Organic electroluminescent material and organic electroluminescent device comprising same

Abstract

The invention relates to an organic electroluminescent material, which comprises a combination of a first compound and a second compound, the first compound and the second compound are respectively and independently selected from a structure shown in a formula (I), a group of a structure shown in a formula (A) is fused and connected at a dotted line position, and G represents a group of a structure shown in a formula (B) or a formula (C). The organic electroluminescent material provided by the invention has excellent photoelectric properties and carrier transport performance, realizes balanced transport of carriers, and reduces energy loss in a host-guest energy transfer process of a luminescent layer and improves the utilization rate of excitons when being applied to an organic electroluminescent device, thereby significantly improving the luminous efficiency and stability of the device, and reducing the cost of the device. The service life of the device is prolonged. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the technical field of organic electroluminescence, and particularly relates to an organic electroluminescent material and an organic electroluminescent device comprising the same. Background Art

[0002] As a new display technology, organic electroluminescent (OLED) devices have the advantages of being thin, light, wide viewing angle, active light-emitting, continuously adjustable emission color, low cost, fast response speed, low energy consumption, low driving voltage, wide operating temperature range, simple production process, high luminous efficiency, flexible display, etc., and have received great attention from the industrial and scientific communities and have achieved commercial success in the field of information display.

[0003] OLED devices usually have a stacked structure including two electrodes and an organic functional thin film, and the core thereof is an organic functional thin film containing various organic functional materials. Common organic functional materials include: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, light-emitting host materials, light-emitting guests (dyes), etc. When powered on, electrons and holes are respectively injected and transported to the light-emitting region and recombined here, thereby generating excitons and emitting light.

[0004] With the continuous advancement of OLED technology in the fields of lighting and display, in recent years, industry insiders have continuously tried and explored to improve the efficiency and stability of devices. Specific methods include innovation of device structures and improvement of organic materials, among which seeking new materials to improve device performance is more common. Researchers have developed a large number of novel materials for use in organic electroluminescent devices. Although they have certain improvements on device performance, there are still problems such as a large amount of carrier accumulation at the interface and low device efficiency.

[0005] There is an urgent need in this field to develop organic electroluminescent devices with higher performance to meet their application requirements in lighting and display. Therefore, the industry urgently expects electroluminescent materials with more perfect optoelectronic properties. Summary of the Invention

[0006] Aiming at the deficiencies of the prior art, the purpose of the present invention is to provide an organic electroluminescent material and an organic electroluminescent device comprising the same. Through the design and mutual cooperation of a first compound and a second compound with a specific structure, the organic electroluminescent material has excellent optoelectronic properties, so that the organic electroluminescent device comprising the same has higher efficiency and longer lifespan.

[0007] To achieve the purpose of this invention, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides an organic electroluminescent material, comprising a combination of a first compound and a second compound, wherein the first compound and the second compound are each independently selected from the structures represented by Formula (I):

[0009]

[0010] In Formula (I), a group represented by Formula (A) is fused and connected at the dotted line position;

[0011] In the first compound, G in Formula (A) represents a group represented by Formula (B), and in the second compound, G in Formula (A) represents a group represented by Formula (C); “—*” represents a connection site;

[0012] In Formula (I), R1 and R2 are each independently selected from any one of hydrogen, halogen, amino, unsubstituted or R'-substituted C1-C20 linear alkyl, unsubstituted or R'-substituted C2-C10 alkenyl, unsubstituted or R'-substituted C3-C20 cycloalkyl, unsubstituted or R'-substituted C1-C20 alkoxy, unsubstituted or R'-substituted C1-C20 alkylthio, unsubstituted or R'-substituted C1-C20 alkylsilyl, unsubstituted or R'-substituted C1-C20 alkylamino, unsubstituted or R'-substituted C6-C30 aryl, unsubstituted or R'-substituted C3-C30 heteroaryl, unsubstituted or R'-substituted C6-C30 aryloxy, unsubstituted or R'-substituted C6-C30 arylthio, unsubstituted or R'-substituted C6-C30 arylsilyl, and unsubstituted or R'-substituted C6-C30 arylamino;

[0013] In Formula (B) and Formula (C), Ar1, Ar2, Ar3, and Ar4 are each independently selected from one of unsubstituted or R”-substituted C6-C30 aryl and unsubstituted or R”-substituted C3-C30 heteroaryl;

[0014] In formula (B) and formula (C), Y1, Y2, and Y3 are each independently selected from CR or N, and at least one of Y1, Y2, and Y3 is N; R is selected from hydrogen, halogen, amino, unsubstituted or R'-substituted C1-C20 linear alkyl, unsubstituted or R'-substituted C2-C10 alkenyl, unsubstituted or R'-substituted C3-C20 cycloalkyl, unsubstituted or R'-substituted C1-C20 alkoxy, unsubstituted or R'-substituted C1-C20 alkylthio, unsubstituted or R'-substituted C1-C20 alkylsilyl, unsubstituted or R'-substituted C1-C20 alkylamino, unsubstituted or R'-substituted C6-C30 aryl, unsubstituted or R'-substituted C3-C30 heteroaryl, unsubstituted or R'-substituted C6-C30 aryloxy, unsubstituted or R'-substituted C6-C30 arylthio, unsubstituted or R'-substituted C6-C30 arylsilyl, unsubstituted or R'-substituted C6-C30 arylamino;

[0015] Each of the above R' and R” is independently selected from deuterium, halogen, cyano, C1-C20 linear alkyl, C3-C20 cycloalkyl, C1-C10 alkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C6-C30 aryl, C6-C60 arylboron, C3-C30 heteroaryl, or a combination of one or two of them.

[0016] Preferably, the first compound and the second compound of the present invention are each independently selected from the structures represented by any one of formulas (1-1) to (1-6):

[0017]

[0018] In formulas (1-1) to (1-6), the definitions of G, R1, and R2 have the same ranges as those in formulas (I) and (A).

[0019] In the present invention, the "substituted or unsubstituted" group may be substituted with one substituent or multiple substituents. When there are multiple substituents, they may be selected from different substituents. When the same expression is involved in the present invention, it has the same meaning, and the selection range of the substituents is as shown above and will not be elaborated one by one.

[0020] In this specification, the expression of Ca-Cb represents that the group has a carbon atom number of a-b. Generally, unless otherwise specified, the carbon atom number does not include the carbon atom number of the substituent.

[0021] In this specification, the expression of a ring structure with a "-" drawn through it indicates that the bonding site is at any position on the ring structure where bonding can occur.

[0022] In this specification, "independently of each other" means that when there are multiple subjects, they can be the same or different from each other.

[0023] In the present invention, for the description of chemical elements, unless otherwise specified, it generally includes the concept of its isotopes. For example, the description of "hydrogen (H)" includes its isotopes 1 H (protium or H), 2 H (deuterium or D); carbon (C) includes 12 C, 13 C, etc., and will not be elaborated further.

[0024] In the present invention, the heteroatoms usually refer to atoms or atomic groups selected from N, O, S, P, Si, and Se, preferably selected from N, O, and S.

[0025] In this specification, examples of halogens include: fluorine, chlorine, bromine, iodine, etc.

[0026] In the present invention, unless otherwise specified, aryl and heteroaryl both include monocyclic and fused-ring cases.

[0027] In the present invention, the C6-C60 can all be C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, C48, C50, C52, C54, C56, or C58, etc.

[0028] The C3-C60 can all be C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, C30, C32, C34, C36, C38, C40, C42, C44, C46, C48, C50, C52, C54, C56, or C58, etc.

[0029] The C1-C20 can all be C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, or C19, etc.

[0030] The C3-C20 can all be C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, or C19, etc.

[0031] The C6-C30 can all be C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, or C28, etc.

[0032] Any of C3-C30 may be C3, C4, C5, C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26 or C28, etc.

[0033] Any of C2-C10 may be C2, C3, C4, C5, C6, C7, C8, C9 or C10.

[0034] In the present invention, the substituted or unsubstituted C6-C60 aryl group includes monocyclic aryl groups and polycyclic aryl groups, preferably C6-C30 aryl groups, and more preferably C6-C20 aryl groups. The so-called monocyclic aryl group means that the molecule contains at least one phenyl group. When the molecule contains at least two phenyl groups, the phenyl groups are independent of each other and are connected by single bonds. Exemplarily, such as: phenyl group, biphenyl group, terphenyl group, etc. Specifically, the biphenyl group includes 2-biphenyl group, 3-biphenyl group and 4-biphenyl group; 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 polycyclic aryl group means that the molecule contains at least two aromatic rings, and the aromatic rings are not independent of each other but are fused together by sharing two adjacent carbon atoms. Exemplarily, such as: naphthyl group, anthryl group, phenanthryl group, indenyl group, fluorenyl group, fluoranthenyl group, triphenylenyl group, pyrenyl group, perylenyl group, group, tetracenyl group and their derivative groups, etc. The naphthyl group includes 1-naphthyl group or 2-naphthyl group; the anthryl group is selected from 1-anthryl group, 2-anthryl group and 9-anthryl group; the fluorenyl group is selected from 1-fluorenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group and 9-fluorenyl group; the pyrenyl group is selected from 1-pyrenyl group, 2-pyrenyl group and 4-pyrenyl group; the tetracenyl group is selected from 1-tetracenyl group, 2-tetracenyl group and 9-tetracenyl group. The derivative groups of fluorene are selected from 9,9-dimethylfluorenyl group, 9,9-diethylfluorenyl group, 9,9-dipropylfluorenyl group, 9,9-dibutylfluorenyl group, 9,9-dipentylfluorenyl group, 9,9-dihexylfluorenyl group, 9,9-diphenylfluorenyl group, 9,9-dinaphthylfluorenyl group, 9,9'-spirobifluorenyl group and benzofluorenyl group.

[0035] The C3-C60 heteroaryl groups mentioned in the present invention include monocyclic heteroaryl groups and fused-ring heteroaryl groups, preferably C3-C30 heteroaryl groups, more preferably C4-C20 heteroaryl groups, and even more preferably C5-C12 heteroaryl groups. A monocyclic heteroaryl group refers to a group containing at least one heteroaryl group in the molecule. When the molecule contains one heteroaryl group and other groups (such as aryl groups, heteroaryl groups, alkyl groups, etc.), the heteroaryl group and other groups are independent of each other and are connected by a single bond. Examples of monocyclic heteroaryl groups include, for example, furyl, thienyl, pyrrolyl, pyridyl, etc. A fused-ring heteroaryl group refers to a group containing at least one aromatic heterocycle and an aromatic ring (aromatic heterocycle or aryl ring) in the molecule, and the two are not independent of each other but are fused together by sharing two adjacent atoms. Examples of fused-ring heteroaryl groups include: benzofuryl, benzothienyl, isobenzofuryl, indolyl, dibenzofuryl, dibenzothienyl, carbazolyl, acridinyl, isobenzofuryl, isobenzothienyl, benzocarbazolyl, azacarbazolyl, phenothiazinyl, phenazinyl, 9-phenylcarbazolyl, 9-naphthylcarbazolyl, dibenzocarbazolyl, indolocarbazolyl, etc.

[0036] The aryloxy group in the present invention may include a monovalent group composed of the above-mentioned aryl group, heteroaryl group and oxygen.

[0037] In the present invention, an arylamino group represents a group formed by substituting one or two hydrogens on an amino group with aryl groups, wherein the connection site of the arylamino group can be connected to the aryl group in the arylamino group or to the N in the arylamino group. The exemplary carbon numbers and specific groups of the aryl groups in the arylamino group are the same as those described above.

[0038] Examples of the C6-C30 arylamino groups mentioned in the present invention include, for example, phenylamino, methylphenylamino, naphthylamino, anthrylamino, phenanthrylamino, biphenylamino, etc.

[0039] Examples of the C3-C30 heteroarylamino groups mentioned in the present invention include, for example, pyridylamino, pyrimidinylamino, dibenzofurylamino, etc.

[0040] The linear alkyl groups mentioned in the present invention, unless otherwise specified, include straight-chain alkyl groups and branched-chain alkyl groups. Specifically, substituted or unsubstituted C1-C30 linear alkyl groups, preferably substituted or unsubstituted C1-C16 linear alkyl groups, more preferably substituted or unsubstituted C1-C10 linear alkyl groups. Examples of substituted or unsubstituted C1-C10 linear alkyl groups include, for example, 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, 2-ethylhexyl, etc.

[0041] In the present invention, the cycloalkyl group includes a monocyclic alkyl group and a polycyclic alkyl group; wherein, the monocyclic alkyl group refers to an alkyl group containing a single cyclic structure; the polycyclic alkyl group refers to a structure formed by two or more cycloalkyl groups sharing one or more ring carbon atoms; examples of the C3-C20 cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, etc.

[0042] In the present specification, as the substituted or unsubstituted C1-C20 alkoxy group is preferably a substituted or unsubstituted C1-C10 alkoxy group, examples of the C1-C10 alkoxy group include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, etc., among which methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, sec-butoxy, isobutoxy, isopentyloxy are preferred, and methoxy is more preferred.

[0043] It should be noted that in the present application, for the convenience of description, the possible functions of each group / feature are described separately, but this does not mean that these groups / features act independently. In fact, the reason for obtaining good performance is essentially the optimized combination of the entire molecule, which is the result of the synergistic effect between each group, rather than the effect of a single group.

[0044] Further preferably, in formula (I), R1 and R2 are each independently selected from one of hydrogen, an unsubstituted or R'-substituted C1-C20 linear alkyl group, an unsubstituted or R'-substituted C6-C30 aryl group, and an unsubstituted or R'-substituted C3-C30 heteroaryl group;

[0045] Preferably, R1 and R2 are each independently selected from one of hydrogen, an unsubstituted or R'-substituted C6-C30 aryl group, and an unsubstituted or R'-substituted C3-C30 heteroaryl group; More preferably, R1 and R2 are each independently selected from one of hydrogen, an unsubstituted or R'-substituted C6-C30 aryl group; Even more preferably, R1 and R2 are each independently selected from hydrogen or a C6-C30 aryl group; Most preferably, R1 and R2 are each independently selected from one of hydrogen, phenyl, naphthyl, anthracenyl, benzanthracenyl, and phenanthryl.

[0046] Even further preferably, in formula (C), Y1, Y2, and Y3 are all N;

[0047] In formula (B) and formula (C), Ar1, Ar2, Ar3, and Ar4 are each independently selected from one of the following unsubstituted or R”-substituted groups: phenyl, naphthyl, anthracenyl, benzanthracenyl, phenanthryl, furyl, benzofuryl, dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indolocarbazolyl, pyridyl, quinolinyl, acridinyl, phenanthridinyl, benzo-5,6-quinolinyl, benzo-6,7-quinolinyl, benzo-7,8-quinolinyl, pyrazolyl, indazolyl, imidazolyl, phenanthroline;

[0048] R” is selected from one of C1-C10 linear alkyl, C3-C10 cycloalkyl, C6-C30 aryl, and C3-C30 heteroaryl.

[0049] More preferably, in the compound of the present invention, formula (I) is selected from one of the following structures, where “—*” represents the site connecting to G:

[0050]

[0051]

[0052] Even more preferably, in the compound of the present invention, G in the first compound is selected from any one of the following formulas B1-B81, and G in the second compound is selected from any one of the following formulas C1-C28:

[0053]

[0054]

[0055]

[0056] Among them, “—*” in formulas B1-B81 and formulas C1-C28 represents the connection site with formula (I).

[0057] Most preferably, for the organic electroluminescent material of the present invention, the first compound is selected from the following compounds:

[0058]

[0059] The second compound is selected from the following compounds:

[0060]

[0061] In a second aspect, the present invention provides an application of the organic electroluminescent material as described in the first aspect, and the organic electroluminescent material is applied to an organic electronic device.

[0062] Preferably, the organic electronic device includes an organic electroluminescent device, an optical sensor, a solar cell, an illumination 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 an electronic paper.

[0063] More preferably, the organic electroluminescent material is applied to an organic electroluminescent device. Continuing preferably, the organic electroluminescent material is used as a light-emitting layer material in the organic electroluminescent device.

[0064] Preferably, the organic electroluminescent material is used as a host material of the light-emitting layer in the organic electroluminescent device, and more preferably as a host material of the red light-emitting layer.

[0065] In a third aspect, the present invention provides an organic electroluminescent device, which includes a first electrode, a second electrode, and an organic electroluminescent unit disposed between the first electrode and the second electrode. Each organic electroluminescent unit includes at least one hole-transporting layer, one electron-transporting layer, and one organic light-emitting layer, and the organic light-emitting layer includes the organic electroluminescent material as described in the first aspect.

[0066] Preferably, the organic electroluminescent material as described in the first aspect of the present invention is used as a host material of the light-emitting layer.

[0067] As a preferred technical solution of the present invention, the organic electroluminescent material is used as a host material of the light-emitting layer, which is a dual-host material system. The first compound (the first host material) has excellent hole mobility and hole transport / injection ability. The second compound (the second host material) has a D-A structure and bipolar characteristics. While having excellent electron transport performance, it also has certain hole transport performance. Moreover, it has a low triplet energy level, reducing the energy level difference from the doping material (dye / guest), reducing the energy loss in the host-guest energy transfer, and improving the exciton utilization rate. The two types of compounds are synergistically compounded and used as a dual-host material for an organic electroluminescent device, which can increase the carrier recombination probability in the light-emitting layer, promote the transport balance of carriers, effectively regulate the recombination center position of electrons and holes in the light-emitting layer to be at the center of the light-emitting layer, far from the electron blocking layer and also far from the hole blocking layer, avoid a large accumulation of carriers at the interface, improve the exciton utilization rate, thereby significantly improving the light-emitting efficiency of the device and extending the service life.

[0068] Preferably, in the organic electroluminescent material of the present invention used as the host material of the light-emitting layer, the mass ratio of the first compound to the second compound is (0.1 - 2):1, and for example, it can be 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, etc., and more preferably (0.5 - 1.5):1.

[0069] Continuing preferably, the light-emitting layer further includes a doping material.

[0070] Preferably, the doping material is a phosphorescent doping material, and more preferably a red phosphorescent doping material.

[0071] Preferably, based on the mass of the organic electroluminescent material being 100%, the mass of the doping material is 1 - 10%, and for example, it can be 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%, etc.

[0072] Preferably, the thickness of the light-emitting layer is 10 - 60 nm, and for example, it can be 12 nm, 15 nm, 18 nm, 20 nm, 22 nm, 25 nm, 28 nm, 30 nm, 32 nm, 35 nm, 38 nm, 40 nm, 42 nm, 45 nm, 48 nm, 50 nm, 52 nm, 55 nm or 58 nm, etc., and more preferably 20 - 50 nm.

[0073] In a fourth aspect, the present invention provides a display device, and the display device includes the organic electroluminescent device as described in the third aspect.

[0074] Preferably, the display device includes a display screen or a display panel.

[0075] The present invention also provides an electronic device, and the electronic device includes the aforementioned display device.

[0076] Compared with the prior art, the present invention has the following beneficial effects:

[0077] In the organic electroluminescent material provided by the present invention, through the design and co - compounding of the first compound and the second compound with specific structures, the organic electroluminescent material has excellent optoelectronic properties and carrier transport properties, realizing the balanced transport of carriers. When it is used in an organic electroluminescent device, it can effectively regulate and achieve the injection / transport balance of holes and electrons, regulate the position of the electron - hole recombination center in the light - emitting layer to occur at the center of the light - emitting layer, avoid the large accumulation of carriers at the interface, reduce the energy loss in the energy transfer process between the host and guest in the light - emitting layer, improve the exciton utilization rate, thereby significantly improving the luminous efficiency and stability of the device, prolonging the working life of the device, and obtaining an organic electroluminescent device with more excellent comprehensive performance. Brief Description of the Drawings

[0078] Figure 1 It is a schematic structural diagram of an organic electroluminescent device provided in a specific embodiment of the present invention;

[0079] Among them, 1 - substrate, 2 - anode, 3 - hole injection layer, 4 - hole transport layer, 5 - electron blocking layer, 6 - light - emitting layer, 7 - hole blocking layer, 8 - electron transport layer, 9 - electron injection layer, 10 - cathode, 11 - external power supply. Detailed Embodiments

[0080] The technical solutions of the present invention will be further described in more detail below. Those skilled in the art should understand that the detailed embodiments and examples are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0081] Specific Synthesis Examples

[0082] Obtaining the compounds of the present invention: The compounds represented by formula (I) of the present invention can be obtained by known methods, for example, by known organic synthesis methods. The following gives exemplary synthetic routes, but those skilled in the art can also obtain them by other known methods.

[0083] Synthesis of Intermediate M1 - A

[0084]

[0085] The synthesis of intermediate Mx-A was carried out according to the method in the reference Journal of Organic Chemistry (2019) 84(11), 6928 - 6939: In the first step, the ring-closing reaction of 2-aminopyridine chloride with α-bromoarylacetone gave the chloride intermediate M1-A1; in the second step, the chloride intermediate was converted into the corresponding borate intermediate M1-A2; in the third step, the coupling reaction of intermediate M1-A2 with the chloride of 2-bromobenzaldehyde gave intermediate M1-A3; in the fourth step, intermediate M1-A3 reacted with methoxymethyltriphenylphosphonium chloride to synthesize intermediate M1-A4; in the fourth step, intermediate M1-A4 was cyclized under acidic conditions to synthesize intermediate M1-A.

[0086] Synthesis of intermediate M1-B

[0087]

[0088] The synthesis of intermediate Mx-B was carried out according to the method in the reference Synthesis (2011), (14), 2255 - 2260: In the first step, the ring-closing reaction of 2-aminopyridine chloride with α-bromoarylacetylene gave the chloride intermediate M1-B1; in the second step, the chloride intermediate was converted into the corresponding borate intermediate M1-B2; in the third step, the coupling reaction of intermediate M1-B2 with the chloride of 2-bromobenzaldehyde gave intermediate M1-B3; in the fourth step, intermediate M1-B3 reacted with methoxymethyltriphenylphosphonium chloride to synthesize intermediate M1-B4; in the fifth step, intermediate M1-B4 was cyclized under acidic conditions to synthesize intermediate M1-B.

[0089] Intermediates M2-A, M3-A, and M4-A were synthesized using a synthetic method similar to that of M1-A; intermediates M2-B, M3-B, and M4-B were synthesized using a synthetic method similar to that of M1-B:

[0090]

[0091]

[0092] Synthesis Example 1: Synthesis of compound A1B9

[0093]

[0094] Preparation of compound A1B9-1

[0095] Dissolve the raw material 2-amino-3-chloropyridine (128 g) and α-bromoacetophenone (198 g) in a three-necked flask containing 5 L of ethanol. Add sodium carbonate (212 g) with stirring. After addition, continue stirring and reacting for 8 hours, and monitor the reaction by TLC until completion. Remove the solvent by rotary evaporation under reduced pressure. Dissolve the residue in DCM and water, separate the layers, dry the organic phase with anhydrous sodium sulfate, filter, remove the solvent by rotary evaporation under reduced pressure, and purify by column chromatography to obtain intermediate compound A1B9-1 (208 g).

[0096] Preparation of Compound A1B9-2

[0097] Dissolve intermediate compound A1B9-1 (114 g), bis(pinacolato)diboron (191 g), potassium acetate (144 g), tris(dibenzylideneacetone)dipalladium(0) (4.6 g), and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (4.1 g) in a three-necked flask containing 3 L of 1,4-dioxane. After displacing nitrogen, reflux and react for 12 hours. Monitor the reaction by TLC until completion. Cool the reaction solution to room temperature, remove the solvent by rotary evaporation under reduced pressure. Dissolve the residue in DCM and water, separate the layers, dry the organic phase with anhydrous sodium sulfate, filter, remove the solvent by rotary evaporation under reduced pressure, and purify by column chromatography to obtain intermediate compound A1B9-2 (130 g).

[0098] Preparation of Intermediate A1B9-3

[0099] Dissolve intermediate A1B9-2 (64 g), 2-bromo-4-chlorobenzaldehyde (44 g), potassium carbonate (83 g), and tetrakis(triphenylphosphine)palladium(0) (2.3 g) in a three-necked flask containing 3 / 1 / 1 L of toluene / ethanol / water. After displacing nitrogen, reflux and react for 6 hours. Monitor the reaction by TLC until completion. Cool the reaction solution to room temperature, separate the layers, extract the aqueous phase with toluene, combine the organic phases, dry with anhydrous sodium sulfate, filter, remove the solvent by rotary evaporation under reduced pressure, and purify by column chromatography to obtain intermediate compound A1B9-3 (50 g).

[0100] Preparation of Intermediate A1B9-4

[0101] Add intermediate A1B9-3 (49.8 g) and methoxymethyl(triphenyl)phosphonium chloride (57 g) to a three-necked flask containing 1 L of anhydrous tetrahydrofuran (THF). Replace the air with N2, and add sodium tert-butoxide (30 g) portionwise under ice-bath cooling. After addition, allow the mixture to warm to room temperature naturally and react overnight under N2 protection. Monitor the reaction by TLC until completion. Quench the reaction by adding saturated NH4Cl under ice-bath cooling. Extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, filter, and evaporate under reduced pressure to obtain a crude product as a gray oil, which is used for the next step reaction.

[0102] Preparation of Intermediate A1B9-5

[0103] Add the crude intermediate A1B9-4 obtained from the previous step reaction and dichloromethane (2L) to a three-necked flask. After dissolution, cool the mixture to -5 °C, and dropwise add methanesulfonic acid (29 g) with stirring. After the addition is complete, let it rise to room temperature naturally and continue the reaction for 2 hours. Monitor the reaction by TLC until it is completed. Quench the reaction by adding saturated NaHCO3. Separate the layers, extract the aqueous phase with dichloromethane, combine the organic phases, dry over anhydrous sodium sulfate, filter, and remove the solvent by rotary evaporation under reduced pressure. Purify the crude product by column chromatography to obtain the intermediate compound A1B9-5 (33 g).

[0104] Preparation of Compound A1B9-6

[0105] Dissolve the raw materials 3-aminodibenzofuran (18.3 g), 2-bromobiphenyl (23.2 g), sodium tert-butoxide (29 g), tris(dibenzylideneacetone)dipalladium(0) (916 mg), and 1,3-bis(2,6-diisopropylphenyl)-2-chloroimidazolium hydrochloride (460 mg) in a three-necked flask containing 500 mL of toluene. After replacing the nitrogen, reflux the reaction mixture for 12 hours. Monitor the reaction by TLC until it is completed. Let the reaction solution cool to room temperature, wash it with water, separate the layers, dry the organic phase over anhydrous sodium sulfate, filter, remove the solvent by rotary evaporation under reduced pressure, and purify by column chromatography to obtain the intermediate compound A1B9-6 (25 g).

[0106] Preparation of Compound A1B9

[0107] Dissolve the intermediate A1B9-6 (7 g), intermediate A1B9-5 (6.6 g), sodium tert-butoxide (6 g), tris(dibenzylideneacetone)dipalladium(0) (200 mg), and 2-bis(cyclohexylphosphino)-2',6'-dimethoxybiphenyl (200 mg) in a three-necked flask containing 200 mL of xylene. After replacing the nitrogen, reflux the reaction mixture for 20 hours. Monitor the reaction by TLC until it is completed. Let the reaction solution cool to room temperature, wash it with water, separate the layers, dry the organic phase over anhydrous sodium sulfate, filter, remove the solvent by rotary evaporation under reduced pressure, and purify by column chromatography to obtain compound A1B9 (8.5 g). Calculated molecular weight: 627.23, measured value m / z: 628.2 (M+1).

[0108] Synthesis Example 2: Synthesis of Compound A9B19

[0109]

[0110] The compound A9B19 was prepared by a synthetic method similar to that of compound A1B9, except that the raw material 2-amino-3-chloropyridine was replaced with 2-amino-4-chloropyridine, the raw material 3-aminodibenzofuran was replaced with 2-aminodibenzofuran, and the raw material 2-bromobiphenyl was replaced with 4-chloro-o-terphenyl. The calculated molecular weight of the obtained compound A9B19 is 703.26, and the measured value m / z: 704.3 (M+1).

[0111] Synthesis Example 3: Synthesis of Compound A21B31

[0112]

[0113] Preparation of Compound A21B31-1

[0114] Dissolve the raw materials 2-amino-4-chloropyridine (128 g) and α-bromoacetophenone (189 g) in a three-necked flask containing 3 L of DMF. Add sodium bicarbonate (252 g) with stirring. After addition, heat to 120 °C and continue stirring for 30 hours. Monitor the reaction by TLC until completion. Pour the reaction solution into ice water, filter the precipitated solid, wash it with water and ethanol respectively, dry it, and purify it by column chromatography to obtain the intermediate compound A21B31-1 (165 g).

[0115] Preparation of Compound A21B31-2

[0116] Dissolve the intermediate compound A21B31-1 (114 g), bis(pinacolato)diboron (191 g), potassium acetate (144 g), tris(dibenzylideneacetone)dipalladium(0) (4.6 g), and 2-(dicyclohexylphosphino)-2',6'-dimethoxybiphenyl (4.1 g) in a three-necked flask containing 3 L of 1,4-dioxane. After replacing the nitrogen, reflux for 10 hours. Monitor the reaction by TLC until completion. Cool the reaction solution to room temperature, remove the solvent under reduced pressure, dissolve it with DCM and water, separate the layers, dry the organic layer with anhydrous sodium sulfate, filter, remove the solvent by rotary evaporation under reduced pressure, and purify it by column chromatography to obtain the intermediate compound A21B31-2 (121 g).

[0117] Preparation of Intermediate A21B31-3

[0118] Dissolve the intermediate A21B31-2 (64 g), 2-bromo-5-chlorobenzaldehyde (44 g), potassium carbonate (83 g), and tetrakis(triphenylphosphine)palladium(0) (2.3 g) in a three-necked flask containing 3 / 1 / 1 L of toluene / ethanol / water. After replacing the nitrogen, reflux for 6 hours. Monitor the reaction by TLC until completion. Cool the reaction solution to room temperature, separate the layers, extract the aqueous phase with toluene, combine the organic phases, dry with anhydrous sodium sulfate, filter, remove the solvent by rotary evaporation under reduced pressure, and purify it by column chromatography to obtain the intermediate compound A21B31-3 (57 g).

[0119] Preparation of Intermediate A21B31-4

[0120] Intermediate A21B31-3 (50 g) and methoxymethyltriphenylphosphonium chloride (60 g) were added to a three-necked flask containing anhydrous tetrahydrofuran (THF, 1 L). After purging with N2, sodium tert-butoxide (33 g) was added portionwise under ice-bath cooling. After addition, the mixture was allowed to warm to room temperature naturally and reacted overnight under N2 protection. The reaction was monitored by TLC until completion. The reaction was quenched by adding saturated NH4Cl under ice-bath cooling. The mixture was extracted with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to obtain a crude product as a gray oil, which was used for the next reaction.

[0121] Preparation of Intermediate A21B31-5

[0122] The crude product of Intermediate A21B31-4 obtained from the previous step was added to a three-necked flask, followed by dichloromethane (2 L). After dissolution, the temperature was lowered to -5 °C, and methanesulfonic acid (30 g) was added dropwise with stirring. After the addition was complete, the mixture was allowed to warm to room temperature naturally and reacted for another 2 hours. The reaction was monitored by TLC until completion. The reaction was quenched by adding saturated NaHCO3. The layers were separated, the aqueous phase was extracted with dichloromethane, the organic phases were combined, dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The crude product was purified by column chromatography to obtain Intermediate Compound A21B31-5B1 (11 g) and A21B31-5B2 (18 g).

[0123] Preparation of Compound A21B31-6

[0124] Aniline (9.3 g), 2-chlorobenzo[b]naphtho[2,3-d]furan (25.2 g), sodium tert-butoxide (30 g), tris(dibenzylideneacetone)dipalladium(0) (916 mg), and 1,3-bis(2,6-diisopropylphenyl)-2-chloroimidazolium hydrochloride (460 mg) were dissolved in a three-necked flask containing 500 mL of toluene. After purging with nitrogen, the mixture was refluxed for 15 hours. The reaction was monitored by TLC until completion. The reaction solution was cooled to room temperature, washed with water, the layers were separated, the organic phase was dried over anhydrous sodium sulfate, filtered, the solvent was removed by rotary evaporation under reduced pressure, and the product was purified by column chromatography to obtain Intermediate Compound A21B31-6 (23 g).

[0125] Preparation of Compound A21B31

[0126] Intermediate A21B31-6 (6.2 g), Intermediate A21B31-5 (6.6 g), sodium tert-butoxide (6 g), tris(dibenzylideneacetone)dipalladium(0) (200 mg), and 2-bis(cyclohexylphosphino)-2',6'-dimethoxybiphenyl (200 mg) were dissolved in a three-necked flask containing 200 mL of xylene. After purging with nitrogen, the mixture was refluxed for 15 hours. The reaction was monitored by TLC until completion. The reaction solution was cooled to room temperature, washed with water, the layers were separated, the organic phase was dried over anhydrous sodium sulfate, filtered, the solvent was removed by rotary evaporation under reduced pressure, and the product was purified by column chromatography to obtain Compound A21B31 (8.5 g). Calculated molecular weight: 601.22, measured m / z: 602.2 (M+1).

[0127] Synthesis Example 4: Synthesis of Compound A28B63

[0128]

[0129] Intermediate A28B63-5B1 was prepared by a synthetic method similar to that of Compound A21B31-5B1, except that the raw material 2-amino-4-chloropyridine was replaced with 2-amino-5-chloropyridine.

[0130] Preparation of Intermediate A28B63-6

[0131] 3-Bromodibenzofuran (49.2 g), 3-chlorophenylboronic acid (34 g), potassium carbonate (80 g), and tetrakis(triphenylphosphine)palladium(0) (2 g) were dissolved in a three-necked flask containing 1500 / 500 / 500 mL of toluene / ethanol / water. After replacing nitrogen, the mixture was refluxed for 4 hours. The reaction was monitored by TLC until completion. The reaction solution was cooled to room temperature, and the layers were separated. The aqueous phase was extracted with toluene, and the combined organic phases were dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to remove the solvent. The residue was purified by column chromatography to obtain Intermediate Compound A28B63-6 (47 g).

[0132] Preparation of Compound A28B63-7

[0133] Aniline (9.3 g), A28B63-6 (27.8 g), sodium tert-butoxide (30 g), tris(dibenzylideneacetone)dipalladium(0) (900 mg), and 1,3-bis(2,6-diisopropylphenyl)-2-chloroimidazolium hydrochloride (460 mg) were dissolved in a three-necked flask containing 500 mL of toluene. After replacing nitrogen, the mixture was refluxed for 22 hours. The reaction was monitored by TLC until completion. The reaction solution was cooled to room temperature, washed with water, and the layers were separated. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to remove the solvent. The residue was purified by column chromatography to obtain Intermediate Compound A28B63-7 (25 g).

[0134] Preparation of Compound A28B63

[0135] Intermediate A28B63-7 (6.7 g), Intermediate A28B63-5B1 (6.6 g), sodium tert-butoxide (6 g), tris(dibenzylideneacetone)dipalladium(0) (200 mg), and 2-bis(cyclohexylphosphino)-2',6'-dimethoxybiphenyl (200 mg) were dissolved in a three-necked flask containing 200 mL of xylene. After replacing nitrogen, the mixture was refluxed for 24 hours. The reaction was monitored by TLC until completion. The reaction solution was cooled to room temperature, washed with water, and the layers were separated. The organic phase was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to remove the solvent. The residue was purified by column chromatography to obtain Compound A28B63 (7.7 g). Calculated molecular weight: 627.75, measured value m / z: 628.8 (M+1).

[0136] Synthesis Example 5: Synthesis of Compound A36B41

[0137]

[0138] Compound A36B41 was prepared using a synthetic method similar to that of Compound A28B63, except that 2-bromo-4-chlorobenzaldehyde was replaced with 2-bromo-5-chlorobenzaldehyde, and intermediate A28B63-7 was replaced with N-(2-biphenyl)-benzidine. The calculated molecular weight of the resulting Compound A36B41 was 613.25, and the measured value was m / z: 614.3 (M+1).

[0139] Synthesis Example 6: Synthesis of Compound A41B77

[0140]

[0141] Intermediate A41B77-5 was synthesized using a synthetic method similar to that of Intermediate A1B9-5, except that 2-amino-3-chloropyridine was replaced with 2-amino-6-chloropyridine.

[0142] Preparation of Compound A41B77-6

[0143] 3-Aminobiphenyl (16.9 g), 1-(4-chlorophenyl)dibenzofuran (27.8 g), sodium tert-butoxide (29 g), tris(dibenzylideneacetone)dipalladium(0) (916 mg), and 1,3-bis(2,6-diisopropylphenyl)-2-chloroimidazolium hydrochloride (460 mg) were dissolved in a three-necked flask containing 500 mL of toluene. After replacing the nitrogen, the mixture was refluxed for 10 hours. The reaction was monitored by TLC until completion. The reaction solution was cooled to room temperature, washed with water, separated, and the organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The product was purified by column chromatography to obtain intermediate Compound A41B77-6 (23 g).

[0144] Preparation of Compound A41B77

[0145] Intermediate A41B77-6 (8.3 g), Intermediate A41B77-5 (6.6 g), sodium tert-butoxide (6 g), tris(dibenzylideneacetone)dipalladium(0) (200 mg), and 2-bis(cyclohexylphosphino)-2',6'-dimethoxybiphenyl (200 mg) were dissolved in a three-necked flask containing 200 mL of xylene. After replacing the nitrogen, the mixture was refluxed for 20 hours. The reaction was monitored by TLC until completion. The reaction solution was cooled to room temperature, washed with water, separated, and the organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The product was purified by column chromatography to obtain Compound A41B77 (9 g). The calculated molecular weight was 703.26, and the measured value was m / z: 704.3 (M+1).

[0146] Synthesis Example 7: Synthesis of Compound A2C6

[0147]

[0148] The synthesis of intermediate A2C6-3 was carried out using a synthetic method similar to that of compound A1B9-5, except that the raw material 2-bromo-4-chlorobenzaldehyde was replaced with 2-bromo-5-chlorobenzaldehyde.

[0149] Preparation of Intermediate A2C6-4

[0150] Intermediate compound A2C6-3 (33 g), bis(pinacolato)diboron (38 g), potassium acetate (29 g), tris(dibenzylideneacetone)dipalladium(0) (1 g), and 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (1 g) were dissolved in a three-necked flask containing 1 L of 1,4-dioxane. After displacing nitrogen, the mixture was refluxed for 8 hours. The reaction was monitored by TLC until completion. The reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation under reduced pressure, and the residue was dissolved in DCM and water. The layers were separated, and the organic layer was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by column chromatography to obtain intermediate compound A2C6-4 (31 g).

[0151] Preparation of Compound A2C6

[0152] Raw material A2C6-4 (8.4 g), 2-(3-biphenylyl)-4-chloro-6-(dibenzofuran-1-yl)-1,3,5-triazine (8.7 g), potassium carbonate (8 g), and tetrakis(triphenylphosphine)palladium (230 mg) were dissolved in a three-necked flask containing 150 / 50 / 50 mL of toluene / ethanol / water. After displacing nitrogen, the mixture was refluxed for 4 hours. The reaction was monitored by TLC until completion. The reaction solution was cooled to room temperature, filtered, washed with water, washed with ethanol, dried, and purified by column chromatography to obtain compound A2C6 (9 g). Calculated molecular weight: 691.24, measured m / z: 692.2 (M+1).

[0153] Synthesis Example 8: Synthesis of Compound A8C1

[0154]

[0155] Preparation of Intermediate A8C1-1

[0156] Intermediate compound A9B19-5A1 (32 g), bis(pinacolato)diboron (38 g), potassium acetate (29 g), tris(dibenzylideneacetone)dipalladium(0) (1 g), and 2-(dicyclohexylphosphino)-2',6'-dimethoxybiphenyl (1 g) were dissolved in a three-necked flask containing 1 L of 1,4-dioxane. After replacing nitrogen, the mixture was refluxed for 6 hours. The reaction was monitored by TLC until completion. The reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation under reduced pressure, and the residue was dissolved in DCM and water. After liquid separation, the organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by column chromatography to obtain intermediate compound A8C1-1 (29 g).

[0157] Preparation of Compound A8C1

[0158] Raw material A8C1-1 (8.4 g), 2-chloro-4-(dibenzofuran-1-yl)-6-phenyl-(1,3,5)triazine (7.2 g), potassium carbonate (8 g), and tetrakis(triphenylphosphine)palladium(0) (230 mg) were dissolved in a three-necked flask containing 150 / 50 / 50 mL of toluene / ethanol / water. After replacing nitrogen, the mixture was refluxed for 3 hours. The reaction was monitored by TLC until completion. The reaction solution was cooled to room temperature, filtered, washed with water, washed with ethanol, dried, and purified by column chromatography to obtain compound A8C1 (8.5 g). Calculated molecular weight: 615.21, measured m / z: 616.2 (M+1).

[0159] Synthesis Example 9: Synthesis of Compound A21C14

[0160]

[0161] Preparation of Intermediate A21C14-1

[0162] Intermediate compound A21B31-5B2 (30 g), bis(pinacolato)diboron (35 g), potassium acetate (25 g), tris(dibenzylideneacetone)dipalladium(0) (0.8 g), and 2-(dicyclohexylphosphino)-2',6'-dimethoxybiphenyl (0.8 g) were dissolved in a three-necked flask containing 1 L of 1,4-dioxane. After replacing nitrogen, the mixture was refluxed for 8 hours. The reaction was monitored by TLC until completion. The reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation under reduced pressure, and the residue was dissolved in DCM and water. After liquid separation, the organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by column chromatography to obtain intermediate compound A21C14-1 (25 g).

[0163] Preparation of Compound A21C14

[0164] Dissolve raw material A21C14-1 (8.4 g), 2-chloro-4,6-diphenyl-(1,3,5)-triazine (5.4 g), potassium carbonate (8 g), and tetrakis(triphenylphosphine)palladium (230 mg) in a three-necked flask containing 150 / 50 / 50 mL of toluene / ethanol / water. After displacing nitrogen, reflux the reaction for 4 hours. Monitor the reaction by TLC until completion. Cool the reaction solution to room temperature, filter, wash with water, wash with ethanol, dry, and purify by column chromatography to obtain compound A21C14 (7.1 g). Calculated molecular weight: 525.20, measured m / z: 526.2 (M+1).

[0165] Synthesis Example 10: Synthesis of Compound A24C1

[0166]

[0167] Intermediate A24C1-5A1 was prepared using a synthetic method similar to that of Intermediate A1B9-5, except that the raw material 2-amino-3-chloropyridine was replaced with 2-amino-5-chloropyridine.

[0168] Synthesis of Intermediate A24C1-6

[0169] Intermediate compound A24C1-5A1 (16 g), bis(pinacolato)diboron (18 g), potassium acetate (13 g), tris(dibenzylideneacetone)dipalladium(0) (0.4 g), and 2-(dicyclohexylphosphino)-2',6'-dimethoxybiphenyl (0.4 g) were dissolved in a three-necked flask containing 500 mL of 1,4-dioxane. After displacing nitrogen, reflux the reaction for 7 hours. Monitor the reaction by TLC until completion. Cool the reaction solution to room temperature, remove the solvent under reduced pressure, dissolve with DCM and water, separate the layers, dry the organic phase with anhydrous sodium sulfate, filter, remove the solvent by rotary evaporation under reduced pressure, and purify by column chromatography to obtain intermediate compound A24C1-6 (15 g).

[0170] Preparation of Compound A24C1

[0171] Dissolve raw material A24C1-6 (8.4 g), 2-chloro-4-(dibenzofuran-1-yl)-6-phenyl-(1,3,5)-triazine (7.2 g), potassium carbonate (8 g), and tetrakis(triphenylphosphine)palladium (230 mg) in a three-necked flask containing 150 / 50 / 50 mL of toluene / ethanol / water. After displacing nitrogen, reflux the reaction for 5 hours. Monitor the reaction by TLC until completion. Cool the reaction solution to room temperature, filter, wash with water, wash with ethanol, dry, and purify by column chromatography to obtain compound A24C1 (7.7 g). Calculated molecular weight: 615.21, measured m / z: 616.2 (M+1).

[0172] Synthesis Example 11: Synthesis of Compound A32C20

[0173]

[0174] The preparation of intermediate A32C20-3A1 adopts a synthetic method similar to that of intermediate A24C1-5A, except that the raw material 2-bromo-4-chlorobenzaldehyde is replaced by 2-bromo-5-chlorobenzaldehyde.

[0175] Synthesis of intermediate A32C20-4

[0176] Intermediate compound A32C20-3A1 (15 g), bis(pinacolato)diboron (18 g), potassium acetate (13 g), tris(dibenzylideneacetone)dipalladium(0) (0.4 g), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.4 g) were dissolved in a three-necked flask containing 500 mL of 1,4-dioxane. After replacing nitrogen, the mixture was refluxed for 7 hours. The reaction was monitored by TLC until completion. The reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation under reduced pressure, dissolved in DCM and water, separated, the organic phase was dried over anhydrous sodium sulfate, filtered, the solvent was removed by rotary evaporation under reduced pressure, and purified by column chromatography to obtain intermediate compound A32C20-4 (13 g).

[0177] Preparation of compound A32C20

[0178] Raw material A32C20-4 (8.4 g), 2-chloro-4-(2-naphthyl)-6-phenyl-(1,3,5)triazine (6.4 g), potassium carbonate (8 g), tetrakis(triphenylphosphine)palladium (230 mg) were dissolved in a three-necked flask containing 150 / 50 / 50 mL of toluene / ethanol / water. After replacing nitrogen, the mixture was refluxed for 6 hours. The reaction was monitored by TLC until completion. The reaction solution was cooled to room temperature, filtered, washed with water, washed with ethanol, dried, and purified by column chromatography to obtain compound A24C1 (6.5 g). Calculated molecular weight: 575.21, measured value m / z: 576.2 (M+1).

[0179] Synthesis Example 12: Synthesis of compound A40C25

[0180]

[0181] The preparation of intermediate A40C25-3 adopts a synthetic method similar to that of intermediate A41B77-5, except that the raw material 2-bromo-4-chlorobenzaldehyde is replaced by 2-bromo-5-chlorobenzaldehyde.

[0182] Synthesis of intermediate A40C25-4

[0183] Intermediate compound A40C25-3 (32 g), bis(pinacolato)diboron (35 g), potassium acetate (25 g), tris(dibenzylideneacetone)dipalladium(0) (0.8 g), and 2-(dicyclohexylphosphino)-2',6'-dimethoxybiphenyl (0.8 g) were dissolved in a three-necked flask containing 500 mL of 1,4-dioxane. After purging with nitrogen, the mixture was refluxed for 9 hours. The reaction was monitored by TLC until completion. The reaction solution was cooled to room temperature, the solvent was removed by rotary evaporation under reduced pressure, and the residue was dissolved in DCM and water. After liquid separation, the organic phase was dried over anhydrous sodium sulfate, filtered, and the solvent was removed by rotary evaporation under reduced pressure. The residue was purified by column chromatography to obtain intermediate compound A40C25-4 (30 g).

[0184] Preparation of Compound A40C25

[0185] Raw material A40C25-4 (8.4 g), 2-chloro-4-(2-naphthyl)-6-(4-biphenylyl)-1,3,5-triazine (7.8 g), potassium carbonate (8 g), and tetrakis(triphenylphosphine)palladium(0) (230 mg) were dissolved in a three-necked flask containing 150 / 50 / 50 mL of toluene / ethanol / water. After purging with nitrogen, the mixture was refluxed for 4 hours. The reaction was monitored by TLC until completion. The reaction solution was cooled to room temperature, filtered, washed with water and ethanol successively, dried, and purified by column chromatography to obtain compound A40C25 (7.3 g). Calculated molecular weight: 651.24, measured m / z: 652.2 (M+1).

[0186] In a preferred technical solution, the organic electroluminescent device (OLED device) includes a first electrode and a second electrode, and an organic layer located between the electrodes. The organic layer can be further divided into multiple regions, such as a hole transport region, a light-emitting layer, and an electron transport region; the light-emitting layer contains the organic electroluminescent material provided by the present invention.

[0187] In a preferred technical solution, the organic electroluminescent device includes a first electrode, a plurality of light-emitting functional layers (organic layers), and a second electrode arranged in sequence; the organic layer includes a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer arranged in sequence, and the hole injection layer is in contact with the first electrode (anode). The organic layer (preferably the light-emitting layer) contains the organic electroluminescent material provided by the present invention.

[0188] In a preferred technical solution, a substrate can be used below the first electrode or above the second electrode. The substrates are all glass or polymer materials with excellent mechanical strength, thermal stability, water resistance, and transparency. In addition, a thin film transistor (TFT) can also be provided on the substrate for display use.

[0189] The first electrode can be formed by sputtering or depositing a material serving as the first electrode on a substrate. When the first electrode is used as an anode, oxide transparent conductive materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), zinc oxide (ZnO), etc., and any combination thereof can be adopted. When the first electrode is used 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), magnesium-silver (Mg-Ag), etc., and any combination among them can be adopted.

[0190] The organic layer can be formed on the electrode by methods such as vacuum thermal evaporation, spin coating, printing, etc. The compounds serving as the organic layer can be organic small molecules, organic macromolecules or polymers, and their combinations.

[0191] 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 a single-layer hole transport layer containing only one compound and a single-layer hole transport layer containing multiple compounds. The hole transport region can also be a multi-layer structure including at least one of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL); where the HIL is located between the anode and the HTL, and the EBL is located between the HTL and the light-emitting layer.

[0192] The materials 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 poly(phenylene vinylene), 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, where the aromatic amine derivatives include the compounds shown as HT-1 to HT-52 below; or any combination thereof.

[0193]

[0194]

[0195]

[0196] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer can be a single compound material or a combination of multiple compounds. For example, the hole injection layer can adopt one or more of the above-mentioned compounds HT-1 to HT-52, or one or more of the following compounds HI-1 to HI-3; it can also adopt one or more of the compounds HT-1 to HT-52 doped with one or more of the compounds HI-1 to HI-3.

[0197]

[0198] The light-emitting layer includes a host material (Host, the organic electroluminescent material provided by the present invention), and at the same time includes a light-emitting dye (i.e., a doping material, dopant) that can emit spectra of different wavelengths. At the same time, the light-emitting layer can be a monochromatic light-emitting layer that emits a single color such as red, green, or blue. Multiple monochromatic light-emitting layers of different colors can be arranged in a planar pattern according to a pixel pattern, or stacked together to form a color light-emitting layer. When the 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 blue.

[0199] According to different technologies, the light-emitting layer material can adopt phosphorescent electroluminescent materials. In an OLED device, a single light-emitting technology can be adopted, or a combination of multiple different light-emitting technologies can be adopted. These different light-emitting materials classified by technology can emit light of the same color or light of different colors.

[0200] In a preferred technical solution of the present invention, the material of the light-emitting layer is a phosphorescent host material, and the phosphorescent host material is the organic electroluminescent material provided by the present invention, including a combination of a first compound (the structure shown in Formula I) and a second compound (the structure shown in Formula II).

[0201] In one aspect of the present invention, the light-emitting layer adopts the technology of phosphorescent electroluminescence. The phosphorescent doping material of the light-emitting layer can be selected from, but not limited to, one or more combinations of the following listed GPD-1 to GPD-47.

[0202]

[0203]

[0204] Where D is deuterium.

[0205] In one aspect of the present invention, the light-emitting layer employs the technology of phosphorescent electroluminescence. The phosphorescent dopant material of the light-emitting layer can be selected from, but not limited to, one or a combination of more than one of the following listed RPD-1 to RPD-28.

[0206]

[0207]

[0208] In one aspect of the present invention, the light-emitting layer employs the technology of phosphorescent electroluminescence. The phosphorescent dopant material of the light-emitting layer can be selected from, but not limited to, one or a combination of more than one of the following listed YPD-1 to YPD-11.

[0209]

[0210] The organic layer may further include an electron transport region between the light-emitting layer and the cathode. The electron transport region may be a single-layer electron transport layer (ETL), including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing multiple compounds. The electron transport region may also be a multi-layer structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL); wherein the HBL is located between the light-emitting layer and the ETL, and the EIL is located between the cathode and the ETL.

[0211] In one aspect of the present invention, the electron transport layer material can be selected from, but not limited to, one or a combination of more than one of the following listed ET-1 to ET-74.

[0212]

[0213]

[0214]

[0215]

[0216] In one aspect of the present invention, the hole blocking layer (HBL) is located between the electron transport layer and the light-emitting layer. The hole blocking layer can employ, but not limited to, one or more compounds of the above ET-1 to ET-74.

[0217] The device may further include an electron injection layer between the electron transport layer and the cathode. The electron injection layer material includes but is not limited to one or a combination of more than one of the following listed: LiQ, LiF, NaCl, CsF, Li2O, Cs2CO3, BaO, Na, Li, Ca, Mg, Yb.

[0218] Specific device embodiments

[0219] Device embodiment 1-1

[0220] Prepare an organic electroluminescent device comprising the organic electroluminescent material of the present invention, wherein the organic electroluminescent material comprises a combination of a first compound A1B9 and a second compound A2C6, and the mass ratio of the first compound A1B9 to the second compound A2C6 is 1:1.

[0221] The structural schematic diagram of the organic electroluminescent device of this embodiment is as Figure 1 shown, and it includes a substrate 1 (glass substrate), an anode 2 (ITO), a hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light-emitting layer 6, a hole blocking layer 7, an electron transport layer 8, an electron injection layer 9, and a cathode 10 (Al) stacked in sequence; an external power supply 11 is applied between the anode 2 and the cathode 10.

[0222] The preparation method of the organic electroluminescent device is as follows:

[0223] (1) Ultrasonically treat the glass substrate coated with the ITO transparent conductive layer in a commercial cleaning agent, rinse it in deionized water, ultrasonically degrease it in a mixed solvent of acetone / ethanol, bake it in a clean environment until all moisture is removed, clean it with ultraviolet light and ozone, and bombard the surface with a low-energy cation beam;

[0224] (2) Place the glass substrate with the anode in a vacuum chamber, evacuate to <1×10 -5 Pa, and vacuum deposit a mixture of compounds HT-4:HI-3 (97 / 3, w / w) on the anode layer film as the hole injection layer at a deposition rate of 0.1 nm / s and a deposited film thickness of 10 nm;

[0225] (3) Vacuum deposit compound HT-4 on the hole injection layer as the hole transport layer at a deposition rate of 0.1 nm / s and a total deposited film thickness of 60 nm;

[0226] (4) Vacuum deposit compound HT-52 on the hole transport layer as the electron blocking layer at a deposition rate of 0.1 nm / s and a total deposited film thickness of 60 nm;

[0227] (5) Vacuum deposit the light-emitting layer of the device on the electron blocking layer. The light-emitting layer includes a ternary mixture of a host material (the organic electroluminescent material, A1B9:A2C6 = 1:1) and a doping material (dye, RPD-18). The mass percentage content of the doping material in the light-emitting layer is 3%; the deposition rate is 0.1 nm / s and the total deposited film thickness is 40 nm;

[0228] (6) Vacuum deposit compound ET-74 on the light-emitting layer as the hole blocking layer at a deposition rate of 0.1 nm / s and a total deposited film thickness of 5 nm;

[0229] (7) A mixture of compounds ET-61:ET-57 (50 / 50, w / w) was vacuum-evaporated onto the hole-blocking layer as the electron transport layer at a deposition rate of 0.1 nm / s, with a total deposited film thickness of 25 nm;

[0230] (8) LiF with a thickness of 1 nm was vacuum-evaporated onto the electron transport layer as the electron injection layer at a deposition rate of 0.1 nm / s;

[0231] (9) Aluminum metal with a thickness of 150 nm was vacuum-evaporated onto the electron injection layer as the cathode at a deposition rate of 1 nm / s; Thus, the organic electroluminescent device of Example 1-1 was obtained.

[0232] Device Examples 1-2 to 9-3:

[0233] The difference from Device Example 1-1 is only that the organic electroluminescent material (the host material of the light-emitting layer) is replaced with the compounds in Tables 1 and 2, and the other structures, materials, and preparation methods of the device are the same as those in Example 1-1;

[0234] The "mass ratio" in Tables 1 and 2 represents the mass ratio of the first compound to the second compound, and "--" means that the compound is not added / the ratio does not exist.

[0235] The host materials in the examples are as follows:

[0236]

[0237] The compound structures in the comparative examples are as follows:

[0238]

[0239] Performance testing of the organic electroluminescent device prepared by the present invention:

[0240] At the same brightness of 3000 cd / m 2 , the current density of the organic electroluminescent device was measured using a digital source meter and a luminance meter, and the ratio of luminance to current density was the current efficiency; while maintaining a constant current, the time taken for the device to decay from an initial brightness of 10000 cd / m 2 to 9700 cd / m 2 was recorded to obtain the measured value of the LT97 lifetime.

[0241] Taking the measured values of the current efficiency and LT97 lifetime of Comparative Example 1 as 1, the current efficiency and LT97 lifetime of other examples and comparative examples were the ratios of their respective measured values to the measured values of Comparative Example 1; the test results are shown in Tables 1 and 2.

[0242] Table 1:

[0243]

[0244]

[0245]

[0246] Table 2:

[0247]

[0248]

[0249] Combined with the performance data in Table 1 and Table 2, it can be seen that in the present invention, the organic electroluminescent device prepared by using the compound having the structure shown in Formula I as a dual-emitting host material has obtained beneficial effects of higher luminous efficiency and longer service life, which proves that the device prepared by the present invention has better comprehensive performance.

[0250] In the organic electroluminescent material of the present invention, the combination of the above two compounds as a dual host material significantly improves the device performance. The reason is speculated as follows: when the first compound having the structure shown in Formula I is used alone, the injection and transport of holes are strong, resulting in unbalanced carrier transport. The luminescence recombination center is close to the hole blocking layer (HBL), causing poor device life and low efficiency when used alone; after introducing the second compound having the structure shown in Formula I of the present invention, due to the excellent electron transport performance of this type of compound, through the synergistic compounding with the first compound, balanced carrier transport is achieved. The luminescence layer recombination center is far from the HBL layer, and while the life is greatly improved, the efficiency is also improved to a certain extent. Similarly, when the second compound having the structure shown in Formula I is used alone, the injection and transport capabilities of holes do not match, resulting in low exciton formation efficiency and recombination efficiency. The luminescence recombination center is close to the electron blocking layer (EBL), which also causes short device life and low efficiency. Compared with the comparative compounds D1 and D2 in Comparative Examples 5 and 6, the compound of the present invention has a lower operating voltage and higher device efficiency when used alone as an N-type red light host. Analyzing the reasons, on the one hand, it may be that dibenzofuran is introduced into the N-type structure of the present invention, which can improve the efficiency of transferring the excited state energy to the dye for luminescence as a host material. On the other hand, the introduction of the electron-deficient large conjugated phenanthro[9,10-b]pyrazole ring is also beneficial to the injection and transport of carriers.

[0251] In addition, for the first compound, i.e., the hole-type host molecular structure, in the embodiments of the present invention, an electron-deficient group of pyrazole derivatives is introduced to the periphery of the molecule with triarylamine as the core building unit, so as to effectively improve the electron mobility on the premise of ensuring good hole injection and transport. For the second compound, i.e., the electron-type host molecular structure, in the present invention, a large-conjugated electron-deficient group of pyrazole derivatives is introduced to the periphery of the molecule with triazine as the core building unit, so as to improve the hole mobility on the premise of ensuring good electron injection and transport. At the same time, the first compound and the second compound can form an exciplex, thereby improving the energy transfer efficiency between the host and the dye in the excited state and enhancing the overall performance of the device.

[0252] The applicant declares that the organic electroluminescent material and the organic electroluminescent device of the present invention are illustrated by the above embodiments, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of the raw materials selected for the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. An organic electroluminescent material, comprising a combination of a first compound and a second compound, wherein the first compound and the second compound are each independently selected from the structures represented by formula (I): In formula (I), a group represented by formula (A) is fused and connected at the dotted position; In the first compound, G in formula (A) represents a group represented by formula (B), and in the second compound, G in formula (A) represents a group represented by formula (C); "—*" represents a connection site; In formula (I), R1 and R2 are each independently selected from hydrogen, halogen, amino, unsubstituted or R'-substituted C1-C20 linear alkyl, unsubstituted or R'-substituted C2-C10 alkenyl, unsubstituted or R'-substituted C3-C20 cycloalkyl, unsubstituted or R'-substituted C1-C20 alkoxy, unsubstituted or R'-substituted C1-C20 alkylthio, unsubstituted or R'-substituted C1-C20 alkylsilyl, unsubstituted or R'-substituted C1-C20 alkylamino, unsubstituted or R'-substituted C6-C30 aryl, unsubstituted or R'-substituted C3-C30 heteroaryl, unsubstituted or R'-substituted C6-C30 aryloxy, unsubstituted or R'-substituted C6-C30 arylthio, unsubstituted or R'-substituted C6-C30 arylsilyl, unsubstituted or R'-substituted C6-C30 arylamino; In formula (B) and formula (C), Ar1, Ar2, Ar3, and Ar4 are each independently selected from unsubstituted or R''-substituted C6-C30 aryl, unsubstituted or R''-substituted C3-C30 heteroaryl; In formula (B) and formula (C), Y1, Y2, and Y3 are each independently selected from CR or N, and at least one of Y1, Y2, and Y3 is N; R is selected from hydrogen, halogen, amino, unsubstituted or R'-substituted C1-C20 linear alkyl, unsubstituted or R'-substituted C2-C10 alkenyl, unsubstituted or R'-substituted C3-C20 cycloalkyl, unsubstituted or R'-substituted C1-C20 alkoxy, unsubstituted or R'-substituted C1-C20 alkylthio, unsubstituted or R'-substituted C1-C20 alkylsilyl, unsubstituted or R'-substituted C1-C20 alkylamino, unsubstituted or R'-substituted C6-C30 aryl, unsubstituted or R'-substituted C3-C30 heteroaryl, unsubstituted or R'-substituted C6-C30 aryloxy, unsubstituted or R'-substituted C6-C30 arylthio, unsubstituted or R'-substituted C6-C30 arylsilyl, unsubstituted or R'-substituted C6-C30 arylamino; The above R' and R'' are each independently selected from deuterium, halogen, cyano, C1-C20 linear alkyl, C3-C20 cycloalkyl, C1-C10 alkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C6-C30 aryl, C6-C60 arylboron, C3-C30 heteroaryl, or a combination of one or two of them.

2. The organic electroluminescent material according to claim 1, characterized in that, The first compound and the second compound are each independently selected from the structures represented by any one of formulas (1-1) to (1-6): In formulas (1-1) to (1-6), the definitions of G, R1, and R2 have the same scope as those in formulas (I) and (A).

3. The organic electroluminescent material according to claim 1 or 2, characterized in that, In formula (I), R1 and R2 are each independently selected from one of hydrogen, unsubstituted or R'-substituted C1-C20 linear alkyl, unsubstituted or R'-substituted C6-C30 aryl, and unsubstituted or R'-substituted C3-C30 heteroaryl; Preferably, R1 and R2 are each independently selected from one of hydrogen, unsubstituted or R'-substituted C6-C30 aryl, and unsubstituted or R'-substituted C3-C30 heteroaryl; more preferably, R1 and R2 are each independently selected from one of hydrogen, unsubstituted or R'-substituted C6-C30 aryl; even more preferably, R1 and R2 are each independently selected from hydrogen or C6-C30 aryl; most preferably, R1 and R2 are each independently selected from one of hydrogen, phenyl, naphthyl, anthracenyl, benzoanthracenyl, and phenanthryl.

4. The organic electroluminescent material according to claim 1 or 3, characterized in that, In formula (C), Y1, Y2, and Y3 are all N; In formulas (B) and (C), Ar1, Ar2, Ar3, and Ar4 are each independently selected from one of the following groups which are unsubstituted or R''-substituted: phenyl, naphthyl, anthracenyl, benzoanthracenyl, phenanthryl, furyl, benzofuryl, dibenzofuryl, thienyl, benzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, indolocarbazolyl, pyridyl, quinolinyl, acridinyl, phenanthridinyl, benzo-5,6-quinolinyl, benzo-6,7-quinolinyl, benzo-7,8-quinolinyl, pyrazolyl, indazolyl, imidazolyl, and phenanthroline; R'' is selected from one of C1-C10 linear alkyl, C3-C10 cycloalkyl, C6-C30 aryl, and C3-C30 heteroaryl.

5. The organic electroluminescent material according to claim 1, characterized in that, Formula (I) is selected from one of the following structures, where "—*" represents the site connecting to G:

6. The organic electroluminescent material according to claim 1 or 5, characterized in that, G in the first compound is selected from any one of the following formulas B1-B81, and G in the second compound is selected from any one of the following formulas C1-C28: Among them, "—*" in formulas B1-B81 and formulas C1-C28 represents the connection site to formula (I).

7. The organic electroluminescent material according to claim 1, characterized in that, The first compound is selected from the following compounds: The second compound is selected from the following compounds:

8. The application of the organic electroluminescent material according to claim 1, wherein the organic electroluminescent material is applied to an organic electronic device; 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 information tag, an electronic artificial skin sheet, a sheet-type scanner, or an electronic paper.

9. An organic electroluminescent device, comprising the following structure: a first electrode, a second electrode, and at least one organic electroluminescent unit disposed between the first electrode and the second electrode, each of the organic electroluminescent units comprising at least one hole transport layer, an electron transport layer, and an organic light emitting layer, characterized in that: The organic light-emitting layer includes the organic electroluminescent material according to claim 1; Preferably, the organic light-emitting layer includes a light-emitting host material and a light-emitting dye, the host material is the organic electroluminescent material according to claim 1, and the mass ratio of the first compound to the second compound is (0.1-2):1; More preferably, the mass ratio of the first compound to the second compound is (0.5 - 1.5):

1.

10. The organic electroluminescent device according to claim 9, wherein, The light-emitting dye in the organic light-emitting layer is a phosphorescent material, and the doping mass percentage of the phosphorescent material in the organic light-emitting layer is 1 - 10%; Preferably, the phosphorescent material is a red phosphorescent material.

11. A display device, characterized in that, The display device includes the organic electroluminescent device as claimed in claim 9.

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