Diazanaphthalene compound, intermediate and organic electroluminescent device

Abstract

The invention provides a phthalazinone compound, an intermediate and an organic electroluminescent device. The compound has a structure as shown in a formula I or a formula II. The intermediates are used for preparing the compounds. The structure of the compound is designed, so that the compound is suitable for being used as a main body material of a light-emitting layer of the organic light-emitting device, and the organic light-emitting device has relatively high current efficiency and relatively long service life.

Description

Technical Field

[0001] The invention belongs to the technical field of organic electroluminescent materials, and in particular relates to a naphthyridine compound, an intermediate and an organic electroluminescent device. Background Art

[0002] Compared with other flat panel displays (for example, liquid crystal displays (LCDs), plasma display panels (PDPs), field emission displays (FEDs), etc.), organic electroluminescent devices (OLEDs) have a simpler structure, various processing advantages, higher brightness, excellent viewing angle characteristics, faster response speeds, and lower driving voltages. Therefore, they are also fully developed to be used as light sources for flat panel displays (for example, wall-mounted TVs, etc.), or as backlight units for displays, illuminators, billboards, etc.

[0003] The structure of an organic electroluminescent device specifically includes an anode, a cathode, and an organic layer therebetween. In order to improve the efficiency and stability of an organic electroluminescent element, the organic material layer includes multiple layers with different materials. In order to meet people's higher requirements for OLED devices, the field urgently needs to develop more types of materials to improve the performance of OLED devices in terms of current efficiency, life span, etc. Summary of the invention

[0004] In view of the shortcomings of the prior art, the present invention aims to provide a naphthyridine compound, an intermediate and an organic electroluminescent device. In the present invention, the structure of the compound is designed to make it suitable as a main material of the light-emitting layer of the organic electroluminescent device, so that the organic electroluminescent device has a higher current efficiency and a longer life.

[0005] To achieve this object, the present invention adopts the following technical solutions:

[0006] In a first aspect, the present invention provides a naphthyridine compound, wherein the naphthyridine compound has a structure shown in Formula I or a structure shown in Formula II:

[0007]

[0008] Wherein, in the naphthyridine compound represented by formula I and the naphthyridine compound represented by formula II, X is independently selected from C or Si;

[0009] Dashed lines indicate single bonds or their absence;

[0010] In the naphthyridine compound represented by formula I and the naphthyridine compound represented by formula II, Ar1 is independently selected from any one of a C6-C40 arylene group and a C6-C30 heteroarylene group;

[0011] In the naphthyridine compound represented by formula I and the naphthyridine compound represented by formula II, Ar2 is independently selected from any one of a single bond, a C6-C40 arylene group, and a C6-C30 heteroarylene group;

[0012] In the naphthyridine compound represented by formula I and the naphthyridine compound represented by formula II, Ar3, Ar4, and Ar5 are each independently selected from any one of H, C6-C40 aryl, and C6-C30 heteroaryl;

[0013] The hydrogen atoms in the naphthyridine compound represented by formula I and the naphthyridine compound represented by formula II can each independently be substituted by at least one of a deuterium atom (-D), -F, -CN, a C6-C20 aryl group, a C1-C12 alkyl group or a C1-C12 alkoxy group.

[0014] In the present invention, the structure of the naphthyridine compound is designed to make it suitable for use as the main material of the light-emitting layer of the organic electroluminescent device. The organic electroluminescent device prepared thereby has higher current efficiency and longer lifespan.

[0015] It should be noted that, in the present invention, "-D" represents a deuterium atom, and the same applies hereinafter.

[0016] In the present invention, C6-C40 can be C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.

[0017] C6-C30 can be C6, C8, C10, C12, C16, C20, C24, C28 or C30, etc.

[0018] C1-C12 can be C1, C2, C4, C6, C8, C10 or C12, etc.

[0019] C6-C20 can be C6, C8, C10, C12, C16 or C20, etc.

[0020] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0021] As a preferred technical solution of the present invention, the C6-C40 aromatic group is selected from any one or a combination of at least two of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthfluoroenyl, pyrene, perylenyl, spirofluorenyl, triphenylene, fluoranthenyl, hydrogenated benzanthryl, indenofluorenyl, benzoindenofluorenyl, dibenzoindenofluorenyl, naphthfluoroenyl or benzonaphthofluorenyl.

[0022] Preferably, the C6-C40 arylene group is selected from any one of phenylene, biphenylene, terphenylene, naphthylene, anthracene, phenanthrenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthofluorenyl, perylene, perylene, spirofluorenyl, triphenylene, fluoranthenyl, hydrogenated benzanthryl, indenofluorenyl, benzoindenofluorenyl, dibenzoindenofluorenyl, naphthofluorenyl or benzonaphthofluorenyl, or a combination of at least two thereof.

[0023] As a preferred technical solution of the present invention, the C6-C30 heteroaryl group is selected from any one of carbazolyl, dibenzofuranyl, dibenzothiophenyl, naphthobenzofuranyl, naphthobenzothiophenyl, dinaphthofuranyl, dinaphthothiophenyl or carbazolyl, or a combination of at least two thereof.

[0024] Preferably, the C6-C30 heteroarylene group is selected from any one or a combination of at least two of a carbazolylene group, a dibenzofuranyl group, a dibenzothiophenyl group, a naphthobenzofuranyl group, a naphthobenzothiophenyl group, a dinaphthofuranyl group, a dinaphthothiophenyl group or a carbazolylene group.

[0025] As a preferred technical solution of the present invention, the C6-C20 aromatic group is selected from any one or a combination of at least two of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, triphenylene or fluoranthene.

[0026] Preferably, the C1-C12 alkyl group is selected from any one of methyl, ethyl, propyl, butyl, pentyl or adamantyl, or a combination of at least two thereof.

[0027] Preferably, the C1-C12 alkoxy group is selected from any one of methoxy, ethoxy, propoxy, butoxy or pentoxy, or a combination of at least two thereof.

[0028] As a preferred technical solution of the present invention, in the compound represented by Formula I and the compound represented by Formula II, Ar1 is independently selected from phenylene.

[0029] Preferably, in the naphthyridine compounds represented by formula I and the naphthyridine compounds represented by formula II, Ar2 is independently selected from any one or a combination of at least two of a single bond, a carbazolyl group, a phenylene group, a naphthyl group, a biphenylene group, a dibenzofuranyl group, a dibenzothiophenyl group, and a 9,9-dimethylfluorenyl group.

[0030] Preferably, in the naphthyl compound represented by formula I and the naphthyl compound represented by formula II, Ar3, Ar4, and Ar5 are each independently selected from any one or a combination of at least two of a hydrogen atom, a carbazole group, a phenyl group, a dibenzofuran group, a dibenzothienyl group, a 9,9-dimethylfluorenyl group, and a naphthyl group.

[0031] Preferably, the hydrogen atoms in the naphthylamine compound represented by formula I and the naphthylamine compound represented by formula II can be independently substituted by at least one of -D, -F, -CN, phenyl, naphthyl, biphenyl, methyl, ethyl, propyl, tert-butyl, methoxy, ethoxy, propoxy or butoxy.

[0032] As a preferred technical solution of the present invention, the naphthyridine compound is selected from any one of the following substituted or unsubstituted compounds:

[0033]

[0034]

[0035]

[0036]

[0037]

[0038] The substitution means that the hydrogen atoms in the above-mentioned can be substituted by deuterium atoms independently.

[0039] Preferably, the naphthyridine compound further comprises Replace with of compounds.

[0040] The above compounds Replace with For example, the compound P1 Replace with Compound PC1 was obtained by adding Replace with Then compound PC3 was obtained, and other compounds can be understood similarly.

[0041]

[0042] Preferably, the compound is selected from any one of the following compounds:

[0043]

[0044]

[0045]

[0046] The above-mentioned naphthyridine compounds can be prepared by the following method:

[0047] The structural formula of the naphthyridine compound is (The dotted line in the above formula I naphthalene compound indicates that it does not exist, and Ar2 is not a single bond), and its preparation method is as follows:

[0048]

[0049] The structural formula of the naphthyridine compound is (In the above formula I naphthalene compound, the dotted line indicates that it does not exist, and Ar2 is a single bond), and its preparation method is as follows:

[0050]

[0051] The structural formula of the naphthyridine compound is (In the above formula I naphthalene compound, the dotted line represents a single bond, and Ar2 is not a single bond), and its preparation method is as follows:

[0052]

[0053] The structural formula of the naphthyridine compound is (In the above formula I naphthalene compound, the dotted line represents a single bond, and Ar2 is a single bond), and its preparation method is as follows:

[0054]

[0055] The structural formula of the naphthyridine compound is (In the above formula II naphthyridine compound, the dotted line represents a single bond, and Ar2 is not a single bond), and its preparation method is as follows:

[0056]

[0057] The structural formula of the naphthyridine compound is (In the above formula II naphthyridine compound, the dotted line represents a single bond, and Ar2 is a single bond), and its preparation method is as follows:

[0058]

[0059] The structural formula of the naphthyridine compound is (The dotted line in the above formula II naphthyridine compound indicates that it does not exist, and Ar2 is not a single bond), and its preparation method is as follows:

[0060]

[0061] The structural formula of the naphthyridine compound is (The dotted line in the above formula II naphthyridine compound indicates that it does not exist, and Ar2 is a single bond), and its preparation method is as follows:

[0062]

[0063] Wherein, X1 and X2 each independently represent fluorine, chlorine, bromine or iodine;

[0064] X, Ar1, Ar2, Ar3, Ar4, and Ar5 have the same protection scope as above.

[0065] The specific preparation process of the above compounds can refer to conventional preparation methods in the art.

[0066] In a second aspect, the present invention provides an intermediate having a structure shown in Formula IA or a structure shown in Formula II-A:

[0067]

[0068] Wherein, X1 and X2 each independently represent fluorine, chlorine, bromine or iodine;

[0069] X, Ar1, Ar5 have the same protection scope as above;

[0070] The intermediate is used to prepare the naphthyridine compound as described in the first aspect.

[0071] Preferably, the intermediate includes the following compounds:

[0072]

[0073] It should be noted that the present invention does not impose any special restrictions on the preparation method of the intermediate compound, and the intermediate compound can be prepared according to the commonly used preparation method in the art.

[0074] In a third aspect, the present invention provides an organic electroluminescent device, the organic electroluminescent device comprising an anode, a cathode and an organic thin film layer disposed between the anode and the cathode;

[0075] The organic thin film layer includes the naphthyridine compound as described in the first aspect.

[0076] As a preferred technical solution of the present invention, the organic thin film layer includes a light-emitting layer, and the main material of the light-emitting layer includes the diazine compound as described in the first aspect.

[0077] As a preferred technical solution of the present invention, the organic thin film layer includes a hole layer and a light-emitting layer, the light-emitting layer includes the compound as described in the first aspect, the hole layer includes an electron blocking layer, and the material of the electron blocking layer includes a compound having a structure shown in the following formula A:

[0078]

[0079] Among them, R 601Any one selected from tert-butyl substituted phenyl, methylcyclopentyl substituted phenyl, methylcyclohexyl substituted phenyl, methylcyclopentyl, methylcyclohexyl or tert-butyl;

[0080] Ring A and Ring B are each independently selected from a benzene ring or a naphthalene ring;

[0081] Ar 601 is selected from phenyl or naphthyl;

[0082] m, n, and p are each independently selected from 0 or 1;

[0083] The hydrogen atoms in the compounds of formula A may each independently be replaced by a deuterium atom.

[0084] It should be noted that when n is 1, Ar 601 is selected from phenylene or naphthylene.

[0085] Preferably, the compound of formula A is selected from any one of the following substituted or unsubstituted compounds:

[0086]

[0087]

[0088] The substitution means that the hydrogen atoms in the above compounds can each be independently replaced by a deuterium atom.

[0089] As a preferred technical solution of the present invention, the light-emitting layer is a phosphorescent light-emitting layer, and the main material of the phosphorescent light-emitting layer includes the diazonapthyl compound as described in the first aspect.

[0090] Preferably, the organic electroluminescent device is a blue organic electroluminescent device.

[0091] The luminescent layer in the present invention includes a luminescent layer main material and a doping material, wherein the doping material is also called a dye or a phosphorescent luminescent material. The luminescent layer main material can be a single compound or a mixture of two or more compounds.

[0092] The light-emitting layer includes a phosphorescent light-emitting layer, and the phosphorescent light-emitting layer includes a blue phosphorescent light-emitting layer, a green phosphorescent light-emitting layer, a red phosphorescent light-emitting layer, and a yellow phosphorescent light-emitting layer.

[0093] The volume percentage of the main material in the phosphorescent layer is 60% to 99.9% (for example, it can be 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 98% or 99.9%, etc.), preferably 70% to 99.5%, and more preferably 85% to 95%.

[0094] In the present invention, the doping material of the light-emitting layer may be a phosphorescent material, which is also called a triplet light-emitting material, and refers to the light emitted from a triplet excited state. The specific selection of the phosphorescent material in the present invention is not particularly limited, and the doping materials of the light-emitting layer commonly used in the art are applicable, including but not limited to: a compound having a structure shown in Formula PD:

[0095]

[0096] Wherein, M is selected from any one of Ir, Pt, Pd, Os, Ti, Zr, Hf, Eu, Tb, Tm, Cu or Au;

[0097] Y1-Y4 are each independently selected from carbon or nitrogen;

[0098] Y1 and Y2 can be connected by a single bond or a double bond, and Y3 and Y4 can be connected by a single bond or a double bond;

[0099] Cy1 and Cy2 are each independently selected from phenyl, naphthyl, fluorenyl, spirofluorenyl, indenyl, pyrrolyl, thienyl, furanyl, imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolyl, isoquinolyl, benzoquinolyl, quinoxalinyl, quinazolinyl, carbazolyl, benzimidazolyl, benzofuranyl, benzothienyl, isobenzothienyl, benzimidazolyl, benzoxazolyl, triazolyl, tetrazolyl, oxadiazolyl, triazine, dibenzofuranyl, dibenzothienyl, N-heterocarbazolyl, N-heterodibenzofuranyl, wherein Cy1 and Cy2 may be optionally linked to each other via a single bond or an organic linking group;

[0100] Any two ligands of M, or more than two ligands, may be connected by a single bond or a double bond, or may be bridged by O or S, or may be connected by any chemical group or chemical structure to form a structural form that conforms to chemical principles;

[0101] R 91 and R 92each independently selected from -H, -D, -F, -Cl, -Br, -I, hydroxyl, cyano, nitro, amino, amidino, hydrazine, hydrazone, carboxylic acid, carboxylate, sulfonic acid, sulfonate, phosphoric acid, phosphate, -SF5, substituted or unsubstituted C1-C60 (e.g., C1, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55 or C60, etc.) alkyl, substituted or unsubstituted C2-C6 C2-C60 (for example, C2, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55 or C60, etc.) alkynyl, substituted or unsubstituted C1-C60 (for example, C1, C5, C10, C15, C20, C25, C30, C35, C40, C45, C50, C55 or C60, etc.) C2-C10 (for example, C2, C3, C4, C5, C6, C7, C8, C9 or C10) heterocycloalkyl, substituted or unsubstituted C6-C60 (for example, C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54 or C60) aryl, substituted or unsubstituted C6-C60 (for example, C2, C3, C4, C5, C6, C7, C8, C9 or C10) For example, it may be any one of C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54 or C60) aryloxy, substituted or unsubstituted C6-C60 (for example, it may be C6, C12, C15, C18, C24, C30, C32, C36, C40, C42, C54 or C60) arylthio, substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group;

[0102] a1 and a2 are each independently an integer selected from 1-5, for example, 1, 2, 3, 4 or 5;

[0103] b is an integer selected from 0-4, for example, 0, 1, 2, 3 or 4;

[0104] a is selected from 1, 2 or 3;

[0105] L1 is a monovalent organic ligand, a divalent organic ligand or a trivalent organic ligand.

[0106] Preferably, the compound of formula PD is selected from any one of the following compounds:

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113] In the present invention, the organic thin film layer includes a hole layer, and the hole layer includes a hole injection layer, a hole transport layer and an electron blocking layer.

[0114] The hole injection layer material includes a P-type dopant. The P-type dopant refers to a dopant that coexists with the hole injection layer material in the OLED device and can oxidize the hole injection layer material, thereby acting as an electron acceptor and promoting the movement of holes in the hole injection layer to the anode. In the present invention, the difference between the absolute value of the LUMO of the P-type dopant and the absolute value of the HOMO of the hole layer material is greater than -0.2V, preferably greater than -0.1eV, more preferably greater than 0eV, more preferably greater than 0.1eV, and more preferably greater than 0.2eV.

[0115] The P-type dopant is present in the hole injection layer in a volume percentage of 1% to 10% (e.g., 1%, 2%, 4%, 6%, 8% or 10%). In the present invention, there is no particular limitation on the type of the P-type dopant, and illustratively, the compounds D-1 to D-13 disclosed in CN113728453A or the compounds HI-1 to HI-9 described below can be selected:

[0116]

[0117]

[0118] In the present invention, the material of the hole layer (including the hole injection layer, the hole transport layer and the electron blocking layer) may have a structure as shown in the following formula HT-GH4:

[0119]

[0120] Among them, L 41 is selected from a single bond, a C6-C40 (e.g., C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36, or C40, etc.) aryl, or a C6-C20 (e.g., C6, C8, C10, C12, C16, or C20, etc.) heteroaryl;

[0121] Ar 41 ,Ar42 Each is independently selected from C6-C40 (for example, C6, C8, C10, C12, C16, C20, C24, C28, C30, C32, C36 or C40, etc.) aryl, C6-C20 (for example, C6, C8, C10, C12, C16 or C20, etc.) heteroaryl;

[0122] X is selected from CR 41 R 42 or NR 43 , where R 41 , R 42 , R 43 Each independently selected from substituted or unsubstituted phenyl (the substituted substituent is selected from C1-C6 (for example, C1, C2, C3, C4, C5 or C6) alkyl, C1-C6 (for example, C1, C2, C3, C4, C5 or C6) alkoxy, dibenzofuranyl), naphthyl, triphenylene, fluoranthene, 9,9-dimethylfluorenyl, biphenyl, substituted or unsubstituted dibenzofuranyl (the substituted substituent is phenyl), substituted or unsubstituted dibenzothiophene (the substituted substituent is phenyl), dibenzofuran-substituted thienyl, C1-C6 (for example, C1, C2, C3, C4, C5 or C6) alkyl, any one of R 41 , R 42 They can be linked to form rings via single bonds.

[0123] Preferably, the compound of formula HT-GH4 is selected from any one of the following compounds:

[0124]

[0125]

[0126]

[0127] The hole blocking layer (HBL) can confine holes and / or excitons within the EL to improve the current efficiency and lifetime of the device. Compared with the EL material closest to the HBL interface, the HBL material has a lower HOMO (larger absolute value) and / or higher triplet energy.

[0128] The electron transport layer (ETL) may include a material capable of transporting electrons. The electron transport layer may be intrinsic (undoped) or doped, and doping may be used to enhance conductivity. In the present invention, there is no particular restriction on the ETL material, and any metal complex or organic compound may be used as long as it can transport electrons. The general electron transport layer material contains the following structural fragments: at least one of a pyridine structure, a pyrimidine structure, a triazine structure, a benzimidazole structure, a benzoxazole structure, a benzothiazole structure, a naphthalene structure, a phenanthracene structure, a quinazoline structure, a quinazoline carbazole structure, a benzodibenzofuran structure, and a benzodibenzothiophene structure.

[0129] In the present invention, there is no special restriction on the electron transport layer material, and exemplary materials include but are not limited to the following compounds:

[0130]

[0131] In the present invention, the material of the cathode is a metal with a low work function (e.g., alkaline earth metal, alkali metal, main group metal or lanthanide element (e.g., Ca, Ba, Mg, Al, In, Mg, Yb, Sm, etc.)), a metal alloy composed of multiple metals (alloy composed of alkali metal or alkaline earth metal and silver, such as an alloy composed of magnesium and silver) or a multilayer structure. If the cathode material is a multilayer structure, in addition to the metals mentioned above, other metals with relatively high work functions, such as Ag or Al, can also be used. In this case, a combination of the metals is usually used, such as Ca / Ag, Mg / Ag or Ba / Ag.

[0132] It is also possible to introduce a thin intermediate layer of a material with a high dielectric constant between the metal cathode and the organic semiconductor to form a multilayer structure; the material with a high dielectric constant can also be called an electron injection material, and fluorides of alkali metals or alkaline earth metals, and corresponding oxides or carbonates (such as LiF, Li2O, BaF2, MgO, NaF, CsF, Cs2CO3, etc.) or lithium quinoline (LiQ) can be selected.

[0133] Compared with the prior art, the present invention has the following beneficial effects:

[0134] In the present invention, the structure of the naphthyridine compound is designed to make it suitable as the main material of the light-emitting layer of the organic electroluminescent device, so that the organic electroluminescent device has higher current efficiency and longer life. DETAILED DESCRIPTION

[0135] For the convenience of understanding the present invention, the present invention lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0136] Preparation Example 1

[0137] This preparation example provides an intermediate P1-1 and a synthesis method thereof, the synthesis method is as follows:

[0138]

[0139] Under nitrogen protection, 100 mL of toluene, 40 mL of ethanol and 20 mL of water were added to a 500 mL three-necked flask in sequence, and then 0.01 mol of 2,3-dichloroquinoxaline, 0.01 mol of triphenylsilylphenylboric acid, 2.12 g (0.02 mol) of sodium carbonate and 0.23 g (0.0002 mol) of tetrakistriphenylphosphine palladium were added thereto. The temperature was slowly raised to 30°C for reaction for 2 hours, and then raised to 40°C for reaction for 6 hours. The temperature was lowered to room temperature, and water was added to separate the organic layer. The organic layer was washed with water, dried with magnesium sulfate, and after removing the desiccant, it was concentrated to dryness and separated by silica gel column chromatography. Petroleum ether: ethyl acetate = 10: 1 (volume ratio) was used as the eluent to obtain 3.6 g of intermediate P1-1.

[0140] The obtained intermediate P1-1 was subjected to mass spectrometry detection, and the mass-to-charge ratio (m / z) was measured to be 498.13.

[0141] Preparation Example 2 to Preparation Example 6

[0142] Preparation Examples 2 to 6 respectively provide an intermediate, and the synthesis method thereof refers to the synthesis method provided in Preparation Example 1, wherein the 2,3-dichloroquinoxaline in Preparation Example 1 is replaced by an equal amount of chloro compound, and the triphenylsilylphenylboronic acid in Preparation Example 1 is replaced by an equal amount of boronic acid compound (as shown in Table 1 below). The specific structural formulas of the corresponding chloro compound, boronic acid compound and the prepared intermediate are shown in Table 1 below, and the prepared intermediate is subjected to mass spectrometry detection, and the mass-to-charge ratio (m / z) data are shown in Table 1 below.

[0143] Table 1

[0144]

[0145]

[0146] Synthesis Example 1

[0147] This synthesis example provides compound P1 and its synthesis method, and the synthesis method is as follows:

[0148]

[0149] Under nitrogen protection, dry toluene (100 mL), intermediate P1-1 (0.01 mol), carbazole (0.01 mol), Pd(dba)2 (bis(dibenzylideneacetonepalladium, 0.0575 g, 0.0001 mol), 10% tri-tert-butylphosphine toluene solution (the mass of tri-tert-butylphosphine solution is 0.4 g, and the amount of tri-tert-butylphosphine is 0.0002 mol) and sodium tert-butoxide (1.44 g, 0.015 mol) were added to a 250 mL three-necked flask, heated to 60° C., reacted for 6 hours, cooled to room temperature, and water was added to separate. The organic layer was then washed with water until neutral, dried with magnesium sulfate, filtered to remove magnesium sulfate, concentrated to dryness, separated by silica gel column chromatography, and eluted with a solvent of petroleum ether: ethyl acetate = 20:1 (volume ratio) to obtain 4.9 g of compound P1.

[0150] The mass spectrometry detection of compound P1 was performed: the mass-to-charge ratio (m / z) was measured to be 629.23.

[0151] Synthesis Example 2 to Synthesis Example 7

[0152] Synthesis Examples 2 to 7 respectively provide a naphthyridine compound. The synthesis method of the naphthyridine compound refers to the synthesis method provided in Synthesis Example 1. The corresponding naphthyridine compound is obtained by reacting a carbazole compound with a chlorinated compound. The specific structural formulas of the corresponding carbazole compound, chlorinated compound and the prepared naphthyridine compound are shown in Table 2 below. The prepared naphthyridine compound is subjected to mass spectrometry detection, and the mass-to-charge ratio (m / z) data are shown in Table 2 below.

[0153] Table 2

[0154]

[0155]

[0156] Synthesis Example 8

[0157] This synthesis example provides compound P5 and its synthesis method, and the synthesis method is as follows:

[0158]

[0159] Under nitrogen protection, 100 mL of toluene, 40 mL of ethanol and 20 mL of water were added to a 500 mL three-necked flask in sequence, and then 0.01 mol of P1-1, 0.01 mol of 4-carbazolylphenylboronic acid, 2.12 g (0.02 mol) of sodium carbonate and 0.23 g (0.0002 mol) of tetrakistriphenylphosphine palladium were added thereto. The temperature was slowly raised to reflux for reaction for 6 hours, the temperature was lowered to room temperature, water was added to separate, the organic layer was washed with water, dried with magnesium sulfate, the desiccant was removed, and the mixture was concentrated to dryness. The mixture was separated by silica gel column chromatography and eluted with petroleum ether: ethyl acetate = 20: 1 (volume ratio) to obtain 5.1 g of compound P5.

[0160] The obtained intermediate P5 was subjected to mass spectrometry detection, and the mass-to-charge ratio (m / z) was measured to be 705.26.

[0161] Synthesis Example 9 to Synthesis Example 11

[0162] Synthesis Examples 9 to 11 respectively provide a naphthyridine compound. The synthesis method of the naphthyridine compound refers to the synthesis method provided in Synthesis Example 8. The corresponding naphthyridine compound is obtained by reacting a carbazole compound with a chlorinated compound. The specific structural formulas of the corresponding carbazole compound, chlorinated compound and the prepared naphthyridine compound are shown in Table 3 below. The prepared naphthyridine compound is subjected to mass spectrometry detection, and the mass-to-charge ratio (m / z) data are shown in Table 3 below.

[0163] Table 3

[0164]

[0165]

[0166] Other naphthyridine compounds whose specific synthesis methods are not listed can be synthesized by referring to the above embodiments in combination with common knowledge in the art.

[0167] The specific structures of some compounds used in the following application examples and comparative application examples are as follows:

[0168]

[0169]

[0170] Application Example 1

[0171] This application example provides a blue light organic electroluminescent device, using the compound provided by the present invention as a main material of the light-emitting layer, and the structure of the blue light organic electroluminescent device is:

[0172] ITO / HT-1: HI-2 [5%] (80nm) / HT-1 (30nm) / EB-1 (20nm) / host material: PBD-1 [5%] (35nm) / ETL-1 (25nm) / LiF (0.5nm) / Al (150nm).

[0173] The preparation method of the blue light organic electroluminescent device is as follows:

[0174] The material was placed in a vacuum chamber and evacuated to 1×10 -5 ~1×10 -6 Pa was vacuum evaporated onto the cleaned ITO substrate in sequence to prepare an OLED device.

[0175] Among them, PBD-1[5%] refers to the doping ratio of the dye, that is, the volume ratio of the main material to the dye PBD-1 is 95:5; HT-1:HI-2[5%] refers to the ratio of the P-type dopant, that is, the volume ratio of the hole material HT-1 and the P-type dopant HI-2 is 95:5. HT-1 is a hole transport material; HT-1:HI-2[5%] is used as a hole injection layer, and EB-1 is an electron blocking layer.

[0176] The main material of the light-emitting layer of the blue light organic electroluminescent device provided in this application example is compound P1.

[0177] Application Example 2-10

[0178] Application Examples 2-10 respectively provide a blue light organic electroluminescent device, which differs from Application Example 1 only in that the main material compound P1 of the light-emitting layer is replaced with other compounds (see Table 4 below for details), and the other preparation steps and conditions are the same as those of Application Example 1.

[0179] Comparative application example 1

[0180] Comparative Application Example 1 provides an organic electroluminescent device, which differs from Application Example 1 only in that the main material compound P1 of the light-emitting layer is replaced by other compounds (see Table 4 below for details), and the other preparation steps and conditions are the same as those of Application Example 1.

[0181] Performance Testing

[0182] The OLED-1000 multi-channel accelerated aging life and light color performance analysis system produced by Hangzhou Yuanfang was used to test the brightness, driving voltage, current efficiency and LT95 of the organic electroluminescent devices provided above. Among them, the current efficiency is the brightness of 1000cd / m 2 The corresponding value, LT95, refers to maintaining the initial current density of the device at 10mA / cm 2The time required for the device efficiency to drop to 95% of the efficiency corresponding to the initial current density, where the current efficiency and LT95 are relative values. The specific test results are shown in Table 4 below:

[0183] Table 4

[0184] Main material <![CDATA[Luminance / (cd / m 2 )]]> Current efficiency LT95 Application Example 1 P1 1000 1.56 1.89 Application Example 2 P2 1000 1.69 1.99 Application Example 3 PC1 1000 1.71 1.65 Application Example 4 P2-D 1000 1.66 2.38 Application Example 5 P5 1000 2.02 1.46 Application Example 6 P6 1000 2.11 1.53 Application Example 7 P9 1000 1.64 3.08 Application Example 8 P10 1000 1.76 2.71 Application Example 9 P11 1000 1.48 2.71 Application Example 10 P12 1000 2.13 1.50 Application Example 11 P13 1000 1.26 2.89 Application Example 12 P14 1000 1.09 1.18 Application Example 13 P15 1000 1.21 1.03 Application Example 14 P16 1000 1.68 3.08 Comparative application example 1 H1 1000 1 1

[0185] It can be seen from the contents of Table 4 that in the present invention, by designing the structure of the compound and using the compound as the main material of the light-emitting layer, the organic electroluminescent device prepared has higher current efficiency and longer life.

[0186] Application Example 15

[0187] This application example provides a blue light organic electroluminescent device, using the compound provided by the present invention as a main material of the light-emitting layer, and the structure of the blue light organic electroluminescent device is:

[0188] ITO / HT-1: HI-2[5%](80nm) / HT-1(30nm) / EB-1(20nm) / host material: PBD-2[5%](35nm) / ETL-1(25nm) / LiF(0.5nm) / Al(150nm).

[0189] The preparation method of the blue light organic electroluminescent device is as follows:

[0190] The material was placed in a vacuum chamber and evacuated to 1×10 -5 ~1×10 -6 Pa was vacuum evaporated onto the cleaned ITO substrate in sequence to prepare an OLED device.

[0191] Among them, PBD-2[5%] refers to the doping ratio of the dye, that is, the volume ratio of the main material to the dye PBD-2 is 95:5; HT-1:HI-2[5%] refers to the ratio of the P-type dopant, that is, the volume ratio of the hole material HT-1 and the P-type dopant HI-2 is 95:5. HT-1 is a hole transport material; HT-1:HI-2[5%] is used as a hole injection layer, and EB-1 is an electron blocking layer.

[0192] The main material of the light-emitting layer of the blue light organic electroluminescent device provided in this application example is compound P3.

[0193] Application Examples 16-21

[0194] Application Examples 16-21 each provide a blue light organic electroluminescent device, which differs from Application Example 15 only in that the main material compound P3 of the light-emitting layer is replaced with other compounds (see Table 5 below for details), and the other preparation steps and conditions are the same as those of Application Example 15.

[0195] Comparative Application Example 2-4

[0196] Comparative Application Examples 2-4 each provide an organic electroluminescent device, which differs from Application Example 15 only in that the main material compound P3 of the light-emitting layer is replaced by other compounds (see Table 5 below for details), and the other preparation steps and conditions are the same as those of Application Example 15.

[0197] The performance of the organic electroluminescent devices provided in the above application examples and comparative application examples was tested using the same test methods as above. The specific test results are shown in Table 5 below:

[0198] Table 5

[0199] Main material <![CDATA[Luminance / (cd / m 2 )]]> Current efficiency LT95 Application Example 16 P3 1000 1.35 2.09 Application Example 17 P4 1000 1.26 1.88 Application Example 18 PC3 1000 1.47 1.65 Application Example 19 P7 1000 1.76 1.60 Application Example 20 P8 1000 1.62 1.59 Application Example 21 P17 1000 1.51 1.82 Comparative Application Example 2 H2 1000 1 1 Comparative Application Example 3 H3 1000 1.11 1.36 Comparative Application Example 4 H4 1000 0.98 1.11

[0200] It can be seen from Table 5 that in the present invention, by designing the structure of the compound and using the compound as the main material of the light-emitting layer, the organic electroluminescent device prepared has higher current efficiency and longer life.

[0201] By comparing the relevant data of application examples 16-21 with those of comparative application examples 2-4, it can be seen that the present invention With nitrogen-containing naphthalene ring ( Curve representation The obtained compound is suitable for being used as the main material of the light-emitting layer, and the organic electroluminescent device prepared thereby has a higher current efficiency and a higher lifespan.

[0202] Application Examples 22-23

[0203] Application Examples 22-23 respectively provide a blue light organic electroluminescent device, which differs from Application Examples 16-17 only in that the electron blocking layer EB-1 is replaced by EB-2, and the other preparation steps and conditions are the same as those of Application Examples 16-17.

[0204] The performance of the organic electroluminescent device provided in the above application example was tested using the above test method. The test data is shown in Table 6 below.

[0205] Table 6

[0206] Main material <![CDATA[Luminance / (cd / m 2 )]]> Current efficiency LT95 Application Example 22 P3 1000 1.54 2.57 Application Example 23 P4 1000 1.68 2.33

[0207] It can be seen from the data in Table 5 and Table 6 that the use of compound EB-2 as an electron blocking layer material can further improve the current efficiency and life of the organic electroluminescent device.

[0208] In summary, the present invention designs the structure of the compound to make it suitable as the main material of the light-emitting layer of the organic electroluminescent device, so that the organic electroluminescent device has higher current efficiency and longer life.

[0209] The applicant declares that the present invention illustrates the detailed process flow of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process flow to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A naphthyridine compound, characterized in that: The naphthyridine compound has a structure shown in Formula I or a structure shown in Formula II: Wherein, in the naphthyridine compound represented by formula I and the naphthyridine compound represented by formula II, X is independently selected from C or Si; Dashed lines indicate single bonds or their absence; In the naphthyridine compound represented by formula I and the naphthyridine compound represented by formula II, Ar1 is independently selected from any one of a C6-C40 arylene group and a C6-C30 heteroarylene group; In the naphthyridine compound represented by formula I and the naphthyridine compound represented by formula II, Ar2 is independently selected from any one of a single bond, a C6-C40 arylene group, and a C6-C30 heteroarylene group; In the naphthyridine compound represented by formula I and the naphthyridine compound represented by formula II, Ar3, Ar4, and Ar5 are each independently selected from any one of H, C6-C40 aryl, and C6-C30 heteroaryl; The hydrogen atoms in the naphthyridine compound represented by formula I and the naphthyridine compound represented by formula II can each independently be substituted by at least one of a deuterium atom, -F, -CN, a C6-C20 aryl group, a C1-C12 alkyl group or a C1-C12 alkoxy group.

2. The naphthyridine compound according to claim 1, characterized in that The C6-C40 aryl group is selected from any one or a combination of at least two of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthfluoroenyl, pyrenyl, peryl, spirofluorenyl, triphenylene, fluoranthenyl, hydrogenated benzanthryl, indenofluorenyl, benzoindenofluorenyl, dibenzoindenofluorenyl, naphthfluoroenyl or benzonaphthfluoroenyl; Preferably, the C6-C40 arylene group is selected from any one of phenylene, biphenylene, terphenylene, naphthylene, anthracene, phenanthrenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, naphthofluorenyl, perylene, perylene, spirofluorenyl, triphenylene, fluoranthenyl, hydrogenated benzanthryl, indenofluorenyl, benzoindenofluorenyl, dibenzoindenofluorenyl, naphthofluorenyl or benzonaphthofluorenyl, or a combination of at least two thereof.

3. The naphthyridine compound according to claim 1 or 2, characterized in that: The C6-C30 heteroaryl group is selected from any one or a combination of at least two of a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, a naphthobenzofuranyl group, a naphthobenzothiophenyl group, a dinaphthofuranyl group, a dinaphthothiophenyl group or a carbazolyl group; Preferably, the C6-C30 heteroarylene group is selected from any one or a combination of at least two of a carbazolylene group, a dibenzofuranyl group, a dibenzothiophenyl group, a naphthobenzofuranyl group, a naphthobenzothiophenyl group, a dinaphthofuranyl group, a dinaphthothiophenyl group or a carbazolylene group.

4. The naphthyridine compound according to any one of claims 1 to 3, characterized in that: The C6-C20 aryl group is selected from any one or a combination of at least two of phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, triphenylene or fluoranthenyl; Preferably, the C1-C12 alkyl group is selected from any one or a combination of at least two of methyl, ethyl, propyl, butyl, pentyl or adamantyl; Preferably, the C1-C12 alkoxy group is selected from any one of methoxy, ethoxy, propoxy, butoxy or pentoxy, or a combination of at least two thereof.

5. The naphthyridine compound according to any one of claims 1 to 4, characterized in that: In the naphthyridine compound represented by formula I and the naphthyridine compound represented by formula II, Ar1 is independently selected from phenylene; Preferably, in the naphthyridine compound represented by formula I and the naphthyridine compound represented by formula II, Ar2 is independently selected from any one or a combination of at least two selected from a single bond, a carbazolyl group, a phenylene group, a naphthyl group, a biphenylene group, a dibenzofuranyl group, a dibenzothienyl group, and a 9,9-dimethylfluorenyl group; Preferably, in the naphthyridine compound represented by formula I and the naphthyridine compound represented by formula II, Ar3, Ar4, and Ar5 are each independently selected from any one or a combination of at least two of a hydrogen atom, a carbazole group, a phenyl group, a dibenzofuranyl group, a dibenzothienyl group, a 9,9-dimethylfluorenyl group, and a naphthyl group; Preferably, the hydrogen atoms in the naphthylamine compound represented by formula I and the naphthylamine compound represented by formula II can be independently substituted by at least one of -D, -F, -CN, phenyl, naphthyl, biphenyl, methyl, ethyl, propyl, tert-butyl, methoxy, ethoxy, propoxy or butoxy.

6. The naphthyridine compound according to any one of claims 1 to 5, characterized in that: The naphthyridine compound is selected from any one of the following substituted or unsubstituted compounds: The substitution means that the hydrogen atoms in the above compounds can each independently be replaced by deuterium atoms; Preferably, the naphthyridine compound further comprises Replace with of compounds.

7. An intermediate, characterized in that The intermediate has a structure shown in Formula IA or a structure shown in Formula II-A: Wherein, X1 and X2 each independently represent fluorine, chlorine, bromine or iodine; X, Ar1, Ar5 have the same protection scope as claim 1; The intermediate is used to prepare the naphthyridine compound according to any one of claims 1 to 6; Preferably, the intermediate includes the following compounds:

8. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises an anode, a cathode and an organic thin film layer arranged between the anode and the cathode; The organic thin film layer comprises the naphthyridine compound according to any one of claims 1 to 6; Preferably, the organic thin film layer comprises a light-emitting layer, and a main material of the light-emitting layer comprises the naphthyridine compound according to any one of claims 1 to 6.

9. The organic electroluminescent device according to claim 8, characterized in that: The organic thin film layer comprises a hole layer and a light-emitting layer, and the light-emitting layer comprises the naphthyridine compound according to any one of claims 1 to 6; The hole layer includes an electron blocking layer, and the material of the electron blocking layer includes a compound having a structure shown in the following formula A: Among them, R 601 Any one selected from tert-butyl substituted phenyl, methylcyclopentyl substituted phenyl, methylcyclohexyl substituted phenyl, methylcyclopentyl, methylcyclohexyl or tert-butyl; Ring A and Ring B are each independently selected from a benzene ring or a naphthalene ring; Ar 601 is selected from phenyl or naphthyl; m, n, and p are each independently selected from 0 or 1; The hydrogen atoms in the compound of formula A may each independently be replaced by a deuterium atom; Preferably, the compound of formula A is selected from any one of the following substituted or unsubstituted compounds: The substitution means that the hydrogen atoms in the above compounds can each be independently replaced by a deuterium atom.

10. The organic electroluminescent device according to claim 8 or 9, characterized in that: The organic thin film layer comprises a light-emitting layer, the light-emitting layer is a phosphorescent light-emitting layer, and the main material of the phosphorescent light-emitting layer comprises the diazonium compound according to any one of claims 1 to 6; Preferably, the organic electroluminescent device is a blue organic electroluminescent device.

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