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. The spiro compound has the advantages of low driving voltage, high luminous efficiency, long service life of a device and the like when applied to the luminescent device.

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] As a new generation of display technology, organic light-emitting devices (OLED) have received increasing attention in both display and lighting technologies, 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 improved.

[0003] The basic structure of a general OLED device is a thin film of organic functional materials with various functions sandwiched between metal electrodes, like a sandwich structure. Driven by 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 Spirofluorene is bonded to a triazine ring. These compounds can be used as electron / hole transport materials in light-emitting devices, and the efficiency of the devices needs to be improved. Patent document 2 (CN117777035A) records A type of naphthospirofluorene triazine electron transport / hole transport material, the device performance of this type of material as an electron / hole transport material needs to be further improved, especially the device efficiency and life; Patent document 3 (KR1020220042658A) records The efficiency and life of the devices with similar structures of oxaspirofluorene-connected triazine materials also need to be improved; Patent document 4 (CN110234632A) records A type of electron transport material with a dimethyl spiro structure connected to a triazine ring. The device voltage, luminous efficiency, lifespan and other performance of this type of material 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 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 of 1-6. When n=0, they are not connected to form a ring, and m is 1, 2 or 3, and Rx is hydrogen or deuterium; when n≥1, they are connected to form a ring; when n≥2, each X is the same or different, and only one X is selected from O, S or NR2;

[0012] X1, X2, and X3 are independently selected from N or CR3, and at least one is N;

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

[0014]

[0015]

[0016] Wherein, * represents the site connected to formula (1);

[0017] R1, R2, and 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-C40 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 alkylboryl, substituted or unsubstituted C6-C60 arylboryl, substituted or unsubstituted C6-C60 arylphosphino, or substituted or unsubstituted C6-C60 arylamine;

[0018] Wherein, Ar1, Ar2, and Ar3 are independently selected from substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C2-C30 heteroaryl groups;

[0019] The substitution is substituted by 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 ranges from single substitution to the maximum number of substitutions;

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

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0022] The spiro compound of the present invention is a compound formed by connecting spirofluorene with an electron-withdrawing group such as pyrimidine, triazine and similar structures. 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 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 the LED, OLED, and AMOLED industries. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 Compound A11 of the present application 1 H NMR spectrum;

[0024] Figure 2 This is a schematic structural diagram of an organic electroluminescent device of the present application. DETAILED DESCRIPTION

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

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

[0030] 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.

[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] As a specific example of an aryl group, an aromatic hydrocarbon group derived from an aromatic ring compound by removing a hydrogen atom may be a monocyclic aryl group or a polycyclic aryl group. At least one ring in a polycyclic aryl group is an aromatic ring system. In a polycyclic aryl group, multiple rings may be connected to each other via a single bond or may be fused to each other. The number of carbon atoms in the aryl group may be 6 to 60, 6 to 40, 6 to 30, 6 to 20, 6 to 12, or 6 to 10. For example, when a polycyclic aryl group contains a fused ring structure, it may be specifically formed by condensing 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, by condensing a C3-C20 aliphatic ring and a C6-C30 aromatic ring. For example, an aryl group is selected from phenyl, naphthyl, anthracenyl, phenanthrenyl, naphthyl, pyrenyl, dinaphthylenyl, 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.

[0033] 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.

[0034] In some embodiments, a spirocyclic compound has a general structural formula as shown in formula (1):

[0035]

[0036] wherein ring A is selected from a substituted or unsubstituted benzene 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 of 1-6. When n=0, they are not connected to form a ring, and m is 1, 2 or 3, and Rx is hydrogen or deuterium; when n≥1, they are connected to form a ring; when n≥2, each X is the same or different, and only one X is selected from O, S or NR2;

[0039] X1, X2, and X3 are 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 shown in the following formulas (A-1) to (A-6):

[0041]

[0042]

[0043] Wherein, * represents the site connected to formula (1);

[0044] R1, R2, and 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-C40 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 alkylboryl, substituted or unsubstituted C6-C60 arylboryl, substituted or unsubstituted C6-C60 arylphosphino, or substituted or unsubstituted C6-C60 arylamine;

[0045] Wherein, Ar1, Ar2, and Ar3 are independently selected from substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C2-C30 heteroaryl groups;

[0046] Substitution is substituted by at least one of deuterium, halogen, cyano, isocyano, phosphino, C1-C6 alkyl, C3-C16 cycloalkyl, C1-C6 alkyl substituted amine, C1-C6 alkyl substituted or unsubstituted C6-C30 aryl, C1-C6 alkyl substituted or unsubstituted C3-C30 heteroaryl, wherein the number of substitutions ranges from single substitution to the maximum number of substitutions;

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

[0048] In some embodiments of the present application, the substituted or unsubstituted C6-C60 aryl phosphino group includes a substituted or unsubstituted C6-C60 monoaryl phosphino group or a substituted or unsubstituted C6-C60 diaryl phosphino group.

[0049] In some embodiments of the present application, R1, R2, and R3 are 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 a substituted C5-C40 heteroaryl group, a substituted or unsubstituted C1-C30 alkoxy group, a substituted or unsubstituted C6-C40 aryloxy group, a substituted or unsubstituted C3-C20 alkylsilyl group, a substituted or unsubstituted C6-C40 arylsilyl group, a substituted or unsubstituted C1-C20 alkylboryl group, a substituted or unsubstituted C6-C40 arylboryl group, a substituted or unsubstituted C6-C40 arylphosphino group, or a substituted or unsubstituted C6-C40 arylamine group.

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

[0051] In some embodiments of the present application, the substitution is by at least one of deuterium, halogen, cyano, isocyano, phosphino, C1-C6 alkyl, C3-C12 cycloalkyl, C1-C6 alkyl substituted amine, C1-C6 hydrocarbon substituted or unsubstituted C6-C20 aryl, C1-C6 hydrocarbon substituted or unsubstituted C3-C20 heteroaryl, wherein the number of substitutions ranges from a single substitution to a maximum number of substitutions.

[0052] In some embodiments of the present application, X1-X3 contains at least two 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 alkylboryl, substituted or unsubstituted C6-C30 arylboryl, substituted or unsubstituted C6-C30 arylphosphino, 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 the following formulas (B-1) to (B-9):

[0054]

[0055]

[0056] Wherein, X, X1-X3, L, Ar1, Ar2, n are the same as above;

[0057] In some embodiments of the present application, in formula (B-1) to formula (B-9) Any one of the structures selected from the following formula (C-1) to formula (C-8):

[0058]

[0059] In some embodiments of the present application, X1-X3 contains at least two N. X1-X3 may also all be N.

[0060] In some embodiments of the present application, X1-X3 are all 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 alkylboryl, substituted or unsubstituted C6-C30 arylboryl, substituted or unsubstituted C6-C30 arylphosphino, or substituted or unsubstituted C6-C30 arylamine.

[0062] In some embodiments of the present application, Ar1, Ar2, and Ar3 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 the foregoing.

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

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

[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, wherein at least one of the organic layers comprises a spiro compound represented by formula (1).

[0080] 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, and the spiro compound is a material in the light-emitting layer, the hole blocking layer, or the electron transport layer.

[0081] 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.

[0082] 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.

[0083] The raw materials and solvents involved in the synthesis of the spirocyclic compounds in the present invention are all purchased from suppliers well known to those skilled in the art, such as Alfa and Acros.

[0084] Synthesis of Compound A5

[0085] The synthetic 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(diphenylphosphine)diphenylferrocene palladium chloride (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 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 (thin layer chromatography, by volume ratio, ethyl acetate: n-hexane = 1:15 as the developing solvent). Compound A5-1 was completely 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 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 by volume as the eluent). After elution, the mixture was concentrated under reduced pressure at 70°C for 1 hour to obtain a white solid as compound A5-3 (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), and deionized water (150 mL) were added to a 1000 mL three-necked round-bottom flask. The vacuum nitrogen was replaced three times, the oil temperature was raised to 75 ° C, and the reaction was carried out for 4 hours. Under TLC monitoring (ethyl acetate: n-hexane = 1:15 as the developing solvent), compound A5-1 was completely consumed and heating was stopped.

[0092] 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 15 g of white solid. Toluene (340 mL) was added, and the oil temperature was raised to 105°C to dissolve and clarify. The temperature was naturally cooled to room temperature and stirred for 1 hour, filtered, and dried in vacuo at 70°C for 3 hours to obtain a white solid as compound A5-5 (14.25 g, mass purity: 99.52%, yield: 69.67%), and the mass spectrum result was: 495.16 (M+H).

[0093] Synthesis of Compound A5-8

[0094] Compound A5-7 (20.00 g, 74.75 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 (38.87 mL, 97.18 mmol, concentration 2.5 mol / L) was added dropwise, and the temperature in the system was controlled not to be higher than -70 ° C. The addition was completed in 20 minutes, and the temperature was maintained at -78 ° C for 1 hour. Finally, compound A5-6 (23.26 g, 104.65 mmol) was slowly added dropwise, and the addition was completed in 10 minutes. The temperature was maintained at -78 ° C for 1.5 hours. TLC monitoring (ethyl acetate: n-hexane = 1:20 as the developing solvent) showed that compound A5-7 was completely consumed.

[0095] Deionized water (100 mL) was added dropwise to the system to quench the reaction. The mixture was heated to room temperature and then separated directly. 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-loaded onto the column. Purification was performed by silica gel column chromatography (200-300 mesh silica gel, ethyl acetate:n-hexane = 1:30 as eluent). After elution, the mixture was concentrated under reduced pressure at 65°C for 1.5 hours to obtain a white solid as compound A5-8 (15.74 g, mass purity: 99.77%, yield: 51.24%). The mass spectrum 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, and then the system was cooled to 0°C, and trifluoromethanesulfonic acid (TfOH, 11.32 g, 75.44 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 A5-8 was completely consumed.

[0098] 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 column for purification 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 A5-9 (12.06 g, mass purity: 99.90%, yield: 81.37%), and the mass spectrum 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-dicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (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, and the vacuum was replaced with nitrogen three times. The system was then heated to 100°C for 2 hours. The reaction was monitored by TLC (ethyl acetate: n-hexane = 1:20 as the developing solvent). Compound 1-9 was completely consumed.

[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 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=1:30 as eluent). After elution, the mixture was concentrated under reduced pressure at 70°C for 2 hours to obtain a white solid as compound A5-10 (10.49 g, mass purity: 99.24%, yield: 70.90%), and the mass spectrum 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), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) (Pd(aMphos)Cl2, 0.15 g, 0.21 mmol), potassium carbonate (7.13 g, 51.61 mmol), 1,4-dioxane (225 mL), and deionized water (75 mL) were added to a 500 mL three-necked round-bottom flask. The vacuum was replaced with nitrogen 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 A5-10 was completely consumed, the heating was stopped.

[0104] After the reaction, a large amount of solid was precipitated, which was directly filtered to obtain 15g 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. 14g 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 A5 (12.16g, mass purity: 99.95%, yield: 72.10%). 12.16 grams of crude compound A5 was purified by sublimation to obtain sublimation pure compound A5 (10.46g, mass purity: 99.98%, yield: 86.02%), and the mass spectrum result was: 817.35 (M+H).

[0105] The NMR characterization results of compound A5 are: 1H NMR(400MHz, CDCl3) δ8.40(dd,J=7.7,5.1Hz,4H),8.30(d,J=15.0Hz,2H),8.23(s,1 H),8.16(s,1H),8.08(d,J=15.0Hz,1H),7.94(d,J=2.9Hz,1H),7.87(s,1H),7.85(d ,J=15.0Hz,2H),7.82–7.72(m,4H),7.68(dd,J=15.0,2.9Hz,1H),7.61–7.56(m,1H) ,7.54–7.36(m,13H),7.26–7.21(m,2H),7.15(dd,J=11.1,6.9Hz,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, it is only necessary to change the corresponding raw materials to obtain the target compound A11-2 (10.09 g, mass purity: 99.75%, yield: 75.61%), and 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%). 13.04 g of crude compound A11 was purified by sublimation to obtain sublimation pure compound A11 (11.32 g, mass purity: 99.93%, yield: 86.81%), and the mass spectrum result was: 742.31 (M+H).

[0113] The NMR characterization results of compound A11 are: 1H NMR (400MHz, CDCl3) δ8.72(dd,J=18.4,5.3Hz,6H),7.81(dd,J=7.6,3.6Hz,2H),7.61-7.51(m,9H),7.36(dd,J=18.6,7.7Hz,2H),7.21–7. 12(m,3H),7.04(d,J=6.8Hz,2H),7.01–6.92(m,3H),6.86(t,J=7.0Hz,3H),6.56(s,1H),6.27(d,J=7.3Hz,2H),1.87(s,3H),1.73(s,3H).

[0114] Figure 1 Compound A11 of the present application 1 H NMR spectrum, where “f1 (ppm)” represents the 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) and deionized water (75 mL) were added to a 500 mL three-necked round-bottom flask. The vacuum was replaced with nitrogen three times, the oil temperature was raised to 60°C, the reaction was carried out for 4 hours, and TLC monitoring (ethyl acetate: n-hexane = 1:20 as the developing solvent) was performed. When compound A23-1 was completely consumed, 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, and the mixture was washed three times with deionized water (300 mL*3). The mixture was separated, mixed with silica gel and dry-loaded onto a column, and purified by silica gel column chromatography (200-300 mesh silica gel, ethyl acetate:n-hexane = 1:30 as eluent). After elution, the mixture was concentrated under reduced pressure at 70 °C for 2 hours to obtain a white solid as 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] Referring to the synthesis and purification method of compound A5-3, it is only necessary to change the corresponding raw materials to obtain the target compound A23-4 (9.42 g, mass purity: 99.20%, yield: 74.58%), and the mass spectrum result is: 365.14 (M+H).

[0123] Synthesis of Compound A23-5

[0124] Referring to the synthesis and purification method of compound A5-5, it is only necessary to change the corresponding raw materials to obtain the target compound A23-5 (8.31 g, mass purity: 99.79%, yield: 71.65%), and the mass spectrum result is: 470.13 (M+H).

[0125] Synthesis of Compound A23

[0126] Referring to the synthesis and purification method of compound A5, only the corresponding raw materials need to be changed to obtain the target compound A23 (9.16 g, mass purity: 99.95%, yield: 67.94%). 9.16 g of crude compound A23 was purified by sublimation to obtain sublimation pure compound A23 (7.21 g, mass purity: 99.94%, yield: 78.71%), and the mass spectrum result was: 792.33 (M+H).

[0127] The NMR characterization results of compound A23 are: 1 H NMR(400MHz, CDCl3)δ8.52(d,J=2.8Hz,1H),8.41–8.31(m,4H),8.15(d,J=15.0Hz,1H),8.12–8.02(m,4H),7.99(dd,J=15.0,2.9Hz,1H),7.94–7 .85(m,2H),7.68(dd,J=15.1,2.9Hz,1H),7.62(dd,J=14.4,4.0Hz,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 synthetic route for the synthesis of compound A48 is as follows:

[0130]

[0131] Synthesis of Compound A48-3

[0132] Referring to the synthesis and purification method of compound A5-5, it is only necessary to change the corresponding raw materials to obtain the target compound A48-3 (12.39 g, mass purity: 99.38%, yield: 72.90%), and 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, it is only necessary to change the corresponding raw materials to obtain the target compound A48-4 (10.29 g, mass purity: 99.24%, yield: 72.96%), and 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, it is only necessary to change the corresponding raw materials to obtain the target compound A48-5 (9.15 g, mass purity: 99.57%, yield: 68.61%), and 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 to obtain the target compound A48 (10.38 g, mass purity: 99.92%, mass purity: 99.24%, yield: 65.34%). 10.38 g of crude compound A48 was purified by sublimation to obtain sublimation pure compound A48 (8.57 g, mass purity: 99.93%, yield: 82.56%), and the mass spectrum result was: 743.31 (M+H).

[0139] The NMR characterization results of compound A48 are: 1 H NMR (400MHz, CDCl3) δ8.44–8.30(m,6H),8.15(d,J=15.0Hz,1H),8.08(d,J=15.0Hz,1H),7.98(d,J=2.9Hz,1H),7.93–7.85(m,1H),7.68(dd,J=15 .0,2.9Hz,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, it is only necessary to change the corresponding raw materials 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, it is only necessary to change the corresponding raw materials 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, it is only necessary to change the corresponding raw materials 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, it is only necessary to change the corresponding raw materials 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, it is only necessary to change the corresponding raw materials 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, it is only necessary to change the corresponding raw materials to obtain the target compound A62-8 (5.72 g, mass purity: 99.51%, yield: 71.38%), and 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 to obtain the target compound A62 (6.13 g, mass purity: 99.94%, yield: 71.38%). 6.13 g of crude compound A62 was purified by sublimation to obtain sublimation pure compound A62 (4.17 g, mass purity: 99.94%, yield: 68.03%), and the mass spectrum result was: 832.33 (M+H).

[0158] The NMR characterization results of compound A62 are: 1 H NMR (400MHz, CDCl3) δ8.43–8.31(m,5H),8.15(d,J=15.0Hz,1H),8.06(dd,J=15 .0,2.9Hz,1H),7.98(dd,J=14.6,3.4Hz,1H),7.93–7.86(m,1H),7.78(d,J=15. 0Hz,1H),7.68(dd,J=14.9,3.0Hz,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=15.0,3.1Hz,1H),1.68(s,6H).

[0159] Synthesis of compound A102

[0160] The synthetic 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, it is only necessary to change the corresponding raw materials to obtain the target compound A102-2 (8.36 g, mass purity: 99.16%, yield: 71.63%), and the mass spectrum result is: 329.14 (M+H).

[0164] Synthesis of Compound A102-3

[0165] Referring to the synthesis and purification method of compound A5-5, it is only necessary to change the corresponding raw materials to obtain the target compound A102-3 (8.71 g, mass purity: 99.43%, yield: 70.29%), and the mass spectrum result is: 509.17 (M+H).

[0166] Synthesis of Compound A102-5

[0167] Referring to the synthesis and purification method of compound A5-8, it is only necessary to change the corresponding raw materials to obtain the target compound A102-5 (14.38 g, mass purity: 99.29%, yield: 55.63%), and the mass spectrum result is: 449.02 (M+H).

[0168] Synthesis of Compound A102-6

[0169] Referring to the synthesis and purification method of compound A5-9, it is only necessary to change the corresponding raw materials to obtain the target compound A102-6 (9.75 g, mass purity: 99.64%, yield: 72.56%), and the mass spectrum result is: 431.01 (M+H).

[0170] Synthesis of Compound A102-8

[0171] Referring to the synthesis and purification method of compound A5-8, it is only necessary to change the corresponding raw materials to obtain the target compound A102-8 (5.58 g, mass purity: 99.28%, yield: 58.03%), and the mass spectrum result is: 437.16 (M+H).

[0172] Synthesis of Compound A102-9

[0173] Referring to the synthesis and purification method of compound A5-9, it is only necessary to change the corresponding raw materials to obtain the target compound A102-9 (3.94 g, mass purity: 99.67%, yield: 74.72%), and the mass spectrum result is: 419.15 (M+H).

[0174] Synthesis of Compound A102-10

[0175] Referring to the synthesis and purification method of compound A5-3, it is only necessary to change the corresponding raw materials to obtain the target compound A102-10 (3.51 g, mass purity: 99.34%, yield: 73.86%), and the mass spectrum result is: 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 to obtain the target compound A102 (3.86 g, mass purity: 99.94%, yield: 63.68%). 3.86 grams of crude compound A102 was purified by sublimation to obtain sublimation pure compound A102 (2.71, mass purity: 99.95%, yield: 70.21%), and the mass spectrum result was: 857.38 (M+H).

[0178] The NMR characterization results of compound A102 are: 1 H NMR(400MHz, CDCl3)δ8.44–8.25(m,6H),8.23(s,1H),8.15(d,J=15.0Hz,1H),8 .08(d,J=15.0Hz,1H),7.92–7.80(m,4H),7.79–7.72(m,2H),7.68(dd,J=15.0, 2.9Hz,1H),7.62–7.54(m,2H),7.54–7.36(m,8H),7.28–7.20(m,2H),7.20–7.1 0(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 synthetic 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, it is only necessary to change the corresponding raw materials to obtain the target compound A118-2 (7.84 g, mass purity: 99.15%, yield: 66.67%), 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, it is only necessary to change the corresponding raw materials to obtain the target compound A118-3 (7.62 g, mass purity: 99.71%, yield: 76.12%), and the mass spectrum result is: 420.12 (M+H).

[0186] Synthesis of Compound A118-5

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

[0188] Synthesis of Compound A118-6

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

[0190] Synthesis of Compound A118-7

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

[0192] Synthesis of Compound A118

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

[0194] The NMR characterization results of compound A118 are as follows: 1 H NMR (400MHz, CDCl3) δ8.41–8.31(m,4H),8.20(d,J=3.1Hz,1H),8.15(d,J=15.0Hz,1H ),8.08(d,J=15.0Hz,1H),7.97(d,J=3.1Hz,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=15.0,2.9Hz,1H),7.27–7.21(m, 2H), 7.15 (dd, J=11.1, 6.9Hz, 4H), 5.73 (s, 1H), 2.34–2.26 (m, 4H), 1.61–1.53 (m, 6H).

[0195] Synthesis of Compound A137

[0196] The synthetic 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, it is only necessary to change the corresponding raw materials 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, it is only necessary to change the corresponding raw materials 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, it is only necessary to change the corresponding raw materials 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, it is only necessary to change the corresponding raw materials 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, it is only necessary to change the corresponding raw materials 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 to obtain the target compound A137 (6.74 g, mass purity: 99.97%, yield: 65.68%). 6.74 g of crude compound A137 was purified by sublimation to obtain sublimation pure compound A137 (4.93 g, mass purity: 99.97%, yield: 73.14%), and the mass spectrum result was: 810.38 (M+H).

[0210] The NMR characterization results of compound A137 are: 1 H NMR (400MHz, CDCl3) δ8.39-8.33(m,5H),8.15(d,J=7.4Hz,1H),8.10–8.03(m,3H) ,7.89(d,J=9.0Hz,1H),7.82–7.75(m,4H),7.68(dd,J=7.5,1.4Hz,1H),7.56–7.4 3(m,10H),7.41(d,J=7.2Hz,1H),7.27–7.20(m,2H),7.15(dd,J=5.5,3.4Hz,4H), 5.75(d,J=9.1Hz,1H), 2.32(t,J=6.0Hz,4H), 1.50(t,J=6.0Hz,4H), 0.87(s,6H).

[0211] Synthesis of compound A153

[0212] The synthetic 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, it is only necessary to change the corresponding raw materials to obtain the target compound A153-3 (10.64 g, mass purity: 99.31%, yield: 74.36%), 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, it is only necessary to change the corresponding raw materials to obtain the target compound A153-4 (8.36 g, mass purity: 99.52%, yield: 54.85%), 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, it is only necessary to change the corresponding raw materials to obtain the target compound A153-5 (5.71 g, mass purity: 99.46%, yield: 71.08%), and 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, it is only necessary to change the corresponding raw materials to obtain the target compound A153-6 (4.75 g, mass purity: 99.33%, yield: 71.58%), and 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 to obtain the target compound A153 (4.81 g, mass purity: 99.95%, yield: 72.14%). 4.81 g of crude compound A153 was purified by sublimation to obtain sublimation pure compound A153 (3.05 g, mass purity: 99.95%, yield: 63.41%), and the mass spectrum result was: 792.33 (M+H).

[0224] The NMR characterization results of compound A153 are: 1 H NMR (400MHz, CDCl3) δ8.90 (dd, J=7.1, 1.8Hz, 1H), 8.42 (d, J=7.5Hz, 1H), 8.39 ( d,J=1.5Hz,1H),8.38–8.33(m,4H),8.15(d,J=7.4Hz,1H),8.06(dd,J=7.5,1.4H z,1H),7.99(d,J=1.4Hz,1H),7.87(dd,J=7.5,1.4Hz,1H),7.81–7.76(m,3H),7. 67(dd,J=5.5,3.4Hz,2H),7.60(dd,J=7.5,1.4Hz,1H),7.52–7.48(m,6H),7.48–

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

[0226] Synthesis of Compound A169

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

[0228]

[0229] Synthesis of Compound A169-2

[0230] 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 A169-2 (14.36 g, mass purity: 99.47%, yield: 75.27%), and the mass spectrum result is: 316.97 (M+H). TBAB is tetrabutylammonium bromide.

[0231] Synthesis of Compound A169-3

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

[0233] Synthesis of Compound A169-4

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

[0235] Synthesis of Compound A169-5

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

[0237] Synthesis of Compound A169-6

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

[0239] Synthesis of Compound A169-7

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

[0241] Synthesis of Compound A169-9

[0242] Referring to the synthesis and purification method of compound A5-5, it is only necessary to change the corresponding raw materials to obtain the target compound A169-9 (3.74 g, mass purity: 99.82%, yield: 73.17%), and the mass spectrum result is: 536.18 (M+H).

[0243] Synthesis of Compound A169

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

[0245] The NMR characterization results of compound A169 are as follows: 1 H NMR (400MHz, CDCl3) δ8.94–8.87(m,1H),8.50(d,J=2.9Hz,1H),8.41–8.31(m,2H),8.24(d,J= 2.9Hz,1H),8.15(d,J=15.0Hz,1H),8.12–8.02(m,2H),7.94-7.84(m,2H),7.83–7.74(m,4H), 7.70(dd,J=11.1,6.9Hz,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=15.0,2.9Hz,1H),2.35–2.22(m,4H),1.69(s,6H),1.63–1.50(m,6H).

[0246] Synthesis of compound A201

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

[0248]

[0249] Synthesis of Compound A201-2

[0250] Referring to the synthesis and purification method of compound A5-5, it is only necessary to change the corresponding raw materials to obtain the target compound A201-2 (7.24 g, mass purity: 99.58%, yield: 74.78%), and the mass spectrum result is: 469.16 (M+H).

[0251] Synthesis of Compound A201-3

[0252] Referring to the synthesis and purification method of compound A5-3, it is only necessary to change the corresponding raw materials to obtain the target compound A201-3 (5.93 g, mass purity: 99.31%, yield: 70.88%), and 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 to obtain the target compound A201 (6.07 g, mass purity: 99.97%, yield: 75.62%). 6.07 g of crude compound A201 was purified by sublimation to obtain sublimation pure compound A201 (4.16 g, mass purity: 99.97%, yield: 68.53%), and the mass spectrum result was: 818.35 (M+H).

[0255] The NMR characterization results of compound A201 are: 1 H NMR (400MHz, CDCl3) δ9.27(t,J=2.9Hz,1H),8.46(d,J=2.9Hz,1H),8.43–8.29(m,4H),8.15(d,J=15.0Hz,1H),8.11–8.03(m,2H),8.00(d,J=2.9Hz,1H ),7.92–7.85(m,1H),7.83–7.76(m,2H),7.75–7.58(m,6H),7.55–7.39(m,1 1H),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 synthetic 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, it is only necessary to change the corresponding raw materials to obtain the target compound A210-3 (6.52 g, mass purity: 99.62%, yield: 77.05%), and 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, it is only necessary to change the corresponding raw materials to obtain the target compound A210-4 (8.67 g, mass purity: 99.53%, yield: 65.59%), and 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, it is only necessary to change the corresponding raw materials to obtain the target compound A210-5 (7.35 g, mass purity: 99.20%, yield: 74.06%), and 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 to obtain the target compound A210 (5.86 g, mass purity: 99.92%, yield: 65.17%). 5.86 g of crude compound A210 was purified by sublimation to obtain sublimation pure compound A210 (3.62 g, mass purity: 99.95%, yield: 61.77%), and the mass spectrum result was: 819.34 (M+H).

[0267] The NMR characterization results of compound A210 are: 1 H NMR (400MHz, CDCl3) δ8.74–8.66(m,1H),8.41–8.30(m,5H),8.26(d,J=2.9Hz,1H),8.15(d,J=15.0Hz,1H),8.08( d,J=15.0Hz,1H),8.01–7.85(m,4H),7.71–7.58(m,3H),7.55–7.41(m,10H),7.35(dd,J=15.0,2.9Hz,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 synthetic 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, it is only necessary to change the corresponding raw materials to obtain the target compound A234-1 (14.35 g, mass purity: 99.37%, yield: 70.43%), and 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, it is only necessary to change the corresponding raw materials to obtain the target compound A234-2 (11.12 g, mass purity: 99.24%, yield: 68.01%), and 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, it is only necessary to change the corresponding raw materials to obtain the target compound A234-4 (7.32 g, mass purity: 99.49%, yield: 61.09%), and 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 to obtain the target compound A234 (9.96 g, mass purity: 99.95%, yield: 70.06%). 9.96 g of crude compound A234 was purified by sublimation to obtain sublimation pure compound A234 (6.29 g, mass purity: 99.96%, yield: 63.15%), and the mass spectrum result was: 934.41 (M+H).

[0280] The NMR characterization results of compound A234 are as follows: 1 H NMR (400MHz, CDCl3) δ8.93(d,J=2.9Hz,1H),8.39–8.33(m,3H),8.15(d,J=15.0Hz,1H),8.09(dd,J=15.0,4.9Hz,2H),7.99–7.93(m,2H),7.93–7.86( m,2H),7.83–7.72(m,6H),7.68(dd,J=14.9,3.0Hz,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, it is only necessary to change the corresponding raw materials 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, it is only necessary to change the corresponding raw materials 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, it is only necessary to change the corresponding raw materials 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 means toluene.

[0292] Synthesis of Compound A269-6

[0293] Referring to the synthesis and purification method of compound A5-3, it is only necessary to change the corresponding raw materials 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 to obtain the target compound A269 (3.29 g, mass purity: 99.96%, yield: 69.37%). 3.29 g of crude compound A269 was purified by sublimation to obtain sublimation pure compound A269 (2.21 g, mass purity: 99.96%, yield: 67.20%), and the mass spectrum result was: 910.41 (M+H).

[0296] The NMR characterization results of compound A269 are: 1 H NMR (400MHz, CDCl3) δ8.47(d,J=2.9Hz,1H),8.36(dd,J=9.8,8.3Hz,4H),8.23(s,1H),8.14(s,1 H),8.08(d,J=14.9Hz,2H),7.93–7.86(m,1H),7.77(t,J=3.1Hz,3H),7.74–7.57(m,4H),7.54–7 .36(m,11H),7.28–7.19(m,2H),7.15(dd,J=11.0,7.0Hz,4H),6.98(dd,J=11.1,7.1Hz,2H),5.8 5–5.74(m,1H),2.46(t,J=7.2Hz,2H),2.21(s,2H),1.72(t,J=7.3Hz,5H),1.07(t,J=7.3Hz,5H).

[0297] Synthesis of compound A295

[0298] The synthetic 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, it is only necessary to change the corresponding raw materials to obtain the target compound A295-1 (9.62 g, mass purity: 99.72%, yield: 71.60%), 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, it is only necessary to change the corresponding raw materials to obtain the target compound A295-2 (8.04 g, mass purity: 99.26%, yield: 73.35%), and the mass spectrum result is: 687.34 (M+H).

[0304] Synthesis of compound A295

[0305] Referring to the synthesis and purification method of compound A5, only the corresponding raw materials need to be changed to obtain the target compound A295 (7.16 g, mass purity: 99.90%, yield: 70.80%). 5.84 g of crude compound A295 was purified by sublimation to obtain sublimation pure compound A295 (5.04 g, mass purity: 99.95%, yield: 70.39%), and the mass spectrum result was: 868.36 (M+H).

[0306] The NMR characterization results of compound A295 are: 1 H NMR(400MHz, CDCl3)δ9.03(d,J=3.1Hz,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=14.8Hz,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 synthetic route of compound A346 is as follows:

[0309]

[0310] Synthesis of Compound A346-2

[0311] Referring to the synthesis and purification method of compound A23-3, it is only necessary to change the corresponding raw materials to obtain the target compound A346-2 (9.68 g, mass purity: 99.45%, yield: 75.13%), and the mass spectrum result is: 271.98 (M+H).

[0312] Synthesis of Compound A346-3

[0313] Referring to the synthesis and purification method of compound A5-3, it is only necessary to change the corresponding raw materials to obtain the target compound A346-3 (8.07 g, mass purity: 99.41%, yield: 72.44%), and the mass spectrum result is: 320.16 (M+H).

[0314] Synthesis of Compound A346-4

[0315] Referring to the synthesis and purification method of compound A5-5, it is only necessary to change the corresponding raw materials to obtain the target compound A346-4 (7.58 g, mass purity: 99.76%, yield: 71.27%), and the mass spectrum result is: 425.15 (M+H).

[0316] Synthesis of Compound A346

[0317] Referring to the synthesis and purification method of compound A5, only the corresponding raw materials need to be changed to obtain the target compound A346 (8.62 g, mass purity: 99.94%, yield: 65.38%). 8.62 g of crude compound A346 was purified by sublimation to obtain sublimation pure compound A346 (6.72 g, mass purity: 99.96%, yield: 77.95%), and the mass spectrum result was: 747.35 (M+H).

[0318] The NMR characterization results of compound A346 are: 1 H NMR (400MHz, CDCl3) δ8.40–8.32(m,5H),8.15(d,J=15.0Hz,1H),8.11–8.03(m,2H),7.92–7.86(m,2H),7.68(dd,J=15.0, 2.9Hz,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 synthetic route of compound A380 is as follows:

[0321]

[0322] Synthesis of Compound A380-2

[0323] Referring to the synthesis and purification method of compound A23-3, it is only necessary to change the corresponding raw materials to obtain the target compound A380-2 (9.86 g, mass purity: 99.34%, yield: 76.53%), and the mass spectrum result is: 271.98 (M+H).

[0324] Synthesis of Compound A380-3

[0325] Referring to the synthesis and purification method of compound A5-3, it is only necessary to change the corresponding raw materials to obtain the target compound A380-3 (8.34 g, mass purity: 99.50%, yield: 72.57%), and the mass spectrum result is: 320.16 (M+H).

[0326] Synthesis of Compound A380-5

[0327] Referring to the synthesis and purification method of compound A5-5, it is only necessary to change the corresponding raw materials 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] Referring to the synthesis and purification method of compound A5-8, it is only necessary to change the corresponding raw materials 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] Referring to the synthesis and purification method of compound A5-9, it is only necessary to change the corresponding raw materials 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] Referring to the synthesis and purification method of compound A5-8, it is only necessary to change the corresponding raw materials 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] Referring to the synthesis and purification method of compound A5-9, it is only necessary to change the corresponding raw materials 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] Referring to the synthesis and purification method of compound A5-3, it is only necessary to change the corresponding raw materials 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%). 6.19 g of crude compound A380 was purified by sublimation to obtain sublimation pure compound A380 (4.76 g, mass purity: 99.97%, yield: 76.89%), and the mass spectrum result was: 989.46 (M+H).

[0340] The NMR characterization results of compound A380 are: 1 H NMR(400MHz, CDCl3)δ8.42(d,J=15.0Hz,1H),8.20–8.12(m,3H),8.02–7.92(m,5H),7.90–7.79(m,3H),7.78–7.7 1(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–

[0341] 1.49 (m, 6H).

[0342] Synthesis of compound A391

[0343] The synthetic 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, it is only necessary to change the corresponding raw materials to obtain the target compound A391-2 (13.59 g, mass purity: 99.46%, yield: 78.31%), and the mass spectrum result is: 342.98 (M+H).

[0347] Synthesis of Compound A391-3

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

[0349] Synthesis of Compound A391-5

[0350] Referring to the synthesis and purification method of compound A5-5, it is only necessary to change the corresponding raw materials to obtain the target compound A391-5 (10.14 g, mass purity: 99.84%, yield: 71.17%), and the mass spectrum result is: 506.21 (M+H).

[0351] Synthesis of Compound A391-7

[0352] Referring to the synthesis and purification method of compound A5-8, it is only necessary to change the corresponding raw materials to obtain the target compound A391-7 (18.07 g, mass purity: 99.50%, yield: 52.45%), and the mass spectrum result is: 449.02 (M+H).

[0353] Synthesis of Compound A391-8

[0354] Referring to the synthesis and purification method of compound A5-9, it is only necessary to change the corresponding raw materials to obtain the target compound A391-8 (12.19 g, mass purity: 99.36%, yield: 70.51%), and the mass spectrum result is: 431.01 (M+H).

[0355] Synthesis of Compound A391-10

[0356] Referring to the synthesis and purification method of compound A5-8, it is only necessary to change the corresponding raw materials to obtain the target compound A391-10 (7.61 g, mass purity: 99.75%, yield: 60.45%), and the mass spectrum result is: 453.15 (M+H).

[0357] Synthesis of Compound A391-11

[0358] Referring to the synthesis and purification method of compound A5-9, it is only necessary to change the corresponding raw materials to obtain the target compound A391-11 (5.16 g, mass purity: 99.63%, yield: 71.65%), and the mass spectrum result is: 435.14 (M+H).

[0359] Synthesis of Compound A391-12

[0360] Referring to the synthesis and purification method of compound A5-3, it is only necessary to change the corresponding raw materials to obtain the target compound A391-12 (4.62 g, mass purity: 99.57%, yield: 76.34%), and the mass spectrum result is: 527.27 (M+H).

[0361] Synthesis of compound A391

[0362] Referring to the synthesis and purification method of compound A5, only the corresponding raw materials need to be changed to obtain the target compound A391 (5.37 g, mass purity: 99.91%, yield: 72.19%). 5.37 g of crude compound A391 was purified by sublimation to obtain sublimation pure compound A391 (3.26 g, mass purity: 99.96%, yield: 60.70%), and the mass spectrum result was: 870.42 (M+H).

[0363] The NMR characterization results of compound A391 are: 1 H NMR (400MHz, CDCl3) δ8.47(d,J=2.9Hz,1H),8.15(d,J=15.0Hz,1H),8.06(dd,J=15.0,2.9Hz,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=21.0Hz,4H),2.45(t,J=21.0Hz,4H).

[0364] Synthesis of Compound A396

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

[0366]

[0367] Synthesis of Compound A396-2

[0368] Referring to the synthesis and purification method of compound A5-5, it is only necessary to change the corresponding raw materials to obtain the target compound A396-2 (9.76 g, mass purity: 99.60%, yield: 73.47%), and the mass spectrum result is: 418.13 (M+H).

[0369] Synthesis of Compound A396-4

[0370] Referring to the synthesis and purification method of compound A5-8, it is only necessary to change the corresponding raw materials to obtain the target compound A396-4 (9.47 g, mass purity: 99.59%, yield: 58.12%), and the mass spectrum result is: 469.13 (M+H).

[0371] Synthesis of Compound A396-5

[0372] Referring to the synthesis and purification method of compound A5-9, it is only necessary to change the corresponding raw materials to obtain the target compound A396-5 (6.15 g, mass purity: 99.48%, yield: 71.06%), and the mass spectrum result is: 451.12 (M+H).

[0373] Synthesis of Compound A396-6

[0374] Referring to the synthesis and purification method of compound A5-3, it is only necessary to change the corresponding raw materials to obtain the target compound A396-6 (5.70 g, mass purity: 99.17%, yield: 78.97%), and the mass spectrum result is: 543.25 (M+H).

[0375] Synthesis of Compound A396

[0376] Referring to the synthesis and purification method of compound A5, only the corresponding raw materials need to be changed to obtain the target compound A396 (5.92 g, mass purity: 99.97%, yield: 73.17%). 5.92 g of crude compound A396 was purified by sublimation to obtain sublimation pure compound A396 (3.95 g, mass purity: 99.97%, yield: 66.72%), and the mass spectrum result was: 798.31 (M+H).

[0377] The NMR characterization results of compound A396 are: 1 H NMR(400MHz, CDCl3)δ8.33–8.27(m,4H),8.23(d,J=2.9Hz,1H),8.20(s,2H),8.1 6(dd,J=9.8,9.0Hz,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=12.2Hz,4H),2.55(dd,J=18.3,6.3Hz,4H).

[0378] Synthesis of compound A397

[0379] The synthetic route of compound A397 is as follows:

[0380]

[0381] Synthesis of Compound A397-3

[0382] Referring to the synthesis and purification method of compound A23-3, it is only necessary to change the corresponding raw materials to obtain the target compound A397-3 (5.76 g, mass purity: 99.64%, yield: 64.02%), and the mass spectrum result is: 284.94 (M+H).

[0383] Synthesis of Compound A397-4

[0384] Referring to the synthesis and purification method of compound A5-5, it is only necessary to change the corresponding raw materials to obtain the target compound A397-4 (7.26 g, mass purity: 99.37%, yield: 66.93%), and the mass spectrum result is: 563.19 (M+H).

[0385] Synthesis of Compound A397-5

[0386] Referring to the synthesis and purification method of compound A5-3, it is only necessary to change the corresponding raw materials to obtain the target compound A397-5 (6.11 g, mass purity: 99.19%, yield: 75.08%), and the mass spectrum result is: 655.31 (M+H).

[0387] Synthesis of compound A397

[0388] Referring to the synthesis and purification method of compound A5, only the corresponding raw materials need to be changed to obtain the target compound A397 (5.65 g, mass purity: 99.98%, yield: 71.18%). 5.65 g of crude compound A397 was purified by sublimation to obtain sublimation pure compound A397 (3.29 g, mass purity: 99.98%, yield: 58.23%), and the mass spectrum result was: 866.29 (M+H).

[0389] The NMR characterization results of compound A397 are: 1 H NMR(400MHz, CDCl3)δ8.45(dd,J=7.5,1.4Hz,1H),8.39(d,J=1.4Hz,1H),8.38–8.34(m ,2H),8.15(d,J=7.4Hz,1H),8.10–8.04(m,2H),7.96(dd,J=7.5,1.4Hz,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 stacked 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.

[0392] 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;

[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] 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;

[0395] 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;

[0396] 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;

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

[0398] 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;

[0399] 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;

[0400] 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.

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

[0402]

[0403]

[0404] Effect evaluation:

[0405] 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).

[0406] Table 1

[0407]

[0408]

[0409] 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.

[0410] The above results show that the spiro compounds of the present application have 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, they have the possibility of being applied to the AMOLED industry. The spiro compounds of the present application also have the advantages of good optical, electrical and thermal stability and low sublimation temperature.

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 substituted or unsubstituted naphthalene ring; X is independently selected from C(R1)2, O, S or NR2; n is independently selected from 0 or an integer of 1-6. When n=0, they are not connected to form a ring, and m is 1, 2 or 3, and Rx is hydrogen or deuterium; when n≥1, they are connected to form a ring; when n≥2, each X is the same or different, and only one X is selected from O, S or NR2; X1, X2, and 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 structures shown in the following formulas (A-1) to (A-6): Wherein, * represents the site connected to formula (1); R1, R2, and 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-C40 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 alkylboryl, substituted or unsubstituted C6-C60 arylboryl, substituted or unsubstituted C6-C60 arylphosphino, or substituted or unsubstituted C6-C60 arylamine; Wherein, Ar1, Ar2, and Ar3 are independently selected from substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted C2-C30 heteroaryl groups; The substitution is substituted by 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 ranges from single substitution to the maximum number of substitutions; The heteroatoms in the heteroaryl, heteroalkyl or heterocycloalkyl are independently selected from at least one heteroatom of O, S, N, Se, Si and Ge.

2. The spiro compound according to claim 1, characterized in that The structure represented by formula (1) is selected from any one of the structures represented by formula (B-1) to formula (B-9): Among them, X, X1-X3, L, Ar1, Ar2, and n are consistent with claim 1.

3. The spiro compound according to claim 2, characterized in that (B-1) to (B-9) Any one of the structures selected from the following formula (C-1) to formula (C-8):

4. The spiro compound according to claim 1 or 2, characterized in that R1, R2, and R3 are 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 an unsubstituted C6-C40 aryloxy group, a substituted or unsubstituted C3-C20 alkylsilyl group, a substituted or unsubstituted C6-C40 arylsilyl group, a substituted or unsubstituted C1-C20 alkylboryl group, a substituted or unsubstituted C6-C40 arylboryl group, a substituted or unsubstituted C6-C40 arylphosphino group or a substituted or unsubstituted C6-C40 arylamine group; and / or Ar1, Ar2, and Ar3 are independently selected from substituted or unsubstituted C6-C20 aryl groups and substituted or unsubstituted C2-C20 heteroaryl groups.

5. The spiro compound according to claim 1 or 2, characterized in that X1-X3 contains at least two nitrogens, 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 alkylboryl, substituted or unsubstituted C6-C30 arylboryl, substituted or unsubstituted C6-C30 arylphosphino, or substituted or unsubstituted C6-C30 arylamine.

6. The spiro compound according to claim 1 or 2, characterized in that X1-X3 are all N, and n is 0.

7. The spiro compound according to claim 1 or 2, characterized in that Ar1, Ar2, Ar3 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 the foregoing.

8. The spiro compound according to claim 1 or 2, characterized in that The spirocyclic compound represented by formula (1) is one of the following structural formulas, or a structure in which hydrogen is partially or completely replaced by deuterium or fluorine in one of the following structural formulas:

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, and the spiro compound is a material in the light-emitting layer, the hole blocking layer, or the electron transport layer.

Images