Aromatic amine compound and organic electroluminescent device containing aromatic amine compound

Abstract

The invention provides a luminescent material of an aromatic amine compound and application of the compound as a luminescent auxiliary layer material in an organic electroluminescent device, can realize the technical effects of high luminous efficiency, low driving voltage and long service life of the organic electroluminescent device, and belongs to the technical field of organic electroluminescence. Aromatic amine compound is characterized in that the compound has a structure as shown in formula (1): # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the technical field of organic electroluminescence, and particularly relates to an aromatic amine compound and the application of the compound in an organic electroluminescent device. Background Art

[0002] An organic electroluminescent device (OLED) is a self-luminous display device based on organic electroluminescent materials. Different from existing liquid crystal display devices, it has the characteristics of not requiring a backlight source and being thin, and is a technology suitable for flexible device devices (flexible light-emitting display devices). An organic electroluminescent device utilizing organic luminescence phenomena usually has a structure including an anode, a cathode, and an organic layer therebetween. In order to improve the efficiency and stability of the organic electroluminescent device, the organic layer is usually composed of a multi-layer structure formed of various different substances. For example, it is composed of a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer, and the like.

[0003] Usually, a light-emitting auxiliary layer is added between the hole transport layer and the light-emitting layer to improve the lifetime and efficiency. The light-emitting auxiliary layer mainly plays a role in assisting the hole transport layer, can reduce the potential barrier between the hole transport layer and the light-emitting layer, reduce the driving voltage of the organic electroluminescent device, further increase the utilization rate of holes, and thus improve the light-emitting efficiency and lifetime of the device.

[0004] Therefore, it has very important practical application value to develop a compound with excellent hole transport performance and capable of being used in an organic electroluminescent device to improve the current efficiency, extend the service life, and reduce the driving voltage. Summary of the Invention

[0005] The purpose of the present invention is to provide a light-emitting material of an aromatic amine compound and the application of the compound as a light-emitting auxiliary layer material in an organic electroluminescent device, which can achieve the technical effects of high light-emitting efficiency, low driving voltage, and long service life of the organic electroluminescent device.

[0006] An aromatic amine compound, characterized in that the compound has the structure shown in formula (1):

[0007]

[0008] Wherein, Cy is present or absent. When Cy is present, it is selected from a 5-6 membered ring which may be deuterated or non-deuterated.

[0009] L 1 -L 3 Each independently is selected from a single bond, a substituted or unsubstituted C6-C12 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group, a substituted or unsubstituted C3-C30 heteroaromatic ring group, L 1 -L 3At least one of them is not a single bond;

[0010] Ar 1 Selected from hydrogen, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroarylene;

[0011] Ar 2 Selected from hydrogen, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C3-C30 Heteroaryl , substituted or unsubstituted C3-C30 heteroarylene;

[0012] Ar 3 Selected from hydrogen, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C3-C12 arylene, substituted or unsubstituted C3-C30 Heteroaryl , substituted or unsubstituted C3-C30 heteroarylene;

[0013] R 1 -R 4 Each independently selected from hydrogen or deuterium;

[0014] When substituted in the "substituted or unsubstituted", the substituents are each independently selected from one or a combination of deuterium, halogen, cyano, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 arylene, C3-C30 heteroaryl, C3-C30 heteroarylene.

[0015] The heteroatoms of the heteroaryl, heteroarylene, heteroarylene, heteroarylene are selected from one or more of oxygen and sulfur.

[0016] Preferably, the 5-6 membered ring is selected from 5-6 membered cycloalkenyl groups, and the cycloalkenyl groups are all deuterated or partially deuterated or non-deuterated.

[0017] Preferably, the compound has the structures shown in formula (2) - formula (4):

[0018]

[0019] Preferably, the Ar 1 Selected from substituted or unsubstituted dibenzofuran and its derivatives.

[0020] Preferably, Ar 2 Selected from hydrogen, substituted or unsubstituted C6-C12 aryl, substituted or unsubstituted C6-C30 Heteroaromatic group;

[0021] Preferably, L 3 Selected from a single bond, substituted or unsubstituted C6-C12 arylene, substituted or unsubstituted C3-C30 heteroarylene;

[0022] More preferably, the Ar 1 is independently selected from the following substituted or unsubstituted groups: wherein represents the bonding site.

[0023] Preferably, the Ar 2 -Ar 3 are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl.

[0024] More preferably, the Ar 2 is selected from hydrogen, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted dibenzofuranyl.

[0025] More preferably, the Ar 3 is selected from hydrogen, substituted or unsubstituted phenyl.

[0026] Preferably, the L 1 -L 3 are each independently selected from a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted dibenzothiophenylene.

[0027] Preferably, R 1 -R 4 are all selected from hydrogen.

[0028] More preferably, when R 1 -R 4 are all selected from hydrogen, Cy, if present, is selected from non-deuterated 5- to 6-membered rings.

[0029] Preferably, R 1 -R 4 are all selected from deuterium.

[0030] More preferably, when R 1 -R 4 are all selected from deuterium, Cy, if present, is selected from deuterated 5- to 6-membered rings.

[0031] Preferably, when the substituents in the "substituted or unsubstituted" are substituted, the substituents are each independently selected from one or more combinations of deuterium, halogen, cyano, methyl, ethyl, tert-butyl, cyclohexyl, phenyl, biphenyl, naphthyl, dibenzofuranyl, dibenzothiophenyl.

[0032] As a preferred embodiment, the aromatic amine compound has the structure shown in Formula (5)-Formula (8):

[0033]

[0034]

[0035] As a preferred embodiment, the Ar 1 is selected from the following substituted or unsubstituted groups: wherein represents the connection site.

[0036] As a preferred embodiment, the -L 3 -Ar 2 is selected from the following substituted or unsubstituted groups: wherein represents the connection site.

[0037] As a preferred embodiment, the -L 1 -L 2 - is selected from a single bond, the following substituted or unsubstituted groups: wherein represents the connection site.

[0038] In a specific embodiment of the present invention, the aromatic amine compound is selected from any one of the following compounds numbered 1-1 to 1-198, 2-1 to 2-228:

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060] An organic electroluminescent element, characterized in that the organic electroluminescent element includes: a cathode, an anode, and one or more organic material layers disposed between the cathode and the anode and including a light-emitting layer, and one or more layers of the organic material layer contain the aromatic amine compound of the present invention. When two or more layers contain the above-mentioned aromatic amine compound, the aromatic amine compounds are the same or different.

[0061] Preferably, the organic electroluminescent element includes a substrate, an anode, a hole transport region, a light-emitting layer, an electron transport region, and a cathode. The light-emitting layer is located between the anode and the cathode. The hole transport region is located between the anode and the light-emitting layer. The electron transport region is located between the light-emitting layer and the cathode. The hole transport region contains the aromatic amine compound of the present invention.

[0062] More preferably, the hole transport region includes a hole injection layer, a hole transport layer, and a light-emitting auxiliary layer. The light-emitting auxiliary layer contains the aromatic amine compound of the present invention. The hole injection layer is between the anode and the light-emitting layer. The hole transport layer is between the hole injection layer and the light-emitting layer. The light-emitting auxiliary layer is located between the hole transport layer and the light-emitting layer.

[0063] An electronic device, including: one or several of a display, a monitor, and a lighting device, including the organic electroluminescent element of the present invention; and a control unit for driving the above-mentioned display device.

[0064] The beneficial effects of the present invention are:

[0065] The aromatic amine compound of the present invention contains a structure of deuterated or non-deuterated hydro-phenanthrene or hydro-pyrene, and is connected to dibenzofuran through a substituted or unsubstituted amine group. As a light-emitting auxiliary layer material applied in an organic electroluminescent device, it can effectively improve the hole transport performance of the compound. Through this specific connection method, the thin film effect of the compound in the device is greatly increased, thereby effectively improving the efficiency and lifespan of the compound in the device. At the same time, the aromatic amine compound of the present invention can reduce the driving voltage of the device, and the comprehensive performance of the fabricated device is improved. Brief Description of the Drawings

[0066] Figure 1 It is a schematic structural diagram of the organic electroluminescent element described in Application Example 1, where 1 is the anode, 2 is the hole injection layer, 3 is the hole transport layer, 4 is the light-emitting auxiliary layer, 5 is the light-emitting layer, 6 is the electron transport layer, 7 is the electron injection layer, and 8 is the cathode. Detailed Embodiments

[0067] To more fully describe the present invention to those skilled in the art, embodiments of the present invention are provided. The scope of the present invention is not limited to the following embodiments. These embodiments can make the present invention more thorough and complete, and fully convey the concept of the present invention to those skilled in the art.

[0068] By referring to the following detailed embodiments and the examples included therein, the present disclosure can be more easily understood. Before disclosing and describing the compounds, devices, and / or methods of the present invention, it should be understood that unless otherwise specified, they are not limited to specific synthesis methods or specific reagents, as these can vary. It should also be understood that the terms used in the present invention are only for describing specific aspects and are not intended to be limiting. Although any methods and materials similar or equivalent to those described in the present invention can be used for this practice or test, exemplary methods and materials are now described.

[0069] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods; unless otherwise specified, the reagents, materials, etc. used in the following examples can all be obtained from commercial sources.

[0070] As used in the present invention, the term "halogen" can include fluorine, chlorine, bromine, or iodine.

[0071] As used in the present invention, the term "C1-C10 alkyl" refers to a monovalent substituent derived from a straight-chain or branched-chain saturated hydrocarbon having 1 to 10 carbon atoms, and its examples include but are not limited to methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl.

[0072] As used in the present invention, the term "C3-C10 cycloalkyl" refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 10 carbon atoms. Examples of such cycloalkyls include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, etc.

[0073] As used in the present invention, the term "cycloalkenyl group" refers to a group having an unsaturated carbon ring and not having aromaticity, including, but not limited to, cyclopentadienyl, 1,3-cyclohexadienyl, etc.

[0074] As used in the present invention, the term "C6-C12 aryl" refers to a monovalent substituent derived from an aromatic hydrocarbon having a single ring or a combination of two or more rings and having 6 to 12 carbon atoms. Further, such aryl refers to a simple aryl, i.e., phenyl; or a linked aryl, including, but not limited to, biphenyl, etc.; or a fused aryl, including, but not limited to, naphthyl, etc.

[0075] As used in the present invention, the term "arylene" refers to a divalent aryl derived by removing one hydrogen atom from "aryl". For example, removing one hydrogen atom from phenyl forms phenylene, and removing one hydrogen atom from naphthyl forms naphthylene.

[0076] As used in the present invention, the term "C6-C12 aryl ring group" refers to the following system, which does not necessarily contain only aryls, but also includes groups in which multiple aryls can be formed by connecting through non-aromatic units such as one or more optionally substituted Cs. Examples of such aryl ring groups include, but are not limited to, benzocyclopentyl, etc., and the present invention is not limited thereto.

[0077] As used in the present invention, the term "arylene ring group" refers to a divalent aryl ring group derived by removing one hydrogen atom from "aryl". For example, removing one hydrogen atom from benzocyclopentyl forms benzocyclopentylene.

[0078] As used in the present invention, the term "C3-C30 heteroaryl" refers to an aryl in which at least one carbon, preferably 1-3 carbons, is replaced by a heteroatom selected from N, O, S, P, B, Si, etc. Examples of such heteroaryls include, but are not limited to, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenanthrolinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, etc., and the present invention is not limited thereto.

[0079] As used in the present invention, the term "heteroarylene" refers to a divalent heteroaryl derived by removing one hydrogen atom from "heteroaryl". For example, removing one hydrogen atom from pyridyl forms pyridylene.

[0080] As used in the present invention, the term "heteroaryl group having 3 to 30 carbon atoms" refers to the following systems, which do not necessarily contain only heteroaryl groups, but also include groups formed by connecting multiple aryl groups through non-aromatic units (such as one or more optionally substituted C, Si, N, O, or S atoms). At least one carbon atom, preferably 1 to 3 carbon atoms, in the aryl group is substituted by a heteroatom such as N, O, S, P, B, or Si. Examples of such heteroaryl groups include, but are not limited to, indolizinyl, indolyl, indolopyridinyl, purinyl, benzofuranyl, benzothiophenyl, benzothiazolyl, benzimidazolyl, benzoxazolyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, etc.

[0081] As used in the present invention, the term "heteroarylene" refers to a divalent heteroaryl group derived by removing one hydrogen atom from a "heteroaryl group". For example, dibenzofuranyl becomes dibenzofuranylene after removing one hydrogen atom.

[0082] As used in the present invention, in the expression "Z group having AA to BB carbon atoms" or "Z group of C(AA - BB)", "having AA to BB carbon atoms" means the number of carbon atoms of the Z group when it is unsubstituted, excluding the carbon atoms of the substituents when it is substituted. For example, an aryl group having 6 to 30 carbon atoms means that when unsubstituted, the number of carbon atoms in the aryl group is any integer from 6 to 30, that is, when unsubstituted, the number of carbon atoms can be 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20... 30.

[0083] As used in the present invention, the term "single bond" means that the groups are directly connected. For example, in formula (1), where L 1 is a single bond, which means

[0084] As used in the present invention, "Cy is present or absent". When absent,

[0085] As used in the present invention, "Cy is selected from deuterated or non-deuterated 5- or 6-membered rings". The 5- or 6-membered ring is a ring group having 5 to 6 carbon atoms as ring-forming atoms, where the number of four C atoms including C1 - C4 is specifically shown by the following structure represents the connection site.

[0086] As used in the present invention, the term "amine group" refers to represents the connection site.

[0087] As used in the present invention, the term "phenylnaphthyl" refers to represents the connection site.

[0088] As used in the present invention, the term "phenylnaphthyl" includes indicating the connection site.

[0089] As used in the present invention, " indicating the connection site" means that the group in the present invention can be connected to the corresponding site at any position, such as L 1 selected from specifically can be represented as

[0090]

[0091] As used in the present invention, the term "substituted" means that a hydrogen atom in a compound is replaced by another substituent. The position where substitution occurs can be the position where the hydrogen atom is replaced. That is, this position is not limited to a specific position, as long as the hydrogen at this position can be replaced by a substituent. For example, the carbazolyl group, as long as it is not otherwise specified in this specification, includes any of the following groups, but is not limited thereto,

[0092]

[0093] indicating the substitution position. "Unsubstituted" means retaining a hydrogen atom, and in this case, the hydrogen atom includes protium, deuterium, and tritium.

[0094] When there are two or more substituents, the two or more substituents can be the same or different.

[0095] As used in the present invention, the hydrogen atom includes protium, deuterium, and tritium. The compounds described in the present invention can contain deuterium atoms of natural origin, or deuterium atoms can be introduced by deuterating a part or all of the starting compounds. If deuterium atoms are introduced from the starting materials, the deuteration rate can be 100%, or less than 100%, or less than 95%, or less than 90%, or less than 80%. The deuteration rate can also be 1% or more, or 5% or more, or 10% or more. If the deuteration rate is not 100%, it represents a mixture of deuterated compounds and non-deuterated compounds, or a mixture of fully deuterated compounds and incompletely deuterated compounds, or a mixture of fully deuterated compounds, non-deuterated compounds, and incompletely deuterated compounds.

[0096] As used in the present invention, terms such as the first, the second, A, B, etc. are used. The above terms are only used to distinguish the components and do not limit the essence or order of the components corresponding to the terms.

[0097] Organic electroluminescent element

[0098] The structure used in the organic electroluminescent device of the present invention is a publicly known structure, which includes an anode, a cathode, and an organic layer located between the anode and the cathode. The organic layer includes a light-emitting layer, and at least one layer of the organic layer contains the compound of the present invention.

[0099] The organic layer may further include one or more of a hole injection layer, a hole transport layer, a light-emitting auxiliary layer, a hole blocking layer, an electron transport layer, and an electron injection layer, but is not limited thereto.

[0100] The light-emitting device of the present invention can emit fluorescence, phosphorescence, or a combination thereof. The light-emitting device can be a single light-emitting device or a series type of multiple light-emitting units.

[0101] As a simple light-emitting device, the following can be cited, but are not limited thereto.

[0102] (1) Hole transport layer / Fluorescent light-emitting layer / Electron transport layer;

[0103] (2) Hole transport layer / Phosphorescent light-emitting layer / Electron transport layer;

[0104] (3) Hole transport layer / First fluorescent light-emitting layer / Second fluorescent light-emitting layer / Electron transport layer;

[0105] (4) Hole transport layer / First phosphorescent light-emitting layer / Second phosphorescent light-emitting layer / Electron transport layer;

[0106] (5) Hole transport layer / Fluorescent light-emitting layer / Spacer layer / Phosphorescent light-emitting layer / Electron transport layer;

[0107] (6) Hole transport layer / Light-emitting auxiliary layer / Fluorescent light-emitting layer / Electron transport layer;

[0108] (7) Hole transport layer / Light-emitting auxiliary layer / Fluorescent light-emitting layer / Hole blocking layer / Electron transport layer;

[0109] (8) Hole transport layer / Light-emitting auxiliary layer / Phosphorescent light-emitting layer / Electron transport layer;

[0110] (9) Hole transport layer / Light-emitting auxiliary layer / Phosphorescent light-emitting layer / Hole blocking layer / Electron transport layer;

[0111] (10) Hole injection layer / Hole transport layer / Phosphorescent light-emitting layer / Electron transport layer / Electron injection layer;

[0112] (11) Hole injection layer / Hole transport layer / Fluorescent light-emitting layer / Electron transport layer / Electron injection layer;

[0113] (12) Hole injection layer / Hole transport layer / Light-emitting auxiliary layer / Phosphorescent light-emitting layer / Electron transport layer / Electron

[0114] injection layer;

[0115] (13) Hole injection layer / hole transport layer / light emission assisting layer / fluorescent light emission layer / electron transport layer / electron injection layer;

[0116] Each of the above-mentioned phosphorescent / fluorescent light emission layers can emit light of different colors.

[0117] As a tandem organic electroluminescent device, it can be an anode / first light emitting unit / intermediate layer / second light emitting unit / cathode. The intermediate layer can generally also be referred to as a charge generation layer, an electron extraction layer, a connection layer, etc. For example, when stacking a fluorescent light emission layer and a phosphorescent light emission layer, in order to prevent the excitons generated in the phosphorescent light emission layer from diffusing into the fluorescent light emission layer or to adjust the carrier balance, an intermediate layer is placed between the fluorescent light emission layer and the phosphorescent light emission layer.

[0118] When the organic light emitting device includes a plurality of organic material layers, the organic material layers can be formed of the same material or different materials.

[0119] The organic electroluminescent device of the present specification can be manufactured by materials and methods known in the art, except that one or more of the organic material layers are formed by using the compound of formula (1).

[0120] As the anode material, a material having a relatively large work function can be used, and a transparent conductive oxide, a metal, a conductive polymer, etc. can be used.

[0121] As the cathode material, a material having a low work function is usually used to facilitate electron injection into the organic material layer, and a metal, a metal oxide, a conductive polymer, etc. can be used.

[0122] The hole injection layer is a layer that injects holes from the electrode and has the ability to transport holes. In order to reduce the energy level difference between the electrodes, the hole injection layer is mainly prepared based on aromatic amine compounds, and other materials having hole transport ability can also be used.

[0123] The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light emitting layer, and the hole transport material can appropriately be a material having a high hole mobility that can receive holes from the anode or the hole injection layer and transfer the holes to the light emitting layer.

[0124] The light emission assisting layer is a layer that blocks electrons from reaching the anode, can adjust the energy level difference between the hole transport region and the light emitting layer, facilitates holes to enter the light emitting layer, and at the same time reduces the probability of electrons entering the hole transport region from the light emitting layer. Commonly used ones are aromatic amine derivatives.

[0125] A luminescent material is a material that can respectively receive holes and electrons from a hole transport layer and an electron transport layer and cause the holes and electrons to combine to emit light in the visible light region. The luminescent layer material includes a host material and a dopant material. Red, green, or blue luminescent materials can be used, and if necessary, two or more luminescent materials can be mixed. As the luminescent material, a fluorescent material can be used, or a phosphorescent material can also be used. As the luminescent material, a single-component material can be adopted, or a multi-component material can also be adopted.

[0126] An electron transport layer is a layer that receives electrons from an electron injection layer and transports the electrons to the luminescent layer, and the electron transport material is a material with a high electron mobility that can receive electrons from the cathode and transfer the electrons to the luminescent layer. Metal complexes such as triazine derivatives, oxadiazole derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, 8-hydroxyquinoline and its derivatives, etc. can be used, and polymer materials and small molecule materials can also be used.

[0127] An electron injection layer is a layer that injects electrons from an electrode.

[0128] According to the materials used, the organic light-emitting device of this specification can be a top-emitting device, a bottom-emitting device, or a dual-emission type device.

[0129] Synthesis general formula: The following general formula is only one synthesis method of the compounds of the present invention, and the compounds of the present invention can also be synthesized by other methods.

[0130]

[0131] Wherein X represents a halogen. For different substitution positions, the same synthesis method can be adopted. Cy, L 1 -L 3 、Ar 1 -Ar 3 、R 1 -R 4 Have the same meanings as those represented in Claim 1.

[0132] Compound preparation examples

[0133] The present invention will be specifically described through Examples 1-9.

[0134] Example 1: Preparation of Compound 1-1

[0135]

[0136] 1-1-1 (42.00 g, 149.44 mmol) was dissolved in ethyl acetate (500 mL), then Raney nickel (20.00 g) was added and the reaction was carried out at room temperature for 48 hours. After the reaction was completed, the catalyst was removed using a diatomaceous earth column. At room temperature, pd / C (10.00 g) catalyst was added, and the hydrogenation reaction was carried out under a hydrogen pressure of about 100 psi. After 72 hours, the reaction was completed, the solvent was removed under reduced pressure, and the product was separated and purified by silica gel column to obtain compound 1-1-2 (35.40 g, yield 83%).

[0137] LC-MS (APCI): 285.82 (M+H) + 。

[0138]

[0139] Under a nitrogen atmosphere, compound 1-1-3 (7.40 g, 43.02 mmol) and compound 1-1-4 (5.24 g, 43.00 mmol) were added to a three-necked flask, a mixed solution of 150 mL of tetrahydrofuran and 50 mL of water was added, potassium carbonate (8.95 g, 64.83 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.93 g, 0.80 mmol) were added, and the reaction was heated to 70 - 80 °C. After the reaction was completed, extraction and liquid separation were carried out, and the organic phase was concentrated and then obtained compound 1-1-5 (5.24 g, yield 72%) by column chromatography.

[0140] LC-MS (APCI): 169.54 (M+H) + 。

[0141]

[0142] 1-1-5 (7.06 g, 41.78 mmol) and compound 1-1-2 (12.23 g, 42.79 mmol) were completely dissolved in 200 mL of xylene, then NaOt-Bu (8.30 g, 86.49 mmol) was added, and after bis(tri-tert-butylphosphine)palladium(0) (0.32 g, 0.63 mmol) was added, the mixture was heated and stirred for 3 hours. After cooling to room temperature, extraction was carried out with distilled water and ethyl acetate, the organic layer was dried over MgSO4, filtered and concentrated. Using ethyl acetate and n-hexane as the eluent, the product was purified by column chromatography to obtain compound 1-1-6 (14.02 g, yield 90%).

[0143] LC-MS (APCI): 373.76 (M+H) + 。

[0144]

[0145] Under a nitrogen atmosphere, compound 1-1-7 (12.65 g, 43.00 mmol) and compound 1-1-8 (8.64 g, 43.00 mmol) were added to a three-necked flask, dissolved in a mixed solution of 150 mL of tetrahydrofuran and 50 mL of water, potassium carbonate (8.95 g, 64.83 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.93 g, 0.80 mmol) were added, and the mixture was heated to 70 - 80 °C for reaction. After the reaction was completed, extraction and liquid separation were carried out. The organic phase was concentrated and then purified by column chromatography to obtain compound 1-1-9 (9.73 g, yield 70%).

[0146] LC-MS(APCI): 323.45 (M+H) + 。

[0147]

[0148] Under a nitrogen atmosphere, compound 1-1-9 (13.90 g, 43.00 mmol) and compound 1-1-10 (6.72 g, 43.00 mmol) were added to a three-necked flask, dissolved in a mixed solution of 150 mL of tetrahydrofuran and 50 mL of water, potassium carbonate (8.95 g, 64.83 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.93 g, 0.80 mmol) were added, and the mixture was heated to 70 - 80 °C for reaction. After the reaction was completed, extraction and liquid separation were carried out. The organic phase was concentrated and then purified by column chromatography to obtain compound 1-1-11 (10.38 g, yield 68%).

[0149] LC-MS(APCI): 355.18 (M+H) + 。

[0150]

[0151] 1-1-11 (12.88 g, 36.28 mmol) and 1-1-6 (13.56 g, 36.35 mmol) were completely dissolved in 200 mL of xylene, then NaOt-Bu (8.30 g, 86.59 mmol) was added, and bis(tri-tert-butylphosphine)palladium(0) (0.32 g, 0.63 mmol) was added. The mixture was heated and stirred for 3 hours. After cooling to room temperature, extraction was carried out with distilled water and ethyl acetate. The organic layer was dried over MgSO4, filtered and concentrated. Using ethyl acetate and n-hexane as the eluent, purification by column chromatography gave compound 1-1 (17.58 g, yield 70%).

[0152] LC-MS(APCI): 692.17 (M+H) + 。

[0153] Example 2: Synthesis of compound 1-83

[0154]

[0155] Prepared according to the same synthesis method as in Example 1. Replace compound 1-1-7 with compound 1-83-7, and compound 1-1-8 with compound 1-83-8. The compound 1-83 (21.55 g, yield 80%, the yield is the synthesis yield of the reaction of 1-83-11 and 1-1-6) can be synthesized according to the above synthetic route.

[0156] LC-MS (APCI): 742.23 (M+H) + 。

[0157] Example 3: Synthesis of compound 1-123

[0158]

[0159]

[0160] Prepared according to the same synthesis method as in Example 1. Replace compound 1-1-4 with compound 1-123-4, compound 1-1-7 with compound 1-83-7, compound 1-1-8 with compound 1-123-8, and compound 1-1-10 with compound 1-123-10. The compound 1-123 (19.63 g, yield 65%, the yield is the synthesis yield of the reaction of 1-123-11 and 1-123-6) can be synthesized according to the above synthetic route.

[0161] LC-MS (APCI): 832.48 (M+H) + 。

[0162] Example 4: Synthesis of compound 1-182

[0163]

[0164] Synthesis of intermediate 1-182-12: Put heavy water (35 mL) and cyclohexane (30 mL) into a flask. Slowly drop methanesulfonic anhydride (15.00 g, 86.2 mmol) and 1-1-2 (9.37 g, 32.85 mmol) into the flask and react at 50 °C for 6 hours. After the reaction is completed, cool the temperature to room temperature, add ethyl acetate and potassium carbonate hydrate to make the pH value reach 7-8. Separate the organic layer, dry the organic layer with magnesium sulfate, filter and concentrate to remove the solvent to obtain intermediate 1-182-12 (9.44 g, yield 98%).

[0165]

[0166]

[0167] Prepared according to the same synthesis method as in Example 1, replacing compound 1-1-3 with compound 1-182-3, compound 1-1-2 with compound 1-182-12, compound 1-1-9 with compound 1-182-9, and compound 1-1-10 with compound 1-182-10. The compound 1-182 can be synthesized according to the above synthetic route (17.89 g, yield 79%, the yield is the synthetic yield of the reaction of 1-182-11 and 1-182-6).

[0168] LC-MS(APCI): 624.24(M+H) + 。

[0169] Example 5: Synthesis of compound 1-184

[0170]

[0171] Prepared according to the same synthesis method as in Example 4, replacing compound 1-182-9 with compound 1-184-9. The compound 1-184 can be synthesized according to the above synthetic route (18.57 g, yield 82%, the yield is the synthetic yield of the reaction of 1-184-11 and 1-182-6).

[0172] LC-MS(APCI): 624.24(M+H) + 。

[0173] Example 6: Synthesis of compound 1-198

[0174]

[0175] Prepared according to the same synthesis method as in Example 4, replacing compound 1-182-11 with compound 1-186-11. The compound 1-186 can be synthesized according to the above synthetic route (14.10 g, yield 65%, the yield is the synthetic yield of the reaction of 1-186-11 and 1-182-6).

[0176] LC-MS(APCI): 598.18(M+H) + 。

[0177] Example 7: Synthesis of compound 2-184

[0178]

[0179] Compound 2-184-2 was synthesized according to the synthesis method of 1-1-2 in Example 1, replacing compound 1-1-1 with compound 2-184-1; compound 2-184-12 was synthesized according to the synthesis method of 1-182-12 in Example 4, replacing compound 1-1-2 with compound 2-184-2; it was prepared according to the same synthesis method as in Example 4, replacing compound 1-182-12 with compound 2-184-12 and compound 1-182-11 with compound 1-184-11. The compound of 2-184 can be synthesized according to the above synthetic route (17.24 g, yield 80%, and the yield is the synthetic yield of the reaction of 1-184-11 and 2-184-6).

[0180] LC-MS(APCI): 594.05(M+H) + 。

[0181] Example 8: Synthesis of Compound 2-201

[0182]

[0183] It was prepared according to the same synthesis method as in Example 1, replacing compound 1-1-1 with compound 2-184-1, compound 1-1-3 with compound 2-201-3, and compound 1-1-7 with compound 1-83-7. The compound of 2-201 can be synthesized according to the above synthetic route (18.31 g, yield 68%, and the yield is the synthetic yield of the reaction of 2-201-11 and 2-201-6).

[0184] LC-MS(APCI): 742.24(M+H) + 。

[0185] Example 9: Synthesis of Compound 2-221

[0186]

[0187] It was prepared according to the same synthesis method as in Example 8, replacing compound 2-201-5 with compound 1-182-4, compound 2-201-9 with compound 1-1-7, and compound 1-1-10 with compound 2-221-10. The compound of 2-221 can be synthesized according to the above synthetic route (18.75 g, yield 76%, and the yield is the synthetic yield of the reaction of 2-221-11 and 2-221-6).

[0188] LC-MS(APCI): 680.24(M+H) + 。

[0189] Device Preparation Example

[0190] Through Application Example 1, the application effect of the compound of the present invention as a light-emitting auxiliary layer in a device is illustrated.

[0191] Application Example 1

[0192] This embodiment provides an organic electroluminescent element, as Figure 1 shown, comprising, stacked from bottom to top: 1. an anode, 2. a hole injection layer, 3. a hole transport layer, 4. a light-emitting auxiliary layer, 5. a light-emitting layer, 6. an electron transport layer, 7. an electron injection layer, and 8. a cathode.

[0193] The specific device structure is:

[0194] ITO / HT:HAT-CN(10nm,97:3) / HT(120nm) / BP(10nm) / BH-1:BD-1(97:3v / v%)(30nm) / ET:Liq(35nm,1:1) / LiF(0.2nm) / Al(150nm).

[0195] Device preparation process:

[0196] Evaporate HT:HAT-CN(97:3) on the ITO substrate to form a hole injection layer (HIL) with a thickness of 10 nm, evaporate HT on the above hole injection layer to form a hole transport layer (HTL) with a thickness of 120 nm, evaporate BP-1 on the above hole transport layer to form a light-emitting auxiliary layer (EBL) with a thickness of 10 nm, evaporate BH:BD(97:3v / v%) on the light-emitting auxiliary layer to form a light-emitting layer (EML) with a thickness of 30 nm, successively evaporate ET:Liq(1:1) to form an electron transport layer (ETL) with a thickness of 35 nm, evaporate LiF to form an electron injection layer with a thickness of 0.2 nm, and evaporate Al to form a cathode with a thickness of 150 nm, thereby manufacturing an organic electroluminescent device.

[0197] Denoted as Comparative Example 1.

[0198]

[0199] Device Comparative Example 2

[0200] Replace the light-emitting auxiliary layer material BP-1 with compound BP-2 to prepare the light-emitting auxiliary layer 4, and fabricate an organic electroluminescent device by the same method as in the above Comparative Example 1 implementation.

[0201] Device Embodiment

[0202] The light-emitting auxiliary layer was prepared by replacing the BP-1 material with compounds 1-1, 1-83, 1-123, 1-182, 1-184, 1-198, 2-184, 2-201, and 2-221 respectively to form the light-emitting auxiliary layer 4. Organic electroluminescent devices were fabricated using the same method as in Comparative Example 1 described above, and were denoted as Examples 1 to 9 in sequence.

[0203] Test results

[0204] Lifetime test method: A voltage was applied to the obtained organic electroluminescent element such that the current density reached 30 mA / cm 2 , and the time until the luminance became 95% of the initial luminance (LT95 (unit: hours)) was measured. Taking the lifetime of Comparative Example 1 as 100%, the relative lifetime values of each comparative example and example were obtained.

[0205] The driving voltage was measured at a current density of 15 mA / cm 2 . Taking the driving voltage of Comparative Example 1 as 100%, the relative driving voltage values of each comparative example and example were obtained.

[0206] The current efficiency was measured at a current density of 15 mA / cm 2 . Taking the current efficiency of Comparative Example 1 as 100%, the relative current efficiency values of each comparative example and example were obtained. The test results are shown in Table 1.

[0207] Table 1

[0208]

[0209] As can be seen from the results shown in Table 1 above, applying the aromatic amine compound of the present invention in the light-emitting auxiliary layer can reduce the driving voltage of the organic electroluminescent device, improve the luminous efficiency and lifetime, and can be used as an efficient organic electroluminescent material.

[0210] The above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments. The above embodiments and the descriptions in the specification only illustrate the principles of the present invention. Without departing from the spirit and scope of the present invention, various changes and improvements will occur to the present invention, and these changes and improvements all fall within the scope of the present invention claimed. The scope of the present invention claimed is defined by the appended claims and their equivalents.

Claims

1. An aromatic amine compound, characterized in that The compound has the structure shown in formula (1): wherein Cy is present or absent, and when Cy is present, it is selected from deuterated or non-deuterated 5- to 6-membered rings L 1 -L 3 Each independently selected from a single bond, a substituted or unsubstituted C6-C12 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group, a substituted or unsubstituted C3-C30 heteroaromatic ring group, L 1 -L 3 at least one of which is not a single bond; Ar 1 selected from hydrogen, a substituted or unsubstituted C3-C30 heteroaryl group, or a substituted or unsubstituted C3-C30 heteroarylene group; Ar 2 selected from hydrogen, a substituted or unsubstituted C6-C12 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, and a substituted or unsubstituted C3-C30 heteroaromatic ring group; Ar 3 selected from hydrogen, a substituted or unsubstituted C6-C12 aryl group, a substituted or unsubstituted C3-C12 aryl ring group, a substituted or unsubstituted C3-C30 heteroaryl group, and a substituted or unsubstituted C3-C30 heteroaryl ring group; R 1 -R 4 each independently selected from hydrogen or deuterium; when the "substituted or unsubstituted" is substituted, the substituents are each independently selected from one or a combination of deuterium, halogen, cyano, C1-C10 alkyl, C3-C10 cycloalkyl, C6-C12 aryl, C6-C12 aryl ring group, C3-C30 heteroaryl, C3-C30 heteroaryl ring group the heteroatoms of the heteroaryl, heteroaryl ring group, heteroarylene, heteroarylene ring group are selected from one or more of oxygen and sulfur the 5- to 6-membered ring is selected from cycloalkene groups with 5 to 6 carbons, and the cycloalkene groups can be fully deuterated or partially deuterated 2. The compound according to claim 1, wherein: The compound has the structures shown in formula (2) - formula (4):

3. The aromatic amine compound according to claim 1, characterized in that: The Ar 1 is selected from substituted or unsubstituted dibenzofuran and its derivatives.

4. The aromatic amine compound according to claim 1, characterized in that: The Ar 2 -Ar 3 are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted dibenzofuranyl, and substituted or unsubstituted dibenzothiophenyl.

5. The aromatic amine compound according to claim 1, characterized in that: The said L 1 -L 3 Each independently selected from a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted dibenzofuranyl, a substituted or unsubstituted dibenzothiophenyl.

6. The aromatic amine compound according to claim 1, wherein The compound is selected from any one of the following compounds numbered 1-1 to 1-198, 2-1 to 2-228:

7. An organic electroluminescent element, characterized in that, The organic electroluminescent element includes: a cathode, an anode, and one or more organic material layers disposed between the cathode and the anode and including a light-emitting layer wherein one or more of the organic material layers contain the aromatic amine compound according to any one of claims 1-6, and when two or more layers contain the aromatic amine compound according to claims 1-6, the aromatic amine compounds are the same or different 8. The organic electroluminescent element according to claim 7, characterized in that: The organic electroluminescent element includes a substrate, an anode, a hole transport region, a light-emitting layer, an electron transport region, and a cathode. The light-emitting layer is located between the anode and the cathode, the hole transport region is located between the anode and the light-emitting layer, and the electron transport region is located between the light-emitting layer and the cathode; The hole transport region contains the aromatic amine compound according to any one of claims 1-6 9. The organic electroluminescent element according to claim 7, characterized in that: The hole transport region contains a hole injection layer, a hole transport layer, and a light-emitting auxiliary layer; The light-emitting auxiliary layer contains the aromatic amine compound according to any one of claims 1-6. The hole injection layer is between the anode and the light-emitting layer, the hole transport layer is between the hole injection layer and the light-emitting layer, and the light-emitting auxiliary layer is located between the hole transport layer and the light-emitting layer 10. An electronic device, comprising: One or more of a display, a monitor, and a lighting device, including the organic electroluminescent element according to claim 7; and a control unit for driving the above display device

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