CN115304491A - Hole organic electroluminescent compound and preparation method and application thereof - Google Patents

Hole organic electroluminescent compound and preparation method and application thereof Download PDF

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CN115304491A
CN115304491A CN202211067801.0A CN202211067801A CN115304491A CN 115304491 A CN115304491 A CN 115304491A CN 202211067801 A CN202211067801 A CN 202211067801A CN 115304491 A CN115304491 A CN 115304491A
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subjected
general formula
reaction
organic electroluminescent
hole
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CN115304491B (en
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汪康
贾宇
赵贺
孟范贵
杨冰
王勇壮
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Jilin Optical and Electronic Materials Co Ltd
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The invention discloses a hole organic electroluminescent compound, belongs to the technical field of luminescent materials, has a general structural formula shown in the specification, and provides a hole transport material with indene as a parent nucleus. The indene parent nucleus reduces the symmetry of molecules, increases conformational isomers of the molecules, and inhibits the aggregation of the molecules so as to improve the hole mobility. Meanwhile, the amine unit has lower ionization potential, better electron donating property and higher hole mobility, and the molecular weight is increased, so that the molecules are not easy to crystallize and aggregate, and the material has higher photo-thermal stability. The obtained hole transport material is used for an organic electroluminescent device, and the device with improved luminous efficiency, low driving voltage and longer service life is obtained.

Description

Hole organic electroluminescent compound and preparation method and application thereof
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a hole organic electroluminescent compound and a preparation method and application thereof.
Background
Organic electroluminescent diodes (hereinafter referred to as OLEDs) are important electroluminescent devices, and attract the attention of many researchers due to the advantages of no need of backlight source for active light emission, high luminous efficiency, large visual angle, high response speed, large temperature adaptation range, low energy consumption, lightness, thinness, flexible display and the like, and huge application prospects.
In such an organic light emitting diode, when a voltage is applied between an anode and a cathode, holes from the anode and electrons from the cathode are injected into an organic material layer. The generated excitons generate light having a specific wavelength while migrating to a ground state. It has the following structure: an anode, a cathode, and an organic material layer therebetween. In order to improve efficiency and stability of the organic EL element, the organic material layer includes a plurality of layers having different materials, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer, an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL). Among them, a layer having a function of transporting holes, such as a hole injection layer, a hole transport layer, an electron blocking layer, and the like, can change hole transport efficiency from holes to a light emitting layer, light emitting efficiency, lifetime, and the like, and has a great influence on performance data of an electronic device.
The lifetime of the conventional organic EL device is not ideal, and therefore, how to develop a device having excellent current efficiency, lower driving voltage and long service life is a technical problem that needs to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention provides a hole-type organic electroluminescent compound, a method for preparing the same, and an application of the hole-type organic electroluminescent compound in a device preparation.
In order to achieve the purpose, the invention adopts the following technical scheme:
a hole organic electroluminescent compound has a structural general formula shown in a general formula I:
Figure BDA0003828630460000011
in formula I, X is selected from: a single bond, O, S, siR, se, CR or NR, wherein R is substituted or unsubstituted aryl of C6-C24, or, in NR, R is connected with Cy2 to form an aliphatic ring;
l1 and L2 are respectively and independently selected from C4-C20 aromatic ring or heteroaromatic ring, or C1-C20 alkyl, C1-C20 heteroalkyl, C6-C30 aryl or C6-C30 heteroaryl substituted C4-C20 aromatic ring or heteroaromatic ring, wherein the heteroatom is any one of oxygen, nitrogen and sulfur;
ar1-Ar8 are independently selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C6-C60 heteroaryl, or substituted or unsubstituted C3-C20 cycloalkyl, wherein the heteroatom is any one of oxygen, nitrogen and sulfur;
cy1-Cy2 are independently selected from C4-C30 aromatic ring or heteroaromatic ring, or C1-C20 alkyl, C1-C20 heteroalkyl, C6-C30 aryl or C6-C30 heteroaryl substituted C4-C30 aromatic ring or heteroaromatic ring, wherein the heteroatom is any one of oxygen, nitrogen and sulfur;
n1-n4 represent 0 or 1, and 1. Ltoreq. N1+ n2+ n3+ n 4. Ltoreq.4.
Further, L1 and L2 are independently selected from C4-C10 aromatic ring or heteroaromatic ring, or C1-C10 alkyl, C1-C10 heteroalkyl, C6-C20 aryl or C6-C20 heteroaryl substituted C4-C10 aromatic ring or heteroaromatic ring, wherein the heteroatom is any one of oxygen, nitrogen and sulfur.
Further, ar1 to Ar8 are independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C6-C30 heteroaryl, or substituted or unsubstituted C3-C10 cycloalkyl, wherein the heteroatom is any one of oxygen, nitrogen and sulfur.
Further, the Cy1-Cy2 are independently selected from C4-C6 aromatic ring or heteroaromatic ring, or C1-C10 alkyl, C1-C10 heteroalkyl, C6-C20 aryl or C6-C20 heteroaryl substituted C4-C6 aromatic ring or heteroaromatic ring, wherein the heteroatom is any one of oxygen, nitrogen and sulfur.
Further, n1+ n2+ n3+ n4=1, and the structural general formula of the hole-based organic electroluminescent compound is represented by general formula a-1, general formula a-2, or general formula a-3:
Figure BDA0003828630460000021
or n1+ n2+ n3+ n4=2, and the structural general formula of the hole-based organic electroluminescent compound is represented by general formula b-1, general formula b-2, general formula b-3, or general formula b-4:
Figure BDA0003828630460000022
or n1+ n2+ n3+ n4=3 or 4, and the structural general formula of the hole-based organic electroluminescent compound is represented by general formula c-1, general formula c-2, general formula c-3, or general formula d-1:
Figure BDA0003828630460000031
preferably, the hole-based organic electroluminescent compound is selected from any one of the compounds represented by the following structural formula:
Figure BDA0003828630460000041
Figure BDA0003828630460000051
Figure BDA0003828630460000061
Figure BDA0003828630460000071
Figure BDA0003828630460000081
Figure BDA0003828630460000091
Figure BDA0003828630460000101
Figure BDA0003828630460000111
Figure BDA0003828630460000121
Figure BDA0003828630460000131
Figure BDA0003828630460000141
Figure BDA0003828630460000151
Figure BDA0003828630460000161
Figure BDA0003828630460000171
Figure BDA0003828630460000181
Figure BDA0003828630460000191
Figure BDA0003828630460000201
Figure BDA0003828630460000211
the invention also provides a preparation method of the hole organic electroluminescent compound,
n1+ n2+ n3+ n4=1, comprising the steps of:
the intermediate a1 and the intermediate a2 are subjected to Suzuki reaction to obtain an intermediate a3, the intermediate a3 and the intermediate a4 are subjected to Suzuki reaction to obtain an intermediate a5, the intermediate a5 and a lithium reagent of the intermediate a6 are subjected to Grignard reaction to obtain an intermediate a7, and the intermediate a7 is subjected to dehydrative cyclization reaction to obtain a series of compounds shown in a general formula a-2;
or, the intermediate a1 and the intermediate b1 are subjected to Suzuki reaction to obtain an intermediate b2, the intermediate b2 and the intermediate b3 are subjected to Suzuki reaction to obtain an intermediate b4, the intermediate b4 and a lithium reagent of the intermediate b5 are subjected to Grignard reaction to obtain an intermediate b6, and the intermediate b6 is subjected to dehydrative cyclization reaction to obtain a series of compounds shown in a general formula a-1;
or, the intermediate a1 and the intermediate b1 are subjected to Suzuki reaction to obtain an intermediate b2, the intermediate b2 and the intermediate c1 are subjected to Suzuki reaction to obtain an intermediate c2, the intermediate c2 and a lithium reagent of the intermediate c3 are subjected to Grignard reaction to obtain an intermediate c4, the intermediate c4 is subjected to dehydrative cyclization reaction to obtain an intermediate c5, and the intermediate c5 and the intermediate c6 are subjected to Buhward-Hartvich reaction to obtain a series of compounds shown in a general formula a-3;
the synthetic route is as follows:
Figure BDA0003828630460000212
Figure BDA0003828630460000221
or, n1+ n2+ n3+ n4=2, comprising the steps of:
the intermediate a1 and the intermediate d1 are subjected to Suzuki reaction to obtain an intermediate d2, the intermediate d2 and the intermediate d3 are subjected to Suzuki reaction to obtain an intermediate d4, the intermediate d4 and a lithium reagent of the intermediate d5 are subjected to Grignard reaction to obtain an intermediate d6, and the intermediate d6 is subjected to dehydration cyclization reaction to obtain a series of compounds shown in a general formula b-1;
or the intermediate a1 and the intermediate d1 are subjected to Suzuki reaction to obtain an intermediate d2, the intermediate d2 and the intermediate e1 are subjected to Suzuki reaction to obtain an intermediate e2, the intermediate e2 and a lithium reagent of the intermediate e3 are subjected to Grignard reaction to obtain an intermediate e4, the intermediate e4 is subjected to dehydrative cyclization reaction to obtain a general formula e5, and the intermediate e5 and the intermediate e6 are subjected to Buhward-Hartvich reaction to obtain a series of compounds shown in a general formula b-3;
or, the synthesis process of the series of compounds shown in the general formula b-2 is the same as that of the series of compounds shown in the general formula b-3;
or the intermediate a1 and the intermediate f1 react through suzuki to obtain an intermediate f2, the intermediate f2 and the intermediate g1 react through suzuki to obtain an intermediate g2, the intermediate g2 and a lithium reagent of the intermediate g3 react through Grignard reaction to obtain an intermediate g4, the intermediate g4 reacts through dehydration cyclization reaction to obtain an intermediate g5, the intermediate g5 and the intermediate g6 react through Buhward-Hartvich reaction to obtain an intermediate g7, and the intermediate g7 and the intermediate g8 react through Buhward-Hartvich reaction to obtain a series of compounds shown in a general formula b 4; the synthetic route is as follows:
Figure BDA0003828630460000231
Figure BDA0003828630460000241
or, n1+ n2+ n3+ n4=3 or 4, comprising the steps of:
the intermediate a1 and the intermediate h1 are subjected to Suzuki reaction to obtain an intermediate h2, the intermediate h2 and the intermediate h3 are subjected to Suzuki reaction to obtain an intermediate h4, the intermediate h4 and a lithium reagent of the intermediate h5 are subjected to Grignard reaction to obtain an intermediate h6, the intermediate h6 is subjected to dehydration cyclization reaction to obtain an intermediate h7, and the intermediate h7 and the intermediate h8 are subjected to Buhward-Hart-Vickers reaction to obtain a series of compounds shown in a general formula c-1;
or, the intermediate a1 and the intermediate h1 are subjected to Suzuki reaction to obtain an intermediate h2, the intermediate h2 and the intermediate h3 are subjected to Suzuki reaction to obtain an intermediate h4, the intermediate h4 and a lithium reagent of the intermediate i1 are subjected to Grignard reaction to obtain an intermediate i2, the intermediate i2 is subjected to dehydration cyclization reaction to obtain an intermediate i3, the intermediate i3 and the intermediate i4 are subjected to Buhward-Hartvich reaction and subjected to reaction kinetics regulation to obtain an intermediate i5, and the intermediate i5 and the intermediate i6 are subjected to Buhward-Hartvich reaction to obtain a series of compounds shown in a general formula d-1;
or the synthetic route of the series of compounds shown in the general formula c-2 and the general formula c-3 is the same as that of the general formula d-1;
the synthetic route is as follows:
Figure BDA0003828630460000251
Figure BDA0003828630460000261
the borate compounds such as intermediate a2 and the like in the above synthetic route can be obtained by the reaction of palace Pu Peng with related halides, and can also be obtained by the reaction of Buhward-Hartvich, and related methods are common practice in the industry and are also described in large numbers in the patent publication, so they are not described in detail in this patent.
The invention also provides an application of the hole organic electroluminescent compound or the hole organic electroluminescent compound prepared by the method in preparing an organic electroluminescent device.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a hole transport material with indene as a parent nucleus. The indene parent nucleus reduces the symmetry of molecules, increases conformational isomers of the molecules, and inhibits the aggregation of the molecules so as to improve the hole mobility. Meanwhile, the amine unit has lower ionization potential, better electron donating property and higher hole mobility, and the molecular weight is increased, so that the molecules are not easy to crystallize and aggregate, and the material has higher photo-thermal stability. After the obtained hole transport material is used for an organic electroluminescent device, the device with improved luminous efficiency, low driving voltage and longer service life is obtained.
Drawings
FIG. 1 is a NMR chart of a hole type organic electroluminescent compound of example 1;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of a hole type organic electroluminescent compound in example 2;
FIG. 3 is a NMR hydrogen spectrum of a hole type organic electroluminescent compound of example 3;
FIG. 4 is a NMR hydrogen spectrum of a hole type organic electroluminescent compound of example 4;
FIG. 5 is a NMR hydrogen spectrum of a hole type organic electroluminescent compound of example 5;
FIG. 6 is a NMR hydrogen spectrum of a hole type organic electroluminescent compound of example 6;
FIG. 7 is a NMR hydrogen spectrum of a hole type organic electroluminescent compound of example 7;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Figure BDA0003828630460000271
Intermediate a1 (62 mmol), intermediate b1 (68 mmol), and K 2 CO 3 (123 mmol) was added to a three-necked flask, THF 100mL and purified water 50mL were added, ventilation was carried out three times, and Pd (PPh) was added 3 ) 4 ( 0.6 mmol), heating to 85 ℃, stirring 2h, cooling to room temperature, separating, collecting the organic phase, drying with anhydrous sodium sulfate, stirring with silica gel, spin-drying, and performing column chromatography (DCM: PE =1: 3) Intermediate c1 (14.17 g, yield: 95%) )
Intermediate c1 (58 mmol), intermediate d1 (64 mmol), cs 2 CO 3 (116 mmol) was added to a three-necked flask, 150mL of anhydrous dioxane was added, ventilation was carried out three times, and Pd was added 2 (dba) 3 (0.6 mmol) and X-PhOS (3 mmol), heating to 120 deg.C and stirring for 10h, cooling to room temperature, adding purified water, stirring for 30min, separating, collecting organic phase, adding DCM into aqueous phase and extracting three times, combining organic phases, adding anhydrous sodium sulfate, drying, spin-drying, and performing column chromatography (DCM: PE = 1:1) to obtain intermediate e1 (31.76 g, yield: 91%).
Adding the intermediate f1 (58 mmol) into a three-neck flask, adding 100mL of anhydrous tetrahydrofuran, cooling to-78 ℃, dropwise adding butyl lithium (58 mmol), stirring for 2h, adding the intermediate e1 (53 mmol), heating to room temperature, and stirring for 10h. Adding diluted hydrochloric acid, stirring for 30min, separating, collecting organic phase, extracting water phase with ethyl acetate for 3 times, combining organic phases, drying with anhydrous sodium sulfate, and performing column chromatography (DCM: PE = 1:1) to obtain intermediate g1 (34.85 g, yield: 87%).
Adding the intermediate g1 (46 mmol) into a single-neck bottle, adding DCM 100mL, adding MSA (231 mmol), stirring at room temperature for 2h, adding water, stirring for 30min, separating, collecting an organic phase, extracting an aqueous phase with DCM for 3 times, combining the organic phases, drying with anhydrous sodium sulfate, and performing column chromatography to obtain the target molecule M1 (27.49 g, yield: 81%). 1 H NMR(400MHz，)δ 7.63(m，8H)，7.52(m，20H)，7.34(m，5H)，7.27(m，6H).
Example 2
Figure BDA0003828630460000281
Intermediate a2 (41 mmol), intermediate b2 (45 mmol), and K 2 CO 3 (82 mmol) was added to a three-necked flask, THF 100mL and purified water 50mL were added, the mixture was ventilated three times, and Pd (PPh) was added 3 ) 4 (0.4 mmol), warmed to 85 ℃, stirred for 2h, cooled to room temperature, separated, collected organic phase, dried over anhydrous sodium sulfate, stirred with silica gel, spin-dried and column chromatographed (DCM: PE =1: 3) to give intermediate c2 (19.98 g, yield: 87%).
Intermediate c2 (36 mmol), intermediate d2 (39 mmol), cs 2 CO 3 (71 mmol) was added to a three-necked flask, 100mL of anhydrous dioxane was added, ventilation was carried out three times, and Pd was added 2 (dba) 3 (0.35 mmol) and X-PhOS (0.71 mmol), heating to 120 deg.C and stirring for 10h, cooling to room temperature, adding purified water, stirring for 30min, separating, collecting organic phase, adding DCM into water phase and extracting three times, combining organic phases, adding anhydrous sodium sulfate, drying by spin drying, and performing column chromatography (DCM: PE = 1:1) to obtain intermediate e2 (18.04 g, yield: 83%).
Adding the intermediate f2 (33 mmol) into a three-neck flask, adding 100mL of anhydrous tetrahydrofuran, cooling to-78 ℃, dropwise adding butyl lithium (32.8 mmol), stirring for 2h, adding the intermediate e2 (30 mmol), heating to room temperature, and stirring for 10h. Diluted hydrochloric acid was added, stirred for 30min, separated, the organic phase was collected, the aqueous phase was extracted 3 times with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, and column chromatography (DCM: PE = 1:1) gave intermediate g2 (20.12 g, yield: 88.5%).
Adding the intermediate g2 (26 mmol) into a single-neck bottle, adding 100mL of DCM, adding MSA (132 mmol), stirring at room temperature for 2h, adding water, stirring for 30min, separating, collecting an organic phase, extracting an aqueous phase with DCM for 3 times, combining the organic phases, drying with anhydrous sodium sulfate, and carrying out column chromatography to obtain the target molecule M11 (14.81 g, yield: 77%). 1 HNMR(400MHz，)δ: 9.00(s，2H)，8.92(s，1H)，7.59(m，7H)，7.51(d，8H)，7.47(m，5H)，7.43(d，2H)，7.38(d， 4H)，7.28(m，5H)，7.23(s，1H)，7.20(d，2H).
Example 3
Figure BDA0003828630460000291
Will be inIntermediate a3 (41 mmol), intermediate b3 (45 mmol), and K 2 CO 3 (82 mmol) was added to a three-necked flask, THF 100mL and purified water 50mL were added, purging was carried out three times, and Pd (PPh) was added 3 ) 4 Heating to 85 ℃, stirring for 2h, cooling to room temperature, separating liquid, collecting organic phase, drying with anhydrous sodium sulfate, stirring with silica gel, spin-drying, and performing column chromatography (DCM: PE = 1:3) to obtain intermediate c3 (21.90 g, yield: 89%)
Intermediate c3 (37 mmol), intermediate d3 (40 mmol), cs 2 CO 3 (73 mmol) was added to a three-necked flask, 100mL of anhydrous dioxane was added, ventilation was carried out three times, and Pd was added 2 (dba) 3 (0.4 mmol) and X-PhOS (0.7 mmol), heating to 120 deg.C and stirring for 10h, cooling to room temperature, adding purified water, stirring for 30min, separating, collecting organic phase, adding DCM to the aqueous phase for extraction three times, combining the organic phases, adding anhydrous sodium sulfate for drying, spin-drying, and performing column chromatography (DCM: PE = 1:1) to obtain intermediate e3 (21.20 g, yield: 89%).
Adding the intermediate f3 (36 mmol) into a three-neck flask, adding 100mL of anhydrous tetrahydrofuran, cooling to-78 ℃, dropwise adding butyl lithium (36 mmol), stirring for 2h, adding the intermediate e3 (33 mmol), heating to room temperature, and stirring for 10h. Diluted hydrochloric acid was added, stirred for 30min, separated, the organic phase collected, the aqueous phase extracted 3 times with ethyl acetate, the organic phases combined, dried over anhydrous sodium sulfate, and column chromatographed (DCM: PE = 1:1) to give intermediate g3 (20.20 g, yield: 69%).
Adding the intermediate g3 (23 mmol) into a single-neck bottle, adding 100mL of DCM, adding MSA (113 mmol), stirring at room temperature for 2h, adding water, stirring for 30min, separating, collecting an organic phase, extracting an aqueous phase with DCM for 3 times, combining the organic phases, drying with anhydrous sodium sulfate, and carrying out column chromatography to obtain the target molecule M226 (16.19 g, 81% yield). 1 H NMR(400MHz，)δ 9.01(s，2H)，8.92(s，1H)，8.12(d，1H)，7.90(d，1H)，7.83(d，1H)，7.76(d，2H)，7.73(d， 1H)，7.69(d，1H)，7.64(d，2H)，7.59(d，2H)，7.55(d，1H)，7.49(d，3H)，7.46(m，6H)， 7.42(d，2H)，7.38(m，5H)，7.34(d，1H)，7.30(d，2H)，7.25(m，3H)，7.06(d，1H)，1.61(s， 3H)，1.56(s，3H).
Example 4
Figure BDA0003828630460000301
Intermediate a4 (41 mmol), intermediate b4 (45 mmol), and K 2 CO 3 (82 mmol) was added to a three-necked flask, THF 100mL and purified water 50mL were added, the mixture was ventilated three times, and Pd (PPh) was added 3 ) 4 ( 0.4 mmol), warming to 85 ℃, stirring for 2h, cooling to room temperature, separating, collecting the organic phase, drying over anhydrous sodium sulfate, stirring with silica gel, spin-drying, and performing column chromatography (DCM: PE =1: 3) Intermediate c4 (8.98 g, yield: 91%) )
Intermediate c4 (37 mmol), intermediate d4 (41 mmol), cs 2 CO 3 (74 mmol) was added to a three-necked flask, 100mL of anhydrous dioxane was added, ventilation was carried out three times, and Pd was added 2 (dba) 3 (0.37 mmol) and X-PhOS (0.74 mmol), heating to 120 ℃ and stirring for 10h, cooling to room temperature, adding purified water, stirring for 30min, separating, collecting the organic phase, adding DCM to the aqueous phase and extracting three times, combining the organic phases, adding anhydrous sodium sulfate, drying by spin drying, and performing column chromatography (DCM: PE = 1:1) to obtain intermediate e4 (10.88, yield: 88.5%).
Adding the intermediate f4 (33 mmol) into a three-neck flask, adding 100mL of anhydrous tetrahydrofuran, cooling to-78 ℃, dropwise adding butyl lithium (33 mmol), stirring for 2h, adding the intermediate e4 (30 mmol), heating to room temperature, and stirring for 10h. Diluted hydrochloric acid was added, stirred for 30min, separated, the organic phase was collected, the aqueous phase was extracted 3 times with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, and column chromatography (DCM: PE = 1:1) gave intermediate g4 (11.95, yield: 76.5%).
Adding the intermediate g4 (23 mmol) into a single-neck bottle, adding DCM 100mL, adding MSA (115 mmol), stirring at room temperature for 2h, adding water, stirring for 30min, separating, collecting an organic phase, extracting an aqueous phase with DCM for 3 times, combining the organic phases, drying with anhydrous sodium sulfate, and performing column chromatography to obtain an intermediate h4 (9.95, yield: 86%).
Adding the intermediate h4 (20 mmol), the intermediate i4 (22 mmol) and t-BuONa (40 mmol) into a three-neck flask, adding 100mL of anhydrous toluene, ventilating for three times, and adding Pd 2 (dba) 3 (0.2mmol)，P(t-Bu) 3 (0.2 mmol), the temperature is raised to 110 ℃ and stirring is carried out for 10h. Cooling to room temperature, adding purified water, stirring for 30min, separating, collecting organic phase, extracting water phase with ethyl acetate for 3 times, mixing organic phases, drying with anhydrous sodium sulfate, and subjecting to column chromatography to obtain target molecule M32 (14.07, yield: 85%). 1 HNMR (400MHz，)δ:8.00(s，1H)，7.94(d，1H)，7.91(d，1H)，7.87(d，1H)，7.76(d，1H)，7.72(m， 3H)，7.58(m，4H)，7.54(s，5H)，7.51(d，2H)，7.48(m，5H)，7.38(m，8H)，7.30(d，1H)， 7.29(d，2H)，7.25(s，1H)，7.23(t，1H)，7.17(d，1H)，7.13(d，1H)，1.62(s，3H)，1.57(s， 3H).
Example 5
Figure BDA0003828630460000311
Intermediate a5 (41 mmol), intermediate b5 (45 mmol), and K 2 CO 3 (82 mmol) was added to a three-necked flask, THF 100mL and purified water 50mL were added, the mixture was ventilated three times, and Pd (PPh) was added 3 ) 4 ( 0.4 mmol), warmed to 85 ℃, stirred for 2h, cooled to room temperature, separated, collected organic phase, dried over anhydrous sodium sulfate, stirred with silica gel, spin-dried, and column chromatographed (DCM: PE =1: 3) Intermediate c5 (19.06 g, yield: 83%) )
Intermediate c5 (34 mmol), intermediate d5 (37 mmol), cs 2 CO 3 (68 mmol) is added into a three-neck flask, 100mL of anhydrous dioxane is added, air exchange is carried out for three times, and Pd is added 2 (dba) 3 (0.34 mmol) and X-PhOS (0.68 mmol), heating to 120 deg.C and stirring for 10h, cooling to room temperature, adding purified water, stirring for 30min, separating, collecting organic phase, adding DCM to the aqueous phase for extraction three times, combining the organic phases, adding anhydrous sodium sulfate for drying, spin-drying, and performing column chromatography (DCM: PE = 1:1) to obtain intermediate e5 (28.10 g, yield: 86%).
Adding the intermediate f5 (32 mmol) into a three-neck flask, adding 100mL of anhydrous tetrahydrofuran, cooling to-78 ℃, dropwise adding butyl lithium (32 mmol), stirring for 2h, adding the intermediate e5 (28 mmol), heating to room temperature, and stirring for 10h. Diluted hydrochloric acid was added, stirred for 30min, separated, the organic phase collected, the aqueous phase extracted 3 times with ethyl acetate, the organic phases combined, dried over anhydrous sodium sulfate, and column chromatographed (DCM: PE = 1:1) to give intermediate g5 (24.05 g, yield: 77%).
Adding the intermediate g5 (22 mmol) into a single-neck bottle, adding 100mL of DCM, adding MSA (110 mmol), stirring at room temperature for 2h, adding water, stirring for 30min, separating, collecting an organic phase, extracting an aqueous phase with DCM for 3 times, combining the organic phases, drying with anhydrous sodium sulfate, and carrying out column chromatography to obtain the target molecule M245 (17.6 g, yield: 73%). 1 HNMR(400MHz，)δ: 8.42(d，2H)，7.76(m，3H)，7.66(d，3H)，7.61(m，12H)，7.52(d，3H)，7.47(t，2H)，7.46(m， 6H)，7.42(s，2H)，7.39(m，9H)，7.30(d，4H)，7.23(s，2H)，7.22(s，1H)，7.07(d，1H)， 7.05(d，4H)，1.46(s，6H).
Example 6
Figure BDA0003828630460000321
Intermediate a6 (41 mmol), intermediate b6 (45 mmol), and K 2 CO 3 (82 mmol) was added to a three-necked flask, THF 100mL and purified water 50mL were added, the mixture was ventilated three times, and Pd (PPh) was added 3 ) 4 (0.4 mmol), warmed to 85 ℃, stirred for 2h, cooled to room temperature, separated, the organic phase collected, dried over anhydrous sodium sulfate, stirred with silica gel, spin-dried and column chromatographed (DCM: PE =1: 3) to give intermediate c6 (8.98 g, yield: 91%).
Intermediate c6 (37 mmol), intermediate d6 (41 mmol), cs 2 CO 3 (74 mmol) was added to a three-necked flask, 100mL of anhydrous dioxane was added, ventilation was carried out three times, and Pd was added 2 (dba) 3 (0.37 mmol) and X-PhOS (0.75 mmol), heating to 120 deg.C and stirring for 10h, cooling to room temperature, adding purified water, stirring for 30min, separating, collecting organic phase, adding DCM to the aqueous phase for extraction three times, combining the organic phases, adding anhydrous sodium sulfate for drying, spin-drying, and performing column chromatography (DCM: PE = 1:1) to obtain intermediate e6 (17.81 g, yield: 80%).
Adding the intermediate f6 (33 mmol) into a three-neck flask, adding 100mL of anhydrous tetrahydrofuran, cooling to-78 ℃, dropwise adding butyl lithium (33 mmol), stirring for 2h, adding the intermediate e6 (30 mmol), heating to room temperature, and stirring for 10h. Diluted hydrochloric acid was added, stirred for 30min, separated, the organic phase collected, the aqueous phase extracted 3 times with ethyl acetate, the organic phases combined, dried over anhydrous sodium sulfate, and column chromatographed (DCM: PE = 1:1) to give intermediate g6 (19.92 g, yield: 84%).
Adding the intermediate g6 (25 mmol) into a single-neck bottle, adding 100mL of DCM, adding MSA (127 mmol), stirring at room temperature for 2h, adding water, stirring for 30min, separating, collecting an organic phase, extracting an aqueous phase with DCM for 3 times, combining the organic phases, drying with anhydrous sodium sulfate, and carrying out column chromatography to obtain an intermediate h6 (15.83 g, yield: 82%).
Adding the intermediate h6 (20 mmol), the intermediate i6 (22 mmol) and t-BuONa40mmol into a three-necked flask, adding 100mL of anhydrous toluene, ventilating for three times, and adding Pd 2 (dba) 3 (0.20mmol)，P(t-Bu) 3 (0.40 mmol), the temperature is raised to 110 ℃ and stirring is carried out for 10h. Cooling to room temperature, adding purified water, stirring for 30min, separating, collecting organic phase, extracting water phase with ethyl acetate for 3 times, mixing organic phases, drying with anhydrous sodium sulfate, and subjecting to column chromatography to obtain target molecule M242 (14.48 g, yield: 66%). 1 HNMR (400MHz，)δ8.19(d，4H)，8.05(d，4H)，7.70(m，4H)，7.66(m，3H)，7.59(m，7H)，7.54(m，3H)，7.46(d，4H)，7.43(d，6H)，7.39(m，2H)，7.37(m，4H)，7.35(d，3H)，7.31(d，1H)， 7.27(t，4H)，7.20(d，2H)，7.15(s，1H)，7.07(d，1H)，6.97(d，1H)，1.61(s，3H)，1.56(s， 3H).
Example 7
Figure BDA0003828630460000331
Intermediate a7 (41 mmol), intermediate b7 (45 mmol), and K 2 CO 3 (82 mmol) was added to a three-necked flask, THF 100mL and purified water 50mL were added, purging was carried out three times, and Pd (PPh) was added 3 ) 4 (0.4 mmol), warmed to 85 ℃, stirred for 2h, cooled to room temperature, separated, the organic phase collected, dried over anhydrous sodium sulfate, stirred with silica gel, spin-dried and column chromatographed (DCM: PE =1: 3) to give intermediate c7 (8.98 g, yield: 91%).
Intermediate c7 (37 mmol), intermediateBody d7 (41 mmol), cs 2 CO 3 (74 mmol) was added to a three-necked flask, 100mL of anhydrous dioxane was added, ventilation was carried out three times, and Pd was added 2 (dba) 3 (0.37 mmol) and X-PhOS (0.74 mmol), heating to 120 deg.C and stirring for 10h, cooling to room temperature, adding purified water, stirring for 30min, separating, collecting organic phase, adding DCM to the aqueous phase for extraction three times, combining the organic phases, adding anhydrous sodium sulfate for drying, spin-drying, and performing column chromatography (DCM: PE = 1:1) to obtain intermediate e7 (8.87 g, yield: 85%).
Adding the intermediate f7 (35 mmol) into a three-neck flask, adding 100mL of anhydrous tetrahydrofuran, cooling to-78 ℃, dropwise adding butyl lithium, stirring for 2h, adding the intermediate e7 (31 mmol), heating to room temperature, and stirring for 10h. Diluted hydrochloric acid was added, stirred for 30min, and the organic phase was collected by liquid separation, the aqueous phase was extracted 3 times with ethyl acetate, the organic phases were combined, dried over anhydrous sodium sulfate, and column chromatographed (DCM: PE = 1:1) to give intermediate g7 (12.53yield.
Adding the intermediate g7 (24 mmol) into a single-neck bottle, adding 100mL of DCM, adding MSA (119 mmol), stirring at room temperature for 2h, adding water, stirring for 30min, separating, collecting an organic phase, extracting an aqueous phase with DCM for 3 times, combining the organic phases, drying over anhydrous sodium sulfate, and carrying out column chromatography to obtain an intermediate h7 (9.81 g, yield: 84%).
Adding the intermediate h7 (20 mmol), the intermediate i7 (22 mmol) and t-BuONa (40 mmol) into a three-necked flask, adding 100mL of anhydrous toluene, ventilating for three times, and adding Pd 2 (dba) 3 (0.2mmol)，P(t-Bu) 3 (0.2 mmol), the temperature is raised to 110 ℃ and stirring is carried out for 10h. Cooling to room temperature, adding purified water, stirring for 30min, separating, collecting organic phase, extracting water phase with ethyl acetate for 3 times, combining organic phases, drying with anhydrous sodium sulfate, and performing column chromatography to obtain intermediate j7 (yield: 88%).
Adding the intermediate j7 (17 mmol), the intermediate k7 (19 mmol) and t-BuONa into a three-necked flask, adding 100mL of anhydrous toluene, ventilating for three times, and adding Pd 2 (dba) 3 (0.2mmol)，P(t-Bu) 3 (0.2 mmol), the temperature is raised to 110 ℃ and stirring is carried out for 10h. Cooling to room temperature, adding purified water, stirring for 30min, separating, collecting organic phase, extracting water phase with ethyl acetate for 3 times, mixing organic phases, drying with anhydrous sodium sulfate, and performing column chromatography to obtain the final productThe target molecule M242 (14.38g, yield. 1 HNMR(400 MHz，)δ:8.69(d，2H)，8.67(m，1H)，8.26(d，2H)，7.95(d，1H)，7.91(m，3H)，7.86(d， 2H)，7.81(d，1H)，7.59(m，6H)，7.55(d，1H)，7.54(m，4H)，7.45(m，8H)，7.39(m，8H)， 7.33(d，1H)，7.30(m，2H)，7.23(s，1H)，7.19(m，2H)，7.13(d，5H)，7.04(d，4H).
The synthesis methods of other compounds are the same as the above examples, which are not repeated herein, and the mass spectra and molecular formulas and yields of other synthesis examples are shown in table 1 below:
TABLE 1
Compound (I) Molecular formula Calculated mass spectrum Mass spectrometric test values Yield (%)
Compound M3 C57H39N 737.95 737.69 80.5
Compound M7 C63H45N3 844.07 844.22 65.94
Compound M14 C61H41N3 816.02 816.34 61.08
Compound M19 C55H37N3 739.92 739.76 80.49
Compound M25 C63H43N 814.04 814.22 79.72
Compound M30 C64H45N 828.07 828.26 58.83
Compound M36 C62H47N 806.07 806.18 74.88
Compound M38 C62H47N 806.07 805.87 66.38
Compound M40 C66H47N 854.11 854.33 73.61
Compound M44 C64H45N3 856.09 856.28 62.38
Compound M50 C61H45N 792.04 791.91 71.75
Compound M57 C65H46N2 855.10 855.33 67.1
Compound M64 C62H41NO 816.02 816.19 70.86
Compound M70 C63H41NO 828.03 827.79 71.78
Compound M75 C62H40N2O 829.02 829.26 80.09
Compound M85 C63H41NO 828.03 828.15 57.6
Compound M96 C62H47N 806.07 806.24 72.71
Compound M105 C65H46N2 855.10 855.43 72.95
Compound M113 C63H51NSi 850.19 850.34 58.31
Compound M120 C67H49N 868.14 868.37 74.47
Compound M130 C66H47NO 870.11 869.26 58.37
Compound M146 C66H47NO 870.11 870.28 73.84
Compound M155 C61H51N 834.12 834.36 73.4
Compound M163 C61H47N3 822.07 822.18 62.04
Compound M177 C68H52N2 897.18 897.39 66.53
Compound M186 C68H52N2 897.18 896.92 80.93
Compound M201 C66H48N2 869.12 869.35 68
Compound M210 C75H52N2 981.28 981.06 70.6
Device example 1: production of organic electroluminescent devices containing Compound M1
a. An ITO anode: washing an ITO (indium tin oxide) -Ag-ITO (indium tin oxide) glass substrate with the coating thickness of 150nm in distilled water for 2 times, ultrasonically washing for 30min, repeatedly washing for 2 times by using distilled water, ultrasonically washing for 10min, transferring to a spin dryer for spin-drying after washing is finished, baking for 2 hours at 220 ℃ by using a vacuum oven, and cooling after baking is finished. And (3) taking the substrate as an anode, performing a device evaporation process by using an evaporation machine, and sequentially evaporating other functional layers on the substrate.
b. HIL (hole injection layer): to be provided with
Figure BDA0003828630460000351
The chemical formulas of compounds M1 and P-dopant provided in the above examples were as follows. The evaporation rate ratio of the compounds M1 and P-dopant of the above example was 97: 3, the thickness is 10nm;
c. HTL (hole transport layer): to be provided with
Figure BDA0003828630460000352
The compound M1 provided in the above example, which was 130nm, was vacuum-deposited on the hole injection layer as a hole transport layer.
d. A light-emitting auxiliary layer: to be provided with
Figure BDA0003828630460000353
The evaporation rate of (2), and performing vacuum evaporation on the hole transport layer to form 10nm EBL-1 as a light-emitting auxiliary layer;
e. EML (light-emitting layer): then on the above-mentioned luminescence auxiliary layer so as to
Figure BDA0003828630460000354
The chemical formulae of Host and Dopant (span) are shown below, where Host and Dopant (span) materials with a thickness of 20nm are vacuum-deposited as the light-emitting layer. Wherein the evaporation rate ratio of Host to Dopantt is 98:2.
f. HBL (hole blocking layer): to be provided with
Figure BDA0003828630460000355
The evaporation rate of (2) is that 5nm of HB-1 is evaporated on the luminescent layer in vacuum to be used as a hole blocking layer, and the structure is shown as the following figure:
g. ETL (electron transport layer): to be provided with
Figure BDA0003828630460000356
And (3) vacuum evaporating ET-1 on the hole blocking layer to form an electron transport layer.
h. EIL (electron injection layer): to be provided with
Figure BDA0003828630460000357
The evaporation rate of (2) and the evaporation of the Yb film layer is 1.0nm to form the electron injection layer.
i. Cathode: to be provided with
Figure BDA0003828630460000358
The evaporation rate ratio of (1) is that the evaporation rate ratio of magnesium to silver is 18nm, and is 1:9, so that the OLED device is obtained.
j. Light extraction layer: to be provided with
Figure BDA0003828630460000359
CPL-1 was vacuum-deposited on the cathode at a thickness of 70nm to form a light extraction layer. And then packaging the evaporated substrate. Firstly, coating the cleaned cover plate by using UV glue through gluing equipment, then moving the coated cover plate to a pressing working section, placing the evaporated substrate on the upper end of the cover plate, finally, attaching the substrate and the cover plate under the action of attaching equipment, and simultaneously, finishing the illumination and solidification of the UV glue.
The structural formula of the used material is shown as follows:
Figure BDA0003828630460000361
device example 2-device example 35 with reference to the above-mentioned method, compounds M1 used in device example 1 were replaced with compounds M11, M226, M32, M245, M242, M3, M7, M14, M19, M25, M30, M36, M38, M40, M44, M50, M57, M64, M70, M75, M85, M96, M105, M113, M120, M130, M146, M155, M163, M177, M186, M201, M210, respectively, as hole transport layers, to prepare corresponding organic electroluminescent devices.
Device control example 1: this comparative example provides an organic electroluminescent device, and the only difference between the method of fabricating the organic electroluminescent device and device example 1 is that the organic electroluminescent device was fabricated by vapor deposition using the existing comparative compounds a, b, c, d, respectively, instead of the hole transport layer (compound M1) in device example 1 above, and device comparative examples 1 to 4 were fabricated. Wherein the chemical structural formulas of the comparative compounds a, b, c and d are as follows:
Figure BDA0003828630460000371
the organic electroluminescent devices obtained in the above device examples 1 to 35 and the device comparative examples 1 to 4 were characterized for driving voltage, luminous efficiency, BI value and lifetime at a luminance of 1000 (nits), and the test results are as follows in table 2:
TABLE 2
Figure BDA0003828630460000372
Figure BDA0003828630460000381
Figure BDA0003828630460000391
From the above table, it can be seen that: compared with an organic electroluminescent device prepared by taking a comparative compound as a hole transport layer, the organic electroluminescent device prepared by taking the organic electroluminescent compound provided by the invention as the hole transport layer has lower starting voltage, and the luminous efficiency and the service life are obviously improved.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (7)

1. A hole organic electroluminescent compound is characterized in that the structural general formula of the hole organic electroluminescent compound is shown as a general formula I:
Figure FDA0003828630450000011
in formula I, X is selected from: the compound is a single bond, O, S, siR, se, CR or NR, wherein R is substituted or unsubstituted C6-C24 aryl, or R in NR is connected with Cy2 to form an aliphatic ring;
l1 and L2 are respectively and independently selected from C4-C20 aromatic ring or heteroaromatic ring, or C1-C20 alkyl, C1-C20 heteroalkyl, C6-C30 aryl or C6-C30 heteroaryl substituted C4-C20 aromatic ring or heteroaromatic ring, wherein the heteroatom is any one of oxygen, nitrogen and sulfur;
ar1-Ar8 are independently selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C6-C60 heteroaryl, or substituted or unsubstituted C3-C20 cycloalkyl, wherein the heteroatom is any one of oxygen, nitrogen and sulfur;
cy1-Cy2 are independently selected from C4-C30 aromatic ring or heteroaromatic ring, or C1-C20 alkyl, C1-C20 heteroalkyl, C6-C30 aryl or C6-C30 heteroaryl substituted C4-C30 aromatic ring or heteroaromatic ring, wherein the heteroatom is any one of oxygen, nitrogen and sulfur;
n1-n4 represent 0 or 1, and 1. Ltoreq. N1+ n2+ n3+ n 4. Ltoreq.4.
2. The hole-type organic electroluminescent compound according to claim 1, wherein L1 and L2 are independently selected from C4-C10 aromatic ring or heteroaromatic ring, or C1-C10 alkyl, C1-C10 heteroalkyl, C6-C20 aryl or C6-C20 heteroaryl substituted C4-C10 aromatic ring or heteroaromatic ring, wherein the heteroatom is any one of oxygen, nitrogen and sulfur.
3. The hole-based organic electroluminescent compound according to claim 1, wherein Ar1-Ar8 are independently selected from a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C6-C30 heteroaryl group, or a substituted or unsubstituted C3-C10 cycloalkyl group, wherein the heteroatom is any one of oxygen, nitrogen, and sulfur.
4. The hole-type organic electroluminescent compound according to claim 1, wherein each of Cy1-Cy2 is independently selected from a C4-C6 aromatic ring or heteroaromatic ring, or a C4-C6 aromatic ring or heteroaromatic ring substituted by a C1-C10 alkyl group, a C1-C10 heteroalkyl group, a C6-C20 aryl group or a C6-C20 heteroaryl group, wherein the heteroatom is any one of oxygen, nitrogen and sulfur.
5. The hole-based organic electroluminescent compound according to claim 1, wherein n1+ n2+ n3+ n4=1 is represented by the general formula a-1, the general formula a-2 or the general formula a-3:
Figure FDA0003828630450000021
or n1+ n2+ n3+ n4=2, and the structural general formula of the hole organic electroluminescent compound is shown as a general formula b-1, a general formula b-2, a general formula b-3 or a general formula b-4:
Figure FDA0003828630450000022
or n1+ n2+ n3+ n4=3 or 4, and the structural general formula of the hole organic electroluminescent compound is shown as a general formula c-1, a general formula c-2, a general formula c-3 or a general formula d-1:
Figure FDA0003828630450000023
6. a method for producing the hole-type organic electroluminescent compound according to claim 5,
n1+ n2+ n3+ n4=1, comprising the steps of:
the intermediate a1 and the intermediate a2 are subjected to Suzuki reaction to obtain an intermediate a3, the intermediate a3 and the intermediate a4 are subjected to Suzuki reaction to obtain an intermediate a5, the intermediate a5 and a lithium reagent of the intermediate a6 are subjected to Grignard reaction to obtain an intermediate a7, and the intermediate a7 is subjected to dehydrative cyclization reaction to obtain a series of compounds shown in a general formula a-2;
or the intermediate a1 and the intermediate b1 are subjected to Suzuki reaction to obtain an intermediate b2, the intermediate b2 and the intermediate b3 are subjected to Suzuki reaction to obtain an intermediate b4, the intermediate b4 and a lithium reagent of the intermediate b5 are subjected to Grignard reaction to obtain an intermediate b6, and the intermediate b6 is subjected to dehydration cyclization reaction to obtain a series of compounds shown in a general formula a-1;
or, the intermediate a1 and the intermediate b1 are subjected to Suzuki reaction to obtain an intermediate b2, the intermediate b2 and the intermediate c1 are subjected to Suzuki reaction to obtain an intermediate c2, the intermediate c2 and a lithium reagent of the intermediate c3 are subjected to Grignard reaction to obtain an intermediate c4, the intermediate c4 is subjected to dehydrative cyclization reaction to obtain an intermediate c5, and the intermediate c5 and the intermediate c6 are subjected to Buhward-Hartvich reaction to obtain a series of compounds shown in a general formula a-3;
the synthesis route is as follows:
Figure FDA0003828630450000031
Figure FDA0003828630450000041
or, n1+ n2+ n3+ n4=2, comprising the steps of:
the intermediate a1 and the intermediate d1 are subjected to Suzuki reaction to obtain an intermediate d2, the intermediate d2 and the intermediate d3 are subjected to Suzuki reaction to obtain an intermediate d4, the intermediate d4 and a lithium reagent of the intermediate d5 are subjected to Grignard reaction to obtain an intermediate d6, and the intermediate d6 is subjected to dehydrative cyclization reaction to obtain a series of compounds shown in a general formula b-1;
or the intermediate a1 and the intermediate d1 are subjected to Suzuki reaction to obtain an intermediate d2, the intermediate d2 and the intermediate e1 are subjected to Suzuki reaction to obtain an intermediate e2, the intermediate e2 and a lithium reagent of the intermediate e3 are subjected to Grignard reaction to obtain an intermediate e4, the intermediate e4 is subjected to dehydrative cyclization reaction to obtain a general formula e5, and the intermediate e5 and the intermediate e6 are subjected to Buhward-Hartvich reaction to obtain a series of compounds shown in a general formula b-3;
or, the synthesis process of the series of compounds shown in the general formula b-2 is the same as that of the series of compounds shown in the general formula b-3;
or, the intermediate a1 and the intermediate f1 are subjected to Suzuki reaction to obtain an intermediate f2, the intermediate f2 and the intermediate g1 are subjected to Suzuki reaction to obtain an intermediate g2, the intermediate g2 and a lithium reagent of the intermediate g3 are subjected to Grignard reaction to obtain an intermediate g4, the intermediate g4 is subjected to dehydrative cyclization reaction to obtain an intermediate g5, the intermediate g5 and the intermediate g6 are subjected to Buhward-Hartvich reaction to obtain an intermediate g7, and the intermediate g7 and the intermediate g8 are subjected to Buhward-Hartvich reaction to obtain a series of compounds shown in a general formula b 4;
the synthetic route is as follows:
Figure FDA0003828630450000051
Figure FDA0003828630450000061
or, n1+ n2+ n3+ n4=3 or 4, comprising the steps of:
the intermediate a1 and the intermediate h1 are subjected to Suzuki reaction to obtain an intermediate h2, the intermediate h2 and the intermediate h3 are subjected to Suzuki reaction to obtain an intermediate h4, the intermediate h4 and a lithium reagent of the intermediate h5 are subjected to Grignard reaction to obtain an intermediate h6, the intermediate h6 is subjected to dehydration cyclization reaction to obtain an intermediate h7, and the intermediate h7 and the intermediate h8 are subjected to Buchwald-Hartvich reaction to obtain a series of compounds shown in a general formula c-1;
or the intermediate a1 and the intermediate h1 react through Suzuki reaction to obtain an intermediate h2, the intermediate h2 and the intermediate h3 react to obtain an intermediate h4, the intermediate h4 and a lithium reagent of the intermediate i1 react through Grignard reaction to obtain an intermediate i2, the intermediate i2 undergoes dehydration cyclization reaction to obtain an intermediate i3, the intermediate i3 and the intermediate i4 undergo Buhward-Hartdivig reaction and reaction kinetics regulation to obtain an intermediate i5, and the intermediate i5 and the intermediate i6 undergo Buhward-Hartdivig reaction to obtain a series of compounds shown in a general formula d-1;
or the synthetic route of the series of compounds shown in the general formula c-2 and the general formula c-3 is the same as that of the general formula d-1;
the synthesis route is as follows:
Figure FDA0003828630450000062
Figure FDA0003828630450000071
Figure FDA0003828630450000081
7. use of the hole-based organic electroluminescent compound according to any one of claims 1 to 5 or the hole-based organic electroluminescent compound prepared by the method of claim 6 for the preparation of an organic electroluminescent device.
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CN112480115A (en) * 2020-11-30 2021-03-12 吉林奥来德光电材料股份有限公司 Organic electroluminescent compound containing nitrogen heterocycle and preparation method and application thereof
CN113307770A (en) * 2021-05-21 2021-08-27 吉林奥来德光电材料股份有限公司 Luminescent auxiliary material and preparation method and application thereof
CN114716330A (en) * 2022-04-27 2022-07-08 吉林奥来德光电材料股份有限公司 Luminescent auxiliary material, preparation method and application thereof

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CN112480115A (en) * 2020-11-30 2021-03-12 吉林奥来德光电材料股份有限公司 Organic electroluminescent compound containing nitrogen heterocycle and preparation method and application thereof
CN113307770A (en) * 2021-05-21 2021-08-27 吉林奥来德光电材料股份有限公司 Luminescent auxiliary material and preparation method and application thereof
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