Anthracene compound with multi-arm structure as well as preparation method and application of anthracene compound

Abstract

The invention discloses a multi-arm structure anthracene compound and a preparation method and application thereof, and belongs to the technical field of organic electroluminescent device display. The structure of the anthracene compound with the multi-arm structure is shown as a formula (I). Wherein X is selected from C, Si or Ge atoms; d in Da, Db, Dc and Dd is a deuterium atom of substituted hydrogen on phenyl connected with X, and a, b, c and d are the number of the deuterium atom and are selected from integers of 0-5; r < 1 >, R < 2 >, R < 3 > and R < 4 > are independently selected from C6-C60 aryl groups or C4-C60 heteroaryl groups; m and n are independently selected from 0 or 1. The multi-arm structure anthracene compound is used as a main body material of a light-emitting layer of the blue light-emitting device, and the light coupling output efficiency of the blue light-emitting device can be greatly improved by co-doping with a blue dye, so that the external quantum efficiency of the blue light-emitting device is improved. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescent device display, and in particular to a multi-arm structure anthracene compound and a preparation method and application thereof. Background Art

[0002] Organic light-emitting devices have the advantages of high efficiency, high contrast, fast response speed and flexibility. They are a new generation of display technology. Their device structure is usually composed of an anode, a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a cathode. Its light-emitting principle is: holes are injected from the anode and enter the light-emitting layer through the hole injection layer, the hole transport layer and the electron blocking layer. At the same time, electrons are injected from the cathode and enter the light-emitting layer through the electron injection layer, the electron transport layer and the hole blocking layer. Then, holes and electrons recombine in the light-emitting layer to form 25% singlet excitons and 75% triplet excitons. Singlet excitons can directly radiate light, while triplet excitons are difficult to directly radiate light due to spin inversion prohibition.

[0003] Among them, blue light OLED devices have always had the problem of poor performance, which directly restricts the display effect of blue light OLED panels. The key functional layer that affects the performance of OLED devices is the light-emitting layer, which is usually composed of a host and a dye. The functions of the host include injecting charges, transmitting charges, generating excitons, and converting excitons. Therefore, the energy level structure, transmission characteristics, and excited state behavior of the host have a decisive effect on the performance of OLED devices. The commonly used host for blue light OLED devices is a triplet-triplet annihilation (TTA) type host, which has the outstanding feature of being able to convert two non-luminescent triplet excitons into one luminescent singlet exciton, thereby converting and utilizing triplet excitons that are forbidden to radiate luminescence. At the same time, it has the advantage of a low triplet energy level, which can effectively avoid the generation of high-energy excited states that damage the device.

[0004] The TTA-type hosts reported so far are mainly small molecule structures with only one TTA unit. When the light-emitting layer thin film is prepared by evaporation or solution processing, it is generally randomly arranged and has a low polarity, which makes it impossible to effectively induce the transition dipole moment of the blue light dye molecules to be arranged in the horizontal direction. Therefore, the optical coupling output efficiency of the existing blue light devices based on the TTA host is generally low, resulting in the device's external quantum efficiency being difficult to meet application requirements.

[0005] Therefore, it is of great significance to research and develop a new type of host material to improve the performance of blue light OLED devices. Summary of the invention

[0006] In view of this, the technical problem to be solved by the present invention is to provide a multi-arm anthracene compound and a preparation method and application thereof. The multi-arm anthracene compound induces the orientation of blue light dye molecules through electrostatic attraction, so that the transition dipole moment is arranged in the horizontal direction, greatly improving the light coupling output efficiency, thereby achieving the improvement of the efficiency of blue light devices based on TTA main body.

[0007] In order to achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0008] The present invention provides a multi-arm anthracene compound, the structure of which is shown in formula (I):

[0009]

[0010] wherein X is selected from C, Si or Ge atoms;

[0011] D a , D b , D c , D d Where D is a deuterium atom replacing hydrogen on the phenyl group connected to X, and a, b, c, and d are the numbers of the deuterium atoms and are selected from integers between 0 and 5;

[0012] R 1 , R 2 , R 3 , R 4 Independently selected from C 6 -C 60 Aryl or C 4 -C 60 heteroaryl;

[0013] m and n are independently selected from 0 or 1.

[0014] When m and n are both selected from 1, the formula (I) is an anthracene compound with a four-arm structure;

[0015] When m is selected from 0, n is selected from 1 or m is selected from 1, n is selected from 0, the formula (I) is an anthracene compound with a three-arm structure;

[0016] When m and n are both selected from 0, the formula (I) is an anthracene compound with a two-arm structure.

[0017] Preferably, the structure of the multi-arm anthracene compound is as shown in formula (I-1), formula (I-2) or formula (I-3):

[0018]

[0019] The above formula (I-1) is an anthracene compound with a two-arm structure, the formula (I-2) is an anthracene compound with a three-arm structure, and the formula (I-3) is an anthracene compound with a four-arm structure.

[0020] Wherein, preferably, X is selected from C, Si or Ge atom; more preferably, X is selected from C or Si.

[0021] Preferably, D a , D b , D c , D d Where D is a deuterium atom replacing hydrogen on the phenyl group connected to X, and a, b, c, d are the numbers of the deuterium atoms and are independently selected from 0, 4 or 5;

[0022] Preferably, R 1 , R 2 , R 3 , R 4 Independently selected from C 10 -C 60 Aryl or C 10 -C 60 Heteroaryl.

[0023] Preferably, the C 10 -C 60 The aryl group and the C 10 -C 60 The heteroaryl group may also contain substituents independently selected from C 1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, C 1 -C 3 One or more of nitrile groups;

[0024] The C 1 -C 10 Alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl, decyl, and the like.

[0025] The C 3 -C 6 Cycloalkyl includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

[0026] The C 1 -C 3 The nitrile group includes, but is not limited to, a nitrile group, an acetonitrile group, a propionitrile group, and the like.

[0027] Preferably, the number of the substituents is independently selected from an integer between 1 and 5; more preferably, the number of the substituents is independently selected from 1, 2 or 3.

[0028] When the number of the substituent is 2, the position of the substituent includes meta-position, para-position, or ortho-position substitution, preferably meta-position substitution or para-position substitution.

[0029] Preferably, the R 1 , R 2 , R 3 , R 4 Independently selected from any of the following structures:

[0030]

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[0041] Preferably, the multi-arm anthracene compound is selected from any of the following structures:

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[0129] The present invention also provides a method for preparing the multi-arm anthracene compound represented by the above formula (I-1), comprising the following steps:

[0130] (1) The compound represented by formula A and compound R 1 -Br, R 2 -Br reaction to obtain compounds represented by formula B-1 and formula B-2 respectively;

[0131] (2) the compounds represented by formula B-1 and formula B-2 are subjected to borylation and hydrolysis reactions in sequence to obtain the compounds represented by formula C-1 and formula C-2;

[0132] (3) reacting the compound represented by formula D-1 with formula C-1, and then reacting the product with the compound represented by formula C-2 to obtain the multi-arm anthracene compound represented by formula (I-1);

[0133]

[0134] Among them, R 1 and R 2 Independently selected from C 10 -C 60 Aryl or C 10 -C 60 heteroaryl;

[0135] X is selected from C, Si or Ge atoms;

[0136] D a , D b , D c , D d Wherein D is a deuterium atom replacing hydrogen on the phenyl group connected to X, and a, b, c, d are the numbers of the deuterium atoms and are independently selected from 0, 4 or 5.

[0137] The method for preparing the multi-arm anthracene compound represented by the above formula (I-1) specifically includes the following steps:

[0138] First case:

[0139] R 1 , R 2 When they are the same, the compounds represented by formula B-1 and formula B-2 are the same, and the compounds represented by formula C-1 and formula C-2 are also the same;

[0140] Furthermore, the compound represented by formula A and compound R in step (1) 1 (or R 2 )-Br has a molar ratio of 1:2.

[0141] Second case:

[0142] R 1, R 2 When they are different, the compounds represented by formula B-1 and formula B-2 are different, and the compounds represented by formula C-1 and formula C-2 are also different;

[0143] Furthermore, the compound represented by formula A and compound R in step (1) 1 -Br and R 2 The molar ratio of -Br is 1:1:1.

[0144] In addition, the step (3) requires that the compound represented by formula D-1 and formula C-1 are reacted in a 1:1 molar ratio, and then the product is reacted with the compound represented by formula C-2 in a 1:1 molar ratio to obtain a multi-arm anthracene compound represented by formula (I-1). The specific reaction equation is as follows:

[0145]

[0146] The present invention also provides a method for preparing the multi-arm anthracene compound represented by the above formula (I-2), comprising the following steps:

[0147] (1) The compound represented by formula A and compound R 1 -Br, R 2 -Br, R 3 -Br reaction to obtain compounds represented by formula B-1, formula B-2, and formula B-3, respectively;

[0148] (2) the compounds represented by formula B-1, formula B-2, and formula B-3 are subjected to borylation and hydrolysis reactions in sequence to obtain the compounds represented by formula C-1, formula C-2, and formula C-3;

[0149] (3) reacting the compound represented by formula D-2 with formula C-1, and then reacting the product with formula C-2. After the reaction is completed, the product is reacted with the compound represented by formula C-3 to obtain the multi-arm anthracene compound represented by formula (I-2);

[0150]

[0151] Among them, R 1 , R 2 , R 3 Independently selected from C 10 -C 60 Aryl or C 10 -C 60 heteroaryl;

[0152] X is selected from C, Si or Ge atoms;

[0153] D a , D b , D c , D dWherein D is a deuterium atom replacing hydrogen on the phenyl group connected to X, and a, b, c, d are the numbers of the deuterium atoms and are independently selected from 0, 4 or 5.

[0154] The method for preparing the multi-arm anthracene compound represented by the above formula (I-2) specifically includes the following steps:

[0155] First case:

[0156] R 1 , R 2 , R 3 When the same, the compounds represented by formula B-1, formula B-2, and formula B-3 are the same, and the compounds represented by formula C-1, formula C-2, and formula C-3 are also the same;

[0157] Furthermore, the compound represented by formula A and compound R in step (1) 1 (or R 2 or R 3 )-Br has a molar ratio of 1:3.

[0158] Second case:

[0159] R 1 , R 2 , R 3 When they are different from each other, the compounds represented by formula B-1, formula B-2, and formula B-3 are different, and the compounds represented by formula C-1, formula C-2, and formula C-3 are also different;

[0160] Furthermore, the compound represented by formula A and compound R in step (1) 1 -Br, R 2 -Br, R 3 The molar ratio of -Br is 1:1:1:1.

[0161] In addition, the step (3) requires that the compound represented by formula D-2 and formula C-1 are reacted in a 1:1 molar ratio, and then the product is reacted with the compound represented by formula C-2 in a 1:1 molar ratio, and the obtained product is reacted with the compound represented by formula C-3 in a 1:1 molar ratio, and finally the multi-arm structure anthracene compound represented by formula (I-2) is obtained. The specific reaction equation is as follows:

[0162]

[0163] The multi-arm anthracene compound represented by the above formula (I-2) further comprises R 1 , R 2 , R 3 The situation where two of the three substituents are the same and one is different.

[0164] The present invention also provides a method for preparing the multi-arm anthracene compound represented by the above formula (I-3), comprising the following steps:

[0165] (1) The compound represented by formula A and compound R 1 -Br, R 2 -Br, R 3 -Br, R 4 -Br reaction to obtain compounds represented by formula B-1, formula B-2, formula B-3, and formula B-4, respectively;

[0166] (2) The compounds represented by formula B-1, formula B-2, formula B-3, and formula B-4 are subjected to borylation and hydrolysis reactions in sequence to obtain compounds represented by formula C-1, formula C-2, formula C-3, and formula C-4;

[0167] (3) reacting the compound represented by formula D-3 with formula C-1, and then reacting the product with formula C-2. After the reaction, the product is reacted with the compound represented by formula C-3. After the reaction, the product is reacted with the compound represented by formula C-4 to obtain the multi-arm anthracene compound represented by formula (I-3);

[0168]

[0169] Among them, R 1 , R 2 , R 3 , R 4 Independently selected from C 10 -C 60 Aryl or C 10 -C 60 heteroaryl;

[0170] X is selected from C, Si or Ge atoms;

[0171] D a , D b , D c , D d Wherein D is a deuterium atom replacing hydrogen on the phenyl group connected to X, and a, b, c, d are the numbers of the deuterium atoms and are independently selected from 0, 4 or 5.

[0172] The method for preparing the multi-arm anthracene compound represented by the above formula (I-3) specifically includes the following:

[0173] First case:

[0174] R 1 , R 2 , R 3 , R 4When the same, the compounds represented by formula B-1, formula B-2, formula B-3, and formula B-4 are the same, and the compounds represented by formula C-1, formula C-2, formula C-3, and formula C-4 are also the same;

[0175] Furthermore, the compound represented by formula A and compound R in step (1) 1 (or R 2 or R 3 or R 4 )-Br has a molar ratio of 1:4.

[0176] Second case:

[0177] R 1 , R 2 , R 3 , R 4 When they are different from each other, the compounds represented by formula B-1, formula B-2, formula B-3, and formula B-4 are different, and the compounds represented by formula C-1, formula C-2, formula C-3, and formula C-4 are also different;

[0178] Furthermore, the compound represented by formula A and compound R in step (1) 1 -Br, R 2 -Br, R 3 -Br, R 4 The molar ratio of -Br is 1:1:1:1:1.

[0179] In addition, the step (3) requires that the compound represented by formula D-3 and formula C-1 are reacted in a 1:1 molar ratio, and then the product is reacted with the compound represented by formula C-2 in a 1:1 molar ratio. After the reaction, the obtained product is reacted with the compound represented by formula C-3 in a 1:1 molar ratio. After the reaction, the obtained product is reacted with the compound represented by formula C-4 in a 1:1 molar ratio, and finally a multi-arm anthracene compound represented by formula (I-3) is obtained. The specific reaction equation is as follows:

[0180]

[0181] The multi-arm anthracene compound represented by the above formula (I-3) further comprises R 1 , R 2 , R 3 , R 4 Among the four substituents, two are the same and two are different, or three are the same and one is different.

[0182] Preferably, the C 10 -C 60 The aryl group and the C 10 -C 60 The heteroaryl group may also contain substituents independently selected from C1 -C 10 Alkyl, C 3 -C 6 Cycloalkyl, C 1 -C 3 One or more nitrile groups.

[0183] Preferably, the number of the substituents is independently selected from an integer between 1 and 5; more preferably 1, 2 or 3.

[0184] The C 1 -C 10 The alkyl group and the C 3 -C 6 Cycloalkyl and C 1 -C 3 The scope of the nitrile group is the same as above and will not be repeated here.

[0185] The present invention also provides the use of the multi-arm anthracene compound or the multi-arm anthracene compound prepared by the above preparation method as a molecular orientation host material in a blue electroluminescent device.

[0186] The multi-arm anthracene compound of the present invention can be applied to flat display devices, flexible display devices, lighting sources, etc. The multi-arm anthracene compound of the present invention is used as a molecular orientation host material and co-doped with a blue light dye to prepare a light-emitting layer of a vapor-deposited blue light-emitting device or a light-emitting layer of a solution-processed blue light-emitting device.

[0187] The blue light dyes include but are not limited to traditional fluorescent blue light dyes and multiple resonance thermally activated delayed fluorescent blue light dyes.

[0188] In some specific embodiments of the present invention, the blue light dye of the light-emitting layer of the vapor-deposited blue light-emitting device is selected from BD-1, BD-2 or BD-3, which is co-doped with the multi-arm structure anthracene compound as a molecular orientation host material to prepare the light-emitting layer of the blue electroluminescent device.

[0189] The light-emitting layer enables the maximum external quantum efficiency of the evaporated blue light-emitting device to reach 8.9%-12.3%, and the horizontal dipole orientation ratio of the light-emitting layer is 88.4°-95.3°.

[0190] In some specific embodiments of the present invention, the blue light dye of the light-emitting layer of the solution-processed blue light-emitting device is selected from BD-1, BD-2 or BD-3, which is co-doped with the multi-arm structure anthracene compound of the present invention as a molecular orientation host material to prepare the light-emitting layer of the blue electroluminescent device.

[0191] The light-emitting layer enables the maximum external quantum efficiency of the solution-processed blue light-emitting device to reach 7.5%-10.6%, and the horizontal dipole orientation ratio of the light-emitting layer is 79.1°-87.6°.

[0192] The structure of the above blue dye BD-1, BD-2 or BD-3 is shown below:

[0193]

[0194] The blue electroluminescent device comprises, in addition to the light-emitting layer, an anode and a cathode located on both sides of the light-emitting layer.

[0195] The multi-arm structure anthracene compound described in the present invention can be used as the main material of the light-emitting layer of a vapor-deposited or solution-processed blue light-emitting device. During the preparation of the light-emitting layer film, the dye molecule transition dipole moment can be promoted to be arranged along the horizontal direction of the substrate through strong electrostatic attraction, thereby significantly improving the light coupling output efficiency of the organic light-emitting diode device and further improving the luminous efficiency of the device.

[0196] Compared with the prior art, the structure of the multi-arm anthracene compound provided by the present invention is as shown in formula (I); wherein X is selected from C, Si or Ge atoms; D a , D b , D c , D d Where D is a deuterium atom replacing hydrogen on the phenyl group connected to X, a, b, c, d are the number of deuterium atoms and are selected from integers between 0 and 5; R 1 , R 2 , R 3 , R 4 Independently selected from C 6 -C 60 Aryl or C 4 -C 60 Heteroaryl; m and n are independently selected from 0 or 1. The multi-arm anthracene compound as the main material of the light-emitting layer of the blue light-emitting device can greatly improve the light coupling output efficiency of the blue light-emitting device by co-doping with a blue dye, thereby improving the external quantum efficiency of the blue light-emitting device. DETAILED DESCRIPTION

[0197] In order to further illustrate the present invention, the multi-arm structure anthracene compound provided by the present invention and its preparation method and application are described in detail below in conjunction with embodiments.

[0198] Example 1

[0199]

[0200] Under argon atmosphere, 1-1 (12.32 g, 40 mmol), 1-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 1-3 (14.75 g, yield 76.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 79.18; H, 4.36 test value C, 79.17; H, 4.32. Mass spectrum: theoretical value 484.08, experimental value 484.1 (M+).

[0201] Under argon atmosphere, 1-3 (12.10 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 1-4 (8.81 g, yield 78.0%). Elemental analysis (%): theoretical value C, 85.35; H, 5.15; test value C, 85.32; H, 5.17. Mass spectrum: theoretical value 450.18, experimental value 450.2 (M+).

[0202] Under argon atmosphere, 1-4 (6.78 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-1 (6.83 g, yield 79.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 92.27; H, 5.28; test value C, 92.22; H, 5.33. Mass spectrum: theoretical value 1144.45, experimental value 1144.5 (M+).

[0203] Example 2

[0204]

[0205] Under argon atmosphere, 2-1 (11.89 g, 40 mmol), 2-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 2-3 (14.01 g, yield 74.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.13; H, 3.63. Mass spectrum: theoretical value 472.05, experimental value 472.0 (M+).

[0206] Under argon atmosphere, 2-3 (11.83 g, 25 mmol), bipyraclostrobin (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 2-4 (8.44 g, yield 77.1%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.22; H, 4.36. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0207] Under argon atmosphere, 2-4 (2.63 g, 6 mmol), bis(3-bromophenyl)diphenylsilane (1.48 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-136 (2.53 g, yield 75.3%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.97; H, 4.67; test value C, 89.96; H, 4.66. Mass spectrum: theoretical value 1120.37, experimental value 1120.4 (M+).

[0208] Example 3

[0209]

[0210] Under argon atmosphere, 3-1 (11.89 g, 40 mmol), 3-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 3-3 (14.01 g, yield 74.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.13; H, 3.63. Mass spectrum: theoretical value 472.05, experimental value 472.0 (M+).

[0211] Under argon atmosphere, 3-3 (11.83 g, 25 mmol), bipyralidone (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 3-4 (8.44 g, yield 77.1%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.22; H, 4.36. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0212] Under argon atmosphere, 3-4 (2.63 g, 6 mmol), 3-5 (1.53 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-137 (2.52 g, yield 73.7%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 88.54; H, 6.19; test value C, 88.55; H, 6.18. Mass spectrum: theoretical value 1138.49, experimental value 1138.5 (M+).

[0213] Example 4

[0214]

[0215] Under argon atmosphere, 4-1 (11.89 g, 40 mmol), 4-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 4-3 (14.01 g, yield 74.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.13; H, 3.63. Mass spectrum: theoretical value 472.05, experimental value 472.0 (M+).

[0216] Under argon atmosphere, 4-3 (11.83 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 4-4 (8.44 g, yield 77.1%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.22; H, 4.36. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0217] Under argon atmosphere, 4-4 (2.63 g, 6 mmol), 4-5 (1.43 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-303 (2.35 g, yield 70.8%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 92.36; H, 4.74; test value C, 92.35; H, 4.75. Mass spectrum: theoretical value 1104.40, experimental value 1104.4 (M+).

[0218] Example 5

[0219]

[0220] Under argon atmosphere, 5-1 (11.89 g, 40 mmol), 5-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 5-3 (14.01 g, yield 74.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.13; H, 3.63. Mass spectrum: theoretical value 472.05, experimental value 472.0 (M+).

[0221] Under argon atmosphere, 5-3 (11.83 g, 25 mmol), bipyralidone (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 5-4 (8.44 g, yield 77.1%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.22; H, 4.36. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0222] Under argon atmosphere, 5-4 (2.63 g, 6 mmol), 5-5 (1.48 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-129 (2.62 g, yield 77.8%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 90.87; H, 6.28; test value C, 90.87; H, 6.28. Mass spectrum: theoretical value 1122.51, experimental value 1122.5 (M+).

[0223] Example 6

[0224]

[0225] Under argon atmosphere, 6-1 (12.29 g, 40 mmol), 6-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 6-3 (14.56 g, yield 75.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 79.51; H, 3.96; test value C, 79.58; H, 3.91. Mass spectrum: theoretical value 482.07, experimental value 482.1 (M+).

[0226] Under argon atmosphere, 6-3 (12.09 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd (dppf) Cl2 (1.10 g, 1.5 mmol) were added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 6-4 (8.31 g, yield 74.2%). Elemental analysis (%): theoretical value C, 85.73; H, 4.72; test value C, 85.70; H, 4.77;. Mass spectrum: theoretical value 448.16, experimental value 448.2 (M+).

[0227] Under argon atmosphere, 6-4 (2.69 g, 6 mmol), bis(3-bromophenyl)diphenylsilane (1.48 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-210 (2.58 g, yield 75%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 92.59; H, 4.95; test value C, 92.52; H, 4.99. Mass spectrum: theoretical value 1140.42, experimental value 1140.4 (M+).

[0228] Example 7

[0229]

[0230] Under argon atmosphere, 7-1 (12.29 g, 40 mmol), 7-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 7-3 (14.56 g, yield 75.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 79.51; H, 3.96; test value C, 79.58; H, 3.91. Mass spectrum: theoretical value 482.07, experimental value 482.1 (M+).

[0231] Under argon atmosphere, 7-3 (12.09 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd (dppf) Cl2 (1.10 g, 1.5 mmol) were added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 7-4 (8.31 g, yield 74.2%). Elemental analysis (%): theoretical value C, 85.73; H, 4.72; test value C, 85.70; H, 4.77;. Mass spectrum: theoretical value 448.16, experimental value 448.2 (M+).

[0232] Under argon atmosphere, 7-4 (2.69 g, 6 mmol), 7-5 (1.53 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-140 (2.54 g, yield 73.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 91.15; H, 6.43; test value C, 91.17; H, 6.40. Mass spectrum: theoretical value 1158.53, experimental value 1158.5 (M+).

[0233] Example 8

[0234]

[0235] Under argon atmosphere, 8-1 (12.29 g, 40 mmol), 8-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 8-3 (14.56 g, yield 75.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 79.51; H, 3.96; test value C, 79.58; H, 3.91. Mass spectrum: theoretical value 482.07, experimental value 482.1 (M+).

[0236] Under argon atmosphere, 8-3 (12.09 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd (dppf) Cl2 (1.10 g, 1.5 mmol) were added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 8-4 (8.31 g, yield 74.2%). Elemental analysis (%): theoretical value C, 85.73; H, 4.72; test value C, 85.70; H, 4.77;. Mass spectrum: theoretical value 448.16, experimental value 448.2 (M+).

[0237] Under argon atmosphere, 8-4 (2.69 g, 6 mmol), 8-5 (1.43 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-296 (2.45 g, yield 72.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 94.98; H, 5.02; test value C, 94.97; H, 5.03. Mass spectrum: theoretical value 1124.44, experimental value 1124.4 (M+).

[0238] Example 9

[0239]

[0240] Under argon atmosphere, 9-1 (12.29 g, 40 mmol), 9-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 9-3 (14.56 g, yield 75.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 79.51; H, 3.96; test value C, 79.58; H, 3.91. Mass spectrum: theoretical value 482.07, experimental value 482.1 (M+).

[0241] Under argon atmosphere, 9-3 (12.09 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd (dppf) Cl2 (1.10 g, 1.5 mmol) were added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 9-4 (8.31 g, yield 74.2%). Elemental analysis (%): theoretical value C, 85.73; H, 4.72; test value C, 85.70; H, 4.77;. Mass spectrum: theoretical value 448.16, experimental value 448.2 (M+).

[0242] Under argon atmosphere, 9-4 (2.69 g, 6 mmol), 9-5 (1.48 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-125 (2.53 g, yield 73.9%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 93.48; H, 6.52; test value C, 93.45; H, 6.53. Mass spectrum: theoretical value 1142.55, experimental value 1142.6 (M+).

[0243] Example 10

[0244]

[0245] Under argon atmosphere, 10-1 (8.28 g, 40 mmol), 10-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 10-3 (12.11 g, yield 79.0%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 78.44; H, 4.17; test value C, 78.42; H, 4.19. Mass spectrum: theoretical value 382.04, experimental value 382.0 (M+).

[0246] Under argon atmosphere, 10-3 (9.58 g, 25 mmol), biboric acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 10-4 (6.45 g, yield 74.1%). Elemental analysis (%): theoretical value C, 82.79; H, 4.92; test value C, 82.75; H, 4.95. Mass spectrum: theoretical value 348.13, experimental value 348.1 (M+).

[0247] Under argon atmosphere, 10-4 (2.09 g, 6 mmol), 10-5 (1.53 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-335 (2.08 g, yield 72.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 90.14; H, 6.93; test value C, 90.12; H, 6.95. Mass spectrum: theoretical value 958.47, experimental value 958.5 (M+).

[0248] Embodiment 11

[0249]

[0250] Under argon atmosphere, 11-1 (8.28 g, 40 mmol), 11-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 11-3 (12.11 g, yield 79.0%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 78.44; H, 4.17; test value C, 78.42; H, 4.19. Mass spectrum: theoretical value 382.04, experimental value 382.0 (M+).

[0251] Under argon atmosphere, 11-3 (9.58 g, 25 mmol), biboric acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 11-4 (6.45 g, yield 74.1%). Elemental analysis (%): theoretical value C, 82.79; H, 4.92; test value C, 82.75; H, 4.95. Mass spectrum: theoretical value 348.13, experimental value 348.1 (M+).

[0252] Under argon atmosphere, 11-4 (2.09 g, 6 mmol), 11-5 (1.43 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-262 (1.97 g, yield 70.9%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 94.77; H, 5.23; test value C, 94.75; H, 5.24. Mass spectrum: theoretical value 924.38, experimental value 924.4 (M+).

[0253] Example 12

[0254]

[0255] Under argon atmosphere, 12-1 (8.28 g, 40 mmol), 12-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 12-3 (12.11 g, yield 79.0%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 78.44; H, 4.17; test value C, 78.42; H, 4.19. Mass spectrum: theoretical value 382.04, experimental value 382.0 (M+).

[0256] Under argon atmosphere, 12-3 (9.58 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 12-4 (6.45 g, yield 74.1%). Elemental analysis (%): theoretical value C, 82.79; H, 4.92; test value C, 82.75; H, 4.95. Mass spectrum: theoretical value 348.13, experimental value 348.1 (M+).

[0257] Under argon atmosphere, 12-4 (2.09 g, 6 mmol), 12-5 (1.48 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product H1-24 (2.04 g, yield 72.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 92.95; H, 7.05; test value C, 92.94; H, 7.02. Mass spectrum: theoretical value 942.49, experimental value 942.5 (M+).

[0258] Embodiment 13

[0259]

[0260] Under argon atmosphere, 13-1 (9.36 g, 40 mmol), 13-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 13-3 (13.02 g, yield 79.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 70.09; H, 3.68 test value C, 70.08; H, 3.65. Mass spectrum: theoretical value 410.04, experimental value 410.0 (M+).

[0261] Under argon atmosphere, 13-3 (10.25 g, 25 mmol), bipyralidone (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 13-4 (7.54 g, yield 80.2%). Elemental analysis (%): theoretical value C, 76.62; H, 4.55; test value C, 76.60; H, 4.56. Mass spectrum: theoretical value 376.14, experimental value 376.1 (M+).

[0262] Under argon atmosphere, 13-4 (5.64 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-30 (5.84 g, yield 78.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 86.71; H, 4.85; test value C, 86.70; H, 4.87. Mass spectrum: theoretical value 996.36, experimental value 996.4 (M+).

[0263] Embodiment 14

[0264]

[0265] Under argon atmosphere, 14-1 (20.32 g, 40 mmol), 14-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 14-3 (21.92 g, yield 80.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 84.08; H, 4.26 test value C, 84.09; H, 4.24. Mass spectrum: theoretical value 684.15, experimental value 684.2 (M+).

[0266] Under argon atmosphere, 14-3 (17.10 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 14-4 (12.94 g, yield 79.6%). Elemental analysis (%): theoretical value C, 88.62; H, 4.80; test value C, 88.64; H, 4.82. Mass spectrum: theoretical value 650.24, experimental value 650.2 (M+).

[0267] Under argon atmosphere, 14-4 (9.75 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-33 (9.00 g, yield 77.7%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 93.23; H, 4.96; test value C, 93.22; H, 4.97. Mass spectrum: theoretical value 1544.57, experimental value 1544.6 (M+).

[0268] Embodiment 15

[0269]

[0270]

[0271] Under argon atmosphere, 15-1 (11.33 g, 40 mmol), 15-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 15-3 (12.86 g, yield 70.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 78.44; H, 4.17; test value C, 78.45; H, 4.16. Mass spectrum: theoretical value 458.07, experimental value 458.1 (M+).

[0272] Under argon atmosphere, 15-3 (11.48 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 15-4 (7.66 g, yield 72.3%). Elemental analysis (%): theoretical value C, 84.92; H, 4.99; test value C, 84.95; H, 4.97. Mass spectrum: theoretical value 424.16, experimental value 424.2 (M+).

[0273] Under argon atmosphere, 15-4 (2.55 g, 6 mmol), bis(3-bromophenyl)diphenylsilane (1.48 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-38 (2.45 g, yield 74.9%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 92.27; H, 5.16; test value C, 92.26; H, 5.15. Mass spectrum: theoretical value 1092.42, experimental value 1092.4 (M+).

[0274] Example 16

[0275]

[0276] Under argon atmosphere, 16-1 (11.33 g, 40 mmol), 16-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 16-3 (12.86 g, yield 70.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 78.44; H, 4.17; test value C, 78.45; H, 4.16. Mass spectrum: theoretical value 458.07, experimental value 458.1 (M+).

[0277] Under argon atmosphere, 16-3 (11.48 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 16-4 (7.66 g, yield 72.3%). Elemental analysis (%): theoretical value C, 84.92; H, 4.99; test value C, 84.95; H, 4.97. Mass spectrum: theoretical value 424.16, experimental value 424.2 (M+).

[0278] Under argon atmosphere, 16-4 (2.55 g, 6 mmol), 16-5 (1.53 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-141 (2.31 g, yield 69.3%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 90.77; H, 6.71; test value C, 90.76; H, 6.72. Mass spectrum: theoretical value 1110.53, experimental value 1110.5 (M+).

[0279] Embodiment 17

[0280]

[0281] Under argon atmosphere, 17-1 (11.33 g, 40 mmol), 17-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 17-3 (12.86 g, yield 70.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 78.44; H, 4.17; test value C, 78.45; H, 4.16. Mass spectrum: theoretical value 458.07, experimental value 458.1 (M+).

[0282] Under argon atmosphere, 17-3 (11.48 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 17-4 (7.66 g, yield 72.3%). Elemental analysis (%): theoretical value C, 84.92; H, 4.99; test value C, 84.95; H, 4.97. Mass spectrum: theoretical value 424.16, experimental value 424.2 (M+).

[0283] Under argon atmosphere, 17-4 (2.55 g, 6 mmol), 17-5 (1.43 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-64 (2.51 g, yield 77.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 94.76; H, 5.24; test value C, 94.75; H, 5.25. Mass spectrum: theoretical value 1076.44, experimental value 1076.4 (M+).

[0284] Embodiment 18

[0285]

[0286] Under argon atmosphere, 18-1 (11.33 g, 40 mmol), 18-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 18-3 (12.86 g, yield 70.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 78.44; H, 4.17; test value C, 78.45; H, 4.16. Mass spectrum: theoretical value 458.07, experimental value 458.1 (M+).

[0287] Under argon atmosphere, 18-3 (11.48 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 18-4 (7.66 g, yield 72.3%). Elemental analysis (%): theoretical value C, 84.92; H, 4.99; test value C, 84.95; H, 4.97. Mass spectrum: theoretical value 424.16, experimental value 424.2 (M+).

[0288] Under argon atmosphere, 18-4 (2.55 g, 6 mmol), 18-5 (1.48 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-124 (2.35 g, yield 71.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 93.19; H, 6.81; test value C, 93.18; H, 6.82. Mass spectrum: theoretical value 1094.55, experimental value 1094.5 (M+).

[0289] Embodiment 19

[0290]

[0291] Under argon atmosphere, 19-1 (15.48 g, 40 mmol), 19-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 19-3 (17.23 g, yield 76.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 74.47; H, 3.93 test value C, 74.46; H, 3.94. Mass spectrum: theoretical value 563.10, experimental value 563.1 (M+).

[0292] Under argon atmosphere, 19-3 (14.08 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 19-4 (10.47 g, yield 79.2%). Elemental analysis (%): theoretical value C, 79.41; H, 4.57; test value C, 79.43; H, 4.56. Mass spectrum: theoretical value 529.20, experimental value 529.2 (M+).

[0293] Under argon atmosphere, 19-4 (7.94 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-43 (7.60 g, yield 77.8%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 86.61; H, 4.79; test value C, 86.60; H, 4.77. Mass spectrum: theoretical value 1302.48, experimental value 1302.5 (M+).

[0294] Embodiment 20

[0295]

[0296] Under argon atmosphere, 20-1 (8.28 g, 40 mmol), 20-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 20-3 (12.16 g, yield 79.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 75.21; H, 3.94 test value C, 75.23; H, 3.92. Mass spectrum: theoretical value 382.04, experimental value 382.0 (M+).

[0297] Under argon atmosphere, 20-3 (10.83 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 20-4 (6.98 g, yield 80.2%). Elemental analysis (%): theoretical value C, 82.79; H, 4.92; test value C, 82.81; H, 4.90. Mass spectrum: theoretical value 348.13, experimental value 348.1 (M+).

[0298] Under argon atmosphere, 20-4 (2.09 g, 6 mmol), 20-5 (1.48 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-130 (2.22 g, yield 78.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 92.95; H, 7.05; test value C, 92.90; H, 7.07. Mass spectrum: theoretical value 942.49, experimental value 942.5 (M+).

[0299] Embodiment 21

[0300]

[0301] Under argon atmosphere, 21-1 (8.28 g, 40 mmol), 21-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 21-3 (12.16 g, yield 79.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 75.21; H, 3.94 test value C, 75.23; H, 3.92. Mass spectrum: theoretical value 382.04, experimental value 382.0 (M+).

[0302] Under argon atmosphere, 21-3 (10.83 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 21-4 (6.98 g, yield 80.2%). Elemental analysis (%): theoretical value C, 82.79; H, 4.92; test value C, 82.81; H, 4.90. Mass spectrum: theoretical value 348.13, experimental value 348.1 (M+).

[0303] Under argon atmosphere, 21-4 (2.09 g, 6 mmol), 21-5 (1.43 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-263 (1.95 g, yield 70.3%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 94.77; H, 5.23; test value C, 94.79; H, 5.20. Mass spectrum: theoretical value 924.38, experimental value 924.4 (M+).

[0304] Embodiment 22

[0305]

[0306]

[0307] Under argon atmosphere, 22-1 (8.28 g, 40 mmol), 22-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 22-3 (12.16 g, yield 79.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 75.21; H, 3.94 test value C, 75.23; H, 3.92. Mass spectrum: theoretical value 382.04, experimental value 382.0 (M+).

[0308] Under argon atmosphere, 22-3 (10.83 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 22-4 (6.98 g, yield 80.2%). Elemental analysis (%): theoretical value C, 82.79; H, 4.92; test value C, 82.81; H, 4.90. Mass spectrum: theoretical value 348.13, experimental value 348.1 (M+).

[0309] Under argon atmosphere, 22-4 (2.09 g, 6 mmol), 22-5 (1.53 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product H1-322 (2.12 g, yield 73.7%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 90.14; H, 6.93; test value C, 90.10; H, 6.95. Mass spectrum: theoretical value 958.47, experimental value 958.5 (M+).

[0310] Embodiment 23

[0311]

[0312] Under argon atmosphere, 23-1 (8.28 g, 40 mmol), 23-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 23-3 (12.16 g, yield 79.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 75.21; H, 3.94 test value C, 75.23; H, 3.92. Mass spectrum: theoretical value 382.04, experimental value 382.0 (M+).

[0313] Under argon atmosphere, 23-3 (10.83 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 23-4 (6.98 g, yield 80.2%). Elemental analysis (%): theoretical value C, 82.79; H, 4.92; test value C, 82.81; H, 4.90. Mass spectrum: theoretical value 348.13, experimental value 348.1 (M+).

[0314] Under argon atmosphere, 23-4 (5.53 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-47 (5.53 g, yield 78.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 91.88; H, 5.14; test value C, 91.89; H, 5.13. Mass spectrum: theoretical value 940.35, experimental value 940.4 (M+).

[0315] Embodiment 24

[0316]

[0317] Under argon atmosphere, 24-1 (9.28 g, 40 mmol), 24-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 24-3 (13.09 g, yield 80.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.29; H, 4.19 test value C, 76.18; H, 4.22. Mass spectrum: theoretical value 408.05, experimental value 408.1 (M+).

[0318] Under argon atmosphere, 24-3 (10.20 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 24-4 (7.55 g, yield 80.7%). Elemental analysis (%): theoretical value C, 83.44; H, 5.12; test value C, 83.40; H, 5.19. Mass spectrum: theoretical value 374.15, experimental value 374.2 (M+).

[0319] Under argon atmosphere, 24-4 (5.61 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-48 (5.76 g, yield 77.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 91.90; H, 5.28; test value C, 91.85; H, 5.33. Mass spectrum: theoretical value 992.38, experimental value 992.4 (M+).

[0320] Embodiment 25

[0321]

[0322] Under argon atmosphere, 25-1 (9.28 g, 40 mmol), 25-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 25-3 (13.09 g, yield 80.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.29; H, 4.19 test value C, 76.18; H, 4.22. Mass spectrum: theoretical value 408.05, experimental value 408.1 (M+).

[0323] Under argon atmosphere, 25-3 (10.20 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 25-4 (7.55 g, yield 80.7%). Elemental analysis (%): theoretical value C, 83.44; H, 5.12; test value C, 83.40; H, 5.19. Mass spectrum: theoretical value 374.15, experimental value 374.2 (M+).

[0324] Under argon atmosphere, 25-4 (2.25 g, 6 mmol), 25-5 (1.53 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-146 (2.20 g, yield 72.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 90.25; H, 6.97; test value C, 90.27; H, 6.95. Mass spectrum: theoretical value 1010.50, experimental value 1010.5 (M+).

[0325] Embodiment 26

[0326]

[0327] Under argon atmosphere, 26-1 (9.28 g, 40 mmol), 26-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 26-3 (13.09 g, yield 80.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.29; H, 4.19 test value C, 76.18; H, 4.22. Mass spectrum: theoretical value 408.05, experimental value 408.1 (M+).

[0328] Under argon atmosphere, 26-3 (10.20 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 26-4 (7.55 g, yield 80.7%). Elemental analysis (%): theoretical value C, 83.44; H, 5.12; test value C, 83.40; H, 5.19. Mass spectrum: theoretical value 374.15, experimental value 374.2 (M+).

[0329] Under argon atmosphere, 26-4 (2.25 g, 6 mmol), 26-5 (1.43 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-264 (2.04 g, yield 69.7%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 94.64; H, 5.36; test value C, 94.62; H, 5.39. Mass spectrum: theoretical value 976.41, experimental value 976.4 (M+).

[0330] Embodiment 27

[0331]

[0332] Under argon atmosphere, 27-1 (9.28 g, 40 mmol), 27-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 27-3 (13.09 g, yield 80.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.29; H, 4.19 test value C, 76.18; H, 4.22. Mass spectrum: theoretical value 408.05, experimental value 408.1 (M+).

[0333] Under argon atmosphere, 27-3 (10.20 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 27-4 (7.55 g, yield 80.7%). Elemental analysis (%): theoretical value C, 83.44; H, 5.12; test value C, 83.40; H, 5.19. Mass spectrum: theoretical value 374.15, experimental value 374.2 (M+).

[0334] Under argon atmosphere, 27-4 (2.25 g, 6 mmol), 27-5 (1.48 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-128 (2.14 g, yield 71.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 92.91; H, 7.09; test value C, 92.90; H, 7.04. Mass spectrum: theoretical value 994.52, experimental value 994.5 (M+).

[0335] Embodiment 28

[0336]

[0337]

[0338] Under argon atmosphere, 28-1 (16.89 g, 40 mmol), 28-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 28-3 (18.22 g, yield 76.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 80.27; H, 4.04; test value C, 80.21; H, 4.05. Mass spectrum: theoretical value 597.11, experimental value 597.1 (M+).

[0339] Under argon atmosphere, 28-3 (14.96 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 28-4 (10.75 g, yield 76.3%). Elemental analysis (%): theoretical value C, 85.27; H, 4.65; test value C, 85.22; H, 4.69. Mass spectrum: theoretical value 563.21, experimental value 563.2 (M+).

[0340] Under argon atmosphere, 28-4 (3.38 g, 6 mmol), bis(3-bromophenyl)diphenylsilane (1.48 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-143 (3.02 g, yield 73.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 91.06; H, 4.85; test value C, 91.00; H, 4.86. Mass spectrum: theoretical value 1370.50, experimental value 1370.5 (M+).

[0341] Embodiment 29

[0342]

[0343] Under argon atmosphere, 29-1 (10.24 g, 40 mmol), 29-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 29-3 (13.87 g, yield 80.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 77.61; H, 3.95 test value C, 77.60; H, 3.96. Mass spectrum: theoretical value 432.05, experimental value 432.1 (M+).

[0344] Under argon atmosphere, 29-3 (13.84 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 29-4 (7.92 g, yield 79.6%). Elemental analysis (%): theoretical value C, 84.44; H, 4.81; test value C, 84.46; H, 4.82. Mass spectrum: theoretical value 398.15, experimental value 398.2 (M+).

[0345] Under argon atmosphere, 29-4 (5.97 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-60 (6.15 g, yield 78.9%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 92.27; H, 5.03; test value C, 92.28; H, 5.04. Mass spectrum: theoretical value 1040.38, experimental value 1040.4 (M+).

[0346] Embodiment 30

[0347]

[0348] Under argon atmosphere, 30-1 (16.89 g, 40 mmol), 30-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 30-3 (18.22 g, yield 76.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 80.27; H, 4.04; test value C, 80.21; H, 4.05. Mass spectrum: theoretical value 597.11, experimental value 597.1 (M+).

[0349] Under argon atmosphere, 30-3 (14.96 g, 25 mmol), biboric acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 30-4 (10.75 g, yield 76.3%). Elemental analysis (%): theoretical value C, 85.27; H, 4.65; test value C, 85.22; H, 4.69. Mass spectrum: theoretical value 563.21, experimental value 563.2 (M+).

[0350] Under argon atmosphere, 30-4 (3.38 g, 6 mmol), 30-5 (1.53 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-144 (2.89 g, yield 69.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.87; H, 6.09; test value C, 89.86; H, 6.05. Mass spectrum: theoretical value 1388.61, experimental value 1388.6 (M+).

[0351] Embodiment 31

[0352]

[0353] Under argon atmosphere, 31-1 (16.89 g, 40 mmol), 31-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 31-3 (18.22 g, yield 76.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 80.27; H, 4.04; test value C, 80.21; H, 4.05. Mass spectrum: theoretical value 597.11, experimental value 597.1 (M+).

[0354] Under argon atmosphere, 31-3 (14.96 g, 25 mmol), bipyralidone (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 31-4 (10.75 g, yield 76.3%). Elemental analysis (%): theoretical value C, 85.27; H, 4.65; test value C, 85.22; H, 4.69. Mass spectrum: theoretical value 563.21, experimental value 563.2 (M+).

[0355] Under argon atmosphere, 31-4 (3.38 g, 6 mmol), 31-5 (1.43 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-266 (2.83 g, yield 69.7%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 93.03; H, 4.91; test value C, 93.05; H, 4.93. Mass spectrum: theoretical value 1354.52, experimental value 1354.5 (M+).

[0356] Embodiment 32

[0357]

[0358]

[0359] Under argon atmosphere, 32-1 (16.89 g, 40 mmol), 32-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 32-3 (18.22 g, yield 76.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 80.27; H, 4.04; test value C, 80.21; H, 4.05. Mass spectrum: theoretical value 597.11, experimental value 597.1 (M+).

[0360] Under argon atmosphere, 32-3 (14.96 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 32-4 (10.75 g, yield 76.3%). Elemental analysis (%): theoretical value C, 85.27; H, 4.65; test value C, 85.22; H, 4.69. Mass spectrum: theoretical value 563.21, experimental value 563.2 (M+).

[0361] Under argon atmosphere, 32-4 (3.38 g, 6 mmol), 32-5 (1.48 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-127 (3.10 g, yield 75.3%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 91.80; H, 6.16; test value C, 91.87; H, 6.12. Mass spectrum: theoretical value 1372.64, experimental value 1372.6 (M+).

[0362] Embodiment 33

[0363]

[0364] Under argon atmosphere, 33-1 (12.89 g, 40 mmol), 33-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 33-3 (15.73 g, yield 78.9%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 77.11; H, 4.04; test value C, 77.15; H, 4.02. Mass spectrum: theoretical value 497.08, experimental value 497.1 (M+).

[0365] Under argon atmosphere, 33-3 (12.46 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 33-4 (8.36 g, yield 72.2%). Elemental analysis (%): theoretical value C, 82.95; H, 4.79; test value C, 82.93; H, 4.75. Mass spectrum: theoretical value 463.17, experimental value 463.2 (M+).

[0366] Under argon atmosphere, 33-4 (2.78 g, 6 mmol), bis(3-bromophenyl)diphenylsilane (1.48 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-222 (2.56 g, yield 72.7%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 90.22; H, 4.99; test value C, 90.25; H, 4.97. Mass spectrum: theoretical value 1170.44, experimental value 1170.4 (M+).

[0367] Embodiment 34

[0368]

[0369] Under argon atmosphere, 34-1 (12.89 g, 40 mmol), 34-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 34-3 (15.73 g, yield 78.9%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 77.11; H, 4.04; test value C, 77.15; H, 4.02. Mass spectrum: theoretical value 497.08, experimental value 497.1 (M+).

[0370] Under argon atmosphere, 34-3 (12.46 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 34-4 (8.36 g, yield 72.2%). Elemental analysis (%): theoretical value C, 82.95; H, 4.79; test value C, 82.93; H, 4.75. Mass spectrum: theoretical value 463.17, experimental value 463.2 (M+).

[0371] Under argon atmosphere, 34-4 (2.78 g, 6 mmol), 34-5 (1.53 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-142 (2.55 g, yield 71.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 88.85; H, 6.44; test value C, 88.81; H, 6.46. Mass spectrum: theoretical value 1188.55, experimental value 1188.6 (M+).

[0372] Embodiment 35

[0373]

[0374] Under argon atmosphere, 35-1 (12.89 g, 40 mmol), 35-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 35-3 (15.73 g, yield 78.9%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 77.11; H, 4.04; test value C, 77.15; H, 4.02. Mass spectrum: theoretical value 497.08, experimental value 497.1 (M+).

[0375] Under argon atmosphere, 35-3 (12.46 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 35-4 (8.36 g, yield 72.2%). Elemental analysis (%): theoretical value C, 82.95; H, 4.79; test value C, 82.93; H, 4.75. Mass spectrum: theoretical value 463.17, experimental value 463.2 (M+).

[0376] Under argon atmosphere, 35-4 (2.78 g, 6 mmol), 35-5 (1.43 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-265 (2.51 g, yield 72.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 92.52; H, 5.06; test value C, 92.54; H, 5.02. Mass spectrum: theoretical value 1154.46, experimental value 1154.5 (M+).

[0377] Embodiment 36

[0378]

[0379] Under argon atmosphere, 36-1 (12.89 g, 40 mmol), 36-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 36-3 (15.73 g, yield 78.9%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 77.11; H, 4.04; test value C, 77.15; H, 4.02. Mass spectrum: theoretical value 497.08, experimental value 497.1 (M+).

[0380] Under argon atmosphere, 36-3 (12.46 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 36-4 (8.36 g, yield 72.2%). Elemental analysis (%): theoretical value C, 82.95; H, 4.79; test value C, 82.93; H, 4.75. Mass spectrum: theoretical value 463.17, experimental value 463.2 (M+).

[0381] Under argon atmosphere, 36-4 (2.78 g, 6 mmol), 36-5 (1.48 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-126 (2.68 g, yield 76.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 91.09; H, 6.52; test value C, 91.07; H, 6.55. Mass spectrum: theoretical value 1172.57, experimental value 1172.6 (M+).

[0382] Embodiment 37

[0383]

[0384] Under argon atmosphere, 37-1 (20.48 g, 40 mmol), 37-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 37-3 (21.74 g, yield 79.0%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 80.11; H, 3.65; test value C, 80.10; H, 3.66. Mass spectrum: theoretical value 688.09, experimental value 688.1 (M+).

[0385] Under argon atmosphere, 37-3 (17.20 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 37-4 (13.13 g, yield 80.3%). Elemental analysis (%): theoretical value C, 84.40; H, 4.16; test value C, 84.41; H, 4.17. Mass spectrum: theoretical value 654.18, experimental value 654.2 (M+).

[0386] Under argon atmosphere, 37-4 (9.81 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-85 (8.55 g, yield 79.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.66; H, 4.41; test value C, 89.65; H, 4.40. Mass spectrum: theoretical value 1552.45, experimental value 1552.5 (M+).

[0387] Embodiment 38

[0388]

[0389]

[0390] Under argon atmosphere, 38-1 (10.88 g, 40 mmol), 38-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 38-3 (13.68 g, yield 78.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 77.07; H, 4.62; test value C, 77.08; H, 4.61. Mass spectrum: theoretical value 435.07, experimental value 435.1 (M+).

[0391] Under argon atmosphere, 38-3 (10.88 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 38-4 (8.01 g, yield 77.4%). Elemental analysis (%): theoretical value C, 84.07; H, 5.60; test value C, 84.05; H, 5.62. Mass spectrum: theoretical value 414.18, experimental value 414.2 (M+).

[0392] Under argon atmosphere, 38-4 (6.21 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-90 (6.45 g, yield 80.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 91.75; H, 5.63; test value C, 91.76; H, 5.62. Mass spectrum: theoretical value 1072.45, experimental value 1072.5 (M+).

[0393] Embodiment 39

[0394]

[0395] Under argon atmosphere, 39-1 (19.84 g, 40 mmol), 39-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 39-3 (20.83 g, yield 77.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 82.02; H, 3.74; test value C, 82.01; H, 3.76. Mass spectrum: theoretical value 672.11, experimental value 672.1 (M+).

[0396] Under argon atmosphere, 39-3 (16.80 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 39-4 (12.54 g, yield 78.6%). Elemental analysis (%): theoretical value C, 86.53; H, 4.26; test value C, 86.52; H, 4.27. Mass spectrum: theoretical value 638.21, experimental value 638.2 (M+).

[0397] Under argon atmosphere, 39-4 (9.57 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-97 (8.91 g, yield 78.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 91.55; H, 4.50; test value C, 91.54; H, 4.51. Mass spectrum: theoretical value 1520.50, experimental value 1520.5 (M+).

[0398] Embodiment 40

[0399]

[0400] Under argon atmosphere, 40-1 (18.48 g, 40 mmol), 40-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 40-3 (19.76 g, yield 78.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 78.87; H, 3.62; test value C, 78.86; H, 3.63. Mass spectrum: theoretical value 638.07, experimental value 638.1 (M+).

[0401] Under argon atmosphere, 40-3 (15.75 g, 25 mmol), bipyraclostrobin (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 40-4 (11.96 g, yield 79.2%). Elemental analysis (%): theoretical value C, 83.45; H, 4.17; test value C, 83.43; H, 4.18. Mass spectrum: theoretical value 604.17, experimental value 604.2 (M+).

[0402] Under argon atmosphere, 40-4 (9.06 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-98 (8.45 g, yield 77.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.22; H, 4.44; test value C, 89.21; H, 4.43. Mass spectrum: theoretical value 1452.42, experimental value 1452.4 (M+).

[0403] Embodiment 41

[0404]

[0405] Under argon atmosphere, 41-1 (22.40 g, 40 mmol), 41-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 41-3 (23.29 g, yield 79.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 83.04; H, 3.96; test value C, 83.02; H, 3.98. Mass spectrum: theoretical value 736.14, experimental value 736.1 (M+).

[0406] Under argon atmosphere, 41-3 (18.40 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 41-4 (14.09 g, yield 80.3%). Elemental analysis (%): theoretical value C, 87.18; H, 4.45; test value C, 87.15; H, 4.44. Mass spectrum: theoretical value 702.24, experimental value 702.2 (M+).

[0407] Under argon atmosphere, 41-4 (10.53 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-99 (9.70 g, yield 78.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 91.72; H, 4.64; test value C, 91.71; H, 4.63. Mass spectrum: theoretical value 1648.56, experimental value 1648.6 (M+).

[0408] Embodiment 42

[0409]

[0410] Under argon atmosphere, 42-1 (13.92 g, 40 mmol), 42-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 42-3 (16.79 g, yield 80.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 80.00; H, 4.80; test value C, 80.03; H, 4.82. Mass spectrum: theoretical value 524.11, experimental value 524.1 (M+).

[0411] Under argon atmosphere, 42-3 (13.10 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 42-4 (9.58 g, yield 78.2%). Elemental analysis (%): theoretical value C, 85.72; H, 5.55; test value C, 85.71; H, 5.56. Mass spectrum: theoretical value 490.21, experimental value 490.2 (M+).

[0412] Under argon atmosphere, 42-4 (7.35 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-103 (7.27 g, yield 79.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 92.12; H, 5.59; test value C, 92.14; H, 5.57. Mass spectrum: theoretical value 1224.51, experimental value 1224.5 (M+).

[0413] Embodiment 43

[0414]

[0415] Under argon atmosphere, 43-1 (15.96 g, 40 mmol), 43-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 43-3 (18.67 g, yield 81.3%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 81.39; H, 4.73; test value C, 81.38; H, 4.75. Mass spectrum: theoretical value 574.13, experimental value 574.1 (M+).

[0416] Under argon atmosphere, 43-3 (14.35 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 43-4 (10.68 g, yield 79.1%). Elemental analysis (%): theoretical value C, 86.67; H, 5.41; test value C, 86.68; H, 5.42. Mass spectrum: theoretical value 540.23, experimental value 540.2 (M+).

[0417] Under argon atmosphere, 43-4 (8.10 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-104 (8.01 g, yield 80.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 92.41; H, 5.47; test value C, 92.43; H, 5.48. Mass spectrum: theoretical value 1324.54, experimental value 1324.5 (M+).

[0418] Embodiment 44

[0419]

[0420] Under argon atmosphere, 44-1 (17.52 g, 40 mmol), 44-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 44-3 (20.21 g, yield 82.3%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 80.00; H, 4.42; test value C, 80.03; H, 4.44. Mass spectrum: theoretical value 614.12, experimental value 614.1 (M+).

[0421] Under argon atmosphere, 44-3 (15.3 g, 25 mmol), bipyraclostrobin (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 44-4 (11.77 g, yield 81.2%). Elemental analysis (%): theoretical value C, 84.83; H, 5.04; test value C, 84.82; H, 5.03. Mass spectrum: theoretical value 580.22, experimental value 580.2 (M+).

[0422] Under argon atmosphere, 44-4 (8.70 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-106 (8.17 g, yield 77.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 90.56; H, 5.16; test value C, 90.59; H, 5.15. Mass spectrum: theoretical value 1404.53, experimental value 1404.5 (M+).

[0423] Embodiment 45

[0424]

[0425]

[0426] Under argon atmosphere, 45-1 (19.52 g, 40 mmol), 45-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 45-3 (21.30 g, yield 80.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 81.20; H, 4.39; test value C, 81.21; H, 4.38. Mass spectrum: theoretical value 664.14, experimental value 664.1 (M+).

[0427] Under argon atmosphere, 45-3 (16.60 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 45-4 (12.46 g, yield 79.1%). Elemental analysis (%): theoretical value C, 85.72; H, 4.96; test value C, 85.71; H, 4.95. Mass spectrum: theoretical value 630.24, experimental value 630.2 (M+).

[0428] Under argon atmosphere, 45-4 (9.45 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-107 (8.85 g, yield 78.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 90.92; H, 5.09 test value C, 90.98; H, 5.10. Mass spectrum: theoretical value 1504.56, experimental value 1504.6 (M+).

[0429] Embodiment 46

[0430]

[0431] Under argon atmosphere, 46-1 (18.16 g, 40 mmol), 46-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 46-3 (20.44 g, yield 81.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 77.96; H, 4.31; test value C, 77.98; H, 4.33. Mass spectrum: theoretical value 630.10, experimental value 630.1 (M+).

[0432] Under argon atmosphere, 46-3 (15.75 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 46-4 (12.02 g, yield 80.7%). Elemental analysis (%): theoretical value C, 82.55; H, 4.90; test value C, 82.54; H, 4.92. Mass spectrum: theoretical value 596.20, experimental value 596.2 (M+).

[0433] Under argon atmosphere, 46-4 (8.94 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-108 (8.53 g, yield 79.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 88.54; H, 5.05; test value C, 88.55; H, 5.06. Mass spectrum: theoretical value 1436.48, experimental value 1436.5 (M+).

[0434] Embodiment 47

[0435]

[0436] Under argon atmosphere, 47-1 (11.88 g, 40 mmol), 47-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 47-3 (15.12 g, yield 80.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.14; H, 3.61. Mass spectrum: theoretical value 472.05, experimental value 472.0 (M+).

[0437] Under argon atmosphere, 47-3 (11.80 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 47-4 (8.74 g, yield 79.8%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.26; H, 4.38. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0438] Under argon atmosphere, 47-4 (2.63 g, 6 mmol), 47-5 (1.53 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-364 (2.63 g, yield 76.9%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 88.54; H, 6.19; test value C, 88.55; H, 6.18. Mass spectrum: theoretical value 1138.49, experimental value 1138.5 (M+).

[0439] Embodiment 48

[0440]

[0441] Under argon atmosphere, 48-1 (11.88 g, 40 mmol), 48-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 48-3 (15.12 g, yield 80.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.14; H, 3.61. Mass spectrum: theoretical value 472.05, experimental value 472.0 (M+).

[0442] Under argon atmosphere, 48-3 (11.80 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 48-4 (8.74 g, yield 79.8%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.26; H, 4.38. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0443] Under argon atmosphere, 48-4 (2.63 g, 6 mmol), 48-5 (1.43 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-133 (2.40 g, yield 72.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 92.36; H, 4.74; test value C, 92.35; H, 4.75. Mass spectrum: theoretical value 1104.40, experimental value 1104.4 (M+).

[0444] Embodiment 49

[0445]

[0446] Under argon atmosphere, 49-1 (11.88 g, 40 mmol), 49-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 49-3 (15.12 g, yield 80.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.14; H, 3.61. Mass spectrum: theoretical value 472.05, experimental value 472.0 (M+).

[0447] Under argon atmosphere, 49-3 (11.80 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 49-4 (8.74 g, yield 79.8%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.26; H, 4.38. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0448] Under argon atmosphere, 49-4 (2.63 g, 6 mmol), 49-5 (1.48 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-122 (2.34 g, yield 69.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 90.87; H, 6.28; test value C, 90.89; H, 6.26. Mass spectrum: theoretical value 1122.51, experimental value 1122.5 (M+).

[0449] Embodiment 50

[0450]

[0451]

[0452] Under argon atmosphere, 50-1 (14.48 g, 40 mmol), 50-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product compound 50-3 (17.02 g, yield 79.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 75.70; H, 4.30; test value C, 75.72; H, 4.31. Mass spectrum: theoretical value 538.10, experimental value 538.1 (M+).

[0453] Under argon atmosphere, 50-3 (13.45 g, 25 mmol), bipyralidone (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd (dppf) Cl2 (1.10 g, 1.5 mmol) were added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain the product compound 50-4 (9.87 g, yield 78.3%). Elemental analysis (%): theoretical value C, 80.96; H, 5.00; test value C, 80.97; H, 5.02. Mass spectrum: theoretical value 504.20, experimental value 504.2 (M+).

[0454] Under argon atmosphere, 50-4 (7.56 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product compound H1-118 (7.29 g, yield 77.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 88.14; H, 5.15; test value C, 88.12; H, 5.16. Mass spectrum: theoretical value 1252.49, experimental value 1252.5 (M+).

[0455] Embodiment 51

[0456]

[0457] Under argon atmosphere, 51-1 (9.84 g, 40 mmol), 51-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 51-3 (13.42 g, yield 79.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 73.77; H, 3.57; test value C, 73.76; H, 3.58. Mass spectrum: theoretical value 422.03, experimental value 422.0 (M+).

[0458] Under argon atmosphere, 51-3 (10.55 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 51-4 (7.80 g, yield 80.4%). Elemental analysis (%): theoretical value C, 80.44; H, 4.41; test value C, 80.41; H, 4.43. Mass spectrum: theoretical value 388.13, experimental value 388.1 (M+).

[0459] Under argon atmosphere, 51-4 (5.82 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-149 (6.24 g, yield 81.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.38; H, 4.74; test value C, 89.37; H, 4.75. Mass spectrum: theoretical value 1020.34, experimental value 1020.3 (M+).

[0460] Embodiment 52

[0461]

[0462] Under argon atmosphere, 52-1 (11.88 g, 40 mmol), 52-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 52-3 (15.12 g, yield 80.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.14; H, 3.61. Mass spectrum: theoretical value 472.05, experimental value 472.0 (M+).

[0463] Under argon atmosphere, 52-3 (11.80 g, 25 mmol), bipyralidone (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 52-4 (8.74 g, yield 79.8%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.26; H, 4.38. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0464] Under argon atmosphere, 52-4 (6.57 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-150 (6.75 g, yield 80.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.97; H, 4.67; test value C, 89.96; H, 4.68. Mass spectrum: theoretical value 1120.37, experimental value 1120.4 (M+).

[0465] Embodiment 53

[0466]

[0467] Under argon atmosphere, 53-1 (12.08 g, 40 mmol), 53-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 53-3 (15.32 g, yield 80.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 75.16; H, 4.84; test value C, 75.14; H, 4.86. Mass spectrum: theoretical value 478.09, experimental value 478.1 (M+).

[0468] Under argon atmosphere, 53-3 (11.95 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 53-4 (8.86 g, yield 79.8%). Elemental analysis (%): theoretical value C, 81.09; H, 5.67; test value C, 81.05; H, 5.68. Mass spectrum: theoretical value 444.19, experimental value 444.2 (M+).

[0469] Under argon atmosphere, 53-4 (6.66 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-151 (6.84 g, yield 80.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.01; H, 5.69; test value C, 89.02; H, 5.68. Mass spectrum: theoretical value 1132.47, experimental value 1132.5 (M+)

[0470] Embodiment 54

[0471]

[0472] Under argon atmosphere, 54-1 (14.12 g, 40 mmol), 54-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 54-3 (16.56 g, yield 78.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 77.13; H, 4.76; test value C, 77.12; H, 4.77. Mass spectrum: theoretical value 528.11, experimental value 528.1 (M+).

[0473] Under argon atmosphere, 54-3 (13.20 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 54-4 (9.71 g, yield 78.6%). Elemental analysis (%): theoretical value C, 82.60; H, 5.50; test value C, 82.57; H, 5.52. Mass spectrum: theoretical value 494.21, experimental value 494.2 (M+).

[0474] Under argon atmosphere, 54-4 (7.41 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-152 (7.48 g, yield 81.0%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.57; H, 5.56; test value C, 89.56; H, 5.57. Mass spectrum: theoretical value 1232.50, experimental value 1232.5 (M+).

[0475] Embodiment 55

[0476]

[0477] Under argon atmosphere, 55-1 (12.72 g, 40 mmol), 55-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 55-3 (14.76 g, yield 79.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 72.72; H, 4.68; test value C, 72.71; H, 4.69. Mass spectrum: theoretical value 494.07, experimental value 494.1 (M+).

[0478] Under argon atmosphere, 55-3 (11.60 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 55-4 (9.22 g, yield 80.2%). Elemental analysis (%): theoretical value C, 78.26; H, 5.47; test value C, 78.27; H, 5.48. Mass spectrum: theoretical value 460.17, experimental value 460.2 (M+).

[0479] Under argon atmosphere, 55-4 (6.90 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-153 (6.91 g, yield 79.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 86.56; H, 5.53; test value C, 86.58; H, 5.52. Mass spectrum: theoretical value 1164.42, experimental value 1164.4 (M+).

[0480] Embodiment 56

[0481]

[0482]

[0483] Under argon atmosphere, 56-1 (16.32 g, 40 mmol), 56-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 56-3 (18.71 g, yield 80.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 77.94; H, 5.68; test value C, 77.92; H, 5.69. Mass spectrum: theoretical value 584.17, experimental value 584.2 (M+).

[0484] Under argon atmosphere, 56-3 (14.60 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 56-4 (11.18 g, yield 81.3%). Elemental analysis (%): theoretical value C, 82.91; H, 6.41; test value C, 82.90; H, 6.42. Mass spectrum: theoretical value 550.27, experimental value 550.3 (M+).

[0485] Under argon atmosphere, 56-4 (8.25 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-154 (8.28 g, yield 82.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.24; H, 6.29; test value C, 89.28; H, 6.30. Mass spectrum: theoretical value 1344.62, experimental value 1344.6 (M+).

[0486] Embodiment 57

[0487]

[0488] Under argon atmosphere, 57-1 (15 g, 40 mmol), 57-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 57-3 (15.64 g, yield 78.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 74.04; H, 5.67; test value C, 74.06; H, 5.68. Mass spectrum: theoretical value 550.13, experimental value 550.1 (M+).

[0489] Under argon atmosphere, 57-3 (12.50 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 57-4 (9.95 g, yield 77.1%). Elemental analysis (%): theoretical value C, 79.06; H, 6.44; test value C, 79.07; H, 6.45. Mass spectrum: theoretical value 516.23, experimental value 516.2 (M+).

[0490] Under argon atmosphere, 57-4 (7.74 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-155 (7.62 g, yield 79.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 86.47; H, 6.31; test value C, 86.46; H, 6.32. Mass spectrum: theoretical value 1276.55, experimental value 1276.6 (M+).

[0491] Embodiment 58

[0492]

[0493] Under argon atmosphere, 58-1 (16.96 g, 40 mmol), 58-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 58-3 (19.01 g, yield 79.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 75.86; H, 5.53; test value C, 75.85; H, 5.54. Mass spectrum: theoretical value 600.15, experimental value 600.2 (M+).

[0494] Under argon atmosphere, 58-3 (15.00 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 58-4 (11.19 g, yield 79.1%). Elemental analysis (%): theoretical value C, 80.56; H, 6.23; test value C, 80.54; H, 6.25. Mass spectrum: theoretical value 566.25, experimental value 566.25 (M+).

[0495] Under argon atmosphere, 58-4 (8.49 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-156 (8.42 g, yield 81.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 87.16; H, 6.14; test value C, 87.15; H, 6.16. Mass spectrum: theoretical value 1376.58, experimental value 1376.6 (M+).

[0496] Embodiment 59

[0497]

[0498] Under argon atmosphere, 59-1 (14.48 g, 40 mmol), 59-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product compound 59-3 (17.02 g, yield 79.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 75.70; H, 4.30; test value C, 75.72; H, 4.31. Mass spectrum: theoretical value 538.10, experimental value 538.1 (M+).

[0499] Under argon atmosphere, 59-3 (13.45 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd (dppf) Cl2 (1.10 g, 1.5 mmol) were added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain the product compound 59-4 (9.87 g, yield 78.3%). Elemental analysis (%): theoretical value C, 80.96; H, 5.00; test value C, 80.97; H, 5.02. Mass spectrum: theoretical value 504.20, experimental value 504.2 (M+).

[0500] Under argon atmosphere, 59-4 (3.03 g, 6 mmol), 59-5 (1.43 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-132 (2.75 g, yield 72.9%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 88.96; H, 6.58; test value C, 88.95; H, 6.55. Mass spectrum: theoretical value 1254.63, experimental value 1254.6 (M+).

[0501] Embodiment 60

[0502]

[0503]

[0504] Under argon atmosphere, 60-1 (14.48 g, 40 mmol), 60-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product compound 60-3 (17.02 g, yield 79.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 75.70; H, 4.30; test value C, 75.72; H, 4.31. Mass spectrum: theoretical value 538.10, experimental value 538.1 (M+).

[0505] Under argon atmosphere, 60-3 (13.45 g, 25 mmol), bipyralidinol (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd (dppf) Cl2 (1.10 g, 1.5 mmol) were added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and an aqueous sodium hydroxide solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain the product compound 60-4 (9.87 g, yield 78.3%). Elemental analysis (%): theoretical value C, 80.96; H, 5.00; test value C, 80.97; H, 5.02. Mass spectrum: theoretical value 504.20, experimental value 504.2 (M+).

[0506] Under argon atmosphere, 60-4 (7.71 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-161 (7.56 g, yield 79.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 90.53; H, 4.75; test value C, 90.55; H, 4.78. Mass spectrum: theoretical value 1272.44, experimental value 1272.4 (M+).

[0507] Embodiment 61

[0508]

[0509] Under argon atmosphere, 61-1 (14.72 g, 40 mmol), 61-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 61-3 (17.17 g, yield 78.9%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 74.86; H, 4.62; test value C, 74.84; H, 4.63. Mass spectrum: theoretical value 544.09, experimental value 544.1 (M+).

[0510] Under argon atmosphere, 61-3 (13.60 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 61-4 (10.25 g, yield 80.4%). Elemental analysis (%): theoretical value C, 80.00; H, 5.33; test value C, 80.04; H, 5.35. Mass spectrum: theoretical value 510.18, experimental value 510.2 (M+).

[0511] Under argon atmosphere, 61-4 (7.65 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-163 (7.40 g, yield 78.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 87.30; H, 5.42; test value C, 87.32; H, 5.44. Mass spectrum: theoretical value 1264.45, experimental value 1264.5 (M+).

[0512] Embodiment 62

[0513]

[0514] Under argon atmosphere, 62-1 (14.72 g, 40 mmol), 62-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 62-3 (11.44 g, yield 79.7%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.26; H, 5.84; test value C, 76.24; H, 5.86. Mass spectrum: theoretical value 534.16, experimental value 534.2 (M+).

[0515] Under argon atmosphere, 62-3 (8.98 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 62-4 (10.67 g, yield 79.9%). Elemental analysis (%): theoretical value C, 81.60; H, 6.65; test value C, 81.62; H, 6.63. Mass spectrum: theoretical value 500.25, experimental value 500.3 (M+).

[0516] Under argon atmosphere, 62-4 (8.01 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-164 (7.52 g, yield 80.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 88.70; H, 6.47; test value C, 88.68; H, 6.48. Mass spectrum: theoretical value 1244.59, experimental value 1244.6 (M+).

[0517] Embodiment 63

[0518]

[0519] Under argon atmosphere, 63-1 (10.88 g, 40 mmol), 63-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 63-3 (14.05 g, yield 78.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 77.51; H, 4.71; test value C, 77.50; H, 4.72. Mass spectrum: theoretical value 448.08, experimental value 448.1 (M+).

[0520] Under argon atmosphere, 63-3 (11.20 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 63-4 (8.29 g, yield 80.1%). Elemental analysis (%): theoretical value C, 84.07; H, 5.60; test value C, 84.04; H, 5.62. Mass spectrum: theoretical value 414.18, experimental value 414.2 (M+).

[0521] Under argon atmosphere, 63-4 (6.21 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-168 (6.23 g, yield 77.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 91.75; H, 5.63; test value C, 91.76; H, 5.62. Mass spectrum: theoretical value 1072.45, experimental value 1072.5 (M+).

[0522] Embodiment 64

[0523]

[0524] Under argon atmosphere, 64-1 (14.48 g, 40 mmol), 64-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product compound 64-3 (17.02 g, yield 79.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 75.70; H, 4.30; test value C, 75.72; H, 4.31. Mass spectrum: theoretical value 538.10, experimental value 538.1 (M+).

[0525] Under argon atmosphere, 64-3 (13.45 g, 25 mmol), bipyralidone (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd (dppf) Cl2 (1.10 g, 1.5 mmol) were added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain the product compound 64-4 (9.87 g, yield 78.3%). Elemental analysis (%): theoretical value C, 80.96; H, 5.00; test value C, 80.97; H, 5.02. Mass spectrum: theoretical value 504.20, experimental value 504.2 (M+).

[0526] Under argon atmosphere, 64-4 (3.03 g, 6 mmol), 64-5 (1.48 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-123 (2.63 g, yield 69.7%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 88.96; H, 6.58; test value C, 88.99; H, 6.56. Mass spectrum: theoretical value 1254.63, experimental value 1254.6 (M+).

[0527] Embodiment 65

[0528]

[0529]

[0530] Under argon atmosphere, 65-1 (9.84 g, 40 mmol), 65-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 65-3 (13.61 g, yield 80.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 73.77; H, 3.57; test value C, 73.78; H, 3.56. Mass spectrum: theoretical value 422.03, experimental value 422.0 (M+).

[0531] Under argon atmosphere, 65-3 (10.55 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 65-4 (7.85 g, yield 80.9%). Elemental analysis (%): theoretical value C, 80.44; H, 4.41; test value C, 80.45; H, 4.40. Mass spectrum: theoretical value 388.13, experimental value 388.1 (M+).

[0532] Under argon atmosphere, 65-4 (5.82 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-170 (6.01 g, yield 78.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.38; H, 4.74; test value C, 89.37; H, 4.75. Mass spectrum: theoretical value 1020.34, experimental value 1020.3 (M+).

[0533] Embodiment 66

[0534]

[0535] Under argon atmosphere, 66-1 (9.88 g, 40 mmol), 66-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 66-3 (13.72 g, yield 81.3%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.15; H, 3.63. Mass spectrum: theoretical value 472.05, experimental value 472.0 (M+).

[0536] Under argon atmosphere, 66-3 (10.55 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 66-4 (7.74 g, yield 79.8%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.24; H, 4.37. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0537] Under argon atmosphere, 66-4 (5.82 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-171 (6.09 g, yield 79.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.97; H, 4.67; test value C, 89.97; H, 4.66. Mass spectrum: theoretical value 1120.37, experimental value 1120.4 (M+).

[0538] Embodiment 67

[0539]

[0540] Under argon atmosphere, 67-1 (10.88 g, 40 mmol), 67-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 67-3 (14.71 g, yield 82.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 77.51; H, 4.71; test value C, 77.53; H, 4.70. Mass spectrum: theoretical value 448.08, experimental value 448.1 (M+).

[0541] Under argon atmosphere, 67-3 (11.20 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 67-4 (8.17 g, yield 78.9%). Elemental analysis (%): theoretical value C, 84.07; H, 5.60; test value C, 84.08; H, 5.62. Mass spectrum: theoretical value 414.18, experimental value 414.2 (M+).

[0542] Under argon atmosphere, 67-4 (6.21 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-172 (6.38 g, yield 79.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 91.75; H, 5.63; test value C, 91.76; H, 5.65. Mass spectrum: theoretical value 1072.45, experimental value 1072.5 (M+).

[0543] Embodiment 68

[0544]

[0545] Under argon atmosphere, 68-1 (10.92 g, 40 mmol), 68-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 68-3 (14.53 g, yield 81.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.15; H, 3.62. Mass spectrum: theoretical value 472.05, experimental value 472.0 (M+).

[0546] Under argon atmosphere, 68-3 (11.20 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 68-4 (8.26 g, yield 79.8%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.25; H, 4.37. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0547] Under argon atmosphere, 68-4 (6.21 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-173 (6.29 g, yield 78.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.97; H, 4.67; test value C, 89.97; H, 4.66. Mass spectrum: theoretical value 1120.37, experimental value 1120.4 (M+).

[0548] Embodiment 69

[0549]

[0550] Under argon atmosphere, 69-1 (10.48 g, 40 mmol), 69-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 69-3 (14.41 g, yield 80.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 71.08; H, 3.44; test value C, 71.06; H, 3.45. Mass spectrum: theoretical value 438.01, experimental value 438.0 (M+).

[0551] Under argon atmosphere, 69-3 (11.20 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 69-4 (8.25 g, yield 79.7%). Elemental analysis (%): theoretical value C, 77.24; H, 4.24; test value C, 77.22; H, 4.25. Mass spectrum: theoretical value 404.10, experimental value 404.1 (M+).

[0552] Under argon atmosphere, 69-4 (6.21 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-174 (6.37 g, yield 79.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 86.65; H, 4.59; test value C, 86.66; H, 4.58. Mass spectrum: theoretical value 1052.30, experimental value 1052.3 (M+).

[0553] Embodiment 70

[0554]

[0555] Under argon atmosphere, 70-1 (9.84 g, 40 mmol), 70-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 70-3 (13.71 g, yield 81.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 73.77; H, 3.57; test value C, 73.78; H, 3.56. Mass spectrum: theoretical value 422.03, experimental value 422.0 (M+).

[0556] Under argon atmosphere, 70-3 (10.55 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 70-4 (7.81 g, yield 80.5%). Elemental analysis (%): theoretical value C, 80.44; H, 4.41; test value C, 80.46; H, 4.42. Mass spectrum: theoretical value 388.13, experimental value 388.1 (M+).

[0557] Under argon atmosphere, 70-4 (5.82 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-176 (6.01 g, yield 78.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.38; H, 4.74; test value C, 89.36; H, 4.75. Mass spectrum: theoretical value 1020.34, experimental value 1020.3 (M+).

[0558] Embodiment 71

[0559]

[0560] Under argon atmosphere, 71-1 (10.48 g, 40 mmol), 71-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 71-3 (14.47 g, yield 82.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 71.08; H, 3.44; test value C, 71.11; H, 3.45. Mass spectrum: theoretical value 438.01, experimental value 438.0 (M+).

[0561] Under argon atmosphere, 71-3 (10.95 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 71-4 (8.21 g, yield 81.3%). Elemental analysis (%): theoretical value C, 77.24; H, 4.24; test value C, 77.26; H, 4.25. Mass spectrum: theoretical value 404.10, experimental value 404.1 (M+).

[0562] Under argon atmosphere, 71-4 (6.06 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-177 (6.25 g, yield 79.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 86.65; H, 4.59; test value C, 86.63; H, 4.57. Mass spectrum: theoretical value 1052.30, experimental value 1052.3 (M+).

[0563] Embodiment 72

[0564]

[0565]

[0566] Under argon atmosphere, 72-1 (11.88 g, 40 mmol), 72-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 72-3 (15.33 g, yield 81.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.10; H, 3.64. Mass spectrum: theoretical value 472.05, experimental value 472.1 (M+).

[0567] Under argon atmosphere, 72-3 (11.80 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 72-4 (8.80 g, yield 80.4%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.24; H, 4.38. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0568] Under argon atmosphere, 72-4 (6.57 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-178 (6.80 g, yield 80.9%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.97; H, 4.67; test value C, 89.95; H, 4.69. Mass spectrum: theoretical value 1120.37, experimental value 1120.4 (M+).

[0569] Embodiment 73

[0570]

[0571] Under argon atmosphere, 73-1 (12.48 g, 40 mmol), 73-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 73-3 (15.48 g, yield 79.3%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 73.62; H, 3.50; test value C, 73.60; H, 3.52. Mass spectrum: theoretical value 488.02, experimental value 488.0 (M+).

[0572] Under argon atmosphere, 73-3 (12.20 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 73-4 (9.16 g, yield 80.7%). Elemental analysis (%): theoretical value C, 79.31; H, 4.22; test value C, 79.34; H, 4.23. Mass spectrum: theoretical value 454.12, experimental value 454.1 (M+).

[0573] Under argon atmosphere, 73-4 (6.81 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-179 (6.77 g, yield 78.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 87.46; H, 4.54; test value C, 87.44; H, 4.56. Mass spectrum: theoretical value 1152.33, experimental value 1152.3 (M+).

[0574] Embodiment 74

[0575]

[0576] Under argon atmosphere, 74-1 (10.24 g, 40 mmol), 74-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 74-3 (13.62 g, yield 78.8%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 77.61; H, 3.95; test value C, 77.62; H, 3.97. Mass spectrum: theoretical value 432.05, experimental value 432.1 (M+).

[0577] Under argon atmosphere, 74-3 (10.80 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 74-4 (8.08 g, yield 81.2%). Elemental analysis (%): theoretical value C, 84.44; H, 4.81; test value C, 84.41; H, 4.83. Mass spectrum: theoretical value 398.15, experimental value 398.2 (M+).

[0578] Under argon atmosphere, 74-4 (5.97 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-167 (6.17 g, yield 79.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 92.27; H, 5.03; test value C, 92.29; H, 5.05. Mass spectrum: theoretical value 1040.38, experimental value 1040.4 (M+).

[0579] Embodiment 75

[0580]

[0581] Under argon atmosphere, 75-1 (11.84 g, 40 mmol), 75-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 75-3 (15.03 g, yield 79.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.14; H, 3.61. Mass spectrum: theoretical value 472.05, experimental value 472.1 (M+).

[0582] Under argon atmosphere, 75-3 (11.80 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 75-4 (8.79 g, yield 80.3%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.26; H, 4.38. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0583] Under argon atmosphere, 75-4 (6.57 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-181 (6.59 g, yield 78.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.97; H, 4.67; test value C, 89.96; H, 4.68. Mass spectrum: theoretical value 1120.37, experimental value 1120.4 (M+).

[0584] Embodiment 76

[0585]

[0586] Under argon atmosphere, 76-1 (11.84 g, 40 mmol), 76-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 76-3 (15.64 g, yield 80.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 73.62; H, 3.50; test value C, 73.60; H, 3.52. Mass spectrum: theoretical value 488.02, experimental value 488.0 (M+).

[0587] Under argon atmosphere, 76-3 (12.20 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 76-4 (8.94 g, yield 78.8%). Elemental analysis (%): theoretical value C, 79.31; H, 4.22; test value C, 79.33; H, 4.26. Mass spectrum: theoretical value 454.12, experimental value 454.1 (M+).

[0588] Under argon atmosphere, 76-4 (6.81 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-182 (6.67 g, yield 77.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 87.46; H, 4.54; test value C, 87.44; H, 4.53. Mass spectrum: theoretical value 1152.33, experimental value 1152.3 (M+).

[0589] Embodiment 77

[0590]

[0591] Under argon atmosphere, 77-1 (11.84 g, 40 mmol), 77-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 77-3 (15.35 g, yield 81.3%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.14; H, 3.64. Mass spectrum: theoretical value 472.05, experimental value 472.1 (M+).

[0592] Under argon atmosphere, 77-3 (11.80 g, 25 mmol), biboric acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 77-4 (8.67 g, yield 79.2%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.25; H, 4.32. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0593] Under argon atmosphere, 77-4 (6.57 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-184 (6.62 g, yield 78.8%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.97; H, 4.67; test value C, 89.94; H, 4.69. Mass spectrum: theoretical value 1120.37, experimental value 1120.4 (M+).

[0594] Embodiment 78

[0595]

[0596] Under argon atmosphere, 78-1 (12.48 g, 40 mmol), 78-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110 ° C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, deionized water and dichloromethane were added for extraction, and washed with deionized water 3 times. The organic phase was separated, and the product 78-3 (16.05 g, yield 82.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 73.62; H, 3.50; test value C, 73.60; H, 3.52. Mass spectrum: theoretical value 488.02, experimental value 488.0 (M+).

[0597] Under argon atmosphere, 78-3 (12.20 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 78-4 (9.05 g, yield 79.7%). Elemental analysis (%): theoretical value C, 79.31; H, 4.22; test value C, 79.34; H, 4.23. Mass spectrum: theoretical value 454.12, experimental value 454.1 (M+).

[0598] Under argon atmosphere, 78-4 (6.81 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-185 (6.86 g, yield 79.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 87.46; H, 4.54; test value C, 87.44; H, 4.57. Mass spectrum: theoretical value 1152.33, experimental value 1152.3 (M+).

[0599] Embodiment 79

[0600]

[0601]

[0602] Under argon atmosphere, 79-1 (11.88 g, 40 mmol), 79-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 79-3 (15.33 g, yield 81.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.13; H, 3.64. Mass spectrum: theoretical value 472.05, experimental value 472.1 (M+).

[0603] Under argon atmosphere, 79-3 (11.80 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 79-4 (8.60 g, yield 78.5%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.22; H, 4.35. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0604] Under argon atmosphere, 79-4 (6.57 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-187 (6.39 g, yield 76.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.97; H, 4.67; test value C, 89.93; H, 4.69. Mass spectrum: theoretical value 1120.37, experimental value 1120.4 (M+).

[0605] Embodiment 80

[0606]

[0607] Under argon atmosphere, 80-1 (12.48 g, 40 mmol), 80-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 80-3 (15.71 g, yield 80.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 73.62; H, 3.50; test value C, 73.64; H, 3.52. Mass spectrum: theoretical value 488.02, experimental value 488.0 (M+).

[0608] Under argon atmosphere, 80-3 (12.20 g, 25 mmol), bipyraclostrobin (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 80-4 (9.05 g, yield 79.7%). Elemental analysis (%): theoretical value C, 79.31; H, 4.22; test value C, 79.33; H, 4.24. Mass spectrum: theoretical value 454.12, experimental value 454.1 (M+).

[0609] Under argon atmosphere, 80-4 (6.81 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-188 (6.78 g, yield 78.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 87.46; H, 4.54; test value C, 87.47; H, 4.56. Mass spectrum: theoretical value 1152.33, experimental value 1152.3 (M+).

[0610] Embodiment 81

[0611]

[0612] Under argon atmosphere, 81-1 (11.84 g, 40 mmol), 81-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 81-3 (15.35 g, yield 81.3%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.17; H, 3.65. Mass spectrum: theoretical value 472.05, experimental value 472.1 (M+).

[0613] Under argon atmosphere, 81-3 (11.80 g, 25 mmol), biboric acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 81-4 (8.66 g, yield 79.1%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.24; H, 4.39. Mass spectrum: theoretical value 438.14, experimental value 438.2 (M+).

[0614] Under argon atmosphere, 81-4 (6.57 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-190 (6.59 g, yield 78.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.97; H, 4.67; test value C, 89.94; H, 4.65. Mass spectrum: theoretical value 1120.37, experimental value 1120.4 (M+).

[0615] Embodiment 82

[0616]

[0617] Under argon atmosphere, 82-1 (12.48 g, 40 mmol), 82-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 82-3 (15.69 g, yield 80.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 73.62; H, 3.50; test value C, 73.64; H, 3.54. Mass spectrum: theoretical value 488.02, experimental value 488.0 (M+).

[0618] Under argon atmosphere, 82-3 (12.20 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 82-4 (9.03 g, yield 79.6%). Elemental analysis (%): theoretical value C, 79.31; H, 4.22; test value C, 79.35; H, 4.24. Mass spectrum: theoretical value 454.12, experimental value 454.1 (M+).

[0619] Under argon atmosphere, 82-4 (6.81 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-191 (6.83 g, yield 79.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 87.46; H, 4.54; test value C, 87.43; H, 4.57. Mass spectrum: theoretical value 1152.33, experimental value 1152.3 (M+).

[0620] Embodiment 83

[0621]

[0622] Under argon atmosphere, 83-1 (12.88 g, 40 mmol), 83-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 83-3 (16.18 g, yield 81.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.96; H, 3.83; test value C, 76.94; H, 3.82. Mass spectrum: theoretical value 498.06, experimental value 498.1 (M+).

[0623] Under argon atmosphere, 83-3 (12.45 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 83-4 (9.09 g, yield 78.4%). Elemental analysis (%): theoretical value C, 82.78; H, 4.56; test value C, 82.74; H, 4.58. Mass spectrum: theoretical value 464.16, experimental value 464.2 (M+).

[0624] Under argon atmosphere, 83-4 (6.96 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-193 (7.01 g, yield 79.8%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 90.07; H, 4.81; test value C, 90.04; H, 4.83. Mass spectrum: theoretical value 1172.40, experimental value 1172.4 (M+).

[0625] Embodiment 84

[0626]

[0627] Under argon atmosphere, 84-1 (13.52 g, 40 mmol), 84-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 84-3 (16.59 g, yield 80.7%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 74.56; H, 3.72; test value C, 74.58; H, 3.71. Mass spectrum: theoretical value 514.04, experimental value 514.0 (M+).

[0628] Under argon atmosphere, 84-3 (12.85 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 84-4 (9.59 g, yield 79.9%). Elemental analysis (%): theoretical value C, 80.01; H, 4.41; test value C, 80.04; H, 4.43. Mass spectrum: theoretical value 480.14, experimental value 480.1 (M+).

[0629] Under argon atmosphere, 84-4 (7.20 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-194 (7.26 g, yield 80.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 87.67; H, 4.68; test value C, 87.65; H, 4.64. Mass spectrum: theoretical value 1204.36, experimental value 1204.4 (M+).

[0630] Embodiment 85

[0631]

[0632] Under argon atmosphere, 85-1 (9.84 g, 40 mmol), 85-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 85-3 (13.42 g, yield 79.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 73.77; H, 3.57; test value C, 73.76; H, 3.58. Mass spectrum: theoretical value 422.03, experimental value 422.0 (M+).

[0633] Under argon atmosphere, 85-3 (10.55 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 85-4 (7.80 g, yield 80.4%). Elemental analysis (%): theoretical value C, 80.44; H, 4.41; test value C, 80.41; H, 4.43. Mass spectrum: theoretical value 388.13, experimental value 388.1 (M+).

[0634] Under argon atmosphere, 85-4 (2.33 g, 6 mmol), 85-5 (1.48 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-121 (2.39 g, yield 78%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 90.38; H, 6.50; test value C, 90.37; H, 6.51. Mass spectrum: theoretical value 1022.48, experimental value 1022.5 (M+).

[0635] Embodiment 86

[0636]

[0637]

[0638] Under argon atmosphere, 86-1 (9.84 g, 40 mmol), 86-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 86-3 (13.42 g, yield 79.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 73.77; H, 3.57; test value C, 73.76; H, 3.58. Mass spectrum: theoretical value 422.03, experimental value 422.0 (M+).

[0639] Under argon atmosphere, 86-3 (10.55 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 86-4 (7.80 g, yield 80.4%). Elemental analysis (%): theoretical value C, 80.44; H, 4.41; test value C, 80.41; H, 4.43. Mass spectrum: theoretical value 388.13, experimental value 388.1 (M+).

[0640] Under argon atmosphere, 86-4 (5.82 g, 15 mmol), 86-5 (3.83 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-352 (6.06 g, yield 77.9%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 87.82; H, 6.40; test value C, 87.84; H, 6.45. Mass spectrum: theoretical value 1038.46, experimental value 1038.5 (M+).

[0641] Embodiment 87

[0642]

[0643] Under argon atmosphere, 87-1 (9.84 g, 40 mmol), 87-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 87-3 (13.42 g, yield 79.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 73.77; H, 3.57; test value C, 73.76; H, 3.58. Mass spectrum: theoretical value 422.03, experimental value 422.0 (M+).

[0644] Under argon atmosphere, 87-3 (10.55 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 87-4 (7.80 g, yield 80.4%). Elemental analysis (%): theoretical value C, 80.44; H, 4.41; test value C, 80.41; H, 4.43. Mass spectrum: theoretical value 388.13, experimental value 388.1 (M+).

[0645] Under argon atmosphere, 87-4 (5.82 g, 15 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-376 (5.91 g, yield 78.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 92.00; H, 4.81; test value C, 92.04; H, 4.83. Mass spectrum: theoretical value 1004.37, experimental value 1004.4 (M+).

[0646] Embodiment 88

[0647]

[0648] Under argon atmosphere, 88-1 (11.88 g, 40 mmol), 88-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 88-3 (15.16 g, yield 80.3%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.14; H, 3.61. Mass spectrum: theoretical value 472.05, experimental value 472.1 (M+).

[0649] Under argon atmosphere, 88-3 (11.80 g, 25 mmol), biboric acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 88-4 (8.60 g, yield 78.5%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.26; H, 4.38. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0650] Under argon atmosphere, 88-5 (12.48 g, 40 mmol), 88-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 88-6 (16.08 g, yield 82.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 73.62; H, 3.50; test value C, 73.61; H, 3.53. Mass spectrum: theoretical value 488.02, experimental value 488.0 (M+).

[0651] Under argon atmosphere, 88-6 (12.20 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 88-7 (9.12 g, yield 78.6%). Elemental analysis (%): theoretical value C, 79.31; H, 4.22; test value C, 79.32; H, 4.24. Mass spectrum: theoretical value 454.12, experimental value 454.1 (M+).

[0652] Under argon atmosphere, 88-4 (3.29 g, 7.5 mmol), bis(3-bromophenyl)diphenylsilane (3.69 g, 7.5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and 88-8 (3.36 g, yield 55.6%) was obtained by column separation and solvent removal. Elemental analysis (%): theoretical value C, 80.29; H, 4.37; test value C, 80.31; H, 4.33. Mass spectrum: theoretical value 806.16, experimental value 806.2 (M+).

[0653] Under argon atmosphere, 88-8 (2.42 g, 3 mmol), 88-7 (1.36 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H1-397 (1.85 g, yield 54.3%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 88.70; H, 4.61; test value C, 88.73; H, 4.62. Mass spectrum: theoretical value 1136.35, experimental value 1136.4 (M+).

[0654] Embodiment 89

[0655]

[0656] Under argon atmosphere, 89-1 (9.28 g, 40 mmol), 89-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 89-3 (13.09 g, yield 80.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.29; H, 4.19 test value C, 76.18; H, 4.22. Mass spectrum: theoretical value 408.05, experimental value 408.1 (M+).

[0657] Under argon atmosphere, 89-3 (10.20 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 89-4 (7.55 g, yield 80.7%). Elemental analysis (%): theoretical value C, 83.44; H, 5.12; test value C, 83.40; H, 5.19. Mass spectrum: theoretical value 374.15, experimental value 374.2 (M+).

[0658] Under argon atmosphere, 89-4 (3.37 g, 9 mmol), tris(3-bromophenyl)phenylsilane (1.71 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-65 (2.90 g, yield 73.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 92.69; H, 5.19; test value C, 92.64; H, 5.22. Mass spectrum: theoretical value 1320.51, experimental value 1320.5 (M+).

[0659] Embodiment 90

[0660]

[0661] Under argon atmosphere, 90-1 (11.89 g, 40 mmol), 90-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 90-3 (14.01 g, yield 74.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.13; H, 3.63. Mass spectrum: theoretical value 472.05, experimental value 472.0 (M+).

[0662] Under argon atmosphere, 90-3 (11.83 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 90-4 (8.44 g, yield 77.1%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.22; H, 4.36. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0663] Under argon atmosphere, 90-4 (3.94 g, 9 mmol), tris(3-bromophenyl)phenylsilane (1.71 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-136 (3.59 g, yield 79.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 90.45; H, 4.53; test value C, 90.44; H, 4.54. Mass spectrum: theoretical value 1512.49, experimental value 1512.5 (M+).

[0664] Embodiment 91

[0665]

[0666] Under argon atmosphere, 91-1 (9.28 g, 40 mmol), 91-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 91-3 (13.09 g, yield 80.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.29; H, 4.19 test value C, 76.18; H, 4.22. Mass spectrum: theoretical value 408.05, experimental value 408.1 (M+).

[0667] Under argon atmosphere, 91-3 (10.20 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 91-4 (7.55 g, yield 80.7%). Elemental analysis (%): theoretical value C, 83.44; H, 5.12; test value C, 83.40; H, 5.19. Mass spectrum: theoretical value 374.15, experimental value 374.2 (M+).

[0668] Under argon atmosphere, 91-4 (3.37 g, 9 mmol), 91-5 (1.76 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-146 (2.87 g, yield 76.3%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 91.51; H, 6.40; test value C, 91.47; H, 6.43. Mass spectrum: theoretical value 1337.62, experimental value 1337.6 (M+).

[0669] Embodiment 92

[0670]

[0671]

[0672] Under argon atmosphere, 92-1 (11.89 g, 40 mmol), 92-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 92-3 (14.01 g, yield 74.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.13; H, 3.63. Mass spectrum: theoretical value 472.05, experimental value 472.0 (M+).

[0673] Under argon atmosphere, 92-3 (11.83 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 92-4 (8.44 g, yield 77.1%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.22; H, 4.36. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0674] Under argon atmosphere, 92-4 (3.94 g, 9.0 mmol), 92-5 (1.76 g, 3.0 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-137 (3.40 g, yield 74.0%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.44; H, 5.59; test value C, 89.45; H, 5.58. Mass spectrum: theoretical value 1529.60, experimental value 1529.6 (M+).

[0675] Embodiment 93

[0676]

[0677] Under argon atmosphere, 93-1 (11.89 g, 40 mmol), 93-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 93-3 (14.01 g, yield 74.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.13; H, 3.63. Mass spectrum: theoretical value 472.05, experimental value 472.0 (M+).

[0678] Under argon atmosphere, 93-3 (11.83 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd (dppf) Cl2 (1.10 g, 1.5 mmol) were added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 93-4 (8.44 g, yield 77.1%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.22; H, 4.36. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0679] Under argon atmosphere, 93-4 (3.94 g, 9 mmol), 93-5 (1.66 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-303 (3.37 g, yield 75.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 92.22; H, 4.58; test value C, 92.23; H, 4.57. Mass spectrum: theoretical value 1496.52, experimental value 1496.5 (M+).

[0680] Embodiment 94

[0681]

[0682] Under argon atmosphere, 94-1 (11.89 g, 40 mmol), 94-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 94-3 (14.01 g, yield 74.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.13; H, 3.63. Mass spectrum: theoretical value 472.05, experimental value 472.0 (M+).

[0683] Under argon atmosphere, 94-3 (11.83 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd (dppf) Cl2 (1.10 g, 1.5 mmol) were added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 94-4 (8.44 g, yield 77.1%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.22; H, 4.36. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0684] Under argon atmosphere, 94-4 (3.94 g, 9 mmol), 94-5 (1.71 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-129 (3.51 g, yield 77.3%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 91.18; H, 5.65; test value C, 91.17; H, 5.64. Mass spectrum: theoretical value 1513.62, experimental value 1513.6 (M+).

[0685] Embodiment 95

[0686]

[0687] Under argon atmosphere, 95-1 (14.48 g, 40 mmol), 95-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product compound 95-3 (17.02 g, yield 79.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 75.70; H, 4.30; test value C, 75.72; H, 4.31. Mass spectrum: theoretical value 538.10, experimental value 538.1 (M+).

[0688] Under argon atmosphere, 95-3 (13.45 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd (dppf) Cl2 (1.10 g, 1.5 mmol) were added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain the product compound 95-4 (9.87 g, yield 78.3%). Elemental analysis (%): theoretical value C, 80.96; H, 5.00; test value C, 80.97; H, 5.02. Mass spectrum: theoretical value 504.20, experimental value 504.2 (M+).

[0689] Under argon atmosphere, 95-4 (7.62 g, 15 mmol), tris(3-bromophenyl)phenylsilane (2.85 g, 5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product compound H2-57 (6.55 g, yield 76.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 88.39; H, 5.06; test value C, 88.37; H, 5.07. Mass spectrum: theoretical value 1710.67, experimental value 1710.7 (M+).

[0690] Embodiment 96

[0691]

[0692] Under argon atmosphere, 96-1 (9.84 g, 40 mmol), 96-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 96-3 (13.42 g, yield 79.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 73.77; H, 3.57; test value C, 73.76; H, 3.58. Mass spectrum: theoretical value 422.03, experimental value 422.0 (M+).

[0693] Under argon atmosphere, 96-3 (10.55 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 96-4 (7.80 g, yield 80.4%). Elemental analysis (%): theoretical value C, 80.44; H, 4.41; test value C, 80.41; H, 4.43. Mass spectrum: theoretical value 388.13, experimental value 388.1 (M+).

[0694] Under argon atmosphere, 96-4 (5.82 g, 15 mmol), tris(3-bromophenyl)phenylsilane (2.85 g, 5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-149 (5.27 g, yield 77.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.84; H, 4.58; test value C, 89.87; H, 4.59. Mass spectrum: theoretical value 1362.45, experimental value 1362.5 (M+).

[0695] Embodiment 97

[0696]

[0697]

[0698] Under argon atmosphere, 97-1 (9.28 g, 40 mmol), 97-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 97-3 (13.09 g, yield 80.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.29; H, 4.19 test value C, 76.18; H, 4.22. Mass spectrum: theoretical value 408.05, experimental value 408.1 (M+).

[0699] Under argon atmosphere, 97-3 (10.20 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 97-4 (7.55 g, yield 80.7%). Elemental analysis (%): theoretical value C, 83.44; H, 5.12; test value C, 83.40; H, 5.19. Mass spectrum: theoretical value 374.15, experimental value 374.2 (M+).

[0700] Under argon atmosphere, 97-4 (3.37 g, 9 mmol), 97-5 (1.66 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-264 (2.80 g, yield 71.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 94.75; H, 5.25; test value C, 94.74; H, 5.27. Mass spectrum: theoretical value 1304.53, experimental value 1304.5 (M+).

[0701] Embodiment 98

[0702]

[0703] Under argon atmosphere, 98-1 (11.33 g, 40 mmol), 98-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 98-3 (12.86 g, yield 70.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 78.44; H, 4.17; test value C, 78.45; H, 4.16. Mass spectrum: theoretical value 458.07, experimental value 458.1 (M+).

[0704] Under argon atmosphere, 98-3 (11.48 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 98-4 (7.66 g, yield 72.3%). Elemental analysis (%): theoretical value C, 84.92; H, 4.99; test value C, 84.95; H, 4.97. Mass spectrum: theoretical value 424.16, experimental value 424.2 (M+).

[0705] Under argon atmosphere, 98-4 (3.82 g, 9 mmol), tris(3-bromophenyl)phenylsilane (1.71 g, 3.0 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-38 (3.11 g, yield 70.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 93.02; H, 5.07; test value C, 93.03; H, 5.06. Mass spectrum: theoretical value 1470.56, experimental value 1470.6 (M+).

[0706] Embodiment 99

[0707]

[0708] Under argon atmosphere, 99-1 (9.28 g, 40 mmol), 99-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 99-3 (13.09 g, yield 80.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.29; H, 4.19 test value C, 76.18; H, 4.22. Mass spectrum: theoretical value 408.05, experimental value 408.1 (M+).

[0709] Under argon atmosphere, 99-3 (10.20 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 99-4 (7.55 g, yield 80.7%). Elemental analysis (%): theoretical value C, 83.44; H, 5.12; test value C, 83.40; H, 5.19. Mass spectrum: theoretical value 374.15, experimental value 374.2 (M+).

[0710] Under argon atmosphere, 99-4 (3.37 g, 9 mmol), 99-5 (1.71 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-128 (2.76 g, yield 69.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 93.53; H, 6.47; test value C, 93.57; H, 6.45. Mass spectrum: theoretical value 1321.64, experimental value 1321.6 (M+).

[0711] Embodiment 100

[0712]

[0713] Under argon atmosphere, 100-1 (8.28 g, 40 mmol), 100-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 100-3 (12.16 g, yield 79.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 75.21; H, 3.94 test value C, 75.23; H, 3.92. Mass spectrum: theoretical value 382.04, experimental value 382.0 (M+).

[0714] Under argon atmosphere, 100-3 (10.83 g, 25 mmol), biboric acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 100-4 (6.98 g, yield 80.2%). Elemental analysis (%): theoretical value C, 82.79; H, 4.92; test value C, 82.81; H, 4.90. Mass spectrum: theoretical value 348.13, experimental value 348.1 (M+).

[0715] Under argon atmosphere, 100-4 (3.13 g, 9 mmol), tris(3-bromophenyl)phenylsilane (1.71 g, 3.0 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-47 (2.87 g, yield 77.0%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 92.72; H, 5.03; test value C, 92.70; H, 5.07. Mass spectrum: theoretical value 1242.46, experimental value 1242.5 (M+).

[0716] Embodiment 101

[0717]

[0718] Under argon atmosphere, 101-1 (11.33 g, 40 mmol), 101-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 101-3 (12.86 g, yield 70.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 78.44; H, 4.17; test value C, 78.45; H, 4.16. Mass spectrum: theoretical value 458.07, experimental value 458.1 (M+).

[0719] Under argon atmosphere, 101-3 (11.48 g, 25 mmol), biboric acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 101-4 (7.66 g, yield 72.3%). Elemental analysis (%): theoretical value C, 84.92; H, 4.99; test value C, 84.95; H, 4.97. Mass spectrum: theoretical value 424.16, experimental value 424.2 (M+).

[0720] Under argon atmosphere, 101-4 (3.82 g, 9 mmol), 101-5 (1.76 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-141 (3.07 g, yield 68.9%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 91.96; H, 6.16; test value C, 91.95; H, 6.15. Mass spectrum: theoretical value 1487.66, experimental value 1487.6 (M+).

[0721] Embodiment 102

[0722]

[0723]

[0724] Under argon atmosphere, 102-1 (11.33 g, 40 mmol), 102-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 102-3 (12.86 g, yield 70.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 78.44; H, 4.17; test value C, 78.45; H, 4.16. Mass spectrum: theoretical value 458.07, experimental value 458.1 (M+).

[0725] Under argon atmosphere, 102-3 (11.48 g, 25 mmol), bipyralidone (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 102-4 (7.66 g, yield 72.3%). Elemental analysis (%): theoretical value C, 84.92; H, 4.99; test value C, 84.95; H, 4.97. Mass spectrum: theoretical value 424.16, experimental value 424.2 (M+).

[0726] Under argon atmosphere, 102-4 (3.82 g, 9 mmol), 102-5 (1.66 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-64 (3.20 g, yield 73.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 94.88; H, 5.12; test value C, 94.87; H, 5.13. Mass spectrum: theoretical value 1454.58, experimental value 1454.6 (M+).

[0727] Embodiment 103

[0728]

[0729] Under argon atmosphere, 103-1 (11.33 g, 40 mmol), 103-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 103-3 (12.86 g, yield 70.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 78.44; H, 4.17; test value C, 78.45; H, 4.16. Mass spectrum: theoretical value 458.07, experimental value 458.1 (M+).

[0730] Under argon atmosphere, 103-3 (11.48 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 103-4 (7.66 g, yield 72.3%). Elemental analysis (%): theoretical value C, 84.92; H, 4.99; test value C, 84.95; H, 4.97. Mass spectrum: theoretical value 424.16, experimental value 424.2 (M+).

[0731] Under argon atmosphere, 103-4 (3.82 g, 9 mmol), 103-5 (1.71 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-124 (3.04 g, yield 68.8%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 93.77; H, 6.23; test value C, 93.78; H, 6.24. Mass spectrum: theoretical value 1471.69, experimental value 1471.67 (M+).

[0732] Embodiment 104

[0733]

[0734] Under argon atmosphere, 104-1 (11.88 g, 40 mmol), 104-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 104-3 (15.12 g, yield 80.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.14; H, 3.61. Mass spectrum: theoretical value 472.05, experimental value 472.0 (M+).

[0735] Under argon atmosphere, 104-3 (11.80 g, 25 mmol), biboric acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 104-4 (8.74 g, yield 79.8%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.26; H, 4.38. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0736] Under argon atmosphere, 104-4 (3.94 g, 9 mmol), tris(3-bromophenyl)phenylsilane (1.71 g, 3.0 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-150 (3.30 g, yield 72.8%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 90.45; H, 4.53; test value C, 90.44; H, 4.54. Mass spectrum: theoretical value 1512.49, experimental value 1512.5 (M+).

[0737] Embodiment 105

[0738]

[0739] Under argon atmosphere, 105-1 (11.88 g, 40 mmol), 105-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 105-3 (15.12 g, yield 80.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.14; H, 3.61. Mass spectrum: theoretical value 472.05, experimental value 472.0 (M+).

[0740] Under argon atmosphere, 105-3 (11.80 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 105-4 (8.74 g, yield 79.8%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.26; H, 4.38. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0741] Under argon atmosphere, 105-4 (3.94 g, 9 mmol), 105-5 (1.76 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-364 (3.28 g, yield 71.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.44; H, 5.59; test value C, 89.45; H, 5.58. Mass spectrum: theoretical value 1529.60, experimental value 1529.6 (M+).

[0742] Embodiment 106

[0743]

[0744] Under argon atmosphere, 106-1 (11.88 g, 40 mmol), 106-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 106-3 (15.12 g, yield 80.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.14; H, 3.61. Mass spectrum: theoretical value 472.05, experimental value 472.0 (M+).

[0745] Under argon atmosphere, 106-3 (11.80 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 106-4 (8.74 g, yield 79.8%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.26; H, 4.38. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0746] Under argon atmosphere, 106-4 (3.94 g, 9 mmol), 106-5 (1.66 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-133 (3.15 g, yield 70.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 92.22; H, 4.58; test value C, 92.23; H, 4.57. Mass spectrum: theoretical value 1496.52, experimental value 1496.5 (M+).

[0747] Embodiment 107

[0748]

[0749] Under argon atmosphere, 107-1 (11.88 g, 40 mmol), 107-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 107-3 (15.12 g, yield 80.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.14; H, 3.61. Mass spectrum: theoretical value 472.05, experimental value 472.0 (M+).

[0750] Under argon atmosphere, 107-3 (11.80 g, 25 mmol), biboric acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 107-4 (8.74 g, yield 79.8%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.26; H, 4.38. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0751] Under argon atmosphere, 107-4 (3.94 g, 9 mmol), 107-5 (1.71 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-122 (3.15 g, yield 69.3%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 91.18; H, 5.65; test value C, 91.17; H, 5.64. Mass spectrum: theoretical value 1513.62, experimental value 1513.6 (M+).

[0752] Embodiment 108

[0753]

[0754]

[0755] Under argon atmosphere, 108-1 (12.29 g, 40 mmol), 108-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 108-3 (14.56 g, yield 75.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 79.51; H, 3.96; test value C, 79.58; H, 3.91. Mass spectrum: theoretical value 482.07, experimental value 482.1 (M+).

[0756] Under argon atmosphere, 108-3 (12.09 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd (dppf) Cl2 (1.10 g, 1.5 mmol) were added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 108-4 (8.31 g, yield 74.2%). Elemental analysis (%): theoretical value C, 85.73; H, 4.72; test value C, 85.70; H, 4.77;. Mass spectrum: theoretical value 448.16, experimental value 448.2 (M+).

[0757] Under argon atmosphere, 108-4 (4.03 g, 9 mmol), tris(3-bromophenyl)phenylsilane (1.71 g, 3.0 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-210 (3.45 g, yield 74.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 93.35; H, 4.83; test value C, 93.30; H, 4.87. Mass spectrum: theoretical value 1542.56, experimental value 1542.6 (M+).

[0758] Embodiment 109

[0759]

[0760] Under argon atmosphere, 109-1 (12.29 g, 40 mmol), 109-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 109-3 (14.56 g, yield 75.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 79.51; H, 3.96; test value C, 79.58; H, 3.91. Mass spectrum: theoretical value 482.07, experimental value 482.1 (M+).

[0761] Under argon atmosphere, 109-3 (12.09 g, 25 mmol), bipyralidinol (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd (dppf) Cl2 (1.10 g, 1.5 mmol) were added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 109-4 (8.31 g, yield 74.2%). Elemental analysis (%): theoretical value C, 85.73; H, 4.72; test value C, 85.70; H, 4.77;. Mass spectrum: theoretical value 448.16, experimental value 448.2 (M+).

[0762] Under argon atmosphere, 109-4 (4.03 g, 9 mmol), 109-5 (1.76 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-140 (3.31 g, yield 70.8%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 92.33; H, 5.87; test value C, 92.35; H, 5.82. Mass spectrum: theoretical value 1559.66, experimental value 1559.7 (M+).

[0763] Embodiment 110

[0764]

[0765] Under argon atmosphere, 110-1 (9.84 g, 40 mmol), 110-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 110-3 (13.42 g, yield 79.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 73.77; H, 3.57; test value C, 73.76; H, 3.58. Mass spectrum: theoretical value 422.03, experimental value 422.0 (M+).

[0766] Under argon atmosphere, 110-3 (10.55 g, 25 mmol), bipyralidone (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 110-4 (7.80 g, yield 80.4%). Elemental analysis (%): theoretical value C, 80.44; H, 4.41; test value C, 80.41; H, 4.43. Mass spectrum: theoretical value 388.13, experimental value 388.1 (M+).

[0767] Under argon atmosphere, 110-4 (3.49 g, 9 mmol), 110-5 (1.71 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-211 (3.16 g, yield 77%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 90.65; H, 5.83; test value C, 90.64; H, 5.84. Mass spectrum: theoretical value 1363.58, experimental value 1363.6 (M+).

[0768] Embodiment 111

[0769]

[0770] Under argon atmosphere, 111-1 (8.28 g, 40 mmol), 111-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 111-3 (12.16 g, yield 79.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 75.21; H, 3.94 test value C, 75.23; H, 3.92. Mass spectrum: theoretical value 382.04, experimental value 382.0 (M+).

[0771] Under argon atmosphere, 111-3 (10.83 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 111-4 (6.98 g, yield 80.2%). Elemental analysis (%): theoretical value C, 82.79; H, 4.92; test value C, 82.81; H, 4.90. Mass spectrum: theoretical value 348.13, experimental value 348.1 (M+).

[0772] Under argon atmosphere, 111-4 (5.22 g, 15 mmol), 111-5 (2.94 g, 5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-322 (4.88 g, yield 77.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 91.46; H, 6.31; test value C, 91.45; H, 6.33. Mass spectrum: theoretical value 1259.57, experimental value 1259.6 (M+).

[0773] Embodiment 112

[0774]

[0775] Under argon atmosphere, 112-1 (9.84 g, 40 mmol), 112-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 112-3 (13.42 g, yield 79.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 73.77; H, 3.57; test value C, 73.76; H, 3.58. Mass spectrum: theoretical value 422.03, experimental value 422.0 (M+).

[0776] Under argon atmosphere, 112-3 (10.55 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 112-4 (7.80 g, yield 80.4%). Elemental analysis (%): theoretical value C, 80.44; H, 4.41; test value C, 80.41; H, 4.43. Mass spectrum: theoretical value 388.13, experimental value 388.1 (M+).

[0777] Under argon atmosphere, 112-4 (3.49 g, 9 mmol), 112-5 (1.66 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-376 (3.15 g, yield 78%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 91.80; H, 4.64; test value C, 91.81; H, 4.65. Mass spectrum: theoretical value 1346.47, experimental value 1346.5 (M+).

[0778] Embodiment 113

[0779]

[0780]

[0781] Under argon atmosphere, 113-1 (9.84 g, 40 mmol), 113-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 113-3 (13.42 g, yield 79.5%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 73.77; H, 3.57; test value C, 73.76; H, 3.58. Mass spectrum: theoretical value 422.03, experimental value 422.0 (M+).

[0782] Under argon atmosphere, 113-3 (10.55 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 113-4 (7.80 g, yield 80.4%). Elemental analysis (%): theoretical value C, 80.44; H, 4.41; test value C, 80.41; H, 4.43. Mass spectrum: theoretical value 388.13, experimental value 388.1 (M+).

[0783] Under argon atmosphere, 113-4 (5.82 g, 15 mmol), 113-5 (2.94 g, 5 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-352 (5.40 g, yield 78.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 88.73; H, 5.76; test value C, 88.71; H, 5.78. Mass spectrum: theoretical value 1379.55, experimental value 1379.6 (M+).

[0784] Embodiment 114

[0785]

[0786] Under argon atmosphere, 114-1 (8.28 g, 40 mmol), 114-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 114-3 (12.16 g, yield 79.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 75.21; H, 3.94 test value C, 75.23; H, 3.92. Mass spectrum: theoretical value 382.04, experimental value 382.0 (M+).

[0787] Under argon atmosphere, 114-3 (10.83 g, 25 mmol), biboric acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 114-4 (6.98 g, yield 80.2%). Elemental analysis (%): theoretical value C, 82.79; H, 4.92; test value C, 82.81; H, 4.90. Mass spectrum: theoretical value 348.13, experimental value 348.1 (M+).

[0788] Under argon atmosphere, 114-4 (3.13 g, 9 mmol), 114-5 (1.71 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-130 (2.67 g, yield 71.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 93.60; H, 6.40; test value C, 93.63; H, 6.47. Mass spectrum: theoretical value 1243.59, experimental value 1243.59 (M+).

[0789] Embodiment 115

[0790]

[0791] Under argon atmosphere, 115-1 (8.28 g, 40 mmol), 115-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 115-3 (12.16 g, yield 79.6%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 75.21; H, 3.94 test value C, 75.23; H, 3.92. Mass spectrum: theoretical value 382.04, experimental value 382.0 (M+).

[0792] Under argon atmosphere, 115-3 (10.83 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 115-4 (6.98 g, yield 80.2%). Elemental analysis (%): theoretical value C, 82.79; H, 4.92; test value C, 82.81; H, 4.90. Mass spectrum: theoretical value 348.13, experimental value 348.1 (M+).

[0793] Under argon atmosphere, 115-4 (3.13 g, 9 mmol), 115-5 (1.66 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-263 (2.81 g, yield 76.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 94.91; H, 5.09; test value C, 94.97; H, 5.08. Mass spectrum: theoretical value 1226.49, experimental value 1226.5 (M+).

[0794] Embodiment 116

[0795]

[0796] Under argon atmosphere, 116-1 (8.28 g, 40 mmol), 116-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 116-3 (12.11 g, yield 79.0%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 78.44; H, 4.17; test value C, 78.42; H, 4.19. Mass spectrum: theoretical value 382.04, experimental value 382.0 (M+).

[0797] Under argon atmosphere, 116-3 (9.58 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated under reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 116-4 (6.45 g, yield 74.1%). Elemental analysis (%): theoretical value C, 82.79; H, 4.92; test value C, 82.75; H, 4.95. Mass spectrum: theoretical value 348.13, experimental value 348.1 (M+).

[0798] Under argon atmosphere, 116-4 (3.13 g, 9 mmol), 116-5 (2.77 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-131 (2.60 g, yield 69.8%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 93.60; H, 6.40; test value C, 93.62; H, 6.43. Mass spectrum: theoretical value 1243.59, experimental value 1243.6 (M+).

[0799] Embodiment 117

[0800]

[0801] Under argon atmosphere, 117-1 (8.28 g, 40 mmol), 117-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 117-3 (12.11 g, yield 79.0%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 78.44; H, 4.17; test value C, 78.42; H, 4.19. Mass spectrum: theoretical value 382.04, experimental value 382.0 (M+).

[0802] Under argon atmosphere, 117-3 (9.58 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 117-4 (6.45 g, yield 74.1%). Elemental analysis (%): theoretical value C, 82.79; H, 4.92; test value C, 82.75; H, 4.95. Mass spectrum: theoretical value 348.13, experimental value 348.1 (M+).

[0803] Under argon atmosphere, 117-4 (3.13 g, 9 mmol), 117-5 (1.66 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-262 (2.84 g, yield 77.1%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 94.91; H, 5.09; test value C, 94.97; H, 5.05. Mass spectrum: theoretical value 1226.49, experimental value 1226.5 (M+).

[0804] Embodiment 118

[0805]

[0806]

[0807] Under argon atmosphere, 118-1 (8.28 g, 40 mmol), 118-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 118-3 (12.11 g, yield 79.0%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 78.44; H, 4.17; test value C, 78.42; H, 4.19. Mass spectrum: theoretical value 382.04, experimental value 382.0 (M+).

[0808] Under argon atmosphere, 118-3 (9.58 g, 25 mmol), bipyraclostrobin (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 118-4 (6.45 g, yield 74.1%). Elemental analysis (%): theoretical value C, 82.79; H, 4.92; test value C, 82.75; H, 4.95. Mass spectrum: theoretical value 348.13, experimental value 348.1 (M+).

[0809] Under argon atmosphere, 118-4 (3.13 g, 9 mmol), 118-5 (1.76 g, 3 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-335 (2.66 g, yield 70.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 91.46; H, 6.31; test value C, 91.40; H, 6.34. Mass spectrum: theoretical value 1259.57, experimental value 1259.6 (M+).

[0810] Embodiment 119

[0811]

[0812] Under argon atmosphere, 119-1 (11.84 g, 40 mmol), 119-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 119-3 (14.80 g, yield 78.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 76.12; H, 3.62; test value C, 76.11; H, 3.63. Mass spectrum: theoretical value 472.05, experimental value 472.1 (M+).

[0813] Under argon atmosphere, 119-3 (11.80 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 119-4 (8.35 g, yield 76.3%). Elemental analysis (%): theoretical value C, 82.21; H, 4.37; test value C, 82.20; H, 4.38. Mass spectrum: theoretical value 438.14, experimental value 438.1 (M+).

[0814] Under argon atmosphere, 119-5 (15.48 g, 40 mmol), 119-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 119-6 (17.43 g, yield 77.4%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 74.47; H, 3.93; test value C, 74.45; H, 3.94. Mass spectrum: theoretical value 563.10, experimental value 563.1 (M+).

[0815] Under argon atmosphere, 119-6 (14.08 g, 25 mmol), biboronic acid pinacol ester (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the reaction was completed, the mixture was cooled, the solvent was removed, and sodium hydroxide aqueous solution was added for hydrolysis. The mixture was extracted with dichloromethane, dried, and concentrated. The crude product was purified by column chromatography to obtain product 119-7 (10.06 g, yield 76.1%). Elemental analysis (%): theoretical value C, 79.41; H, 4.57; test value C, 79.40; H, 4.59. Mass spectrum: theoretical value 529.20, experimental value 529.2 (M+).

[0816] Under argon atmosphere, 119-4 (4.38 g, 10 mmol), tris(3-bromophenyl)phenylsilane (2.85 g, 5.0 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 119-8 (3.31 g, yield 55.2%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 84.05; H, 4.28; test value C, 84.03; H, 4.27. Mass spectrum: theoretical value 1198.28, experimental value 1198.3 (M+).

[0817] Under argon atmosphere, 119-8 (1.06 g, 2 mmol), 119-7 (1.13 g, 2 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 60 mL) and anisole (90 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product H2-397 (1.35 g, yield 67.7%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 89.05; H, 4.58; test value C, 89.03; H, 4.56. Mass spectrum: theoretical value 1603.55, experimental value 1603.6 (M+).

[0818] Embodiment 120

[0819]

[0820]

[0821] Under argon atmosphere, 120-1 (19.52 g, 40 mmol), 120-2 (12.00 g, 40 mmol), Pd-132 (0.28 g, 0.4 mmol), potassium carbonate aqueous solution (2.5 M, 100 mL) and anisole (150 mL) were added to a round-bottom flask, and the mixture was heated and stirred at 110°C for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, extracted with deionized water and dichloromethane, and washed with deionized water 3 times. The organic phase was separated, and the product 120-3 (20.27 g, yield 76.3%) was obtained by column separation and desolvation. Elemental analysis (%): theoretical value C, 79.40; H, 3.79; test value C, 79.42; H, 3.77. Mass spectrum: theoretical value 664.10, experimental value 664.1 (M+).

[0822] Under argon atmosphere, 120-3 (16.60 g, 25 mmol), bipyraclostrobin (7.56 g, 30 mmol), potassium acetate (4.93 g, 50 mmol), dioxane (250 mL), Pd(dppf)Cl 2 (1.10 g, 1.5 mmol) was added to a round-bottom flask and heated to reflux for 12 hours. After the r...

Claims

1. A multi-arm anthracene compound, characterized in that: The structure is shown in formula (I): wherein X is selected from C, Si or Ge atoms; D a , D b , D c , D d Where D is a deuterium atom replacing hydrogen on the phenyl group connected to X, and a, b, c, and d are the numbers of the deuterium atoms and are selected from integers between 0 and 5; R1, R2, R3, and R4 are independently selected from C6-C 60 Aryl or C4-C 60 heteroaryl; m and n are independently selected from 0 or 1.

2. The multi-arm anthracene compound according to claim 1, characterized in that: The structure of the multi-arm anthracene compound is shown in formula (I-1), formula (I-2) or formula (I-3): wherein X is selected from C, Si or Ge atoms; D a , D b , D c , D d Where D is a deuterium atom replacing hydrogen on the phenyl group connected to X, and a, b, c, d are the numbers of the deuterium atoms and are independently selected from 0, 4 or 5; R1, R2, R3, R4 are independently selected from C 10 -C 60 Aryl or C 10 -C 60 Heteroaryl.

3. The multi-arm anthracene compound according to claim 2, characterized in that: The C 10 -C 60 The aryl group and the C 10 -C 60 The heteroaryl group may also contain substituents independently selected from C1-C 10 One or more of an alkyl group, a C3-C6 cycloalkyl group, and a C1-C3 nitrile group; The number of the substituents is independently selected from an integer between 1-5.

4. The multi-arm anthracene compound according to claim 1, characterized in that: The R1, R2, R3, and R4 are independently selected from any of the following structures:

5. The multi-arm anthracene compound according to claim 1, characterized in that: The multi-arm anthracene compound is selected from any of the following structures:

6. The method for preparing the multi-arm anthracene compound represented by formula (I-1) according to claim 2, characterized in that: The following steps are involved: (1) reacting the compound represented by formula A with compounds R1-Br and R2-Br to obtain compounds represented by formula B-1 and formula B-2, respectively; (2) the compounds represented by formula B-1 and formula B-2 are subjected to borylation and hydrolysis reactions in sequence to obtain the compounds represented by formula C-1 and formula C-2; (3) reacting the compound represented by formula D-1 with formula C-1, and then reacting the product with the compound represented by formula C-2 to obtain the multi-arm anthracene compound represented by formula (I-1); Wherein R1 and R2 are independently selected from C 10 -C 60 Aryl or C 10 -C 60 heteroaryl; X is selected from C, Si or Ge atoms; D a , D b , D c , D d Wherein D is a deuterium atom replacing hydrogen on the phenyl group connected to X, and a, b, c, d are the numbers of the deuterium atoms and are independently selected from 0, 4 or 5.

7. The method for preparing the multi-arm anthracene compound represented by formula (I-2) according to claim 2, characterized in that: The following steps are involved: (1) reacting the compound represented by formula A with compounds R1-Br, R2-Br, and R3-Br, respectively, to obtain compounds represented by formula B-1, formula B-2, and formula B-3, respectively; (2) the compounds represented by formula B-1, formula B-2, and formula B-3 are subjected to borylation and hydrolysis reactions in sequence to obtain the compounds represented by formula C-1, formula C-2, and formula C-3; (3) reacting the compound represented by formula D-2 with formula C-1, and then reacting the product with formula C-2. After the reaction is completed, the product is reacted with the compound represented by formula C-3 to obtain the multi-arm anthracene compound represented by formula (I-2); Wherein, R1, R2, and R3 are independently selected from C 10 -C 60 Aryl or C 10 -C 60 heteroaryl; X is selected from C, Si or Ge atoms; D a , D b , D c , D d Wherein D is a deuterium atom replacing hydrogen on the phenyl group connected to X, and a, b, c, d are the numbers of the deuterium atoms and are independently selected from 0, 4 or 5.

8. The method for preparing the multi-arm anthracene compound represented by formula (I-3) according to claim 2, characterized in that: The following steps are involved: (1) reacting the compound represented by formula A with compounds R1-Br, R2-Br, R3-Br, and R4-Br, respectively, to obtain compounds represented by formula B-1, formula B-2, formula B-3, and formula B-4, respectively; (2) The compounds represented by formula B-1, formula B-2, formula B-3, and formula B-4 are subjected to borylation and hydrolysis reactions in sequence to obtain compounds represented by formula C-1, formula C-2, formula C-3, and formula C-4; (3) reacting the compound represented by formula D-3 with formula C-1, and then reacting the product with formula C-2. After the reaction, the product is reacted with the compound represented by formula C-3. After the reaction, the product is reacted with the compound represented by formula C-4 to obtain the multi-arm anthracene compound represented by formula (I-3); Wherein, R1, R2, R3, and R4 are independently selected from C 10 -C 60 Aryl or C 10 -C 60 heteroaryl; X is selected from C, Si or Ge atoms; D a , D b , D c , D d Wherein D is a deuterium atom replacing hydrogen on the phenyl group connected to X, and a, b, c, d are the numbers of the deuterium atoms and are independently selected from 0, 4 or 5.

9. The preparation method according to any one of claims 6 to 8, characterized in that: The C 10 -C 60 The aryl group and the C 10 -C 60 The heteroaryl group may also contain substituents independently selected from C1-C 10 One or more of an alkyl group, a C3-C6 cycloalkyl group, and a C1-C3 nitrile group; The number of the substituents is independently selected from an integer between 1-5.

10. Use of the multi-arm anthracene compound according to any one of claims 1 to 5 or the multi-arm anthracene compound prepared by the preparation method according to any one of claims 6 to 9 as a molecular orientation host material in a blue electroluminescent device.

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