A396-6

[0374] The synthesis and purification method of compound A5-3 were referred to, only the corresponding raw materials were changed, and the target compound A396-6 (5.70 g, mass purity: 99.17%, yield: 78.97%) was obtained. The mass spectrum result was 543.25 (M+H).

[0375] Synthesis of compound A396

[0376] The synthesis and purification method of compound A5 were referred to, only the corresponding raw materials were changed, and the target compound A396 (5.92 g, mass purity: 99.97%, yield: 73.17%) was obtained. After sublimation purification of 5.92 g of compound A396 crude product, sublimation compound A396 (3.95 g, mass purity: 99.97%, yield: 66.72%) was obtained. The mass spectrum result was 798.31 (M+H).

[0377] The nuclear magnetic characterization result of compound A396 was as follows: 1 H NMR (400 MHz, CDCl3) δ 8.33-8.27 (m, 4H), 8.23 (d, J = 2.9 Hz, 1H), 8.20 (s, 2H), 8.16 (dd, J = 9.8, 9.0 Hz, 2H), 7.92-7.87 (m, 1H), 7.81-7.76 (m, 2H), 7.70-7.59 (m, 4H), 7.57-7.39 (m, 11H), 7.37-7.32 (m, 1H), 7.27-7.21 (m, 2H), 7.15 (dd, J = 11.1, 6.9 Hz, 4H), 5.64-5.59 (m, 1H), 2.96 (t, J = 12.2 Hz, 4H), 2.55 (dd, J = 18.3, 6.3 Hz, 4H).

[0378] Synthesis of compound A397

[0379] The synthesis route of compound A397 was as follows:

[0380]

[0381] Synthesis of compound A397-3

[0382] The synthesis and purification method of compound A23-3 were referred to, only the corresponding raw materials were changed, and the target compound A397-3 (5.76 g, mass purity: 99.64%, yield: 64.02%) was obtained. The mass spectrum result was 284.94 (M+H).

[0383] Synthesis of compound A397-4

[0384] The synthesis and purification method of compound A5-5 were referred to, only the corresponding raw materials were changed, and the target compound A397-4 (7.26 g, mass purity: 99.37%, yield: 66.93%) was obtained. The mass spectrum result was 563.19 (M+H).

[0385] Synthesis of compound A397-5

[0386] The synthesis and purification method of compound A5-3 were referred to, only the corresponding raw materials were changed, and the target compound A397-5 (6.11 g, mass purity: 99.19%, yield: 75.08%) was obtained. The mass spectrum result was 655.31 (M+H).

[0387] Synthesis of compound A397

[0388] The synthesis and purification method of compound A5 were referred to, only the corresponding raw materials were changed, and the target compound A397 (5.65 g, mass purity: 99.98%, yield: 71.18%) was obtained. After sublimation purification of 5.65 g of compound A397 crude product, sublimation compound A397 (3.29 g, mass purity: 99.98%, yield: 58.23%) was obtained. The mass spectrum result was 866.29 (M+H).

[0389] The nuclear magnetic resonance characterization result of compound A397 was as follows: 1 H NMR (400 MHz, CDC13) δ 8.45 (dd, J = 7.5, 1.4 Hz, 1H), 8.39 (d, J = 1.4 Hz, 1H), 8.38-8.34 (m, 2H), 8.15 (d, J = 7.4 Hz, 1H), 8.10-8.04 (m, 2H), 7.96 (dd, J = 7.5, 1.4 Hz, 1H), 7.92-7.84 (m, 2H), 7.71-7.62 (m, 5H), 7.58-7.53 (m, 1H), 7.53-7.44 (m, 6H), 7.42-7.36 (m, 2H), 7.33-7.29 (m, 1H), 7.27-7.21 (m, 2H), 7.19-7.12 (m, 6H), 5.48-5.45 (m, 1H), 1.69 (s, 6H).

[0390] Application example: Fabrication of organic electroluminescent devices

[0391] As attached Figure 2 As shown, an organic electroluminescent device includes a glass substrate 1, an anode 2, a hole injection layer 3, a first hole transport layer 4, a second hole transport layer 5, a light-emitting layer 6, a hole blocking layer 7, an electron transport layer 8, and a cathode 9, which are stacked together.

[0392] A glass substrate 1 with an ITO transparent electrode (anode 2) on its surface is provided, wherein the thickness of the ITO transparent electrode is 100 nm;

[0393] 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.

[0394] A HATCN compound is vapor-deposited on the surface of the ITO transparent electrode (anode 2) to form a hole injection layer 3 with a thickness of 5 nm.

[0395] Compound HTM1 is vapor-deposited on the surface of one side of hole injection layer 3 to form first hole transport layer 4, the thickness of first hole transport layer 4 being 60 nm.

[0396] Compound HTM2 is vapor-deposited on the surface of one side of the first hole transport layer 4 to form a second hole transport layer 5 with a thickness of 10 nm.

[0397] A host material and a guest material are co-deposited 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%; and the thickness of the light-emitting layer is 25nm.

[0398] HBL material is vapor-deposited on one side of the light-emitting layer 6 to form a hole blocking layer 7 with a thickness of 5 nm; the HBL material is a spirocyclic compound of this application or a comparative compound;

[0399] Electron transport material is vapor-deposited on the surface of one side of hole blocking layer 7 to form electron transport layer 8. The electron transport layer has a thickness of 350 nm. The electron transport material is a mixture of compound ETL, spirocyclic compound of the present application or comparative compound and LiQ. The weight ratio of compound ETL, spirocyclic compound of the present application or comparative compound to LiQ is 1:1.

[0400] Metals Mg and Ag are co-deposited on the surface of one side of electron transport layer 8 to form cathode 9, which is composed of magnesium-silver alloy material. The thickness of cathode 9 is 100 nm, and the weight ratio of Mg to Ag is 1:9.

[0401] The structures of the compounds involved in each embodiment or comparative example are as follows:

[0402]

[0403]

[0404] Effect evaluation:

[0405] The organic electroluminescent device is subjected to device performance test, and the spiro compound prepared in the application and comparative compounds 1-4 are respectively used as a hole blocking layer material and an electron transport layer material for comparison. A constant current power supply (Keithley 2400) is used, a fixed current density is used to flow through the light-emitting element, and a spectroradiometer (CS2000) is used to test the luminescence spectrum. Meanwhile, the device is tested at 10 mA / cm 2 2 The IVL (current-voltage-luminance) performance of the device is determined, and the LT95 device lifetime is tested at 50 mA / cm 2 The results are shown in Table 1 (in Table 1, the examples use the spiro compound of the application, and the comparative examples use the comparative compounds).

[0406] Table 1

[0407]

[0408]

[0409] As can be seen from Table 1, the spiro compound of the application applied to the organic electroluminescent device as a hole blocking layer material and an electron transport layer material shows more superior performance in driving voltage, luminous efficiency, and device lifetime compared to the comparative compounds 1-4.

[0410] The above results show that the spiro compound of the application has the advantages of high luminous efficiency, low voltage, long lifetime, etc., and can be used in organic light-emitting devices. In particular, as a hole blocking layer material and an electron transport layer material, it has the potential to be applied to the AMOLED industry. The spiro compound of the application also has the advantages of good photoelectric and thermal stability, low sublimation temperature, etc.

Claims

1. A spiro compound, characterized by, The general structure is shown in formula (1): Formula (1), Wherein, ring A is selected from benzene ring or naphthalene ring; X is independently selected from C(R1)2, O or S; n is independently selected from 0 or an integer from 1 to 6, when n = 0, no ring is connected, and m is 1, 2 or 3, Rx is hydrogen or deuterium; when n ≥ 1, a ring is connected; and when n ≥ 2, each X is the same or different, and only one X is selected from O or S; X1, X2, X3 are independently selected from N or CR3, and at least one is N; L in formula (1) is selected from any one of the following structures of formula (A-1) to formula (A-6): Wherein, * represents the site connected with formula (1); R1, R3 are independently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C1-C40 heteroalkyl, substituted or unsubstituted C2-C40 alkenyl, substituted or unsubstituted C2-C40 alkynyl, substituted or unsubstituted C3-C40 cycloalkyl, substituted or unsubstituted C3-C40 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C3-C40 alkylsilyl, substituted or unsubstituted C6-C60 arylsilyl, substituted or unsubstituted C1-C40 alkylboron, substituted or unsubstituted C6-C60 arylboron, substituted or unsubstituted C6-C60 arylphosphine or substituted or unsubstituted C6-C60 arylamine; Wherein, Ar1, Ar2, Ar3 are independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl; The substitution of R1, R3, Ar1, Ar2 is independently substituted by at least one of deuterium, halogen, cyano, isocyano, phosphine, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl-substituted amine, C1-C6 hydrocarbon-substituted or unsubstituted C6-C30 aryl, C1-C6 hydrocarbon-substituted or unsubstituted C3-C30 heteroaryl, wherein the number of substitution is single substitution to maximum number of substitution; The substitution of Ar3 is substituted by at least one of deuterium, halogen, C1-C6 alkyl, C3-C16 cycloalkyl, wherein the number of substitution is single substitution to maximum number of substitution; The spiro compound is not of the following structure: ; The heteroatom in the heteroaryl, heteroalkyl or heterocycloalkyl is independently selected from at least one of O, S, N, Se, Si, Ge.

2. The spiro compound according to claim 1, characterized by The structure shown in formula (1) is selected from any one of the following structures of formula (B-1) to formula (B-9): (B-1) (B-2) (B-3) (B-4) (B-5) (B-6) (B-7) (B-8) (B-9), Wherein, X, X1-X3, L, Ar1, Ar2, n are consistent with claim 1.

3. The spiro compound according to claim 2, characterized by (B-1) to any one of the structures represented by the following formulae (B-9): selected from any one of the structures represented by the following formulae (C-1) to (C-8): (C-1) (C-2) (C-3) (C-4) (C-5) (C-6) (C-8).

4. The spiro compound according to claim 1 or 2, characterized by R1, R3are each independently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 heteroalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C5-C40 heteroaryl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C6-C40 aryloxy, substituted or unsubstituted C3-C20 alkylsilyl, substituted or unsubstituted C6-C40 arylsilyl, substituted or unsubstituted C1-C20 alkylboron, substituted or unsubstituted C6-C40 arylboron, substituted or unsubstituted C6-C40 arylphosphine, or substituted or unsubstituted C6-C40 arylamine; and / or, Ar1, Ar2, Ar3are independently selected from substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C2-C20 heteroaryl.

5. The spiro compound according to claim 1 or 2, characterized by X1-X3contain at least two N, R3is selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 heteroalkyl, substituted or unsubstituted C2-C20 alkenyl, substituted or unsubstituted C2-C20 alkynyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 heterocycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C5-C30 heteroaryl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C20 alkylsilyl, substituted or unsubstituted C6-C30 arylsilyl, substituted or unsubstituted C1-C20 alkylboron, substituted or unsubstituted C6-C30 arylboron, substituted or unsubstituted C6-C30 arylphosphine, or substituted or unsubstituted C6-C30 arylamine.

6. The spiro compound according to claim 1 or 2, characterized by X1-X3are all N, and n is 0.

7. The spiro compound according to claim 1 or 2, characterized by Ar1, Ar2, Ar3are each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted 9,9-dimethylfluorenyl, substituted or unsubstituted 9,9-diphenylfluorenyl, substituted or unsubstituted spirobifluorenyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted pyrenyl, substituted or unsubstituted chrysenyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted benzotriazolyl, substituted or unsubstituted benzophenanthryl, or a combination of at least two of the foregoing.

8. The spiro compound according to claim 1 or 2, characterized by The spiro compound represented by formula (1) is one of the following structural formulae, or a structure in which hydrogen in one of the following structural formulae is partially or completely replaced by deuterium or fluorine, except for ring A: 。 9. An organic electroluminescent device, characterized by The organic electroluminescent device comprises an anode, a cathode, and one or more organic layers between the anode and the cathode, at least one of the organic layers comprising the spiro compound according to any one of claims 1-8.

10. The organic electroluminescent device according to claim 9, characterized in that The organic layer comprises at least one of a light-emitting layer, a hole-blocking layer, and an electron-transporting layer, and the spiro compound is a material in the light-emitting layer, the hole-blocking layer, or the electron-transporting layer.

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