Arylamine compound, organic electroluminescent device and electronic equipment

Abstract

According to the organic compound, the organic electroluminescent element and the electronic equipment provided by the invention, the compound with the benzocarbazole structure and the phenylene-dibenzofuran structure is high in hole transmission capability, can rapidly transmit holes to a light-emitting layer, has a proper energy level, can limit current carriers in the light-emitting layer, and improves the light-emitting efficiency. The organic electroluminescent element prepared from the compound disclosed by the invention has lower driving voltage and higher current efficiency, and is suitable for preparing the high-performance organic electroluminescent element. The compound has a structure as shown in a formula (1), # imgabs0, Ar3 has the following structure: # imgabs1 # A1 is selected from aromatic rings, A2 is selected from aromatic rings, L5 is selected from arylene, L4 is selected from dibenzofuranyl and dibenzothienyl, L1-L3 are respectively and independently selected from single bonds, arylene and heteroaryl, and Ar1 and Ar2 are respectively and independently selected from hydrogen, deuterium, halogen, cyano, alkyl, cycloalkyl, alkoxy, alkenyl, alkynyl, aryl and heteroaryl.

Description

Technical Field

[0001] The present invention relates to the technical field of organic electroluminescence, and more specifically, to an arylamine compound, an organic electroluminescent device, and an electronic device. Background Art

[0002] An organic light emitting diode is a self-luminous display device based on organic electroluminescent materials, which has the characteristics of not requiring a backlight source and being thin, and is a technology suitable for flexible light emitting display devices.

[0003] Organic electroluminescent materials are polymer or small molecule organic materials that can emit light under the action of an electric field. In order to improve the stability and efficiency of the organic electroluminescent materials in an organic electroluminescent device, multiple layers of organic thin films are prepared between the anode and the cathode. The above-mentioned organic thin film layers can be divided into a hole injection layer, a hole transport layer, a host of the light emitting layer, a dopant of the light emitting layer, an electron transport layer, and an electron injection layer.

[0004] When an electric field is applied between the anode and the cathode of an organic electroluminescent device, holes are injected from the anode, and the injected holes move to the light emitting layer through the hole transport layer. At the same time, electrons are injected from the cathode, and the injected electrons move to the light emitting layer through the electron transport layer. The holes and electrons that move to the light emitting layer combine to form excitons. When the excitons transition from the excited state to the ground state, energy will be released in the form of light, realizing the light emission of the device.

[0005] To ensure the high performance (longer lifespan, higher current efficiency, lower driving voltage, higher color saturation, etc.) of an organic electroluminescent device, it is particularly important to improve the exciton generation efficiency of the light emitting layer. In order to prevent the diffusion of excitons, as a hole transport material, it is required to have a high triplet energy.

[0006] Currently, although there are reports on high-performance organic electroluminescent devices, the performance of the hole transport region has not been fully developed, and the existing hole transport region materials still cannot meet the requirements for high-performance organic electroluminescent devices. Summary of the Invention

[0007] In view of the above-mentioned defects or improvement requirements of the prior art, the present invention provides an arylamine derivative with a specific parent nucleus, which is used as an organic electroluminescent material, and especially shows excellent performance when used as a material for the hole transport region.

[0008] To achieve the above object, the present invention provides an arylamine compound, which has the structure shown in formula (1).

[0009]

[0010] Among them, Ar3 has the following structure:

[0011]

[0012] indicating the connection position;

[0013] A1 is selected from a substituted or unsubstituted C6-C14 aromatic ring,

[0014] A2 is selected from a substituted or unsubstituted C10-C14 aromatic ring,

[0015] L5 is selected from a substituted or unsubstituted C6-C60 arylene group,

[0016] L4 is selected from a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothiophenylene group,

[0017] L1-L3 are each independently selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, a substituted or unsubstituted C3-C60 heteroarylene group,

[0018] Ar1 and Ar2 are each independently selected from hydrogen, deuterium, halogen, cyano, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C3-C60 heteroaryl group;

[0019] When substituted in the "substituted or unsubstituted", the substituents are selected from deuterium, halogen, cyano, a C1-C10 alkyl group, a C3-C10 cycloalkyl group, a C1-C10 alkoxy group, a C2-C10 alkenyl group, a C2-C10 alkynyl group, a C6-C60 aryl group, a C3-C60 heteroaryl group, a C6-C60 carbocyclic group, a C3-C60 heterocyclic group,

[0020] The heteroatoms in the heterocyclic group and heteroaryl group are selected from at least one of N, O, S, Si, P.

[0021] Furthermore, in an alternative embodiment of the present invention, the compound has the structure shown in formula (2),

[0022]

[0023] R2 is selected from deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;

[0024] b is selected from integers between 0 and 10;

[0025] The definitions of L1-L5, Ar1, and Ar2 are the same as those defined in formula (1) in the above embodiments;

[0026] Preferably, L3 is a single bond;

[0027] Preferably, L5 is selected from phenylene, naphthylene, biphenylene;

[0028] More preferably, L4 is selected from dibenzofuranyl, dibenzothiophenyl.

[0029] Most preferably, L4 is selected from dibenzofuranyl.

[0030] Furthermore, in an alternative embodiment of the present invention, the aromatic amine compound has the structure shown in formula (2-1),

[0031]

[0032] Furthermore, in an alternative embodiment of the present invention, the aromatic amine compound has the structures shown in formulas (3)-(8),

[0033]

[0034] Wherein, R1-R3 are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;

[0035] a is selected from integers between 0 and 4; b is selected from integers between 0 and 10; c is selected from integers between 0 and 6;

[0036] X is selected from O or S;

[0037] The definitions of L1, L2, Ar1, and Ar2 are the same as those defined in formula (1) in the above embodiments.

[0038] In an alternative embodiment of the present invention, in the structures represented by formulas (3)-(8) of the arylamine compound, R1-R3 are each independently selected from deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl.

[0039] Furthermore, in an alternative embodiment of the present invention, the arylamine compound has the following structure:

[0040]

[0041] R1-R3, X, a, b, c, L1, L2, Ar1, and Ar2 are defined as in formulas (3)-(8) of the above embodiments.

[0042] Furthermore, in an alternative embodiment of the present invention, the arylamine compound has the following structure:

[0043]

[0044]

[0045] R1-R3, X, a, b, c, L1, L2, Ar1, and Ar2 are defined as in formulas (3)-(8) of the above embodiments.

[0046] Furthermore, in an alternative embodiment of the present invention, the arylamine compound has the structures represented by formulas (9)-(26),

[0047]

[0048]

[0049] wherein R1-R3, X, a, b, c, L1, L2, Ar1, and Ar2 are defined as in formulas (3)-(8) of the above embodiments.

[0050] Preferably, R1-R3 are each independently selected from deuterium, halogen, phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, fluoranthenyl, pyrenyl, perylenyl, triphenylenyl, pyrrolyl, furyl, thienyl, indenyl, indolyl, benzofuryl, benzothienyl, dibenzofuryl, dibenzothienyl, carbazolyl, carbolinyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirobifluorenyl;

[0051] a is an integer selected from 0 to 4; b is an integer selected from 0 to 10; c is an integer selected from 0 to 6;

[0052] Preferably, X is selected from O or S; more preferably, X is selected from O;

[0053] Preferably, L1 and L2 are each independently selected from a single bond, phenylene, biphenylene, naphthylene, anthracene, phenanthrene, fluoranthene, pyrene, perylene, triphenylene, pyrrole, furan, thiophene, indene, indole, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, carbazole, carboline, 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirobifluorene;

[0054] Preferably, Ar1 and Ar2 are each independently selected from hydrogen, deuterium, halogen, phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, fluoranthenyl, pyrenyl, perylenyl, triphenylenyl, pyrrolyl, furyl, thienyl, indenyl, indolyl, benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, carbolinyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirobifluorenyl, benzonaphthofuranyl, benzonaphthothiophenyl, phenyl-substituted carbazole, naphthyl-substituted carbazolyl, biphenyl-substituted carbazolyl.

[0055] Furthermore, in an alternative embodiment of the present invention, L1 and L2 are each independently selected from a single bond and the following substituted or unsubstituted groups:

[0056]

[0057] Furthermore, in an alternative embodiment of the present invention, Ar1 and Ar2 are each independently selected from hydrogen and the following substituted or unsubstituted groups:

[0058]

[0059] Furthermore, in an alternative embodiment of the present invention, Ar3-L5-L4-L3- is selected from the following structures: X-m-n is the substituent number represented by Ar3-L5-L4-L3-, and X-m-n represents all substituents represented by X-1-1 to X-1-24, X-2-1 to X-2-24, X-3-1 to X-3-24,

[0060]

[0061]

[0062]

[0063]

[0064] Further, in an alternative embodiment of the present invention, each of -L1-Ar1 and -L2-Ar2 is independently selected from the following structures:

[0065]

[0066]

[0067]

[0068]

[0069] Preferably, each of -L1-Ar1 and -L2-Ar2 is independently selected from the substituents numbered Y1 to Y85.

[0070] Further, in an alternative embodiment of the present invention, the arylamine compound is selected from the following structures: wherein, Ar3-L5-L4-L3-, -L1-Ar1, and -L2-Ar2 are respectively connected to N;

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113] When Ar3-L5-L4-L3- is selected from X-1-1, the compound numbers are X-1-1-1 to X-1-1-3655,

[0114] When Ar3-L5-L4-L3- is replaced with X-1-2 for X-1-1, the compound numbers are X-1-2-1 to X-1-2-3655,

[0115] When Ar3-L5-L4-L3- is replaced with X-1-3 for X-1-1, the compound numbers are X-1-3-1 to X-1-3-3655,

[0116] When Ar3-L5-L4-L3- is replaced with X-1-4 for X-1-1, the compound numbers are X-1-4-1 to X-1-4-3655,

[0117] When Ar3-L5-L4-L3- is replaced with X-1-5 for X-1-1, the compound numbers are X-1-5-1 to X-1-5-3655,

[0118] When Ar3-L5-L4-L3- is replaced with X-1-6 for X-1-1, the compound numbers are X-1-6-1 to X-1-6-3655,

[0119] When Ar3-L5-L4-L3- is replaced with X-1-7 for X-1-1, the compound numbers are X-1-7-1 to X-1-7-3655,

[0120] When Ar3-L5-L4-L3- is replaced with X-1-8 for X-1-1, the compound numbers are X-1-8-1 to X-1-8-3655,

[0121] When X-1-1 is replaced by X-1-9 in Ar3-L5-L4-L3, the compound numbers are X-1-9-1 to X-1-9-3655. When X-1-1 is replaced by X-1-10 in Ar3-L5-L4-L3, the compound numbers are X-1-10-1 to X-1-10-3655. When X-1-1 is replaced by X-1-11 in Ar3-L5-L4-L3, the compound numbers are X-1-11-1 to X-1-11-3655. When X-1-1 is replaced by X-1-12 in Ar3-L5-L4-L3, the compound numbers are X-1-12-1 to X-1-12-3655. When X-1-1 is replaced by X-1-13 in Ar3-L5-L4-L3, the compound numbers are X-1-13-1 to X-1-13-3655. When X-1-1 is replaced by X-1-14 in Ar3-L5-L4-L3, the compound numbers are X-1-14-1 to X-1-14-3655. When X-1-1 is replaced by X-1-15 in Ar3-L5-L4-L3, the compound numbers are X-1-15-1 to X-1-15-3655. When X-1-1 is replaced by X-1-16 in Ar3-L5-L4-L3, the compound numbers are X-1-16-1 to X-1-16-3655. When X-1-1 is replaced by X-1-17 in Ar3-L5-L4-L3, the compound numbers are X-1-17-1 to X-1-17-3655. When X-1-1 is replaced by X-1-18 in Ar3-L5-L4-L3, the compound numbers are X-1-18-1 to X-1-18-3655. When X-1-1 is replaced by X-1-19 in Ar3-L5-L4-L3, the compound numbers are X-1-19-1 to X-1-19-3655. When X-1-1 is replaced by X-1-20 in Ar3-L5-L4-L3, the compound numbers are X-1-20-1 to X-1-20-3655. When X-1-1 is replaced by X-1-21 in Ar3-L5-L4-L3, the compound numbers are X-1-21-1 to X-1-21-3655,

[0122] When X-1-1 is replaced by X-1-22 in Ar3-L5-L4-L3, the compound numbers are X-1-22-1 to X-1-22-3655,

[0123] When X-1-1 is replaced by X-1-23 in Ar3-L5-L4-L3, the compound numbers are X-1-23-1 to X-1-23-3655,

[0124] When X-1-1 is replaced by X-1-24 in Ar3-L5-L4-L3, the compound numbers are X-1-24-1 to X-1-24-3655,

[0125] When X-1-1 is replaced with X-2-1 in Ar3-L5-L4-L3, the compound numbers are X-2-1-1 to X-2-1-3655,

[0126] When X-1-1 is replaced with X-2-2 in Ar3-L5-L4-L3, the compound numbers are X-2-2-1 to X-2-2-3655,

[0127] When X-1-1 is replaced with X-2-3 in Ar3-L5-L4-L3, the compound numbers are X-2-3-1 to X-2-3-3655,

[0128] When X-1-1 is replaced with X-2-4 in Ar3-L5-L4-L3, the compound numbers are X-2-4-1 to X-2-4-3655,

[0129] When X-1-1 is replaced with X-2-5 in Ar3-L5-L4-L3, the compound numbers are X-2-5-1 to X-2-5-3655,

[0130] When X-1-1 is replaced with X-2-6 in Ar3-L5-L4-L3, the compound numbers are X-2-6-1 to X-2-6-3655,

[0131] When X-1-1 is replaced with X-2-7 in Ar3-L5-L4-L3, the compound numbers are X-2-7-1 to X-2-7-3655,

[0132] When X-1-1 is replaced with X-2-8 in Ar3-L5-L4-L3, the compound numbers are X-2-8-1 to X-2-8-3655,

[0133] When X-1-1 is replaced with X-2-9 in Ar3-L5-L4-L3, the compound numbers are X-2-9-1 to X-2-9-3655,

[0134] When X-1-1 is replaced with X-2-10 in Ar3-L5-L4-L3, the compound numbers are X-2-10-1 to X-2-10-3655,

[0135] When X-1-1 is replaced with X-2-11 in Ar3-L5-L4-L3, the compound numbers are X-2-11-1 to X-2-11-3655,

[0136] When X-1-1 is replaced with X-2-12 in Ar3-L5-L4-L3, the compound numbers are X-2-12-1 to X-2-12-3655,

[0137] When X-1-1 is replaced by X-2-13 in Ar3-L5-L4-L3, the compound numbers are X-2-13-1 to X-2-13-3655,

[0138] When X-1-1 is replaced by X-2-14 in Ar3-L5-L4-L3, the compound numbers are X-2-14-1 to X-2-14-3655,

[0139] When X-1-1 is replaced by X-2-15 in Ar3-L5-L4-L3, the compound numbers are X-2-15-1 to X-2-15-3655,

[0140] When X-1-1 is replaced by X-2-16 in Ar3-L5-L4-L3, the compound numbers are X-2-16-1 to X-2-16-3655,

[0141] When X-1-1 is replaced by X-2-17 in Ar3-L5-L4-L3, the compound numbers are X-2-17-1 to X-2-17-3655,

[0142] When X-1-1 is replaced by X-2-18 in Ar3-L5-L4-L3, the compound numbers are X-2-18-1 to X-2-18-3655,

[0143] When X-1-1 is replaced by X-2-19 in Ar3-L5-L4-L3, the compound numbers are X-2-19-1 to X-2-19-3655,

[0144] When X-1-1 is replaced by X-2-20 in Ar3-L5-L4-L3, the compound numbers are X-2-20-1 to X-2-20-3655,

[0145] When X-1-1 is replaced by X-2-21 in Ar3-L5-L4-L3, the compound numbers are X-2-21-1 to X-2-21-3655,

[0146] When X-1-1 is replaced by X-2-22 in Ar3-L5-L4-L3, the compound numbers are X-2-22-1 to X-2-22-3655,

[0147] When X-1-1 is replaced by X-2-23 in Ar3-L5-L4-L3, the compound numbers are X-2-23-1 to X-2-23-3655,

[0148] When X-1-1 is replaced by X-2-24 in Ar3-L5-L4-L3, the compound numbers are X-2-24-1 to X-2-24-3655,

[0149] When X-1-1 is replaced by X-3-1 in Ar3-L5-L4-L3, the compound numbers are X-3-1-1 to X-3-1-3655,

[0150] When X-1-1 is replaced by X-3-2 in Ar3-L5-L4-L3, the compound numbers are X-3-2-1 to X-3-2-3655,

[0151] When X-1-1 is replaced by X-3-3 in Ar3-L5-L4-L3, the compound numbers are X-3-3-1 to X-3-3-3655,

[0152] When X-1-1 is replaced by X-3-4 in Ar3-L5-L4-L3, the compound numbers are X-3-4-1 to X-3-4-3655,

[0153] When X-1-1 is replaced by X-3-5 in Ar3-L5-L4-L3, the compound numbers are X-3-5-1 to X-3-5-3655,

[0154] When X-1-1 is replaced by X-3-6 in Ar3-L5-L4-L3, the compound numbers are X-3-6-1 to X-3-6-3655,

[0155] When X-1-1 is replaced by X-3-7 in Ar3-L5-L4-L3, the compound numbers are X-3-7-1 to X-3-7-3655,

[0156] When X-1-1 is replaced by X-3-8 in Ar3-L5-L4-L3, the compound numbers are X-3-8-1 to X-3-8-3655,

[0157] When X-1-1 is replaced by X-3-9 in Ar3-L5-L4-L3, the compound numbers are X-3-9-1 to X-3-9-3655,

[0158] When X-1-1 is replaced by X-3-10 in Ar3-L5-L4-L3, the compound numbers are X-3-10-1 to X-3-10-3655,

[0159] When X-1-1 is replaced by X-3-11 in Ar3-L5-L4-L3, the compound numbers are X-3-11-1 to X-3-11-3655,

[0160] When X-1-1 is replaced by X-3-12 in Ar3-L5-L4-L3, the compound numbers are X-3-12-1 to X-3-12-3655,

[0161] When X-1-1 is replaced with X-3-13 in Ar3-L5-L4-L3, the compound numbers are X-3-13-1 to X-3-13-3655,

[0162] When X-1-1 is replaced with X-3-14 in Ar3-L5-L4-L3, the compound numbers are X-3-14-1 to X-3-14-3655,

[0163] When X-1-1 is replaced with X-3-15 in Ar3-L5-L4-L3, the compound numbers are X-3-15-1 to X-3-15-3655,

[0164] When X-1-1 is replaced with X-3-16 in Ar3-L5-L4-L3, the compound numbers are X-3-16-1 to X-3-16-3655,

[0165] When X-1-1 is replaced with X-3-17 in Ar3-L5-L4-L3, the compound numbers are X-3-17-1 to X-3-17-3655,

[0166] When X-1-1 is replaced with X-3-18 in Ar3-L5-L4-L3, the compound numbers are X-3-18-1 to X-3-18-3655,

[0167] When X-1-1 is replaced with X-3-19 in Ar3-L5-L4-L3, the compound numbers are X-3-19-1 to X-3-19-3655,

[0168] When X-1-1 is replaced with X-3-20 in Ar3-L5-L4-L3, the compound numbers are X-3-20-1 to X-3-20-3655,

[0169] When X-1-1 is replaced with X-3-21 in Ar3-L5-L4-L3, the compound numbers are X-3-21-1 to X-3-21-3655,

[0170] When X-1-1 is replaced with X-3-22 in Ar3-L5-L4-L3, the compound numbers are X-3-22-1 to X-3-22-3655,

[0171] When X-1-1 is replaced with X-3-23 in Ar3-L5-L4-L3, the compound numbers are X-3-23-1 to X-3-23-3655,

[0172] When X-1-1 is replaced with X-3-24 in Ar3-L5-L4-L3, the compound numbers are X-3-24-1 to X-3-24-3655.

[0173] According to another aspect of the present invention, the present invention provides an application of the compound as an organic electroluminescent material.

[0174] An organic electroluminescent device includes a substrate, an anode, a hole transport region, a light-emitting layer, an electron transport region, and a cathode. The light-emitting layer is located between the anode and the cathode, the hole transport region is located between the anode and the light-emitting layer, the electron transport region is located between the light-emitting layer and the cathode, and the hole transport region contains the arylamine compound of the present invention.

[0175] Preferably, the hole transport region includes a first hole transport layer and a second hole transport layer. The second hole transport layer is located between the first hole transport layer and the light-emitting layer, and the second hole transport layer contains the arylamine compound of the present invention.

[0176] An electronic device includes one or more of a display, a monitor, and a lighting device, including the organic electroluminescent device of the present invention; and a control unit for driving the above display device.

[0177] Generally speaking, compared with the prior art by the above technical solutions conceived by the present invention, the following beneficial effects can be achieved:

[0178] 1. For the arylamine compound of the present invention, the compound with the specific parent nucleus structure of the present invention used as an organic electroluminescent material, especially as a material for the hole transport region, exhibits excellent performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0179] Figure 1 It is a schematic structural diagram of the organic electroluminescent device described in Application Example 1; wherein: 1. Substrate, 2. Anode, 3. Hole injection layer, 4. First hole transport layer, 5. Second hole transport layer, 6. Light-emitting layer, 7. Hole blocking layer, 8. Electron transport layer, 9. Cathode. DETAILED DESCRIPTION

[0180] Now, exemplary embodiments will be described in detail, and their examples are illustrated in the drawings, where the same reference numerals always refer to the same elements. In this regard, the present exemplary embodiments may have different forms and should not be construed as limited to the description set forth herein. Therefore, the following only describes the exemplary embodiments by referring to the drawings to illustrate aspects. As used herein, the term "and / or" includes any and all combinations of one or more of the related listed items. Expressions such as "at least one (kind) of" modify the entire list of elements when before or after the list of elements and do not modify the individual elements of the list.

[0181] It will be understood that when an element is referred to as being "on" another element, it can be in direct contact with the other element or there can be intervening elements therebetween. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements.

[0182] It will be further understood that the terms "comprises" or "comprising", when used in this specification, specify the presence of the stated features, regions, wholes, steps, operations, elements, and / or components, but do not preclude the presence or addition of one or more other features, regions, wholes, steps, operations, elements, components, and / or groups thereof.

[0183] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this general inventive concept belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and this disclosure, and will not be interpreted in an idealized or overly formal sense unless clearly so defined herein.

[0184] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and not to limit the protection scope of the present invention. In addition, it should be understood that after reading the content disclosed in the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also fall within the protection scope defined by the present invention.

[0185] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods; the reagents, materials, etc. used in the following examples can all be obtained from commercial sources unless otherwise specified.

[0186] Term Explanation

[0187] As used in the present invention, "X-m-n", "Y1……Y85", "Y1……Y85" are the substituent numbers corresponding to Ar3-L5-L4-L3-, -L1-Ar1, -L2-Ar2 respectively. According to the substituents corresponding to this numbering, the compounds of this application can be determined. For example, when m = 1 and n = 1, Ar3-L5-L4-L3- is selected from the substituent numbered "X-1-1" If at this time -L1-Ar1 is selected from the substituent numbered "Y1" -L2-Ar2 is selected from the substituent numbered "Y1" At this time, the corresponding compound number is X-1-1-1, and the compound structure is

[0188] As used in the present invention, indicates the substitution position.

[0189] As used in the present invention, the above-mentioned A1 selected from substituted or unsubstituted C6-C14 aromatic rings means derived from a combination of a single ring or two or more aromatic hydrocarbon rings, where the number of carbon atoms is the number of ring-forming atoms, excluding the carbon atoms in the substituents, and the number of ring-forming atoms includes the number of carbon atoms in C1 and C2;

[0190] The above-mentioned A2 selected from substituted or unsubstituted C10-C14 aromatic rings means derived from a combination of a single ring or two or more aromatic hydrocarbon rings, where the number of carbon atoms is the number of ring-forming atoms, excluding the carbon atoms in the substituents, and the number of ring-forming atoms includes the number of carbon atoms in C3 and C4.

[0191] As used in the present invention, the term "halogen group" may include fluorine, chlorine, bromine or iodine.

[0192] As used in the present invention, the term "C6-C14 aromatic ring" means an aromatic hydrocarbon ring derived from a combination of a single ring or two or more rings and having 6 to 14 carbon atoms, which may be fused with adjacent rings, and the shared carbon atoms during fusion should also be included in the 6 to 14 carbon atoms. The term "C10-C14 aromatic ring" should be understood in the same way.

[0193] As used in the present invention, the term "C1-C10 alkyl" means a monovalent substituent derived from a straight-chain or branched-chain saturated hydrocarbon having 1 to 10 carbon atoms, and its examples include but are not limited to methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl and hexyl.

[0194] As used in the present invention, the term "C3-C10 cycloalkyl" means a monovalent substituent derived from a single-ring or poly-ring non-aromatic hydrocarbon having 3 to 10 carbon atoms. Examples of such cycloalkyls include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantane, etc.

[0195] As used in the present invention, the term "C2-C10 heterocycloalkyl" means a monovalent substituent derived from a single-ring or poly-ring having 2 to 10 carbon atoms, and the ring contains at least one heteroatom selected from O, S, N, P, Si.

[0196] As used in the present invention, the term "alkoxy" refers to a straight-chain, branched-chain or cyclic chain. The number of carbon atoms in the alkoxy is not particularly limited herein, but the alkoxy preferably has 1 to 10 carbon atoms. Specific examples thereof include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, benzyloxy.

[0197] As used in the present invention, the term "cycloalkenyl" refers to an unsaturated carbocyclic ring and does not have aromaticity.

[0198] As used in the present invention, the term "heterocycloalkenyl" refers to an unsaturated heterocyclic ring and does not have aromaticity.

[0199] As used in the present invention, the term "aryl having 6 to 60 carbon atoms" refers to a monovalent substituent derived from an aromatic hydrocarbon having a single ring or a combination of two or more rings and having 6 to 60 carbon atoms. Further, such an aryl may have a form in which two or more of these rings are simply joined to each other or fused to each other. Examples of such aryls include, but are not limited to, phenyl, biphenyl, naphthyl, phenanthryl, anthryl, pyrenyl, triphenylenyl, fluoranthenyl, dimethyl 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirobifluorenyl, and the like.

[0200] As used in the present invention, the term "arylene" refers to a divalent aryl derived by removing one hydrogen atom from "aryl". For example, phenyl becomes phenylene by removing one hydrogen atom, and naphthyl becomes naphthylene by removing one hydrogen atom.

[0201] As used in the present invention, the term "heteroaryl having 3 to 60 carbon atoms" refers to a monovalent substituent derived from a monocyclic or polycyclic aromatic hydrocarbon having 3 to 60 carbon atoms. In this connection, at least one carbon, preferably 1 to 3 carbons, in the ring is replaced by a heteroatom such as N, O, S, P, B or Si. Further, such a heteroaryl may have a form in which two or more of these rings are simply joined to each other or fused to each other or fused to an aryl. Examples of such heteroaryls include, but are not limited to, pyrrolyl, furyl, thienyl, benzofuryl, benzothienyl, carbazolyl, dibenzofuryl, dibenzothienyl, and the like, and the present invention is not limited thereto.

[0202] As used in the present invention, the term "heteroarylene" refers to a divalent heteroaryl derived by removing one hydrogen atom from "heteroaryl". For example, pyridyl becomes pyridylene by removing one hydrogen atom.

[0203] As used in the present invention, "arylamine" includes arylamine, heteroarylamine, arylheteroarylamine.

[0204] As used in the present invention, the expression "K group having M to N carbon atoms" or "K group of C(M-N)" means that the number of carbon atoms of the K group when unsubstituted does not include the carbon atoms of the substituents during substitution. For example, an aryl group having 6 to 60 carbon atoms means that when unsubstituted, the number of carbon atoms in the aryl group is any integer from 6 to 60, that is, when unsubstituted, the number of carbon atoms can be 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20... 60.

[0205] As used in the present invention, the term "substituted" means that a hydrogen atom in a compound is replaced by another substituent. The position where substitution occurs can be the position where the hydrogen atom is replaced. That is, the position is not limited to a specific position as long as the hydrogen at that position can be replaced by a substituent. For example, a carbazolyl group, unless otherwise specified in this specification, includes any of the following groups, but is not limited thereto,

[0206] "retains a hydrogen atom, in which case the hydrogen atom includes protium, deuterium, and tritium, and the substituted case may also include the case of deuterium or tritium substitution.

[0207] When there are two or more substituents, the two or more substituents may be the same or different.

[0208] As used in the present invention, the term "terphenyl" includes

[0209] As used in the present invention, the hydrogen atom includes protium, deuterium, and tritium. The compounds described in the present invention may contain deuterium atoms of natural origin, or deuterium atoms may be introduced by deuterating part or all of the starting compounds. If deuterium atoms are introduced from the starting materials, the deuteration rate may be 100%, or less than 100%, or less than 95%, or less than 90%, or less than 80%, and the deuteration rate may also be 1% or more, or 5% or more, or 10% or more. If the deuteration rate is not 100%, it means a mixture of deuterated compounds and non-deuterated compounds, or a mixture of fully deuterated compounds and incompletely deuterated compounds, or a mixture of fully deuterated compounds, non-deuterated compounds, and incompletely deuterated compounds.

[0210] As used in the present invention, terms such as the first, the second, A, B, etc. are used. The above terms are only used to distinguish the constituent elements and do not limit the nature or order of the constituent elements corresponding to the terms.

[0211] Organic electroluminescent element

[0212] The structure used in the organic electroluminescent element of the present invention is a publicly known structure, which includes an anode, a cathode, and an organic layer located between the anode and the cathode. The organic layer includes a light-emitting layer, and at least one layer of the organic layer contains the compound of the present invention.

[0213] The organic layer may further include one or more of a hole injection layer, a hole transport layer, a second hole transport layer, a hole blocking layer, an electron transport layer, and an electron injection layer, but is not limited thereto.

[0214] The light-emitting element of the present invention can be fluorescent light-emitting, phosphorescent light-emitting, or a combination thereof. The light-emitting element can be a single light-emitting element or a series type of multiple light-emitting units.

[0215] As a simple light-emitting element, the following can be cited, but are not limited thereto.

[0216] (1) Hole transport layer / Fluorescent light-emitting layer / Electron transport layer;

[0217] (2) Hole transport layer / Phosphorescent light-emitting layer / Electron transport layer;

[0218] (3) Hole transport layer / First fluorescent light-emitting layer / Second fluorescent light-emitting layer / Electron transport layer;

[0219] (4) Hole transport layer / First phosphorescent light-emitting layer / Second phosphorescent light-emitting layer / Electron transport layer;

[0220] (5) Hole transport layer / Fluorescent light-emitting layer / Spacer layer / Phosphorescent light-emitting layer / Electron transport layer;

[0221] (6) Hole transport layer / Second hole transport layer / Fluorescent light-emitting layer / Electron transport layer;

[0222] (7) Hole transport layer / Second hole transport layer / Fluorescent light-emitting layer / Hole blocking layer / Electron transport layer;

[0223] (8) Hole transport layer / Second hole transport layer / Phosphorescent light-emitting layer / Electron transport layer;

[0224] (9) Hole transport layer / Second hole transport layer / Phosphorescent light-emitting layer / Hole blocking layer / Electron transport layer;

[0225] (10) Hole injection layer / Hole transport layer / Phosphorescent light-emitting layer / Electron transport layer / Electron injection layer;

[0226] (11) Hole injection layer / Hole transport layer / Fluorescent light-emitting layer / Electron transport layer / Electron injection layer;

[0227] (12) Hole injection layer / Hole transport layer / Second hole transport layer / Phosphorescent light-emitting layer / Electron transport layer / Electron injection layer;

[0228] (13)Hole injection layer / hole transport layer / second hole transport layer / fluorescent light-emitting layer / electron transport layer / electron injection layer;

[0229] The above-mentioned phosphorescent / fluorescent light-emitting layers can each emit light of different colors.

[0230] As a tandem organic electroluminescent device, it can be an anode / first light-emitting unit / intermediate layer / second light-emitting unit / cathode. The intermediate layer is generally also referred to as a charge generation layer, an electron extraction layer, a connection layer, etc. For example, when stacking a fluorescent light-emitting layer and a phosphorescent light-emitting layer, in order to prevent the excitons generated in the phosphorescent light-emitting layer from diffusing to the fluorescent light-emitting layer, or to adjust the carrier balance, an intermediate layer is placed between the fluorescent light-emitting layer and the phosphorescent light-emitting layer.

[0231] When the organic light-emitting device includes a plurality of organic material layers, the organic material layers can be formed of the same material or different materials.

[0232] The organic electroluminescent device of this specification can be manufactured by materials and methods known in the art, except that one or more of the organic material layers are formed by using the compounds described in the present invention.

[0233] As the anode material, a material having a relatively large work function can be used, and transparent conductive oxides, metals, conductive polymers, etc. can be used. Specific examples of anode materials include: metals, such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides, such as ZnO:Al or SnO2:Sb; conductive polymers, such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, etc., but not limited thereto.

[0234] As the cathode material, a material having a low work function is usually used to facilitate electron injection into the organic layer, and metals, metal oxides, conductive polymers, etc. can be used. Specific examples of cathode materials include: metals, such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; multilayer structure materials, such as LiF / Al or LiO2 / Al, etc., but not limited thereto.

[0235] The hole injection layer is a layer that injects holes from the electrode and has the ability to transport holes. To reduce the energy level difference between the electrodes, the hole injection layer is mainly prepared based on aromatic amine compounds, and can also be prepared with the following materials. For example, copper phthalocyanine is selected from metal complexes, and HATCN (2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene) with a phenylene structure is selected from materials with the lowest unoccupied molecular orbital energy level. When used as a light-emitting host and a dopant, F4-TCNQ (2,3,5,6-tetrafluoro-7,7',8,8'-tetracyanoquinodimethane) inducer with the lowest unoccupied molecular orbital energy level can be doped in the aromatic amine compound.

[0236] The hole transport layer is a layer that receives holes from the hole injection layer and transports the holes to the light-emitting layer, and the hole transport material is appropriately a material with a high hole mobility that can receive holes from the anode or the hole injection layer and transfer the holes to the light-emitting layer. Arylamine derivatives, triphenyl diamine derivatives, etc. can be used, and low molecular weight or high molecular weight materials can also be used.

[0237] The second hole transport layer can adjust the energy level difference between the hole transport region and the light-emitting layer, facilitate the entry of holes into the light-emitting layer, and at the same time reduce the probability of electrons entering the hole transport region from the light-emitting layer. Commonly used are aromatic amine derivatives.

[0238] The light-emitting material is a material that can receive holes and electrons from the hole transport layer and the electron transport layer respectively and combine the holes and electrons to emit light in the visible light region. The light-emitting layer material includes a host material and a dopant material. Red, green, or blue light-emitting materials can be used, and if necessary, two or more light-emitting materials can be mixed. As the light-emitting material, fluorescent materials can be used, and phosphorescent materials can also be used. As the light-emitting material, single-component materials can be used, or multi-component materials can be used.

[0239] The electron transport layer is a layer that receives electrons from the electron injection layer and transports the electrons to the light-emitting layer, and the electron transport material is a material with a high electron mobility that can receive electrons from the cathode and transfer the electrons to the light-emitting layer. Metal complexes such as triazine derivatives, oxadiazole derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, fluorenone derivatives, diphenyl dicyanoethylene and its derivatives, 8-hydroxyquinoline and its derivatives, etc. can be used, and high molecular weight materials and small molecular weight materials can also be used.

[0240] The electron injection layer is a layer that injects electrons from the electrode.

[0241] According to the materials used, the organic light-emitting device of this specification can be a top-emitting device, a bottom-emitting device, or a dual-emission type device.

[0242] The charge generation layer refers to the intermediate layer located between the anode and the cathode in a tandem structure device, and is a layer that generates holes and electrons by charge separation. The charge generation layer is usually formed by a P-type layer on the cathode side and an N-type layer on the anode side, and can effectively separate charges and efficiently transport carriers.

[0243] In one embodiment of the present invention, the formation method of each layer is not particularly limited. Formation methods based on vacuum evaporation, spin coating, etc., which are well-known in the art, can be used. Each layer such as the light-emitting layer can be formed by well-known methods such as vacuum evaporation, molecular beam epitaxy (MBE method), or coating methods such as dipping, spin coating, casting, bar coating, roll coating, etc. of a solution dissolved in a solvent.

[0244] In one embodiment of the present invention, the film thickness of each layer is not particularly limited, and generally several nanometers to several hundred nanometers can be used. In order to suppress defects such as pinholes, reduce the driving voltage, and improve the luminous efficiency, a range of several nm to 1 μm is usually preferred.

[0245] Those skilled in the art can synthesize the compounds of the present invention by referring to the synthesis of the following compounds and well-known synthesis methods. There are various synthesis methods for the compounds of the present invention, and the following methods are only examples for illustration.

[0246] LC-MS brand: Waters, model: SQ Detector 2

[0247] Nuclear magnetic resonance brand: Bruker, model: AVANCE NEO 400

[0248] Those skilled in the art can synthesize the compounds of the present invention by referring to the synthesis of the following compounds and well-known synthesis methods. An exemplary synthesis general formula of the present invention is as follows:

[0249] Synthesis general formula 1:

[0250]

[0251] Synthesis general formula 2:

[0252]

[0253] Among them, X and Y are each independently a halogen (including F, Cl, Br, I), and those skilled in the art can select according to the selectivity of the reaction. A1, A2, L1-L5, Ar1, and Ar2 refer to the definitions in the above embodiments, and Bpin is indicating the connection position.

[0254] Synthesis of intermediates

[0255] 1. Synthesis of intermediate 1:

[0256] Step 1: Synthesis of Intermediate 1-1

[0257]

[0258] Under a nitrogen atmosphere, 7H-benzo[c]carbazole (15.0 g, 69.04 mmol), 1-bromo-2-fluorobenzene (48.3 g, 276.15 mmol), and cesium carbonate (22.5 g, 207.12 mmol) were added to a 500 mL four-necked flask. 200 mL of N,N-dimethylformamide was added, and the mixture was stirred at 140 °C for 6 h. Heating was stopped after the reaction was completed. The mixture was extracted and separated with dichloromethane and water. The organic phase was dried by rotation and mixed with a sample, and the sample was purified by column chromatography (volume ratio of n-hexane:dichloromethane = 30:1) to obtain 10.0 g of Intermediate 1-1 with a yield of 40%.

[0259] LC-MS (APCI): 372.11 [M+H] +

[0260] Step 2: Synthesis of Intermediate 1

[0261]

[0262]

[0263] Under a nitrogen atmosphere, Intermediate 1-1 (5.0 g, 13.43 mmol), 2-(1-chlorodibenzo[b,d]furan-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.4 g, 13.43 mmol), tetrakis(triphenylphosphine)palladium (310 mg, 0.27 mmol), and potassium carbonate (5.6 g, 40.29 mmol) were added to a 250 mL four-necked flask. 90 mL of tetrahydrofuran (THF) and 30 mL of deionized water were added, and the temperature was raised to reflux the reaction system, followed by stirring at a constant temperature for 6 h. Samples were taken for TLC analysis and sent for inspection. After the test results were confirmed, the mixture was extracted and separated with ethyl acetate and water. The organic phase was dried by rotation and mixed with a sample, and the sample was purified by column chromatography (volume ratio of n-hexane:dichloromethane = 10:1) to obtain 4.2 g of Intermediate 1 with a yield of 63%.

[0264] LC-MS (APCI): 494.26 [M+H] +

[0265] 2. Synthesis of Intermediate 2

[0266] Step 1: Synthesis of Intermediate 2-1

[0267]

[0268] Under a nitrogen atmosphere, 2,3-benzo[c]carbazole (15.0 g, 69.038 mmol), 1-bromo-2-fluorobenzene (48.3 g, 276.154 mmol), and cesium carbonate (22.5 g, 207.115 mmol) were added to a 500 mL four-necked flask. 200 mL of N,N-dimethylformamide was added, and the mixture was stirred at 140 °C for 6 h. Samples were taken for TLC analysis and sent for testing. After the test results were confirmed, heating was stopped to end the reaction. The mixture was extracted with dichloromethane and water, and the organic phase was evaporated to dryness and mixed with samples. The sample was purified by column chromatography (n-hexane:dichloromethane = 30:1) to obtain 12 g of intermediate 2-1 with a yield of 46%.

[0269] LC-MS (APCI): 372.11 [M+H] +

[0270] Step 2: Synthesis of intermediate 2

[0271]

[0272] Under a nitrogen atmosphere, intermediate 2-1 (5.0 g, 13.431 mmol), 2-(1-chlorodibenzo[b,d]furan-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.4 g, 13.431 mmol), tetrakis(triphenylphosphine)palladium (310 mg, 0.268 mmol), and potassium carbonate (5.6 g, 40.293 mmol) were added to a 250 mL four-necked flask. 90 mL of tetrahydrofuran (THF) and 30 mL of deionized water were added, and the reaction system was heated to reflux and then stirred at a constant temperature for 6 h. After the reaction ended, the mixture was extracted with ethyl acetate and water, and the organic phase was evaporated to dryness and mixed with samples. The sample was purified by column chromatography (volume ratio of n-hexane:dichloromethane = 10:1) to obtain 4.4 g of intermediate 2 with a yield of 66%.

[0273] LC-MS (APCI): 494.26 [M+H] +

[0274] Synthesis examples:

[0275] Synthesis example 1: Synthesis of compound T1

[0276]

[0277] Under a nitrogen atmosphere, intermediate 2 (5 g, 10.1 mmol), 4-(4-dibenzofuranyl)-N-phenylaniline (3.4 g, 10.1 mmol), t-BuONa (1.9 g, 20.2 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.25 g, 0.6 mmol) and tris(dibenzylideneacetone)dipalladium(0) (0.27 g, 0.3 mmol) were placed in a four-necked reaction flask, and then 50 mL of toluene was added. The temperature was raised to reflux for reaction. After the reaction was completed (about 2 h), the reaction solution was cooled to room temperature, 100 mL of water was added, and the mixture was extracted with dichloromethane, concentrated to dryness, and then purified by refluxing and slurrying with 60 mL of ethanol to obtain 4.8 g of the final product with a yield of 60%.

[0278] LC-MS(APCI): 793.43[M+H] +

[0279] 1 H NMR(400 MHz, CD2Cl2) δ 8.29(s, 1H), 7.95(ddd, 3H), 7.91–7.87(m, 1H), 7.84(dd, 1H), 7.82–7.78(m, 1H), 7.74–7.66(m, 2H), 7.59–6.94(m, 19H), 6.87–6.78(m, 2H), 6.72(d, 1H), 6.64–6.52(m, 5H).

[0280] Synthesis Example 2: Synthesis of Compound T2

[0281] 1. Synthesis of Intermediate T2-1

[0282]

[0283] Under a nitrogen atmosphere, 2,3-benzo[c]carbazole (15.0 g, 69.038 mmol), 1-bromo-3-fluorobenzene (48.3 g, 276.154 mmol), and cesium carbonate (22.5 g, 207.115 mmol) were added to a 500 mL four-necked flask. 200 mL of N,N-dimethylformamide was added, and the mixture was stirred at 140 °C for 6 h. Heating was stopped after the reaction was completed. The mixture was extracted and separated with dichloromethane and water, and the organic phase was dried by evaporation and sampled. The sample was purified by column chromatography (volume ratio: n-hexane:dichloromethane = 30:1) to obtain 14 g of intermediate T2-1 with a yield of 54%.

[0284] LC-MS(APCI): 372.11[M+H] +

[0285] 2. Synthesis of Intermediate T2-2

[0286]

[0287] Under a nitrogen atmosphere, the intermediate T2-1 (5.0 g, 13.431 mmol), 2-(1-chlorodibenzo[b,d]furan-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (4.4 g, 13.431 mmol), tetrakis(triphenylphosphine)palladium (310 mg, 0.268 mmol), and potassium carbonate (5.6 g, 40.293 mmol) were added to a 250 mL four-necked flask. 90 mL of THF and 30 mL of deionized water were added, and the reaction system was heated to reflux. Then, it was stirred at a constant temperature for 6 h. Samples were taken for TLC and sent for inspection. After the test results were confirmed, extraction and liquid separation were carried out with ethyl acetate and water. The organic phase was rotary evaporated and stirred for column chromatography purification of the sample (volume ratio: n-hexane:dichloromethane = 10:1), and 5.3 g of intermediate T2-2 was obtained with a yield of 80%.

[0288] LC-MS(APCI): 494.26[M+H] +

[0289] 3. Synthesis of Compound T2

[0290]

[0291] Under a nitrogen atmosphere, the intermediate T2-2 (5 g, 10.1 mmol), intermediate T2-a (3.4 g, 10.1 mmol), t-BuONa (1.9 g, 20.2 mmol), 2-bis(cyclohexylphosphino)-2',6'-dimethoxybiphenyl (0.25 g, 0.6 mmol), and tris(dibenzylideneacetone)dipalladium (0.27 g, 0.3 mmol) were placed in a four-necked reaction flask, and then 50 mL of toluene was added. The reaction system was heated to reflux. After the reaction was completed (about 2 h), the reaction solution was cooled to room temperature, 100 mL of water was added, and it was extracted with dichloromethane, concentrated to dryness, and then purified by refluxing and pulping with 60 mL of ethanol to obtain 5.6 g of the final product with a yield of 70%.

[0292] LC-MS(APCI): 793.43[M+H] +

[0293] 11H NMR (400 MHz, Methylene Chloride-d2) δ 8.58 (s, 1H), 8.30–8.20 (m, 2H), 8.04–7.96 (m, 2H), 7.94–7.89 (m, 2H), 7.88–7.82 (m, 2H), 7.81–7.75 (m, 3H), 7.68 (dd, 2H), 7.59 (d, 1H), 7.55–7.44 (m, 4H), 7.43–7.32 (m, 5H), 7.31–7.23 (m, 3H), 7.23–7.14 (m, 7H), 7.06–6.94 (m, 2H).

[0294] Synthesis Example 3: Synthesis of Compound T3

[0295]

[0296] Under a nitrogen atmosphere, 4 g (13.5 mmol) of N-[4-(1-naphthyl)phenyl]-phenyl-4-amine, 7 g (14.2 mmol) of Intermediate 1, 0.25 g (0.27 mmol) of Pd2dba3, 0.26 g (0.54 mmol) of Xphos (2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl), and 2.6 g (27.1 mmol) of sodium tert-butoxide were added, and then 50 ml of toluene was added. The temperature was raised to 110 °C for reaction. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with dichloromethane, and dried over anhydrous sodium sulfate, and then the solvent was removed. Purification was carried out by silica gel chromatography (developing solvent volume ratio: n-hexane:dichloromethane = 3:1). Thus, Compound T3 (9 g, yield 88%) was obtained.

[0297] LC-MS (APCI): 753.41 [M+H] +

[0298] 1 1H NMR (400 MHz, Methylene Chloride-d2) δ 8.52 (d, 1H), 8.36–8.24 (m, 1H), 8.00–

[0299] 7.89 (m, 1H), 7.88–7.64 (m, 7H), 7.55–7.16 (m, 11H), 7.12–6.76 (m, 10H), 6.70–6.56 (m, 4H), 6.50 (d, 1H).

[0300] Synthesis Example 4: Synthesis of Compound T4

[0301]

[0302] Under nitrogen atmosphere, N-(4-(naphthalene-1-yl)phenyl)-[1,1'-biphenyl]-4-amine (7 g, 18.8 mmol), intermediate 1 (8.2 g, 16.6 mmol), Pd2(dba)3 (0.5 g, 0.54 mmol), sodium tert-butoxide (3.6 g, 37 mmol), Xphos (0.46 g, 1.1 mmol), and 140 ml of toluene were added to the reaction bottle and reacted at 90°C for 4 h. After the reaction was completed, the reaction solution was extracted with dichloromethane, dried with anhydrous sodium sulfate, and the solvent was removed. Crystallized with ethyl acetate (for purification). Compound T4 (12 g) was obtained. Yield: 77%.

[0303] LC-MS (APCI): 830.50 [M+H] +

[0304] 1 H NMR(400MHz,Methylene Chloride-d2)δ8.54(d,1H),8.36–8.27(m,1H),8.01–7.92(m,1H),7.85–7.65(m,7H),7.53–7. 17(m,16H),7.16–7.00(m,6H),6.91(d,1H),6.88–6.81(m,2H),6.75–6.62(m,4H),6.55(d,1H).

[0305] Synthesis Example 5: Synthesis of Compound T5

[0306]

[0307] In a 500ml four-necked bottle, 4-bromo-1-chlorodibenzo[b,d]furan (10.0g, 35.52mmol), 3-(naphthalene-2-yl)-N-phenylaniline (10.5g, 35.52mmol), sodium tert-butoxide (6.8g, 71.04mmol), Pd2(dba)3 (650mg, 0.71mmol), tri-tert-butylphosphine (570mg, 2.84mmol), toluene (200ml) were added in sequence, and refluxed for 3 hours under nitrogen protection. After the reaction was completed, column chromatography (n-hexane: dichloromethane = 10:1) was performed to obtain intermediate T5-1 (14.7g, 29.75mmol).

[0308] LC-MS:496.30[M+H] +

[0309]

[0310] Into a 500 ml four-necked flask, intermediate T5-1 (14.7 g, 29.75 mmol), (2-(7H-benzo[c]carbazol-7-yl)phenyl)boronic acid (10.0 g, 29.75 mmol), Pd(dppf)Cl2 (435 mg, 0.595 mmol), potassium carbonate (8.2 g, 59.5 mmol), toluene (150 ml), ethanol (50 ml), and water (50 ml) were successively added, and the reaction was refluxed for 6 hours under nitrogen protection. After the reaction was completed, column chromatography (n-hexane:dichloromethane = volume ratio 5:1) was performed to obtain T5 (18.7 g, 24.82 mmol).

[0311] LC-MS: 753.41[M+H] +

[0312] 1H NMR(400MHz,Methylene Chloride-d2)δ8.73(d,1H),8.55(d,1H),8.01(qt,3H),7.92–7.73(m,15H),7.34–7.20(m,7H),7.08–6.90(m,5H),6.55–6.38(m,4H).

[0313] Synthesis Example 6: Synthesis of Compound T6

[0314]

[0315] Under a nitrogen atmosphere, N-(4-biphenyl)-2-benzidine (6 g, 18.6 mmol), intermediate 1 (9.2 g, 18.6 mmol), Pd2(dba)3 (0.5 g, 0.54 mmol), sodium tert-butoxide (3.6 g, 37 mmol), Xphos (0.46 g, 1.1 mmol), and 140 ml of toluene were added to a reaction flask and reacted at 90 °C for 4 h. After the reaction was completed, the reaction solution was extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was removed. Crystallization (purification) was performed with ethyl acetate. Thereby, compound T6 (12 g) was obtained. Yield: 82%.

[0316] LC-MS(APCI): 779.98[M+H] +

[0317] 11H NMR (400 MHz, Methylene Chloride-d2) δ 8.56 (s, 1H), 8.31 (s, 1H), 7.82 (d, 2H), 7.69 (s, 3H), 7.57 (s, 2H), 7.39 (s, 15H), 6.95 (s, 1H), 6.83 (s, 4H), 6.65 (s, 3H), 6.52 (s, 1H), 6.43 (s, 3H), 6.27 (s, 1H), 5.71 (s, 1H).

[0318] Synthesis Example 7: Synthesis of Compound T7

[0319]

[0320] Under a nitrogen atmosphere, 9-(3-chlorophenyl)phenanthrene (15 g, 51.9 mmol), 4-aminobiphenyl (9.7 g, 57.3 mmol), sodium tert-butoxide (9.9 g, 103 mmol), tris(dibenzylideneacetone)dipalladium (0.95 g, 1 mmol), and 2-dicyclohexylphosphino-2′,6′-dimethoxy-biphenyl (0.85 g, 2 mmol) were added to a four-necked reaction flask. Then, anhydrous toluene (125 ml) was added as a solvent, and the mixture was heated to 110 °C. After the reaction was completed, heating was stopped, and the temperature was cooled to room temperature. 100 ml of water was added to quench the reaction, and the reaction solution was extracted with 100 ml of dichloromethane. The organic phase was separated, washed with water three times, dried over anhydrous sodium sulfate, filtered, and the organic phase was rotary evaporated to obtain a viscous solid of 21.3 g. Column chromatography was used for separation, and the eluent was n-hexane:ethyl acetate = 20:1 (volume ratio). 15 g of product T7-1 was obtained, and then 14 g of intermediate T7-1 was obtained by refluxing and slurrying with ethanol:ethyl acetate = 5:1, with a yield of 63.9%.

[0321] LC-MS (APCI): 422.44 [M+H] +

[0322]

[0323] Under nitrogen environment, T7-1 (6g, 12.1mmol), intermediate 1 (4.7g, 11.1mmol), sodium tert-butoxide (1.95g, 20.2mmol), tris(dibenzylideneacetone)dipalladium (0.95g, 0.2mmol) and tri-tert-butylphosphine (0.85g, 2mmol) were added to a four-mouth reaction bottle, and then anhydrous toluene (125ml) solvent was added, heated to 110°C, and the heating was stopped after the reaction was completed, and the temperature was cooled to room temperature, 100ml of water was added to quench the reaction, and 100ml of dichloromethane was used to extract the reaction liquid. The organic phase was washed with water three times, dried and filtered with anhydrous sodium sulfate, and the organic phase was spin-dried to obtain 15g of black solid. Column chromatography separation, eluent n-hexane: dichloromethane = volume ratio 10:1, 8.3g product T7 was obtained, and the yield was 78.3%.

[0324] LC-MS (APCI): 880.65 [M+H] +

[0325] 1H NMR(400MHz,Methylene Chloride-d2)δ8.63(ddd,2H),8.14(s,1H),7.94–7.87(m,1H),7.84–7.62(m,6H),7.61–7.38(m,9 H),7.34–7.28(m,2H),7.27–7.17(m,6H),7.15–7.06(m,3H),7.06–6.74(m,8H),6.68–6.51(m,4H).

[0326] Synthesis Example 8: Synthesis of Compound T8

[0327]

[0328] Under nitrogen atmosphere, N-phenyl[1,1′:3′,1′-triphenyl]-3-amine (4.95 g, 0.015 mol), intermediate 1 (7.61 g, 0.015 mol), palladium acetate (0.093 g, 0.42 mmol), XPhos (0.40 g, 0.83 mmol) and sodium tert-butoxide (2.96 g, 0.031 mol) were added to a four-necked reaction flask, 120 ml of toluene was added, and refluxed for 2 hours. The reaction solution was cooled to room temperature, water was added to quench the reaction, and dichloromethane was used for extraction. The organic phase was concentrated and passed through a chromatography column, and the developing solvent was n-hexane / dichloromethane = volume ratio 3 / 1. Thus, a white solid of T8 (5.1 g, yield 43%) was obtained.

[0329] LC-MS(APCI):779.61[M+H] +

[0330] 11H NMR (400 MHz, DMSO-d6) δ 8.61 (d, 1H), 8.51–8.37 (m, 1H), 8.08–7.90 (m, 3H), 7.89–7.78 (m, 3H), 7.72–6.80 (m, 26H), 6.73–6.61 (m, 1H), 6.56–6.26 (m, 3H).

[0331] Synthesis Example 9: Synthesis of Compound T9

[0332]

[0333] Under a nitrogen atmosphere, 4-(dibenzo[b,d]thiophen-4-yl)-N-phenylaniline (5.6 g, 15.95 mmol), Intermediate 1 (15.19 g, 15.19 mmol), tetrakis(triphenylphosphine)palladium (346 mg, 0.30 mmol), and sodium tert-butoxide (2.9 g, 30.4 mmol) were added to 150 ml of toluene, and the temperature was raised to reflux for 4 hours. After the reaction was completed, the mixture was filtered, the filter cake was washed with water, and then refluxed with 100 ml of ethyl acetate for 30 minutes and filtered to obtain 9.6 g of T10 (yield 77%).

[0334] LC-MS (APCI): 811.59 [M+H] +

[0335] 1 1H NMR (400 MHz, Methylene Chloride-d2) δ 8.37 (s, 1H), 8.26–8.19 (m, 1H), 8.15 (dd, 1H), 8.07–8.01 (m, 2H), 8.00–7.94 (m, 1H), 7.89 (dt, 2H), 7.78 (qd, 2H), 7.60–7.38 (m, 8H), 7.35–6.99 (m, 10H), 6.97–6.87 (m, 2H), 6.82 (d, 1H), 6.75–6.70 (m, 2H), 6.64 (t, 3H).

[0336] Synthesis Example 10: Synthesis of Compound T10

[0337]

[0338] Under a nitrogen atmosphere, intermediate T2-2 (5.0 g, 10.1 mmol), N-[4-(1-naphthyl)phenyl]-phenyl-4-amine (3.2 g, 11.4 mmol), t-BuONa (3 g, 21 mmol), Pd2(dba)3 (0.37 g, 0.4 mmol), and SPhos (2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl) (0.8 g, 2.0 mmol) were placed in a four-necked reaction flask. A total of 50 mL of toluene was added, and the mixture was heated to reflux. After the reaction was completed in 2 h, the reaction solution was cooled to room temperature and purified by flash column chromatography with toluene to obtain 5 g with a yield of 68%.

[0339] LC-MS (APCI): 753.48 [M+H] +

[0340] 1 H NMR (400 MHz, Methylene Chloride-d2) δ 8.56 (s, 1H), 8.25–8.20 (m, 2H), 8.01–7.93 (m, 2H), 7.88 (s, 1H), 7.83 (ddd, 2H), 7.81–7.76 (m, 1H), 7.75–7.71 (m, 2H), 7.67–7.62 (m, 2H), 7.56 (dt, 1H), 7.50–7.12 (m, 20H), 7.03 (td, 1H), 6.96 (tt, 1H).

[0341] Synthesis Example 11: Synthesis of Compound T11

[0342]

[0343] Under a nitrogen atmosphere, intermediate 1 (5.0 g, 10.1 mmol), T11-1 (3.4 g, 10.1 mmol), t-BuONa (1.9 g, 20.2 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.4 g, 1.0 mmol), and tris(dibenzylideneacetone)dipalladium (0.18 g, 0.2 mmol) were placed in a four-necked reaction flask. Then 50 mL of toluene was added, and the mixture was heated to reflux. After the reaction was completed (about 3 h), the reaction solution was cooled to room temperature, 100 mL of water was added, and the mixture was extracted with dichloromethane, concentrated to dryness, and then purified by refluxing and slurrying with a mixed solvent of 30 mL of ethyl acetate and 30 mL of ethanol to obtain 4.3 g of the final product with a yield of 53%.

[0344] LC-MS (APCI): 793.50 [M+H] + .

[0345] 11H NMR (400 MHz, Methylene Chloride-d2) δ 8.33 (d, 1H), 8.26–8.18 (m, 1H), 8.02–7.91 (m, 1H), 7.83–7.67 (m, 4H), 7.54–7.30 (m, 6H), 7.28–7.18 (m, 4H), 7.16–6.86 (m, 11H), 6.85–6.69 (m, 5H), 6.56 (d, 1H), 6.47 (d, 2H).

[0346] Synthesis Example 12: Synthesis of Compound T12

[0347]

[0348] 4-Bromo-N-phenylaniline (12.00 g, 0.0483 mol), 3-biphenylboronic acid (11.49 g, 0.0582 mol) were successively added into a 2 L four-necked flask, followed by potassium carbonate (6.68 g, 0.0725 mol) and bis(triphenylphosphine)palladium(II) dichloride (0.68 g, 0.967 mmol). THF (120 ml) and H2O (30 ml) were added. The reaction was carried out at 75 °C for 15 h under nitrogen protection. After the reaction was completed, the water was separated, and the solvent was evaporated under reduced pressure. The residue was recrystallized from ethyl acetate to obtain T12-1 (9.5 g, 0.0295 mol).

[0349] LC-MS: 322.57 [M+H] + .

[0350]

[0351] T12-1 (4.5 g, 0.014 mol), Intermediate 1 (8.3 g, 0.017 mol), potassium carbonate (2.69 g, 0.028 mol), tris(dibenzylideneacetone)dipalladium(0) (0.13 g, 0.14 mmol) and 2-(dicyclohexylphosphino)-2′,6′-dimethoxybiphenyl (0.23 g, 0.556 mmol) were successively added into a 250 ml four-necked flask. Toluene (100 ml) was added. The reaction was carried out at 95 °C for 16 h under N2 protection. After the reaction was completed, the water was separated, and the solvent was evaporated under reduced pressure. The residue was slurried with ethyl acetate to obtain T12 (3.5 g, 4.48 mmol).

[0352] LC-MS: 781.37 [M+H] +

[0353] 11H NMR (400 MHz, Methylene Chloride-d2) δ 8.54 (dd, 1H), 8.35–8.26 (m, 1H), 7.96–7.87 (m, 1H), 7.81 (dd, 1H), 7.73–7.64 (m, 3H), 7.63–7.54 (m, 3H), 7.52–7.33 (m, 9H), 7.32–7.18 (m, 6H), 7.12–7.02 (m, 3H), 7.01–6.89 (m, 3H), 6.85 (d, 1H), 6.82–6.75 (m, 3H), 6.68–6.60 (m, 2H), 6.53–6.47 (m, 2H), 6.44 (d, 1H).

[0354] Synthesis Example 13: Synthesis of Compound T13

[0355]

[0356] Under nitrogen protection, raw material T13-1 (6 g, 12.3 mmol), aniline (2.2 g, 12.6 mmol), t-BuONa (2.5 g, 24.9 mmol), 2-bis(cyclohexylphosphino)-2',6'-dimethoxybiphenyl (0.4 g, 1.0 mmol) and tris(dibenzylideneacetone)dipalladium (0.18 g, 0.2 mmol) were placed in a four-necked reaction flask, and a total of 60 mL of toluene was added. The temperature was raised to reflux for reaction. After 2 h of reaction, the reaction solution was cooled to room temperature, extracted with dichloromethane, and purified by column chromatography (n-hexane:dichloromethane = 5:1) to obtain 6.2 g with a yield of 88%.

[0357] LC-MS (APCI): 322.30 [M+H] + .

[0358]

[0359] Under nitrogen protection, intermediate T13-2 (5.0 g, 13.2 mmol), intermediate 1 (3.6 g, 13.6 mmol), t-BuONa (2 g, 26 mmol), 2-bis(cyclohexylphosphino)-2',6'-dimethoxybiphenyl (0.4 g, 1.0 mmol) and tris(dibenzylideneacetone)dipalladium (0.18 g, 0.2 mmol) were placed in a four-necked reaction flask, and a total of 50 mL of toluene was added. The temperature was raised to reflux for reaction. After 2 h of reaction, the reaction solution was cooled to room temperature and purified by flash column chromatography with toluene to obtain 6.2 g with a yield of 72%.

[0360] LC-MS (APCI): 779.58 [M+H] +

[0361] 1H NMR (400 MHz, Methylene Chloride-d2) δ 8.55 (dd, 1H), 8.31–8.26 (m, 1H), 7.98–7.92 (m, 1H), 7.83–7.78 (m, 1H), 7.75–7.66 (m, 3H), 7.57–7.48 (m, 2H), 7.36–7.24 (m, 3H), 7.20–7.15 (m, 2H), 7.11–7.00 (m, 8H), 6.96–6.74 (m, 12H), 6.59–6.54 (m, 2H), 6.49 (d, 1H), 6.38 (dd, 1H).

[0362] Synthesis Example 14: Synthesis of Compound T14

[0363]

[0364] Under a nitrogen atmosphere, intermediate 1 (5.0 g, 10.1 mmol), T14-1 (3.0 g, 10.1 mmol), t-BuONa (1.9 g, 20.2 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.4 g, 1.0 mmol) and tris(dibenzylideneacetone) dipalladium (0.18 g, 0.2 mmol) were placed in a four-necked reaction flask, and then 50 mL of toluene was added. The temperature was raised to reflux for reaction. After the reaction was completed (2 h), the reaction solution was cooled to room temperature, 100 mL of water was added, and the mixture was extracted with dichloromethane and concentrated to dryness. Then, it was purified by refluxing and slurrying with 50 mL of ethyl acetate to obtain 4.2 g of the final product with a yield of 55%.

[0365] LC-MS (APCI): 758.49 (M+H+)

[0366] 1H NMR (400 MHz, Methylene Chloride-d2) δ 8.52 (dd, 1H), 8.39–8.26 (m, 1H), 8.02–7.92 (m, 1H), 7.86–7.65 (m, 7H), 7.55–7.39 (m, 4H), 7.38–7.16 (m, 7H), 7.08 (ddd, 1H), 7.03–6.95 (m, 3H), 6.92–6.78 (m, 3H), 6.69–6.56 (m, 2H), 6.50 (d, 1H).

[0367] The following application examples further illustrate the application of the nitrogen-containing fused-ring compound described in the present invention in the preparation of organic electroluminescent elements.

[0368] Application Example 1:

[0369] This example provides an organic electroluminescent element, such asFigure 1 As shown, it includes a substrate 1, an anode 2, a hole injection layer 3, a first hole transport layer 4, a second hole transport layer 5, a light-emitting layer 6, a hole blocking layer 7, an electron transport layer 8, and a cathode 9 that are stacked from bottom to top. The hole injection layer 3, the first hole transport layer 4, and the second hole transport layer 5 are hole transport regions, and the hole blocking layer 7 and the electron transport layer 8 are electron transport regions.

[0370] The specific device structure is as follows:

[0371] ITO / HT1-PD3%(10nm) / HT1(60nm) / HT2(5nm) / BH-BD3%(20nm) /

[0372] HB(5nm) / ET-LiQ50%(30nm) / Mg:Ag 1:9(100nm)

[0373] Device preparation process:

[0374] The bottom-emitting glass substrate 1 used in this embodiment is purchased from Guangdong Trulyst Display Technology Co., Ltd., and ITO is used as the anode 2. First, the bottom-emitting glass substrate is cleaned successively with ITO cleaning agent, deionized water, and isopropyl alcohol, and then the bottom-emitting glass substrate is baked at 180 degrees Celsius for 30 minutes to dry it.

[0375] Then the bottom-emitting glass substrate is placed in the evaporation chamber, and each organic layer is deposited on the ITO anode successively by thermal vacuum evaporation at a rate of 0.2 - 2 Å / s under a vacuum of about 10 -8 Torr. Among them, 3% of PD is doped on HT1 to form a thickness of 10 nm as the hole injection layer 3, HT1 is formed into a thickness of 60 nm as the first hole transport layer 4, HT2 with a thickness of 5 nm is evaporated on HT1 as the second hole transport layer 5, 3% of BD is doped on the anthracene host BH to form a thickness of 20 nm for the blue light-emitting layer 6, HB is formed into a thickness of 5 nm as the hole blocking layer 7, ET doped with 50% Liq is formed into a thickness of 30 nm as the electron transport layer 8, and Mg:Ag(1:9) is formed into a thickness of 100 nm as the cathode 9. Finally, the device is transferred back to the glove box and encapsulated with a glass cover and a moisture absorbent to complete the device, denoted as organic electronic component 1. In this device embodiment, the same layer is co-evaporated with different materials and exists in the layer in a certain volume ratio. For example, 50% of Liq is in a volume ratio of ET 50% and Liq 50%. The compound of the present invention is used after sublimation purification, HPLC: 99.9%.

[0376] The specific structures of the compounds involved are as follows. The synthesis of HT2 can refer to the synthesis methods of Intermediate 2 and Synthesis Example 1. Only replace the initial raw material 2,3-benzo[c]carbazole with carbazole in the steps of Intermediate 2. LC-MS (APCI): 744.59 (M+H + ).

[0377]

[0378] Examples and Comparative Examples

[0379] Use the compound T1 (corresponding to compound X-2-1-56) prepared in Synthesis Example 1 of the present invention to replace HT2 to prepare the second hole transport layer, and fabricate the organic electronic device 2 in the same method.

[0380] Use the compound T2 (corresponding to compound X-2-5-56) prepared in Synthesis Example 2 of the present invention to replace HT2 to prepare the second hole transport layer, and fabricate the organic electronic device 3 in the same method.

[0381] Use the compound T3 (corresponding to compound X-3-1-28) prepared in Synthesis Example 3 of the present invention to replace HT2 to prepare the second hole transport layer, and fabricate the organic electronic device 4 in the same method.

[0382] Use the compound T4 (corresponding to compound X-3-1-277) prepared in Synthesis Example 4 of the present invention to replace HT2 to prepare the second hole transport layer, and fabricate the organic electronic device 5 in the same method.

[0383] Use the compound T5 (corresponding to compound X-3-2-26) prepared in Synthesis Example 5 of the present invention to replace HT2 to prepare the second hole transport layer, and fabricate the organic electronic device 6 in the same method.

[0384] Use the compound T6 (corresponding to compound X-3-1-88) prepared in Synthesis Example 6 of the present invention to replace HT2 to prepare the second hole transport layer, and fabricate the organic electronic device 7 in the same method.

[0385] Use the compound T7 (corresponding to compound X-3-1-283) prepared in Synthesis Example 7 of the present invention to replace HT2 to prepare the second hole transport layer, and fabricate the organic electronic device 8 in the same method.

[0386] Use the compound T8 (corresponding to compound X-3-1-11) prepared in Synthesis Example 8 of the present invention to replace HT2 to prepare the second hole transport layer, and fabricate the organic electronic device 9 in the same method.

[0387] Use the compound T9 (corresponding to compound X-3-1-59) prepared in Synthesis Example 9 of the present invention to replace HT2 to prepare the second hole transport layer, and fabricate the organic electronic device 10 in the same method.

[0388] The compound T10 (corresponding to compound X-2-5-28) prepared in Synthesis Example 10 of the present invention was used to replace HT2 to prepare the second hole transport layer, and the organic electronic device 11 was fabricated in the same manner.

[0389] The compound T11 (corresponding to compound X-3-1-78) prepared in Synthesis Example 11 of the present invention was used to replace HT2 to prepare the second hole transport layer, and the organic electronic device 12 was fabricated in the same manner.

[0390] The compound T12 (corresponding to compound X-3-1-10) prepared in Synthesis Example 12 of the present invention was used to replace HT2 to prepare the second hole transport layer, and the organic electronic device 13 was fabricated in the same manner.

[0391] The compound T13 (corresponding to compound X-3-1-9) prepared in Synthesis Example 13 of the present invention was used to replace HT2 to prepare the second hole transport layer, and the organic electronic device 14 was fabricated in the same manner.

[0392] The compound T14 (partially deuterated X-3-1-28) prepared in Synthesis Example 14 of the present invention was used to replace HT2 to prepare the second hole transport layer, and the organic electronic device 15 was fabricated in the same manner.

[0393] Evaluation of Organic Electroluminescent Devices

[0394] IVL test instrument: F STAR Optical Measurement Systems, model: FS-2000GA4; ambient atmosphere, room temperature.

[0395] The current efficiency was measured at a current density of 15 mA / cm 2 2.

[0396] The driving voltage was measured at a current density of 15 mA / cm 2 2.

[0397]

[0398]

[0399] The organic electroluminescent devices 2-15 prepared from the compounds of the present application and the organic electronic device 1, the compounds with a benzocarbazole structure and a phenylene-dibenzofuran structure have strong hole transport ability, can rapidly transfer holes to the light-emitting layer, and have appropriate energy levels, can confine the carriers in the light-emitting layer, reduce the efficiency decline caused by carrier spillage. The organic electroluminescent devices prepared from the compounds of the present application have lower driving voltages and higher current efficiencies. Therefore, the compounds of the present invention are suitable for preparing high-performance organic electroluminescent devices.

[0400] Those skilled in the art can easily understand that the above are only the preferred embodiments of the present invention and are not used to limit the present invention. Any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. An aromatic amine compound, characterized in that, The compound has the structure shown in formula (1), wherein, Ar3 has the following structure: "----" represents the connection position; A1 is selected from a substituted or unsubstituted C6-C14 aromatic ring, A2 is selected from a substituted or unsubstituted C10-C14 aromatic ring, L5 is selected from a substituted or unsubstituted C6-C60 arylene group, L4 is selected from a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothiophenylene group, L1-L3 are each independently selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, a substituted or unsubstituted C3-C60 heteroarylene group, Ar1 and Ar2 are each independently selected from hydrogen, deuterium, halogen, cyano, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C3-C60 heteroaryl group; In the "substituted or unsubstituted", the substituents during substitution are independently selected from deuterium, halogen, cyano, a C1-C10 alkyl group, a C3-C10 cycloalkyl group, a C1-C10 alkoxy group, a C2-C10 alkenyl group, a C2-C10 alkynyl group, a C6-C60 aryl group, a C3-C60 heteroaryl group, a C6-C60 carbocyclic group, a C3-C60 heterocyclic group, The heteroatoms in the heterocyclic group and heteroaryl group are selected from at least one of N, O, S, Si, P.

2. The arylamine compound according to claim 1, wherein The compound has the structure shown in formula (2), R2 is selected from deuterium, halogen, cyano, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C3-C60 heteroaryl group; b is an integer between 0 and 10; The definitions of L1-L5, Ar1, and Ar2 are the same as those defined in claim 1.

3. An aromatic amine compound according to claim 1, wherein, L5 is selected from a phenylene group, a naphthylene group, a biphenylene group.

4. The arylamine compound according to claim 1, wherein The aromatic amine compound has the structures shown in formula (3)-(8), wherein, R1-R3 are each independently selected from deuterium, halogen, cyano, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C3-C60 heteroaryl group; a is an integer between 0 and 4; b is an integer between 0 and 10; c is an integer between 0 and 6; X is selected from O or S; The definitions of L1, L2, Ar1, and Ar2 are the same as those defined in claim 1.

5. The arylamine compound according to claim 1, wherein The aromatic amine compound has the structures shown in formula (9)-(26), Among them, R1-R3 are each independently selected from deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; a is an integer selected from 0 to 4; b is an integer selected from 0 to 10; c is an integer selected from 0 to 6; X is selected from O or S; The definitions of L1, L2, Ar1, and Ar2 are the same as those defined in claim 1.

6. The arylamine compound according to any one of claims 1-5, wherein Said L1 and L2 are each independently selected from a single bond, substituted or unsubstituted groups as follows:

7. The arylamine compound according to any one of claims 1-5, characterized in that, Said Ar1 and Ar2 are each independently selected from hydrogen, substituted or unsubstituted groups as follows:

8. The aromatic amine compound according to claim 1, wherein Said Ar3-L5-L4-L3- is selected from the following structures: X-m-n is the substituent number represented by Ar3-L5-L4-L3-, and X-m-n represents all substituents represented by X-1-1 to X-1-24, X-2-1 to X-2-24, X-3-1 to X-3-24; 9. An aromatic amine compound according to claim 8, wherein Said -L1-Ar1 and -L2-Ar2 are each independently selected from the following structures:

10. An arylamine compound according to claim 9, characterized in that, Said aromatic amine compound is selected from the following structures: Among them, Ar3-L5-L4-L3-, -L1-Ar1, and -L2-Ar2 are respectively connected to N; When Ar3-L5-L4-L3- is selected from X-1-1, the compound numbers are X-1-1-1 to X-1-1-3655; When Ar3-L5-L4-L3- replaces X-1-1 with X-1-2, the compound numbers are X-1-2-1 to X-1-2-3655; When Ar3-L5-L4-L3- replaces X-1-1 with X-1-3, the compound numbers are X-1-3-1 to X-1-3-3655; When Ar3-L5-L4-L3- replaces X-1-1 with X-1-4, the compound numbers are X-1-4-1 to X-1-4-3655; When Ar3-L5-L4-L3- replaces X-1-1 with X-1-5, the compound numbers are X-1-5-1 to X-1-5-3655; When Ar3-L5-L4-L3- replaces X-1-1 with X-1-6, the compound numbers are X-1-6-1 to X-1-6-3655; When Ar3-L5-L4-L3- replaces X-1-1 with X-1-7, the compound numbers are X-1-7-1 to X-1-7-3655; When Ar3-L5-L4-L3- replaces X-1-1 with X-1-8, the compound numbers are X-1-8-1 to X-1-8-3655; When Ar3-L5-L4-L3- replaces X-1-1 with X-1-9, the compound numbers are X-1-9-1 to X-1-9-3655; When Ar3-L5-L4-L3- replaces X-1-1 with X-1-10, the compound numbers are X-1-10-1 to X-1-10-3655; When X-1-1 is replaced by X-1-11 in Ar3-L5-L4-L3, the compound numbers are X-1-11-1 to X-1-11-3655, When X-1-1 is replaced by X-1-12 in Ar3-L5-L4-L3, the compound numbers are X-1-12-1 to X-1-12-3655, When X-1-1 is replaced by X-1-13 in Ar3-L5-L4-L3, the compound numbers are X-1-13-1 to X-1-13-3655, When X-1-1 is replaced by X-1-14 in Ar3-L5-L4-L3, the compound numbers are X-1-14-1 to X-1-14-3655, When X-1-1 is replaced by X-1-15 in Ar3-L5-L4-L3, the compound numbers are X-1-15-1 to X-1-15-3655, When X-1-1 is replaced by X-1-16 in Ar3-L5-L4-L3, the compound numbers are X-1-16-1 to X-1-16-3655, When X-1-1 is replaced by X-1-17 in Ar3-L5-L4-L3, the compound numbers are X-1-17-1 to X-1-17-3655, When X-1-1 is replaced by X-1-18 in Ar3-L5-L4-L3, the compound numbers are X-1-18-1 to X-1-18-3655, When X-1-1 is replaced by X-1-19 in Ar3-L5-L4-L3, the compound numbers are X-1-19-1 to X-1-19-3655, When X-1-1 is replaced by X-1-20 in Ar3-L5-L4-L3, the compound numbers are X-1-20-1 to X-1-20-3655, When X-1-1 is replaced by X-1-21 in Ar3-L5-L4-L3, the compound numbers are X-1-21-1 to X-1-21-3655, When X-1-1 is replaced by X-1-22 in Ar3-L5-L4-L3, the compound numbers are X-1-22-1 to X-1-22-3655, When X-1-1 is replaced by X-1-23 in Ar3-L5-L4-L3, the compound numbers are X-1-23-1 to X-1-23-3655, When X-1-1 is replaced by X-1-24 in Ar3-L5-L4-L3, the compound numbers are X-1-24-1 to X-1-24-3655, When X-1-1 is replaced by X-2-1 in Ar3-L5-L4-L3, the compound numbers are X-2-1-1 to X-2-1-3655, When X-1-1 is replaced by X-2-2 in Ar3-L5-L4-L3, the compound numbers are X-2-2-1 to X-2-2-3655, When X-1-1 is replaced by X-2-3 in Ar3-L5-L4-L3, the compound numbers are X-2-3-1 to X-2-3-3655, When X-1-1 is replaced by X-2-4 in Ar3-L5-L4-L3, the compound numbers are X-2-4-1 to X-2-4-3655, When X-1-1 is replaced by X-2-5 in Ar3-L5-L4-L3, the compound numbers are X-2-5-1 to X-2-5-3655, When X-1-1 is replaced by X-2-6 in Ar3-L5-L4-L3, the compound numbers are X-2-6-1 to X-2-6-3655, When X-1-1 is replaced by X-2-7 in Ar3-L5-L4-L3, the compound numbers are X-2-7-1 to X-2-7-3655, When X-1-1 is replaced by X-2-8 in Ar3-L5-L4-L3, the compound numbers are X-2-8-1 to X-2-8-3655, When X-1-1 is replaced by X-2-9 in Ar3-L5-L4-L3, the compound numbers are X-2-9-1 to X-2-9-3655, When X-1-1 is replaced by X-2-10 in Ar3-L5-L4-L3, the compound numbers are X-2-10-1 to X-2-10-3655, When X-1-1 is replaced by X-2-11 in Ar3-L5-L4-L3, the compound numbers are X-2-11-1 to X-2-11-3655, When X-1-1 is replaced by X-2-12 in Ar3-L5-L4-L3, the compound numbers are X-2-12-1 to X-2-12-3655, When X-1-1 is replaced by X-2-13 in Ar3-L5-L4-L3, the compound numbers are X-2-13-1 to X-2-13-3655, When X-1-1 is replaced by X-2-14 in Ar3-L5-L4-L3, the compound numbers are X-2-14-1 to X-2-14-3655, When X-1-1 is replaced by X-2-15 in Ar3-L5-L4-L3, the compound numbers are X-2-15-1 to X-2-15-3655, When X-1-1 is replaced by X-2-16 in Ar3-L5-L4-L3, the compound numbers are X-2-16-1 to X-2-16-3655, When X-1-1 is replaced by X-2-17 in Ar3-L5-L4-L3, the compound numbers are X-2-17-1 to X-2-17-3655, When X-1-1 is replaced by X-2-18 in Ar3-L5-L4-L3, the compound numbers are X-2-18-1 to X-2-18-3655, When X-1-1 is replaced by X-2-19 in Ar3-L5-L4-L3, the compound numbers are X-2-19-1 to X-2-19-3655, When X-1-1 is replaced by X-2-20 in Ar3-L5-L4-L3, the compound numbers are X-2-20-1 to X-2-20-3655, When X-1-1 is replaced by X-2-21 in Ar3-L5-L4-L3, the compound numbers are X-2-21-1 to X-2-21-3655, When X-1-1 is replaced by X-2-22 in Ar3-L5-L4-L3, the compound numbers are X-2-22-1 to X-2-22-3655, When X-1-1 is replaced by X-2-23 in Ar3-L5-L4-L3, the compound numbers are X-2-23-1 to X-2-23-3655, When X-1-1 is replaced by X-2-24 in Ar3-L5-L4-L3, the compound numbers are X-2-24-1 to X-2-24-3655, When X-1-1 is replaced by X-3-1 in Ar3-L5-L4-L3, the compound numbers are X-3-1-1 to X-3-1-3655, When X-1-1 is replaced by X-3-2 in Ar3-L5-L4-L3, the compound numbers are X-3-2-1 to X-3-2-3655, When X-1-1 is replaced by X-3-3 in Ar3-L5-L4-L3, the compound numbers are X-3-3-1 to X-3-3-3655, When X-1-1 is replaced by X-3-4 in Ar3-L5-L4-L3, the compound numbers are X-3-4-1 to X-3-4-3655, When X-1-1 is replaced by X-3-5 in Ar3-L5-L4-L3, the compound numbers are X-3-5-1 to X-3-5-3655, When X-1-1 is replaced by X-3-6 in Ar3-L5-L4-L3, the compound numbers are X-3-6-1 to X-3-6-3655, When X-1-1 is replaced by X-3-7 in Ar3-L5-L4-L3, the compound numbers are X-3-7-1 to X-3-7-3655, When X-1-1 is replaced by X-3-8 in Ar3-L5-L4-L3, the compound numbers are X-3-8-1 to X-3-8-3655, When X-1-1 is replaced by X-3-9 in Ar3-L5-L4-L3, the compound numbers are X-3-9-1 to X-3-9-3655, When X-1-1 is replaced by X-3-10 in Ar3-L5-L4-L3, the compound numbers are X-3-10-1 to X-3-10-3655, When X-1-1 is replaced by X-3-11 in Ar3-L5-L4-L3, the compound numbers are X-3-11-1 to X-3-11-3655, When X-1-1 is replaced by X-3-12 in Ar3-L5-L4-L3, the compound numbers are X-3-12-1 to X-3-12-3655, When X-1-1 is replaced by X-3-13 in Ar3-L5-L4-L3, the compound numbers are X-3-13-1 to X-3-13-3655, When X-1-1 is replaced by X-3-14 in Ar3-L5-L4-L3, the compound numbers are X-3-14-1 to X-3-14-3655, When X-1-1 is replaced by X-3-15 in Ar3-L5-L4-L3, the compound numbers are X-3-15-1 to X-3-15-3655, When X-1-1 is replaced by X-3-16 in Ar3-L5-L4-L3, the compound numbers are X-3-16-1 to X-3-16-3655, When X-1-1 is replaced with X-3-17 in Ar3-L5-L4-L3, the compound numbers are X-3-17-1 to X-3-17-3655, When X-1-1 is replaced with X-3-18 in Ar3-L5-L4-L3, the compound numbers are X-3-18-1 to X-3-18-3655, When X-1-1 is replaced with X-3-19 in Ar3-L5-L4-L3, the compound numbers are X-3-19-1 to X-3-19-3655, When X-1-1 is replaced with X-3-20 in Ar3-L5-L4-L3, the compound numbers are X-3-20-1 to X-3-20-3655, When X-1-1 is replaced with X-3-21 in Ar3-L5-L4-L3, the compound numbers are X-3-21-1 to X-3-21-3655, When X-1-1 is replaced with X-3-22 in Ar3-L5-L4-L3, the compound numbers are X-3-22-1 to X-3-22-3655, When X-1-1 is replaced with X-3-23 in Ar3-L5-L4-L3, the compound numbers are X-3-23-1 to X-3-23-3655, When X-1-1 is replaced with X-3-24 in Ar3-L5-L4-L3, the compound numbers are X-3-24-1 to X-3-24-3655.

11. An organic electroluminescent element, comprising a substrate, an anode, a hole transport region, a light-emitting layer, an electron transport region, and a cathode, wherein the light-emitting layer is located between the anode and the cathode, the hole transport region is located between the anode and the light-emitting layer, the electron transport region is located between the light-emitting layer and the cathode, and the hole transport region contains the compound according to any one of claims 1-10; Preferably, the hole transport region includes a first hole transport layer and a second hole transport layer, the second hole transport layer is located between the first hole transport layer and the light-emitting layer, and the second hole transport layer contains the compound according to any one of claims 1-10.

Images