A triphenylenoxazole compound and application thereof

Abstract

The application provides a triphenylenoxazole compound and application thereof, and the structure of the triphenylenoxazole compound is shown as formula I; wherein L, L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 7 , L 8 are independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group. The triphenylenoxazole compound provided by the application is applied to an organic electroluminescent device, and can effectively improve the current efficiency and service life of the device.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of organic electroluminescent materials, and particularly relates to a triphenylenoxazole compound and application thereof, in particular to a triphenylenoxazole compound with high current efficiency and application thereof. BACKGROUND

[0002] Recently, as the size of displays increases, there is an increasing interest in flat display elements that occupy less space. In the art, technology of organic light emitting displays including organic light emitting diodes (OLEDs) as flat display elements has rapidly developed. An organic light emitting diode realizes light emission by annihilation of hole and electron pairs generated by injecting holes and electrons from a hole injection electrode (anode) and an electron injection electrode (cathode) into an emission layer interposed between the anode and the cathode. Such an organic light emitting diode can be formed on a flexible transparent substrate such as plastic, can be operated at low voltage, consumes relatively low power, and has good color reproduction.

[0003] In 1987, Tang et al. of Eastman Kodak Company first developed a small-molecule green organic electroluminescent device OLED consisting of a light-emitting layer and an electron transport layer. Since then, research on organic electroluminescent devices has rapidly expanded, and has been successfully commercialized

[0004] CN108290875A discloses a new compound capable of improving the light-emitting efficiency, stability and life of an element, and an organic electronic element using the compound, and an electronic device thereof. The compound improves the high light-emitting efficiency, low driving voltage, high heat resistance of the element, and can improve the color purity and life, and the structure of the compound is as follows:

[0005]

[0006] As people's requirements for organic electroluminescent devices gradually increase, the demand for new materials for organic electroluminescent devices is more urgent, and for long-time use and high resolution of displays, OLEDs with higher light-emitting efficiency and / or longer service life are needed. Therefore, how to provide a material for an organic electroluminescent device with high efficiency and long service life has become a problem to be solved. SUMMARY

[0007] In view of the deficiencies of the prior art, the purpose of the present application is to provide a triphenylenoxazole compound and application thereof, in particular to provide a triphenylenoxazole compound with high current efficiency and application thereof. The triphenylenoxazole compound provided by the present application can effectively improve the current efficiency and service life of the device when applied to an organic electroluminescent device.

[0008] To achieve the purpose of the present application, the following technical solutions are adopted:

[0009] In a first aspect, the present application provides a triphenoxazole compound, the structure of which is shown in Formula I:

[0010]

[0011] wherein L, L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 7 , L 8 are independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group.

[0012] Ar, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 are independently selected from any one of hydrogen, deuterium, halogen, cyano, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1-C30 alkyl group in which one or more non-adjacent methylene is independently replaced with an O atom or an S atom, a substituted or unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkenyl group in which one or more non-adjacent methylene is independently replaced with an O atom or an S atom, a substituted or unsubstituted C7-C60 aralkyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C3-C60 heteroaryl group, a substituted or unsubstituted C4-C60 heteroaralkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 heterocycloalkyl group, a substituted or unsubstituted C3-C30 cycloalkenyl group, a substituted or unsubstituted C1-C30 alkylamino group, a substituted or unsubstituted C6-C60 arylamino group, a substituted or unsubstituted C3-C60 heteroarylamino group, a substituted or unsubstituted C6-C60 aryl C3-C60 heteroarylamino group.

[0013] The substituents of the substituted substituent are selected from any one of deuterium, halogen, cyano, an unsubstituted or R'-substituted C1-C6 alkyl group, an unsubstituted or R'-substituted C6-C12 aryl group, and an unsubstituted or R'-substituted C2-C20 heteroaryl group.

[0014] R' is selected from any one of deuterium, halogen, cyano, deuterium-substituted methyl, and halogen-substituted methyl.

[0015] The specific-structure triphenylenoxazole compound is applied to an organic electroluminescent device, and can effectively improve the current efficiency and service life of the device.

[0016] Preferably, the Ar is an electron transport type group;

[0017] Preferably, the Ar is selected from

[0018] wherein Z 1 is selected from N or CR Z1 , Z 2 is selected from N or CR Z2 , Z 3 is selected from N or CR Z3 , Z 4 is selected from N or CR Z4 , Z 5 is selected from N or CR Z5 .

[0019] R Z1 , R Z2 , R Z3 , R Z4 , R Z5 are each independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30alkyl, substituted or unsubstituted C7-C60aralkyl, substituted or unsubstituted C6-C60aryl, substituted or unsubstituted C3-C60heteroaryl, substituted or unsubstituted C4-C60heteroaralkyl, substituted or unsubstituted C3-C30cycloalkyl, substituted or unsubstituted C3-C30heterocycloalkyl, substituted or unsubstituted C3-C30cycloalkenyl, R Z1 , R Z2 , R Z3 , R Z4 , R Z5 are each independently present or two adjacent ones are linked to form a ring C selected from substituted or unsubstituted C6-C30aromatic ring, substituted or unsubstituted C3-C30heteroaromatic ring;

[0020] Preferably, the Ar is selected from wherein Z 2 , Z 4 have the same defined range as described above.

[0021] Preferably, the Ar is selected from wherein Z 2 , Z 3 , Z 4 have the same defined range as described above.

[0022] Preferably, the Ar is selected from wherein Z 2 , Z 4 , Z 5 have the same defined ranges as described above.

[0023] Preferably, the ring C is a benzene ring.

[0024] Preferably, the Ar is selected from wherein R Z2 have the same defined ranges as described above.

[0025] Preferably, the Ar is selected from wherein R Z1 have the same defined ranges as described above.

[0026] Preferably, the R Z1 , R Z2 , R Z3 , R Z4 , R Z5 are independently selected from hydrogen, deuterium, halogen, cyano, any one of the following groups substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthryl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, pyridyl, binaphthyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl (selected from ), dimethylfluorenyl (9'9-dimethylfluorenyl, selected from ), diphenylfluorenyl (9'9-diphenylfluorenyl, selected from ), spirobifluorenyl, dibenzofuranyl-substituted phenyl, dibenzothiophenyl-substituted phenyl, dimethylfluorenyl-substituted phenyl, carbazolyl, benzonaphthofuranyl, benzonaphthothiophenyl.

[0027] Preferably, the Ar is selected from any one of the following groups:

[0028]

[0029]

[0030]

[0031]

[0032] Preferably, the Ar is a hole-transporting group.

[0033] Preferably, the Ar is selected from

[0034] wherein Ar 1 , Ar 2It is independently selected from any one of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C1-C30 alkyl with one or more non-adjacent methylene groups independently substituted by O or S atoms, substituted or unsubstituted C7-C60 aralkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C4-C60 heteroaryl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, and substituted or unsubstituted C3-C30 cycloalkenyl.

[0035] L P1 L P2 Aryl groups independently selected from single-bonded, substituted, or unsubstituted C6-C30 groups.

[0036] Preferably, the Ar 1 Ar 2 The group is independently selected from any one of the following groups: hydrogen, deuterium, halogen, cyano, substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracene, phenyl-substituted naphthyl, naphthyl-substituted phenyl, pyridyl, cyclopyridyl, dibenzofuranyl, dibenzothiophene, carbazolyl, dimethylfluorenyl, diphenylfluorenyl, spirodifluorenyl, benzocarbazolyl, benzonaphthofuranyl, benzonaphthothiophene.

[0037] Preferably, the Ar is selected from any one of the following groups:

[0038]

[0039]

[0040] Preferably, the L 1 L 2 L 3 L 4 L 5 L 6 L 7 L 8 Selected from hydrogen, R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 Selected from hydrogen.

[0041] Preferably, the L is selected from phenylene.

[0042] Preferably, the L P1 Selected from single bonds or phenylene.

[0043] Preferably, the L P2 is selected from a single bond or phenylene.

[0044] Preferably, the trioxazepine compound is an electron transport type compound, and the electron transport type compound is selected from any one of compounds N-1 to N-68:

[0045]

[0046]

[0047]

[0048]

[0049] Preferably, the trioxazepine compound is a hole transport type compound, and the hole transport type compound is selected from any one of compounds P-1 to P-80:

[0050]

[0051]

[0052]

[0053]

[0054]

[0055] The above compounds can be prepared, for example, by a method comprising the following steps

[0056] The starting material is subjected to Suzuki coupling to obtain compound A; then ring closure is performed in the presence of a palladium catalyst to obtain compound B; then demethylation is performed to obtain compound C; then nitro reduction is performed to obtain compound D; then nitro reduction and ring closure are performed using DDQ reagent to obtain compound E; compound E is subjected to Suzuki coupling to obtain compound F; in addition, compound E is subjected to bromine conversion to boronic acid in the presence of a palladium catalyst to obtain compound G; then Suzuki coupling is performed to obtain compound H.

[0057] wherein L, L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 7 , L 8 , Ar, R 1 , R 2 , R 3 , R4 R 5 R 6 R 7 R 8 have the same range of limitations as described above.

[0058] In a second aspect, the present application provides a composition comprising the triphenylenoxazole compound as described above.

[0059] Preferably, the composition comprises any one of the electron-transporting compound as described above and any one of the hole-transporting compound as described above.

[0060] Preferably, the mass ratio of the electron-transporting compound and the hole-transporting compound is 1:9-9:1, wherein the fraction of the mass ratio of the electron-transporting compound can be 1, 2, 3, 4, 5, 6, 7, 8, or 9, and the fraction of the mass ratio of the hole-transporting compound can be 1, 2, 3, 4, 5, 6, 7, 8, or 9, but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are also applicable.

[0061] Preferably, the mass ratio of the electron-transporting compound and the hole-transporting compound is 2:8-8:2.

[0062] Preferably, the mass ratio of the electron-transporting compound and the hole-transporting compound is 3:7-7:3.

[0063] Preferably, the mass ratio of the electron-transporting compound and the hole-transporting compound is 4:6-6:4.

[0064] In a third aspect, the present application provides the use of the triphenylenoxazole compound as described above or the composition as described above in the preparation of an organic electroluminescent diode.

[0065] In a fourth aspect, the present application provides an organic electroluminescent diode, comprising a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode, wherein the organic layer comprises at least one triphenylenoxazole compound as described above and / or at least one composition as described above.

[0066] Preferably, the organic layer comprises any one of a hole-injection layer, a first hole-transporting layer, a second hole-transporting layer, an electron-blocking layer, a light-emitting layer, a hole-blocking layer, an electron-transporting layer, or an electron-injection layer, or a combination of at least two of them, such as a combination of a hole-injection layer and a first hole-transporting layer, a combination of a first hole-transporting layer and a second hole-transporting layer, or a combination of an electron-transporting layer and an electron-injection layer, but is not limited to the above-mentioned combinations, and other combinations not mentioned in the above-mentioned range are also applicable.

[0067] Preferably, the hole blocking layer comprises at least one trioxadiazole compound as described above.

[0068] Preferably, the electron transport layer comprises at least one trioxadiazole compound as described above.

[0069] Preferably, the light emitting layer comprises at least one trioxadiazole compound as described above.

[0070] Preferably, the light emitting layer comprises a composition as described above.

[0071] In a fifth aspect, the present application also provides an organic electroluminescent device comprising an organic electroluminescent diode as described above.

[0072] Compared with the prior art, the present application has the following beneficial effects:

[0073] The present application provides a trioxadiazole compound with a specific structure, which is applied in an organic electroluminescent device, and can effectively improve the current efficiency and service life of the device. BRIEF DESCRIPTION OF DRAWINGS

[0074] Figure 1 is a structural schematic diagram of the organic electroluminescent device in application examples 1-4, wherein 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light emitting layer, 6 is an electron buffer layer, 7 is an electron transport layer, 8 is an electron injection layer, and 9 is a cathode. DETAILED DESCRIPTION

[0075] The technical solutions of the present application will be further described below through specific embodiments. Those skilled in the art should understand that the examples are only to help understand the present application, and should not be regarded as a specific limitation on the present application.

[0076] As used in the present application, the term "organic electroluminescent compound" means a compound that can be used in an organic electroluminescent device and can be included in any layer constituting an organic electroluminescent device as needed.

[0077] As used in the present application, the term "organic electroluminescent material" refers to a material that can be used in an organic electroluminescent element and can include at least one compound. If necessary, the organic electroluminescent material can be included in any layer constituting an organic electroluminescent element. For example, the organic electroluminescent material can be a hole injection material, a hole transport material, an electron blocking material, a light emitting auxiliary material, a light emitting layer material (including a host material and a dopant material), an electron buffer material, a hole blocking material, an electron transport material, an electron injection material, etc.

[0078] The organic electroluminescent material of the present disclosure can include at least one compound represented by Formula 1. Although not limited thereto, the compound having Formula 1 can be included in a light-emitting layer. In this case, the compound having Formula 1 can be included as a host. If necessary, the host material can include two or more compounds of Formula 1. Also, the compound having Formula 1 can be included in an electron transport region, and / or the compound having Formula 1 can be included in an electron buffer layer, and is not limited thereto.

[0079] Hereinafter, each layer of the organic electroluminescent element containing the compound of Formula 1 according to the present disclosure will be described.

[0080] Substrate

[0081] The organic EL element is generally produced on a light-transmitting substrate. The light-transmitting substrate is a substrate for supporting the organic EL element, and the transmittance of light in the visible region of wavelength 400-700 nm is preferably 50% or more, and further preferably a smooth substrate is used.

[0082] As such a light-transmitting substrate, for example, a glass plate, a synthetic resin plate, etc. can be exemplified. As the glass plate, a plate formed of soda-lime glass, barium / strontium-containing glass, lead glass, aluminum silicate glass, borosilicate glass, barium borosilicate glass, quartz, etc. can be exemplified. In addition, as the synthetic resin plate, a plate of polycarbonate resin, acrylic resin, polyethylene terephthalate resin, polyether sulfide resin, polysulfone resin, etc. can be exemplified.

[0083] Anode

[0084] The anode functions to inject holes into the hole transport layer or the light-emitting layer, and it is effective to have a work function of 4 eV or more (preferably 4.45 eV or more). As a specific example of the anode material, carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum, palladium, etc. and alloys thereof, tin oxide, indium oxide, etc. used in ITO substrates, NESA substrates, metal oxides, organic conductive resins such as polythiophene or polypyrrole can be exemplified.

[0085] Cathode

[0086] As the cathode, a cathode using a metal, an alloy, a conductive compound, and a mixture thereof having a small work function (less than 4 eV) as an electrode material can be used. As a specific example of such an electrode material, magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminum, lithium fluoride, etc. and alloys thereof can be used, and are not particularly limited. As the alloy, magnesium / silver, magnesium / indium, lithium / aluminum, etc. can be exemplified as representative examples, and are not particularly limited. The ratio of the alloy is controlled by the temperature, atmosphere, vacuum degree, etc. of the evaporation source, and an appropriate ratio is selected. The anode and the cathode can also be formed by two or more layers as needed.

[0087] Light-emitting layer

[0088] The light-emitting layer has a function of carrier injection, carrier transport, and light emission. The light-emitting layer material includes a host material, a guest material, and the guest material includes a phosphorescent guest material, a fluorescent guest material, a TADF guest material, and the like.

[0089] Hole injection layer / hole transport layer

[0090] The hole injection layer / hole transport layer is a layer that contributes to injection of holes into the light-emitting layer and transport of holes to the light-emitting region, and has a large hole mobility and a typically small ionization energy of 5.7 eV or less. As such a hole injection layer / hole transport layer, a material that transports holes to the light-emitting layer at a lower electric field strength is preferred, and further preferred is a material having a hole mobility of 10-4 cm2 / V·sec or more at an applied electric field of 104 to 106 V / cm. Examples of known materials as a hole transport layer material include bis(N-(1-naphthyl-n-phenyl))benzidine (a-NPD), N,N'-di(naphthalen-1-yl)-N,N'-diphenylbenzidine (NPB), or N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), and the like.

[0091] Electron injection layer / electron transport layer

[0092] The electron injection layer / electron transport layer is a layer that contributes to injection of electrons into the light-emitting layer and transport of electrons to the light-emitting region, and has a large electron mobility. The adhesion-improving layer is an electron injection layer that contains a material that particularly well adheres to the cathode.

[0093] As a material used in the electron injection layer, specifically, LiF, Liq, Li2O, BaO, NaCl, CsF, and the like can be listed, and are not particularly limited thereto.

[0094] The functions of the OLED can be achieved by combining the various layers described above, or some layers can be completely omitted. It can also include other layers not explicitly described. Within each layer, a single material or a mixture of multiple materials can be used to achieve the best performance. Any functional layer can include several sub-layers. For example, the light-emitting layer can have two layers of different light-emitting materials to achieve the desired light-emitting spectrum.

[0095] To form each layer of the organic electroluminescent device of the present disclosure, a dry film formation method such as vacuum evaporation, sputtering, plasma, ion plating method, or the like, or a wet film formation method such as inkjet printing, nozzle printing, slot coating, spin coating, dip coating, flow coating method, and the like, can be used. The organic electroluminescent compound of the present disclosure can be film-formed by a co-evaporation method or a mixture evaporation method.

[0096] As used in the present application, the term "halogen" can include fluorine, chlorine, bromine or iodine, preferably fluorine.

[0097] As used in the present application, the term "C1-C30alkyl" refers to a monovalent substituent derived from a straight chain or branched chain saturated hydrocarbon of from 1 to 30 carbon atoms, examples of which include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, t-butyl, pentyl, isopentyl, and hexyl.

[0098] As used in the present application, the term "C3-C30cycloalkyl" refers to a monocyclic or polycyclic hydrocarbon having from 1 to 30 ring backbone carbon atoms, which cycloalkane can include cyclopropyl, cyclobutyl, adamantyl, and the like.

[0099] As used in the present application, the term "C3-C30heterocycloalkyl" refers to a monocyclic or polycyclic hydrocarbon having from 1 to 30 ring backbone carbon atoms, and at least one carbon atom is replaced by a heteroatom selected from at least one of O, S, N, Si, P, preferably O, S, N. Additionally, the heterocycloalkyl group can be optionally substituted.

[0100] As used in the present application, the term "C2-C30alkenyl" refers to and includes straight chain and branched chain alkenyl groups. Alkenyl groups essentially are alkyl groups that include at least one carbon-carbon double bond in the alkyl chain. Cycloalkenyl groups are cycloalkyl groups that include at least one carbon-carbon double bond in the cycloalkyl ring.

[0101] As used in the present application, the term "C1-C30alkylamino" refers to

[0102] As used in the present application, the term "C6-C60arylaminocycloalkyl" refers to

[0103] As used in the present application, the term "C3-C60heteroarylamino" refers to

[0104] As used in the present application, the term "C6-C60arylC3-C60heteroarylamino" refers to

[0105] Aryl, arylene groups in the present application include monocyclic, polycyclic or fused ring aryl groups, which rings can be interrupted by short non-aromatic units, and can contain spiro structures, including but not limited to phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthryl, fluorenyl, spirobifluorenyl, and the like.

[0106] In the present application, heteroaryl group, heteroarylene group include monocyclic, polycyclic or fused ring heteroaryl group, the rings can be interrupted by short non-aromatic units, the heteroatom includes nitrogen, oxygen, sulfur. Including but not limited to furanyl, phenylthio, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoaxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, and derivatives thereof, etc.

[0107] As used in the present application, the term "substituted" means that the hydrogen atom in the 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 two or more substituents are present, the two or more substituents can be the same or different.

[0108] As used in the present application, unless otherwise specified, hydrogen atom includes protium, deuterium and tritium.

[0109] In the present application, the range of the number of carbon atoms is defined in the definition of the group, and the number of carbon atoms is any integer within the defined range, for example, C6-C60 aryl, the number of carbon atoms of the aryl group can be any integer within the range of 6-60, such as 6, 8, 10, 15, 20, 30, 35, 40, 45, 50, 55 or 60, etc.

[0110] In the present application, The substitution site of the substituent.

[0111] Synthesis of intermediates

[0112]

[0113] Synthesis of intermediate 1-1: Mix raw material 1 (1 mmol), raw material 2 (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), add tetraphenylphosphonium palladium (0.05 mmol), potassium carbonate (2 mmol), heat to 80 degrees Celsius, react for 5 hours, after the reaction is completed, reduce to 20 degrees Celsius, extract with ethyl acetate, dry the organic phase with anhydrous magnesium sulfate, remove the solvent using a rotary evaporator, separate the crude product by column chromatography (volume ratio ethyl acetate: n-hexane = 1:50), obtain intermediate 1-1 (0.16 g, yield 47%).

[0114] MS (APCI) m / z [M+H] + : Calcd: 340.07; Found: 340.14.

[0115] Synthesis of intermediate 1-2: Intermediate 1-1 (1 mmol), triphenylphosphine (10 mL), palladium valerate (0.05 mmol), potassium acetate (1.2 mmol), pivalic acid (1 mmol) were mixed and the reaction was heated to reflux. After the reaction was completed, water was added to quench the reaction, and the organic phase was dried over anhydrous magnesium sulfate. The organic solvent was removed by rotary evaporation, and the crude product was separated by column chromatography (volume ratio ethyl acetate: n-hexane = 1:50) to obtain intermediate 1-2 (0.19 g, yield 64%).

[0116] MS (APCI) m / z [M+H] + : Calcd: 304.09; Found: 304.18.

[0117] Synthesis of intermediate 1-3: Intermediate 1-2 (10 mmol) was dissolved in 20 mL of acetic acid, and hydrobromic acid (48%, 10 mL) was added. The reaction was refluxed for 24 hours, 50 mL of water was added, and the organic phase was extracted with dichloromethane. The combined organic phase was washed with saturated brine three times, dried over anhydrous sodium sulfate, filtered, and the organic solvent was removed by rotary evaporation. The crude product was separated by column chromatography (volume ratio dichloromethane / methanol / n-hexane = 20:1:30) to obtain intermediate 1-3 (2.49 g, yield 86%).

[0118] MS (APCI) m / z [M+H] + : Calcd: 290.07; Found: 290.16.

[0119] Synthesis of intermediate 1-4: Intermediate 1-3 (10 mmol) was added to a mixture of ethyl acetate and 1,2-dichlorobenzene, and Pd / C (10% Pd) was added under nitrogen protection. The reaction system was stirred at 20°C for 2 hours under 1 atm hydrogen pressure. The reaction solution was filtered with diatomite, and the organic solvent was removed by distillation under reduced pressure to obtain intermediate 1-4 (2.36 g, yield 91%).

[0120] MS (APCI) m / z [M+H] + : Calcd: 260.10; Found: 260.19.

[0121] Synthesis of intermediate 1-5: Intermediate 1-4 (12 mmol) and raw material 3 (10 mmol) were added to anhydrous ethanol (20 mL) respectively, stirred at 20°C for 1 hour, then DDQ (10 mmol) was added, stirred at 20°C for 2 hours, the reaction solution was filtered, the filtered product was washed with dichloromethane, the organic phase was combined, washed with saturated sodium bicarbonate, dried over anhydrous sodium sulfate, the organic solvent was removed by reduced pressure distillation, and the crude product was separated by column chromatography (volume ratio of dichloromethane: n-hexane = 1:20) to obtain intermediate 1-5 (3.47 g, yield 82%).

[0122] MS (APCI) m / z [M+H] + : Theoretical value: 424.03; Found: 424.21.

[0123] Synthesis of intermediate 1: Intermediate 1-5 (10 mmol), pinacol diboronic acid (12 mmol), sodium acetate (20 mmol), tris(dibenzylideneacetone)dipalladium (0.5 mmol) and 2-bis(cyclohexylphosphino)-2',6'-dimethoxybiphenyl (1.5 mmol) were added to 1,4-dioxane (20 mL) and replaced with nitrogen three times. Under the condition of nitrogen protection, heated to 100°C for reaction. After the reaction was completed, water was added for quenching, dichloromethane was used for extraction, and the organic solvent was removed by rotary evaporation. The crude product was separated by column chromatography (volume ratio of ethyl acetate: n-hexane = 1:50) to obtain intermediate 1 (3.15 g, yield 81%).

[0124] MS (APCI) m / z [M+H] + : Theoretical value: 424.03; Found: 424.21.

[0125] Reference to the above method, using intermediate 1-4 as raw material, changing different other raw materials to obtain intermediate 2-4, 3-4, and then obtaining intermediate 2 and intermediate 3

[0126]

[0127]

[0128] Example 1

[0129] This example provides a triphenylenoxazole compound N-4, and the synthesis reaction formula is as follows:

[0130]

[0131] Synthesis of N-4: Intermediate 3 (10 mmol), raw material 6 (10 mmol), sodium bicarbonate (23 mmol), tetrakis triphenylphosphine palladium (0.5 mmol), dichloro di-tert-butyl- (4-dimethylaminophenyl) palladium (0.5 mmol) were added to toluene (25 mL), ethanol (7 mL), and water (7 mL) was added while replacing with nitrogen three times. Under the condition of nitrogen protection, it was heated to 80°C for 8 hours, and after the reaction was completed, it was extracted with ethyl acetate, and the obtained extract was sequentially added with magnesium sulfate, dried, filtered and rotary evaporated; the crude product was purified by chromatography (volume ratio ethyl acetate: n-hexane = 1:10) to obtain N-4 (5.20 g, yield 83%).

[0132] MS (APCI) m / z [M+H] + : Theoretical value: 627.21; Found: 627.38.

[0133] Examples 2-9

[0134] Referring to the preparation method of Example 1, different products were obtained by changing different raw materials, as follows:

[0135]

[0136]

[0137] Example 10

[0138] This example provides a triphenylenoxazole compound P-1, and the synthesis reaction formula is as follows:

[0139]

[0140] Synthesis of P-1: Intermediate 1-5 (10 mmol), raw material 7 (10 mmol), Pd2(dba)3 (0.5 mmol), 50% tri-tert-butyl phosphine solution (1 mmol), NaOtBu (22 mmol), toluene (30 mL) were mixed and refluxed and stirred for 5 hours, after the reaction was completed, it was cooled to 20°C, and the organic solvent was removed by distillation under reduced pressure, and the crude product was purified by chromatography (volume ratio ethyl acetate: n-hexane = 1:10) to obtain P-1 (4.64 g, yield 77%)

[0141] MS (APCI) m / z [M+H] + : Theoretical value: 603.20; Found: 603.36.

[0142] Examples 11-15

[0143] Referring to the preparation method of Example 10, different products were obtained by changing different raw materials, as follows:

[0144]

[0145]

[0146] Application Examples 1-15 and Comparative Application Example 1

[0147] The triphenylenoxazole compound provided in the above examples was used to prepare an organic electroluminescent device having the following layer structure: substrate (indium tin oxide (ITO) as an anode-coated glass substrate) / hole injection layer (HIL) / hole transport layer (HTL) / emitting layer (EML) / electron buffer layer (optional) / electron transport layer (ETL) / electron injection layer (EIL), and finally a cathode, the structural diagram of which is shown in Figure 1 , wherein 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an emitting layer, 6 is an electron buffer layer, 7 is an electron transport layer, 8 is an electron injection layer, and 9 is a cathode.

[0148] The materials required for the manufacture of the OLED are as follows:

[0149]

[0150] The preparation method is as follows:

[0151] (1) Substrate cleaning: the glass substrate coated with transparent ITO was treated with ultrasonic waves in an aqueous cleaning agent (composition and concentration of the aqueous cleaning agent: ethylene glycol solvent ≤ 10 wt%, triethanolamine ≤ 1 wt%), rinsed in deionized water, treated with ultrasonic waves in an acetone: ethanol mixed solvent (volume ratio 1:1) to remove oil, baked in a clean environment until the water was completely removed, and then cleaned with ultraviolet light and ozone.

[0152] (2) Evaporation of organic light-emitting functional layer:

[0153] The above glass substrate with an anode layer was placed in a vacuum chamber, vacuumed to 1 x 10 -6 to 2 x 10 -4 Pa, and a mixture of HATCN and HT was vacuum evaporated on the anode layer film, wherein the mass ratio of HATCN to HT was 3:97, as a hole injection layer (HIL), and the evaporation thickness was 10 nm.

[0154] A hole transport layer (HTL, material: HT) was evaporated on the hole injection layer, and the evaporation film thickness was 80 nm.

[0155] A light-emitting layer (EML) is evaporated on the hole transport layer, and the specific preparation method is as follows: the light-emitting host material (selected from the compounds provided in the examples and CBP) and the guest material (piq)2Ir(acac) are co-evaporated by vacuum evaporation, and the total film thickness is 30 nm;

[0156] Optionally, an electron buffer layer (the materials are N-2, N-21, N-37 and N-58, respectively) is evaporated on the light-emitting layer, and the total thickness is 10 nm;

[0157] An electron transport layer (ETL) is evaporated on the light-emitting layer (if there is an electron buffer layer, the electron buffer layer), and the specific preparation method is as follows: BCP and LiQ are co-evaporated by vacuum evaporation, and the total film thickness is 30 nm;

[0158] An electron injection layer (EIL, the material is LiQ) is evaporated on the electron transport layer, and the total film thickness is 1 nm;

[0159] Al is evaporated on the electron injection layer, and the total film thickness is 90 nm.

[0160] The material parameters of each layer are as follows:

[0161]

[0162]

[0163] Performance test:

[0164] The organic electroluminescent devices provided in the above application examples 1-15 and the comparative application example 1 are tested, and the PR650 spectrum scanning luminance meter and the Keithley K 2400 digital source table system are synchronously tested. The photoelectric property test condition is that the current density is 10 mA / cm 2 , the service life test condition is that the current density is 10 mA / cm 2 , and the time (in hours) is recorded when the device brightness decreases to 96% of the original brightness, and the results are as follows:

[0165]

[0166] The above results show that the organic electroluminescent device prepared by using the compound provided in the application can significantly improve the current efficiency and service life of the product.

[0167] The applicant declares that the triphenylenoxazole compound and the application thereof of the present application are illustrated by the above-mentioned embodiments, but the present application is not limited to the above-mentioned embodiments, that is, it does not mean that the present application must rely on the above-mentioned embodiments to be implemented. It should be understood by those skilled in the art that any improvement of the present application, equivalent replacement of each raw material of the product of the present application, addition of auxiliary ingredients, selection of specific modes, etc. fall within the protection scope and disclosure scope of the present application.

[0168] The preferred embodiments of the present application are described in detail above, but the present application is not limited to the specific details in the above-mentioned embodiments, and various simple modifications can be made to the technical solutions of the present application within the technical concept of the present application, and these simple modifications all belong to the protection scope of the present application.

[0169] In addition, it should be noted that each specific technical feature described in the above-mentioned specific embodiments can be combined by any suitable method without contradiction, and in order to avoid unnecessary repetition, the present application will not further describe various possible combination methods.

Claims

1. A tribenzoxazole compound, characterized in that, The structure of the triphenylenoxazole compound is shown in Formula I: ； L is selected from the group consisting of phenylene; L 1 , L 2 , L 3 , L 4 , L 5 , L 6 , L 7 , L 8 is independently selected from a single bond; Ar is selected from , , or ; wherein Z 2 selected from CR Z2 , Z 4 selected from N or CR Z4 ; R Z1 , R Z2 , R Z4 is independently selected from substituted or unsubstituted phenyl, unsubstituted naphthyl, unsubstituted dibenzofuranyl, unsubstituted biphenyl, unsubstituted 9,9 dimethylfluorenyl; L P1 , L P2 is independently selected from a single bond or phenylene; Ar 1 , Ar 2 is independently selected from substituted or unsubstituted phenyl, unsubstituted biphenyl, unsubstituted dibenzofuranyl, unsubstituted 9,9-dimethylfluorenyl, unsubstituted N-phenylcarbazolyl, unsubstituted N-pyridylcarbazolyl; The substituted substituent is selected from the group consisting of deuterium, cyano, phenyl. R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 is independently selected from hydrogen.

2. The trioxazolyl compound according to claim 1, characterized by Ar is selected from , or ; wherein Z 2 selected from CR Z2 , Z 4 selected from N or CR Z4 ; R Z1 , R Z2 , R Z4 are independently selected from substituted or unsubstituted phenyl, unsubstituted naphthyl, unsubstituted dibenzofuranyl, unsubstituted biphenyl, unsubstituted 9,9 dimethylfluorenyl; The substituted substituent is selected from the group consisting of deuterium, cyano, phenyl.

3. The trioxazolyl compound according to claim 2, characterized by Ar is selected from any one of the following groups: ； ； ； ； ； ； ； ； ； ； ； ； ； ； 。 4. The trioxazolyl compound according to claim 1, wherein Ar is selected from ; wherein L P1 , L P2 is independently selected from a single bond or phenylene; Ar 1 , Ar 2 is independently selected from substituted or unsubstituted phenyl, unsubstituted biphenyl, unsubstituted dibenzofuranyl, unsubstituted 9,9-dimethylfluorenyl, unsubstituted N-phenylcarbazolyl, unsubstituted N-pyridylcarbazolyl; The substituted substituent is selected from the group consisting of deuterium, cyano, phenyl.

5. The trioxazolyl compound according to claim 4, wherein Ar is selected from any one of the following groups: ； ； ； ； ； ； 。 6. The trioxazolyl compound according to claim 1, wherein The triphenylenoxazole compound is an electron transport type compound, and the electron transport type compound is selected from any one of the following compounds: ； ； ； ； ； ； ； ； ； 。 7. The trioxazolyl compound according to claim 1, wherein The triphenylenoxazole compound is a hole transport type compound, and the hole transport type compound is selected from any one of the following compounds: ； ； ； ； ； ； ； ； ； 。 8. A composition characterized in that, The composition comprises the triphenylenoxazole compound of any one of claims 1-7.

9. The composition of claim 8, wherein, The composition comprises any one of the electron transport type compounds of claim 6 and any one of the hole transport type compounds of claim 7.

10. The composition of claim 9, wherein, The mass ratio of the electron transport type compound and the hole transport type compound is 1:9-9:

1.

11. The composition of claim 10, wherein, The mass ratio of the electron transport type compound and the hole transport type compound is 2:8-8:

2.

12. The composition of claim 11, wherein, The mass ratio of the electron transport type compound and the hole transport type compound is 3:7-7:

3.

13. The composition of claim 12, wherein, The mass ratio of the electron transport type compound and the hole transport type compound is 4:6-6:

4.

14. Use of the triphenylenoxazole compound of any one of claims 1-7 or the composition of any one of claims 8-13 in the preparation of an organic electroluminescent diode.

15. An organic electroluminescent diode, characterized by The organic electroluminescent diode comprises a first electrode, a second electrode, an organic layer between the first electrode and the second electrode, and the organic layer comprises at least one triphenylenoxazole compound of any one of claims 1-7 and / or at least one composition of any one of claims 8-13.

16. The organic electroluminescence diode according to claim 15, characterized in that, The organic layer comprises any one of a hole injection layer, a first hole transport layer, a second hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, or an electron injection layer, or a combination of at least two thereof.

17. The organic electroluminescence diode according to claim 16, characterized in that, The hole blocking layer comprises at least one triphenylenoxazole compound of any one of claims 1-7.

18. The organic electroluminescence diode according to claim 16, characterized in that, The electron transport layer comprises at least one triphenylenoxazole compound of any one of claims 1-7.

19. The organic electroluminescence diode according to claim 16, wherein The light emitting layer comprises at least one triphenylenoxazole compound of any one of claims 1-7.

20. The organic electroluminescence diode according to claim 16, wherein The light emitting layer comprises the composition of any one of claims 8-13.

21. An organic electroluminescent device, characterized by The organic electroluminescent device comprises the organic electroluminescent diode of any one of claims 15-20.

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