Organic Compounds and Mixtures, Compositions, and Organic Electronic Devices Comprising the Same

Abstract

The present invention discloses an organic compound having a structure represented by the general formula (1): #imgabs0# wherein: M1 is selected from the structures of formula (A-1) or (A-2), and M2 is selected from the structures of formula (A-3) or (A-4): #imgabs1# Additionally, the present invention also discloses a mixture, a composition, and an organic electronic device. In the organic compound of the present invention, a boron-nitrogen group is connected to dimethylacridinesilicon, enabling the molecular structure of the overall compound to have better conjugation and planarity, enhancing the rigidity and stability of the material molecules. The introduction of diphenylsilicon further improves the solubility of the molecules, making the compound easier to purify, and thus a compound with higher purity can be obtained. When used as a blue light emitting material in an organic electronic device, it can achieve the purpose of extending the light emitting efficiency and service life of the device. In addition, the organic compound of the present invention can be used as a blue light guest material, and by cooperating with a suitable host material, it can improve the light emitting efficiency and life of the electroluminescent device.

Description

Technical Field

[0001] The present invention relates to the technical field of organic materials, and in particular to an organic compound, a mixture, a composition and an organic electronic device including the organic compound. Background Art

[0002] Organic semiconductor materials are diverse in synthesis, relatively low in manufacturing cost, and have excellent optical and electrical properties. Organic light-emitting diodes (OLEDs) have advantages such as wide viewing angles, fast response times, low operating voltages, and thin panel thicknesses in the applications of optoelectronic devices (such as flat panel displays and lighting), and thus have broad development potential.

[0003] In order to improve the luminous efficiency of organic light-emitting diodes, various luminescent material systems based on fluorescence and phosphorescence have been developed. Among them, the organic light-emitting diode using a fluorescent material has the characteristic of high reliability, but its internal electroluminescence quantum efficiency is limited to 25% under electrical excitation because the branching ratio of the singlet excited state and the triplet excited state of excitons is 1:3. The organic light-emitting diode using a phosphorescent material has achieved an almost 100% internal electroluminescence quantum efficiency, but there is a major difficulty with phosphorescent OLEDs: the Roll-off effect, that is, the luminous efficiency rapidly decreases with the increase of current or brightness, which is particularly disadvantageous for high-brightness applications.

[0004] So far, the traditional phosphorescent materials with practical use value are complexes containing iridium and platinum. However, such raw materials are rare and expensive, and the synthesis of the complexes is very complicated, so the cost is quite high. To overcome the above problems, Adachi proposed the concept of reverse internal conversion, so that an organic compound can be used, that is, without using a metal complex, to achieve high efficiency comparable to that of phosphorescent OLEDs. This concept has been realized through various material combinations, such as: 1) using composite excited state materials; 2) using thermally activated delayed fluorescence (TADF) materials.

[0005] However, the performance of traditional blue TADF materials still has a certain gap compared with phosphorescent luminescent materials in terms of both efficiency and lifespan. Summary of the Invention

[0006] In view of this, the present invention provides an organic compound, aiming to provide new organic functional materials to improve the performance and lifespan of devices.

[0007] The present invention is achieved through the following technical solutions:

[0008] An organic compound has a structure represented by the general formula (1):

[0009]

[0010] Wherein:

[0011] M1 is selected from the structures of formula (A-1) or (A-2):

[0012]

[0013] M2 is selected from the structures of formula (A-3) or (A-4):

[0014]

[0015] X1 is selected from CR4R5, NR6, O, S or a single bond;

[0016] Each occurrence of R1, R2, R3, R4, R5, R6 is independently selected from: -H, -D, a straight-chain alkyl group having 1 to 20 C atoms, a straight-chain alkoxy group having 1 to 20 C atoms, a straight-chain thioalkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, a branched or cyclic alkoxy group having 3 to 20 C atoms, a branched or cyclic thioalkoxy group having 3 to 20 C atoms, a silyl group, a keto group having 1 to 20 C atoms, an alkoxycarbonyl group having 2 to 20 C atoms, an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group, a carbamoyl group, a halocarbonyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, an amino group, -CF3, -Cl, -Br, -F, -I, a substituted or unsubstituted alkenyl group having 2 - 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 50 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 50 ring atoms, a substituted or unsubstituted aryloxy group having 6 to 50 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5 to 50 ring atoms, or a combination of these groups;

[0017] Ar1 - Ar5 are independently selected from: a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms;

[0018] m1 is selected from 0, 1, 2, 3 or 4; m2 is selected from 0, 1, 2, 3, 4 or 5;

[0019] * represents the connection site.

[0020] Correspondingly, the present invention also provides a mixture, comprising the above-mentioned organic compound and at least one organic functional material, and the organic functional material is selected from a hole injection material, a hole transport material, an electron transport material, an electron injection material, an electron blocking material, a hole blocking material, a light-emitting guest material, a light-emitting host material or an organic dye.

[0021] Correspondingly, the present invention further provides a composition, comprising the above-mentioned organic compound or the above-mentioned mixture, and at least one organic solvent.

[0022] Correspondingly, the present invention further provides an organic electronic device, comprising at least one functional layer, wherein the functional layer contains the above-mentioned organic compound or the above-mentioned mixture, or the functional layer is prepared from the above-mentioned composition.

[0023] Compared with the prior art, the organic compound of the present invention has the following beneficial effects:

[0024] In the organic compound of the present invention, a boron-nitrogen group is connected to dimethylacridinesilicon, so that the molecular structure of the whole compound has better conjugation and planarity, improving the rigidity and stability of the material molecule and the device efficiency of the device. The introduction of diphenylsilicon further improves the solubility of the molecule, making the compound easier to purify, so that a compound with higher purity can be obtained. When used as a blue light emitting material in an organic electronic device, the compound with higher purity can reduce the content of impurities, thereby reducing the negative impact of impurities on the device, and achieving the purpose of prolonging the luminous efficiency and service life of the device. In addition, the organic compound of the present invention can be used as a blue light guest material, and by cooperating with a suitable host material, the luminous efficiency and life of the electroluminescent device can be improved. Description of the Drawings

[0025] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those skilled in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0026] Figure 1 It is a schematic diagram of the OLED device shown in Embodiment 1 of the device of the present invention;

[0027] Among them, 10 is a substrate, 20 is an anode, 30 is a hole injection layer, 40 is a hole transport layer, 50 is a light emitting layer, 60 is an electron transport layer, and 70 is a cathode. Detailed Embodiments

[0028] The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative efforts belong to the scope of protection of the present invention. In addition, it should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0029] In the description of the present invention, the term "comprising" means "including but not limited to", and the term "a plurality of" means "two or more than two". Various embodiments of the present invention may exist in the form of a range; it should be understood that the description in the form of a range is only for convenience and conciseness, and should not be construed as a rigid limitation on the scope of the present invention; therefore, it should be considered that the described range description has specifically disclosed all possible sub-ranges and single values within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, which applies regardless of the range. Additionally, whenever a numerical range is indicated herein, it means including any cited number (fraction or integer) within the indicated range.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which the present invention pertains. The terms used in the description of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention.

[0031] The selection scope of the terms "and / or", "or / and", and "and / or" used in the present invention includes any one of two or more than two related listed items, and also includes any and all combinations of the related listed items. The said any and all combinations include combinations of any two related listed items, any more than two related listed items, or all related listed items. It should be noted that when at least two conjunctions selected from "and / or", "or / and", and "and / or" are used to connect at least three items, it should be understood that in the present invention, this technical solution undoubtedly includes the technical solution connected by "logical AND", and also undoubtedly includes the technical solution connected by "logical OR". For example, "A and / or B" includes three parallel solutions: A, B, and A + B. Another example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (that is, the technical solution connected by "logical OR"), and also includes any and all combinations of A, B, C, and D, that is, includes combinations of any two or any three of A, B, C, and D, and also includes the combination of the four items A, B, C, and D (that is, the technical solution connected by "logical AND").

[0032] In the present application, the composition and the printing ink, or the ink have the same meaning and can be interchanged.

[0033] In the present application, the aromatic group, the aromatic, and the aromatic ring system have the same meaning and can be interchanged.

[0034] In this application, the heteroaromatic group, heteroaromatic, and heteroaromatic ring system have the same meaning and can be used interchangeably.

[0035] In this application, "substituted" means that a hydrogen atom in the substituent is replaced by a substituent.

[0036] In the present invention, when the same substituent appears multiple times, it can be independently selected from different groups. For example, if the general formula contains multiple Rs, the Rs can be independently selected from different groups.

[0037] In the present invention, "substituted or unsubstituted" means that the defined group can be substituted or unsubstituted. When the defined group is substituted, it should be understood that the defined group can be substituted by one or more substituents R, where R is selected from, but not limited to: deuterium atom, cyano group, isocyano group, nitro group, or halogen, alkyl group containing 1 - 20 C atoms, heterocyclic group containing 3 - 20 ring atoms, aromatic group containing 6 - 20 ring atoms, heteroaromatic group containing 5 - 20 ring atoms, -NR’R”, silyl group, carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, halocarbonyl group, formyl group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, trifluoromethyl group, and the above groups can also be further substituted by substituents acceptable in the art; it is understood that in -NR’R”, R’ and R” are independently selected from, but not limited to: H, deuterium atom, cyano group, isocyano group, nitro group, or halogen, alkyl group containing 1 - 10 C atoms, heterocyclic group containing 3 - 20 ring atoms, aromatic group containing 6 - 20 ring atoms, heteroaromatic group containing 5 - 20 ring atoms. Preferably, R is selected from, but not limited to: deuterium atom, cyano group, isocyano group, nitro group, or halogen, alkyl group containing 1 - 10 C atoms, heterocyclic group containing 3 - 10 ring atoms, aromatic group containing 6 - 20 ring atoms, heteroaromatic group containing 5 - 20 ring atoms, silyl group, carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, halocarbonyl group, formyl group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group, trifluoromethyl group, and the above groups can also be further substituted by substituents acceptable in the art.

[0038] In the present invention, "number of ring atoms" refers to the number of atoms among the atoms constituting the ring itself in a structural compound obtained by bonding atoms in a ring (for example, monocyclic compound, fused-ring compound, crosslinked compound, carbocyclic compound, heterocyclic compound). When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "number of ring atoms" described below under the condition of no special explanation. For example, the number of ring atoms in a benzene ring is 6, the number of ring atoms in a naphthalene ring is 10, and the number of ring atoms in a thiophenyl group is 5.

[0039] "Aryl or aromatic group" refers to an aromatic hydrocarbon group derived by removing one hydrogen atom from an aromatic ring compound, which can be a monocyclic aryl group, or a fused-ring aryl group, or a polycyclic aryl group. For polycyclic ring species, at least one is an aromatic ring system. For example, "substituted or unsubstituted aryl group having 6 to 40 ring atoms" refers to an aryl group containing 6 to 40 ring atoms, preferably a substituted or unsubstituted aryl group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aryl group having 6 to 18 ring atoms, particularly preferably a substituted or unsubstituted aryl group having 6 to 14 ring atoms, and the aryl group is optionally further substituted; suitable examples include but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, tetracenyl, fluorenyl, binaphthylenyl, acenaphthylenyl and their derivatives. It can be understood that multiple aryl groups can also be interrupted by short non-aromatic units (e.g., <10% of non-H atoms, such as C, N or O atoms), specifically such as acenaphthene, fluorene, or 9,9-diarylfluorene, triarylamine, diaryl ether systems should also be included in the definition of aryl groups.

[0040] "Heteroaryl or heteroaromatic group" refers to a group in which at least one carbon atom in the aryl group is replaced by a non-carbon atom, and the non-carbon atom can be an N atom, an O atom, an S atom, etc. For example, "substituted or unsubstituted heteroaryl group having 5 to 40 ring atoms" refers to a heteroaryl group having 5 to 40 ring atoms, preferably a substituted or unsubstituted heteroaryl group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted heteroaryl group having 6 to 18 ring atoms, particularly preferably a substituted or unsubstituted heteroaryl group having 6 to 14 ring atoms, and the heteroaryl group is optionally further substituted. Suitable examples include but are not limited to: thienyl, furyl, pyrrolyl, dioxazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothienyl, benzofuryl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothienyl, furanopyrrolyl, furanofuryl, thienofuryl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, phthalazinyl, phenanthridinyl, peridinyl, quinazolinone, dibenzothienyl, dibenzofuryl, carbazolyl and their derivatives.

[0041] In the present invention, "alkyl" can represent a straight-chain, branched-chain and / or cyclic alkyl group. The number of carbon atoms in the alkyl group can be 1 to 50, 1 to 30, 1 to 20, 1 to 10 or 1 to 6. Phrases containing this term, for example, "C 1-9"Alkyl" refers to an alkyl group containing 1 to 9 carbon atoms, and each occurrence can independently be a C1 alkyl group, C2 alkyl group, C3 alkyl group, C4 alkyl group, C5 alkyl group, C6 alkyl group, C7 alkyl group, C8 alkyl group or C9 alkyl group. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, t-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-t-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, t-octyl, 2-ethyloctyl, 2-butyl octyl, 2-hexyloctyl, 3,7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, etc.

[0042] In the present invention, the abbreviations of substituents correspond to: n - normal, sec - secondary, i - iso, t - tertiary, o - ortho, m - meta, p - para, Me - methyl, Et - ethyl, Pr - propyl, Bu - butyl, Am - n-pentyl, Hx - hexyl, Cy - cyclohexyl.

[0043] In the present invention, a silyl group can be represented by the chemical formula -Si(Y101)(Y102)(Y103), and Y101, Y102 and Y103 can each be hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. Examples of silyl groups include trialkylsilyl and triarylsilyl, and specific examples thereof include trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl, phenylsilyl, etc., but the examples are not limited thereto.

[0044] "Amino group" refers to derivatives of amines, having the structural feature of the formula -N(X)2, where each "X" is independently H, substituted or unsubstituted alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclic group, etc. Non-limiting types of amino groups include -NH2, -N(alkyl)2, -NH(alkyl), -N(cycloalkyl)2, -NH(cycloalkyl), -N(heterocyclic group)2, -NH(heterocyclic group), -N(aryl)2, -NH(aryl), -N(alkyl)(aryl), -N(alkyl)(heterocyclic group), -N(cycloalkyl)(heterocyclic group), -N(aryl)(heteroaryl), -N(alkyl)(heteroaryl), etc.

[0045] In the present invention, unless otherwise specifically defined, the hydroxyl group refers to -OH, the carboxyl group refers to -COOH, the carbonyl group refers to -C(=O)-, the amino group refers to -NH2, the formyl group refers to -C(=O)H, the halocarbonyl group refers to -C(=O)Z (where Z represents a halogen), the carbamoyl group refers to -C(=O)NH2, the isocyanate group refers to -NCO, and the isothiocyanate group refers to -NCS.

[0046] The term "alkoxy group" refers to a group having the structure "-O-alkyl", that is, the alkyl group as defined above is connected to other groups via an oxygen atom. Suitable examples of phrases containing this term include, but are not limited to: methoxy (-O-CH3 or -OMe), ethoxy (-O-CH2CH3 or -OEt), and tert-butoxy (-O-C(CH3)3 or -OtBu).

[0047] In the present invention, "*" connected to a single bond represents a connection or fusion site;

[0048] In the present invention, when the connection site is not specified in a group, it means that any optional connection site in the group can be used as the connection site;

[0049] In the present invention, when the fusion site is not specified in a group, it means that any optional fusion site in the group can be used as the fusion site, and preferably two or more sites adjacent to each other in the group are used as the fusion sites;

[0050] In the present invention, when a group contains multiple substituents with the same symbol, each substituent can be the same or different from each other. For example The 6 Rs on the benzene ring can be the same or different from each other.

[0051] In the present invention, the single bond to which a substituent is attached passes through the corresponding ring, indicating that the substituent can be connected to any optional position of the ring. For example In, R is connected to any substitutable site of the benzene ring, such as represents can form a fused ring with any optional substitutable position on.

[0052] In the present invention, "adjacent groups" means that there is no substitutable site between two substituents.

[0053] In the present invention, "two adjacent Rs form a ring with each other" means a ring system formed by connecting two adjacent Rs to each other, and the ring system can be selected from an aliphatic hydrocarbon ring, an aliphatic heterocyclic ring, an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Preferably, an aromatic group or a heteroaromatic group with 5-10 ring atoms, which may be substituted or unsubstituted, can be formed; more preferably, an aromatic group or a heteroaromatic group with 6 ring atoms, which may be substituted or unsubstituted, is formed. Preferably, it can form

[0054] In the present invention, "their combination", "any combination thereof", "any combination mode thereof", "combination", etc. include all suitable combination modes of any two or more items in the listed groups.

[0055] In the present invention, "further", "even further", "especially", etc. are used for descriptive purposes, indicating differences in content, but should not be construed as limiting the scope of protection of the present invention.

[0056] In the present invention, "optionally", "optional", "option", means that it may or may not be present, that is, it refers to any one of the two parallel options of "present" or "absent". If "optional" appears multiple times in a technical solution, without special instructions and without contradictions or mutual restrictions, each "optional" is independent of each other.

[0057] In the present invention, among the technical features described in an open-ended manner, a closed technical solution composed of the listed features is included, and an open-ended technical solution containing the listed features is also included.

[0058] The present invention provides an organic compound having a structure represented by the general formula (1):

[0059]

[0060] Wherein:

[0061] M1 is selected from the structures of formula (A-1) or (A-2):

[0062]

[0063] M2 is selected from the structures of formula (A-3) or (A-4):

[0064]

[0065] X1 is selected from CR4R5, NR6, O, S or a single bond;

[0066] Each occurrence of R1, R2, R3, R4, R5, and R6 is independently selected from: -H, -D, a straight-chain alkyl group having 1 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, a straight-chain thioalkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, a branched or cyclic alkoxy group having 3 to 20 carbon atoms, a branched or cyclic thioalkoxy group having 3 to 20 carbon atoms, a silyl group, a keto group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group, a carbamoyl group, a halocarbonyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, an amino group, -CF3, -Cl, -Br, -F, -I, a substituted or unsubstituted alkenyl group having 2 - 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 50 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 50 ring atoms, a substituted or unsubstituted aryloxy group having 6 to 50 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5 to 50 ring atoms, or a combination of these groups;

[0067] Ar1 - Ar5 are each independently selected from: a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms;

[0068] m1 is selected from 0, 1, 2, 3, or 4; m2 is selected from 0, 1, 2, 3, 4, or 5;

[0069] * represents the connection site.

[0070] In one embodiment, (A - 3) is selected from any one of the structures of formula (B - 1) - (B - 5):

[0071]

[0072] In one embodiment, M1 is selected from (A - 1); M2 is selected from (B - 1), (B - 2), (B - 3), (B - 4), (B - 5), or (A - 4).

[0073] In another embodiment, M1 is selected from (A - 2); M2 is selected from (B - 1), (B - 2), (B - 3), (B - 4), (B - 5), or (A - 4).

[0074] In one embodiment, Ar1 - Ar5 are each independently selected from: a substituted or unsubstituted aromatic group having 6 to 30 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 30 ring atoms; further, Ar1 - Ar5 are each independently selected from: a substituted or unsubstituted aromatic group having 6 to 13 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 13 ring atoms.

[0075] In a specific example, each occurrence of Ar1 - Ar5 is independently selected from any one of the following groups or a combination of the following groups:

[0076]

[0077] Wherein:

[0078] Each occurrence of X is independently selected from N or CR7;

[0079] Each occurrence of Y is independently selected from CR8R9, SiR8R9, NR 10 , PR 10 , C=O, S or O;

[0080] R7, R8, R9, R 10 Each occurrence is independently selected from: -H, -D, a straight-chain alkyl group having 1 to 20 C atoms, a straight-chain alkoxy group having 1 to 20 C atoms, a straight-chain thioalkoxy group having 1 to 20 C atoms, a branched or cyclic alkyl group having 3 to 20 C atoms, a branched or cyclic alkoxy group having 3 to 20 C atoms, a branched or cyclic thioalkoxy group having 3 to 20 C atoms, a silyl group, a keto group having 1 to 20 C atoms, an alkoxycarbonyl group having 2 to 20 C atoms, an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group, a carbamoyl group, a halocarbonyl group, a formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, an amino group, -CF3, -Cl, -Br, -F, a substituted or unsubstituted aromatic group having 6 to 20 C atoms, a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms, a substituted or unsubstituted aryloxy group having 6 to 20 ring atoms, a substituted or unsubstituted heteroaryloxy group having 5 to 20 ring atoms, or a combination of these groups.

[0081] It should be noted that when X is a connection site, X is selected from a C atom.

[0082] In one embodiment, each occurrence of Ar2, Ar3 is independently selected from the following groups:

[0083]

[0084] Wherein: * represents a fusion site.

[0085] In one embodiment, formula (A-1) is selected from the structures of formula (C-1) to (C-10):

[0086]

[0087] In one embodiment, the formula (A-2) is selected from the structures of formula (D-1) to (D-10):

[0088]

[0089]

[0090] In one embodiment, each occurrence of Ar1, Ar4, and Ar5 is independently selected from the following groups:

[0091]

[0092] where: * represents the attachment site.

[0093] In one embodiment, each occurrence of X is independently selected from N or CR7; each occurrence of R7 is independently selected from: -H, -D, a straight-chain alkyl group having 1 to 10 C atoms, a branched or cyclic alkyl group having 3 to 10 C atoms, a substituted or unsubstituted aromatic group having 6 to 10 C atoms, a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms, or a combination of these groups; specifically, each occurrence of R7 is independently selected from: -H, -D, methyl, Et, tBu, iPr, tAm, or phenyl, or a combination of these groups.

[0094] In one embodiment, each occurrence of Y is independently selected from NR 10 , S or O;

[0095] R 10 each occurrence is independently selected from: -H, -D, a straight-chain alkyl group having 1 to 10 C atoms, a branched or cyclic alkyl group having 3 to 10 C atoms, a substituted or unsubstituted aromatic group having 6 to 10 C atoms, a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms, or a combination of these groups; specifically, each occurrence of R 10 is independently selected from: -H, -D, methyl, Et, tBu, iPr, tAm, or phenyl, or a combination of these groups.

[0096] In one embodiment, each occurrence of R1, R2, R3, R4, R5, and R6 is independently selected from: -H, -D, a straight-chain alkyl group having 1 to 10 C atoms, a branched or cyclic alkyl group having 3 to 10 C atoms, a substituted or unsubstituted aromatic group having 6 to 10 C atoms, a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms, or a combination of these groups; specifically, each occurrence of R1 and R2 is independently selected from: -H, -D, methyl, Et, tBu, iPr, tAm, or phenyl, or a combination of these groups.

[0097] Specifically, the organic compounds according to the present invention are selected from the following structures but are not limited thereto:

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105] The molecular structure of the organic compounds of the present invention has good conjugation and planarity, which can improve the rigidity and stability of the material molecules, thereby improving the device efficiency of the device. The introduction of diphenylsilicon further improves the solubility of the molecule, making the compound easier to purify, so that a compound with higher purity can be obtained. When used as a blue light emitting material in organic electronic devices, the compound with higher purity can reduce the content of impurities, thereby reducing the negative impact of impurities on the device, and can achieve the purpose of prolonging the light emitting efficiency and service life of the device. In addition, the organic compounds of the present invention can be used as blue light guest materials, and by cooperating with suitable light emitting host materials, the light emitting efficiency and service life of the electroluminescent device can be improved.

[0106] The compounds according to the invention can be used as functional materials in electronic devices, especially in OLED devices. Organic functional materials can be divided into hole injection materials (HIM), hole transport materials (HTM), electron transport materials (ETM), electron injection materials (EIM), electron blocking materials (EBM), hole blocking materials (HBM), light emitting guest materials (Emitter), light emitting host materials (Host) and organic dyes.

[0107] In a specific example, the organic compounds according to the present invention are used in the light emitting layer; preferably, they can be used as the light emitting guest material of the light emitting layer in the light emitting layer.

[0108] In a specific example, the organic compounds according to the present invention are used as blue light emitting guest materials in the light emitting layer.

[0109] The present invention also provides a mixture, which comprises the above-mentioned organic compound and at least one organic functional material, and the organic functional material is selected from a hole injection material, a hole transport material, an electron transport material, an electron injection material, an electron blocking material, a hole blocking material, a light-emitting guest material, a light-emitting host material or an organic dye. The light-emitting guest material is selected from singlet emitters (fluorescent emitters), triplet emitters (phosphorescent emitters) and organic thermally activated delayed fluorescence materials (TADF materials). For example, various organic functional materials are described in detail in WO2010135519A1, US20090134784A1 and WO 2011110277A1, and the entire contents of these three patent documents are hereby incorporated herein by reference. The organic functional material can be a small molecule or a polymer material.

[0110] In a specific example, another organic functional material is selected from a light-emitting host material; further, another organic functional material is selected from a blue light-emitting host material. The weight percentage content of the organic compound according to the present invention in the mixture is greater than 0 and less than or equal to 25 wt%, preferably greater than 0 and less than or equal to 15 wt%, and more preferably greater than 0 and less than or equal to 5 wt%.

[0111] The present invention also provides a composition, which comprises the above-mentioned organic compound or the above-mentioned mixture and at least one organic solvent.

[0112] The composition can also be an ink. When used in a printing process, the viscosity and surface tension of the ink are important parameters. The surface tension parameters of a suitable ink are suitable for a specific substrate and a specific printing method. That is, the properties of the ink need to be adapted and matched with the substrate and the printing method.

[0113] In a preferred example, the surface tension of the ink according to the present invention at the working temperature or at 25 °C is about in the range of 19 dyne / cm to 50 dyne / cm; preferably in the range of 22 dyne / cm to 35 dyne / cm; more preferably in the range of 25 dyne / cm to 33 dyne / cm. The composition ink with a surface tension within this range can be preferably used for inkjet printing.

[0114] In another preferred example, the viscosity of the ink according to the present invention at the working temperature or 25 °C is about in the range of 1 cps to 100 cps; preferably in the range of 1 cps to 50 cps; more preferably in the range of 1.5 cps to 20 cps or in the range of 4.0 cps to 20 cps. The composition ink with the above viscosity can be preferably used for inkjet printing.

[0115] Among them, the viscosity can be adjusted by different methods, such as by selecting a suitable solvent and adjusting the concentration of functional materials in the ink, etc. In the composition of the present invention, the weight ratio of the organic compound or mixture of the present invention in the composition ranges from 0.3% to 30 wt%, preferably from 0.5% to 20 wt%, more preferably from 0.5% to 15 wt%, even more preferably from 0.5% to 10 wt%, and most preferably from 1% to 5 wt%.

[0116] In the composition of the present invention, the at least one organic solvent can be selected from aromatic or heteroaromatic, esters, aromatic ketones or aromatic ethers, aliphatic ketones or aliphatic ethers, cycloaliphatic or olefinic compounds, borate or phosphate compounds. That is, the solvent contained in the composition of the present invention can be any one of the above organic solvents, or a mixed solvent of two or more of them. In a preferred embodiment, the at least one organic solvent contained in the composition of the present invention is selected from aromatic or heteroaromatic solvents.

[0117] Specifically, the aromatic or heteroaromatic-based solvents include but are not limited to: p-diisopropylbenzene, pentylbenzene, tetralin, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylcumene, dipentylbenzene, tripentylbenzene, amyltoluene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylcumene, 1-methylnaphthalene, 1,2,4-trichlorobenzene, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, quinoline, isoquinoline, methyl 2-furoate, ethyl 2-furoate, etc.

[0118] The ester-based solvents include but are not limited to: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkanolactones, alkyl oleates, etc. Octyl octanoate, diethyl sebacate, diallyl phthalate, isononyl isononanoate, etc. are particularly preferred.

[0119] The aromatic ketone-based solvents include but are not limited to: 1-tetralone, 2-tetralone, 2-(phenyl epoxy)tetralone, 6-(methoxy)tetralone, acetophenone, propiophenone, or benzophenone and its derivatives; such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, etc.

[0120] Aromatic ether-based solvents include but are not limited to: 3-phenoxytoluene, butoxybenzene, anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxytoluene, 4-ethylbenzyl ether, 1,3-dipropoxybenzene, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-tert-butylanisole, trans-p-anisylpropene, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, etc.

[0121] Aliphatic ketone-based solvents include but are not limited to: 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, 2,6,8-trimethyl-4-nonanone, fenchone, phorone, isophorone, di-n-amyl ketone, etc.; aliphatic ether-based solvents include but are not limited to: pentyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, etc.

[0122] It can be understood that the solvent can be used alone or as a mixture of two or more organic solvents.

[0123] In some embodiments, the composition of the present invention comprises at least one organic compound or mixture as described above, and at least one organic solvent, and may further comprise another organic solvent.

[0124] Another organic solvent includes but is not limited to at least one of methanol, ethanol, 2-methoxyethanol, dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetralin, decalin, indene.

[0125] In some preferred embodiments, the organic solvent suitable for the present invention is a solvent with a Hansen solubility parameter in the following range:

[0126] δd (dispersion force) is in the range of 17.0 - 23.2 MPa 1 / 2 and especially in the range of 18.5 - 21.0 MPa1 / 2 within the range;

[0127] δp (polar force) is within 0.2 - 12.5 MPa 1 / 2 within the range, especially within 2.0 - 6.0 MPa 1 / 2 within the range;

[0128] δh (hydrogen bond force) is within 0.9 - 14.2 MPa 1 / 2 within the range, especially within 2.0 - 6.0 MPa 1 / 2 within the range.

[0129] In some embodiments, for the composition according to the present invention, the boiling point needs to be considered when selecting the organic solvent. In at least some embodiments, the boiling point of the organic solvent ≥ 150 °C; preferably ≥ 180 °C; more preferably ≥ 200 °C; even more preferably ≥ 250 °C; most preferably ≥ 300 °C. The boiling points within these ranges are beneficial for preventing nozzle clogging of the inkjet print head.

[0130] It can be understood that the organic solvent can evaporate from the composition system to form a thin film containing the organic compound of the present invention.

[0131] In some embodiments, the composition is a solution. In other embodiments, the composition is a suspension.

[0132] The present invention also relates to the use of the composition as a coating or printing ink in the preparation of organic electronic devices. In some embodiments, the composition is used to prepare organic electronic devices by a preparation method of printing or coating. The preparation method of printing or coating can be, but is not limited to, inkjet printing, nozzle printing, letterpress printing, screen printing, intaglio printing, dip coating, spin coating, blade coating, roller printing, reverse roller printing, lithographic printing, flexographic printing, rotary printing, spraying, brush coating, pad printing, slot die coating, etc. Preferred are intaglio printing, nozzle printing and inkjet printing.

[0133] The solution or suspension may further include additives for adjusting viscosity, adjusting film-forming properties, improving adhesion, etc. The additives can be selected from at least one of, but not limited to, surface active compounds, lubricants, wetting agents, dispersants, water repellents and adhesives. Different printing or coating methods may have different requirements for the coating or printing ink, and the concentration, viscosity, etc. of the solution or suspension can be adjusted accordingly to adapt to different printing or coating methods.

[0134] The present invention also provides an application of the above-mentioned organic compound, mixture or composition in an organic electronic device. The technical solution is as follows:

[0135] An organic electronic device comprising the organic compound or mixture as described above, or prepared from the composition.

[0136] The present invention relates to an organic electronic device, the organic electronic device comprising: a cathode, an anode, and at least one functional layer located between the cathode and the anode, the at least one functional layer comprising the organic compound or mixture as described above or prepared from the above composition.

[0137] The organic electronic device may be, but is not limited to, an organic light-emitting diode (OLED device), an organic photovoltaic cell (OPV), an organic light-emitting cell (OLEEC), an organic field-effect transistor (OFET), an organic light-emitting field-effect transistor, an organic laser, an organic spintronic device, an organic sensor, and an organic plasmon emitting diode, etc. The organic electronic device is preferably an organic electroluminescent device, such as an OLED, an OLEEC, or an organic light-emitting field-effect transistor.

[0138] The functional layer is selected from a hole injection layer (HIL), a hole transport layer (HTL), a light-emitting layer (EML), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL). Preferably, the at least one functional layer includes a light-emitting layer.

[0139] In a specific embodiment, the organic electronic device includes an anode, a light-emitting layer, and a cathode stacked in sequence. The material of the light-emitting layer comprises the organic compound, mixture as described above, or prepared from the above composition.

[0140] Furthermore, the material of the light-emitting layer includes a light-emitting host material and a light-emitting guest material, the light-emitting guest material being the organic compound, mixture as described above, and the light-emitting host material may be a host material known in the art for the light-emitting layer.

[0141] In one embodiment, the light-emitting host material is selected from anthracene-based organic compounds. The weight percentage of the light-emitting host material in the light-emitting layer is greater than or equal to 75 wt%, preferably greater than or equal to 85 wt%, and more preferably greater than or equal to 95 wt%.

[0142] Further, the organic electronic device further includes a substrate. The substrate may be located on a side of the anode away from the light-emitting layer, or may be located on a side of the cathode away from the light-emitting layer. The substrate may be opaque or transparent. It can be understood that when the substrate is transparent, the organic electronic device is a transparent light-emitting device. For example, see Bulovic et al., Nature 1996, 380, p29, and Gu et al., Appl. Phys. Lett. 1996, 68, p2606. The substrate may also be rigid or flexible. For example, the material of the substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface, and a substrate without surface defects is a particularly ideal choice. In a preferred embodiment, the substrate is a flexible substrate. The material of the flexible substrate may be a polymer film or plastic. The glass transition temperature Tg of the flexible substrate is above 150 °C, preferably above 200 °C, more preferably above 250 °C, and most preferably above 300 °C. As an example, the material of the flexible substrate may be poly(ethylene terephthalate) (PET) or poly(ethylene 2,6-naphthalate) (PEN).

[0143] Among them, the material of the anode may be an anode material known in the art for organic electronic devices, such as a conductive metal, a conductive metal oxide or a conductive polymer. In some embodiments, the absolute value of the difference between the work function of the material of the anode and the HOMO energy level or valence band energy level of the light-emitting body in the light-emitting layer or the p-type semiconductor material serving as a hole injection layer, a hole transport layer or an electron blocking layer is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. As an example, the material of the anode may be selected from, but not limited to, at least one of Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO and aluminum-doped zinc oxide (AZO). Other suitable anode materials are known, and those of ordinary skill in the art can easily select and use them. The anode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), etc. In certain embodiments, the anode is pattern-structured. Patterned ITO conductive substrates are commercially available and can be used to fabricate the devices according to the present invention.

[0144] The material of the cathode can be a cathode material known in the art for use in organic electronic devices, such as a conductive metal or a conductive metal oxide. In some embodiments, the absolute value of the difference between the work function of the material of the cathode and the LUMO energy level or the conduction band energy level of the lumophore in the light-emitting layer or the n-type semiconductor material serving as an electron injection layer, an electron transport layer, or a hole blocking layer is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. In principle, all materials that can be used as the cathode of an OLED may be used as the cathode material of the device of the present invention. By way of example, the material of the cathode may be selected from, but not limited to, at least one of Al, Au, Ag, Ca, Ba, Mg, LiF / Al, MgAg alloy, BaF2 / Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, and ITO. The cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), etc.

[0145] Furthermore, the organic electronic device may further include other functional layers, such as a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL). Materials suitable for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1, and WO2011110277A1, and the entire contents of these three patent documents are hereby incorporated herein by reference.

[0146] The organic electronic device according to the present invention includes a light-emitting layer having a light-emitting wavelength between 300 and 1000 nm, preferably between 350 and 900 nm, and more preferably between 400 and 800 nm.

[0147] In at least one preferred embodiment, the organic electronic device is an OLED device.

[0148] The present invention also relates to an electronic device including the organic electronic device. The present invention relates to the application of an electroluminescent device in various electronic devices. The electronic device may be, but not limited to, a display device, a lighting device, a light source, and a sensor, etc. Specific Embodiments

[0150] The present invention is specifically described below through specific examples. The following examples are only partial examples of the present invention and are not intended to limit the present invention. The raw materials used in the following examples are all commercially available products unless otherwise specified. Among them, Toluene: toluene; K2CO3: potassium carbonate; P(t-Bu)3: tri-tert-butylphosphine; Pd(OAc)2: palladium acetate; t-butylbenzene: tert-butylbenzene; BBr3: boron tribromide; EtN(i-Pr)2: N,N-diisopropylethylamine; t-BuLi: tert-butyllithium; BuLi: n-butyllithium.

[0151] Example 1

[0152] The synthetic route of compound 1 in this example is as follows:

[0153]

[0154] Synthesis of intermediate 1-3: In a dry three-necked flask under nitrogen atmosphere, 20 mmol of intermediate 1-1 and 10 mmol of intermediate 1-2, 0.2 mmol of palladium acetate, 0.2 mmol of tri-tert-butylphosphine and 1.38 g of potassium carbonate were added, 150 ml of toluene was added to dissolve it, and the reaction solution was heated to 80°C until it refluxed, and reacted for 12 hours. After the reaction was complete, water was added to quench the reaction, and then it was extracted with dichloromethane for multiple times, the organic phases were combined, dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove the solvent to obtain a crude product, which was purified by rapid column chromatography to obtain intermediate 1-3, with a molar weight of 8.73 mmol and a yield of 87.3%. MS (ASAP) = 446.5.

[0155] Synthesis of intermediate 1-4: 10 mmol of intermediate 1-3 and 100 ml of dried tert-butylbenzene were added to a 250 ml three-necked flask, cooled to -30 degrees Celsius in a N2 atmosphere, and a n-hexane solution of t-BuLi (30.6 mmol) was added dropwise. The temperature was raised to 60 degrees Celsius for reaction for 2 hours, and the n-hexane solvent was removed by reduced pressure distillation. The reaction solution was cooled to -30 degrees Celsius again, 10.5 mmol of boron tribromide solution was added, and the mixture was stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 degrees Celsius, 21 mmol of N, N-diisopropylethylamine was added, and after the addition was complete, the mixture was heated to room temperature and stirred, and then the temperature was continued to be raised to 120 degrees Celsius and stirred for 3 hours, and the reaction solution was cooled to room temperature. Sodium carbonate aqueous solution and ethyl acetate were added to quench the reaction. The aqueous phase was extracted with ethyl acetate and the organic phase was combined, and the solvent was evaporated to obtain a crude product, which was purified by a rapid silica gel column to obtain a pure product. Recrystallization with toluene and ethyl acetate gave intermediate 1-4 with a molar weight of 7.83 mmol, a reaction yield of 78.3%, and MS (ASAP) = 420.3.

[0156] Synthesis of Intermediate 1-5: Under a nitrogen protection atmosphere, 10 mmol of Intermediate 1-4 and 5 mmol of liquid bromine were added to a dry three-necked flask. 150 ml of concentrated sulfuric acid was added to dissolve them. The mixture was heated to 80 °C until the reaction solution refluxed, and the reaction was carried out for 12 hours. After the reaction was complete, water was added to quench the reaction. The mixture was extracted with dichloromethane multiple times. The organic phases from multiple extractions were combined, dried over anhydrous magnesium sulfate, filtered, and the solvent was evaporated to dryness to obtain the crude product. The crude product was purified by flash column chromatography to obtain Intermediate 1-5 with a molar amount of 9.02 mmol and a yield of 90.2%. MS(ASAP) = 498.4.

[0157] Synthesis of Intermediate 1-7: A dry 500 mL three-necked flask was prepared, and the reaction device was set up to evacuate and then filled with nitrogen. Nitrogen was kept flowing in the reaction flask. 10 mmol of Intermediate 1-5 was weighed and added to THF (250 ml). The mixture was evacuated and filled with nitrogen three times, and then cooled to -78 °C. 20 mmol of a THF solution of n-butyllithium was slowly added dropwise to the reaction flask. After reacting at -78 °C for 30 min, 10 mmol of dimethoxydiphenylsilane (Intermediate 1-6) was quickly added. The reaction system was slowly warmed to room temperature and reacted for 12 h. Water was added, and the mixture was extracted with DCM. After the solvent was evaporated, the product was purified by column chromatography (the eluent was PE) to obtain Intermediate 1-7 with a molar amount of 5.89 mmol and a yield of 58.9%. MS(ASAP) = 632.4.

[0158] Synthesis of Intermediate 1-9: A dry 500 mL three-necked flask was prepared, and the reaction device was set up to evacuate and then filled with nitrogen. Nitrogen was kept flowing in the reaction flask. 10 mmol of 1,4-dibromobenzene (Intermediate 1-8) was weighed and added to THF (250 ml). The mixture was evacuated and filled with nitrogen three times, and then cooled to -78 °C. 2.4 mol / L of a THF solution of n-butyllithium (17.4 ml, 42.6 mmol) was slowly added dropwise to the reaction flask. After reacting at -78 °C for 30 min, 10 mmol of Intermediate 1-7 was quickly added. The reaction system was slowly warmed to room temperature and reacted for 12 h. Water was added, and the mixture was extracted with DCM. After the organic phase was evaporated to remove the solvent, the product was purified by column chromatography (the eluent was PE) to obtain Intermediate 1-9 with a molar amount of 7.11 mmol and a yield of 71.1%. MS(ASAP) = 756.4.

[0159] Synthesis of Compound 1: Under a nitrogen atmosphere, in a dry three-necked flask, 10 mmol of intermediate 1-9 and 10 mmol of intermediate 1-10 were dissolved in a mixed solvent of 1,4-dioxane and water (21 ml / 2 ml), and Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol) were added. Under a nitrogen atmosphere, the reaction was stirred at 100 °C for 6 h. After cooling, most of the solvent was removed by rotary evaporation, and then extracted, washed with water and separated by liquid separation. The organic phase was collected, dried, and purified by column chromatography (eluent: PE) to obtain a yellowish-green solid with a yield of 31.5%. MS(ASAP)=919.5.

[0160] Example 2

[0161] The synthesis route of Compound 2 in this example is as follows:

[0162]

[0163] Synthesis of intermediate 2-3: Weigh 10 mmol of intermediate 2-1, 10 mmol of intermediate 2-2, 0.16 mmol of Pd2(dba)3 0.16 mmol, 0.194 mmol of t-Bu3P, and 16.2 mmol of sodium tert-butoxide, and add them to a 500 ml three-necked flask respectively. Add 200 ml of toluene, displace nitrogen, and react at 80 °C for 12 h. The reaction solution was concentrated to dryness, washed with water, and purified by column chromatography (eluent: PE) to obtain intermediate 2-3 with a molar amount of 8.71 mmol and a yield of 87.1%. MS(ASAP)=259.1.

[0164] Synthesis of intermediate 2-4: Add 10 mmol of intermediate 2-3 to a 500 ml two-necked flask, and add 200 ml of DMF until all the solids are dissolved; weigh 10 mmol of NBS and dissolve it in 100 ml of DMF, and slowly add it dropwise to the two-necked flask and react at room temperature for 12 h. The reaction solution was concentrated to dryness, washed with water, and purified by column chromatography (eluent: PE) to obtain intermediate 2-4 with a molar amount of 8.13 mmol and a yield of 81.3%. MS(ASAP)=337.0.

[0165] Synthesis of intermediate 2-5: Weigh 10 mmol of intermediate 2-4, 15 mmol of (Bpin)2, 100 mmol of AcOK, 1.0 mmol of Pd(dppf)Cl2, and 1.94 mmol of t-Bu3P into a 250 mL three-necked flask, add 100 ml of 1,4-dioxane, displace nitrogen and react at 100 °C for 12 h. Concentrate to dryness, wash with water, and purify by column chromatography (eluent: PE:DCM = 5:1) to obtain intermediate 2-5 with a molar amount of 6.59 mmol and a yield of 65.9%. MS(ASAP)=385.4.

[0166] Synthesis of Compound 2: Under a nitrogen atmosphere, in a dry three-necked flask, 10 mmol of Intermediate 1-9 and 10 mmol of Intermediate 2-5 were dissolved in a mixed solvent of 1,4-dioxane and water (21 ml / 2 ml). Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol) were added. Under a nitrogen atmosphere, the mixture was stirred at 100 °C for 6 h. After cooling, most of the solvent was removed by rotary evaporation, and then the mixture was extracted, washed with water, and separated by liquid-liquid extraction. The organic phase was collected, dried, and purified by column chromatography (eluent: PE) to obtain a yellow-green solid with a yield of 31.5%. MS (ASAP) = 935.6.

[0167] Example 3

[0168] The synthetic route of Compound 3 in this example is as follows:

[0169]

[0170] Synthesis of Intermediate 3-2: Weigh 10 mmol of Intermediate 2-1, 10 mmol of Intermediate 3-1, 0.16 mmol of Pd2(dba)3, 0.194 mmol of t-Bu3P, and 16.2 mmol of sodium tert-butoxide into a 500 ml three-necked flask. Add 200 ml of toluene, displace nitrogen, and react at 80 °C for 12 h. Rotate to dryness, wash with water, and purify by column chromatography (eluent: PE) to obtain Intermediate 3-2 with a molar amount of 8.55 mmol and a yield of 85.5%. MS (ASAP) = 275.3.

[0171] Synthesis of Intermediate 3-3: Add 10 mmol of Intermediate 3-2 to a 500 ml two-necked flask and add 200 ml of DMF until all the solids are dissolved. Weigh 10 mmol of NBS and dissolve it in 100 ml of DMF. Slowly add it dropwise to the two-necked flask and react at room temperature for 12 h. Rotate to dryness, wash with water, and purify by column chromatography (eluent: PE) to obtain Intermediate 3-3 with a molar amount of 7.56 mmol and a yield of 75.6%. MS (ASAP) = 353.3.

[0172] Synthesis of Intermediate 3-4: Weigh 10 mmol of Intermediate 3-3, 15 mmol of (Bpin)2, 100 mmol of AcOK, 1.0 mmol of Pd(dppf)Cl2, and 1.94 mmol of t-Bu3P into a 250 mL three-necked flask. Add 100 ml of 1,4-dioxane, displace nitrogen, and react at 100 °C for 12 h. Rotate to dryness, wash with water, and purify by column chromatography (eluent: PE:DCM = 5:1) to obtain Intermediate 3-4 with a molar amount of 7.22 mmol and a yield of 72.2%. MS (ASAP) = 401.6.

[0173] Synthesis of Compound 3: Under a nitrogen atmosphere, in a dry three-necked flask, 10 mmol of intermediate 1-9 and 10 mmol of intermediate 3-4 were dissolved in a mixed solvent of 1,4-dioxane and water (21 ml / 2 ml), and Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol) were added. Under a nitrogen atmosphere, the mixture was stirred at 100 °C for 6 h. After cooling, most of the solvent was removed by rotary evaporation, and then extraction and washing with water were carried out for liquid separation. The organic phase was collected, dried, and purified by column chromatography (eluent: PE) to obtain a yellow-green solid with a yield of 55.6%. MS (ASAP) = 951.5.

[0174] Example 4

[0175] The synthetic route of Compound 4 in this example is as follows:

[0176]

[0177] Synthesis of intermediate 4-2: Weigh 10 mmol of intermediate 2-1, 10 mmol of intermediate 4-1, 0.16 mmol of Pd2(dba)3, 0.194 mmol of t-Bu3P, and 16.2 mmol of sodium tert-butoxide into a 500 ml three-necked flask, add 200 ml of toluene, displace nitrogen, and react at 80 °C for 12 h. Rotary evaporate to dryness, wash with water, and purify by column chromatography (eluent: PE) to obtain intermediate 4-2 with a molar amount of 7.39 mmol and a yield of 73.9%. MS (ASAP) = 334.3.

[0178] Synthesis of intermediate 4-3: Place 10 mmol of intermediate 4-2 in a 500 ml two-necked flask, add 200 ml of DMF until the solid is completely dissolved. Weigh 10 mmol of NBS and dissolve it in 100 ml of DMF, and slowly add it dropwise to the two-necked flask and react at room temperature for 12 h. Rotary evaporate to dryness, wash with water, and purify by column chromatography (eluent: PE) to obtain intermediate 4-3 with a molar amount of 6.57 mmol and a yield of 65.7%. MS (ASAP) = 412.5.

[0179] Synthesis of intermediate 4-4: Weigh 10 mmol of intermediate 4-3, 15 mmol of (Bpin)2, 100 mmol of AcOK, 1.0 mmol of Pd(dppf)Cl2, and 1.94 mmol of t-Bu3P into a 250 mL three-necked flask, add 100 ml of 1,4-dioxane, displace nitrogen, and react at 100 °C for 12 h. Rotary evaporate to dryness, wash with water, and purify by column chromatography (eluent: PE:DCM = 5:1) to obtain intermediate 4-4 with a molar amount of 8.35 mmol and a yield of 83.5%. MS (ASAP) = 460.4.

[0180] Synthesis of compound 4: Under nitrogen atmosphere, in a dry three-necked flask, 10 mmol of intermediate 1-9 and 10 mmol of intermediate 4-4 were dissolved in a mixed solvent of 1,4-dioxane and water (21 ml / 2 ml), and Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol) were added. Stir at 100°C for 6 h under nitrogen atmosphere. After cooling, most of the solvent was removed by rotary evaporation, and then the liquid was extracted and washed with water. The organic phase was collected, dried, and purified by column chromatography (eluent: PE) to obtain a yellow-green solid with a yield of 60.4%. MS (ASAP) = 1010.6.

[0181] Example 5

[0182] The synthetic route of compound 5 in this example is as follows:

[0183]

[0184] Synthesis of intermediate 5-3: In a dry three-necked flask under nitrogen atmosphere, 20 mmol of intermediate 5-1 and 10 mmol of intermediate 5-2, 0.2 mmol of palladium acetate, 0.2 mmol of tri-tert-butylphosphine, and 1.38 g of potassium carbonate were added, and 150 ml of toluene was added to dissolve it, and the reaction solution was heated to 80°C until it refluxed, and reacted for 12 hours. When the reaction was complete, water was added to quench the reaction, and the organic phase was extracted with dichloromethane at the same time. The organic phases were washed several times, dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove the solvent to obtain a crude product, which was purified by flash column chromatography to obtain intermediate 5-3, with a molar weight of 7.57 mmol and a yield of 75.7%. MS (ASAP) = 608.3.

[0185] Synthesis of intermediate 5-4: 10 mmol of intermediate 5-3 and 100 ml of dried tert-butylbenzene were added to a 250 ml three-necked flask, cooled to -30 degrees Celsius in a N2 atmosphere, and (10 mmol) of n-BuLi n-hexane solution was added dropwise. The temperature was raised to 60 degrees Celsius for reaction for 2 hours, and the solvent n-hexane was removed by reduced pressure distillation. The reaction solution was cooled to -30 degrees Celsius again, 10.5 mmol of boron tribromide solution was added, and the mixture was stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 degrees Celsius, 21 mmol of N, N-diisopropylethylamine was added, and after the addition was complete, the mixture was heated to room temperature and stirred, and then the temperature was continued to be raised to 120 degrees Celsius and stirred for 3 hours, and the reaction solution was cooled to room temperature. Sodium carbonate aqueous solution and ethyl acetate were added to quench the reaction. The aqueous phase was extracted with ethyl acetate and the organic phase was combined, and the solvent was evaporated to obtain a crude product, which was purified by rapid silica gel column. Recrystallization with toluene and ethyl acetate gave intermediate 5-4 with a molar weight of 7.22 mmol. The reaction yield was 72.2%, and MS (ASAP) = 538.4.

[0186] Synthesis of Intermediate 5-6: Under a nitrogen protection atmosphere, in a dry three-necked flask, 10 mmol of Intermediate 5-4 and 10 mmol of Intermediate 5-5 were respectively added and dissolved in a mixed solvent of 1,4-dioxane and water (21 ml / 2 ml). Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol) were also added. Under a nitrogen atmosphere, it was stirred at 100 °C for 6 h. After cooling, most of the solvent was removed by rotary evaporation, and then it was extracted, washed with water, and separated by liquid separation. The organic phase was collected. After drying, concentration under reduced pressure, column chromatography purification, and recrystallization, Intermediate 5-6 was obtained, with a molar amount of 6.91 mmol and a yield of 69.1%. MS (ASAP) = 614.4.

[0187] Synthesis of Intermediate 5-7: Prepare a dry 500 mL three-necked flask, set up the reaction device, evacuate, and introduce nitrogen; keep the nitrogen flowing in the reaction flask, weigh 10 mmol of Intermediate 5-6, and add THF (250 ml). Evacuate and introduce nitrogen in a cycle three times, and cool down to -78 °C; slowly drip 20 mmol of n-butyllithium THF solution into the reaction flask. After reacting at -78 °C for 30 min, quickly add 10 mmol of dimethoxydiphenylsilane (Intermediate 1-6). Let the reaction system slowly rise to room temperature and react for 12 h. Add water, extract with DCM, and after drying the solvent by rotary evaporation, purify it by column chromatography (the eluent is PE) to obtain Intermediate 5-7, with a molar amount of 6.22 mmol and a yield of 62.2%. MS (ASAP) = 792.3.

[0188] Synthesis of Intermediate 5-8: Prepare a dry 500 mL three-necked flask, set up the reaction device, evacuate, and introduce nitrogen; keep the nitrogen flowing in the reaction flask, weigh 10 mmol of 1,4-dibromobenzene (Intermediate 1-8), and add THF (250 ml). Evacuate and introduce nitrogen in a cycle three times, and cool down to -78 °C; slowly drip n-butyllithium solution (17.4 ml, 42.6 mmol, 2.4 mol / L THF solution) into the reaction flask. After reacting at -78 °C for 30 min, quickly add 10 mmol of Intermediate 5-7. Let the reaction system slowly rise to room temperature and react for 12 h. Add water, extract with DCM, and after drying the solvent by rotary evaporation, purify it by column chromatography (the eluent is PE) to obtain Intermediate 5-8, with a molar amount of 7.56 mmol and a yield of 75.6%. MS (ASAP) = 916.7.

[0189] Synthesis of Compound 5: Under a nitrogen protection atmosphere, in a dry three-necked flask, 10 mmol of intermediate 5-8 and 10 mmol of intermediate 3-4 were dissolved in a mixed solvent of 1,4-dioxane and water (21 ml / 2 ml), and Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol) were added. Under a nitrogen atmosphere, it was stirred at 100 °C for 6 h. After cooling, most of the solvent was removed by rotary evaporation, and then it was extracted, washed with water and separated by liquid separation. The organic phase was collected, dried, and purified by column chromatography (the eluent was PE) to obtain a yellow-green solid with a yield of 70.9%. MS(ASAP) = 1111.7.

[0190] Example 6

[0191] The synthetic route of Compound 6 in this example is as follows:

[0192]

[0193] Synthesis of Compound 6: Under a nitrogen protection atmosphere, in a dry three-necked flask, 10 mmol of intermediate 5-8 and 10 mmol of intermediate 4-4 were dissolved in a mixed solvent of 1,4-dioxane and water (21 ml / 2 ml), and Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol) were added. Under a nitrogen atmosphere, it was stirred at 100 °C for 6 h. After cooling, most of the solvent was removed by rotary evaporation, and then it was extracted, washed with water and separated by liquid separation. The organic phase was collected, dried, and purified by column chromatography (the eluent was PE) to obtain a yellow-green solid with a yield of 72.5%. MS(ASAP) = 1170.8.

[0194] Example 7

[0195] The synthetic route of 7 in this example is as follows:

[0196]

[0197] Synthesis of Intermediate 7-2: Weighed 20 mmol of intermediate 2-1, 10 mmol of intermediate 7-1, 0.16 mmol of Pd2(dba)3, 0.194 mmol of t-Bu3P, and 16.2 mmol of sodium tert-butoxide into a three-necked flask, added 200 ml of toluene, displaced nitrogen, and reacted at 80 °C for 12 h. It was rotary evaporated to dryness, washed with water, and purified by column chromatography (the eluent was PE) to obtain intermediate 7-2 with a molar amount of 8.27 mmol and a yield of 82.7%. MS(ASAP) = 409.5.

[0198] Synthesis of Intermediate 7-3: Add 10 mmol of Intermediate 7-2 to a 500-ml two-necked flask, add 200 ml of DMF until all the solids are dissolved. Weigh 10 mmol of NBS and dissolve it in 100 ml of DMF, then slowly add it dropwise to the two-necked flask and react at room temperature for 12 h. Rotavap to dryness, wash with water, and purify by column chromatography (eluent: PE) to obtain Intermediate 7-3 with a molar amount of 7.11 mmol and a yield of 71.1%. MS (ASAP) = 487.3.

[0199] Synthesis of Intermediate 7-4: Weigh 10 mmol of Intermediate 7-3, 15 mmol of (Bpin)2, 100 mmol of AcOK, 1.0 mmol of Pd(dppf)Cl2, and 1.94 mmol of t-Bu3P into a 250-mL three-necked flask, add 100 ml of 1,4-dioxane, displace nitrogen, and react at 100 °C for 12 h. Rotavap to dryness, wash with water, and purify by column chromatography (eluent: PE:DCM = 5:1) to obtain Intermediate 7-4 with a molar amount of 6.59 mmol and a yield of 65.9%. MS (ASAP) = 535.1.

[0200] Synthesis of Compound 7: Under a nitrogen protection atmosphere, in a dry three-necked flask, dissolve 10 mmol of Intermediate 5-8 and 10 mmol of Intermediate 7-4 in a mixed solvent of 1,4-dioxane and water (21 ml / 2 ml), and add Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol). Stir and react at 100 °C for 6 h under a nitrogen atmosphere. After cooling, rotavap to remove most of the solvent, then extract, wash, and separate the liquid phases, collect the organic phase, dry it, and purify by column chromatography (eluent: PE) to obtain a yellow-green solid with a yield of 82.6%. MS (ASAP) = 1245.7.

[0201] Example 8

[0202] The synthetic route of Compound 8 in this example is as follows:

[0203]

[0204] Synthesis of Intermediate 8-2: Weigh 20 mmol of methyl iodide, 10 mmol of Intermediate 8-1, 0.16 mmol of Pd2(dba)3, 0.194 mmol of t-Bu3P, and 16.2 mmol of sodium tert-butoxide into a three-necked flask, add 200 ml of toluene, displace nitrogen, and react at 80 °C for 12 h. Rotavap the reaction solution to dryness, wash with water, and purify by column chromatography (eluent: PE) to obtain Intermediate 8-2 with a molar amount of 7.69 mmol and a yield of 76.9%. MS (ASAP) = 285.7.

[0205] Synthesis of Intermediate 8-3: Add 10 mmol of Intermediate 8-2 into a 500-ml two-necked flask, and add 200 ml of DMF until all the solids are dissolved. Weigh 10 mmol of NBS and dissolve it in 100 ml of DMF, then slowly add it dropwise to the two-necked flask and react at room temperature for 12 h. Rotate the reaction solution to dryness, wash it with water, and purify it by column chromatography (the eluent is PE) to obtain Intermediate 8-3 with a molar amount of 8.41 mmol and a yield of 84.1%. MS (ASAP) = 363.2.

[0206] Synthesis of Intermediate 8-4: Weigh 10 mmol of Intermediate 8-3, 15 mmol of (Bpin)2, 100 mmol of AcOK, 1.0 mmol of Pd(dppf)Cl2, and 1.94 mmol of t-Bu3P into a 250-mL three-necked flask, add 100 ml of 1,4-dioxane, displace nitrogen, and react at 100 °C for 12 h. Rotate to dryness, wash with water, and purify by column chromatography (the eluent is PE:DCM = 5:1) to obtain Intermediate 8-4 with a molar amount of 7.71 mmol and a yield of 77.1%. MS (ASAP) = 411.5.

[0207] Synthesis of Compound 8: Under a nitrogen protection atmosphere, in a dry three-necked flask, dissolve 10 mmol of Intermediate 5-8 and 10 mmol of Intermediate 8-4 in a mixed solvent of 1,4-dioxane and water (21 ml / 2 ml), and add Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol). Stir at 100 °C for 6 h under a nitrogen atmosphere. After cooling, rotate to evaporate most of the solvent, then extract, wash, and separate the liquid, collect the organic phase, dry it, and purify it by column chromatography (the eluent is PE) to obtain a yellow-green solid with a yield of 80.5%. MS (ASAP) = 1121.3.

[0208] Example 9

[0209] The synthetic route of Compound 9 in this example is as follows:

[0210]

[0211] Synthesis of intermediate 9-3: In a dry three-necked flask under nitrogen atmosphere, 10 mmol of intermediate 9-1 and 10 mmol of intermediate 9-2, 0.2 mmol of palladium acetate, 0.2 mmol of tri-tert-butylphosphine, and 1.38 g of potassium carbonate were added, and 150 ml of toluene was added to dissolve it, and the reaction solution was heated to 80°C until it refluxed, and reacted for 12 hours. When the reaction was complete, water was added to quench the reaction, and the organic phase was extracted with dichloromethane. The organic phases were washed several times, dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove the solvent to obtain a crude product, which was purified by rapid column chromatography to obtain intermediate 9-3, with a molar weight of 7.25 mmol and a yield of 72.5%. MS (ASAP) = 209.4.

[0212] Synthesis of intermediate 9-4: In a dry three-necked flask under nitrogen atmosphere, 10 mmol of intermediate 9-3 and 10 mmol of intermediate 1-2, 0.2 mmol of palladium acetate, 0.2 mmol of tri-tert-butylphosphine, and 1.38 g of potassium carbonate were added, and 150 ml of toluene was added to dissolve it, and the reaction solution was heated to 80°C until it refluxed, and reacted for 12 hours. When the reaction was complete, water was added to quench the reaction, and the organic phase was extracted with dichloromethane at the same time. The organic phases were washed several times, dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove the solvent to obtain a crude product, which was purified by flash column chromatography to obtain intermediate 9-4, with a molar weight of 8.11 mmol and a yield of 81.1%. MS (ASAP) = 353.5.

[0213] Synthesis of intermediate 9-5: In a dry three-necked flask under nitrogen atmosphere, 10 mmol of intermediate 9-4 and 10 mmol of intermediate 1-1, 0.2 mmol of palladium acetate, 0.2 mmol of tri-tert-butylphosphine, and 1.38 g of potassium carbonate were added, and 150 ml of toluene was added to dissolve it, and the reaction solution was heated to 80°C until it refluxed, and reacted for 12 hours. When the reaction was complete, water was added to quench the reaction, and the organic phase was extracted with dichloromethane at the same time. The organic phases were washed several times, dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove the solvent to obtain a crude product, which was purified by flash column chromatography to obtain intermediate 9-5, with a molar weight of 7.68 mmol and a yield of 76.8%. MS (ASAP) = 486.3.

[0214] Synthesis of Intermediate 9-6: Add 10 mmol of Intermediate 9-5 and 100 ml of dry tert-butylbenzene into a 250-ml three-necked flask. Under a nitrogen atmosphere, cool it to -30 °C and gradually add a n-hexane solution of t-BuLi (30.6 mmol). Raise the temperature to 60 °C and react for 2 hours. Distill off the n-hexane solvent under reduced pressure. Cool the reaction solution to -30 °C again, add 10.5 mmol of boron tribromide solution, stir at room temperature for 0.5 hour, then cool the reaction solution to 0 °C, add 21 mmol of N,N-diisopropylethylamine. After the addition is complete, raise the temperature to room temperature and stir, then continue to raise the temperature to 120 °C and stir for 3 hours. Cool the reaction solution to room temperature. Quench the reaction by adding an aqueous sodium carbonate solution and ethyl acetate. Extract the aqueous phase with ethyl acetate and combine the organic phases. Rotavaporize to remove the solvent to obtain a crude product, and purify it by flash silica gel column to obtain a pure product. Recrystallize with toluene and ethyl acetate to obtain Intermediate 9-6 with a molar amount of 5.37 mmol and a reaction yield of 53.7%. MS (ASAP) = 460.4.

[0215] Synthesis of Intermediate 9-7: Under a nitrogen protection atmosphere, add 10 mmol of Intermediate 9-6 and 5 mmol of liquid bromine into a dry three-necked flask. Add 150 ml of concentrated sulfuric acid to dissolve it, heat to 80 °C until the reaction solution refluxes, and react for 12 hours. After the reaction is complete, quench the reaction by adding water, and at the same time extract the organic phase with dichloromethane. Combine and wash the organic phase several times, dry it with anhydrous magnesium sulfate, filter, and rotavaporize to dry the solvent to obtain a crude product. Purify it by flash column chromatography to obtain Intermediate 9-7 with a molar amount of 8.15 mmol and a yield of 81.5%. MS (ASAP) = 538.8.

[0216] Synthesis of Intermediate 9-9: Prepare a dry 500-mL three-necked flask, set up the reaction device, evacuate, and introduce nitrogen; keep the nitrogen flowing in the reaction flask, weigh 10 mmol of Intermediate 9-7, and add THF (250 ml). Evacuate and introduce nitrogen three times in a cycle, and cool to -78 °C; slowly drip 20 mmol of a n-butyllithium THF solution into the reaction flask. After reacting at -78 °C for 30 min, quickly add 10 mmol of Intermediate 9-8. Let the reaction system slowly rise to room temperature and react for 12 h. Add water, extract with DCM, and after rotary evaporation of the solvent, purify by column chromatography (eluent: PE) to obtain Intermediate 9-9 with a molar amount of 5.89 mmol and a yield of 58.9%. MS (ASAP) = 700.3.

[0217] Synthesis of intermediate 9-10: Prepare a dry 500mL three-necked flask, set up the reaction device, evacuate and pass nitrogen; keep nitrogen flowing in the reaction flask, weigh 10mmol of 1,4-dibromobenzene (intermediate 1-8), add THF (250ml), evacuate and pass nitrogen for three cycles, and cool to -78°C; slowly drop n-butyl lithium solution (17.4ml, 42.6mmol, 2.4mol / LTHF solution) into the reaction flask, react at -78°C for 30min, and quickly add 10mmol of intermediate 9-9. Let the reaction system slowly rise to room temperature and react for 12h. Add water, extract with DCM, spin dry the solvent, and purify by column chromatography (eluent is PE) to obtain intermediate 9-10, with a molar weight of 7.22mmol and a yield of 72.2%. MS (ASAP) = 824.3.

[0218] Synthesis of compound 9: In a dry three-necked flask under nitrogen atmosphere, 10 mmol of intermediate 9-10 and 10 mmol of intermediate 7-4 were added to a mixed solvent of 1,4-dioxane and water (21 ml / 2 ml), and Pd(PPh3)4 (0.1) and potassium carbonate (30 mmol) were added. Stir at 100°C for 6 h under nitrogen atmosphere. After cooling, most of the solvent was removed by rotary evaporation, and then the liquid was extracted and washed with water. The organic phase was collected, dried, and purified by column chromatography (eluent: PE) to obtain a yellow-green solid with a yield of 53.5%. MS (ASAP) = 1153.7.

[0219] Example 10

[0220] The synthetic route of compound 10 in this example is as follows:

[0221]

[0222] Synthesis of intermediate 10-2: In a dry three-necked flask under nitrogen atmosphere, 10 mmol of intermediate 10-1 and 10 mmol of intermediate 9-2, 0.2 mmol of palladium acetate, 0.2 mmol of tri-tert-butylphosphine, and 1.38 g of potassium carbonate were added, and 150 ml of toluene was added to dissolve it, and the reaction solution was heated to 80°C until it refluxed, and reacted for 12 hours. When the reaction was complete, water was added to quench the reaction, and the organic phase was extracted with dichloromethane at the same time. The organic phases were washed several times, dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove the solvent to obtain a crude product, which was purified by rapid column chromatography to obtain intermediate 10-2 with a molar weight of 8.45 mmol and a yield of 84.5%. MS (ASAP) = 225.3.

[0223] Synthesis of intermediate 10-3: In a dry three-necked flask under nitrogen atmosphere, 10 mmol of intermediate 10-2 and 10 mmol of intermediate 1-2, 0.2 mmol of palladium acetate, 0.2 mmol of tri-tert-butylphosphine, and 1.38 g of potassium carbonate were added, and 150 ml of toluene was added to dissolve it, and the reaction solution was heated to 80°C until it refluxed, and reacted for 12 hours. When the reaction was complete, water was added to quench the reaction, and the organic phase was extracted with dichloromethane at the same time. The organic phases were washed several times, dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove the solvent to obtain a crude product, which was purified by flash column chromatography to obtain intermediate 10-3, with a molar weight of 7.54 mmol and a yield of 75.4%. MS (ASAP) = 369.7.

[0224] Synthesis of intermediate 10-4: In a dry three-necked flask under nitrogen atmosphere, 10 mmol of intermediate 10-3 and 10 mmol of intermediate 1-1, 0.2 mmol of palladium acetate, 0.2 mmol of tri-tert-butylphosphine, and 1.38 g of potassium carbonate were added, and 150 ml of toluene was added to dissolve it, and the reaction solution was heated to 80°C until it refluxed, and reacted for 12 hours. When the reaction was complete, water was added to quench the reaction, and the organic phase was extracted with dichloromethane at the same time. The organic phases were washed several times, dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove the solvent to obtain a crude product, which was purified by flash column chromatography to obtain intermediate 10-4, with a molar weight of 7.16 mmol and a yield of 71.6%. MS (ASAP) = 502.4.

[0225] Synthesis of intermediate 10-5: 10 mmol of intermediate 10-4 and 100 ml of dry tert-butylbenzene were added to a 250 ml three-necked flask, cooled to -30 degrees Celsius in a N2 atmosphere, and (30.6 mmol) of t-BuLi n-hexane solution was added dropwise. The temperature was raised to 60 degrees Celsius for reaction for 2 hours, and the n-hexane solvent was removed by reduced pressure distillation. The reaction solution was cooled to -30 degrees Celsius again, 10.5 mmol of boron tribromide solution was added, and the mixture was stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 degrees Celsius, 21 mmol of N, N-diisopropylethylamine was added, and after the addition was complete, the mixture was heated to room temperature and stirred, and then the temperature was continued to be raised to 120 degrees Celsius and stirred for 3 hours, and the reaction solution was cooled to room temperature. Sodium carbonate aqueous solution and ethyl acetate were added to quench the reaction. The aqueous phase was extracted with ethyl acetate and the organic phase was combined, and the solvent was evaporated to obtain a crude product, which was purified by a rapid silica gel column to obtain a pure product. Recrystallization with toluene and ethyl acetate gave intermediate 10-5 with a molar weight of 4.97 mmol and a reaction yield of 49.7%. MS (ASAP) = 476.3.

[0226] Synthesis of Intermediate 10-6: Under a nitrogen protection atmosphere, in a dry three-necked flask, 10 mmol of Intermediate 10-5 and 5 mmol of liquid bromine were respectively added, and 150 ml of concentrated sulfuric acid was added to dissolve them. The mixture was heated to 80 °C until the reaction solution refluxed, and the reaction was carried out for 12 hours. After the reaction was complete, water was added to quench the reaction, and it was extracted with dichloromethane multiple times. The organic phases extracted multiple times were combined, dried with anhydrous magnesium sulfate, filtered, and the solvent was rotary evaporated to obtain the crude product. The crude product was purified by flash column chromatography to obtain Intermediate 10-6 with a molar amount of 6.25 mmol and a yield of 62.5%. MS(ASAP)=554.3.

[0227] Synthesis of Intermediate 10-7: Prepare a dry 500 mL three-necked flask, set up the reaction device to evacuate and introduce nitrogen; keep the nitrogen flowing in the reaction flask, weigh 10 mmol of Intermediate 10-6, and add THF (250 ml). Evacuate and introduce nitrogen in a cycle three times, and cool down to -78 °C; slowly add 20 mmol of n-butyllithium THF solution dropwise to the reaction flask. After reacting at -78 °C for 30 min, quickly add 10 mmol of Intermediate 1-6. Let the reaction system slowly rise to room temperature and react for 12 h. Add water, extract with DCM, and after rotary evaporation of the solvent, purify by column chromatography (eluent: PE) to obtain Intermediate 10-7 with a molar amount of 5.13 mmol and a yield of 51.3%. MS(ASAP)=688.4.

[0228] Synthesis of Intermediate 10-8: Prepare a dry 500 mL three-necked flask, set up the reaction device to evacuate and introduce nitrogen; keep the nitrogen flowing in the reaction flask, weigh 10 mmol of 1,4-dibromobenzene (Intermediate 1-8), and add THF (250 ml). Evacuate and introduce nitrogen in a cycle three times, and cool down to -78 °C; slowly add n-butyllithium solution (17.4 ml, 42.6 mmol, 2.4 mol / L THF solution) dropwise to the reaction flask. After reacting at -78 °C for 30 min, quickly add 10 mmol of Intermediate 10-7. Let the reaction system slowly rise to room temperature and react for 12 h. Add water, extract with DCM, and after rotary evaporation of the solvent, purify by column chromatography (eluent: PE) to obtain Intermediate 10-8 with a molar amount of 5.75 mmol and a yield of 57.5%. MS(ASAP)=812.6.

[0229] Synthesis of compound 10: Under nitrogen atmosphere, in a dry three-necked flask, 10 mmol of intermediate 10-8 and 10 mmol of intermediate 7-4 were dissolved in a mixed solvent of 1,4-dioxane and water (21 ml / 2 ml), and Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol) were added. Stir at 100°C for 6 h under nitrogen atmosphere. After cooling, most of the solvent was removed by rotary evaporation, and then the liquid was extracted and washed with water. The organic phase was collected, dried, and purified by column chromatography (eluent: PE) to obtain a yellow-green solid with a yield of 80.6%. MS (ASAP) = 1141.7.

[0230] Embodiment 11

[0231] The synthetic route of compound 11 in this example is as follows:

[0232]

[0233] Synthesis of intermediate 11-1: In a dry three-necked flask under nitrogen atmosphere, 20 mmol of intermediate 10-2 and 10 mmol of intermediate 5-2, 0.2 mmol of palladium acetate, 0.2 mmol of tri-tert-butylphosphine, and 1.38 g of potassium carbonate were added, and 150 ml of toluene was added to dissolve it, and the reaction solution was heated to 80°C until it refluxed, and reacted for 12 hours. When the reaction was complete, water was added to quench the reaction, and the organic phase was extracted with dichloromethane at the same time. The organic phases were washed several times, dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove the solvent to obtain a crude product, which was purified by rapid column chromatography to obtain intermediate 11-1 with a molar weight of 7.85 mmol and a yield of 78.5%. MS (ASAP) = 636.3.

[0234] Synthesis of intermediate 11-2: 10 mmol of intermediate 11-1 and 100 ml of dry tert-butylbenzene were added to a 250 ml three-necked flask, cooled to -30 degrees Celsius in a N2 atmosphere, and (30.6 mmol) of n-BuLi n-hexane solution was added dropwise. The temperature was raised to 60 degrees Celsius for 2 hours, and the n-hexane solvent was evaporated under reduced pressure. The reaction solution was cooled to -30 degrees Celsius again, 10.5 mmol of boron tribromide solution was added, and the mixture was stirred at room temperature for 0.5 hours, then the reaction solution was cooled to 0 degrees Celsius, 21 mmol of N, N-diisopropylethylamine was added, and after the addition was complete, the mixture was heated to room temperature and stirred, and then the temperature was continued to be raised to 120 degrees Celsius and stirred for 3 hours, and the reaction solution was cooled to room temperature. Sodium carbonate aqueous solution and ethyl acetate were added to quench the reaction. The aqueous phase was extracted with ethyl acetate and the organic phase was combined, and the solvent was evaporated to obtain a crude product, which was purified by a rapid silica gel column to obtain a pure product. Recrystallization with toluene and ethyl acetate gave intermediate 11-2 with a molar weight of 5.33 mmol. The reaction yield was 53.3%, and MS (ASAP) = 566.3.

[0235] Synthesis of Intermediate 11-3: Under a nitrogen protection atmosphere, in a dry three-necked flask, 10 mmol of Intermediate 11-2 and 10 mmol of Intermediate 5-5 were respectively added and dissolved in a mixed solvent of 1,4-dioxane and water (21 ml / 2 ml), and Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol) were added. Under a nitrogen atmosphere, it was stirred at 100 °C for 6 h. After cooling, most of the solvent was removed by rotary evaporation, then extracted and washed with water for liquid separation, and the organic phase was collected. After drying and purification by column chromatography (the eluent was PE), the molar amount of Intermediate 11-3 obtained was 5.45 mmol, and the yield was 54.5%. MS(ASAP)=642.3.

[0236] Synthesis of Intermediate 11-4: Prepare a dry 500 mL three-necked flask, set up the reaction device to evacuate and introduce nitrogen; keep the nitrogen flowing in the reaction flask, weigh 10 mmol of Intermediate 11-3, and add THF (250 ml), evacuate and introduce nitrogen for three cycles, and cool down to -78 °C; slowly add 20 mmol of n-butyllithium THF solution dropwise to the reaction flask. After reacting at -78 °C for 30 min, quickly add 10 mmol of Intermediate 1-6. Let the reaction system slowly rise to room temperature and react for 12 h. Add water, extract with DCM, and after evaporating the solvent, purify by column chromatography (the eluent was PE) to obtain Intermediate 11-4, with a molar amount of 6.02 mmol and a yield of 60.2%. MS(ASAP)=820.4.

[0237] Synthesis of Intermediate 11-5: Prepare a dry 500 mL three-necked flask, set up the reaction device to evacuate and introduce nitrogen; keep the nitrogen flowing in the reaction flask, weigh 10 mmol of 1,4-dibromobenzene (Intermediate 1-8), and add THF (250 ml), evacuate and introduce nitrogen for three cycles, and cool down to -78 °C; slowly add n-butyllithium solution (17.4 ml, 42.6 mmol, 2.4 mol / L THF solution) dropwise to the reaction flask. After reacting at -78 °C for 30 min, quickly add 10 mmol of Intermediate 11-4. Let the reaction system slowly rise to room temperature and react for 12 h. Add water, extract with DCM, and after evaporating the solvent, purify by column chromatography (the eluent was PE) to obtain Intermediate 11-5, with a molar amount of 6.58 mmol and a yield of 65.8%. MS(ASAP)=944.3.

[0238] Synthesis of compound 11: Under nitrogen atmosphere, in a dry three-necked flask, 10 mmol of intermediate 11-5 and 10 mmol of intermediate 4-4 were dissolved in a mixed solvent of 1,4-dioxane and water (21 ml / 2 ml), and Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol) were added. Stir at 100°C for 6 h under nitrogen atmosphere. After cooling, most of the solvent was removed by rotary evaporation, and then the liquid was extracted and washed with water. The organic phase was collected, dried, and purified by column chromatography (eluent: PE) to obtain a yellow-green solid with a yield of 74.2%. MS (ASAP) = 1198.5.

[0239] Example 12

[0240] The synthetic route of compound 12 in this example is as follows:

[0241]

[0242] Synthesis of compound 12: Under nitrogen atmosphere, in a dry three-necked flask, 10 mmol of intermediate 11-5 and 10 mmol of intermediate 3-4 were dissolved in a mixed solvent of 1,4-dioxane and water (21 ml / 2 ml), and Pd(PPh3)4 (0.1) and potassium carbonate (30 mmol) were added. Stir at 100°C for 6 h under nitrogen atmosphere. After cooling, most of the solvent was removed by rotary evaporation, and then the liquid was extracted and washed with water. The organic phase was collected, dried, and purified by column chromatography (eluent: PE) to obtain a yellow-green solid with a yield of 85.6%. MS (ASAP) = 1139.6.

[0243] Embodiment 13

[0244] The synthetic route of compound 13 in this example is as follows:

[0245]

[0246] Synthesis of intermediate 13-2: In a dry three-necked flask under nitrogen atmosphere, 10 mmol of intermediate 13-1 and 10 mmol of intermediate 9-2, 0.2 mmol of palladium acetate, 0.2 mmol of tri-tert-butylphosphine, and 1.38 g of potassium carbonate were added, and 150 ml of toluene was added to dissolve it, and the reaction solution was heated to 80°C until it refluxed, and reacted for 12 hours. When the reaction was complete, water was added to quench the reaction, and the organic phase was extracted with dichloromethane at the same time. The organic phases were washed several times, dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove the solvent to obtain a crude product, which was purified by flash column chromatography to obtain intermediate 13-2, with a molar weight of 7.22 mmol and a yield of 72.2%. MS (ASAP) = 225.3.

[0247] Synthesis of intermediate 13-3: In a dry three-necked flask under nitrogen atmosphere, add 20 mmol of intermediate 13-2 and 10 mmol of intermediate 5-2, 0.2 mmol of palladium acetate, 0.2 mmol of tri-tert-butylphosphine, and 1.38 g of potassium carbonate, add 150 ml of toluene to dissolve it, heat to 80°C until the reaction solution refluxes, react for 12 hours, and when the reaction is complete, add water to quench the reaction, and extract the organic phase with dichloromethane at the same time, combine the organic phases washed several times, dry with anhydrous magnesium sulfate, filter, and evaporate the filtrate to remove the solvent to obtain a crude product, which is purified by flash column chromatography to obtain intermediate 13-3, with a molar weight of 7.81 mmol and a yield of 78.1%. MS (ASAP) = 636.4.

[0248] Synthesis of intermediate 13-4: 10 mmol of intermediate 13-3 and 100 ml of dry tert-butylbenzene were added to a 250 ml three-necked flask, cooled to -30 degrees Celsius in a N2 atmosphere, and (30.6 mmol) of n-BuLi n-hexane solution was added dropwise. The temperature was raised to 60 degrees Celsius for 2 hours, and the n-hexane solvent was removed under reduced pressure. The reaction solution was cooled to -30 degrees Celsius again, 10.5 mmol of boron tribromide solution was added, and the mixture was stirred at room temperature for 0.5 hours. The reaction solution was then cooled to 0 degrees Celsius, 21 mmol of N,N-diisopropylethylamine was added, and after the addition was complete, the mixture was heated to room temperature and stirred, and then the temperature was continued to be raised to 120 degrees Celsius and stirred for 3 hours, and the reaction solution was cooled to room temperature. Sodium carbonate aqueous solution and ethyl acetate were added to quench the reaction. The aqueous phase was extracted with ethyl acetate and the organic phase was combined, and the solvent was evaporated to obtain a crude product, which was purified by rapid silica gel column. Recrystallization with toluene and ethyl acetate gave intermediate 13-4 with a molar weight of 5.13 mmol, a reaction yield of 51.3%, and MS (ASAP) = 566.5.

[0249] Synthesis of intermediate 13-6: Under nitrogen atmosphere, in a dry three-necked flask, 10 mmol of intermediate 13-4 and 10 mmol of intermediate 13-5 were dissolved in a mixed solvent of 1,4-dioxane and water (21 ml / 2 ml), and Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol) were added. Stir at 100°C for 6 h under nitrogen atmosphere. After cooling, most of the solvent was removed by rotary evaporation, and then the separated liquid was extracted and washed with water. The organic phase was collected, dried, and purified by column chromatography (eluent: PE) to obtain intermediate 13-6 with a molar weight of 5.11 mmol and a yield of 51.1%. MS (ASAP) = 642.6.

[0250] Synthesis of Intermediate 13-7: Prepare a dry 500 mL three-necked flask, set up the reaction apparatus, evacuate it, and purge with nitrogen. Keep the nitrogen flowing in the reaction flask, weigh 10 mmol of Intermediate 13-6, and add THF (250 mL). Evacuate and purge with nitrogen three times, then cool to -78 °C. Slowly add 20 mmol of n-butyllithium THF solution dropwise to the reaction flask. After reacting at -78 °C for 30 min, quickly add 10 mmol of Intermediate 1-6. Let the reaction system slowly warm up to room temperature and react for 12 h. Add water, extract with DCM, and after rotary evaporation of the solvent, purify by column chromatography (eluent: PE) to obtain Intermediate 13-7 with a molar amount of 6.15 mmol and a yield of 61.5%. MS (ASAP) = 820.7.

[0251] Synthesis of Intermediate 13-9: Prepare a dry 500 mL three-necked flask, set up the reaction apparatus, evacuate it, and purge with nitrogen. Keep the nitrogen flowing in the reaction flask, weigh 10 mmol of Intermediate 13-8, and add THF (250 mL). Evacuate and purge with nitrogen three times, then cool to -78 °C. Slowly add n-butyllithium solution (17.4 mL, 42.6 mmol, 2.4 mol / L THF solution) dropwise to the reaction flask. After reacting at -78 °C for 30 min, quickly add 10 mmol of Intermediate 13-7. Let the reaction system slowly warm up to room temperature and react for 12 h. Add water, extract with DCM, and after rotary evaporation of the solvent, purify by column chromatography (eluent: PE) to obtain Intermediate 13-9 with a molar amount of 6.89 mmol and a yield of 68.9%. MS (ASAP) = 944.3.

[0252] Synthesis of Compound 13: Under a nitrogen protection atmosphere, in a dry three-necked flask, dissolve 10 mmol of Intermediate 13-9 and 10 mmol of Intermediate 7-4 in a mixed solvent of 1,4-dioxane and water (21 mL / 2 mL), and add Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol). Stir at 100 °C for 6 h under a nitrogen atmosphere. After cooling, rotary evaporate to remove most of the solvent, then extract, wash, and separate the layers. Collect the organic phase, dry it, and purify by column chromatography (eluent: PE) to obtain a yellowish-green solid with a yield of 81.6%. MS (ASAP) = 1273.6.

[0253] Example 14

[0254] The synthetic route of Compound 14 in this example is as follows:

[0255]

[0256] Synthesis of Intermediate 14-2: Weigh 10 mmol of Intermediate 2-1, 10 mmol of Intermediate 14-1, 0.16 mmol of Pd2(dba)3, 0.194 mmol of t-Bu3P, and 16.2 mmol of sodium tert-butoxide into a three-necked flask. Add 200 ml of toluene, displace nitrogen, and react at 80 °C for 12 h. Rotavapor to dryness, wash with water, and purify by column chromatography (eluent: PE) to obtain Intermediate 14-2 with a molar amount of 8.13 mmol and a yield of 81.3%. MS(ASAP) = 219.3.

[0257] Synthesis of Intermediate 14-4: Weigh 10 mmol of Intermediate 14-2, 10 mmol of Intermediate 14-3, 0.16 mmol of Pd2(dba)3, 0.194 mmol of t-Bu3P, and 16.2 mmol of sodium tert-butoxide into a three-necked flask. Add 200 ml of toluene, displace nitrogen, and react at 80 °C for 12 h. Rotavapor to dryness, wash with water, and purify by column chromatography (eluent: PE) to obtain Intermediate 14-4 with a molar amount of 7.56 mmol and a yield of 75.6%. MS(ASAP) = 449.3.

[0258] Synthesis of Intermediate 14-6: Prepare a dry 500 mL three-necked flask, set up the reaction apparatus, evacuate, and introduce nitrogen; keep nitrogen flowing in the reaction flask, weigh 10 mmol of Intermediate 14-4, and add THF (250 ml), evacuate and introduce nitrogen three times in a cycle, cool down to -78 °C; slowly drip 20 mmol of n-butyllithium THF solution into the reaction flask, react at -78 °C for 30 min, and then quickly add 10 mmol of Intermediate 14-5. Let the reaction system slowly warm up to room temperature and react for 12 h. Add water, extract with DCM, rotavapor the solvent, and purify by column chromatography (eluent: PE) to obtain Intermediate 14-6 with a molar amount of 6.09 mmol and a yield of 60.9%. MS(ASAP) = 611.4.

[0259] Synthesis of Compound 14: Prepare a dry 500 mL three-necked flask, set up the reaction apparatus, evacuate, and introduce nitrogen; keep nitrogen flowing in the reaction flask, weigh 10 mmol of Intermediate 1-5, and add THF (250 ml), evacuate and introduce nitrogen three times in a cycle, cool down to -78 °C; slowly drip 20 mmol of n-butyllithium THF solution into the reaction flask, react at -78 °C for 30 min, and then quickly add 10 mmol of Intermediate 14-6. Let the reaction system slowly warm up to room temperature and react for 12 h. Add water, extract with DCM, rotavapor the solvent, and purify by column chromatography (eluent: PE) to obtain Compound 14 with a yield of 42.6%. MS(ASAP) = 999.6.

[0260] Example 15

[0261] The synthetic route of compound 15 in this example is as follows:

[0262]

[0263] Synthesis of intermediate 15-2: In a dry three-necked flask under nitrogen atmosphere, 20 mmol of intermediate 15-1 and 10 mmol of intermediate 5-2, 0.2 mmol of palladium acetate, 0.2 mmol of tri-tert-butylphosphine, and 1.38 g of potassium carbonate were added, and 150 ml of toluene was added to dissolve it, and the reaction solution was heated to 80°C until it refluxed, and reacted for 12 hours. When the reaction was complete, water was added to quench the reaction, and the organic phase was extracted with dichloromethane at the same time. The organic phases were washed several times, dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove the solvent to obtain a crude product, which was purified by flash column chromatography to obtain intermediate 15-2, with a molar weight of 7.33 mmol and a yield of 73.3%. MS (ASAP) = 624.3.

[0264] Synthesis of intermediate 15-3: Add 10 mmol of intermediate 15-2 and 100 ml of dry tert-butylbenzene to a 250 ml three-necked flask, cool to -30 degrees Celsius in a N2 atmosphere, and add (10 mmol) of n-BuLi n-hexane solution dropwise. Raise the temperature to 60 degrees Celsius for 2 hours, and remove the n-hexane solvent under reduced pressure. Cool the reaction solution to -30 degrees Celsius again, add 10.5 mmol of boron tribromide solution, stir at room temperature for 0.5 hours, then cool the reaction solution to 0 degrees Celsius, add 21 mmol of N,N-diisopropylethylamine, wait for the addition to be completed, heat to room temperature and stir, then continue to heat to 120 degrees Celsius and stir for 3 hours, and cool the reaction solution to room temperature. Add sodium carbonate aqueous solution and ethyl acetate to quench the reaction. Extract the aqueous phase with ethyl acetate and combine the organic phases, and evaporate the solvent to obtain a crude product. After purification by rapid silica gel column, the product was recrystallized from toluene and ethyl acetate to obtain intermediate 15-3 with a molar weight of 7.51 mmol, a reaction yield of 75.1%, and MS (ASAP) = 554.8.

[0265] Synthesis of intermediate 15-4: Under nitrogen atmosphere, in a dry three-necked flask, 10 mmol of intermediate 15-3 and 10 mmol of intermediate 5-5 were dissolved in a mixed solvent of 1,4-dioxane and water (21 ml / 2 ml), and Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol) were added. Stir at 100°C for 6 h under nitrogen atmosphere. After cooling, most of the solvent was removed by rotary evaporation, and then the liquid was extracted and washed with water. The organic phase was collected, dried, concentrated under reduced pressure, purified by column chromatography and recrystallization to obtain intermediate 15-4 with a molar weight of 6.32 mmol and a yield of 63.2%. MS (ASAP) = 630.5.

[0266] Synthesis of Intermediate 15-6: Prepare a dry 500 mL three-necked flask, set up the reaction apparatus, evacuate it, and introduce nitrogen; keep the nitrogen flowing in the reaction flask, weigh 10 mmol of Intermediate 15-4, and add THF (250 mL). Evacuate and introduce nitrogen three times in a cycle, and cool down to -78 °C; slowly drip 20 mmol of n-butyllithium THF solution into the reaction flask. After reacting at -78 °C for 30 min, quickly add 10 mmol of Intermediate 15-5. Let the reaction system slowly warm up to room temperature and react for 12 h. Add water, extract with DCM, and after rotary evaporation of the solvent, purify by column chromatography (the eluent is PE) to obtain Intermediate 15-6 with a molar amount of 5.33 mmol and a yield of 53.3%. MS (ASAP) = 920.4.

[0267] Synthesis of Intermediate 15-7: Prepare a dry 500 mL three-necked flask, set up the reaction apparatus, evacuate it, and introduce nitrogen; keep the nitrogen flowing in the reaction flask, weigh 10 mmol of Intermediate 1-8, and add THF (250 mL). Evacuate and introduce nitrogen three times in a cycle, and cool down to -78 °C; slowly drip 20 mmol of n-butyllithium THF solution into the reaction flask. After reacting at -78 °C for 30 min, quickly add 10 mmol of Intermediate 15-6. Let the reaction system slowly warm up to room temperature and react for 12 h. Add water, extract with DCM, and after rotary evaporation of the solvent, purify by column chromatography (the eluent is PE) to obtain Intermediate 15-7 with a molar amount of 6.25 mmol and a yield of 62.5%. MS (ASAP) = 1044.5.

[0268] Synthesis of Compound 15: Under a nitrogen protection atmosphere, in a dry three-necked flask, dissolve 10 mmol of Intermediate 15-7 and 10 mmol of Intermediate 1-10 in a mixed solvent of 1,4-dioxane and water (21 mL / 2 mL), and add Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol). Stir at 100 °C for 6 h under a nitrogen atmosphere. After cooling, rotary evaporate to remove most of the solvent, then extract and wash with water and separate the layers. Collect the organic phase, dry it, and purify by column chromatography (the eluent is PE) to obtain a yellowish-green solid with a yield of 75.9%. MS (ASAP) = 1207.7.

[0269] Example 16

[0270] The synthesis route of Compound 16 in this example is as follows:

[0271]

[0272] Synthesis of intermediate 16-2: In a dry three-necked flask under nitrogen atmosphere, 10 mmol of intermediate 16-1 and 10 mmol of intermediate 9-2, 0.2 mmol of palladium acetate, 0.2 mmol of tri-tert-butylphosphine, and 1.38 g of potassium carbonate were added, and 150 ml of toluene was added to dissolve it, and the reaction solution was heated to 80°C until it refluxed, and reacted for 12 hours. When the reaction was complete, water was added to quench the reaction, and the organic phase was extracted with dichloromethane at the same time. The organic phases were washed several times, dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove the solvent to obtain a crude product, which was purified by flash column chromatography to obtain intermediate 16-2, with a molar weight of 8.35 mmol and a yield of 83.5%. MS (ASAP) = 209.3.

[0273] Synthesis of intermediate 16-3: In a dry three-necked flask under nitrogen atmosphere, 20 mmol of intermediate 16-2 and 10 mmol of intermediate 1-2, 0.2 mmol of palladium acetate, 0.2 mmol of tri-tert-butylphosphine, and 1.38 g of potassium carbonate were added, and 150 ml of toluene was added to dissolve it, and the reaction solution was heated to 80°C until it refluxed, and reacted for 12 hours. When the reaction was complete, water was added to quench the reaction, and the organic phase was extracted with dichloromethane. The organic phases were washed several times, dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove the solvent to obtain a crude product, which was purified by flash column chromatography to obtain intermediate 16-3, with a molar weight of 7.33 mmol and a yield of 73.3%. MS (ASAP) = 526.3.

[0274] Synthesis of intermediate 16-4: Add 10 mmol of intermediate 16-3 and 100 ml of dry tert-butylbenzene to a 250 ml three-necked flask, cool to -30 degrees Celsius in a N2 atmosphere, and add (30.6 mmol) of t-BuLi n-hexane solution dropwise. Raise the temperature to 60 degrees Celsius and react for 2 hours, and remove the n-hexane solvent under reduced pressure. Cool the reaction solution to -30 degrees Celsius again, add 10.5 mmol of boron tribromide solution, stir at room temperature for 0.5 hours, then cool the reaction solution to 0 degrees Celsius, add 21 mmol of N,N-diisopropylethylamine, and after the addition is complete, heat to room temperature and stir, then continue to heat to 120 degrees Celsius and stir for 3 hours, and cool the reaction solution to room temperature. Add sodium carbonate aqueous solution and ethyl acetate to quench the reaction. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product, which was purified by flash silica gel column and recrystallization with toluene and ethyl acetate to obtain intermediate 16-4 with a molar weight of 4.17 mmol. The reaction yield was 41.7%, MS (ASAP) = 500.3.

[0275] Synthesis of Intermediate 16-5: Under a nitrogen protection atmosphere, in a dry three-necked flask, 10 mmol of Intermediate 16-4 and 5 mmol of liquid bromine were respectively added, and 150 ml of concentrated sulfuric acid was added to dissolve them. The mixture was heated to 80 °C until the reaction solution refluxed, and the reaction was carried out for 12 hours. After the reaction was complete, water was added to quench the reaction, and at the same time, the organic phase was extracted with dichloromethane. The organic phase was washed several times and combined, dried with anhydrous magnesium sulfate, filtered, and the solvent in the filtrate was removed by rotary evaporation to obtain the crude product. The crude product was purified by flash column chromatography to obtain Intermediate 16-5 with a molar amount of 5.71 mmol and a yield of 57.1%. MS(ASAP) = 578.2.

[0276] Synthesis of Intermediate 16-6: Prepare a dry 500 mL three-necked flask, set up the reaction device, evacuate, and introduce nitrogen; keep the nitrogen flowing in the reaction flask, weigh 10 mmol of Intermediate 16-5, and add THF (250 ml). Evacuate and introduce nitrogen in a cycle three times, and cool down to -78 °C; slowly add 20 mmol of n-butyllithium THF solution dropwise to the reaction flask. After reacting at -78 °C for 30 min, quickly add 10 mmol of Intermediate 1-6. Let the reaction system slowly warm up to room temperature and react for 12 h. Add water, extract with DCM, and after evaporating the solvent, purify by column chromatography (eluent is PE) to obtain Intermediate 16-6 with a molar amount of 4.89 mmol and a yield of 48.9%. MS(ASAP) = 712.4.

[0277] Synthesis of Intermediate 16-7: Prepare a dry 500 mL three-necked flask, set up the reaction device, evacuate, and introduce nitrogen; keep the nitrogen flowing in the reaction flask, weigh 10 mmol of 1,4-dibromobenzene (Intermediate 1-8), and add THF (250 ml). Evacuate and introduce nitrogen in a cycle three times, and cool down to -78 °C; slowly add n-butyllithium solution (17.4 ml, 42.6 mmol, 2.4 mol / L THF solution) dropwise to the reaction flask. After reacting at -78 °C for 30 min, quickly add 10 mmol of Intermediate 16-6. Let the reaction system slowly warm up to room temperature and react for 12 h. Add water, extract with DCM, and after evaporating the solvent, purify by column chromatography (eluent is PE) to obtain Intermediate 16-7 with a molar amount of 5.11 mmol and a yield of 51.1%. MS(ASAP) = 836.4.

[0278] Synthesis of compound 16: Under nitrogen atmosphere, in a dry three-necked flask, 10 mmol of intermediate 16-7 and 10 mmol of intermediate 1-10 were dissolved in a mixed solvent of 1,4-dioxane and water (21 ml / 2 ml), and Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol) were added. Stir at 100°C for 6 h under nitrogen atmosphere. After cooling, most of the solvent was removed by rotary evaporation, and then the liquid was extracted and washed with water. The organic phase was collected, dried, and purified by column chromatography (eluent: PE) to obtain a yellow-green solid with a yield of 79.6%. MS (ASAP) = 999.7.

[0279] Embodiment 17

[0280] The synthetic route of compound 17 in this example is as follows:

[0281]

[0282] Synthesis of intermediate 17-2: In a dry three-necked flask under nitrogen atmosphere, 10 mmol of intermediate 17-1 and 10 mmol of intermediate 9-2, 0.2 mmol of palladium acetate, 0.2 mmol of tri-tert-butylphosphine, and 1.38 g of potassium carbonate were added, and 150 ml of toluene was added to dissolve it, and the reaction solution was heated to 80°C until it refluxed, and reacted for 12 hours. When the reaction was complete, water was added to quench the reaction, and the organic phase was extracted with dichloromethane at the same time. The organic phases were washed several times, dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove the solvent to obtain a crude product, which was purified by flash column chromatography to obtain intermediate 16-2, with a molar weight of 7.98 mmol and a yield of 79.8%. MS (ASAP) = 259.4.

[0283] Synthesis of intermediate 17-3: In a dry three-necked flask under nitrogen atmosphere, 20 mmol of intermediate 17-2 and 10 mmol of intermediate 5-2, 0.2 mmol of palladium acetate, 0.2 mmol of tri-tert-butylphosphine, and 1.38 g of potassium carbonate were added, and 150 ml of toluene was added to dissolve it, and the reaction solution was heated to 80°C until it refluxed, and reacted for 12 hours. When the reaction was complete, water was added to quench the reaction, and the organic phase was extracted with dichloromethane. The organic phases were washed several times, dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove the solvent to obtain a crude product, which was purified by flash column chromatography to obtain intermediate 17-3, with a molar weight of 7.29 mmol and a yield of 72.9%. MS (ASAP) = 704.3.

[0284] Synthesis of Intermediate 17-4: 10 mmol of Intermediate 17-3 and 100 ml of dry tert-butylbenzene were added to a 250-ml three-necked flask. Under a nitrogen atmosphere, it was cooled to -30 °C, and a solution of n-BuLi in n-hexane (30.6 mmol) was added dropwise. The temperature was raised to 60 °C and the reaction was carried out for 2 hours. The n-hexane solvent was removed by distillation under reduced pressure. The reaction solution was cooled to -30 °C again, 10.5 mmol of boron tribromide solution was added, and the mixture was stirred at room temperature for 0.5 hour. Then the reaction solution was cooled to 0 °C, 21 mmol of N,N-diisopropylethylamine was added. After the addition was complete, the temperature was raised to room temperature and stirred, and then further raised to 120 °C and stirred for 3 hours. The reaction solution was cooled to room temperature. An aqueous sodium carbonate solution and ethyl acetate were added to quench the reaction. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was removed by rotary evaporation to obtain a crude product, which was purified by flash silica gel column chromatography and recrystallized with toluene and ethyl acetate to obtain Intermediate 17-4 with a molar amount of 5.87 mmol and a reaction yield of 58.7%. MS (ASAP) = 634.5.

[0285] Synthesis of Intermediate 17-5: Under a nitrogen protection atmosphere, 10 mmol of Intermediate 17-4 and 10 mmol of Intermediate 5-5 were dissolved in a mixed solvent of 1,4-dioxane and water (21 ml / 2 ml) in a dry three-necked flask, and Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol) were added. Under a nitrogen atmosphere, the mixture was stirred at 100 °C for 6 h. After cooling, most of the solvent was removed by rotary evaporation, and then extracted and washed with water for liquid separation. The organic phase was collected, dried, concentrated under reduced pressure, and then purified by column chromatography and recrystallized to obtain Intermediate 17-5 with a molar amount of 6.29 mmol and a yield of 62.9%. MS (ASAP) = 710.4.

[0286] Synthesis of Intermediate 17-6: A dry 500-mL three-necked flask was prepared, the reaction device was set up, evacuated, and filled with nitrogen; nitrogen was kept flowing in the reaction flask. 10 mmol of Intermediate 17-5 was weighed and THF (250 ml) was added. The system was evacuated and filled with nitrogen three times, and the temperature was lowered to -78 °C; 20 mmol of a solution of n-butyllithium in THF was slowly added dropwise to the reaction flask. After reacting at -78 °C for 30 min, 10 mmol of Intermediate 1-6 was quickly added. The reaction system was slowly raised to room temperature and reacted for 12 h. Water was added, and the mixture was extracted with DCM. After the solvent was evaporated, it was purified by column chromatography (eluent: PE) to obtain Intermediate 17-6 with a molar amount of 4.22 mmol and a yield of 42.2%. MS (ASAP) = 888.5.

[0287] Synthesis of intermediate 17-7: Prepare a dry 500mL three-necked flask, set up the reaction device, evacuate and pass nitrogen; keep nitrogen flowing in the reaction flask, weigh 1,4-dibromobenzene (intermediate 1-8) 10mmol, add THF (250ml), evacuate and pass nitrogen for three cycles, and cool to -78°C; slowly drop n-butyl lithium solution (17.4ml, 42.6mmol, 2.4mol / LTHF solution) into the reaction flask, react at -78°C for 30min, and quickly add intermediate 17-6 10mmol. Let the reaction system slowly warm to room temperature and react for 12h. Add water, extract with DCM, spin dry the solvent, and purify by column chromatography (eluent is PE) to obtain intermediate 17-7, with a molar weight of 5.81mmol and a yield of 58.1%. MS (ASAP) = 1012.4.

[0288] Synthesis of compound 17: Under nitrogen atmosphere, in a dry three-necked flask, 10 mmol of intermediate 17-7 and 10 mmol of intermediate 1-10 were dissolved in a mixed solvent of 1,4-dioxane and water (21 ml / 2 ml), and Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol) were added. Stir at 100°C for 6 h under nitrogen atmosphere. After cooling, most of the solvent was removed by rotary evaporation, and then the liquid was extracted and washed with water. The organic phase was collected, dried, and purified by column chromatography (eluent: PE) to obtain a yellow-green solid with a yield of 78.6%. MS (ASAP) = 1175.6.

[0289] Embodiment 18

[0290] The synthetic route of compound 18 in this example is as follows:

[0291]

[0292] Synthesis of intermediate 18-2: In a dry three-necked flask under nitrogen atmosphere, 10 mmol of intermediate 18-1 and 10 mmol of intermediate 9-2, 0.2 mmol of palladium acetate, 0.2 mmol of tri-tert-butylphosphine, and 1.38 g of potassium carbonate were added, and 150 ml of toluene was added to dissolve it, and the reaction solution was heated to 80°C until it refluxed, and reacted for 12 hours. When the reaction was complete, water was added to quench the reaction, and the organic phase was extracted with dichloromethane at the same time. The organic phases were washed several times, dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove the solvent to obtain a crude product, which was purified by rapid column chromatography to obtain intermediate 18-2 with a molar weight of 8.34 mmol and a yield of 83.4%. MS (ASAP) = 285.3.

[0293] Synthesis of intermediate 18-3: In a dry three-necked flask under nitrogen atmosphere, 10 mmol of intermediate 18-2 and 10 mmol of intermediate 1-2, 0.2 mmol of palladium acetate, 0.2 mmol of tri-tert-butylphosphine, and 1.38 g of potassium carbonate were added, and 150 ml of toluene was added to dissolve it, and the reaction solution was heated to 80°C until it refluxed, and reacted for 12 hours. When the reaction was complete, water was added to quench the reaction, and the organic phase was extracted with dichloromethane. The organic phases were washed several times, dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove the solvent to obtain a crude product, which was purified by rapid column chromatography to obtain intermediate 18-3 with a molar weight of 7.71 mmol and a yield of 77.1%. MS (ASAP) = 429.3.

[0294] Synthesis of intermediate 18-4: In a dry three-necked flask under nitrogen atmosphere, 10 mmol of intermediate 18-3 and 10 mmol of intermediate 1-1, 0.2 mmol of palladium acetate, 0.2 mmol of tri-tert-butylphosphine, and 1.38 g of potassium carbonate were added, and 150 ml of toluene was added to dissolve it, and the reaction solution was heated to 80°C until it refluxed, and reacted for 12 hours. When the reaction was complete, water was added to quench the reaction, and the organic phase was extracted with dichloromethane at the same time. The organic phases were washed several times, dried with anhydrous magnesium sulfate, filtered, and the filtrate was evaporated to remove the solvent to obtain a crude product, which was purified by flash column chromatography to obtain intermediate 18-4, with a molar weight of 6.59 mmol and a yield of 65.9%. MS (ASAP) = 562.4.

[0295] Synthesis of intermediate 18-5: Add 10 mmol of intermediate 18-4 and 100 ml of dry tert-butylbenzene to a 250 ml three-necked flask, cool to -30 degrees Celsius in a N2 atmosphere, and add (30.6 mmol) of t-BuLi n-hexane solution dropwise. Raise the temperature to 60 degrees Celsius and react for 2 hours, and remove the n-hexane solvent under reduced pressure. Cool the reaction solution to -30 degrees Celsius again, add 10.5 mmol of boron tribromide solution, stir at room temperature for 0.5 hours, then cool the reaction solution to 0 degrees Celsius, add 21 mmol of N,N-diisopropylethylamine, and after the addition is complete, heat to room temperature and stir, then continue to heat to 120 degrees Celsius and stir for 3 hours, and cool the reaction solution to room temperature. Add sodium carbonate aqueous solution and ethyl acetate to quench the reaction. The aqueous phase was extracted with ethyl acetate and the organic phases were combined. The solvent was evaporated to obtain a crude product. The crude product was purified by rapid silica gel column and recrystallized from toluene and ethyl acetate to obtain intermediate 18-5 with a molar weight of 4.21 mmol. The reaction yield was 42.1% and MS (ASAP) = 536.2.

[0296] Synthesis of Intermediate 18-6: Under a nitrogen protection atmosphere, in a dry three-necked flask, 10 mmol of Intermediate 18-5 and 5 mmol of liquid bromine were respectively added, and 150 ml of concentrated sulfuric acid was added to dissolve them. The mixture was heated to 80 °C until the reaction solution refluxed, and the reaction was carried out for 12 hours. After the reaction was complete, water was added to quench the reaction, and at the same time, the organic phase was extracted with dichloromethane. The organic phase was washed multiple times and combined, dried with anhydrous magnesium sulfate, filtered, and the solvent in the filtrate was removed by rotary evaporation to obtain a crude product. The crude product was purified by flash column chromatography to obtain Intermediate 18-6 with a molar amount of 8.39 mmol and a yield of 83.9%. MS(ASAP) = 614.3.

[0297] Synthesis of Intermediate 18-7: Prepare a dry 500 mL three-necked flask, set up the reaction device, evacuate, and introduce nitrogen; keep the nitrogen flowing in the reaction flask, weigh 10 mmol of Intermediate 18-6, and add THF (250 ml). Evacuate and introduce nitrogen in a cycle three times, and cool down to -78 °C; slowly drip 20 mmol of n-butyllithium THF solution into the reaction flask. After reacting at -78 °C for 30 min, quickly add 10 mmol of Intermediate 1-6. Let the reaction system slowly rise to room temperature and react for 12 h. Add water, extract with DCM, and after evaporating the solvent, purify by column chromatography (eluent: PE) to obtain Intermediate 18-7 with a molar amount of 3.97 mmol and a yield of 39.7%. MS(ASAP) = 748.5.

[0298] Synthesis of Intermediate 18-8: Prepare a dry 500 mL three-necked flask, set up the reaction device, evacuate, and introduce nitrogen; keep the nitrogen flowing in the reaction flask, weigh 10 mmol of 1,4-dibromobenzene (Intermediate 1-8), and add THF (250 ml). Evacuate and introduce nitrogen in a cycle three times, and cool down to -78 °C; slowly drip n-butyllithium solution (17.4 ml, 42.6 mmol, 2.4 mol / L THF solution) into the reaction flask. After reacting at -78 °C for 30 min, quickly add 10 mmol of Intermediate 18-7. Let the reaction system slowly rise to room temperature and react for 12 h. Add water, extract with DCM, and after evaporating the solvent, purify by column chromatography (eluent: PE) to obtain Intermediate 18-8 with a molar amount of 5.27 mmol and a yield of 52.7%. MS(ASAP) = 872.6.

[0299] Synthesis of Compound 18: Under a nitrogen atmosphere, in a dry three-necked flask, 10 mmol of intermediate 18-8 and 10 mmol of intermediate 8-4 were dissolved in a mixed solvent of 1,4-dioxane and water (21 ml / 2 ml), and Pd(PPh3)4 (0.1 mmol) and potassium carbonate (30 mmol) were added. Under a nitrogen atmosphere, the mixture was stirred at 100 °C for 6 h. After cooling, most of the solvent was removed by rotary evaporation, and then the mixture was extracted, washed with water and separated by liquid separation. The organic phase was collected, dried and purified by column chromatography (eluent: PE) to obtain a yellowish-green solid with a yield of 84.9%. MS (ASAP) = 1077.8.

[0300] The preparation process of the OLED device including the above compound will be described in detail through specific examples below. The structure of the OLED device is: anode substrate / hole injection layer / hole transport layer / light-emitting layer / electron transport layer / cathode. The schematic diagram of the OLED device is as Figure 1 shown, where 10 is the substrate, 20 is the anode, 30 is the hole injection layer, 40 is the hole transport layer, 50 is the light-emitting layer, 60 is the electron transport layer, and 70 is the cathode.

[0301] The preparation steps of OLED-1 are as follows:

[0302] a. Cleaning of the anode substrate: The ITO (indium tin oxide) conductive glass substrate was cleaned with various solvents (such as one or more of chloroform, acetone or isopropanol), and then treated with ultraviolet ozone.

[0303] b. HIL (hole injection layer, 40 nm): 40 nm of PEDOT (polyethylenedioxythiophene, Clevios TMAI 4083) was spin-coated as the HIL in a clean room and treated on a hot plate at 180 °C for 10 minutes.

[0304] PEDOT (polyethylenedioxythiophene, Clevios TMAI 4083) was spin-coated in a clean room and treated on a hot plate at 180 °C for 10 minutes to form a 40-nm-thick hole injection layer.

[0305] c. HTL (hole transport layer, 20 nm): 20 nm of PVK (Sigma Aldrich, average Mn 25,000 - 50,000) was spin-coated in a nitrogen glove box. The solution used was PVK added to toluene solvent with a solution concentration of 5 mg / ml, and then treated on a hot plate at 180 °C for 60 minutes.

[0306] d, EML (emitting layer, 40 nm): The EML was formed by spin coating in a nitrogen glove box. The solution used was a solution of the host and guest in methyl benzoate. Among them, the weight ratio of the emitting host material to the emitting guest material was 95:5, the solution concentration was 15 mg / ml, and then it was treated on a hot plate at 140 °C for 10 minutes. The emitting host material was BH, and the emitting guest material (i.e., the guest material) was Compound 1.

[0307] e, electron transport layer and cathode: The heat-treated substrate was transferred to a vacuum chamber. Then, ET and LiQ were placed in different evaporation units and co-deposited at a ratio of 50 wt% each in a high vacuum (1×10 -6 mbar) to form a 20-nm electron transport layer on the emitting layer. Subsequently, an Al cathode with a thickness of 100 nm was deposited.

[0308] f, encapsulation: The device was encapsulated with ultraviolet curable resin in a nitrogen glove box.

[0309] The preparation schemes of the devices OLED-2 to OLED-18 in the examples and OLED-Ref1 in the comparative example were the same as that of OLED-1, except that the guest material (i.e., the emitting guest material) in the example OLED-1 was replaced by the corresponding Compounds 2-18 and OLED-Ref1 in Table 1.

[0310] BH, ET, Liq, and BD-Ref1 that may be involved in the OLED preparation process, the structures of which are as follows, were all commercially purchased or prepared by known synthesis methods. For details, refer to the references in the prior art and will not be elaborated here. Among them, BH was used as the host material of the emitting layer, ET was used as the electron transport material, and Liq was used as the electron injection material.

[0311]

[0312] The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization device, and parameters such as the luminous efficiency CE@1knits and the LT90@1knits lifetime were recorded simultaneously. The results are shown in Table 1 below.

[0313] Table 1

[0314]

[0315] As shown in Table 1, OLED-1 to OLED-18 were blue light devices prepared using Compounds 1-18 as the guest material in the emitting layer, and the guest material of OLED-Ref1 was BD-Ref1. Compared with OLED-Ref1, OLED-1 to OLED-18 had better luminous efficiency and lifetime.

[0316] The above has introduced in detail the organic compounds, mixtures, compositions and organic electronic devices provided by the embodiments of the present invention. Specific examples are used herein to elaborate on the principles and implementation manners of the present invention. The description of the above embodiments is only used to help understand the method and its core idea of the present invention; at the same time, for those skilled in the art, according to the idea of the present invention, there will be changes in the specific implementation manners and application scopes. In summary, the content of this specification should not be construed as a limitation to the present invention.

Claims

1. An organic compound, characterized in that, It has a structure shown in the general formula (1): Wherein: M1 is selected from the structures of formula (A-1) or (A-2): M2 is selected from the structures of formula (A-3) or (A-4): X1 is selected from CR4R5, NR6, O, S or a single bond; Each occurrence of R1, R2, R3 is independently selected from: -H, methyl, tBu; Each occurrence of R4, R5, R6 is independently selected from: methyl, phenyl; Each occurrence of Ar1, Ar4, Ar5 is independently selected from the following groups: Each occurrence of Ar2, Ar3 is independently selected from the following groups: X is selected from CR7, and each occurrence of R7 is independently selected from: -H, iPr; Each occurrence of Y is independently selected from CR8R9, S or O, and R8, R9 are selected from methyl; m1 is selected from 0, 1, 2, 3 or 4; m2 is selected from 0, 1, 2, 3, 4 or 5; * represents a connection site or a fusion site.

2. The organic compound according to claim 1, characterized in that, Formula (A-3) is selected from any one of the structures of formula (B-1)-(B-5):

3. The organic compound according to claim 1, wherein The formula (A-1) is selected from the structures of formula (C-1) to (C-10): Formula (A-2) is selected from the structures of formula (D-1) to (D-10):

4. An organic compound, characterized in that, The organic compound is selected from any one of the following structures:

5. A mixture, characterized in that, The mixture includes the organic compound according to any one of claims 1-4 and at least one organic functional material, and the organic functional material is selected from a hole injection material, a hole transport material, an electron transport material, an electron injection material, an electron blocking material, a hole blocking material, a light-emitting guest material, a light-emitting host material or an organic dye.

6. A composition, characterized in that, The composition includes the organic compound according to any one of claims 1-4 or the mixture according to claim 5, and at least one organic solvent.

7. An organic electronic device includes at least one functional layer, characterized in that, The functional layer contains the organic compound according to any one of claims 1-4, or the mixture according to claim 5, or the functional layer is prepared from the composition according to claim 6.

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