Boron-nitrogen-containing organic compound, application thereof and organic electroluminescent device

Abstract

The invention relates to an organic compound, belongs to the technical field of organic light-emitting materials, and also relates to an application of the compound in an organic light-emitting device. The organic compound has a structure as shown in a formula (1), and can be used as a TADF material, a light-emitting layer object material or a dopant. The OLED device prepared from the compound provided by the invention has high luminous efficiency and longer service life. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a boron-nitrogen-containing organic compound, belonging to the technical field of organic luminescent materials. The present invention also relates to the application of the compound in an organic electroluminescent device and the organic electroluminescent device. Background Art

[0002] OLED (Organic Light-Emitting Diode) refers to an organic semiconductor composed of an extremely thin coating of organic material and a glass substrate that emits light when an electric current passes through it. As a next-generation display technology, OLED offers superior display performance compared to LCD, boasting advantages such as self-luminescence, excellent display quality, low power consumption, high flexibility, and ultra-thinness. It is widely used in the screens of smartphones, automotive electronics, smart wearable devices, VR equipment, and other products.

[0003] OLEDs are primarily made of three types of luminescent materials: blue, red, and green. These materials collectively determine the self-luminous performance and lifespan of OLEDs. While blue luminescent materials can emit brighter light, they have lower luminous efficiency and a shorter lifespan than red and green luminescent materials. Currently, red and green OLED phosphorescent materials are already in mass production for OLED screens. However, blue OLED phosphorescent materials have long suffered from limitations in color purity and lifespan, leading to the widespread use of blue fluorescent materials in commercial OLED products.

[0004] As OLED products gradually enter the market, demand for their performance is increasing. Recently, patent documents CN112645968A and CN112174992A reported a class of TADF (Thermally Activated Delayed Fluorescence) multi-resonance fluorescent compounds based on the BN resonance structure. These compounds also consist of a rigid polycyclic aromatic skeleton composed of B, N, and benzene rings. Nitrogen atoms have an opposite resonance effect to that of boron atoms, and the opposite resonance effect is enhanced at the para position. Therefore, this effect can significantly separate the HOMO and LUMO orbitals, resulting in certain TADF properties. Although this series of materials has broad application prospects, they suffer from significant intramolecular rotation, resulting in energy loss due to vibrational and rotational energy levels, resulting in low external quantum efficiency. Even when dimethylfluorene structures are used to suppress intramolecular rotational energy levels, as reported in some of the compounds described in the patents, the imbalanced charge transfer leads to poor device lifetimes. This type of organic electroluminescent material still has a lot of room for improvement in terms of luminescence performance, and the industry urgently needs to develop new blue light emitting material systems to meet commercial needs.

[0005] However, due to its particularly planar rigid structure, it is easy to cause molecular stacking and exciton annihilation, resulting in serious efficiency roll-off. Therefore, this type of organic electroluminescent material still has a lot of room for improvement in terms of luminescence performance, and the industry urgently needs to develop new luminescent material systems to meet commercial needs. Although this series of materials has broad application prospects, due to the existence of serious intramolecular rotation, this type of material will lose energy due to vibrational-rotational energy levels, resulting in low external quantum efficiency; even as disclosed in the prior art, some compound structures use dimethylfluorene structures to suppress intramolecular rotational energy levels, but due to unbalanced charge transfer, the device life is poor.

[0006] Therefore, existing organic electroluminescent materials still have significant room for improvement in their luminescent properties, and the industry urgently needs to develop new luminescent material systems to meet commercialization needs. Through careful consideration and continuous experimentation, the researchers of the present invention have discovered an ingenious molecular design, which is described in detail below. Surprisingly, the compounds disclosed in this invention are highly suitable for use in OLEDs and improve device lifespan. Summary of the Invention

[0007] In response to the shortcomings of the prior art, the present invention provides an organic compound, its application, and an organic electroluminescent device. The compound of the present invention can be used as a TADF material, a guest material in the light-emitting layer, or a dopant (dye). OLED devices prepared using the compound of the present invention exhibit high luminous efficiency and extended device life.

[0008] In a first aspect, the present invention provides a boron-nitrogen-containing organic compound having a structure shown in formula (1):

[0009]

[0010] In formula (1), X represents O, S, NR 0 、C(R 0 )2, wherein each R 0 are independently selected from hydrogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, R 0 They are connected to each other by chemical bonds to form a ring or not;

[0011] Ring A, B, and C are each independently selected from a C6-C60 aromatic ring and a C3-C60 heteroaromatic ring;

[0012] R a 、R b 、R c represents single substitution to maximum substitution, R a 、Rb 、R c Each is independently selected from any one of hydrogen, halogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 heterocycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylamino, cyano, nitro, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; said R a 、R b 、R c They are independently connected to each other by chemical bonds to form a ring or are not connected;

[0013] Z 1 ~Z 8 are independently selected from CR or N, wherein R is independently selected from hydrogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 heterocycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylamino, halogen, cyano, nitro, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, adjacent R are not connected or connected by chemical bonds to form a ring, and the R is not connected to the adjacent ring structure or connected by chemical bonds to form a ring;

[0014] R z1 、R z2 are independently selected from one of hydrogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl; wherein, R z1 、R z2 At least one of the compounds comprises a structure of formula (a) or formula (b),

[0015]

[0016] In formula (a) and formula (b), R 1 、R 2 、R 3 、R 4 、R 5 、R 6R is independently selected from one of hydrogen, substituted or unsubstituted C1-C20 chain alkyl, and substituted or unsubstituted C3-C20 cycloalkyl; 1 、R 2 Connect or not connect; R 3 、R 4 Connect or not connect, R 5 、R 6 Connect or not connect;

[0017] Y 1 are independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group;

[0018] The above-mentioned substituents are each independently selected from any one or a combination of at least two of halogen, C1-C20 chain alkyl, C3-C20 cycloalkyl, C2-C20 heterocycloalkyl, C1-C20 alkoxy, C1-C20 alkylamino, cyano, nitro, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, and C3-C60 heteroaryl. The expression of the ring structure crossed out by “—” indicates that the connection site is any position on the ring structure that can form a bond, and the * indicates the connection site.

[0019] The polycyclic aromatic compound provided by the present invention has a specific molecular structure shown in formula (1) (a fused structure containing a five-membered heterocyclic ring), has good stability and spatial configuration, can utilize triplet excitons to achieve high luminous efficiency, has excellent carrier transport characteristics, and effectively avoids molecular aggregation, which has an improvement effect on the stability and efficiency of the device. Other more polycyclic core structures are not as long as the device life caused by the specific core structure in the present invention. In addition, the present invention also makes the polycyclic aromatic compound have excellent photoelectric properties through the design of the BN core structure and the introduction of formula (a) or formula (b) structure on both sides of the core. On the one hand, it is beneficial to suppress the vibration of the molecular excited state, significantly narrow the half-peak width of the material, and improve the color purity of the blue light material. The unique connection site of the structure of formula (a) or formula (b) is very important. The high steric group part is located in the adjacent position connected to N. It is speculated that this connection method can enhance the bond energy of the adjacent CN bond and improve the overall stability of the material molecule. The study also found that this connection method can also achieve good optoelectronic properties. The reason is not very clear. It is speculated that it may be because the existence of this structure extends the axial length of the molecule and increases the horizontal transition dipole of the molecule, which is beneficial to improving the efficiency of the device.

[0020] It should be noted that, unless otherwise defined below, all technical and scientific terms used herein are intended to have the same meaning as those commonly understood by those skilled in the art. References to technology used herein are intended to refer to technology commonly understood in the art, including variations of technology or substitutions of equivalent technologies that would be apparent to those skilled in the art. While it is believed that the following terms are well understood by those skilled in the art, the following definitions are set forth to better explain the present invention.

[0021] In this specification, the expression of Ca to Cb indicates that the number of carbon atoms in the group is a to b. Unless otherwise specified, the number of carbon atoms generally does not include the number of carbon atoms in the substituent. When describing C1 to C30, it includes but is not limited to C1, C2, C3, C4, C3, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C22, C24, C26, C28, etc. Other numerical ranges are not repeated here.

[0022] The terms "comprises," "comprising," "having," "containing," or "involving," and other variations thereof herein, are inclusive or open-ended and do not exclude additional unrecited elements or method steps.

[0023] In the present invention, unless otherwise specified, the expression of chemical elements generally includes the concept of isotopes with the same chemical properties. For example, the expression "hydrogen" also includes the concepts of "deuterium" and "tritium" with the same chemical properties, and carbon (C) includes 12 C. 13 C, etc., no further details.

[0024] The heteroatom in the present invention is generally selected from N, O, S, P, Si and Se, and is preferably selected from N, O and S.

[0025] As used herein, the terms "heterocyclyl" and "heterocycle" refer to a saturated (i.e., heterocycloalkyl) or partially unsaturated (i.e., having one or more double and / or triple bonds within the ring) cyclic group having at least one ring atom that is a heteroatom selected from N, O, and S and the remaining ring atoms being C.

[0026] As used herein, the terms "(ylidene)aryl" and "aromatic ring" refer to an all-carbon monocyclic or fused-ring polycyclic aromatic group having a conjugated π electron system. As used herein, the terms "(ylidene)heteroaryl" and "heteroaromatic ring" refer to a monocyclic, bicyclic, or tricyclic aromatic ring system. As used herein, the term "aralkyl" preferably refers to an alkyl group substituted with an aryl or heteroaryl group, wherein the aryl, heteroaryl, and alkyl groups are as defined herein.

[0027] As used herein, the term "halo" or "halogen" group is defined to include F, Cl, Br, or I.

[0028] The term "substituted" means that one or more (e.g., one, two, three, or four) hydrogen atoms on the designated atom are replaced with a group selected from the indicated group, provided that the designated atom's normal valence is not exceeded in the current context and that the substitution results in a stable compound. Combinations of substituents and / or variables are permissible only if such combinations result in stable compounds.

[0029] If substituents are described as being "independently selected" from a group, each substituent is selected independently of the other. Thus, each substituent may be the same as or different from another (other) substituent.

[0030] As used herein, the term "one or more" means 1 or more than 1, such as 2, 3, 4, 5 or 10, where reasonable.

[0031] Unless otherwise indicated, as used herein, the point of attachment of a substituent may be from any suitable position of the substituent.

[0032] When a bond to a substituent is shown to pass through a bond connecting two atoms in a ring, then such substituent may be bonded to any ring atom in the substitutable ring.

[0033] The term "about" means within ±10%, preferably within ±5%, and more preferably within ±2% of the stated numerical value.

[0034] In the structural formula disclosed in this specification, the expression of a ring structure crossed by “—” indicates that the connection site is any position on the ring structure that can form a bond.

[0035] The aforementioned C6-C60 aromatic rings and C3-C60 heteroaromatic rings in the present invention, unless otherwise specified, are aromatic groups that satisfy a π-conjugated system, including both monocyclic residues and condensed ring residues. The so-called monocyclic residue refers to a molecule containing at least one phenyl group. When the molecule contains at least two phenyl groups, the phenyl groups are independent of each other and connected by a single bond, such as phenyl, biphenyl, terphenyl, etc.; a fused ring residue refers to a molecule containing at least two benzene rings, but the benzene rings are not independent of each other, but are fused to each other by sharing the ring edge, such as naphthyl, anthracenyl, phenanthrenyl, etc.; a monocyclic heteroaryl refers to a molecule containing at least one heteroaryl group. When the molecule contains one heteroaryl group and other groups (such as aryl, heteroaryl, alkyl, etc.), the heteroaryl group and other groups are independent of each other and connected by a single bond, such as pyridine, furan, thiophene, etc.; a fused heteroaryl refers to a molecule composed of at least one phenyl group and at least one heteroaryl group fused together, or composed of at least two heteroaryl rings fused together, such as quinoline, isoquinoline, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, etc.

[0036] In the present specification, the substituted or unsubstituted C6-C60 aromatic ring is preferably a C6-C30 aromatic ring, more preferably an aromatic ring selected from the group consisting of phenyl, naphthyl, anthracenyl, benzanthryl, phenanthrenyl, triphenylenyl, pyrene, chrysene, peryl, fluoranthenyl, naphthyl, pentacene, benzopyrenyl, biphenyl, biphenyl, terphenyl, triphenyl, tetraphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthrenyl, dihydropyrenyl, tetrahydropyrenyl, cis- or trans-indenofluorenyl, trimerized indenyl, isotrimerized indenyl, spirotrimerized indenyl, and spiroisotrimerized indenyl. Specifically, the biphenyl group is selected from 2-biphenyl, 3-biphenyl and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracenyl group is selected from 1-anthracenyl, 2-anthracenyl and 9-anthracenyl; the fluorenyl group is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the pyrenyl group is selected from 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the tetraphenyl group is selected from 1-tetraphenyl, 2-tetraphenyl and 9-tetraphenyl. Preferred examples of the aromatic ring in the present invention include phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, indenyl, fluorenyl and its derivatives, fluoranthenyl, triphenylene, pyrenyl, perylenyl, The biphenyl group is selected from the group consisting of 2-biphenyl, 3-biphenyl and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracenyl group is selected from the group consisting of 1-anthracenyl, 2-anthracenyl and 9-anthracenyl. The fluorenyl group is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the fluorenyl derivative is selected from the group consisting of 9,9-dimethylfluorene, 9,9-spirobifluorene and benzofluorene; the pyrenyl group is selected from the group consisting of 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the naphthacene group is selected from the group consisting of 1-naphthacene, 2-naphthacene and 9-naphthacene.

[0037] In the present specification, the substituted or unsubstituted C6-C60 aryl group is preferably a C6-C30 aryl group, and more preferably a group selected from the group consisting of phenyl, naphthyl, anthracenyl, benzanthryl, phenanthrenyl, triphenylenyl, pyrene, chrysene, peryl, fluoranthenyl, naphthyl, pentacene, benzopyrenyl, biphenyl, biphenyl, terphenyl, triphenyl, tetraphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthrenyl, dihydropyrenyl, tetrahydropyrenyl, cis- or trans-indenofluorenyl, trimerized indenyl, isotrimerized indenyl, spirotrimerized indenyl, and spiroisotrimerized indenyl. Specifically, the biphenyl group is selected from 2-biphenyl, 3-biphenyl and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracenyl group is selected from 1-anthracenyl, 2-anthracenyl and 9-anthracenyl; the fluorenyl group is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl; the pyrenyl group is selected from 1-pyrenyl, 2-pyrenyl and 4-pyrenyl; the tetraphenyl group is selected from 1-tetraphenyl, 2-tetraphenyl and 9-tetraphenyl. Preferred examples of the aryl group in the present invention include phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, indenyl, fluorenyl and its derivatives, fluoranthenyl, triphenylene, pyrenyl, peryl, The biphenyl group is selected from the group consisting of 2-biphenyl, 3-biphenyl and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracenyl group is selected from the group consisting of 1-anthracenyl, 2-anthracenyl and 9-anthracenyl. wherein the fluorenyl group is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, and 9-fluorenyl; the fluorenyl derivative is selected from the group consisting of 9,9-dimethylfluorene, 9,9-spirobifluorene, and benzofluorene; the pyrenyl group is selected from the group consisting of 1-pyrenyl, 2-pyrenyl, and 4-pyrenyl; and the naphthacene group is selected from the group consisting of 1-naphthacene, 2-naphthacene, and 9-naphthacene. The C6-C60 aryl group of the present invention may also be a combination of the above groups connected by single bonds or / and fused.

[0038] In the present specification, the substituted or unsubstituted C3-C60 heteroaromatic ring is preferably a C3-C30 heteroaromatic ring, which can be a nitrogen-containing heteroaromatic group, an oxygen-containing heteroaromatic group, a sulfur-containing heteroaromatic group, etc. Specific examples include: furyl, thienyl, pyrrolyl, pyridyl, benzofuranyl, benzothienyl, isobenzofuranyl, isobenzothienyl, indolyl, isoindolyl, dibenzofuranyl, dibenzothienyl, carbazolyl and its derivatives, quinolyl, isoquinolyl, acridinyl, phenanthridinyl , benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, phenothiazinyl, phenazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthoxazolyl, anthrazolyl, phenanthroxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthryl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbolinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl, 1, 1,2,3,4-tetrazolyl, 1,2,3,5-tetrazolyl, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazole and the like. Preferred examples of the heteroaromatic ring in the present invention include furyl, thienyl, pyrrolyl, benzofuranyl, benzothienyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothienyl, carbazolyl and derivatives thereof, wherein the carbazolyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole, benzocarbazole, dibenzocarbazole or indolocarbazole.

[0039] In the present specification, the substituted or unsubstituted C3-C60 heteroaryl group is preferably a C3-C30 heteroaryl group, more preferably a nitrogen-containing heteroaryl group, an oxygen-containing heteroaryl group, a sulfur-containing heteroaryl group, etc. Specific examples include: furyl, thienyl, pyrrolyl, pyridyl, benzofuranyl, benzothienyl, isobenzofuranyl, isobenzothienyl, indolyl, isoindolyl, dibenzofuranyl, dibenzothienyl, carbazolyl and its derivatives, quinolyl, isoquinolyl, acridinyl, phenanthridine yl, benzo-5,6-quinolyl, benzo-6,7-quinolyl, benzo-7,8-quinolyl, phenothiazinyl, phenazinyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalinoimidazolyl, oxazolyl, benzoxazolyl, naphthoxazolyl, anthrazolyl, phenanthroxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazinyl, pyrimidazinyl, pyridinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazaanthryl, 2,7-diazapyrenyl, 2,3-diazapyrenyl, 1,6-diazapyrenyl, 1,8-diazapyrenyl, 4,5-diazapyrenyl, 4,5,9,10-tetraazaperyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbolinyl, phenanthrolinyl, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazole, oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazole and the like. Preferred examples of heteroaryl groups in the present invention include furyl, thienyl, pyrrolyl, benzofuranyl, benzothienyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothienyl, carbazolyl, and derivatives thereof, wherein the carbazolyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole, benzocarbazole, dibenzocarbazole, or indolocarbazole. The C3-C60 heteroaryl group of the present invention may also be a combination of the above groups linked by single bonds or / and fused.

[0040] In the present invention, examples of aryloxy and heteroaryloxy groups include groups formed by the aforementioned aryl and heteroaryl groups and oxygen. In the present invention, examples of arylamino and heteroarylamino groups include groups formed by the aforementioned aryl and heteroaryl groups replacing one or two H groups in the -NH2 group.

[0041] In this specification, the term "chain alkyl" encompasses both straight-chain and branched alkyl groups. Examples of C1-C20 chain alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, n-hexyl, neohexyl, n-heptyl, n-octyl, and 2-ethylhexyl. Examples of C1-C20 chain haloalkyl groups include trifluoromethyl, pentafluoroethyl, and 2,2,2-trifluoroethyl.

[0042] In the present specification, the C3-C20 cycloalkyl group includes monocyclic alkyl groups and polycyclic alkyl groups, and specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexyl, cycloheptyl, cyclooctyl, and adamantyl groups.

[0043] The C2 to C20 alkenyl group includes both straight-chain and branched alkenyl groups, and also includes cycloalkenyl groups. The number of carbon atoms in the alkenyl group is preferably 2 to 10. Specific examples include ethenyl, 1-propenyl, 2-propenyl, 2-butenyl, 3-butenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 5-hexenyl, 7-octenyl, and groups in which these groups have substituents such as alkyl groups and alkoxy groups.

[0044] In the present specification, an alkoxy group refers to a group consisting of the above-mentioned chain alkyl group and oxygen, or a group consisting of the above-mentioned cycloalkyl group and oxygen.

[0045] Examples of C1-C20 alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, and dodecyloxy groups. Preferred groups include methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, sec-butoxy, isobutoxy, and isopentyloxy groups, and more preferred groups include methoxy.

[0046] In a preferred embodiment of the present invention, it has the structure shown in formula (1-1),

[0047]

[0048] Ring C, R c 、R z1 and R z2 has the same meaning as in formula (1), where

[0049] R z1 、R z2 At least one of them is a structure of formula (2),

[0050]

[0051] U 1 ~U 5are independently selected from CR' or N, wherein R' is independently selected from one of hydrogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C2-C20 heterocycloalkyl, halogen, cyano, nitro, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl, adjacent R's are not connected or are connected to form a ring by chemical bonds, the R' is not connected to adjacent ring structures or is connected to form a ring by chemical bonds, or at least one R' is a structure of formula (a) or formula (b),

[0052] Y 1 is a single bond or a phenylene group,

[0053] Z 1 ~Z 8 Each is independently selected from CR or N, and R is independently selected from hydrogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylamino, substituted or unsubstituted C2-C20 heterocycloalkyl, halogen, cyano, nitro, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, or substituted or unsubstituted C3-C60 heteroaryl;

[0054] X 1 ~X 4 、X 8 ~X 11 independently selected from CR" or N, wherein R" is independently selected from one of hydrogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 heterocycloalkyl, halogen, cyano, nitro, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl;

[0055] The above-mentioned substituents are each independently selected from any one or a combination of at least two of halogen, C1-C20 chain alkyl, C3-C20 cycloalkyl, C2-C20 heterocycloalkyl, C1-C20 alkoxy, C1-C20 alkylamino, cyano, nitro, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, and C3-C60 heteroaryl. The expression of the ring structure crossed out by “—” indicates that the connection site is any position on the ring structure that can form a bond, and the * indicates the connection site.

[0056] In a preferred embodiment of the present invention, the ring C has a structure as shown in formula (f):

[0057]

[0058] Among them, the dotted line represents the fused bond of the group;

[0059] X 5 ~X 7 Each independently is CR" or N;

[0060] R" are each independently selected from any one of hydrogen, halogen, cyano, nitro, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 heterocycloalkyl, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, or substituted or unsubstituted C3-C60 heteroaryl; adjacent R"s are not connected or are connected to form a ring by chemical bonds, and the R" is not connected to adjacent ring structures or is connected to form a ring by chemical bonds;

[0061] The substituents are each independently selected from any one of halogen, C1-C20 chain alkyl, C3-C20 cycloalkyl, C2-C20 heterocycloalkyl, C1-C20 alkoxy, C1-C20 alkylamino, cyano, nitro, hydroxy, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, and C3-C60 heteroaryl, or a combination of at least two thereof.

[0062] X is preferred 5 ~X 7 Each independently is CR", further preferably X 5 、X 7 Each is CH, X 6is CR", and R" is selected from one of H, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl, cyclohexyl, 2,2,5,5-tetramethylhexyl, phenyl, naphthyl, tert-butylphenyl, pyridine and pyrimidine.

[0063] In a preferred embodiment of the present invention, the compounds have the structures shown in the following formulas (2-1) to (2-8):

[0064]

[0065]

[0066] In formulas (2-1) to (2-8), Z 1 ~Z 8 are each independently selected from CR or N, and R is independently selected from one or a combination of two of hydrogen, C1-C20 chain alkyl, C2-C10 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylamino, C2-C20 heterocycloalkyl, halogen, cyano, nitro, C6-C60 arylamino, C3-C60 heteroarylamino, C6-C60 aryl, and C3-C60 heteroaryl. Preferably, Z 1 ~Z 8 Each is independently selected from CR, and R is independently selected from one or a combination of two of hydrogen, C1-C10 chain alkyl, C3-C11 cycloalkyl, C2-C11 heterocycloalkyl, C6-C20 aryl, and C3-C20 heteroaryl;

[0067] X 1 ~X 11 are each independently selected from CR" or N, wherein R" is independently selected from one or a combination of two of hydrogen, C1-C20 chain alkyl, C3-C20 cycloalkyl, C2-C20 heterocycloalkyl, halogen, cyano, nitro, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 aryl, C3-C60 heteroaryl, preferably, X 1 ~X 11 CR” and R” are each independently selected from hydrogen, C1-C10 chain alkyl, C3-C11 cycloalkyl, C2-C11 heterocycloalkyl, C6-C20 aryl, or C3-C20 heteroaryl, or a combination of two thereof;

[0068] U 1 ~U 5are each independently selected from CR' or N, wherein R' is independently selected from one or a combination of two of hydrogen, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C2-C20 heterocycloalkyl, halogen, cyano, nitro, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 aryl, C3-C60 heteroaryl, preferably, U 1 ~U 5 Each is independently selected from CR', and R' is independently selected from one or a combination of two of hydrogen, C1-C10 chain alkyl, C3-C11 cycloalkyl, C2-C11 heterocycloalkyl, C6-C20 aryl, and C3-C20 heteroaryl;

[0069] R Z1 、R Z2 are independently selected from one or a combination of two of hydrogen, C1-C20 chain alkyl, C3-C20 cycloalkyl, C2-C20 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroaryl. Preferably, R Z1 、R Z2 Each is independently selected from one or a combination of two of hydrogen, C1-C10 chain alkyl, C3-C11 cycloalkyl, C2-C11 heterocycloalkyl, C6-C20 aryl, and C3-C20 heteroaryl;

[0070] R 1 ~R 6 Each independently selected from hydrogen, C1-C20 chain alkyl, C3-C20 cycloalkyl or a combination of two. Preferably, R 1 ~R 6 Each is independently selected from one or a combination of hydrogen, C1-C10 chain alkyl, and C3-C11 cycloalkyl.

[0071] In a preferred embodiment of the present invention, R 1 ~R 6 Each is independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, cyclopentyl, cyclohexyl or a structure as shown below:

[0072]

[0073] * indicates the connection site, and the structure with two * indicates R 1 ~R 6 The two connections in form this structure.

[0074] In a preferred embodiment of the present invention, X 1 、X 2 、X 4 、X 5 、X 7~X 9 、X 11 CH, X 3 、X 6 、X 10 CR", R" are each independently selected from one of H, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl, cyclohexyl, 2,2,5,5-tetramethylhexyl, phenyl, naphthyl, tert-butylphenyl, pyridine, and pyrimidine;

[0075] Z 3 、Z 7 Each is independently CR, and each R is independently selected from H, fluorine, chlorine, cyano, nitro, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl and one of the following groups,

[0076]

[0077] Z 2 、Z 4 、Z 6 、Z 8 CH, Z 1 、Z 5 are independently selected from CR, and the R are independently selected from H, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl, cyclohexyl and one of the following groups,

[0078]

[0079] Or, Z 6 ~Z 8 CH, Z 1 、Z 2 CH, Z 3 and Z 4 Each independently is CR and Z 3 and Z 4 The following structure is formed between R, or Z 2 ~Z 4 CH, Z 5 、Z 6 CH, Z 7 and Z 8 Each independently is CR and Z 7 and Z 8 The following structure is formed between R,

[0080]

[0081] Or, Z 6 ~Z 8 CH, Z 1 、Z 4 CH, Z 2and Z 3 Each independently is CR and Z 2 and Z 3 The following structure is formed between R, or Z 2 ~Z 4 CH, Z 5 、Z 8 CH, Z 6 and Z 7 Each independently is CR and Z 6 and Z 7 The following structure is formed between R,

[0082]

[0083] * indicates the connection site.

[0084] Furthermore, the organic compounds of the present invention may preferably include the specific structural compounds shown below, which are only representative and do not limit the scope of the present invention:

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091] The organic compound has a simple and easy preparation process, readily available raw materials, and is suitable for mass production and expansion. It is used as a material for the light-emitting layer in an organic electroluminescent device, enabling the device to achieve high-quality blue light emitting effects, effectively extending the life of the device and improving luminous efficiency.

[0092] In a second aspect, the present invention provides a use of the organic compound according to the first aspect, wherein the organic compound is used in an organic electronic device.

[0093] Preferably, the organic electronic device includes an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information tag, an electronic artificial skin sheet, a sheet-type scanner or electronic paper, and an organic electroluminescent device is further preferred.

[0094] Preferably, the organic compound is used as a light-emitting layer material in an organic electroluminescent device.

[0095] Preferably, the organic compound is used as a luminescent dye of a light-emitting layer in an organic electroluminescent device.

[0096] In a third aspect, the present invention provides an organic electroluminescent device, comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode; the organic layer comprises at least one organic compound as described in the first aspect, preferably comprising at least one organic compound having the structure shown in the above-mentioned present invention.

[0097] Preferably, the organic layer includes a light-emitting layer, and the light-emitting layer includes at least one organic compound as described in the first aspect, preferably includes at least one organic compound having the structure shown in the above-mentioned present invention.

[0098] Preferably, the light-emitting layer includes a host material and a dye, and the dye includes at least one organic compound as described in the first aspect, and further preferably includes at least one organic compound having the structure shown in the present invention.

[0099] As a preferred technical solution of the present invention, the organic compound, when used as a dye for the light-emitting layer, especially as a luminescent dye, has good luminescence properties, can improve the lifespan and external quantum efficiency of the device, and enable the device to have high luminescence efficiency and better color purity, which can meet the current requirements of panel and display manufacturers for high-performance materials.

[0100] The organic compound provided by the present invention can be used as a TADF material, as a dye (guest material) of the light-emitting layer, and is suitable for organic electroluminescent devices with a TADF mechanism or an organic electroluminescent device with a TASF (thermally activated sensitized fluorescence) mechanism, and can effectively improve the performance of the device. Its good carrier transport performance and high luminous efficiency have potential applications in solving the efficiency roll-off of OLED devices at high current density and extending the device life.

[0101] Preferably, the organic layer further comprises any one of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer, or a combination of at least two thereof.

[0102] In a fourth aspect, the present invention provides a display device, comprising the organic electroluminescent device according to the third aspect.

[0103] The OLED device prepared using the compound of the present invention has low starting voltage, high luminous efficiency and better service life, and can meet the requirements of current panel and display manufacturers for high-performance materials. DETAILED DESCRIPTION

[0104] The technical solution of the present invention is further described in more detail below.

[0105] Synthesis methods of compounds

[0106] In one embodiment, the compounds of the present invention can be obtained by known methods, for example, by known organic synthesis methods. The following is an exemplary synthesis route, but those skilled in the art can also obtain the compounds by other methods known to them. The synthesis route of the compounds represented by the general formula of the present invention can be, for example:

[0107]

[0108] where Y 1 To Y 4 Each independently represents a substituted or unsubstituted Z 1 to Z 8 , or substituted or unsubstituted U 1 to U 5 ;

[0109]

[0110]

[0111] Synthesize the material structure using a similar synthesis method:

[0112]

[0113]

[0114] Use the same synthesis method to synthesize material structures:

[0115]

[0116]

[0117] Similarly, those skilled in the art can synthesize other material structures using roughly the same synthesis method, which will not be described in detail here. Alternatively, those skilled in the art can also prepare them using other methods known in the art. The compounds for which no synthesis method is mentioned in the present invention are all raw materials obtained from commercial sources, or are prepared in-house using these raw materials according to known methods.

[0118] It should be noted that, unless otherwise indicated, "R1", "R 1 ” and “R1” have the same meaning and can be replaced with each other. For other symbols such as R2, similar definitions have the same meaning.

[0119] The following synthesis examples of the present invention illustratively provide specific synthesis methods for representative compounds. The solvents, reagents, intermediates, and chemical reagents such as ethyl acetate, methanol, and ethanol used in the following synthesis examples can all be purchased or customized from the domestic chemical product market.

[0120] The present invention will describe in detail the specific preparation methods of the organic compounds described herein using a number of preparation examples and synthesis examples. However, the preparation methods of the present invention are not limited to these synthesis examples. It should be noted that obtaining the organic compounds described herein is not limited to the synthesis methods and starting materials used in the present invention. Those skilled in the art may also use other methods or routes to obtain the organic compounds described herein.

[0121] In addition, although representative exemplary synthetic routes of the compounds of the present invention are described in the Examples, those skilled in the art can also obtain the compounds by other methods known in the art.

[0122] Organic EL devices

[0123] The OLED structure of the present invention can refer to known technologies. For example, an organic electroluminescent device (OLED) includes a first electrode, a second electrode, and an organic material layer located between the electrodes. The organic material layer can be divided into multiple regions. For example, the organic material layer can include a hole transport region, a light-emitting layer, and an electron transport region.

[0124] In a specific embodiment, a substrate can be used below the first electrode or above the second electrode. The substrate is made of glass or a polymer material with excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, the substrate used for the display can also be provided with thin film transistors (TFTs).

[0125] The first electrode can be formed by sputtering or depositing the material used as the first electrode on the substrate. When the first electrode serves as an anode, transparent conductive oxide materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), and any combination thereof can be used. When the first electrode serves as a cathode, metals or alloys such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), ytterbium (Yb), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag) can be used, as well as any combination thereof.

[0126] The organic material layer can be formed on the electrode by vacuum thermal evaporation, spin coating, printing, etc. The compound used as the organic material layer can be organic small molecules, organic macromolecules and polymers, and combinations thereof.

[0127] The hole transport region is located between the anode and the light-emitting layer. The hole transport region can be a single-layer hole transport layer (HTL), including single-layer hole transport layers containing only one compound and single-layer hole transport layers containing multiple compounds. The hole transport region can also be a multilayer structure comprising at least one of the following: a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL); wherein the HIL is located between the anode and the HTL, and the EBL is located between the HTL and the light-emitting layer.

[0128] The material of the hole transport region can be selected from, but not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylene ethylene, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), aromatic amine derivatives such as the compounds shown in HT-1 to HT-51 below; or any combination thereof.

[0129]

[0130]

[0131]

[0132] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer can be a single compound or a combination of multiple compounds. For example, the hole injection layer can use one or more of the compounds HT-1 to HT-51 described above, or one or more of the compounds HI-1 to HI-3 described below. Alternatively, one or more of the compounds HT-1 to HT-51 can be doped with one or more of the compounds HI-1 to HI-3 described below.

[0133]

[0134] The light-emitting layer includes a luminescent dye (i.e., a dopant) that can emit light at different wavelengths, and may also include a host material. The light-emitting layer can be a monochromatic light-emitting layer that emits a single color, such as red, green, or red. Multiple monochromatic light-emitting layers of different colors can be arranged in a planar pattern according to a pixel pattern, or they can be stacked together to form a multi-color light-emitting layer. When light-emitting layers of different colors are stacked together, they can be separated from each other or connected to each other. The light-emitting layer can also be a single-color light-emitting layer that can simultaneously emit different colors, such as red, green, and red.

[0135] Depending on the technology, the light-emitting layer material can be made of fluorescent electroluminescent materials, phosphorescent electroluminescent materials, thermally activated delayed fluorescence materials, and other materials. An OLED device can use a single light-emitting technology or a combination of multiple technologies. These different light-emitting materials, categorized by technology, can emit light of the same color or different colors.

[0136] In one aspect of the present invention, the light-emitting layer adopts fluorescent electroluminescence technology. The fluorescent host material of the light-emitting layer can be selected from, but not limited to, one or more combinations of BFH-1 to BFH-17 listed below.

[0137]

[0138] In one aspect of the present invention, the barrier layer surrounding the light-emitting layer can be selected from, but not limited to, one or more combinations of PH-1 to PH-85.

[0139]

[0140]

[0141]

[0142]

[0143] In one aspect of the present invention, an electron blocking layer (EBL) is positioned between the hole transport layer and the light emitting layer. The EBL can be composed of, but is not limited to, one or more of the compounds HT-1 to HT-51 described above, or one or more of the compounds PH-47 to PH-77 described above; or a mixture of, but not limited to, one or more of the compounds HT-1 to HT-51 and one or more of the compounds PH-47 to PH-77.

[0144] The OLED organic material layer may also include an electron transport region between the light-emitting layer and the cathode. This region may be a single-layer electron transport layer (ETL), including those containing only one compound and those containing multiple compounds. The region may also be a multilayer structure comprising at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0145] In one aspect of the present invention, the electron transport layer material can be selected from, but not limited to, one or more combinations of ET-1 to ET-73 listed below.

[0146]

[0147]

[0148]

[0149]

[0150] In one aspect of the present invention, a hole-blocking layer (HBL) is positioned between the electron-transporting layer and the light-emitting layer. The hole-blocking layer may be composed of, but is not limited to, one or more of the compounds ET-1 to ET-73 described above, or one or more of the compounds PH-1 to PH-46, or a mixture of, but not limited to, one or more of the compounds ET-1 to ET-73 and one or more of the compounds PH-1 to PH-46.

[0151] The device may also include an electron injection layer located between the electron transport layer and the cathode. The electron injection layer material includes but is not limited to one or more combinations of the following: LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, Mg, and Yb.

[0152] Specific examples are described below. Those skilled in the art should understand that the examples are only provided to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0153] Example

[0154] Synthesis of compounds

[0155] The specific preparation methods of the above-mentioned new compounds of the present invention will be described in detail below using multiple synthesis examples as examples, but the preparation methods of the present invention are not limited to these synthesis examples. It should be noted that obtaining the compounds is not limited to the synthesis methods and raw materials used in the present invention, and those skilled in the art can also choose other methods or routes to obtain the compounds proposed by the present invention. The compounds of the synthesis methods not mentioned in the present invention are all raw materials obtained through commercial channels, or are made by self-production according to known methods using these raw materials. The solvents and reagents used in the present invention, such as dichloromethane, petroleum ether, ethanol, tert-butylbenzene, boron tribromide, carbazole, diphenylamine, and other chemical reagents, can all be purchased from the domestic chemical product market, such as Sinopharm Reagent Company, TCI Company, Shanghai Bid Pharmaceutical Company, Bailingwei Reagent Company, etc. The analysis and detection of the intermediates and compounds in the present invention uses an ABSCIEX mass spectrometer (4000QTRAP). The structural analysis and detection of the intermediates and compounds in the present invention uses a gas chromatography-mass spectrometer (GC-MS, Shimadzu QP2010 SE).

[0156] Synthetic preparation of the compound of the present invention:

[0157] Synthesis Example (1): Synthesis of Intermediate A1

[0158]

[0159] Experimental Procedure: 100 g of 4,4-dimethylcyclohexanone was added to a 3 L single-necked flask, followed by 1 L of THF. A 2.5 M THF solution (370 mL) was slowly added at -10°C under nitrogen. The mixture was returned to room temperature and stirred for 2 hours. Then, 1 L of saturated brine was added. The mixture was separated, dried, concentrated, and purified by vacuum distillation to yield the target intermediate A1 (101.94 g). MS: 142.14 / 142.24 (calcd / measured).

[0160] Synthesis Example (2): Synthesis of Intermediate A2

[0161]

[0162] Experimental Procedure: Intermediate A1 (100 g) and phenol (66.16 g) were placed in a 3-L single-necked flask. 1 L of toluene was then added, followed by the slow addition of boron trifluoride etherate (149.67 g) at 0°C. After the addition was complete, the mixture was allowed to react overnight at room temperature. The next day, the mixture was washed with 1 L of saturated brine, concentrated, and purified by vacuum distillation to yield the target intermediate A2 (102.86 g). MS: 218.17 / 218.85 (calcd / measured).

[0163] Synthesis Example (3): Synthesis of Intermediate A3

[0164]

[0165] Experimental procedure: Intermediate A3 (94.63 g) was synthesized by referring to the method for synthesizing intermediate A2. MS: 232.18 / 232.37 (calculated value / found value).

[0166] Synthesis Example (4): Synthesis of Intermediate A4

[0167]

[0168] Experimental procedure: Intermediate A4 (96.09 g) was synthesized by referring to the method for synthesizing intermediate A2. MS: 266.17 / 266.38 (calculated value / found value).

[0169] Synthesis Example (5): Synthesis of Intermediate A5

[0170]

[0171] Experimental procedure: Intermediate A5 (90.32 g) was synthesized by referring to the method for synthesizing intermediate A2. MS: 246.20 / 246.39 (calculated value / found value).

[0172] Synthesis Example (6): Synthesis of Intermediate A6

[0173]

[0174] Experimental procedure: Intermediate A6 (105.08 g) was synthesized by referring to the method for synthesizing intermediate A2. MS: 190.14 / 190.29 (calculated value / found value).

[0175] Synthesis Example (7): Synthesis of Intermediate A7

[0176]

[0177] Experimental Procedure: Add 4-chloro-2-bromoaniline (50 g), phenylboronic acid (35.43 g), tetrakistriphenylphosphine palladium (5.6 g), and potassium carbonate (50.20 g) to a 1 L single-necked flask. Add 400 mL of 1,4-dioxane and 80 mL of water. React at 100°C under nitrogen for 10 hours. Heating is then stopped, the separated liquid is washed with water, dried, concentrated, and purified by vacuum distillation to yield the target intermediate A7 (31.77 g). MS: 203.05 / 203.67 (calcd / measured).

[0178] Synthesis Example (8): Synthesis of Intermediate A8

[0179]

[0180] Experimental procedure: Intermediate A8 (49.54 g) was synthesized by referring to the method for synthesizing intermediate A7. MS: 313.16 / 313.87 (calculated / found).

[0181] Synthesis Example (9): Synthesis of Intermediate B1

[0182]

[0183] Experimental Procedure: Intermediate A2 (100 g) and triethylamine (69.52 g) were placed in a 1 L single-necked flask and dissolved in 500 mL of dichloromethane. Trifluoromethanesulfonic anhydride (155.06 g) was then slowly added at 0°C. After the addition was complete, the mixture was returned to room temperature and allowed to react for 3 hours. Then, 300 mL of saturated brine was added, the mixture was separated, dried, concentrated, and purified by column chromatography to obtain the target intermediate B1 (114.3 g). MS: 350.12 / 350.54 (calcd / measured).

[0184] Synthesis Example (10): Synthesis of Intermediate B2

[0185]

[0186] Experimental procedure: Intermediate B2 (128.61 g) was synthesized by referring to the method for synthesizing intermediate B1. MS: 364.13 / 364.42 (calculated value / found value).

[0187] Synthesis Example (11): Synthesis of Intermediate B3

[0188]

[0189] Experimental procedure: Intermediate B3 (103.69 g) was synthesized by referring to the method for synthesizing intermediate B1. MS: 322.09 / 322.34 (calculated value / found value).

[0190] Synthesis Example (12): Synthesis of Intermediate B4

[0191]

[0192] Experimental procedure: Intermediate B4 (110.57 g) was synthesized by referring to the method for synthesizing intermediate B1. MS: 378.15 / 378.45 (calculated value / found value).

[0193] Synthesis Example (13): Synthesis of Intermediate B5

[0194]

[0195] Experimental procedure: Intermediate B5 (102.36 g) was synthesized by referring to the method for synthesizing intermediate B1. MS: 398.12 / 398.44 (calculated value / found value).

[0196] Synthesis Example (14): Synthesis of Intermediate B6

[0197]

[0198] Experimental procedures: Intermediate A7 (30 g), (5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)boronic acid (41.03 g), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium (3.14 g), and potassium carbonate (30.54 g) were added to a 1 L single-necked flask. 1,4-dioxane (300 mL) and water (60 mL) were added. The mixture was reacted at 100°C under nitrogen atmosphere for 10 hours. Heating was then stopped, the fraction was washed with water, dried, concentrated, and purified by column chromatography to obtain the target intermediate B6 (38.87 g). MS: 355.23 / 355.84 (calcd / measured).

[0199] Synthesis Example (15): Synthesis of Intermediate B7

[0200]

[0201] Experimental procedure: Intermediate B7 (39.06 g) was synthesized by referring to the method for synthesizing intermediate B6. MS: 355.23 / 355.53 (calculated value / found value).

[0202] Synthesis Example (16): Synthesis of Intermediate B8

[0203]

[0204] Experimental Procedure: Intermediate B2 (100 g), benzophenone imine (60 g), Pd2(dba)3 (7.5 g), cesium carbonate (134.11 g), and S-Phos (11.27 g) were placed in a 1 L single-necked flask. 500 mL of 1,4-dioxane was added and the mixture was reacted at 100°C under nitrogen for 3 hours. Heating was then stopped and the mixture was filtered. The filtrate was washed three times with water and separated. 100 mL of concentrated hydrochloric acid was added and the mixture was reacted at 60°C for 10 hours. The washed fraction was then dried, concentrated, and purified by vacuum distillation to obtain the target intermediate B8 (48 g). MS: 231.20 / 231.38 (calcd / measured).

[0205] Synthesis Example (17): Synthesis of Intermediate B9

[0206]

[0207] Experimental procedure: Intermediate B9 (45.67 g) was synthesized by referring to the method for synthesizing intermediate B8. MS: 245.21 / 245.41 (calculated value / found value).

[0208] Synthesis Example (18): Synthesis of Intermediate C1

[0209]

[0210] Experimental Procedure: Intermediate B3 (50 g), pinacol diboronate (48 g), Pd(dppf)Cl2 (5.7 g), and potassium acetate (23 g) were placed in a 2 L single-necked flask. 500 mL of 1,4-dioxane was added and the mixture was reacted at 100°C under nitrogen for 10 hours. Heating was then stopped and 300 mL of water was added. The washed fraction was dried, concentrated, and purified by column chromatography to obtain the target intermediate C1 (38.84 g). MS: 300.23 / 300.25 (calculated / measured).

[0211] Synthesis Example (19): Synthesis of Intermediate C2

[0212]

[0213] Experimental procedure: Intermediate C2 (35.67 g) was synthesized by referring to the method for synthesizing intermediate C1. MS: 328.26 / 328.30 (calculated value / found value).

[0214] Synthesis Example (20): Synthesis of Intermediate D1

[0215]

[0216] Experimental Procedure: 4-tert-Butylphenylboronic acid (30 g), 2-bromo-4-tert-butylaniline (38.44 g), tetrakistriphenylphosphine palladium (9.74 g), and potassium carbonate (34.93 g) were added to a 1 L single-necked flask. 300 mL of 1,4-dioxane and 60 mL of water were added. The mixture was heated at 100°C for 10 hours. Heating was stopped, and 100 mL of dichloromethane and 100 mL of water were added. The washed fraction was dried, concentrated, and purified by column chromatography to obtain the target intermediate D1 (35.94 g). MS: 281.21 / 281.44 (calcd / measured).

[0217] Synthesis Example (21): Synthesis of Intermediate D2

[0218]

[0219] Experimental procedure: Intermediate D2 (33.76 g) was synthesized by referring to the method for synthesizing intermediate D1. MS: 321.25 / 321.51 (calculated value / found value).

[0220] Synthesis Example (22): Synthesis of Intermediate D3

[0221]

[0222] Experimental procedure: Intermediate D3 (36.07 g) was synthesized by referring to the method for synthesizing intermediate D1. MS: 349.28 / 349.56 (calculated value / found value).

[0223] Synthesis Example (23): Synthesis of Intermediate D4

[0224]

[0225] Experimental procedure: Intermediate D4 (32.85 g) was synthesized by referring to the method for synthesizing intermediate D1. MS: 337.28 / 337.55 (calculated value / found value).

[0226] Synthesis Example (24): Synthesis of Intermediate D5

[0227]

[0228] Experimental procedures: Intermediate D1 (30 g), 4-tert-butylbromobenzene (27.26 g), Pd(dppf)Cl2 (3.9 g), and sodium tert-butoxide (15.37 g) were placed in a 1 L single-necked flask. 300 mL of toluene was added and the mixture was reacted at 100°C under nitrogen for 10 hours. Heating was stopped, and 100 mL of water and 100 mL of dichloromethane were added. The washed fractions were dried, concentrated, and purified by column chromatography to obtain the target intermediate D5 (39.87 g). MS: 413.31 / 413.65 (calcd / measured).

[0229] Synthesis Example (25): Synthesis of Intermediate D6

[0230]

[0231] Experimental procedure: Intermediate D6 (38.06 g) was synthesized by referring to the method for synthesizing intermediate D5. MS: 469.37 / 469.76 (calculated value / found value).

[0232] Synthesis Example (26): Synthesis of Intermediate D7

[0233]

[0234] Experimental steps: Intermediate D7 (35.94 g) was synthesized by referring to the method for synthesizing intermediate D5. MS: 363.29 / 363.59 (calculated value / found value).

[0235] Synthesis Example (27): Synthesis of Intermediate D8

[0236]

[0237] Experimental procedure: Intermediate D8 (36.05 g) was synthesized by referring to the method for synthesizing intermediate D5. MS: 377.31 / 377.62 (calculated value / found value).

[0238] Synthesis Example (28): Synthesis of Intermediate D9

[0239]

[0240] Experimental procedure: Intermediate D9 (38.17 g) was synthesized by referring to the method for synthesizing intermediate D5. MS: 431.36 / 431.71 (calculated value / found value).

[0241] Synthesis Example (29): Synthesis of Material D10

[0242]

[0243] Experimental procedure: Intermediate D10 (37.62 g) was synthesized by referring to the method for synthesizing intermediate D5. MS: 453.34 / 453.71 (calculated value / found value).

[0244] Synthesis Example (30): Synthesis of Material D11

[0245]

[0246] Experimental procedure: Intermediate D11 (36.85 g) was synthesized by referring to the method for synthesizing intermediate D5. MS: 481.37 / 481.77 (calculated value / found value).

[0247] Synthesis Example (31): Synthesis of Material E1

[0248]

[0249] Experimental Procedure: 3,5-Dibromo-tert-butylbenzene (30 g), 4-tert-butylaniline (16.87 g), Pd(dppf)Cl2 (3.76 g), and sodium tert-butoxide (14.81 g) were added to a 1 L single-necked flask. 300 mL of toluene was added and the mixture was reacted at 100°C under nitrogen for 10 hours. Heating was then stopped, and 100 mL of water and 100 mL of dichloromethane were added. The washed fractions were dried, concentrated, and purified by column chromatography to obtain the target intermediate E1 (26.44 g). MS: 359.12 / 359.34 (calcd / measured).

[0250] Synthesis Example (32): Synthesis of Material E2

[0251]

[0252] Experimental Procedure: 3-tert-butyl-1,5-phenylenediamine (30 g), intermediate B2 (66.56 g), Pd(dppf)Cl2 (6.7 g), and sodium tert-butoxide (26.33 g) were added to a 1-L single-necked flask. 300 mL of toluene was added and the mixture was reacted at 100°C under nitrogen for 10 hours. The reaction was terminated, and 100 mL of water and 100 mL of dichloromethane were added. The fraction was washed with water, dried, concentrated, and purified by column chromatography to obtain the target intermediate E2 (48.27 g). MS: 378.30 / 378.60 (calcd / measured).

[0253] Synthesis Example (33): Synthesis of Intermediate E3

[0254]

[0255] Experimental procedures: Isobutyl nitrite (18.39 g) and copper bromide (53.09 g) were added to a 1 L single-necked flask, followed by 400 mL of acetonitrile. After heating at 60°C for 1 hour, an acetonitrile solution of intermediate E2 (45 g) was slowly added. After complete addition, the mixture was maintained at 60°C for 2 hours. Heating was then stopped, the mixture was cooled, filtered, evaporated to dryness under reduced pressure, and purified by column chromatography to obtain the target intermediate E3 (26.73 g). MS: 441.20 / 441.49 (calcd / measured).

[0256] Synthesis Example (34): Synthesis of Intermediate E4

[0257]

[0258] Experimental procedure: Intermediate E4 (45.66 g) was synthesized by referring to the method for synthesizing intermediate E2. MS: 412.29 / 412.62 (calculated value / found value).

[0259] Synthesis Example (35): Synthesis of Intermediate E5

[0260]

[0261] Experimental procedure: Intermediate E5 (24.91) was synthesized by referring to the synthesis procedure of intermediate E3. MS: 475.19 / 475.50 (calculated value / found value).

[0262] Synthesis Example (36): Synthesis of Intermediate E6

[0263]

[0264] Experimental procedure: Intermediate E6 (28.41 g) was synthesized by referring to the synthesis procedure of intermediate E1. MS: 531.25 / 531.61 (calculated value / found value).

[0265] Synthesis Example (37): Synthesis of Intermediate E7

[0266]

[0267] Experimental procedure: Intermediate E7 (29.06 g) was synthesized by referring to the synthesis procedure of intermediate E1. MS: 565.23 / 565.59 (calculated value / found value).

[0268] Synthesis Example (38): Synthesis of Intermediate E8

[0269]

[0270] Experimental procedure: Intermediate E8 (25.54 g) was synthesized by referring to the synthesis procedure of intermediate E1. MS: 565.23 / 565.63 (calculated value / found value).

[0271] Synthesis Example (39): Synthesis of Intermediate F1

[0272]

[0273] Experimental Procedure: Intermediate E1 (25 g), Boc anhydride (22.71 g), and DIEA (4.24 g) were placed in a 1-L single-necked flask. 300 mL of THF was added and the mixture was heated at 60°C for 3 hours. Heating was then stopped, and 100 mL of water and 100 mL of dichloromethane were added. The fraction was washed with water, dried, concentrated, and purified by column chromatography to yield the target intermediate F1 (29.61 g). MS: 459.18 / 459.46 (calcd / measured).

[0274] Synthesis Example (40): Synthesis of Intermediate F2

[0275]

[0276] Experimental procedure: Intermediate F2 (27.54 g) was synthesized by referring to the synthesis procedure of intermediate F1. MS: 541.26 / 541.60 (calculated value / found value).

[0277] Synthesis Example (41): Synthesis of Intermediate F3

[0278]

[0279] Experimental procedure: Intermediate F3 (28.16 g) was synthesized by referring to the synthesis procedure of intermediate F1. MS: 575.24 / 575.62 (calculated value / found value).

[0280] Synthesis Example (42): Synthesis of Intermediate F4

[0281]

[0282] Experimental procedure: Intermediate F4 (27.69 g) was synthesized by referring to the synthesis procedure of intermediate F1. MS: 631.30 / 631.73 (calculated value / found value).

[0283] Synthesis Example (43): Synthesis of Intermediate F5

[0284]

[0285] Experimental procedure: Intermediate F5 (25.66 g) was synthesized by referring to the synthesis procedure of intermediate F1. MS: 665.29 / 665.80 (calculated value / found value).

[0286] Synthesis Example (44): Synthesis of Intermediate F6

[0287]

[0288] Experimental procedure: Intermediate F6 (26.17 g) was synthesized by referring to the synthesis procedure of intermediate F1. MS: 665.29 / 665.74 (calculated value / found value).

[0289] Synthesis Example (45): Synthesis of Intermediate G1

[0290]

[0291] Experimental procedures: Intermediate D5 (25 g), intermediate F2 (32.79 g), Pd2(dba)3 (1.66 g), S-Phos (3.72 g), and sodium tert-butoxide (8.71 g) were placed in a 1 L single-necked flask. 300 mL of toluene was added and the mixture was reacted at 100°C under nitrogen for 2 hours. 100 mL of water and 200 mL of dichloromethane were added, the fraction was washed with water, dried, concentrated, and purified by column chromatography to obtain the target intermediate G1 (37.76 g). MS: 874.34 / 874.64 (calcd / measured).

[0292] Synthesis Example (46): Synthesis of Intermediate G2

[0293]

[0294] Experimental procedure: Intermediate G2 (36.98 g) was synthesized by referring to the synthesis procedure of intermediate G1. MS: 832.26 / 832.64 (calculated value / found value).

[0295] Synthesis Example (47): Synthesis of Intermediate G3

[0296]

[0297] Experimental procedure: Intermediate G3 (36.89 g) was synthesized by referring to the synthesis procedure of intermediate G1. MS: 832.26 / 832.59 (calculated value / found value).

[0298] Synthesis Example (48): Synthesis of Intermediate G4

[0299]

[0300] Experimental procedure: Intermediate G4 (37.21 g) was synthesized by referring to the synthesis procedure of intermediate G1. MS: 930.45 / 930.70 (calculated value / found value).

[0301] Synthesis Example (49): Synthesis of Intermediate G5

[0302]

[0303] Experimental procedure: Intermediate G5 (36.55 g) was synthesized by referring to the synthesis procedure of intermediate G1. MS: 858.30 / 858.61 (calculated value / found value).

[0304] Synthesis Example (50): Synthesis of Intermediate G6

[0305]

[0306] Experimental procedure: Intermediate G6 (37.61 g) was synthesized by referring to the synthesis procedure of intermediate G1. MS: 872.32 / 872.62 (calculated value / found value).

[0307] Synthesis Example (51): Synthesis of Intermediate G7

[0308]

[0309] Experimental procedure: Intermediate G7 (37.22 g) was synthesized by referring to the synthesis procedure of intermediate G1. MS: 1016.54 / 1016.76 (calculated value / found value).

[0310] Synthesis Example (52): Synthesis of Intermediate G8

[0311]

[0312] Experimental procedure: Intermediate G8 (36.48 g) was synthesized by referring to the synthesis procedure of intermediate G1. MS: 1016.54 / 1016.72 (calculated value / found value).

[0313] Synthesis Example (53): Synthesis of Intermediate G9

[0314]

[0315] Experimental procedure: Intermediate G9 (37.25 g) was synthesized by referring to the synthesis procedure of intermediate G1. MS: 860.31 / 860.62 (calculated value / found value).

[0316] Synthesis Example (54): Synthesis of Intermediate G10

[0317]

[0318] Experimental procedures: Intermediate G1 (30 g) was added to a 1 L single-necked flask, along with 300 mL of THF and 60 mL of concentrated hydrochloric acid. The mixture was stirred at 60°C for 10 hours. Heating was stopped, and 200 mL of water and 200 mL of dichloromethane were added. The washed fraction was dried and concentrated, and 100 mL of methanol was added to slurry the mixture, followed by filtration to obtain the target intermediate G10 (23.16 g). MS: 774.22 / 774.59 (calculated / measured).

[0319] Synthesis Example (55): Synthesis of Intermediate G11

[0320]

[0321] Experimental procedure: Intermediate G11 (19.94 g) was synthesized by referring to the synthesis procedure of intermediate G10. MS: 732.14 / 732.66 (calculated value / found value).

[0322] Synthesis Example (56): Synthesis of Intermediate G12

[0323]

[0324] Experimental procedure: Intermediate G12 (21.56 g) was synthesized by referring to the synthesis procedure of intermediate G10. MS: 732.14 / 732.54 (calculated value / found value).

[0325] Synthesis Example (57): Synthesis of Intermediate G13

[0326]

[0327] Experimental procedure: Intermediate G13 (20.89 g) was synthesized by referring to the synthesis procedure of intermediate G10. MS: 830.33 / 830.65 (calculated value / found value).

[0328] Synthesis Example (58): Synthesis of Intermediate G14

[0329]

[0330] Experimental procedure: Intermediate G14 (20.89 g) was synthesized by referring to the synthesis procedure of intermediate G10. MS: 758.18 / 758.55 (calculated value / found value).

[0331] Synthesis Example (59): Synthesis of Intermediate G15

[0332]

[0333] Experimental procedure: Intermediate G15 (21.07 g) was synthesized by referring to the synthesis procedure of intermediate G10. MS: 772.21 / 772.57 (calculated value / found value).

[0334] Synthesis Example (60): Synthesis of Intermediate G16

[0335]

[0336] Experimental procedure: Intermediate G16 (20.76 g) was synthesized by referring to the synthesis procedure of intermediate G10. MS: 916.42 / 916.59 (calculated value / found value).

[0337] Synthesis Example (61): Synthesis of Intermediate G17

[0338]

[0339] Experimental procedure: Intermediate G17 (19.54 g) was synthesized by referring to the synthesis procedure of intermediate G10. MS: 916.42 / 916.66 (calculated value / found value).

[0340] Synthesis Example (62): Synthesis of Intermediate G18

[0341]

[0342] Experimental procedure: Intermediate G18 (19.54 g) was synthesized by referring to the synthesis procedure of intermediate G10. MS: 760.57 / 760.20 (calculated value / found value).

[0343] Synthesis Example (63): Synthesis of Intermediate H1

[0344]

[0345] Experimental procedures: Intermediate G10 (20 g), 3-bromo-5-(tert-butyl)benzo[B]thiophene (8.33 g), Pd2(dba)3 (0.71 g), S-Phos (1.59 g), and sodium tert-butoxide (3.72 g) were placed in a 1-L three-necked flask. 200 mL of toluene was added and the mixture was reacted at 100°C for 2 hours. Heating was then stopped, and 100 mL of water and 100 mL of dichloromethane were added. The fraction was washed with water, dried, concentrated, and purified by column chromatography to obtain the target intermediate H1 (21.07 g). MS: 962.51 / 962.65 (calcd / measured).

[0346] Synthesis Example (64): Synthesis of Intermediate H2

[0347]

[0348] Experimental procedure: Intermediate H2 (20.98 g) was synthesized by referring to the synthesis procedure of intermediate H1. MS: 920.43 / 920.72 (calculated value / found value).

[0349] Synthesis Example (65): Synthesis of Intermediate H3

[0350]

[0351] Experimental procedure: Intermediate H3 (18.94 g) was synthesized by referring to the synthesis procedure of intermediate H1. MS: 920.43 / 920.60 (calculated value / found value).

[0352] Synthesis Example (66): Synthesis of Intermediate H4

[0353]

[0354] Experimental procedure: Intermediate H4 (20.17 g) was synthesized by referring to the synthesis procedure of intermediate H1. MS: 1018.62 / 1018.71 (calculated value / found value).

[0355] Synthesis Example (67): Synthesis of Intermediate H5

[0356]

[0357] Experimental procedure: Intermediate H5 (19.61 g) was synthesized by referring to the synthesis procedure of intermediate H1. MS: 946.47 / 946.62 (calculated value / found value).

[0358] Synthesis Example (68): Synthesis of Intermediate H6

[0359]

[0360] Experimental procedure: Intermediate H6 (20.59 g) was synthesized by referring to the synthesis procedure of intermediate H1. MS: 960.49 / 960.64 (calculated value / found value).

[0361] Synthesis Example (69): Synthesis of Intermediate H7

[0362]

[0363] Experimental procedure: Intermediate H7 (21.34 g) was synthesized by referring to the synthesis procedure of intermediate H1. MS: 1104.71 / 1104.82 (calculated value / found value).

[0364] Synthesis Example (70): Synthesis of Intermediate H8

[0365]

[0366] Experimental procedure: Intermediate H8 (20.66 g) was synthesized by referring to the synthesis procedure of intermediate H1. MS: 1104.71 / 1104.73 (calculated value / found value).

[0367] Synthesis Example (71): Synthesis of Intermediate H9

[0368]

[0369] Experimental procedure: Intermediate H9 (19.54 g) was synthesized by referring to the synthesis procedure of intermediate H1. MS: 948.48 / 948.64 (calculated value / found value).

[0370] Synthesis Example (72): Synthesis of Final Product M-4

[0371]

[0372] Experimental procedures: Intermediate H1 (15 g) was added to a 100 mL shcelk bottle, followed by 30 mL of o-dichlorobenzene and 23.40 g of boron tribromide. The flask was sealed after nitrogen evacuation and the reaction was carried out at 150°C for 24 hours. After heating was stopped, the reaction system was poured into 100 mL of saturated sodium bisulfite solution and diluted with 100 mL of dichloromethane. The liquid was separated, washed, dried, concentrated, and purified by column chromatography to obtain the final product M-4 (2.97 g). MS: 970.30 / 970.64 (calculated / measured).

[0373] Synthesis Example (73): Synthesis of Final Product M-17

[0374]

[0375] Experimental procedure: Referring to the synthesis procedure of the final product M-4, the final product M-17 (2.88 g) was synthesized. MS: 928.22 / 928.46 (calculated value / found value).

[0376] Synthesis Example (74): Synthesis of Final Product M-19

[0377]

[0378] Experimental procedure: Referring to the synthesis procedure of the final product M-4, the final product M-19 (2.88 g) was synthesized. MS: 956.27 / 956.62 (calculated value / found value).

[0379] Synthesis Example (75): Synthesis of Final Product M-33

[0380]

[0381] Experimental procedure: Referring to the synthesis procedure of the final product M-4, the final product M-33 (2.65 g) was synthesized. MS: 928.22 / 928.59 (calculated value / found value).

[0382] Synthesis Example (76): Synthesis of Final Product M-62

[0383]

[0384] Experimental procedure: The final product M-62 (2.71 g) was synthesized by referring to the synthesis procedure of the final product M-4. MS: 1026.40 / 1026.70 (calculated value / found value).

[0385] Synthesis Example (77): Synthesis of Final Product M-81

[0386]

[0387] Experimental procedure: The final product M-81 (2.34 g) was synthesized by referring to the synthesis procedure of the final product M-4. MS: 954.25 / 954.61 (calculated value / found value).

[0388] Synthesis Example (78): Synthesis of Final Product M-93

[0389]

[0390] Experimental procedure: The final product M-93 (2.68 g) was synthesized by referring to the synthesis procedure of the final product M-4. MS: 968.28 / 968.62 (calculated value / found value).

[0391] Synthesis Example (79): Synthesis of Final Product M-103

[0392]

[0393] Experimental procedure: The final product M-103 (2.61 g) was synthesized by referring to the synthesis procedure of the final product M-4. MS: 1112.50 / 1112.68 (calculated value / found value).

[0394] Synthesis Example (80): Synthesis of Final Product M-104

[0395]

[0396] Experimental procedure: The final product M-104 (2.33 g) was synthesized by referring to the synthesis procedure of the final product M-4. MS: 1112.50 / 1112.72 (calculated value / found value).

[0397] Device Examples

[0398] The preparation process of the organic electroluminescent device in this embodiment is as follows:

[0399] Glass plates coated with an ITO transparent conductive layer were ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in an acetone:ethanol mixed solvent, baked in a clean environment to completely remove water, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam.

[0400] Place the glass substrate with the anode in a vacuum chamber and evacuate the chamber to a pressure less than 1*10 -5 Pa, a mixture of HT-4:HI-3 (97 / 3, w / w) was vacuum-deposited on the above-mentioned anode layer as a hole injection layer at a deposition rate of 0.1 nm / s and a film thickness of 10 nm;

[0401] HT-4 was vacuum evaporated on the hole injection layer as the hole transport layer of the device at a deposition rate of 0.1 nm / s and a total film thickness of 60 nm.

[0402] HT-14 was vacuum-deposited on the hole transport layer as the electron blocking layer of the device at a deposition rate of 0.1 nm / s and a total film thickness of 5 nm.

[0403] The light-emitting layer of the device is vacuum-deposited on the electron blocking layer. The light-emitting layer includes a host material and a dye material. A 20 nm thick binary mixture of compound BFH-4 and fluorescent dye (100:3, w / w) is deposited as the light-emitting layer by a multi-source co-evaporation method. The fluorescent dye is compound M-4 of the present invention.

[0404] 5 nm of ET-23 was vacuum-deposited on the light-emitting layer as a hole-blocking layer, and 25 nm of a mixture of compounds ET-69:ET-57 (50 / 50, w / w) was vacuum-deposited as an electron-transporting layer at a rate of 0.1 nm / s.

[0405] LiF with a thickness of 1 nm was vacuum evaporated on the electron transport layer as the electron injection layer, and 150 nm of metal aluminum was used as the cathode. The total evaporation rate of LiF was controlled at 0.1 nm / s, and the evaporation rate of the metal electrode was controlled at 1 nm / s.

[0406] Device Examples 2 to 13, Comparative Examples 1 to 6:

[0407] Device Examples 2 to 13 were prepared in the same manner as in Device Example 1, except that the luminescent dye in the luminescent layer was replaced by the compounds of the present invention listed in Table 1 instead of the compound M-4 of the present invention.

[0408] Device Comparative Examples 1 to 6 were prepared using the same method as in Device Example 1, except that the luminescent dye in the luminescent layer was replaced by the compound M-4 of the present invention with the following compounds N1 to N6 obtained using prior art or according to a similar preparation process to the synthesis examples of the present invention, respectively. The specific structures are shown below:

[0409]

[0410] Device test method (including equipment and test conditions):

[0411] The organic electroluminescent device prepared by the above process was subjected to the following performance tests:

[0412] Use a fluorescence spectrometer to test the fluorescence spectrum of the corresponding material in 0.01 g / mL toluene solution at room temperature, and the luminescence peak wavelength is the peak value of the spectrum;

[0413] The external quantum efficiency (EQE%) of the organic electroluminescent device was measured using an integrating sphere; the external quantum efficiency of the device in comparative example 1 was set to 1.0, and the external quantum efficiencies of the other materials were all ratios thereof;

[0414] The life test of LT97 is as follows: Use a luminance meter at 40mA / cm 2 Initial brightness of the device at a given current density. Maintaining a constant current, measure the time (in hours) for the device brightness to drop to 97% of its initial brightness. Taking the LT97 lifetime test value of Comparative Example 1 as 1.0, calculate the ratio of the LT97 lifetime test values ​​of the other devices to that of Comparative Example 1.

[0415] The performance of the organic electroluminescent devices prepared in the above device embodiments and comparative examples is shown in Table 1 below.

[0416] Table 1:

[0417]

[0418] As shown in Table 1, when the material schemes and preparation processes for the other functional layers in the organic electroluminescent device structure are identical, the organic electroluminescent devices prepared in Examples 1-13 of the present invention effectively maintain substantially the same operating voltage compared to the organic electroluminescent devices prepared in Comparative Examples 1-6. External quantum efficiency increases are generally observed, with the highest increase reaching approximately 15%. This increase is presumably due to improved molecular-level dipole orientation, which increases the device's light extraction rate and, therefore, efficiency. Furthermore, materials such as M-81 and M-93 (benzothiophene side chains with ortho-aryl substitutions on one side and cycloalkyl substitutions on the other) exhibit significantly extended device lifetimes while maintaining their efficiency advantages. In the comparative compounds, the N1 substituent contains benzyl hydrogen, which is unstable when the device is in working state and affects the device life; N2 does not have a benzothiophene structure, and the triplet energy level is relatively high, which easily causes triplet exciton quenching, affecting efficiency and life (at the same time, the stability of 1-methylcyclohexyl is not as good as 1,4,4-trimethylcyclohexyl, resulting in a low life); N3 also has the problem of low stability of 1-methylcyclohexyl, and there is no alkyl protection at the 3-position of benzothiophene, which also leads to a low life of the material; N4 has a methylene position at the Y1 position, resulting in insufficient rigidity of the steric hindering group and no occlusive effect, and the methylene structure is easily oxidized, resulting in a low life; N5 does not have the groups of formula (a) and formula (b), and the life characteristics of other steric hindering groups are not as good as those of the present invention; N6 does not contain a sulfur-containing five-membered heterocyclic condensed system, so the overall photoelectric efficiency is low.

[0419] The specific embodiments described above further illustrate the objectives, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above are only specific embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

[0420] The present invention illustrates the detailed method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented. Although the present invention is described in conjunction with the embodiments, the present invention is not limited to the above-mentioned embodiments. It should be understood that under the guidance of the concept of the present invention, those skilled in the art can make various modifications and improvements. The attached claims summarize the scope of the present invention. The equivalent replacement of the raw materials of the product of the present invention, the addition of auxiliary ingredients, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.

Claims

1. A boron-nitrogen-containing organic compound having a structure shown in formula (1): In formula (1), X represents O, S, NR 0 、C(R 0 )2, wherein, Each R 0 are independently selected from hydrogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, R 0 They are connected to each other by chemical bonds to form a ring or not; Ring A, B, and C are each independently selected from a C6-C60 aromatic ring and a C3-C60 heteroaromatic ring; R a 、R b 、R c represents single substitution to maximum substitution, R a 、R b 、R c Each is independently selected from any one of hydrogen, halogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 heterocycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylamino, cyano, nitro, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; said R a 、R b 、R c They are independently connected to each other by chemical bonds to form a ring or are not connected; Z 1 ~Z 8 are independently selected from CR or N, wherein R is independently selected from hydrogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 heterocycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C1-C20 alkylamino, halogen, cyano, nitro, substituted or unsubstituted C6-C60 arylamino, substituted or unsubstituted C3-C60 heteroarylamino, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, adjacent R are not connected or connected by chemical bonds to form a ring, and the R is not connected to the adjacent ring structure or connected by chemical bonds to form a ring; R z1 、R z2 are independently selected from one of hydrogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl; wherein, R z1 、R z2 At least one of the compounds comprises a structure of formula (a) or formula (b), In formula (a) and formula (b), R 1 、R 2 、R 3 、R 4 、R 5 、R 6 R is independently selected from one of hydrogen, substituted or unsubstituted C1-C20 chain alkyl, and substituted or unsubstituted C3-C20 cycloalkyl; 1 、R 2 Connect or not connect; R 3 、R 4 Connect or not connect, R 5 、R 6 Connect or not connect; Y 1 are independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group; The substituents mentioned above are each independently selected from any one of halogen, C1-C20 chain alkyl, C3-C20 cycloalkyl, C2-C20 heterocycloalkyl, C1-C20 alkoxy, C1-C20 alkylamino, cyano, nitro, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, and C3-C60 heteroaryl, or a combination of at least two thereof. The expression of a ring structure crossed by "—" indicates that the attachment site is any position on the ring structure that can form a bond, and an * indicates the attachment site.

2. The boron-nitrogen-containing organic compound according to claim 1, characterized in that Having the structure shown in formula (1-1), Ring C, R c 、R z1 and R z2 Same as in formula (1), where R z1 、R z2 At least one of them is a structure of formula (2), U 1 ~U 5 are independently selected from CR' or N, wherein R' is independently selected from one of hydrogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C2-C20 heterocycloalkyl, halogen, cyano, nitro, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl, adjacent R's are not connected or are connected to form a ring by chemical bonds, the R' is not connected to adjacent ring structures or is connected to form a ring by chemical bonds, or at least one R' is a structure of formula (a) or formula (b), Y 1 is a single bond or a phenylene group, Z 1 ~Z 8 The meaning is the same as in formula (1); X 1 ~X 4 、X 8 ~X 11 independently selected from CR" or N, wherein R" is independently selected from one of hydrogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 heterocycloalkyl, halogen, cyano, nitro, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl; The substituents mentioned above are each independently selected from any one of halogen, C1-C20 chain alkyl, C3-C20 cycloalkyl, C2-C20 heterocycloalkyl, C1-C20 alkoxy, C1-C20 alkylamino, cyano, nitro, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, and C3-C60 heteroaryl, or a combination of at least two thereof. The expression of a ring structure crossed by "—" indicates that the attachment site is any position on the ring structure that can form a bond, and an * indicates the attachment site.

3. The boron-nitrogen-containing organic compound according to claim 1, wherein the ring C has a structure as shown in formula (f): in, Dashed lines represent fused bonds of groups; X 5 ~X 7 Each independently is CR" or N; R" are each independently selected from any one of hydrogen, halogen, cyano, nitro, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C2-C20 heterocycloalkyl, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroarylamino, substituted or unsubstituted C6-C30 aryloxy, substituted or unsubstituted C3-C30 heteroaryloxy, substituted or unsubstituted C6-C60 aryl, or substituted or unsubstituted C3-C60 heteroaryl; adjacent R"s are not connected or are connected to form a ring by chemical bonds, and the R" is not connected to adjacent ring structures or is connected to form a ring by chemical bonds; The substituents are each independently selected from any one of halogen, C1-C20 chain alkyl, C3-C20 cycloalkyl, C2-C20 heterocycloalkyl, C1-C20 alkoxy, C1-C20 alkylamino, cyano, nitro, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C60 aryl, and C3-C60 heteroaryl, or a combination of at least two thereof. X is preferred 5 ~X 7 Each independently is CR", further preferably X 5 、X 7 Each is CH, X 6 is CR", and R" is selected from one of H, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl, cyclohexyl, 2,2,5,5-tetramethylhexyl, phenyl, naphthyl, tert-butylphenyl, pyridine and pyrimidine.

4. The boron-nitrogen-containing organic compound according to claim 1, characterized in that It has the structures shown in the following formulas (2-1) to (2-8): In formulas (2-1) to (2-8), Z 1 ~Z 8 Each is independently selected from CR or N, and R is independently selected from one or a combination of two of hydrogen, C1-C20 chain alkyl, C2-C10 alkenyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C1-C20 alkylamino, C2-C20 heterocycloalkyl, halogen, cyano, nitro, C6-C60 arylamino, C3-C60 heteroarylamino, C6-C60 aryl, and C3-C60 heteroaryl; X 1 ~X 11 are each independently selected from CR" or N, wherein R" is independently selected from one or a combination of two of hydrogen, C1-C20 chain alkyl, C3-C20 cycloalkyl, C2-C20 heterocycloalkyl, halogen, cyano, nitro, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 aryl, and C3-C60 heteroaryl; U 1 ~U 5 are each independently selected from CR' or N, wherein R' is independently selected from one or a combination of two of hydrogen, C1-C20 chain alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, C2-C20 heterocycloalkyl, halogen, cyano, nitro, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 aryl, and C3-C60 heteroaryl; R Z1 、R Z2 Each is independently selected from one or a combination of two of hydrogen, C1-C20 chain alkyl, C3-C20 cycloalkyl, C2-C20 heterocycloalkyl, C6-C60 aryl, and C3-C60 heteroaryl; R 1 ~R 6 Each is independently selected from one or a combination of hydrogen, C1-C20 chain alkyl, C3-C20 cycloalkyl.

5. The boron-nitrogen-containing organic compound according to any one of claims 1 to 4, characterized in that R 1 ~R 6 Each is independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, cyclopentyl, cyclohexyl or a structure as shown below: * indicates the connection site, and the structure with two * indicates R 1 ~R 6 The two connections in form this structure.

6. The boron-nitrogen-containing organic compound according to claim 4, characterized in that X 1 、X 2 、X 4 、X 5 、X 7 ~X 9 、X 11 CH, X 3 、X 6 、X 10 CR", R" are each independently selected from one of H, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl, cyclohexyl, 2,2,5,5-tetramethylhexyl, phenyl, naphthyl, tert-butylphenyl, pyridine, and pyrimidine; Z 3 、Z 7 Each is independently CR, and each R is independently selected from H, fluorine, chlorine, cyano, nitro, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl and one of the following groups, Z 2 、Z 4 、Z 6 、Z 8 CH, Z 1 、Z 5 are independently selected from CR, and the R are independently selected from H, methyl, ethyl, isopropyl, tert-butyl, tert-pentyl, isobutyl, cyclopentyl, cyclohexyl and one of the following groups, Or, Z 6 ~Z 8 CH, Z 1 、Z 2 CH, Z 3 and Z 4 Each independently is CR and Z 3 and Z 4 The following structure is formed between R, or Z 2 ~Z 4 CH, Z 5 、Z 6 CH, Z 7 and Z 8 Each independently is CR and Z 7 and Z 8 The following structure is formed between R, Or, Z 6 ~Z 8 CH, Z 1 、Z 4 CH, Z 2 and Z 3 Each independently is CR and Z 2 and Z 3 The following structure is formed between R, or Z 2 ~Z 4 CH, Z 5 、Z 8 CH, Z 6 and Z 7 Each independently is CR and Z 6 and Z 7 The following structure is formed between R, * indicates the connection site.

7. The boron-nitrogen-containing organic compound according to claim 1, comprising the following specific compounds:

8. Use of the organic compound according to any one of claims 1 to 7 in an organic electronic device; Preferably, the organic electronic device comprises an organic electroluminescent device; Preferably, the application is application as a light-emitting layer material in an organic electroluminescent device.

9. An organic electroluminescent device comprising a first electrode, a second electrode, and an organic layer interposed between the first electrode and the second electrode, characterized in that: The organic layer contains the organic compound according to any one of claims 1 to 7; Preferably, at least one of the organic layers is a light-emitting layer, and the light-emitting layer contains the organic compound according to any one of claims 1 to 7. Preferably, the light-emitting layer comprises a host material and a dye, and the dye comprises at least one organic compound according to any one of claims 1 to 7.

10. A display device, characterized in that: The display device comprises the organic electroluminescent device according to claim 9.

Images