Benzonaphthofuran-containing organic compound and application thereof

Abstract

The invention relates to the technical field of display, in particular to an organic compound containing benzo-naphthofuran and application of the organic compound. The organic compound containing the benzonaphthofuran, provided by the invention, has the following structure shown in the specification: # imgabs0 #, so that an organic electroluminescent device containing the organic compound containing the benzonaphthofuran has relatively low driving voltage, relatively high luminous efficiency and relatively long service life.

Description

Technical Field

[0001] The present invention relates to the field of display technologies, and particularly to an organic compound containing benzonaphthofuran and its applications. Background Art

[0002] An organic electroluminescent device (OLED) is a device that converts electrical energy into light by applying electricity to an organic electroluminescent material, and generally has a structure including an anode, a cathode, and an organic layer between the anode and the cathode. The organic layer of the organic EL device can be composed of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer (which includes a host material and a doping material), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc., and the materials used for the organic layer are classified into hole injection materials, hole transport materials, electron blocking materials, light-emitting materials, electron buffer materials, hole blocking materials, electron transport materials, electron injection materials, etc. according to their functions. In the organic EL device, due to the applied voltage, holes are injected from the anode into the light-emitting layer, electrons are injected from the cathode into the light-emitting layer, and high-energy excitons are formed by the recombination of holes and electrons. Through this energy, the organic light-emitting compound reaches an excited state, and light is emitted by the energy generated when the excited state of the organic light-emitting compound returns to the ground state, thereby generating luminescence.

[0003] The most important factor determining the luminous efficiency in an organic EL device is the light-emitting material. The light-emitting material must have a high quantum efficiency, as well as high electron and hole mobilities, and the formed light-emitting material layer must be uniform and stable. The light-emitting material is classified into blue-light-emitting materials, green-light-emitting materials, and red-light-emitting materials according to the color of the emitted light, and also yellow-light-emitting materials or orange-light-emitting materials. In addition, the light-emitting material can also be classified into a host material and a doping material according to its function.

[0004] However, the existing organic electroluminescent materials have low stability, and the matching degree between the HOMO and LUMO energy levels and adjacent energy levels is poor, resulting in the problem of unbalanced carrier mobilities, and further causing problems such as a high driving voltage, low luminous efficiency, and short lifespan of the organic electroluminescent device containing the organic electroluminescent material, severely restricting the application of the organic electroluminescent device. Summary of the Invention

[0005] The object of the present invention is to overcome the problems that the existing organic electroluminescent materials have low stability, and the matching degree between the HOMO and LUMO energy levels and adjacent energy levels is poor, resulting in unbalanced carrier mobilities, and further causing a high driving voltage, low luminous efficiency, and short lifespan of the organic electroluminescent device containing the organic electroluminescent material, and thus to provide an organic compound containing benzonaphthofuran and its applications.

[0006] In the present invention, the definitions of substituent terms are as follows:

[0007] As used in the present invention, the term "halogen" may include fluorine, chlorine, bromine, or iodine.

[0008] As used in the present invention, the term "C1-C30 alkyl" refers to a monovalent substituent derived from a straight-chain or branched-chain saturated hydrocarbon having 1 to 30 carbon atoms, and examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, and hexyl.

[0009] As used in the present invention, the term "C3-C30 cycloalkyl" refers to a monocyclic hydrocarbon or polycyclic hydrocarbon derived from a cyclic main chain having 1 to 30 carbon atoms, and the cycloalkanes may include cyclopropyl, cyclobutyl, adamantyl, and the like.

[0010] In the present invention, aryl and arylene include monocyclic, polycyclic, or fused-ring aryl groups, the rings of which may be interrupted by short non-aromatic units and may include spiro structures. Aryl includes, but is not limited to, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthryl, fluorenyl, spirobifluorenyl, and the like. Arylene includes, but is not limited to, phenylene, biphenylene, terphenylene, naphthylene, phenanthrylene, anthrylene, fluorenylene, spirobifluorenylene, and the like.

[0011] In the present invention, the heteroaryl and heteroarylene include monocyclic, polycyclic or fused-ring heteroaryl, and the rings may be interrupted by short non-aromatic units, and the heteroatoms include nitrogen, oxygen and sulfur. The heteroaryl includes but is not limited to furyl, phenylthio, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuryl, benzothienyl, isobenzofuryl, dibenzofuryl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, and their derivatives, etc.; the heteroarylene includes but is not limited to furylene, phenylthionylene, pyrrolylene, imidazolylene, pyrazolylene, thiazolylene, thiadiazolylene, isothiazolylene, isoxazolylene, oxazolylene, oxadiazolylene, triazinylene, tetrazinylene, triazolylene, tetrazolylene, furazanylene, pyridinylene, pyrazinylene, pyrimidinylene, pyridazinylene, benzofurylene, benzothienylene, isobenzofurylene, dibenzofurylene, dibenzothienylene, benzimidazolylene, benzothiazolylene, benzoisothiazolylene, benzoisoxazolylene, benzoxazolylene, isoindolylene, indolylene, indazolylene, benzothiadiazolylene, quinolinylene, isoquinolinylene, cinnolinylene, quinazolinylene, quinoxalinylene, carbazolylene, phenoxazinylene, phenothiazinylene, phenanthridinylene, benzodioxolylene, dihydroacridinylene, and their derivatives, etc.

[0012] As used in the present invention, the term "substituted" means that a hydrogen atom in a compound is replaced by another substituent. The position is not limited to a specific position as long as the hydrogen at that position can be replaced by a substituent. When there are two or more substituents, the two or more substituents may be the same or different.

[0013] As used in the present invention, unless otherwise specified, the hydrogen atom includes protium, deuterium and tritium.

[0014] In the present invention, in the definition of a group, the range of the number of carbon atoms is defined, and the number of carbon atoms is any integer within the defined range. For example, C6-C30 aryl means that the number of carbon atoms of the aryl can be any integer within the range of 6-60, such as 6, 8, 10, 13, 15, 17, 20, 22, 25 or 30, etc.

[0015] In the present invention, represents a connecting bond.

[0016] The solution adopted in the present invention is as follows:

[0017] The present invention provides an organic compound containing benzonaphthofuran, having a structure shown in the following formula (1):

[0018]

[0019] In the formula (1), Ar is selected from a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C3-C60 heteroaryl group;

[0020] The substituents in the substituted C6-C60 aryl group and the substituted C3-C630 heteroaryl group are each independently selected from one or a combination of at least two of deuterium, halogen, cyano, a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C6-C30 aryl group, a C3-C30 heteroaryl group, a C6-C60 arylamino group, and a C3-C60 heteroarylamino group.

[0021] It can be understood that in , the F phenyl group can be substituted at any substitutable position of ring D or ring E; It can be substituted at any substitutable position of ring A, ring B, or ring C and at any substitutable position of ring D or ring E.

[0022] Preferably, the formula (1) is selected from one of the structures shown in the following formulas 1-1 to 1-4:

[0023]

[0024] Preferably, Ar is selected from a substituted or unsubstituted C6-C60 non-fused aryl group, a substituted or unsubstituted C3-C60 non-fused heteroaryl group;

[0025] The substituents in the substituted C6-C60 non-fused aryl group and the substituted C3-C60 non-fused heteroaryl group are each independently selected from one or a combination of at least two of deuterium, halogen, cyano, a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C6-C30 aryl group, a C3-C30 heteroaryl group, a C6-C60 arylamino group, and a C3-C60 heteroarylamino group.

[0026] Preferably, Ar is selected from a substituted or unsubstituted C6-C20 non-fused aryl group, a substituted or unsubstituted C3-C20 non-fused heteroaryl group;

[0027] The substituents in the substituted C6-C20 non-fused aryl group and the substituted C3-C20 non-fused heteroaryl group are each independently selected from one or a combination of at least two of deuterium, halogen, cyano, a C1-C12 alkyl group, a C3-C12 cycloalkyl group, a C6-C30 aryl group, a C3-C30 heteroaryl group, a C6-C60 arylamino group, and a C3-C60 heteroarylamino group.

[0028] Preferably, Ar is selected from a substituted or unsubstituted A group, and the A group is selected from one of the following groups: phenyl, biphenyl, terphenyl;

[0029] Wherein the substituents in the substituted A group are selected from deuterium, phenyl, naphthyl;

[0030] Preferably, Ar is selected from phenyl, biphenyl, terphenyl, naphthylphenyl.

[0031] Preferably, the organic compound is selected from any one of the following M-1 to M-104:

[0032]

[0033]

[0034]

[0035]

[0036]

[0037] The present invention also provides a light-emitting host material, comprising the above-mentioned organic compound containing benzonaphthofuran.

[0038] Preferably, the light-emitting host material comprises a first host material and a second host material, wherein the first host material is the above-mentioned organic compound containing benzonaphthofuran; the second host material is an organic electroluminescent compound having the following formula (2) structure:

[0039]

[0040] In formula (2), Ar 1 , Ar 2 are each independently selected from a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group;

[0041] The substituents in the substituted C6-C30 aryl group and the substituted C3-C30 heteroaryl group are each independently selected from deuterium, an unsubstituted or C1-C6 alkyl group or a C6-C30 aryl group-substituted C6-C30 aryl group; an unsubstituted or C1-C6 alkyl group or a C6-C30 aryl group-substituted C3-C30 heteroaryl group, a C1-C6 alkyl group;

[0042] Preferably, Ar 1 , Ar 2Each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted phenanthryl;

[0043] Preferably, Ar 1 , Ar 2 Each independently selected from substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted biphenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenyl;

[0044] Preferably, Ar 1 Selected from dibenzofuranyl, phenyldibenzofuranyl, dibenzothiophenyl, phenyldibenzothiophenyl, benzonaphthofuranyl, benzonaphthothiophenyl;

[0045] Ar 2 Selected from phenyl, biphenyl, terphenyl, phenanthryl, naphthyl, phenylnaphthyl, naphthylphenyl.

[0046] Preferably, the compound having the structure shown in formula (2) is selected from one of the compounds shown in N-1 to N-15 below:

[0047]

[0048]

[0049] Preferably, the mass ratio of the first host material to the second host material is 9:1 - 1:9;

[0050] Preferably, the mass ratio of the first host material to the second host material is 2:8 - 8:2;

[0051] More preferably, the mass ratio of the first host material to the second host material is 3:7 - 7:3;

[0052] Further preferably, the mass ratio of the first host material to the second host material is 4:6 - 6:4.

[0053] The present invention also provides an organic electroluminescent material, comprising an organic compound containing benzonaphthofuran or the above-mentioned light-emitting host material.

[0054] The present invention also provides an organic electroluminescent device, the organic electroluminescent device comprising a cathode, an anode, and an organic layer located between the cathode and the anode, the organic layer comprising the above-mentioned organic compound containing benzonaphthofuran or the above-mentioned light-emitting host material or the above-mentioned organic electroluminescent material.

[0055] Preferably, the organic layer includes a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer; the organic layer contains the above-mentioned organic compound containing benzonaphthofuran or the above-mentioned light-emitting host material or the above-mentioned organic electroluminescent material;

[0056] Preferably, the light-emitting layer contains the above-mentioned organic compound containing benzonaphthofuran or the above-mentioned light-emitting host material or the above-mentioned organic electroluminescent material.

[0057] The present invention also provides the application of the above-mentioned organic electroluminescent device in optical fiber devices, lighting devices, electrophotographic photoreceptor devices, photoelectric converters, organic solar cells, switching element devices, organic light-emitting field effect transistors, image sensors or dye lasers.

[0058] Advantages of the present invention:

[0059] The organic compound containing benzonaphthofuran provided by the present invention is based on the structure of formula (1). Further limiting the types of substituents can improve the structural stability of the compound, and the HOMO and LUMO energy levels of the organic compound containing benzonaphthofuran have a high degree of matching with adjacent energy levels, making the carrier mobility of the organic compound containing benzonaphthofuran relatively balanced. Furthermore, the organic electroluminescent device containing the organic compound containing benzonaphthofuran has a low driving voltage, a high luminous efficiency, and a long lifespan;

[0060] Furthermore, the organic compound containing benzonaphthofuran provided by the present invention has good electron transport performance and can be used as an electron transport material or a light-emitting material;

[0061] Furthermore, an organic electroluminescent material provided by the present invention includes an organic compound containing benzonaphthofuran based on the structure of formula (1). Furthermore, the organic electroluminescent device containing the organic electroluminescent material has a low driving voltage, a high luminous efficiency, and a long lifespan. BRIEF DESCRIPTION OF THE DRAWINGS

[0062] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings required for use in the description of the specific embodiments or the prior art. Obviously, the following drawings are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0063] Figure 1 It is a structural diagram of the organic electroluminescent device in the device embodiment of the present invention;

[0064] 1 - Substrate; 2 - Anode; 3 - Hole injection layer; 4 - Hole transport layer; 5 - Light-emitting layer; 6 - Electron transport layer; 7 - Electron injection layer; 8 - Cathode. Detailed implementation manners

[0065] The following embodiments are provided to better further understand the present invention. They are not limited to the described best implementation manners, and do not limit the content and protection scope of the present invention. Any product that is the same as or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other existing technologies falls within the protection scope of the present invention.

[0066] For those not indicating specific experimental steps or conditions in the embodiments, the operations or conditions of the conventional experimental steps described in the literature in this field can be followed. For the reagents or instruments not indicating the manufacturer, they are all conventional reagent products that can be obtained through commercial purchase.

[0067] The term "organic electroluminescent material" in the present disclosure means a material that can be used in an organic electroluminescent device and can contain at least one compound. If necessary, the organic electroluminescent material can be contained in any layer constituting the organic electroluminescent device. For example, the organic electroluminescent material can be a hole injection material, a hole transport material, a hole assisting material, a light-emitting assisting material, an electron blocking material, a light-emitting material (including a host material and a dopant material), an electron buffering material, a hole blocking material, an electron transport material, an electron injection material, etc.

[0068] The term "multiple organic electroluminescent materials" in the present disclosure means one or more combinations of organic electroluminescent materials containing at least two compounds, and the materials can be contained in any layer constituting the organic electroluminescent device. It can mean both the materials before being contained in the organic electroluminescent device (for example, before vapor deposition) and the materials after being contained in the organic electroluminescent device (for example, after vapor deposition). For example, the multiple organic electroluminescent materials can be a combination of at least two compounds, and the materials can be contained in at least one of the following: hole injection layer, hole transport layer, hole assisting layer, light-emitting assisting layer, electron blocking layer, light-emitting layer, electron buffering layer, hole blocking layer, electron transport layer, and electron injection layer. The at least two compounds can be contained in the same layer or different layers, and can be co-evaporated or co-evaporated, or can be evaporated individually.

[0069] In the present invention, the compound shown in formula (1) is prepared through the following synthetic route:

[0070]

[0071] The intermediate raw materials A-n, B-n, and C-n can all be directly purchased or synthesized through conventional reaction routes and conditions with reference to the methods reported in existing literature.

[0072] The specific structures of the intermediate raw materials used in the examples provided by the present invention are as follows:

[0073] The specific structure of B-n is:

[0074]

[0075] The specific structure of C-n is:

[0076]

[0077] Preparation of deuterated intermediate:

[0078]

[0079] In a clean 30 mL high-pressure reaction kettle, successively add raw material C-2 (1 mmol), platinum dioxide (20% w / w), heavy water (5 mL), and decahydroquinoline (5 mL). Bubble nitrogen for at least 10 minutes, heat up to 180 °C and react for at least 16 hours. After the reaction is completed, cool down to room temperature, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, and remove the solvent using a rotary evaporator to obtain a crude product. The crude product is subjected to the above reaction process at least 2 more times to ensure that the hydrogen on the aromatic ring is all deuterated. Finally, the crude product is separated by column chromatography (ethyl acetate: n-hexane = 1:50) to obtain intermediate C-2-D (yield 13%).

[0080] Synthesis of compound N-1:

[0081]

[0082] Synthesis of intermediate N-1-1

[0083] Take a 100 mL three-necked round-bottom flask and place a magnetic stir bar and connect it to a reflux condenser. Under nitrogen protection, successively add raw material 3-bromodibenzofuran (1 mmol), 3-aminobiphenyl (1.05 mmol), tris(dibenzylideneacetone)palladium (0.03 mmol), Xphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), and toluene (10 mL). Heat up to 110 °C and react for 5 hours. After the reaction is completed, cool down to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, remove the solvent using a rotary evaporator, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 3:50) to obtain intermediate N-1-1 (yield 85%).

[0084] Take a 100 mL three-necked round-bottom flask, add a magnetic stir bar and connect it to a reflux condenser. Under nitrogen protection, sequentially add intermediate N-1-1 (1 mmol), intermediate A (1.1 mmol), tris(dibenzylideneacetone)palladium(0) (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), and toluene (10 mL). Heat the mixture to 110 °C and react for 5 hours. After the reaction is completed, cool the mixture to room temperature, filter it by suction, wash the filter cake twice with deionized water and twice with ethanol. The obtained crude product is recrystallized and purified twice with toluene and tetrahydrofuran respectively to obtain compound N-1 (yield 65%).

[0085] Elemental analysis: C 45 H 28 Theoretical values for C, H, N2O2: C, 85.97; H, 4.49; N, 4.46; O, 5.09; Measured values: C, 86.07; H, 4.59; N, 4.26; HRMS(ESI) m / z [M+H]+: Theoretical value: 628.22; Measured value: 629.22.

[0086] Synthesis of compound N-14

[0087]

[0088] Synthesis of intermediate N-14-1

[0089] Take a 100 mL three-necked round-bottom flask, add a magnetic stir bar and connect it to a reflux condenser. Under nitrogen protection, sequentially add starting material 10-chlorobenzo[b]naphtho[2,3-d]thiophene (1 mmol), aniline (1.05 mmol), tris(dibenzylideneacetone)palladium(0) (0.03 mmol), Xphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), and toluene (10 mL). Heat the mixture to 110 °C and react for 5 hours. After the reaction is completed, cool the mixture to room temperature, quench it with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, remove the solvent using a rotary evaporator, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 3:50) to obtain intermediate N-14-1 (yield 67%). Take a 100 mL three-necked round-bottom flask, add a magnetic stir bar and connect it to a reflux condenser. Under nitrogen protection, sequentially add intermediate N-14-1 (1 mmol), intermediate A (1.1 mmol), tris(dibenzylideneacetone)palladium(0) (0.03 mmol), Sphos (0.05 mmol), potassium tert-butoxide (2.5 mmol), and toluene (10 mL). Heat the mixture to 110 °C and react for 5 hours. After the reaction is completed, cool the mixture to room temperature, filter it by suction, wash the filter cake twice with deionized water and twice with ethanol. The obtained crude product is recrystallized and purified twice with toluene and tetrahydrofuran respectively to obtain compound N-14 (yield 54%).

[0090] Elemental analysis: C 43 H 26 Theoretical values of N2OS: C, 83.47; H, 4.24; N, 4.53; O, 2.59; S, 5.18; Measured values: C, 83.57; H, 4.34; N, 4.36; S, 5.15; HRMS(ESI) m / z [M+H]+: Theoretical value: 618.18; Measured value: 619.17.

[0091] The compounds in Table 1 can all be synthesized with reference to the above synthetic method. Just change the starting materials to first synthesize intermediate N-n-1, and then carry out a coupling reaction with intermediate A.

[0092] Table 1

[0093]

[0094]

[0095]

[0096] The product characterization data are shown in Table 2

[0097] Table 2

[0098]

[0099] Example 1

[0100] This example provides an organic compound M-3 containing benzonaphthofuran. The synthesis of the organic compound M-3 containing benzonaphthofuran specifically includes the following steps:

[0101]

[0102] Take a 100 mL three-necked round-bottom flask and place a magnetic stir bar in it, and connect it to a reflux condenser. Under nitrogen protection, successively add raw material A-3 (1 mmol), 2,4-dichloro-6-phenyl-1,3,5-triazine (1.2 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium carbonate (2.5 mmol), 1,4-dioxane / water (10 mL / 2 mL). Heat to 60 °C and react for 5 hours. After the reaction is completed, cool to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, remove the solvent using a rotary evaporator, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 1:50) to obtain intermediate M-3-1 (yield 61%).

[0103] Take a 100 mL three-necked round-bottom flask, add a magnetic stir bar and connect a reflux condenser. Under nitrogen protection, successively add intermediate M-3-1 (1 mmol), 4,4,5,5-tetramethyl-2-(naphtho[2,1-b]benzofuran-1-yl)-1,3,2-dioxaborolane, i.e., C-1 (1.2 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium carbonate (2.5 mmol), 1,4-dioxane / water (10 mL / 2 mL). Heat the mixture to 90 °C and react for 5 hours. After the reaction is completed, cool the mixture to room temperature, filter by suction, wash the filter cake twice with deionized water and twice with ethanol. The obtained crude product is recrystallized and purified twice with ortho-dichlorobenzene to obtain compound M-3 (yield 42%).

[0104] Elemental analysis: C 41 H 25 N3. Theoretical values: C, 85.54; H, 4.38; N, 7.30; O, 2.78; Found values: C, 85.48; H, 4.50; N, 7.24; HRMS(ESI) m / z [M+H] + : Theoretical value: 575.20; Found value: 576.20.

[0105] Example 2

[0106] This example provides an organic compound M-54 containing benzonaphthofuran. The synthesis of the organic compound M-54 containing benzonaphthofuran specifically includes the following steps:

[0107]

[0108] Take a 100 mL three-necked round-bottom flask, add a magnetic stir bar and connect a reflux condenser. Under nitrogen protection, successively add raw material A-54 (1 mmol), 2,4-dichloro-6-phenyl-1,3,5-triazine (1.2 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium carbonate (2.5 mmol), 1,4-dioxane / water (10 mL / 2 mL). Heat the mixture to 60 °C and react for 5 hours. After the reaction is completed, cool the mixture to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, remove the solvent using a rotary evaporator, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 1:50) to obtain intermediate M-54-1 (yield 45%).

[0109] Take a 100 mL three-necked round-bottom flask, place a magnetic stir bar in it and connect a reflux condenser above. Under nitrogen protection, successively add intermediate M-54-1 (1 mmol), 4,4,5,5-tetramethyl-2-(naphtho[2,1-b]benzofuran-5-yl)-1,3,2-dioxaborolane, namely C-4 (1.2 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium carbonate (2.5 mmol), 1,4-dioxane / water (10 mL / 2 mL). Heat the mixture to 90 °C and react for 5 hours. After the reaction is completed, cool it to room temperature, filter by suction, wash the filter cake twice with deionized water and twice with ethanol. The obtained crude product is recrystallized and purified twice with o-dichlorobenzene to obtain compound 54 (yield 46%).

[0110] Elemental analysis: C 41 H 25 N3. Theoretical values: C, 85.54; H, 4.38; N, 7.30; O, 2.78; Found values: C, 85.44; H, 4.54; N, 7.24; HRMS(ESI) m / z [M+H] + : Theoretical value: 575.20; Found value: 576.20.

[0111] Example 3

[0112] This example provides an organic compound M-58 containing benzonaphthofuran. The synthesis of the organic compound M-586 containing benzonaphthofuran specifically includes the following steps:

[0113]

[0114] Take a 100 mL three-necked round-bottom flask, place a magnetic stir bar in it and connect a reflux condenser above. Under nitrogen protection, successively add raw material A-58 (1 mmol), 2-([1,1'-biphenyl]-3-yl)-4,6-dichloro-1,3,5-triazine, namely B-2 (1.2 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium carbonate (2.5 mmol), 1,4-dioxane / water (10 mL / 2 mL). Heat the mixture to 60 °C and react for 5 hours. After the reaction is completed, cool it to room temperature, quench with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, remove the solvent using a rotary evaporator, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 1:50) to obtain intermediate M-59-1 (yield 54%).

[0115] Take a 100 mL three-necked round-bottom flask, add a magnetic stir bar and connect a reflux condenser. Under nitrogen protection, sequentially add intermediate M-59-1 (1 mmol), 4,4,5,5-tetramethyl-2-(naphtho[2,1-b]benzofuran-2-yl)-1,3,2-dioxaborolane, namely C-3 (1.2 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium carbonate (2.5 mmol), 1,4-dioxane / water (10 mL / 2 mL). Heat the mixture to 90 °C and react for 5 hours. After the reaction is completed, cool the mixture to room temperature, filter it by suction, wash the filter cake twice with deionized water and twice with ethanol. The obtained crude product is recrystallized and purified twice with ortho-dichlorobenzene to obtain compound M-58 (yield 71%).

[0116] Elemental analysis: C 47 H 29 N3. Theoretical values: C, 86.61; H, 4.49; N, 6.45; O, 2.45; Found values: C, 86.53; H, 4.59; N, 6.41; HRMS(ESI) m / z [M+H] + : Theoretical value: 651.23; Found value: 652.24.

[0117] Example 4

[0118] This example provides an organic compound M-66 containing benzonaphthofuran. The synthesis of the organic compound M-66 containing benzonaphthofuran specifically includes the following steps:

[0119]

[0120] Take a 100 mL three-necked round-bottom flask, add a magnetic stir bar and connect a reflux condenser. Under nitrogen protection, sequentially add raw material A-66 (1 mmol), 2-([1,1':2',1'-terphenyl]-3-yl)-4,6-dichloro-1,3,5-triazine, namely B-5 (1.2 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium carbonate (2.5 mmol), 1,4-dioxane / water (10 mL / 2 mL). Heat the mixture to 60 °C and react for 5 hours. After the reaction is completed, cool the mixture to room temperature, quench it with saturated ammonium chloride aqueous solution, extract it with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, remove the solvent using a rotary evaporator, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 1:50) to obtain intermediate M-66-1 (yield 49%).

[0121] Take a 100 mL three-necked round-bottom flask, place a magnetic stir bar in it and connect a reflux condenser above. Under nitrogen protection, add intermediate M-66-1 (1 mmol), 4,4,5,5-tetramethyl-2-(naphtho[2,1-b]benzofuran-2-yl)-1,3,2-dioxaborolane, namely C-1 (1.2 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium carbonate (2.5 mmol), 1,4-dioxane / water (10 mL / 2 mL) in sequence. Heat the mixture to 90 °C and react for 5 hours. After the reaction is completed, cool it to room temperature, filter by suction, wash the filter cake twice with deionized water and twice with ethanol. The obtained crude product is recrystallized and purified twice with o-dichlorobenzene to obtain compound M-66 (yield 57%).

[0122] Elemental analysis: C 53 H 33 N3O. Theoretical values: C, 87.46; H, 4.57; N, 5.77; O, 2.20; Found values: C, 87.33; H, 4.79; N, 5.68; HRMS(ESI) m / z [M+H] + : Theoretical value: 727.26; Found value: 728.24.

[0123] The preparation methods of Examples 5-12 are similar to that of Example 1. Specifically, the intermediates, raw materials and obtained products used in Examples 5-12 are shown in Table 3 below. The preparation method of the intermediate M-n-1 used is similar to that of M-3-1 in Example 1.

[0124] Table 3

[0125]

[0126]

[0127] The characterization data of the products obtained from the preparation of Examples 5-12 are shown in Table 4:[[]]END]]

[0128]

[0129] Example 13

[0130] This example provides an organic compound M-73 containing benzonaphthofuran. The synthesis of the organic compound M-73 containing benzonaphthofuran specifically includes the following steps:

[0131]

[0132] Take a 100 mL three-necked round-bottom flask, add a magnetic stir bar and connect it to a reflux condenser. Under nitrogen protection, successively add raw material A-73 (1 mmol), deuterated phenylboronic acid-d5 (1.2 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium carbonate (2.5 mmol), 1,4-dioxane / water (10 mL / 2 mL). Heat the mixture to 60 °C and react for 5 hours. After the reaction is completed, cool it to room temperature, quench it with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, remove the solvent using a rotary evaporator, and separate the crude product by column chromatography (ethyl acetate:n-hexane = 1:50) to obtain intermediate M-73-1 (yield 54%).

[0133] Take a 100 mL three-necked round-bottom flask, add a magnetic stir bar and connect it to a reflux condenser. Under nitrogen protection, successively add intermediate M-73-1 (1 mmol), 4,4,5,5-tetramethyl-2-(naphtho[2,1-b]benzofuran-2-yl)-1,3,2-dioxaborolane, namely C-1 (1.2 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium carbonate (2.5 mmol), 1,4-dioxane / water (10 mL / 2 mL). Heat the mixture to 90 °C and react for 5 hours. After the reaction is completed, cool it to room temperature, filter by suction, wash the filter cake twice with deionized water and twice with ethanol. Recrystallize the obtained crude product twice with o-dichlorobenzene to obtain compound M-73 (yield 67%).

[0134] Elemental analysis: C41H20D5N3O. Theoretical values: C, 84.80; H, 5.21; N, 7.24; O, 2.76; Measured values: C, 84.90; H, 5.25; N, 7.10; HRMS(ESI) m / z [M+H]+: Theoretical value: 580.23; Measured value: 581.23.

[0135] Example 14

[0136] This example provides an organic compound M-84 containing benzonaphthofuran. The synthesis of the organic compound M-84 containing benzonaphthofuran specifically includes the following steps:

[0137]

[0138] Take a 100 mL three-necked round-bottom flask, place a magnetic stir bar in it and connect a reflux condenser above. Under nitrogen protection, successively add raw material A-84 (1 mmol), 2,4-dichloro-6-phenyl-1,3,5-triazine, namely B-1 (1.2 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium carbonate (2.5 mmol), 1,4-dioxane / water (10 mL / 2 mL). Heat the mixture to 60 °C and react for 5 hours. After the reaction is completed, cool it to room temperature, quench it with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, remove the solvent using a rotary evaporator, and separate the crude product by column chromatography (ethyl acetate: n-hexane = 1:50) to obtain intermediate M-84-1 (yield 71%).

[0139] Take a 100 mL three-necked round-bottom flask, place a magnetic stir bar in it and connect a reflux condenser above. Under nitrogen protection, successively add intermediate M-84-1 (1 mmol), 4,4,5,5-tetramethyl-2-(naphtho[2,1-b]benzofuran-2-yl-d9)-1,3,2-dioxaborolane, namely C-2-D (1.2 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium carbonate (2.5 mmol), 1,4-dioxane / water (10 mL / 2 mL). Heat the mixture to 90 °C and react for 5 hours. After the reaction is completed, cool it to room temperature, perform suction filtration, wash the filter cake twice with deionized water and twice with ethanol, and recrystallize the obtained crude product twice with o-dichlorobenzene to obtain compound M-84 (yield 72%).

[0140] Elemental analysis: C41H16D9N3O. Theoretical values: C, 84.22; H, 5.86; N, 7.19; O, 2.74; Measured values: C, 84.33; H, 5.94; N, 7.00; HRMS(ESI) m / z [M+H]+: Theoretical value: 584.25; Measured value: 585.25.

[0141] Example 15

[0142] This example provides an organic compound M-96 containing benzonaphthofuran. The synthesis of the organic compound M-96 containing benzonaphthofuran specifically includes the following steps:

[0143]

[0144] Take a 100 mL three-necked round-bottom flask, place a magnetic stir bar in it and connect it to a reflux condenser. Under nitrogen protection, successively add raw material A-96 (1 mmol), 2,4-dichloro-6-phenyl-1,3,5-triazine, i.e., B-1 (1.2 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium carbonate (2.5 mmol), 1,4-dioxane / water (10 mL / 2 mL). Heat the mixture to 60 °C and react for 5 hours. After the reaction is completed, cool it to room temperature, quench it with saturated ammonium chloride aqueous solution, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, remove the solvent using a rotary evaporator, and separate the crude product by column chromatography (ethyl acetate:n-hexane = 1:50) to obtain intermediate M-96-1 (yield 80%).

[0145] Take a 100 mL three-necked round-bottom flask, place a magnetic stir bar in it and connect it to a reflux condenser. Under nitrogen protection, successively add intermediate M-96-1 (1 mmol), 4,4,5,5-tetramethyl-2-(naphtho[2,1-b]benzofuran-2-yl)-1,3,2-dioxaborolane, i.e., C-3 (1.2 mmol), Pd(dppf)Cl2 (0.03 mmol), potassium carbonate (2.5 mmol), 1,4-dioxane / water (10 mL / 2 mL). Heat the mixture to 90 °C and react for 5 hours. After the reaction is completed, cool it to room temperature, perform suction filtration, wash the filter cake twice with deionized water and twice with ethanol. Recrystallize the obtained crude product twice with o-dichlorobenzene to obtain compound M-96 (yield 72%).

[0146] Elemental analysis: C41H20D5N3O. Theoretical values: C, 84.80; H, 5.21; N, 7.24; O, 2.76; Measured values: C, 84.90; H, 5.31; N, 7.03; HRMS(ESI) m / z [M+H]+: Theoretical value: 580.23; Measured value: 581.23.

[0147] Device Example

[0148] This example provides an organic electroluminescent device, as Figure 1 shown, which includes an anode 2, a hole injection layer 3, a hole transport layer 4, a light-emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode 8 that are sequentially stacked on a substrate 1. The device structure is: anode (indium tin oxide (ITO) coated glass substrate) / hole injection layer (HIL) / hole transport layer (HTL) / light-emitting layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) / cathode (Al).

[0149] The materials for manufacturing the organic electroluminescent device are as follows:

[0150]

[0151]

[0152] The preparation of the above-mentioned organic electroluminescent device includes the following steps:

[0153] 1) Substrate cleaning:

[0154] The glass substrate coated with transparent ITO is ultrasonically treated in an aqueous cleaning agent (the composition and concentration of the aqueous cleaning agent: ethylene glycol solvent ≤ 10 wt%, triethanolamine ≤ 1 wt%), then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol (the volume ratio of acetone to ethanol is 1:1), baked in a clean environment until all moisture is removed, and then cleaned with ultraviolet light and ozone.

[0155] 2) Organic layer preparation:

[0156] Transfer the ITO transparent substrate to an evaporation equipment and evacuate to 1×10 -6 to 2×10 -4 Pa, and sequentially evaporate a hole injection layer (HIL) / hole transport layer (HTL) / emitting layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) / thick cathode (Al) on the anode film.

[0157] Among them:

[0158] The material of the hole injection layer (HIL) is a mixture of NDP-9 and HT, and the specific mass ratio is shown in Table 5;

[0159] The material of the hole transport layer (HTL) is shown in Table 5;

[0160] The emitting layer (EML) is vacuum-evaporated in a co-evaporation manner. The material of the emitting layer includes a host material and a guest material, where the guest material is (piq)2Ir(acac), and the specific material of the host material and its ratio to the guest material are shown in Table 5;

[0161] The material of the electron transport layer (ETL) is shown in Table 5;

[0162] The material of the electron injection layer (EIL) is LiQ;

[0163] The cathode is aluminum;

[0164] Some layers of the organic electroluminescent device, their materials and thicknesses are shown in Table 5

[0165] Table 5

[0166]

[0167]

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174]

[0175] The examples in the table represent device examples, and the comparative examples in the table are device comparative examples.

[0176] Test Example

[0177] The organic light-emitting devices obtained from Device Examples 1-46 and Comparative Examples 1-11 in the device examples were tested.

[0178] Instrument: The characteristics of the device such as current, voltage, brightness, and emission spectrum were synchronously tested using a PR 650 spectral scanning luminance meter and a Keithley K 2400 digital source meter system;

[0179] Test conditions: Optoelectronic characteristic test conditions: The current density was 10 mA / cm2.

[0180] Lifetime test: The current density was 50 mA / cm2, and the time (in hours) was recorded when the brightness of the device decreased to 95% of the original brightness.

[0181] The test results of the device performance are shown in Table 6:

[0182] Table 6

[0183]

[0184]

[0185]

[0186] The examples in the table represent device examples, and the comparative examples in the table are device comparative examples.

[0187] The organic compound containing benzonaphthofuran provided by the present invention has the advantage of good stability compared with the naphthyl group in the phenylnaphthyl group of the compound. It is not easily affected by the electron-withdrawing of the triazinyl group on the phenylnaphthyl group, so that the device using this compound as the organic layer material has a longer lifetime;

[0188] An organic compound containing benzonaphthofuran provided by the present invention. Compared with the naphthylphenyl group, the phenylnaphthyl group in the compound has better conjugation with the triazine group, so that the device using this compound as the organic layer material has a lower driving voltage;

[0189] An organic compound containing benzonaphthofuran provided by the present invention. The compound does not contain a dibenzofuranyl group. (Since the benzonaphthofuranyl group and the dibenzofuranyl group are connected in the same triazine group, which leads to a decrease in the electron mobility of the compound and a decrease in the device using this compound as the organic layer material) has a higher electron mobility. The carriers of the device using this compound as the organic layer material are balanced, and it has a higher luminous efficiency and a longer lifespan.

[0190] Obviously, the above embodiments are merely examples for clear illustration and not limitations on the implementation manners. For those of ordinary skill in the art, other different forms of changes or variations can be made based on the above description. It is not necessary and impossible to list all the implementation manners here. And the obvious changes or variations derived therefrom are still within the protection scope of the present invention.

Claims

1. An organic compound containing benzonaphthofuran, characterized in that, It has the structure shown in the following formula (1): In the formula (1), Ar is selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; The substituents in the substituted C6-C60 aryl and the substituted C3-C630 heteroaryl are each independently selected from one or at least two combinations of deuterium, halogen, cyano, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C60 arylamino, C3-C60 heteroarylamino.

2. The organic compound containing benzonaphthofuran according to claim 1, characterized in that, The formula (1) is selected from one of the structures shown in the following formulas 1-1 to 1-4:

3. The organic compound containing benzonaphthofuran according to claim 1 or 2, characterized in that, Ar is selected from substituted or unsubstituted C6-C60 non-fused aryl, substituted or unsubstituted C3-C60 non-fused heteroaryl; The substituents in the substituted C6-C60 non-fused aryl and the substituted C3-C60 non-fused heteroaryl are each independently selected from one or at least two combinations of deuterium, halogen, cyano, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C60 arylamino, C3-C60 heteroarylamino.

4. The organic compound containing benzonaphthofuran according to any one of claims 1-3, characterized in that, Ar is selected from substituted or unsubstituted C6-C20 non-fused aryl, substituted or unsubstituted C3-C20 non-fused heteroaryl; The substituents in the substituted C6-C20 non-fused aryl and the substituted C3-C20 non-fused heteroaryl are each independently selected from one or at least two combinations of deuterium, halogen, cyano, C1-C12 alkyl, C3-C12 cycloalkyl, C6-C30 aryl, C3-C30 heteroaryl, C6-C60 arylamino, C3-C60 heteroarylamino.

5. The organic compound containing benzonaphthofuran according to any one of claims 1-4, characterized in that, Ar is selected from substituted or unsubstituted A group, and the A group is selected from one of the following groups: phenyl, biphenyl, terphenyl; Wherein the substituents in the substituted A group are selected from deuterium, phenyl, naphthyl; Preferably, Ar is selected from phenyl, biphenyl, terphenyl, naphthylphenyl.

6. The organic compound containing benzonaphthofuran according to any one of claims 1-5, characterized in that, The organic compound is selected from any one of the following M-1 to M-104:

7. A light-emitting host material, characterized in that, Including the organic compound containing benzonaphthofuran according to any one of claims 1-6.

8. An organic electroluminescent material, characterized in that, Including an organic compound containing benzonaphthofuran according to any one of claims 1-6 or the light-emitting host material according to claim 7.

9. An organic electroluminescent device, characterized in that, The organic electroluminescent device includes a cathode, an anode, and an organic layer located between the cathode and the anode, and the organic layer contains the organic compound containing benzonaphthofuran according to any one of claims 1-6 or the light-emitting host material according to claim 7 or the organic electroluminescent material according to claim 8; Preferably, the organic layer includes a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer; the electron transport layer contains the organic compound containing benzonaphthofuran according to any one of claims 1-6 or the light-emitting host material according to claim 7 or the organic electroluminescent material according to claim 8; Preferably, the light-emitting layer contains the organic compound containing benzonaphthofuran according to any one of claims 1-6, or the light-emitting host material according to claim 7, or the organic electroluminescent material according to claim 8.

10. Application of the organic electroluminescent device according to claim 9 in an optical fiber device, a lighting device, an electrophotographic photoreceptor device, a photoelectric converter, an organic solar cell, a switching element device, an organic light-emitting field effect transistor, an image sensor or a dye laser.

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