A tetradentate platinum compound, a precursor of a metal compound and an organic light-emitting diode

Abstract

The present application relates to a tetradentate platinum compound, a precursor of a metal compound and an organic light-emitting diode. A tetradentate platinum compound is a compound having a structure of chemical formula (I), which is used in an organic light-emitting diode and has good luminous efficiency and device stability. The present application also provides an organic electrophotoelectric device, including a cathode, an anode and an organic layer, wherein the organic layer is one or more layers of a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer, and at least one of the organic layers contains a compound of structural formula (I).

Description

Technical Field

[0001] The present application relates to compounds used in the field of electroluminescent materials, and in particular to tetradentate platinum compounds and their application in organic light emitting diodes. Background Art

[0002] Organic light-emitting diodes (OLEDs) have many advantages such as self-luminescence, wide color gamut, wide viewing angle, and easy to realize flexible display. They have attracted extensive attention from academia and industry and have become one of the focus of competition in the high-tech field of various countries. However, OLEDs still have problems such as low efficiency and short life span, which need to be further studied.

[0003] The luminous efficiency and stability of OLED devices depend largely on the luminescent materials used. Early fluorescent OLEDs can usually only use singlet excitons to emit light. The triplet excitons generated in the device cannot emit light and return to the ground state in a non-radiative manner, which hinders the improvement of OLED efficiency. In 1998, Professor Zhi Zhiming of the University of Hong Kong and his collaborators used transition metal compounds to achieve triplet luminescence, effectively improving the utilization rate of excitons. In the same year, Thompson et al. also reported the electrophosphorescence phenomenon of transition metal compounds. Phosphorescent OLEDs can effectively utilize triplet and singlet excitons, and theoretically can achieve 100% internal quantum efficiency, which promotes the commercialization of OLEDs. The regulation of OLED luminescent color can be achieved through the structural design of luminescent materials. OLEDs can include one or more luminescent layers to achieve the required spectrum. Green, yellow and red phosphorescent materials have been commercialized. Commercial OLED displays usually use blue fluorescence and yellow, or green and red phosphorescence to achieve full-color display. Luminescent materials with higher efficiency and longer service life are urgently needed by the industry.

[0004] Metal compound luminescent materials have been applied in OLED products, but their performance, such as luminous efficiency and device life, still needs to be further improved. Currently, blue transition metal compounds have made breakthroughs in luminous efficiency, but the device life is short, so the development of efficient and stable blue phosphorescent materials has practical application value.

[0005] Patent US2019009312A1 discloses a platinum compound having the general formula of Pt(LAy)(LBz), wherein LAy can be selected from etc.; LBz can be selected from Etc. The invention also discloses structures such as benzoimidazole and benzophenone, and pays attention to the effect of introducing large steric hindrance groups on the periphery of the molecule on the luminescent properties of the material. However, it does not disclose or teach the effect of further introducing a ring structure on the benzimidazole carbene benzene ring on the photophysical properties of the material and the stability of the device.

[0006] Patent CN112341497A discloses a The platinum metal compound of the structure, wherein Y51 can be *-O-*', *-S-*', *-N(R5)-*', *-C(R5)(R6)-*', *-Si(R5)(R6)-*', etc. This application discloses the specific structure of Y51 being *-O-*', *-S-*' and *-N(R5)-*', and pays attention to The present invention discloses or teaches the specific molecular structures of Y51 as *-C(R5)(R6)-*' and *-Si(R5)(R6)-*', and does not notice the special performance advantages produced when Y51 is *-C(R5)(R6)-*' and *-Si(R5)(R6)-*'.

[0007] The above documents disclose a large number of luminescent materials, which still need further development to obtain higher device efficiency and longer device life. After in-depth research, the present application found that when fluorene or silylfluorene units are introduced into the ligand structure, the obtained new compound luminescent material can provide better device performance. Summary of the invention

[0008] The present application provides a tetradentate platinum compound. Such material can be applied to organic light-emitting diodes, and in particular can be applied as a light-emitting material to the light-emitting layer of an organic light-emitting diode. These new compounds can provide better device performance.

[0009] The present application also provides an organic light emitting diode based on the platinum compound.

[0010] The tetradentate platinum compound is a compound having the structure of formula (1):

[0011]

[0012] in:

[0013] A is carbon or silicon;

[0014] R 1 To R 8 is a substituent on the corresponding ring, R 1 To R 8independently selected from: deuterium, carbonyl, carboxyl, cyano, phosphino, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted silyl having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms;

[0015] Ar 1 R is selected from an aromatic group having 6 to 30 carbon atoms which is substituted or unsubstituted, a heteroaryl group having 3 to 30 carbon atoms which is substituted or unsubstituted, Ar 2 Selected from aromatic rings having 6 to 30 carbon atoms, heteroaromatic rings having 3 to 30 carbon atoms;

[0016] wherein R is deuterium, halogen, cyano, nitro, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 20 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylsilyl groups having 1 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylboryl groups having 1 to 20 carbon atoms, substituted or unsubstituted arylboryl groups having 6 to 20 carbon atoms, substituted or unsubstituted arylphosphino groups having 6 to 20 carbon atoms, or adjacent R substituents are bonded to each other and form an aromatic ring or heteroaromatic ring with the atoms on Ar1;

[0017] a3 to a8 are integers of 0-4, and when a3 is 2 or greater, at least two R 3 The groups are the same or different from each other. When a4 is 2 or greater, at least two R 4 The groups are the same or different from each other. When a5 is 2 or more, at least two R 5 The groups are the same or different from each other. When a6 is 2 or greater, at least two R 6 The groups are the same or different from each other. When a7 is 2 or greater, at least two R 7 The groups are the same or different from each other; when a8 is 2 or greater, at least two R 8 The groups are identical to or different from each other;

[0018] The E ring is a five- to seven-membered ring.

[0019] The substitution is substitution by deuterium, amine, cyano, C1-C4 alkyl, C6-C10 aryl or C5-C10 heteroaryl,

[0020] The heteroatom in the heteroaryl group, heteroaromatic ring, heteroalkyl group or heterocycloalkyl group is at least one of N, S and O.

[0021] Where R is in Ar 1 The substitution position in Ar 1 On the aromatic ring or heteroaromatic ring connected to N in the group, and located at the para and / or meta position of the N atom.

[0022] In some embodiments, Ar 1 Select one of the following structural formulas:

[0023]

[0024] Each X1, X5 is independently selected from CH or N; each X2-X4, X6-X9 is independently selected from C or N; when X2-X4, X6-X9 is N, the substituent R connected thereto is 9 , R 10 or R 11 does not exist;

[0025] Each Y1 is independently selected from O, S;

[0026] Each R 9 , R 10 , R 11 The alkyl radicals are independently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted alkyl radicals having 1 to 10 carbon atoms, substituted or unsubstituted heteroalkyl radicals having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl radicals having 3 to 10 carbon atoms, substituted or unsubstituted heterocycloalkyl radicals having 3 to 10 carbon atoms, substituted or unsubstituted aryl radicals having 6 to 20 carbon atoms, substituted or unsubstituted heteroaryl radicals having 3 to 20 carbon atoms, substituted or unsubstituted 1- The invention further comprises a substituted or unsubstituted alkoxy group having 10 carbon atoms, a substituted or unsubstituted aryloxy group having 6-20 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1-10 carbon atoms, a substituted or unsubstituted arylsilyl group having 6-20 carbon atoms, a substituted or unsubstituted alkylboryl group having 1-10 carbon atoms, a substituted or unsubstituted arylboryl group having 6-20 carbon atoms, or a substituted or unsubstituted arylphosphino group having 1-10 carbon atoms, and a10 is an integer of 1-4.

[0027] In some embodiments, Ar 1 is one of the formulas (2)-(4), R 9 , R 10 , R 11 At least one is not hydrogen; Ar 2Selected from aromatic rings having 6 to 20 carbon atoms and heteroaromatic rings having 3 to 20 carbon atoms.

[0028] In some embodiments, wherein Ar 1 Selected from formula (2), wherein R 10 is hydrogen, R 9 , R 11 is not hydrogen; or R 10 Not hydrogen, R 9 , R 11 For hydrogen.

[0029] In some embodiments, wherein R 10 When it is hydrogen, R 9 , R 11 is selected from substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted aryl groups having 6 to 10 carbon atoms, R 9 , R 11 the same or different; or wherein R 9 , R 11 When it is hydrogen, R 10 It is selected from a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms.

[0030] In some embodiments, R 1 , R 2 is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms. 1 , R 2 Same or different.

[0031] In some embodiments, the E ring is a five-membered ring or a six-membered ring, that is, the A, Ar 2 It is bonded to the ortho position of the benzene ring to form a five-membered ring, or bonded to the meta position of the benzene ring to form a six-membered ring.

[0032] In some embodiments, wherein a3, a5 to a8 are 0, Ar 2 Selected from aromatic rings having 6 to 10 carbon atoms.

[0033] In some embodiments, wherein R 4 Selected from: deuterium, cyano, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms, substituted or unsubstituted silane having 1 to 10 carbon atoms.

[0034] Examples of platinum metal compounds according to the present application are listed below, but are not limited to the listed structures:

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042] The precursor structural formula of the above metal compound is as follows:

[0043]

[0044] Where R 1 To R 8 ,Ar 1 ,Ar 2 , A, a3 to a8, and E are defined the same as above.

[0045] The present application also provides an application of the above-mentioned platinum compound in an organic optoelectronic device, wherein the optoelectronic device includes, but is not limited to, an organic light emitting diode (OLED), an organic thin film transistor (OTFT), an organic photovoltaic device (OPV), a light emitting electrochemical cell (LCE) and a chemical sensor, and in some embodiments, an OLED.

[0046] An organic light emitting diode (OLED) comprising the platinum compound, wherein the platinum compound is a light emitting material in a light emitting device.

[0047] The organic light-emitting diode in the present application comprises a cathode, an anode and an organic layer, wherein the organic layer comprises one or more layers of a hole injection layer, a hole transport layer, a light-emitting layer, a hole blocking layer, an electron injection layer and an electron transport layer, and not all of these organic layers need to be present; at least one of the hole injection layer, the hole transport layer, the hole blocking layer, the electron injection layer, the light-emitting layer and the electron transport layer contains the platinum compound described in formula (1).

[0048] In some embodiments, the layer where the platinum compound described in formula (1) is located is a light-emitting layer or an electron transport layer.

[0049] The total thickness of the organic layer of the device of the present application is 1-1000 nm, and in some embodiments, 1-500 nm.

[0050] In some embodiments, the total thickness of the organic layer is 5-300 nm.

[0051] The organic layer may be formed into a thin film by evaporation or a solution method.

[0052] The series of tetradentate platinum compound luminescent materials disclosed in the present application show unexpected properties, which can effectively inhibit intermolecular interactions, effectively improve the luminescent color purity, and have a short excited state lifetime, which can significantly improve the luminescent efficiency and device stability, and meet the requirements of OLED panels for luminescent materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 This is a schematic diagram of the structure of an organic light emitting diode device according to an embodiment of the present application.

[0054] Among them, 10 represents a glass substrate, 20 represents an anode, 30 represents a hole injection layer, 40 represents a hole transport layer, 50 represents a light emitting layer, 60 represents an electron transport layer, 70 represents an electron injection layer, and 80 represents a cathode. DETAILED DESCRIPTION

[0055] A tetradentate platinum compound having a structure of formula (1):

[0056]

[0057] Wherein: A is carbon or silicon;

[0058] R 1 To R 8 is a substituent of each ring, R 1 To R 8 independently selected from: deuterium, carbonyl, carboxyl, cyano, phosphino, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted silyl having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms;

[0059] Ar 1 R is selected from an aromatic group having 6 to 30 carbon atoms which is substituted or unsubstituted, a heteroaryl group having 3 to 30 carbon atoms which is substituted or unsubstituted, Ar 2 Selected from aromatic rings having 6 to 30 carbon atoms, heteroaromatic rings having 3 to 30 carbon atoms;

[0060] wherein R is deuterium, halogen, cyano, nitro, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 20 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylsilyl groups having 1 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylboryl groups having 1 to 20 carbon atoms, substituted or unsubstituted arylboryl groups having 6 to 20 carbon atoms, substituted or unsubstituted arylphosphino groups having 6 to 20 carbon atoms, or adjacent R substituents are bonded to each other and form an aromatic ring or heteroaromatic ring with the atoms on Ar1;

[0061] a3 to a8 are integers of 0-4, and when a3 is 2 or greater, at least two R 3 The groups are the same or different from each other. When a4 is 2 or greater, at least two R 4 The groups are the same or different from each other. When a5 is 2 or more, at least two R 5 The groups are the same or different from each other. When a6 is 2 or greater, at least two R 6 The groups are the same or different from each other; when a7 is 2 or greater, at least two R 7 The groups are the same or different from each other; when a8 is 2 or greater, at least two R 8 The groups are identical to or different from each other;

[0062] When a3 to a8 are zero, the substituent R 3 -R 8 Does not exist, that is, the corresponding position is hydrogen.

[0063] Since A and Ar 2 Depending on the bonding position, the E ring can form a 5-7 membered ring.

[0064] The substitution is substitution by deuterium, amine, cyano, C1-C4 alkyl, C6-C10 aryl or C5-C10 heteroaryl,

[0065] The heteroatom in the heteroaryl group, heteroaromatic ring, heteroalkyl group or heterocycloalkyl group is at least one of N, S and O.

[0066] In some embodiments, the aryl group refers to an all-carbon monocyclic or polycyclic ring. The polycyclic ring can be a polycyclic ring of a condensed structure, wherein at least one of the rings is an aromatic hydrocarbon group. Including phenyl, naphthyl, biphenyl, vinylphenyl, tolyl, anthracenyl, binaphthyl, phenanthrenyl, dihydrophenanthrene, peryl, tetracene, pentacene, benzoperylene, benzocyclopentadienyl, spirofluorenyl and fluorenyl and the like.

[0067] In some embodiments, the heteroaryl group contains at least one heteroatom selected from N, O or S, and the remaining atoms are C, including but not limited to pyridyl, pyrrolyl, imidazolyl, carbazolyl, quinolyl, isoquinolyl, thienyl, benzothienyl, dibenzothienyl, furanyl, benzofuranyl, dibenzofuranyl, triazine, pyridazine, indole, quinazoline, indazole, pyrazole, pyrazine, pyrimidine, thiazole, isoquinoline, benzothiazole, naphthyridine and the like.

[0068] Synthesis Example 1: Preparation of Compound 1

[0069]

[0070] Synthesis of compound 1c

[0071] Take a 250ml single-mouth bottle, put 1a (10.00g, 39.33mmol), 1b (24.87g, 78.65mmol), copper powder (1.25g, 19.66mmol), cuprous iodide (3.74g, 19.66mmol), L-proline (4.53g, 39.33mmol) and N,N-dimethylacetamide (100ml), protect with nitrogen, and react at 180℃ for 16h. After the reaction, add water (50ml) to quench, add ethyl acetate (50ml*3) to extract, the organic phase is dried at 60℃, and separated by silica gel (50g, 200-300 mesh) column chromatography to obtain 10.5g of red solid. The yield is 60%. HRMS (ESI) (m / z): 443.2693 [M+H] + .

[0072] Synthesis of compound 1d

[0073] Take a 500ml single-mouth bottle, put 1c (5.00g, 11.3mmol, 1.0eq), zinc powder (4.48g, 67.76mmol, 6.0eq) and acetic acid (50ml), protect with nitrogen, and react at 80℃ for 1h. After the reaction, add water (50ml) to quench, add ethyl acetate (100ml*3) for three extractions, spin dry the organic phase at 60℃, and separate by silica gel (100g, 200-300 mesh) column chromatography to obtain 4.1g white solid, with a yield of 88%. HRMS (ESI) (m / z): 413.2951 [M+H] + .

[0074] Synthesis of compound 1f

[0075] Take a 250ml single-mouth bottle, put 1d (4.00g, 9.69mmol, 1.0eq), 1e (6.85g, 14.54mmol, 1.5eq), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) (340mg, 0.48mmol, 0.05eq), XPhos (460mg, 0.47mmol, 0.1eq), cesium carbonate (9.48g, 29.08mmol, 3eq), lithium chloride (410mg, 9.69mmol, 1eq) in 80mL N,N-dimethylacetamide, protect with nitrogen, heat to 180℃ and react for 16h. After the reaction was completed, the mixture was quenched with water (50 ml), and ethyl acetate (50 ml*3) was added for extraction three times. The organic phase was dried at 60°C and separated by silica gel (100 g, 200-300 mesh) column chromatography to obtain 5.90 g of yellow solid with a yield of 71%. HRMS (ESI) (m / z): 803.4683 [M+H] + .Synthesis of compounds 1h and 1i

[0076] Take a 250ml single-mouth bottle, put 1f (3.0g, 3.74mmol, 1.0eq), dissolve it in 1g (50ml) and hydrochloric acid (30ml), protect it with nitrogen, heat it to 85℃, and react it for 16h. After the reaction, add saturated ammonium chloride solution (150ml) to the mother liquor and stir it at room temperature for one hour, then extract it with dichloromethane (30ml*3) three times, and the obtained organic phase is directly spin-dried at 60℃, and separated by silica gel (90g, 200-300 mesh) column chromatography to obtain 2.35g gray solid, which is directly put into the next step. Take a 250ml single-mouth bottle, dissolve the above 1h (2.35g) in methanol / deionized water (30ml / 20ml), then add ammonium hexafluorophosphate (0.54g, 3.32mmol, 1.2eq), protect it with nitrogen, and react it at room temperature for two days. After the reaction, the mother liquor was extracted with dichloromethane (30 ml * 3), the organic phase was dried at 60 ° C, and separated by silica gel (45 g, 200-300 mesh) column chromatography to obtain 1.93 g of gray solid, with a yield of 54%. HRMS (ESI) (m / z): 813.4527 [M] + .

[0077] Synthesis of compound 1

[0078] Take a 100ml single-mouth bottle, put 1i (1.2g, 1.25mmol, 1.0eq), (1,5-cyclooctadiene) platinum (II) dichloride (2.1g, 5.62mmol, 1.2eq), sodium acetate (0.34g, 2.5mmol, 2.0eq) and dissolve in N,N-dimethylacetamide (25ml) under argon protection, and react at 200℃ for 48h. After the reaction is completed, add 100ml of water to quench, stir at room temperature for 1 hour, filter to obtain a solid, dissolve it in dichloromethane (50ml), wash it with water (50ml), spin dry the organic phase at 60℃, and separate it by silica gel (45g, 200-300 mesh) column chromatography to obtain 0.71g of yellow solid, with a yield of 56%. . HRMS (ESI) (m / z): 1006.4007 [M+H] + .

[0079] Synthesis Example 2: Preparation of Compound 2

[0080]

[0081] Synthesis of compound 2c

[0082] Take a 250ml single-mouth bottle, put 2a (7.45g, 29.30mmol, 1.0eq), 1e (16.58g, 35.17mmol, 1.2eq), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) (1.4g, 1.97mmol, 0.05eq), cesium carbonate (23.30g, 71.51mmol, 3eq), lithium chloride (1.79g, 42.23mmol, 1eq) and dissolve in 120mL xylene, nitrogen protection, heat to 180℃ and react for 12h. After the reaction is completed, quench with water (100ml), add ethyl acetate (100ml*3) for three extractions, take the organic phase and spin dry at 60℃, and separate by silica gel (100g, 200-300 mesh) column chromatography to obtain 14.00g red oil, with a yield of 74%. HRMS(ESI)(m / z):645.2860[M+H] + .

[0083] Synthesis of compound 2d

[0084] Take a 500ml single-mouth bottle, put 2c (13.00g, 20.16mmol, 1.0eq), zinc powder (6.59g, 100.81mmol, 5.0eq) and acetic acid (130ml), protect with nitrogen, and react at 80℃ for 2h. After the reaction, add water (50ml) to quench, add ethyl acetate (100ml*3) for three extractions, spin dry the organic phase at 60℃, and separate by silica gel (150g, 200-300 mesh) column chromatography to obtain 11.52g of gray oil, with a yield of 93%. HRMS (ESI) (m / z): 615.3118 [M+H] + .

[0085] Synthesis of compound 2f

[0086] Take a 250ml single-mouth bottle, put 2d (11.00g, 17.89mmol, 1.0eq), 1b (5.78g, 21.47mmol, 1.2eq), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) (0.64g, 0.90mmol, 0.05eq), cesium carbonate (17.49g, 53.68mmol, 3eq), lithium chloride (0.76g, 17.89mmol, 1eq) and xylene (200ml), protect with nitrogen, react at 180℃ for 16h. After the reaction is completed, add water (100ml) to quench, add ethyl acetate (100ml*3) to extract, the organic phase is spin-dried at 60℃, and separated by silica gel (130g, 200-300 mesh) column chromatography to obtain 8.63g of yellow oil, with a yield of 60%. HRMS(ESI)(m / z):803.4683[M+H] + .

[0087] Synthesis of compounds 2h and 2i

[0088] Take a 250ml single-mouth bottle, put 2f (8.00g, 9.96mmol, 1.0eq), dissolve in 1g (80ml) and hydrochloric acid (8ml), protect with nitrogen, heat to 85℃, and react for 16h. After the reaction, add saturated ammonium chloride solution (150ml) to the mother liquor and stir at room temperature for one hour, then extract with dichloromethane (100ml*3) three times, and the obtained organic phase is directly spin-dried at 60℃, and separated by silica gel (110g, 200-300 mesh) column chromatography (the eluent is first used: n-hexane: ethyl acetate = 10:1 to wash away the front impurities, and then dichloromethane: methanol = 10:1 to elute), and 8g of gray solid (2h) is obtained, which is directly put into the next step reaction. Take a 250ml single-mouth bottle, dissolve the above 2h in methanol and water (80ml / 50ml), then add ammonium hexafluorophosphate (2.27g, 13.9mmol, 1.2eq) dropwise, protect with nitrogen, and react at room temperature for two days. After the reaction is completed, add dichloromethane (150ml*3) to extract the mother liquor, spin dry the organic phase at 60℃, and separate by silica gel (45g, 200-300 mesh) column chromatography to obtain 9.00g of gray solid, with a yield of 94% and a purity of 99.91%. HRMS (ESI) (m / z): 813.4527 [M] + .

[0089] Synthesis of compound 2

[0090] Take a 100ml single-mouth bottle, put 2i (600mg, 0.63mmol, 1.0eq), (1,5-cyclooctadiene) platinum (II) dichloride (248mg, 0.66mmol, 1.2eq), sodium acetate (91mg, 1.11mmol, 2.0eq) and dissolve in N,N-dimethylacetamide (30ml) under argon protection, and react at 180℃ for 48h. After the reaction is completed, add 100ml of water to quench, stir at room temperature for 1 hour, filter to obtain a solid, and perform silica gel (45g, 200-300 mesh) column chromatography (eluent is dichloromethane: n-hexane = 1:2) to obtain 0.39g of yellow solid, with a yield of 62% and a purity of 99.88%. HRMS (ESI) (m / z): 1006.4021 [M+H] + .

[0091] Synthesis Example 3: Preparation of Compound 3

[0092]

[0093] Synthesis of compound 3c

[0094] Take a 250ml single-mouth bottle, put 3a (9.98g, 39.33mmol), 1e (22.25g, 47.19mmol), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) (1.4g, 1.97mmol, cesium carbonate (38.44g, 117.98mmol), lithium chloride (1.67g, 39.33mmol) in 100mL xylene, protect with nitrogen, heat to 180℃ and react for 16min. h. After the reaction was completed, the mixture was quenched with water (100 ml), extracted three times with ethyl acetate (50 ml * 3), and the organic phase was spin-dried at 60 ° C and separated by silica gel (100 g, 200-300 mesh) column chromatography (first rinsed with 1 L of n-hexane to flush out the impurities, and then eluted with an eluent of n-hexane: ethyl acetate = 20:1), to obtain 14.00 g of yellow colloid, with a yield of 56%. HRMS (ESI) (m / z): 645.2860 [M+H] + .

[0095] Synthesis of compound 3d

[0096] Take a 500ml single-mouth bottle, put 3c (14.00g, 21.74mmol), zinc powder (6.96g, 108.7mmol) and acetic acid (140ml), protect with nitrogen, and react at 80℃ for 1h. After the reaction is completed, add water (50ml) to quench, add ethyl acetate (100ml*3) for three extractions, spin dry the organic phase at 60℃, and perform silica gel (140g, 200-300 mesh) column chromatography separation (eluent: n-hexane: ethyl acetate = 10:1), take the clean fraction and spin dry at 60℃ to obtain the crude product, and use n-hexane: dichloromethane = (50ml: 10m) to recrystallize overnight at room temperature to obtain 10.54g of white solid, with a yield of 79%. HRMS (ESI) (m / z): 615.3118 [M+H] + .

[0097] Synthesis of compound 3f

[0098] Take a 250ml single-mouth bottle, put 3d (10.00g, 16.28mmol), 1b (6.17g, 19.54mmol), copper powder (521mg, 8.14mmol), cuprous iodide (1.54g, 8.14mmol, 0.5eq), L-proline (1.87g, 16.28mmol) and xylene (120ml), protect with nitrogen, and react at 180℃ for 16h. After the reaction, add water (100ml) to quench, add ethyl acetate (50ml*3) to extract, the organic phase is dried at 60℃, and separated by silica gel (120g, 200-300 mesh) column chromatography (eluent: n-hexane: ethyl acetate = 50:1), take the clean fraction and dry it at 60℃ to obtain 10.05g of yellow colloid. The yield is 77%. HRMS(ESI)(m / z):803.4683[M+H] + .

[0099] Synthesis of compound 3h

[0100] Take a 500ml single-mouth bottle, put 3f (8.00g, 9.97mmol), dissolve it in 1g (60ml) and hydrochloric acid (60ml), protect it with nitrogen, heat it to 85℃, and react for 16h. After the reaction, add saturated ammonium chloride solution (50ml) to the mother liquor and stir it at room temperature for one hour, then extract it with dichloromethane (30ml*3) three times, and the obtained organic phase is directly spin-dried at 60℃, and separated by silica gel (120g, 200-300 mesh) column chromatography (the eluent is first: n-hexane: ethyl acetate = 1:1 to wash away the front impurities, and then elute with dichloromethane: methanol = 50:1), take the clean fraction and spin-dry at 60℃ to obtain the crude product, and recrystallize it with n-hexane: tetrahydrofuran = (100ml: 10ml) at room temperature overnight to obtain 6.00g gray solid, with a yield of 71%. HRMS (ESI) (m / z): 813.4527 [M] + .

[0101] Synthesis of compound 3i

[0102] Take a 250ml single-mouth bottle, put 3h (6.00g, 7.06mmol) into methanol (40ml), then drop ammonium hexafluorophosphate (1.38g, 8.48mmol) dissolved in water (13ml), nitrogen protection, and react at room temperature for 12h. After the reaction is completed, add dichloromethane (30ml*3) to extract the mother liquor, spin dry the organic phase at 60℃, and perform silica gel (90g, 200-300 mesh) column chromatography separation (elution agent first uses: n-hexane: ethyl acetate = 5:1 (1500ml: 300ml) elution), remove the front impurities, and then elute with n-hexane: ethyl acetate = 1:1 (2L: 2L) to obtain a solid product, use n-hexane (100ml) to slurry at room temperature overnight, and filter to obtain 5.61g of gray solid, with a yield of 83%. HRMS (ESI) (m / z): 813.4527 [M] + .

[0103] Synthesis of compound 3

[0104] Take a 250ml single-necked bottle, put 3i (3.00g, 3.12mmol), (1,5-cyclooctadiene) platinum (II) dichloride (1.40g, 3.75mmol), sodium acetate (0.51g, 6.25mmol) in N,N-dimethylacetamide (29ml), protect with argon, and react at 190℃ for 48h. After the reaction, 100 ml of water was added to quench, stirred at room temperature for 1 hour, filtered to obtain a solid, dissolved in dichloromethane (50 ml), washed with water (50 ml), the organic phase was spin-dried at 60°C, and separated by silica gel (45 g, 200-300 mesh) column chromatography. The eluent was first quickly eluted with pure dichloromethane to obtain a crude product, which was separated by silica gel (45 g, 200-300 mesh) column chromatography again (the eluent was dichloromethane: n-hexane = 2:3) to obtain a yellow solid, which was recrystallized at room temperature with dichloromethane: methanol = (10 ml: 20 ml) for 4 hours, and filtered to obtain 1.79 g of yellow powder, with a yield of 57%. HRMS (ESI) (m / z): 1006.4021 [M+H] + .

[0105] Synthesis Example 4: Preparation of Compound 4

[0106]

[0107] Synthesis of compound 4c

[0108] Take a 250ml single-mouth bottle, put 4a (12.00g, 47.19mmol), 1e (26.7g, 58.94mmol), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) (1.68g, 2.36mmol), cesium carbonate (46.13g, 141.57mmol), lithium chloride (2.00g, 47.19mmol) in 120mL of xylene, protect with nitrogen, heat to 180℃ and react for 16h. After the reaction, quench with water (100 ml), add ethyl acetate (50 ml * 3) for three extractions, take the organic phase and spin dry at 60 ° C, perform silica gel (100 g, 200-300 mesh) column chromatography separation (first rinse with 1L of n-hexane to flush out impurities, then elute with eluent: n-hexane: ethyl acetate = 20:1), take the clean fraction and spin dry at 60 ° C to obtain 17.94g of yellow colloid, with a yield of 59%. HRMS (ESI) (m / z): 645.2860 [M+H] + .

[0109] Synthesis of compound 4d

[0110] Take a 500ml single-mouth bottle, put 4c (15.00g, 23.26mmol), zinc powder (7.61g, 116.32mmol) and acetic acid (150ml), protect with nitrogen, and react at 80℃ for 1h. After the reaction is completed, add water (50ml) to quench, add ethyl acetate (100ml*3) for three extractions, spin dry the organic phase at 60℃, and perform silica gel (140g, 200-300 mesh) column chromatography separation (eluent: n-hexane: ethyl acetate = 10:1), take the clean fraction and spin dry at 60℃ to obtain the crude product, and use n-hexane: dichloromethane = (50ml: 10m) to recrystallize overnight at room temperature to obtain 11.01g of white solid, with a yield of 77%. HRMS (ESI) (m / z): 615.3118 [M+H] + .

[0111] Synthesis of compound 4f

[0112] Take a 250ml single-mouth bottle, put 4d (9.28g, 15.12mmol), 1b (5.73g, 18.14mmol), copper powder (571mg, 9.07mmol), cuprous iodide (1.72g, 9.07mmol), L-proline (1.74g, 15.12mmol) and xylene (90ml), protect with nitrogen, react at 180℃ for 16h. After the reaction, add water (100ml) to quench, add ethyl acetate (50ml*3) to extract, the organic phase is dried at 60℃, and separated by silica gel (130g, 200-300 mesh) column chromatography (eluent: n-hexane: ethyl acetate = 50:1), take the clean fraction and dry it at 60℃ to obtain 7.40g yellow colloid. The yield is 61%. HRMS (ESI) (m / z): 803.4683 [M+H] + .

[0113] Synthesis of compound 4h

[0114] Take a 500ml single-mouth bottle, put 4f (7.00g, 8.73mmol), dissolve it in 1g (70ml) and hydrochloric acid (60ml), protect it with nitrogen, heat it to 85℃, and react for 16h. After the reaction, add saturated ammonium chloride solution (50ml) to the mother liquor and stir it at room temperature for one hour, then extract it with dichloromethane (30ml*3) three times, and the obtained organic phase is directly spin-dried at 60℃, and separated by silica gel (130g, 200-300 mesh) column chromatography (the eluent is first: n-hexane: ethyl acetate = 1:1 to wash away the front impurities, and then elute with dichloromethane: methanol = 50:1), take the clean fraction and spin-dry at 60℃ to obtain the crude product, and recrystallize it with n-hexane: tetrahydrofuran = (100ml: 10ml) at room temperature overnight to obtain 5.04g of gray solid, with a yield of 68%. HRMS (ESI) (m / z): 813.4527 [M] + .

[0115] Synthesis of compound 4i

[0116] Take a 250ml single-mouth bottle, put 4h (4.00g, 4.80mmol) into methanol (28ml), then add ammonium hexafluorophosphate (0.94g, 5.75mmol, dissolved in water (9ml)), nitrogen protection, and react at room temperature for 12h. After the reaction, add dichloromethane (30ml*3) to extract the mother liquor, spin dry the organic phase at 60℃, and perform silica gel (100g, 200-300 mesh) column chromatography separation (elution agent first uses: n-hexane: ethyl acetate = 5:1 (1500ml: 300ml) elution), remove the front impurities, and then elute with n-hexane: ethyl acetate = 1:1 (2L: 2L) to obtain a solid product, use n-hexane (100ml) to slurry at room temperature overnight, and filter to obtain 3.73g of gray solid, with a yield of 81%. HRMS (ESI) (m / z): 813.4527 [M] + .

[0117] Synthesis of compound 4

[0118] Take a 250ml single-necked bottle, put 4i (1.00g, 1.04mmol), (1,5-cyclooctadiene) platinum (II) dichloride (468mg, 1.25mmol), sodium acetate (0.17g, 2.08mmol) in N,N-dimethylacetamide (8ml), protect with argon, and react at 190℃ for 48h. After the reaction, 10 ml of water was added to quench, stirred at room temperature for 1 hour, filtered to obtain a solid, dissolved in dichloromethane (10 ml), washed with water (50 ml), extracted, the organic phase was spin-dried at 60°C, and separated by silica gel (45 g, 200-300 mesh) column chromatography. The eluent was first quickly eluted with pure dichloromethane to obtain a crude product, which was separated by silica gel (45 g, 200-300 mesh) column chromatography again (the eluent was dichloromethane: n-hexane = 2:3) to obtain a yellow solid, which was recrystallized at room temperature with dichloromethane: methanol = (10 ml: 20 ml) for 4 hours, and filtered to obtain 0.65 g of yellow powder, with a yield of 62%. HRMS (ESI) (m / z): 1006.4021 [M+H] + .

[0119] Synthesis Example 5: Preparation of Compound 5

[0120]

[0121] Synthesis of compound 5c

[0122] Take a 250ml single-mouth bottle, put 5a (9.00g, 35.40mmol), 1e (20.02g, 42.47mmol), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) (1.26g, 1.77mmol), cesium carbonate (34.59g, 106.18mmol), lithium chloride (1.50g, 35.40mmol) in 90mL of xylene, protect with nitrogen, heat to 180℃ and react for 16h. After the reaction, quench with water (100 ml), add ethyl acetate (50 ml * 3) for three extractions, take the organic phase and spin dry at 60 ° C, perform silica gel (100 g, 200-300 mesh) column chromatography separation (first rinse with 1L of n-hexane to flush out impurities, then elute with eluent: n-hexane: ethyl acetate = 20:1), take the clean fraction and spin dry at 60 ° C to obtain 12.15g of yellow colloid, with a yield of 55%. HRMS (ESI) (m / z): 645.2860 [M+H] + .

[0123] Synthesis of compound 5d

[0124] Take a 500ml single-mouth bottle, put 5c (11.25g, 17.46mmol), zinc powder (5.59g, 87.30mmol) and acetic acid (112ml), protect with nitrogen, and react at 80℃ for 1h. After the reaction is completed, add water (50ml) to quench, add ethyl acetate (100ml*3) for three extractions, spin dry the organic phase at 60℃, and perform silica gel (135g, 200-300 mesh) column chromatography separation (eluent: n-hexane: ethyl acetate = 10:1), take the clean fraction and spin dry at 60℃ to obtain the crude product, and use n-hexane: dichloromethane = (50ml: 10ml) to recrystallize overnight at room temperature to obtain 8.06g of white solid, with a yield of 75%. HRMS (ESI) (m / z): 615.3118 [M+H] + .

[0125] Synthesis of compound 5f

[0126] Take a 250ml single-mouth bottle, put 5d (6.00g, 9.77mmol), 1b (3.70g, 11.73mmol), copper powder (312mg, 4.88mmol), cuprous iodide (0.93g, 4.88mmol), L-proline (1.12g, 9.77mmol) and xylene (6ml), protect with nitrogen, and react at 180℃ for 16h. After the reaction, add water (100ml) to quench, add ethyl acetate (50ml*3) to extract, the organic phase is spin-dried at 60℃, and separated by silica gel (130g, 200-300 mesh) column chromatography (eluent: n-hexane: ethyl acetate = 50:1), take the clean fraction and spin-dry at 60℃ to obtain 5.50g of yellow colloid. The yield is 70%. HRMS (ESI) (m / z): 803.4683 [M+H] + .

[0127] Synthesis of compound 5h

[0128] Take a 500ml single-mouth bottle, put 5f (4.00g, 4.99mmol), dissolve it in 1g (40ml) and hydrochloric acid (30ml), protect it with nitrogen, heat it to 85℃, and react for 16h. After the reaction, add saturated ammonium chloride solution (50ml) to the mother liquor and stir it at room temperature for one hour, then extract it with dichloromethane (30ml*3) three times, and the obtained organic phase is directly spin-dried at 60℃, and separated by silica gel (130g, 200-300 mesh) column chromatography (the eluent is first: n-hexane: ethyl acetate = 1:1 to wash away the front impurities, and then elute with dichloromethane: methanol = 50:1), take the clean fraction and spin-dry at 60℃ to obtain the crude product, and recrystallize it with n-hexane: tetrahydrofuran = (100ml: 10ml) at room temperature overnight to obtain 2.64g of gray solid, with a yield of 63%. HRMS (ESI) (m / z): 813.4527 [M] + .

[0129] Synthesis of compound 5i

[0130] Take a 250ml single-mouth bottle, put 5h (2.00g, 2.36mmol) into methanol (13ml), then add ammonium hexafluorophosphate (0.46g, 2.83mmol, dissolved in water (4ml)), nitrogen protection, and react at room temperature for 12h. After the reaction, add dichloromethane (30ml*2) to extract the mother liquor, spin dry the organic phase at 60℃, and perform silica gel (100g, 200-300 mesh) column chromatography separation (elution agent first uses: n-hexane: ethyl acetate = 5:1) to remove the front impurities, and then elute with n-hexane: ethyl acetate = 1:1 to obtain a solid product, slurry with n-hexane (20ml) at room temperature overnight, and filter to obtain 2.00g of gray solid, with a yield of 88%. HRMS (ESI) (m / z): 813.4527 [M]+ .

[0131] Synthesis of compound 5

[0132] Take a 250ml single-necked bottle, put 5i (1.00g, 1.04mmol), (1,5-cyclooctadiene) platinum (II) dichloride (0.47g, 1.25mmol), sodium acetate (0.17g, 2.08mmol) in N,N-dimethylacetamide (10ml), protect with argon, and react at 190℃ for 48h. After the reaction, 100 ml of water was added to quench, stirred at room temperature for 1 hour, filtered to obtain a solid, dissolved in dichloromethane (50 ml), washed with water (50 ml), the organic phase was spin-dried at 60°C, and separated by silica gel (90 g, 200-300 mesh) column chromatography. The eluent was first quickly eluted with pure dichloromethane to obtain a crude product, which was separated by silica gel (90 g, 200-300 mesh) column chromatography again (the eluent was dichloromethane: n-hexane = 2:3) to obtain a yellow solid, which was recrystallized at room temperature with dichloromethane: methanol = (10 ml: 20 ml) for 4 hours, and filtered to obtain 0.66 g of yellow powder, with a yield of 64%. HRMS (ESI) (m / z): 1006.4021 [M+H] + .

[0133] Synthesis Example 6: Preparation of Compound 6

[0134]

[0135] Synthesis of compound 6c

[0136] Take a 250ml single-mouth bottle, put 6a (10.00g, 39.33mmol), 1e (22.25g, 47.19mmol), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) (1.4g, 1.97mmol), cesium carbonate (38.44g, 117.98mmol), lithium chloride (1.67g, 39.33mmol) in 100mL of xylene, protect with nitrogen, heat to 180℃ and react for 16h. After the reaction, quench with water (100 ml), add ethyl acetate (50 ml * 3) for three extractions, take the organic phase and spin dry at 60 ° C, perform silica gel (100 g, 200-300 mesh) column chromatography (first rinse with 1L of n-hexane to flush out impurities, then elute with eluent: n-hexane: ethyl acetate = 20:1), take the clean fraction and spin dry at 60 ° C to obtain 14.00 g of yellow colloid, with a yield of 55%. HRMS (ESI) (m / z): 645.2860 [M+H] + .

[0137] Synthesis of compound 6d

[0138] Take a 500ml single-mouth bottle, put 6c (8.00g, 12.42mmol), zinc powder (3.98g, 62.11mmol) and acetic acid (80ml), protect with nitrogen, and react at 80℃ for 1h. After the reaction is completed, add water (29ml) to quench, add ethyl acetate (50ml*3) for three extractions, spin dry the organic phase at 60℃, and perform silica gel (140g, 200-300 mesh) column chromatography separation (eluent: n-hexane: ethyl acetate = 10:1), take the clean fraction and spin dry at 60℃ to obtain the crude product, and use n-hexane: dichloromethane = (50ml: 10m) to recrystallize overnight at room temperature to obtain 5.62g of white solid, with a yield of 74%. HRMS (ESI) (m / z): 615.3118 [M+H] + .

[0139] Synthesis of compound 6f

[0140] Take a 250ml single-mouth bottle, put 6d (4.00g, 6.51mmol), 1b (2.47g, 24.43mmol, 1.2eq), copper powder (641.34mg, 10.18mmol, 0.5eq), cuprous iodide (1.93g, 10.18mmol, 0.5eq), L-proline (0.75g, 6.51mmol) and xylene (40ml), protect with nitrogen, react at 180℃ for 16h. After the reaction, add water (30ml) to quench, add ethyl acetate (20ml*3) to extract, the organic phase is dried at 60℃, and separated by silica gel (130g, 200-300 mesh) column chromatography (eluent: n-hexane: ethyl acetate = 50:1), take the clean fraction and dry it at 60℃ to obtain 3.84g yellow colloid. The yield is 73%. HRMS(ESI)(m / z):803.4683[M+H] + .

[0141] Synthesis of compound 6h

[0142] Take a 500ml single-mouth bottle, put 6f (3.00g, 3.74mmol), dissolve it in 1g (30ml) and hydrochloric acid (25ml), protect it with nitrogen, heat it to 85℃, and react for 16h. After the reaction, add saturated ammonium chloride solution (12ml) to the mother liquor and stir it at room temperature for one hour, then extract it with dichloromethane (20ml*3) three times, and the obtained organic phase is directly spin-dried at 60℃, and separated by silica gel (120g, 200-300 mesh) column chromatography (the eluent is first: n-hexane: ethyl acetate = 1:1 to wash away the front impurities, and then elute with dichloromethane: methanol = 50:1), take the clean fraction and spin-dry at 60℃ to obtain the crude product, and recrystallize it with n-hexane: tetrahydrofuran = (100ml: 10ml) at room temperature overnight to obtain 2.5g gray solid, with a yield of 79%. HRMS (ESI) (m / z): 813.4527 [M] + .

[0143] Synthesis of compound 6i

[0144] Take a 250ml single-mouth bottle, put 6h (2.00g, 2.36mmol) into methanol (13ml), then add ammonium hexafluorophosphate (0.46g, 2.83mmol, dissolved in water (4ml)), nitrogen protection, and react at room temperature for 12h. After the reaction is completed, add dichloromethane (20ml*3) to extract the mother liquor, spin dry the organic phase at 60℃, and perform silica gel (100g, 200-300 mesh) column chromatography separation (elution agent first uses: n-hexane: ethyl acetate = 6:1) to remove the front impurities, and then elute with n-hexane: ethyl acetate = 2:1 to obtain a solid product, use n-hexane (100ml) to slurry at room temperature overnight, and filter to obtain 2.0g of gray solid, with a yield of 89%. HRMS (ESI) (m / z): 813.4527 [M] + .

[0145] Synthesis of compound 6

[0146] Take a 250ml single-necked bottle, put 6i (2.00g, 2.08mmol), (1,5-cyclooctadiene) platinum (II) dichloride (0.94g, 2.50mmol), sodium acetate (0.34g, 4.17mmol) in N,N-dimethylacetamide (18ml), protect with argon, and react at 190℃ for 48h. After the reaction, 100 ml of water was added to quench, stirred at room temperature for 1 hour, and filtered to obtain a solid, which was then dissolved in dichloromethane (10 ml), washed with water (10 ml), and the organic phase was dried at 60°C, and separated by silica gel (100 g, 200-300 mesh) column chromatography. The eluent was first quickly eluted with pure dichloromethane to obtain a crude product, which was separated by silica gel (100 g, 200-300 mesh) column chromatography again (the eluent was dichloromethane: n-hexane = 2:3) to obtain a yellow solid, which was recrystallized at room temperature with dichloromethane: methanol = (2 ml: 10 ml) for 4 hours, and filtered to obtain 1.15 g of yellow powder, with a yield of 55%. HRMS (ESI) (m / z): 1006.4021 [M+H] + .

[0147] Synthesis Example 7: Preparation of Compound 7

[0148]

[0149] Synthesis of compound 7c

[0150] Take a 250ml single-mouth bottle, put 7a (11.50g, 42.60mmol), 1b (16.16g, 51.12mmol), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) (1.51g, 2.13mmol), cesium carbonate (41.53g, 127.79mmol), lithium chloride (1.79g, 42.60mmol) in 110mL of xylene, protect with nitrogen, heat to 180℃ and react for 16h. After the reaction, quench with water (100 ml), add ethyl acetate (50 ml * 3) for three extractions, take the organic phase and spin dry at 60 ° C, perform silica gel (100 g, 200-300 mesh) column chromatography (first rinse with 1 L of n-hexane to flush out impurities, then elute with eluent: n-hexane: ethyl acetate = 20:1), take the clean fraction and spin dry at 60 ° C to obtain 9.20 g of yellow colloid, with a yield of 47%. HRMS (ESI) (m / z): 459.2462 [M+H] + .

[0151] Synthesis of compound 7d

[0152] Take a 500ml single-mouth bottle, put 7c (8.00g, 17.47mmol), zinc powder (5.59g, 87.35mmol) and acetic acid (80ml), protect with nitrogen, and react at 80℃ for 1h. After the reaction is completed, add water (50ml) to quench, add ethyl acetate (60ml*3) for three extractions, spin dry the organic phase at 60℃, and perform silica gel (80g, 200-300 mesh) column chromatography separation (eluent: n-hexane: ethyl acetate = 10:1), take the clean fraction and spin dry at 60℃ to obtain the crude product, and use n-hexane: dichloromethane = (50ml: 10m) to recrystallize overnight at room temperature to obtain 5.51g of white solid, with a yield of 74%. HRMS (ESI) (m / z): 429.2721 [M+H] + .

[0153] Synthesis of compound 7f

[0154] Take a 250ml single-mouth bottle, put 7d (5.00g, 11.68mmol), 1e (6.59g, 14.02mmol), copper powder (368mg, 5.84mmol), cuprous iodide (1.11g, 5.84mmol), L-proline (1.34g, 11.68mmol) and xylene (35ml), protect with nitrogen, react at 180℃ for 16h. After the reaction, add water (50ml) to quench, add ethyl acetate (50ml*3) to extract, the organic phase is dried at 60℃, and separated by silica gel (70g, 200-300 mesh) column chromatography (eluent: n-hexane: ethyl acetate = 50:1), take the clean fraction and dry at 60℃ to obtain 6.50g yellow colloid. The yield is 68%. HRMS (ESI) (m / z): 819.4453 [M+H] + .

[0155] Synthesis of compound 7h

[0156] Take a 500ml single-mouth bottle, put 7f (4.00g, 4.89mmol), dissolve it in 1g (40ml) and hydrochloric acid (33ml), protect it with nitrogen, heat it to 85℃, and react for 16h. After the reaction, add saturated ammonium chloride solution (20ml) to the mother liquor and stir it at room temperature for one hour, then extract it with dichloromethane (30ml*3) three times, and the obtained organic phase is directly spin-dried at 60℃, and separated by silica gel (95g, 200-300 mesh) column chromatography (the eluent is first: n-hexane: ethyl acetate = 1:1 to wash away the front impurities, and then elute with dichloromethane: methanol = 50:1), take the clean fraction and spin-dry at 60℃ to obtain the crude product, and recrystallize it with n-hexane: tetrahydrofuran = (100ml: 10ml) at room temperature overnight to obtain 3.54g gray solid, with a yield of 84%. HRMS (ESI) (m / z): 829.4296 [M] +.

[0157] Synthesis of compound 7i

[0158] Take a 250ml single-mouth bottle, put 7h (2.00g, 2.25mmol) into methanol (13ml), then add ammonium hexafluorophosphate (0.44g, 2.70mmol, dissolved in water (4ml)), nitrogen protection, and react at room temperature for 12h. After the reaction, add dichloromethane (30ml*3) to the mother liquor for extraction, spin dry the organic phase at 60℃, and perform silica gel (84g, 200-300 mesh) column chromatography separation (elution agent first uses: n-hexane: ethyl acetate = 5:1 (1500ml: 300ml) elution), remove the front impurities, and then use n-hexane: ethyl acetate = 1:1 (elution to obtain a solid product, use n-hexane (100ml) to slurry at room temperature overnight, and filter to obtain 1.81g of gray solid, with a yield of 80%. HRMS (ESI) (m / z): 829.4296 [M] + .

[0159] Synthesis of compound 7

[0160] Take a 250ml single-necked bottle, put 7i (1.00g, 1.03mmol), (1,5-cyclooctadiene) platinum (II) dichloride (0.46g, 1.23mmol), sodium acetate (0.17g, 2.05mmol) in N,N-dimethylacetamide (10ml), protect with argon, and react at 190℃ for 48h. After the reaction was completed, 12 ml of water was added to quench, stirred at room temperature for 1 hour, and filtered to obtain a solid, which was then dissolved in dichloromethane (6 ml), washed with water (12 ml), and the organic phase was spin-dried at 60°C, and separated by silica gel (80 g, 200-300 mesh) column chromatography. The eluent was first quickly eluted with pure dichloromethane to obtain a crude product, which was separated by silica gel (80 g, 200-300 mesh) column chromatography again (the eluent was dichloromethane: n-hexane = 2:3) to obtain a yellow solid, which was recrystallized at room temperature with dichloromethane: methanol = (10 ml: 20 ml) for 4 hours, and filtered to obtain 0.67 g of yellow powder, with a yield of 65%. HRMS (ESI) (m / z): 1022.3787 [M+H] + .

[0161] Synthesis Example 8: Preparation of Compound 13

[0162]

[0163] Synthesis of compound 13c

[0164] Take a 250ml single-necked bottle, put 13a (10.00g, 26.46mmol), 1b (10.03g, 31.75mmol), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) (939.33mg, 1.32mmol), cesium carbonate (25.80g, 79.38mmol), lithium chloride (1.1g, 26.46mmol) in 100mL of xylene, protect with nitrogen, heat to 180℃ and react for 16h. After the reaction, quench with water (100ml), add ethyl acetate (50ml*3) for three extractions, take the organic phase and spin dry at 60℃, perform silica gel (100g, 200-300 mesh) column chromatography separation (first rinse with 1L of n-hexane to flush out impurities, then elute with eluent: n-hexane: ethyl acetate = 20:1), take the clean fraction and spin dry at 60℃ to obtain a yellow crude product, use methanol: dichloromethane = (20ml: 100ml) to recrystallize overnight at room temperature for 12h, filter, and dry the filter cake at 80℃ for 3h to obtain 11.00g of red solid. The yield is 74%. HRMS (ESI) (m / z): 567.3006 [M+H] +

[0165] Synthesis of compound 13d

[0166] Take a 500ml single-mouth bottle, put 13c (9.00g, 15.90mmol), zinc powder (5.09g, 79.49mmol) and acetic acid (82ml), protect with nitrogen, and react at 80℃ for 1h. After the reaction, add water (50ml) to quench, add ethyl acetate (30ml*3) for three extractions, spin dry the organic phase at 60℃, and perform silica gel (100g, 200-300 mesh) column chromatography separation (eluent: n-hexane: ethyl acetate = 10:1), take the clean fraction and spin dry at 60℃ to obtain the crude product, and use n-hexane: dichloromethane = (40ml: 10ml) to recrystallize overnight at room temperature to obtain 6.92g of white solid, with a yield of 81%. HRMS (ESI) (m / z): 537.3264 [M+H] + .

[0167] Synthesis of compound 13f

[0168] Take a 250ml single-mouth bottle, put 13d (5.00g, 9.33mmol), 1e (5.26g, 11.19mmol), copper powder (294mg, 4.66mmol), cuprous iodide (0.88g, 4.66mmol), L-proline (1.16g, 9.33mmol) and xylene (50ml), protect with nitrogen, and react at 180℃ for 16h. After the reaction, add water (100ml) to quench, add ethyl acetate (50ml*3) to extract, the organic phase is spin-dried at 60℃, and separated by silica gel (70g, 200-300 mesh) column chromatography (eluent: n-hexane: ethyl acetate = 30:1, V / V), take the clean fraction and spin-dry at 60℃ to obtain 6.36g of yellow colloid. The yield is 74%. HRMS (ESI) (m / z): 927.4996 [M+H] + .

[0169] Synthesis of compound 13h

[0170] Take a 500ml single-mouth bottle, put 13f (5.00g, 5.4mmol), dissolve it in 1g (50ml) and hydrochloric acid (36ml), protect it with nitrogen, heat it to 85℃, and react for 16h. After the reaction, add saturated ammonium chloride solution (30ml) to the mother liquor and stir it at room temperature for one hour, then extract it with dichloromethane (30ml*3) three times, and the obtained organic phase is directly spin-dried at 60℃, and separated by silica gel (140g, 200-300 mesh) column chromatography (the eluent is first: n-hexane: ethyl acetate = 1:1 to wash away the front impurities, and then elute with dichloromethane: methanol = 30:1), take the clean fraction and spin-dry at 60℃ to obtain the crude product, and recrystallize it with n-hexane: tetrahydrofuran = (100ml: 13ml) at room temperature overnight to obtain 4.28g of gray solid, with a yield of 82%. HRMS (ESI) (m / z): 937.4840 [M] + .

[0171] Synthesis of compound 13i

[0172] Take a 250ml single-mouth bottle, put 13h (4.00g, 4.11mmol) into methanol (23ml), then add ammonium hexafluorophosphate (0.80g, 4.93mmol, dissolved in water (7ml)), nitrogen protection, and react at room temperature for 12h. After the reaction, add dichloromethane (40ml*3) to the mother liquor for extraction, spin dry the organic phase at 60℃, and perform silica gel (120g, 200-300 mesh) column chromatography separation (elution agent first uses: n-hexane: ethyl acetate = 4:1) to remove the front impurities, and then elute with n-hexane: ethyl acetate = 1:1 to obtain a solid product, slurry with n-hexane (33ml) at room temperature overnight, and filter to obtain 3.83g of gray solid, with a yield of 86%. HRMS (ESI) (m / z): 937.4840 [M] + .

[0173] Synthesis of compound 13

[0174] In a 250 ml single-necked bottle, 13i (2.00 g, 1.85 mmol), (1,5-cyclooctadiene)platinum(II) dichloride (0.83 g, 2.22 mmol), and sodium acetate (0.30 g, 3.69 mmol) were dissolved in N,N-dimethylacetamide (20 ml) under argon protection and reacted at 190 °C for 48 h. After the reaction, 45 ml of water was added to quench, stirred at room temperature for 1 hour, filtered to obtain a solid, dissolved in dichloromethane (8 ml), washed with water (50 ml), extracted, the organic phase was spin-dried at 60 ° C, and separated by silica gel (115 g, 200-300 mesh) column chromatography. The eluent was first quickly eluted with pure dichloromethane to obtain a crude product, which was separated by silica gel (115 g, 200-300 mesh) column chromatography again (the eluent was dichloromethane: n-hexane = 1:2) to obtain a yellow solid, which was recrystallized at room temperature with dichloromethane: methanol = (10 ml: 20 ml) for 4 hours, and filtered to obtain 1.22 g of yellow powder, with a yield of 58%. HRMS (ESI) (m / z): 1130.4331 [M+H] + .

[0175] Synthesis Example 9: Preparation of Compound 19

[0176]

[0177] Synthesis of compound 19c

[0178] Take a 250ml single-mouth bottle, put 19a (11.20g, 28.42mmol), 1b (10.77g, 34.11mmol), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (II) (1.00g, 1.42mmol), cesium carbonate (27.72g, 85.28mmol), lithium chloride (1.19g, 28.42mmol) in 110mL of xylene, protect with nitrogen, heat to 180℃ and react for 16h. After the reaction, quench with water (100ml), add ethyl acetate (50ml*3) for three extractions, take the organic phase and spin dry at 60℃, perform silica gel (100g, 200-300 mesh) column chromatography separation (first rinse with 1L of n-hexane to flush out impurities, then elute with eluent: n-hexane: ethyl acetate = 20:1), take the clean fraction and spin dry at 60℃ to obtain a yellow crude product, use methanol: dichloromethane = (20ml: 100ml) to recrystallize at room temperature overnight for 12h, filter, and dry the filter cake at 80℃ for 3h to obtain 10.65g, red solid. The yield is 64%. HRMS (ESI) (m / z): 583.2775 [M+H] +

[0179] Synthesis of compound 19d

[0180] Take a 500ml single-mouth bottle, put 19c (8.00g, 13.75mmol), zinc powder (4.40g, 68.73mmol) and acetic acid (80ml), protect with nitrogen, and react at 80℃ for 1h. After the reaction is completed, add water (43ml) to quench, add ethyl acetate (30ml*3) for three extractions, spin dry the organic phase at 60℃, and separate by silica gel (110g, 200-300 mesh) column chromatography (eluent: n-hexane: ethyl acetate = 9:1), take the clean fraction and spin dry at 60℃ to obtain the crude product, and recrystallize it with n-hexane: dichloromethane = (30ml:10ml) at room temperature overnight to obtain 5.78g of white solid, with a yield of 76%. HRMS (ESI) (m / z): 553.3034 [M+H] + .

[0181] Synthesis of compound 19f

[0182] Take a 250ml single-mouth bottle, put 19d (4.00g, 7.24mmol), 1e (4.08g, 8.69mmol), copper powder (228mg, 3.62mmol), cuprous iodide (0.68g, 3.62mmol), L-proline (0.83g, 7.24mmol) and xylene (40ml), protect with nitrogen, and react at 180℃ for 16h. After the reaction, add water (40ml) to quench, add ethyl acetate (20ml*3) to extract, the organic phase is dried at 60℃, and separated by silica gel (90g, 200-300 mesh) column chromatography (eluent: n-hexane: ethyl acetate = 60:1, V / V), take the clean fraction and dry it at 60℃ to obtain 4.03g of yellow colloid. The yield is 59%. HRMS (ESI) (m / z): 943.4766 [M+H] + .

[0183] Synthesis of compound 19h

[0184] Take a 500ml single-mouth bottle, put 19f (3.00g, 3.19mmol), dissolve it in 1g (30ml) and hydrochloric acid (23ml), protect it with nitrogen, heat it to 85℃, and react for 16h. After the reaction, add saturated ammonium chloride solution (20ml) to the mother liquor and stir it at room temperature for one hour, then extract it with dichloromethane (30ml*3) three times, and the obtained organic phase is directly spin-dried at 60℃, and separated by silica gel (120g, 200-300 mesh) column chromatography (the eluent is first used: n-hexane: ethyl acetate = 1:1 to wash away the front impurities, and then eluted with dichloromethane: methanol = 40:1), take the clean fraction and spin-dry at 60℃ to obtain the crude product, and recrystallize it with n-hexane: tetrahydrofuran = (100ml: 15ml) at room temperature overnight to obtain 2.63g of gray solid, with a yield of 83%. HRMS (ESI) (m / z): 953.4609 [M] + .

[0185] Synthesis of compound 19i

[0186] Take a 250ml single-mouth bottle, put 19h (2.00g, 2.02mmol) into methanol (14ml), then add ammonium hexafluorophosphate (0.40g, 2.43mmol, dissolved in water (4ml)), nitrogen protection, and react at room temperature for 12h. After the reaction, add dichloromethane (20ml*3) to extract the mother liquor, spin dry the organic phase at 60℃, and perform silica gel (105g, 200-300 mesh) column chromatography separation (elution agent first uses: n-hexane: ethyl acetate = 5:1) to remove the front impurities, and then elute with n-hexane: ethyl acetate = 2:1 to obtain a solid product, slurry with n-hexane (20ml) at room temperature overnight, and filter to obtain 1.77g of gray solid, with a yield of 80%. HRMS (ESI) (m / z): 953.4609 [M] + .

[0187] Synthesis of compound 19

[0188] Take a 250ml single-necked bottle, put 19i (1.50g, 1.36mmol), (1,5-cyclooctadiene) platinum (II) dichloride (0.61g, 1.64mmol), sodium acetate (0.22g, 2.73mmol) in N,N-dimethylacetamide (15ml), protect with argon, and react at 190℃ for 48h. After the reaction, 100 ml of water was added to quench, stirred at room temperature for 1 hour, filtered to obtain a solid, dissolved in dichloromethane (50 ml), washed with water (50 ml), the organic phase was spin-dried at 60°C, and separated by silica gel (110 g, 200-300 mesh) column chromatography. The eluent was first quickly eluted with pure dichloromethane to obtain a crude product, which was separated by silica gel (110 g, 200-300 mesh) column chromatography again (the eluent was dichloromethane: n-hexane = 2:5) to obtain a yellow solid, which was recrystallized at room temperature with dichloromethane: methanol = (10 ml: 30 ml) for 4 hours, and filtered to obtain 0.70 g of yellow powder, with a yield of 45%. HRMS (ESI) (m / z): 1146.4100 [M+H] + .

[0189] Synthesis Example 10: Preparation of Compound 25

[0190]

[0191] Synthesis of compound 25c

[0192] Take a 250ml single-mouth bottle, put compound 1a (11.30g, 44.49mmol), compound 25b (13.22g, 48.93mmol, copper powder (1.41g, 22.21mmol), cuprous iodide (4.23g, 22.21mmol), o-phenanthroline (4.00g, 22.24mmol) and xylene (110ml), protect with nitrogen, and react at 180℃ for 48h. After the reaction, water was added to quench the reaction, and ethyl acetate was added to extract to obtain an organic layer, which was spin-dried and separated by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 50:1) to obtain a yellow crude product, which was recrystallized from methanol / dichloromethane at room temperature overnight for 12h and filtered to obtain 11.30g of a red solid. The yield was 77%. HRMS (ESI) (m / z): 397.1838 [M+H] +

[0193] Synthesis of compound 25d

[0194] Take a 500ml single-mouth bottle, put 25c (8.00g, 19.64mmol), iron powder (6.62g, 117.82mmol) and acetic acid (80ml), protect with nitrogen, and react at 80℃ for 1h. After the reaction is completed, add water (44ml) to quench, add ethyl acetate (30ml*3) for three extractions, spin dry the organic phase at 60℃, and perform silica gel (110g, 200-300 mesh) column chromatography separation (eluent: n-hexane: ethyl acetate = 10: 1, V / V), take the clean fraction and spin dry at 60℃ to obtain the crude product, and use n-hexane: dichloromethane = (40ml: 10ml) to recrystallize overnight at room temperature to obtain 6.48g of white solid, with a yield of 88%. HRMS (ESI) (m / z): 367.2100 [M+H] + .

[0195] Synthesis of compound 25f

[0196] Take a 250ml single-mouth bottle, put 25d (6.00g, 16.4mmol), 1e (8.09g, 17.2mmol), copper powder (1.00g, 16.4mmol), cuprous iodide (3.13g, 16.4mmol), o-phenanthroline (3.13g, 16.4mmol) and xylene (60ml), protect with nitrogen, react at 180℃ for 16h. After the reaction, add water (60ml) to quench, add ethyl acetate (30ml*3) to extract, the organic phase is dried at 60℃, and separated by silica gel (90g, 200-300 mesh) column chromatography (eluent: n-hexane: ethyl acetate = 50:1), take the clean fraction and dry it at 60℃ to obtain 8.00g of yellow colloid. The yield is 65%. HRMS (ESI) (m / z): 757.3838 [M+H] + .

[0197] Synthesis of compound 25h

[0198] Take a 500ml single-mouth bottle, put 25f (7.00g, 9.23mmol), dissolve it in triethyl orthoformate (70ml) and hydrochloric acid (52ml), protect it with nitrogen, heat it to 85℃, and react for 16h. After the reaction, add saturated ammonium chloride solution (47ml) to the mother liquor and stir it at room temperature for one hour, then extract it with dichloromethane (20ml*3), and the obtained organic phase is directly spin-dried at 60℃, and separated by silica gel (120g, 200-300 mesh) column chromatography (the eluent is first used: n-hexane: ethyl acetate = 1:1 to wash away the front impurities, and then eluted with dichloromethane: methanol = 30:1), take the clean fraction and spin-dry it at 60℃ to obtain the crude product, and use n-hexane: tetrahydrofuran = (100ml: 16ml) to recrystallize overnight at room temperature to obtain 5.14g of gray solid, with a yield of 69%. HRMS (ESI) (m / z): 768.3828 [M] + .

[0199] Synthesis of compound 25i

[0200] Take a 250ml single-mouth bottle, put 25h (5.00g, 6.19mmol) into methanol (36ml), then add ammonium hexafluorophosphate (1.21g, 7.48mmol, dissolved in water (10ml)), nitrogen protection, and react at room temperature for 12h. After the reaction, add dichloromethane (40ml*3) to the mother liquor for extraction, spin dry the organic phase at 60℃, and perform silica gel column chromatography (elution agent first uses: n-hexane: ethyl acetate = 5:1) to remove the front impurities, and then use n-hexane: ethyl acetate = 3:1 (elution to obtain a solid product, use n-hexane (47ml) to slurry at room temperature overnight, and filter to obtain 4.34g of gray solid, with a yield of 76%. HRMS (ESI) (m / z): 768.3828 [M] + .

[0201] Synthesis of compound 25

[0202] Take a 250ml single-mouth bottle, put 25i (2.00g, 2.00mmol), (1,5-cyclooctadiene) platinum (II) dichloride (0.90g, 2.4mmol), sodium acetate (0.54g, 4.00mmol) into N, N-dimethylacetamide (20ml) under argon protection, and react at 190℃ for 48h. After the reaction is completed, add 20ml of water to quench, stir at room temperature for 1 hour, filter to obtain a solid, then dissolve in dichloromethane (10ml), wash with water (50ml), spin dry the organic phase at 60℃, and perform silica gel column chromatography. The eluent is first quickly eluted with pure dichloromethane to obtain a crude product, and then perform silica gel column chromatography again (the eluent is dichloromethane: n-hexane = 2:3) to obtain a yellow solid, which is recrystallized at room temperature for 4h with dichloromethane: methanol = (14ml: 20ml), and 1.2g of yellow powder is obtained by suction filtration, with a yield of 60%. HRMS(ESI)(m / z):960.3241[M+H] + .

[0203] Synthesis Example 11: Preparation of Compound 37

[0204]

[0205] Synthesis of compound 37c

[0206] Take a 250ml single-mouth bottle, put compound 1a (9.00g, 35.41mmol, 1.0eq), compound 37b (12.00g, 39.00mmol), copper powder (1.05g, 17.25mmol), cuprous iodide (3.00g, 17.25mmol), o-phenanthroline (3.00g, 17.25mmol) and xylene (75ml), protect with nitrogen, react at 180℃ for 48h. After the reaction, add water to quench the reaction, extract with ethyl acetate to obtain an organic layer, spin dry, and perform silica gel column chromatography (eluent: n-hexane: ethyl acetate = 50:1) to obtain a yellow crude product, which is recrystallized from methanol / dichloromethane at room temperature overnight for 12h, filtered, and 12.00g of a red solid is obtained. The yield is 77%. HRMS (ESI) (m / z): 439.2307 [M+H] +

[0207] Synthesis of compound 37d

[0208] Take a 500ml single-mouth bottle, put 37c (8.00g, 18.24mmol), iron powder (6.20g, 109mmol) and acetic acid (110ml), protect with nitrogen, and react at 80℃ for 1h. After the reaction is completed, add water (60ml) to quench, add ethyl acetate (20ml) to extract three times, spin dry the organic phase at 60℃, and separate by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 10:1). Take the clean fraction and spin dry at 60℃ to obtain the crude product, and use n-hexane: dichloromethane = (50ml: 10ml) to recrystallize at room temperature overnight to obtain 7.13g of white solid, with a yield of 96%. HRMS (ESI) (m / z): 409.2665 [M+H] + .

[0209] Synthesis of compound 37f

[0210] Take a 250ml single-mouth bottle, put 37d (5.00g, 12.24mmol), 1e (6.05g, 12.83mmol), copper powder (0.75g, 11.87mmol), cuprous iodide (2.25g, 11.87mmol), o-phenanthroline (2.25g, 11.87mmol) and xylene (56ml), protect with nitrogen, react at 180℃ for 16h. After the reaction, add water (90ml) to quench, add ethyl acetate (20ml*3) to extract, the organic phase is dried at 60℃, separated by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 30:1), take the clean fraction and dry at 60℃ to obtain 5.69g of yellow colloid. The yield is 58%. HRMS (ESI) (m / z): 798.4298 [M+H] + .

[0211] Synthesis of compound 37h

[0212] Take a 500ml single-mouth bottle, put 37f (3.00g, 3.75mmol), dissolve it in triethyl orthoformate (36ml) and hydrochloric acid (27ml), protect it with nitrogen, heat it to 85℃, and react for 16h. After the reaction, add saturated ammonium chloride solution (24ml) to the mother liquor and stir it at room temperature for one hour, then extract it with dichloromethane (30ml) three times, and the obtained organic phase is directly spin-dried at 60℃, and separated by silica gel column chromatography (the eluent is first: n-hexane: ethyl acetate = 3:1 to wash away the front impurities, and then elute with dichloromethane: methanol = 20:1), take the clean fraction and spin-dry at 60℃ to obtain the crude product, and recrystallize it with n-hexane: tetrahydrofuran = (100ml: 16ml) at room temperature overnight to obtain 2.24g of gray solid, with a yield of 70%. HRMS (ESI) (m / z): 810.4298 [M] + .

[0213] Synthesis of compound 37i

[0214] Take a 250ml single-mouth bottle, put 37h (2.00g, 2.36mmol) into methanol (15ml), then add ammonium hexafluorophosphate (0.49g, 2.82mmol, dissolved in water (4ml)), nitrogen protection, and react at room temperature for 12h. After the reaction, add dichloromethane (20ml*3) to the mother liquor for extraction, spin dry the organic phase at 60℃, and perform silica gel column chromatography (elution with n-hexane: ethyl acetate = 6:1), remove the front impurities, and then elute with n-hexane: ethyl acetate = 2:1 to obtain a solid product, slurry with n-hexane (20ml) at room temperature overnight, and filter to obtain 1.85g of gray solid, with a yield of 82%. HRMS (ESI) (m / z): 810.4298 [M] + .

[0215] Synthesis of compound 37

[0216] Take a 250ml single-mouth bottle, put 37i (1.00g, 1.00mmol), (1,5-cyclooctadiene) platinum (II) dichloride (0.45g, 1.2mmol), sodium acetate (0.27g, 2.00mmol) and dissolve in N,N-dimethylacetamide (10ml) under argon protection, and react at 190℃ for 48h. After the reaction is completed, add 100ml of water to quench, stir at room temperature for 1 hour, filter to obtain a solid, then dissolve in dichloromethane (10ml), wash with water (50ml), spin dry the organic phase at 60℃, and perform silica gel column chromatography. The eluent is first quickly eluted with pure dichloromethane to obtain a crude product, and then perform silica gel column chromatography again (the eluent is dichloromethane: n-hexane = 1:3) to obtain a yellow solid, which is recrystallized at room temperature for 4h with dichloromethane: methanol = (15ml: 20ml), and 0.61g of yellow powder is obtained by suction filtration, with a yield of 59%. HRMS(ESI)(m / z):1002.3711[M+H] + .

[0217] Synthesis Example 12: Preparation of Compound 49

[0218]

[0219] Synthesis of compound 49c

[0220] Take a 250ml single-mouth bottle, put compound 1a (11.60g, 46.00mmol), compound 49b (15.40g, 50mmol), copper powder (1.40g, 23.00mmol), cuprous iodide (4.00g, 23.000mmol), o-phenanthroline (4.00g, 23.00mmol) and xylene (100ml), protect with nitrogen, and react at 180℃ for 48h. After the reaction, add water to quench the reaction, extract with ethyl acetate to obtain an organic layer, spin dry, and perform silica gel column chromatography (eluent: n-hexane: ethyl acetate = 50:1) to obtain a yellow crude product, which is recrystallized from methanol / dichloromethane at room temperature overnight for 12h, filtered, and 14.00g of a red solid is obtained. The yield is 70%. HRMS (ESI) (m / z): 433.1838 [M+H] +

[0221] Synthesis of compound 49d

[0222] Take a 500ml single-mouth bottle, put 49c (7.77g, 18.00mmol), iron powder (6.20g, 109.00mmol) and acetic acid (110ml), protect with nitrogen, and react at 80℃ for 1h. After the reaction, add water (60ml) to quench, add ethyl acetate (10ml) to extract three times, spin dry the organic phase at 60℃, and separate by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 10:1). Take the clean fraction and spin dry at 60℃ to obtain the crude product, and use n-hexane: dichloromethane = (50ml: 14ml) to recrystallize at room temperature overnight to obtain 5.70g of white solid, with a yield of 80%. HRMS (ESI) (m / z): 402.2096 [M+H] + .

[0223] Synthesis of compound 49f

[0224] Take a 250ml single-mouth bottle, put 49d (5.07g, 12.67mmol), 1e (6.27g, 13.33mmol), copper powder (0.80g, 12.67mmol), cuprous iodide (2.40g, 12.67mmol), o-phenanthroline (2.4g, 12.67mmol) and xylene (60ml), protect with nitrogen, react at 180℃ for 16h. After the reaction, add water (60ml) to quench, add ethyl acetate (30ml*3) to extract, the organic phase is dried at 60℃, separated by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 50:1), take the clean fraction and dry at 60℃ to obtain 7.50g of yellow colloid. The yield is 75%. HRMS (ESI) (m / z): 792.3828 [M+H] + .

[0225] Synthesis of compound 49h

[0226] Take a 500ml single-mouth bottle, put 49f (5.00g, 6.25mmol), dissolve it in triethyl orthoformate (50ml) and hydrochloric acid (45ml), protect it with nitrogen, heat it to 85℃, and react for 16h. After the reaction, add saturated ammonium chloride solution (40ml) to the mother liquor and stir it at room temperature for one hour, then extract it with dichloromethane (30ml*3), and the obtained organic phase is directly spin-dried at 60℃ and separated by silica gel column chromatography (the eluent is first: n-hexane: ethyl acetate = 1:1 to wash away the front impurities, and then elute with dichloromethane: methanol = 50:1), take the clean fraction and spin-dry at 60℃ to obtain the crude product, and recrystallize it with n-hexane: tetrahydrofuran = (100ml: 10ml) at room temperature overnight to obtain 4.09g of gray solid, with a yield of 78%. HRMS (ESI) (m / z): 804.4298 [M] + .

[0227] Synthesis of compound 49i

[0228] Take a 250ml single-mouth bottle, put 49h (4.00g, 4.75mmol) into methanol (37ml), then add ammonium hexafluorophosphate (0.93g, 5.55mmol, dissolved in water (11ml)), nitrogen protection, and react at room temperature for 12h. After the reaction, add dichloromethane (20ml*3) to the mother liquor for extraction, spin dry the organic phase at 60℃, and perform silica gel column chromatography (elution agent first uses: n-hexane: ethyl acetate = 4:1) to remove the front impurities, and then elute with n-hexane: ethyl acetate = 2:1 to obtain a solid product, slurry with n-hexane (50ml) at room temperature overnight, and filter to obtain 3.6g of gray solid, with a yield of 80%. HRMS (ESI) (m / z): 804.4298 [M] + .

[0229] Synthesis of compound 49

[0230] Take a 250ml single-mouth bottle, put 49i (2.5g, 2.5mmol), (1,5-cyclooctadiene) platinum (II) dichloride (1.12g, 3mmol), sodium acetate (0.68g, 5.00mmol) into N,N-dimethylacetamide (50ml) under argon protection, and react at 190℃ for 48h. After the reaction is completed, add 100ml of water to quench, stir at room temperature for 1 hour, filter to obtain a solid, then dissolve in dichloromethane (20ml), wash with water (30ml), spin dry the organic phase at 60℃, and perform silica gel column chromatography. The eluent is first quickly eluted with pure dichloromethane to obtain a crude product, and then perform silica gel column chromatography again (the eluent is dichloromethane:n-hexane = 1:3) to obtain a yellow solid, which is recrystallized at room temperature with dichloromethane:methanol = (13ml:20ml) for 4h, and filtered to obtain 1.35g of yellow powder with a yield of 54%. HRMS(ESI)(m / z):995.3711[M+H] + .

[0231] Synthesis Example 13: Preparation of Compound 85

[0232]

[0233] Synthesis of compound 85c

[0234] Two parallel reactions were performed. Two 500 ml single-mouth bottles were used. Compound 1a (5.80 g, 23.00 mmol), compound 85b (8.20 g, 25.00 mmol), cesium carbonate (30.00 g, 92.00 mmol) and N,N-dimethylacetamide (250 ml) were added to each bottle. The mixture was protected by nitrogen and reacted at 150 °C for 48 h. After the reaction was completed, water was added to quench the reaction, and ethyl acetate was added to extract the organic layer, which was spin-dried and separated by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 2:1) to obtain a yellow crude product. The product was recrystallized from methanol / dichloromethane at room temperature overnight for 12 h and filtered to obtain 10.00 g of a red solid. The yield was 40%. HRMS (ESI) (m / z): 562.2165 [M+H] +

[0235] Synthesis of compound 85d

[0236] Take a 500ml single-mouth bottle, put in 85c (10.00g, 18.00mmol), iron powder (6.20g, 109.00mmol) and acetic acid (110ml), protect with nitrogen, and react at 80℃ for 1h. After the reaction is completed, add water (60ml) to quench, add ethyl acetate (20ml*3) to extract, spin dry the organic phase at 60℃, and separate by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 10:1), take the clean fraction and spin dry at 60℃ to obtain the crude product, use n-hexane: dichloromethane = (45ml: 10ml) to recrystallize overnight at room temperature to obtain 8.26g of white solid, with a yield of 87%. HRMS (ESI) (m / z): 531.2423 [M+H] + .

[0237] Synthesis of compound 85f

[0238] Take a 250ml single-mouth bottle, put 85d (7.60g, 14.00mmol), 1e (5.60g, 15.00mmol), copper powder (1.20g, 14.00mmol), cuprous iodide (3.30g, 14.00mmol), o-phenanthroline (3.30g, 14.00mmol) and xylene (90ml), protect with nitrogen, react at 180℃ for 16h. After the reaction, add water (90ml) to quench, add ethyl acetate (50ml*3) to extract, the organic phase is dried at 60℃, separated by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 50:1), take the clean fraction and dry at 60℃ to obtain 8.74g of yellow colloid. The yield is 68%. HRMS (ESI) (m / z): 921.4155 [M+H] + .

[0239] Synthesis of compound 85h

[0240] Take a 500ml single-mouth bottle, put 85f (6.00g, 6.47mmol), dissolve it in triethyl orthoformate (60ml) and hydrochloric acid (60ml), protect it with nitrogen, heat it to 85℃, and react for 16h. After the reaction, add saturated ammonium chloride solution (53ml) to the mother liquor and stir it at room temperature for one hour, then extract it with dichloromethane (30ml) three times, and the obtained organic phase is directly spin-dried at 60℃, and separated by silica gel column chromatography (the eluent is first: n-hexane: ethyl acetate = 2:1 to wash away the front impurities, and then elute with dichloromethane: methanol = 50:5), take the clean fraction and spin-dry at 60℃ to obtain the crude product, and recrystallize it with n-hexane: tetrahydrofuran = (100ml: 14ml) at room temperature overnight to obtain 5.13g of gray solid, with a yield of 82%. HRMS (ESI) (m / z): 932.4298 [M] + .

[0241] Synthesis of compound 85i

[0242] Take a 250ml single-mouth bottle, put 85h (3.5g, 3.6mmol) into methanol (37ml), then drop ammonium hexafluorophosphate (0.75g, 4.3mmol) dissolved in water (11ml), protect with nitrogen, and react at room temperature for 12h. After the reaction, add dichloromethane (20ml*3) to extract the mother liquor, spin dry the organic phase at 60℃, and perform silica gel column chromatography (elution agent first uses: n-hexane: ethyl acetate = 6:1) to remove the front impurities, and then elute with n-hexane: ethyl acetate = 1:1.2 to obtain a solid product, slurry with n-hexane (50ml) at room temperature overnight, and filter to obtain 3.41g of gray solid, with a yield of 88%. HRMS (ESI) (m / z): 932.4298 [M] + .

[0243] Synthesis of compound 85

[0244] Take a 250ml single-mouth bottle, put 85i (2.65g, 2.50mmol), (1,5-cyclooctadiene) platinum (II) dichloride (1.12g, 3.00mmol), sodium acetate (0.67g, 5.00mmol) into N, N-dimethylacetamide (50ml) under argon protection, and react at 190℃ for 48h. After the reaction is completed, add 50ml of water to quench, stir at room temperature for 1 hour, filter to obtain a solid, then dissolve in dichloromethane (20ml), wash with water (50ml), spin dry the organic phase at 60℃, and perform silica gel column chromatography. The eluent is first quickly eluted with pure dichloromethane to obtain a crude product, and then perform silica gel column chromatography again (the eluent is dichloromethane: n-hexane = 1:3) to obtain a yellow solid, which is recrystallized at room temperature for 4h with dichloromethane: methanol = (12ml: 20ml), and 1.05g of yellow powder is obtained by suction filtration, with a yield of 42%. HRMS(ESI)(m / z):1125.3568[M+H] + .

[0245] Synthesis Example 14: Preparation of Compound 109

[0246]

[0247] Synthesis of compound 109c

[0248] Two parallel reactions were performed. A 500 ml single-mouth bottle was used to add compound 109a (10.00 g, 31.60 mmol), compound 109b (15.00 g, 47.4 mmol), cuprous iodide (3.00 g, 15.80 mmol), picolinic acid (1.90 g, 15.80 mmol) and N, N-dimethylacetamide (45 ml). The mixture was protected by nitrogen and reacted at 150 °C for 16 h. After the reaction was completed, water (90 ml) was added to quench the reaction, and ethyl acetate (50 ml*3) was added to extract the reaction. The organic phase was dried at 60 °C and separated by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 50:1). The clean fraction was dried at 60 °C to obtain 1.8 g of yellow colloid. The yield was 21%. HRMS (ESI) (m / z): 543.1389 [M+H] + .

[0249] Synthesis of compound 109f

[0250] Take a 250ml single-mouth bottle, put 109c (1.52g, 2.80mmol), 1d (1.14g, 2.80mmol), copper powder (0.24g, 2.80mmol), cuprous iodide (0.66g, 2.80mmol), o-phenanthroline (0.66g, 2.80mmol) and xylene (45ml), protect with nitrogen, and react at 180℃ for 16h. After the reaction, add water (45ml) to quench, add ethyl acetate (20ml*3) to extract, the organic phase is dried at 60℃, and separated by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 25:1), take the clean fraction and dry it at 60℃ to obtain 1.95g of yellow colloid. The yield is 32%. HRMS (ESI) (m / z): 875.5006 [M+H] + .

[0251] Synthesis of compound 109h

[0252] Take a 500ml single-mouth bottle, put 109f (1.59g, 1.85mmol), dissolve it in triethyl orthoformate (20ml) and hydrochloric acid (33ml), protect it with nitrogen, heat it to 85℃, and react for 16h. After the reaction, add saturated ammonium chloride solution (80ml) to the mother liquor and stir it at room temperature for one hour, then extract it with dichloromethane (30ml*3), and the obtained organic phase is directly spin-dried at 60℃ and separated by silica gel column chromatography (the eluent is first: n-hexane: ethyl acetate = 2.5:1 to wash away the front impurities, and then elute with dichloromethane: methanol = 51:1). Take the clean fraction and spin-dry it at 60℃ to obtain the crude product, and use n-hexane: tetrahydrofuran = (100ml: 16ml) to recrystallize it at room temperature overnight to obtain 1.04g of gray solid, with a yield of 62%. HRMS (ESI) (m / z): 885.5006 [M] +.

[0253] Synthesis of compound 109i

[0254] Take a 250ml single-mouth bottle, put 109h (1.00g, 1.11mmol) into methanol (18ml), then drop ammonium hexafluorophosphate (0.30g, 1.33mmol) dissolved in water (8ml), protect with nitrogen, and react at room temperature for 12h. After the reaction, add dichloromethane (20ml*3) to extract the mother liquor, spin dry the organic phase at 60℃, and perform silica gel column chromatography (elution with n-hexane: ethyl acetate = 5:1) to remove the front impurities, and then elute with n-hexane: ethyl acetate = 1:1.5 to obtain a solid product, slurry with n-hexane (37ml) at room temperature overnight, and filter to obtain 0.89g of gray solid, with a yield of 80%. HRMS (ESI) (m / z): 885.5006 [M] + .

[0255] Synthesis of compound 109

[0256] Take a 250ml single-necked bottle, put 109i (0.51g, 0.50mmol, 1.0eq), (1,5-cyclooctadiene)platinum(II) dichloride (0.23g, 0.60mmol), and sodium acetate (0.14g, 1mmol) in N,N-dimethylacetamide (25ml) under argon protection, and react at 190℃ for 48h. After the reaction, 100 ml of water was added to quench, stirred at room temperature for 1 hour, and filtered to obtain a solid, which was then dissolved in dichloromethane (50 ml), washed with water (50 ml), and the organic phase was dried at 60°C. The crude product was separated by silica gel column chromatography. The eluent was first quickly eluted with pure dichloromethane to obtain a crude product, which was separated by silica gel column chromatography again (the eluent was dichloromethane:n-hexane = 2:3) to obtain a yellow solid. The solid was recrystallized at room temperature with dichloromethane:methanol = (11 ml:27 ml) for 4 hours, and filtered to obtain 0.13 g of yellow powder, with a yield of 30%. HRMS (ESI) (m / z): 1077.3379 [M+H] + .

[0257] Synthesis Example 15: Preparation of Compound 62

[0258]

[0259] Synthesis of compound 62f

[0260] Take a 250ml single-mouth bottle, put 2d (3.00g, 5.00mmol), 62e (1.65g, 5.00mmol), cuprous iodide (0.90g, 5.00mmol), o-phenanthroline (0.90g, 5.00mmol) and xylene (100ml), protect with nitrogen, and react at 180℃ for 16h. After the reaction, add water (100ml) to quench, add ethyl acetate (30ml*3) to extract, the organic phase is dried at 60℃, and separated by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 50:1), take the clean fraction and dry it at 60℃ to obtain 2.70g of yellow colloid. The yield is 65%. HRMS (ESI) (m / z): 857.3777 [M+H] + .

[0261] Synthesis of compound 62h

[0262] Take a 250ml single-mouth bottle, put 62f (2.56g, 3.00mmol), dissolve it in triethyl orthoformate (25ml) and hydrochloric acid (30ml), protect it with nitrogen, heat it to 85℃, and react for 16h. After the reaction, add saturated ammonium chloride solution (50ml) to the mother liquor and stir it at room temperature for one hour, then extract it with dichloromethane (30ml) three times, and the obtained organic phase is directly spin-dried at 60℃, and separated by silica gel (110g, 200-300 mesh) column chromatography (the eluent is first used: n-hexane: ethyl acetate = 1:1.3 to wash away the front impurities, and then eluted with dichloromethane: methanol = 35:1), take the clean fraction and spin-dry at 60℃ to obtain a crude product, and recrystallize it with n-hexane: tetrahydrofuran = (100ml:16ml) at room temperature overnight to obtain 2.00g of gray solid, with a yield of 75%. HRMS (ESI) (m / z): 867.3777 [M] + .

[0263] Synthesis of compound 62i

[0264] Take a 250ml single-mouth bottle, put 62h (1.80g, 2.00mmol) into methanol (30ml), then drop ammonium hexafluorophosphate (0.40g, 2.40mmol) dissolved in water (10ml), protect with nitrogen, and react at room temperature for 12h. After the reaction, add dichloromethane (30ml*3) to extract the mother liquor, spin dry the organic phase at 60℃, and perform silica gel (45g, 200-300 mesh) column chromatography separation (elution agent first uses: n-hexane: ethyl acetate = 5:1, V / V elution), remove the front impurities, and then elute with n-hexane: ethyl acetate = 1:1.3, V / V to obtain a solid product, slurry with n-hexane (20ml) at room temperature overnight, and filter to obtain 1.72g of gray solid, with a yield of 86%. HRMS (ESI) (m / z): 867.3777 [M] + .

[0265] Synthesis of compound 62

[0266] Take a 100ml single-necked bottle, put 62i (1.00g, 1.00mmol), (1,5-cyclooctadiene) platinum (II) dichloride (0.40g, 1.20mmol), sodium acetate (0.20g, 2.00mmol) in N,N-dimethylacetamide (30ml), protect with argon, and react at 190℃ for 48h. After the reaction, 100 ml of water was added to quench, stirred at room temperature for 1 hour, filtered to obtain a solid, dissolved in dichloromethane (50 ml), washed with water (50 ml), the organic phase was spin-dried at 60°C, and separated by silica gel (45 g, 200-300 mesh) column chromatography. The eluent was first quickly eluted with pure dichloromethane to obtain a crude product, which was separated by silica gel (45 g, 200-300 mesh) column chromatography again (the eluent was dichloromethane: n-hexane = 2:3) to obtain a yellow solid, which was recrystallized at room temperature with dichloromethane: methanol = (12 ml: 20 ml) for 4 hours, and filtered to obtain 500 mg of yellow powder, with a yield of 50%. HRMS (ESI) (m / z): 1059.3190 [M+H] + .

[0267] Synthesis Example 16: Preparation of Compound 68

[0268]

[0269] Synthesis of compound 68f

[0270] Take a 250ml single-mouth bottle, put 2d (3.00g, 5.00mmol), 68e (1.68g, 5.00mmol), cuprous iodide (0.90g, 5.00mmol), o-phenanthroline (0.90g, 5.00mmol) and xylene (100ml), protect with nitrogen, and react at 180℃ for 16h. After the reaction, add water (100ml) to quench, add ethyl acetate (30ml*3) to extract, the organic phase is dried at 60℃, and separated by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 40:1), take the clean fraction and dry it at 60℃ to obtain 2.87g of yellow colloid. The yield is 69%. HRMS (ESI) (m / z): 873.3549 [M+H] + .

[0271] Synthesis of compound 68h

[0272] Take a 250ml single-mouth bottle, put 68f (2.56g, 3.00mmol), dissolve it in triethyl orthoformate (25ml) and hydrochloric acid (30ml), protect it with nitrogen, heat it to 85℃, and react for 16h. After the reaction, add saturated ammonium chloride solution (30ml) to the mother liquor and stir it at room temperature for one hour, then extract it with dichloromethane (30ml) three times, and the obtained organic phase is directly spin-dried at 60℃, and separated by silica gel (110g, 200-300 mesh) column chromatography (the eluent is first used: n-hexane: ethyl acetate = 1.2:1 to wash away the front impurities, and then eluted with dichloromethane: methanol = 46:1), take the clean fraction and spin-dry at 60℃ to obtain the crude product, and recrystallize it with n-hexane: tetrahydrofuran = (100ml: 13ml) at room temperature overnight to obtain 2.00g of gray solid, with a yield of 75%. HRMS (ESI) (m / z): 883.3549 [M] + .

[0273] Synthesis of compound 68i

[0274] Take a 250ml single-mouth bottle, put 68h (1.80g, 2.00mmol) into methanol (30ml), then drop ammonium hexafluorophosphate (0.40g, 2.40mmol) dissolved in water (10ml), protect with nitrogen, and react at room temperature for 12h. After the reaction, add dichloromethane (30ml) to extract the mother liquor, spin dry the organic phase at 60℃, and perform silica gel (45g, 200-300 mesh) column chromatography separation (elution agent first uses: n-hexane: ethyl acetate = 5:1 (1500ml: 300ml) elution), remove the front impurities, and then elute with n-hexane: ethyl acetate = 1:1 (2L: 2L) to obtain a solid product, slurry with n-hexane (100ml) at room temperature overnight, and filter to obtain 1.62g of gray solid, with a yield of 81%. HRMS (ESI) (m / z): 883.3549 [M] + .

[0275] Synthesis of compound 68

[0276] Take a 100ml single-necked bottle, put 68i (1.00g, 1.00mmol), (1,5-cyclooctadiene) platinum (II) dichloride (0.40g, 1.20mmol), sodium acetate (0.20g, 2mmol) in N,N-dimethylacetamide (20ml), protect with argon, and react at 190℃ for 48h. After the reaction, 100 ml of water was added to quench, stirred at room temperature for 1 hour, filtered to obtain a solid, dissolved in dichloromethane (50 ml), washed with water (50 ml), the organic phase was spin-dried at 60°C, and separated by silica gel (45 g, 200-300 mesh) column chromatography. The eluent was first quickly eluted with pure dichloromethane to obtain a crude product, which was separated by silica gel (45 g, 200-300 mesh) column chromatography again (the eluent was dichloromethane: n-hexane = 2:3) to obtain a yellow solid, which was recrystallized at room temperature with dichloromethane: methanol = (13 ml: 20 ml) for 4 hours, and filtered to obtain 410 mg of yellow powder, with a yield of 41%. HRMS (ESI) (m / z): 1075.2962 [M+H] + Synthesis Example 17: Preparation of Compound #74

[0277]

[0278] Synthesis of compound 74f

[0279] Take a 250ml single-mouth bottle, put 2d (6.00g, 10.00mmol), 74e (3.96g, 10mmol), cuprous iodide (1.80g, 10mmol), o-phenanthroline (1.8g, 10mmol) and xylene (150ml), protect with nitrogen, and react at 180℃ for 16h. After the reaction, add water (100ml) to quench, add ethyl acetate (50ml*3) to extract, the organic phase is dried at 60℃, and separated by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 50:1), take the clean fraction and dry it at 60℃ to obtain 6.29g of yellow colloid. The yield is 68%. HRMS (ESI) (m / z): 932.4250 [M+H] + .

[0280] Synthesis of compound 74h

[0281] Take a 250ml single-mouth bottle, put 74f (2.70g, 3.00mmol, 1.0eq), dissolve in triethyl orthoformate (30ml) and hydrochloric acid (40ml), protect with nitrogen, heat to 85℃, and react for 16h. After the reaction, add saturated ammonium chloride solution (50ml) to the mother liquor and stir at room temperature for one hour, then extract with dichloromethane (30ml) three times, the obtained organic phase is directly spin-dried at 60℃, and separated by silica gel (110g, 200-300 mesh) column chromatography (the eluent is first used: n-hexane: ethyl acetate = 1.6:1 to wash away the front impurities, and then eluted with dichloromethane: methanol = 30:1), take the clean fraction and spin-dry at 60℃ to obtain the crude product, and recrystallize it with n-hexane: tetrahydrofuran = (100ml: 18ml) at room temperature overnight to obtain 2.14g of gray solid, with a yield of 75%. HRMS (ESI) (m / z): 942.4250 [M] + .

[0282] Synthesis of compound 74i

[0283] Take a 250ml single-mouth bottle, put 74h (1.90g, 2.00mmol) into methanol (30ml), then drop ammonium hexafluorophosphate (0.40g, 2.40mmol) dissolved in water (10ml), protect with nitrogen, and react at room temperature for 12h. After the reaction, add dichloromethane (30ml*3) to extract the mother liquor, spin dry the organic phase at 60℃, and perform silica gel (45g, 200-300 mesh) column chromatography separation (elution agent first uses: n-hexane: ethyl acetate = 6:1), remove the front impurities, and then elute with n-hexane: ethyl acetate = 1:1.3 to obtain a solid product, slurry with n-hexane (100ml) at room temperature overnight, and filter to obtain 1.66g of gray solid, with a yield of 83%. HRMS (ESI) (m / z): 942.4250 [M] + .

[0284] Synthesis of compound 74

[0285] Take a 100ml single-necked bottle, put 74i (1.00g, 1.00mmol), (1,5-cyclooctadiene) platinum (II) dichloride (0.40g, 1.20mmol), sodium acetate (0.20g, 2.00mmol) in N,N-dimethylacetamide (50ml), protect with argon, and react at 190℃ for 48h. After the reaction, 100 ml of water was added to quench, stirred at room temperature for 1 hour, filtered to obtain a solid, dissolved in dichloromethane (50 ml), washed with water (50 ml), the organic phase was spin-dried at 60°C, and separated by silica gel (45 g, 200-300 mesh) column chromatography. The eluent was first quickly eluted with pure dichloromethane to obtain a crude product, which was separated by silica gel (45 g, 200-300 mesh) column chromatography again (the eluent was dichloromethane: n-hexane = 2:3) to obtain a yellow solid, which was recrystallized at room temperature with dichloromethane: methanol = (11 ml: 26 ml) for 4 hours, and filtered to obtain 310 mg of yellow powder, with a yield of 31%. HRMS (ESI) (m / z): 1134.3663 [M+H] + .

[0286] Synthesis Example 18: Preparation of Compound 80

[0287]

[0288] Synthesis of compound 80f

[0289] Take a 250ml single-mouth bottle, put 2d (6.30g, 10.50mmol), 80e (8.40g, 31.50mmol), cesium carbonate (16.80g, 52.50mmol) and N,N-dimethylacetamide (150ml), protect with nitrogen, and react at 180℃ for 16h. After the reaction, add water (100ml) to quench, add ethyl acetate (50ml*3) to extract, the organic phase is spin-dried at 60℃, and separated by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 50:1), take the clean fraction and spin-dry at 60℃ to obtain 3.46g of yellow colloid. The yield is 40%. HRMS (ESI) (m / z): 846.3842 [M+H] + .

[0290] Synthesis of compound 80h

[0291] Take a 250ml single-mouth bottle, put 80f (2.70g, 3mmol, 1.0eq), dissolve in triethyl orthoformate (30ml) and hydrochloric acid (45ml), protect with nitrogen, heat to 85℃, and react for 16h. After the reaction, add saturated ammonium chloride solution (50ml) to the mother liquor and stir at room temperature for one hour, then extract with dichloromethane (30ml) three times, the obtained organic phase is directly spin-dried at 60℃, and separated by silica gel (110g, 200-300 mesh) column chromatography (eluent first uses: n-hexane: ethyl acetate = 1:1.6 to wash away the front impurities, and then elute with dichloromethane: methanol = 30:1), take the clean fraction and spin-dry at 60℃ to obtain the crude product, and use n-hexane: tetrahydrofuran = (100ml: 25ml) to recrystallize overnight at room temperature to obtain 1.00g gray solid, with a yield of 35%. HRMS (ESI) (m / z): 856.3842 [M] + .

[0292] Synthesis of compound 80i

[0293] Take a 250ml single-mouth bottle, put 80h (0.95g, 1.00mmol) into methanol (15ml), then drop ammonium hexafluorophosphate (0.20g, 1.20mmol) dissolved in water (5ml), protect with nitrogen, and react at room temperature for 12h. After the reaction, add dichloromethane (30ml*3) to extract the mother liquor, spin dry the organic phase at 60℃, and perform silica gel (45g, 200-300 mesh) column chromatography separation (elution agent first uses: n-hexane: ethyl acetate = 5:1), remove the front impurities, and then elute with n-hexane: ethyl acetate = 1:1 to obtain a solid product, slurry with n-hexane (100ml) at room temperature overnight, and filter to obtain 0.60g of gray solid, with a yield of 60%. HRMS (ESI) (m / z): 856.3842 [M] + .

[0294] Synthesis of compound 80

[0295] Take a 100ml single-necked bottle, put 80i (0.50g, 0.50mmol), (1,5-cyclooctadiene) platinum (II) dichloride (0.20g, 0.60mmol), sodium acetate (0.10g, 1.00mmol) in N,N-dimethylacetamide (25ml), protect with argon, and react at 190℃ for 48h. After the reaction, 100 ml of water was added to quench, stirred at room temperature for 1 hour, filtered to obtain a solid, dissolved in dichloromethane (50 ml), washed with water (50 ml), the organic phase was spin-dried at 60°C, and separated by silica gel (45 g, 200-300 mesh) column chromatography. The eluent was first quickly eluted with pure dichloromethane to obtain a crude product, which was separated by silica gel (45 g, 200-300 mesh) column chromatography again (the eluent was dichloromethane: n-hexane = 2:3) to obtain a yellow solid, which was recrystallized at room temperature with dichloromethane: methanol = (10 ml: 20 ml) for 4 hours, and filtered to obtain 266 mg of yellow powder, with a yield of 40%. HRMS (ESI) (m / z): 1048.3255 [M+H] + .

[0296] Synthesis Example 19: Preparation of Compound 56

[0297]

[0298] Synthesis of compound 56f

[0299] Take a 250ml single-mouth bottle, put 2d (3.00g, 5.00mmol), 56e (1.58g, 5.00mmol), cuprous iodide (0.90g, 5.00mmol), o-phenanthroline (0.90g, 5.00mmol) and xylene (100ml), protect with nitrogen, and react at 180℃ for 16h. After the reaction, add water (100ml) to quench, add ethyl acetate (30ml*3) to extract, the organic phase is dried at 60℃, and separated by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 20:1), take the clean fraction and dry it at 60℃ to obtain 3.65g of yellow colloid. The yield is 86%. HRMS (ESI) (m / z): 856.3937 [M+H] + .

[0300] Synthesis of compound 56h

[0301] Take a 250ml single-mouth bottle, put 56f (2.50g, 3.00mmol), dissolve it in triethyl orthoformate (25ml) and hydrochloric acid (40ml), protect it with nitrogen, heat it to 85℃, and react for 16h. After the reaction, add saturated ammonium chloride solution (50ml) to the mother liquor and stir it at room temperature for one hour, then extract it with dichloromethane (30ml*3) three times, and the obtained organic phase is directly spin-dried at 60℃, and separated by silica gel (110g, 200-300 mesh) column chromatography (the eluent is first used: n-hexane: ethyl acetate = 1.3:1 to wash away the front impurities, and then eluted with dichloromethane: methanol = 26:1), take the clean fraction and spin-dry at 60℃ to obtain the crude product, and recrystallize it with n-hexane: tetrahydrofuran = (100ml: 10ml) at room temperature overnight to obtain 2.05g of gray solid, with a yield of 72%. HRMS (ESI) (m / z): 866.3937 [M] + .

[0302] Synthesis of compound 56i

[0303] Take a 250ml single-mouth bottle, put 56h (1.90g, 2.00mmol) into methanol (30ml), then drop ammonium hexafluorophosphate (0.40g, 2.40mmol) dissolved in water (10ml), protect with nitrogen, and react at room temperature for 12h. After the reaction, add dichloromethane (30ml*3) to extract the mother liquor, spin dry the organic phase at 60℃, and perform silica gel (45g, 200-300 mesh) column chromatography separation (elution agent first uses: n-hexane: ethyl acetate = 5:1 (1500ml: 300ml) to elute), remove the front impurities, and then elute with n-hexane: ethyl acetate = 1:1 (2L: 2L) to obtain a solid product, slurry with n-hexane (100ml) at room temperature overnight, and filter to obtain 1.74g of gray solid, with a yield of 87%. HRMS (ESI) (m / z): 866.3937 [M] + .

[0304] Synthesis of compound 56

[0305] In a 100 ml single-necked bottle, 56i (1.00 g, 1.00 mmol), (1,5-cyclooctadiene)platinum(II) dichloride (0.40 g, 1.20 mmol), and sodium acetate (0.20 g, 2.00 mmol) were dissolved in N,N-dimethylacetamide (50 ml) under argon protection and reacted at 190 °C for 48 h. After the reaction, 100 ml of water was added to quench, stirred at room temperature for 1 hour, and filtered to obtain a solid, which was then dissolved in dichloromethane (50 ml), washed with water (50 ml), and the organic phase was dried at 60°C, and separated by silica gel (45 g, 200-300 mesh) column chromatography. The eluent was first quickly eluted with pure dichloromethane to obtain a crude product, which was separated by silica gel (45 g, 200-300 mesh) column chromatography again (the eluent was dichloromethane:n-hexane = 2.5:3) to obtain a yellow solid, which was recrystallized at room temperature with dichloromethane:methanol = (15 ml:20 ml) for 4 hours, and filtered to obtain 310 mg of yellow powder, with a yield of 31%. HRMS (ESI) (m / z): 1058.3350 [M+H] + .

[0306] Synthesis Example 20: Synthesis of Compound 132

[0307]

[0308] Synthesis of compound 132c

[0309] Take a 250ml single-mouth bottle, put 132a (10g, 44.2mmol, 1.0eq), iodobenzene (18.04g, 88.41mmol, 2eq), Cu (1.4g, 22.1mmol, 0.05eq), CuI (4.21g, 22.1mmol, 0.05eq), L-proline (2.54g, 22.1mmol, 0.05eq) and Cs2CO3 (36.01g, 110.51mmol, 2.5eq) into 100mL xylene, protect with nitrogen, and heat to 180℃ for 16h. After the reaction, quench with water (100ml), add ethyl acetate (50ml*3) for three extractions, take the organic phase and spin dry at 60℃, and separate by silica gel (100g, 200-300 mesh) column chromatography to obtain 10g red solid with a yield of 75%. HRMS(ESI)(m / z):303.1055[M+H] + .

[0310] Synthesis of compound 132d

[0311] Take a 500ml single-mouth bottle, put 132c (10g, 33.08mmol, 1.0eq), Zn (10.81g, 165.38mmol, 5.0eq) and acetic acid (100ml), protect with nitrogen, and react at 80℃ for 1h. After the reaction, add water (50ml) to quench, add ethyl acetate to extract three times, the organic phase is spin-dried at 60℃, and separated by silica gel (100g, 200-300 mesh) column chromatography to obtain 8.2g of white solid, with a yield of 91%. HRMS (ESI) (m / z): 273.1313 [M+H] + .

[0312] Synthesis of compound 132f

[0313] Take a 250ml single-mouth bottle, put 132d (8.2g, 30.11mmol, 1.0eq), 1e (17.03g, 36.13mmol, 1.2eq), Pd (Amphos) Cl2 (1.07g, 1.51mmol, 0.05eq), xphos (1.44g, 3.01mmol, 0.1eq), Cs2CO3 (24.53g, 75.27mmol, 2.5eq), LiCl (1.28g, 30.11mmol, 1.0eq) and xylene (100ml), protect with nitrogen, react at 180℃ for 16h. After the reaction, add water (100ml) to quench, extract with ethyl acetate, spin dry the organic phase at 60℃, and separate by silica gel (130g, 200-300 mesh) column chromatography to obtain 15.5g of yellow colloid. The yield is 78%. HRMS(ESI)(m / z):663.3046[M+H] + .

[0314] Synthesis of compound 132h

[0315] Take a 500ml single-mouth bottle, put 132f (15.5g, 23.38mmol, 1.0eq), dissolve in triethyl orthoformate (150ml) and HCl (120ml), protect with nitrogen, heat to 85℃, and react for 16h. After the reaction, add saturated NH4Cl solution (80ml) to the mother liquor and stir at room temperature for one hour, then extract with dichloromethane, and the obtained organic phase is directly dried at 60℃, and separated by silica gel (160g, 200-300 mesh) column chromatography to obtain 13g gray solid, with a yield of 78%. HRMS (ESI) (m / z): 672.2284 [M] + .

[0316] Synthesis of compound 132i

[0317] Take a 250ml single-mouth bottle, put 132h (13g, 18.3mmol, 1.0eq) dissolved in MeOH (100ml), then drop NH4PF6 (3.58g, 21.96mmol, 1.2eq) dissolved in H2O (20ml), protect with nitrogen, and react at room temperature for 12h. After the reaction, add dichloromethane to extract the mother liquor, spin dry the organic phase at 60℃, and separate by silica gel column chromatography to obtain 14g of gray solid, with a yield of 93%. HRMS (ESI) (m / z): 672.2284 [M] + .

[0318] Synthesis of compound 132

[0319] Take a 250ml single-mouth bottle, put 132i (14g, 17.1mmol, 1.0eq), Pt(cod)Cl2 (7.67g, 20.52mmol, 1.2eq), NaOAc (2.80g, 34.2mmol, 2.0eq) into N,N-dimethylacetamide (140ml) under argon protection, and react at 190℃ for 48h. After the reaction is completed, add 200ml of water to quench, stir at room temperature for 1 hour, filter to obtain a solid, dissolve it in dichloromethane, wash with water, spin dry the organic phase at 60℃, and separate it by silica gel column chromatography to obtain 9.5g of yellow powder with a yield of 64%. HRMS (ESI) (m / z): 865.2380 [M+H] + .

[0320] Preparation of OLED devices:

[0321] The platinum compound of the present application is used as a light-emitting material to prepare an organic light-emitting diode. The structure of the organic light-emitting diode is shown in FIG. Figure 1 , including a glass substrate 10, on which the glass substrate 10 includes a stacked anode 20, a hole injection layer 30, a hole transport layer 40, a light-emitting layer 50, an electron transport layer 60, an electron injection layer 70, and a cathode 80.

[0322] First, the transparent conductive ITO glass substrate 10 (with the anode 20 thereon) is washed with a detergent solution and deionized water, ethanol, acetone, and deionized water in sequence, and then treated with oxygen plasma for 30 seconds.

[0323] Then, HATCN was evaporated on the ITO to prepare the hole injection layer 30 .

[0324] Then, HT was evaporated on the hole injection layer to form a hole transport layer 40 with a thickness of 40 nm.

[0325] Then, a light-emitting layer 50 is evaporated on the hole blocking layer, and the composition of the light-emitting layer is: platinum compound: BH (host material) = 6%: 100%.

[0326] Then, ET was evaporated on the light-emitting layer to a thickness of 40 nm as the electron transport layer 60 .

[0327] Finally, 1 nm LiF was evaporated as the electron injection layer 70 and 100 nm Al was evaporated as the device cathode 80 .

[0328] The structural formulas of HATCN, HT, BH, ET and platinum compounds in the device are as follows:

[0329]

[0330] The organic electroluminescent devices of device examples 1-20 and comparative examples 1-3 are 2 The device performance at the current density is listed in Table 1:

[0331] Table 1

[0332]

[0333]

[0334] It can be seen from the data in Table 1 that under the same conditions, the platinum compound material of the present application is applied to organic light-emitting diodes, and has better luminous efficiency than the comparative molecules. Especially in terms of device life, the molecules of the present application are significantly better than the comparative examples and have good industrialization potential.

[0335] The above-mentioned various embodiments are only used as examples and are not used to limit the scope of this application. Without departing from the spirit of this application, the various materials and structures in this application can be replaced by other materials and structures. It should be understood that those skilled in the art can make many modifications and changes according to the thinking of this application without creative work. Therefore, the technical solutions that can be obtained by technical personnel through analysis, reasoning or partial research on the basis of the prior art should all be within the scope of protection limited by the claims.

Claims

1. A tetradentate platinum compound having a structure of formula (1): in: A is carbon or silicon; R 1 To R 8 independently selected from: deuterium, carbonyl, carboxyl, cyano, phosphino, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 ring carbon atoms, substituted or unsubstituted silyl having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 30 carbon atoms; Ar 1 R is selected from an aromatic group having 6 to 30 carbon atoms which is substituted or unsubstituted, a heteroaryl group having 3 to 30 carbon atoms which is substituted or unsubstituted, Ar 2 Selected from aromatic rings having 6 to 30 carbon atoms, heteroaromatic rings having 3 to 30 carbon atoms; wherein R is deuterium, halogen, cyano, nitro, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 20 carbon atoms, substituted or unsubstituted heterocycloalkyl having 3 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 20 carbon atoms, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylsilyl groups having 1 to 20 carbon atoms, substituted or unsubstituted arylsilyl groups having 6 to 20 carbon atoms, substituted or unsubstituted alkylboryl groups having 1 to 20 carbon atoms, substituted or unsubstituted arylboryl groups having 6 to 20 carbon atoms, substituted or unsubstituted arylphosphino groups having 6 to 20 carbon atoms, or adjacent R substituents are bonded to each other and form an aromatic ring or heteroaromatic ring with the atoms on Ar1; a3 to a8 are integers of 0-4, and when a3 is 2 or greater, at least two R 3 The groups are the same or different from each other. When a4 is 2 or greater, at least two R 4 The groups are the same or different from each other. When a5 is 2 or more, at least two R 5 The groups are the same or different from each other. When a6 is 2 or greater, at least two R 6 The groups are the same or different from each other; when a7 is 2 or greater, at least two R 7 The groups are the same or different from each other; when a8 is 2 or greater, at least two R 8 The groups may be identical to or different from each other; The E ring is a five- to seven-membered ring. The substitution is substitution by deuterium, amine, cyano, C1-C4 alkyl, C6-C10 aryl or C5-C10 heteroaryl, The heteroatom in the heteroaryl group, heteroaromatic ring, heteroalkyl group or heterocycloalkyl group is at least one of N, S and O.

2. The tetradentate platinum compound according to claim 1, wherein R is in Ar 1 The substitution position in Ar 1 On the aromatic ring or heteroaromatic ring connected to N in the group, and located at the para and / or meta position of the N atom.

3. The tetradentate platinum compound according to claim 2, wherein Ar 1 Select one of the following structural formulas: Each X1, X5 is independently selected from CH or N; each X2-X4, X6-X9 is independently selected from C or N; when X2-X4, X6-X9 is N, the substituent R connected thereto is 9 , R 10 or R 11 does not exist; Each Y1 is independently selected from O, S; Each R 9 , R 10 , R 11 The alkyl radicals are independently selected from hydrogen, deuterium, halogen, cyano, nitro, substituted or unsubstituted alkyl radicals having 1 to 10 carbon atoms, substituted or unsubstituted heteroalkyl radicals having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl radicals having 3 to 10 carbon atoms, substituted or unsubstituted heterocycloalkyl radicals having 3 to 10 carbon atoms, substituted or unsubstituted aryl radicals having 6 to 20 carbon atoms, substituted or unsubstituted heteroaryl radicals having 3 to 20 carbon atoms, substituted or unsubstituted 1- The invention further comprises a substituted or unsubstituted alkoxy group having 10 carbon atoms, a substituted or unsubstituted aryloxy group having 6-20 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1-10 carbon atoms, a substituted or unsubstituted arylsilyl group having 6-20 carbon atoms, a substituted or unsubstituted alkylboryl group having 1-10 carbon atoms, a substituted or unsubstituted arylboryl group having 6-20 carbon atoms, or a substituted or unsubstituted arylphosphino group having 1-10 carbon atoms, and a10 is an integer of 1-4.

4. The tetradentate platinum compound according to claim 3, wherein Ar 1 is selected from one of formulas (2) to (4), wherein R 9 , R 10 , R 11 At least one is not hydrogen, Ar 2 Selected from aromatic rings having 6 to 20 carbon atoms and heteroaromatic rings having 3 to 20 carbon atoms.

5. The tetradentate platinum compound according to claim 4, wherein Ar 1 Selected from formula (2), wherein R 10 is hydrogen, R 9 , R 11 is not hydrogen; or R 10 Not hydrogen, R 9 , R 11 For hydrogen.

6. The tetradentate platinum compound according to claim 5, wherein R 10 When it is hydrogen, R 9 , R 11 is selected from substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, substituted or unsubstituted aryl groups having 6 to 10 carbon atoms, R 9 , R 11 The same or different; where R 9 , R 11 When it is hydrogen, R 10 It is selected from a substituted or unsubstituted cycloalkyl group having 1 to 10 carbon atoms and a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms.

7. The tetradentate platinum compound according to any one of claims 1 to 6, wherein R 1 , R 2 R is independently selected from substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms, substituted or unsubstituted aryl having 6 to 20 carbon atoms, substituted or unsubstituted heteroaryl having 3 to 20 carbon atoms; 1 , R 2 Same or different.

8. The tetradentate platinum compound according to any one of claims 1 to 6, wherein the E ring is a five-membered ring or a six-membered ring.

9. The tetradentate platinum compound according to claim 8, wherein a3, a5 to a8 are 0, Ar 2 Selected from aromatic rings having 6 to 10 carbon atoms.

10. The tetradentate platinum compound according to claim 9, wherein R 4 Selected from: deuterium, cyano, substituted or unsubstituted alkyl having 1 to 10 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 10 ring carbon atoms, substituted or unsubstituted silane having 1 to 10 carbon atoms.

11. The tetradentate platinum compound according to claim 10, which is one of the following structural formulas:

12. A precursor of a metal compound, the structural formula of which is as follows: Where R 1 To R 8 ,Ar 1 ,Ar 2 , A, a3 to a8, and E are defined the same as in claim 1.

13. An organic light emitting diode, comprising a cathode, an anode and an organic layer, wherein the organic layer comprises one or more layers of a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron injection layer and an electron transport layer, and at least one layer of the hole injection layer, the hole transport layer, the hole blocking layer, the electron injection layer, the light emitting layer and the electron transport layer contains the tetradentate platinum compound according to any one of claims 1 to 11. 14 . The organic light emitting diode according to claim 13 , wherein the layer where the tetradentate platinum compound according to any one of claims 1 to 11 is located is a light emitting layer or an electron transport layer.

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