CN113801066B - Imidazole derivatives and uses thereof - Google Patents

Imidazole derivatives and uses thereof Download PDF

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CN113801066B
CN113801066B CN202010864440.7A CN202010864440A CN113801066B CN 113801066 B CN113801066 B CN 113801066B CN 202010864440 A CN202010864440 A CN 202010864440A CN 113801066 B CN113801066 B CN 113801066B
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朱波
姜坤
谢佩
程友文
边坤
李程辉
孙建波
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Beijing Bayi Space LCD Technology Co Ltd
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Abstract

The invention relates to the technical field of organic electroluminescent materials, in particular to an imidazole derivative shown in a formula I and application thereof. The imidazole derivative shown in the formula I increases pi-pi conjugate strength of an imidazole ring, improves thermal stability of a material and capability of transporting electrons, and an organic electroluminescent device prepared by using the material can obviously reduce starting voltage and improve luminous efficiency and brightness.
Figure DDA0002649260240000011

Description

Imidazole derivatives and uses thereof
Technical Field
The invention relates to the technical field of organic electroluminescent materials, in particular to an imidazole derivative and application thereof.
Background
In general, an organic light emitting phenomenon refers to a phenomenon that emits light when electric energy is applied to an organic substance. That is, when an organic layer is disposed between an anode and a cathode, if a voltage is applied between the two electrodes, holes are injected from the anode to the organic layer, and electrons are injected from the cathode to the organic layer. When the injected holes and electrons meet, excitons are formed, and when the excitons transition to a ground state, light and heat are emitted.
As a method for effectively manufacturing an organic electroluminescent element, a study has been made to replace an organic layer in a single-layer manufacturing element with a multilayer structure, and in 1987, a multilayer structure of a functional layer of a hole layer and a light-emitting layer has been proposed, and most of the organic electroluminescent elements currently used include: the light emitting device includes a substrate, an anode, a hole injection layer that receives holes from the anode, a hole transport layer that transports holes, a light emitting layer that emits light by recombination of holes and electrons, an electron transport layer that transports electrons, an electron injection layer that receives electrons from a cathode, and a cathode. The reason why the organic electroluminescent device is fabricated in a plurality of layers is that since the movement speeds of holes and electrons are different, if a hole injection layer and a transport layer, an electron transport layer and an electron injection layer are fabricated appropriately, holes and electrons can be efficiently transported, balance between holes and electrons can be achieved in the device, and the exciton utilization ratio can be improved.
As an earliest report on an electron transport material, an oxadiazole derivative is given. The triazole derivative and the phenanthroline derivative were then reported to exhibit electron transport properties. As an organic single-molecule substance, a substance applicable to an electron transport layer has been reported as a good candidate substance for an organometallic complex having relatively excellent electron stability and electron movement speed, and Liq having excellent stability and large electron affinity has been the most excellent substance, and is also the most basic substance used at present.
As materials that can be used for the electron injection layer and the transport layer in the past, many organic single-molecule materials having an imidazole group, an oxazole group, a thiazole group, and a spirofluorene group have been reported. For example, in CN103833507B, CN107573328B, CN107556310B published by the chinese patent office and TPBI described in U.S. Pat. No. 5,645,948 issued to kodak corporation in 1996, which is an electron transport layer material having an imidazolyl group, three N-phenylbenzimidazolyl groups are contained at the 1,3,5 substitution positions of benzene, and the structure thereof has a function of blocking holes crossing over from the light emitting layer as well as an ability to transport electrons, but there are problems that the thermal stability is low and the driving voltage is high when the device is actually used.
In order to overcome the above-described problems of the conventional techniques and to further improve the characteristics of the organic electroluminescent element, there is a continuing need for the development of a more stable and effective substance that can be used as an electron injection and transport substance in the organic electroluminescent element.
Disclosure of Invention
The invention aims to provide an imidazole derivative.
Another object of the present invention is to provide an organic electroluminescent material comprising the above imidazole derivative.
It is still another object of the present invention to provide an organic electroluminescent device, and an application of the above imidazole derivative in the preparation of an organic electroluminescent device.
In order to achieve the above purpose, the invention adopts the following technical scheme:
an imidazole derivative has a structural formula shown in a formula I:
Figure BDA0002649260220000021
wherein:
R 1 、R 2 each independently selected from one or more of the same or different hydrogen, deuterium, halogen, substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aromatic vinyl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, substituted or unsubstituted C 6 -C 60 Arylamine groups, or substituted or unsubstituted C 2 -C 60 A heterocyclic aryl group;
Ar 1 is a single bond, substituted or unsubstituted C 6 -C 60 Arylene of (2), or substituted or unsubstituted C 2 -C 60 Is a heteroarylene group;
Ar 2 、Ar 3 、Ar 4 each independently selected from substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Condensed ring aryl, or substituted or unsubstituted C 2 -C 60 Heteroaryl, wherein Ar 4 It may be hydrogen, deuterium, fluorine or nitrile groups in addition to the above groups;
wherein two or more adjacent R' s 1 、R 2 、Ar 1 、Ar 2 、Ar 3 Or Ar 4 Optionally forming one or more additional substituted or unsubstituted rings with or without one or more heteroatoms N, P, B, O or S in the formed rings;
n represents an integer of 1 to 5;
x is C or N.
In the present specification, in a substituted or unsubstituted ring formed by bonding adjacent groups to each other, "ring" means a substituted or unsubstituted hydrocarbon ring, or a substituted or unsubstituted heterocyclic ring.
Preferably, in the imidazole derivative, R 1 、R 2 、Ar 2 、Ar 3 、Ar 4 Radicals (C)Any one or more of the C 2 -C 60 The heterocyclic aryl groups independently contain one or more heteroatoms N, O or S in the ring structure.
Preferably, in the imidazole derivative, R 1 、R 2 、Ar 2 、Ar 3 、Ar 4 Any one or more of the substituted or unsubstituted C's in the radical 2 -C 60 The heterocyclic aryl is independently selected from one or more of the following groups II-1 to II-17:
Figure BDA0002649260220000031
wherein, the liquid crystal display device comprises a liquid crystal display device,
Z 1 、Z 2 、Z 3 each independently selected from hydrogen, deuterium, halogen, hydroxy, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, C 1 -C 60 Alkyl, C 2 -C 60 Alkenyl, C 2 -C 60 Alkynyl, C 1 -C 60 Alkoxy, C 3 -C 60 Naphthene radical, C 3 -C 60 Cycloalkenyl radicals, C 6 -C 60 Aryl, C containing at least one-F, -CN or C1-C10 alkyl group 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Aryl sulfide group, or substituted or unsubstituted C 2 -C 60 A heterocyclic aryl group;
x1 represents an integer of 1 to 4; x2 represents an integer of 1 to 3; x3 represents 1 or 2; x4 represents an integer of 1 to 6; x5 represents an integer of 1 to 5;
T 1 represents an oxygen atom or a sulfur atom;
Figure BDA0002649260220000032
represents the bond between the substituent and the main structure.
Preferably, in the imidazole derivative, ar is 1 Any one or more of the groups shown in the following III-1 to III-15:
Figure BDA0002649260220000041
wherein, the liquid crystal display device comprises a liquid crystal display device,
Z 11 and Z 12 Each independently selected from hydrogen, deuterium hydrogen, halogen, hydroxy, nitrile, nitro, amino, amidino, hydrazine, hydrazone, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, C 1 -C 60 Alkyl, C 2 -C 60 Alkenyl, C 2 -C 60 Alkynyl, C 1 -C 60 Alkoxy, C 3 -C 60 Naphthene radical, C 3 -C 60 Cycloalkenyl radicals, C 6 -C 60 Aryl radicals containing at least one-F, -CN or C 1 -C 10 C of alkyl groups 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Aryl sulfide group, or substituted or unsubstituted C 2 -C 60 A heterocyclic aryl group;
Z 13 represents substituted or unsubstituted C 6 -C 60 Aryl, substituted or unsubstituted C 6 -C 60 Aryloxy, substituted or unsubstituted C 6 -C 60 Aryl sulfide group, or substituted or unsubstituted C 2 -C 60 A heterocyclic aryl group;
y1 represents an integer of 1 to 4; y2 represents an integer of 1 to 6; y3 represents an integer of 1 to 3; y4 represents an integer of 1 to 5;
t2 represents an oxygen atom or a sulfur atom;
Figure BDA0002649260220000042
represents the bond between the substituent and the main structure.
In the present specification, the term "substituted or unsubstituted" means that the compound is selected from the group consisting of hydrogen, deuterium, halogen atom, hydroxyl group, nitrile group, nitro group, amino group, amidino group,Hydrazino, hydrazone, carboxyl or carboxylate thereof, sulfonic acid or sulfonate thereof, phosphoric acid or phosphate thereof, C 1 -C 60 Alkyl, C 2 -C 60 Alkenyl, C 2 -C 60 Alkynyl, C 1 -C 60 Alkoxy, C 3 -C 60 Cycloalkyl, C 3 -C 60 Cycloalkenyl, C 6 -C 60 Aryl, C 6 -C 60 Aryloxy, C 6 -C 60 Aryl sulfide group and C 2 -C 60 More than 1 substituent in the heterocyclic aryl group is substituted or unsubstituted, or a substituent which is formed by connecting more than 2 substituents in the above exemplified substituents is substituted or unsubstituted.
Preferably, the imidazole derivative has a structural formula of any one of the following CJH-P01 to CJH-P136:
Figure BDA0002649260220000051
Figure BDA0002649260220000061
Figure BDA0002649260220000071
Figure BDA0002649260220000081
Figure BDA0002649260220000091
Figure BDA0002649260220000101
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Figure BDA0002649260220000111
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Figure BDA0002649260220000121
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Figure BDA0002649260220000131
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Figure BDA0002649260220000141
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Figure BDA0002649260220000151
the invention also provides a material, the raw material of which comprises the imidazole derivative organic electroluminescent material, and preferably the material is an organic electroluminescent material. Materials comprising the imidazole derivatives of the invention have the ability to transport carriers.
The invention also provides an organic electroluminescent device comprising a first electrode, a second electrode and more than one organic layer arranged between the first electrode and the second electrode; the material of at least one of the organic layers comprises the imidazole derivative described above.
The organic electroluminescent device comprises a cathode, an anode and at least one light emitting layer. In addition to these layers, it may also comprise further layers, for example in each case one or more hole-injection layers, hole-transport layers, hole-blocking layers, electron-transport layers, electron-injection layers, exciton-blocking layers, electron-blocking layers and/or charge-generating layers. An intermediate layer having, for example, an exciton blocking function can likewise be introduced between the two light-emitting layers. It should be noted, however, that not every one of these layers need be present. The organic electroluminescent device described herein may comprise one light emitting layer, or it may comprise a plurality of light emitting layers. That is, a plurality of light-emitting compounds capable of emitting light are used in the light-emitting layer. Particularly preferred is a system with three light-emitting layers, wherein the three layers can display blue, green and red light emission. If more than one light-emitting layer is present, at least one of these layers comprises a compound of the invention according to the invention.
Further, the organic electroluminescent device according to the present invention does not comprise a separate hole injection layer and/or hole transport layer and/or hole blocking layer and/or electron transport layer, i.e. the light emitting layer is directly adjacent to the hole injection layer or anode and/or the light emitting layer is directly adjacent to the electron transport layer or electron injection layer or cathode.
In the other layers of the organic electroluminescent device according to the invention, in particular in the hole injection and hole transport layers and in the electron injection and electron transport layers, all materials can be used in the manner generally used according to the prior art. A person of ordinary skill in the art will thus be able to use all materials known in relation to organic electroluminescent elements in combination with the light-emitting layer according to the invention without inventive effort.
Furthermore, an organic electroluminescent device is preferred, which is characterized in that one or more layers are applied by means of a sublimation method, wherein the sublimation is performed in a vacuum at a temperature below 10 -5 Pa, preferably below 10 -6 The material is applied by vapor deposition at an initial pressure of Pa. However, the initial pressure may also be even lower, for example below 10 -7 Pa。
Preference is likewise given to organic electroluminescent devices which are characterized in that one or more layers are applied by means of an organic vapor deposition method or by means of carrier gas sublimation, where at 10 -5 The material is applied at a pressure between Pa and 1 Pa. A particular example of this method is an organic vapor jet printing method, wherein the material is applied directly through a nozzle and is thus structured.
Furthermore, organic electroluminescent devices are preferred in which one or more layers are produced from a solution, for example by spin coating, or by means of any desired printing method, for example screen printing, flexography, lithography, photoinitiated thermal imaging, thermal transfer, inkjet printing or nozzle printing. Soluble compounds, for example, are obtained by appropriate substitution. These methods are also particularly suitable for oligomers, dendrimers and polymers. Furthermore, a hybrid method is possible, in which one or more layers are applied, for example from a solution, and one or more further layers are applied by vapor deposition.
These methods are generally known to those of ordinary skill in the art and they can be applied to organic electroluminescent devices comprising the compounds according to the present invention without inventive effort.
The invention therefore also relates to a method for manufacturing an organic electroluminescent device according to the invention, characterized in that at least one layer is applied by means of a sublimation method, and/or in that at least one layer is applied by means of an organic vapour deposition method or by means of carrier gas sublimation, and/or in that at least one layer is applied from solution by spin coating or by means of a printing method.
Furthermore, the present invention relates to an imidazole derivative comprising at least one of the above indicated invention. The same preferences as indicated above in relation to the organic electroluminescent device apply to the imidazole derivatives of the invention. In particular, the imidazole derivatives may furthermore preferably comprise further compounds. Treatment of the imidazole derivatives according to the invention from the liquid phase, for example by spin coating or by printing methods, requires formulations of the compounds according to the invention. These formulations may be, for example, solutions, dispersions or emulsions. For this purpose, it may be preferable to use a mixture of two or more solvents. Suitable and preferred solvents are, for example, toluene, anisole, o-, m-or p-xylene, methyl benzoate, mesitylene, tetralin, o-dimethoxybenzene, tetrahydrofuran, methyltetrahydrofuran, tetrahydropyran, chlorobenzene, dioxane, phenoxytoluene, in particular 3-phenoxytoluene, (-) -fenchyl ketone, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, 1-methylnaphthalene, 2-methylbenzothiazole, 2-phenoxyethanol, 2-pyrrolidone, 3-methylanisole, 4-methylanisole, 3, 4-dimethylbenzene, 3, 5-dimethylbenzene, acetophenone, alpha-terpineol, benzothiazole, butyl benzoate, cumene, cyclohexanol, cyclohexanone, cyclohexylbenzene, decalin, dodecylbenzene, ethyl benzoate, indane, methyl benzoate, 1-methylpyrrolidone, p-cymene, phenetole, 1, 4-diisopropylbenzene, dibenzyl ether, diethylene glycol butyl methyl ether, triethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, diethylene glycol monobutyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 2-isopropylnaphthalene, pentylbenzene, hexylbenzene, heptylbenzene, octylbenzene, 1-bis (3, 4-dimethylphenyl) ethane, or mixtures of these solvents.
Preferably, in the above organic electroluminescent device, the organic layer includes a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, a light refracting layer, an electron transport layer, an electron injection layer, or an electron blocking layer.
The invention also provides application of the imidazole derivative in preparing an organic electroluminescent device.
In addition, unless otherwise specified, all raw materials used in the present invention are commercially available, and any ranges recited in the present invention include any numerical value between the end values and any sub-range constituted by any numerical value between the end values or any numerical value between the end values.
The beneficial effects obtained by the invention are as follows:
the imidazole derivative shown in the formula I increases pi-pi conjugate strength of an imidazole ring, improves thermal stability of a material and capability of transporting electrons, and an organic electroluminescent device prepared by using the material can obviously reduce starting voltage and improve luminous efficiency and brightness.
Drawings
Fig. 1 is a schematic structural diagram of a bottom emission organic electroluminescent device according to embodiment 12 of the present invention, in which a 1-substrate, a 2-anode layer, a 3-hole injection layer, a 4-hole transport layer, a 5-organic light emitting layer, a 6-electron transport layer, a 7-electron injection layer, and an 8-cathode layer are provided.
Fig. 2 is a schematic structural diagram of a top emission organic electroluminescent device according to embodiment 13 of the present invention, in which 1-substrate, 2-anode layer, 3-hole injection layer, 4-electron blocking layer, 5-organic light emitting layer, 6-hole blocking layer, 7-electron injection layer, 8-cathode layer.
Detailed Description
The present invention is described in further detail below with reference to specific examples, but is not intended to limit the scope of the present invention.
In the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more; the orientation or positional relationship indicated by the terms "upper", "lower", etc. are based on the orientation or positional relationship shown in the drawings, are merely for convenience of description and to simplify the description, and are not indicative or implying that the apparatus or elements in question must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The experimental materials and related equipment used in the examples below, unless otherwise specified, are all commercially available, and the percentages, such as the percentages without otherwise specified, are all mass percentages.
The test instrument and method for testing the performance of the OLED material and the device in the following embodiments are as follows:
OLED device performance detection conditions:
luminance and chromaticity coordinates: photoresearch PR-715 was tested using a spectrum scanner;
current density and lighting voltage: testing using a digital source table Keithley 2420;
power efficiency: NEWPORT 1931-C test was used.
Example 1
The preparation method of the compound CJH-P55 comprises the following steps:
the first step: preparation of intermediate Int-1
Figure BDA0002649260220000181
54.5mmol of N-phenyl benzamidine SM-1, 54.5mmol of chalcone, 1.5g of anhydrous ferric chloride, 1.2g of iodine, 80ml of dichlorobenzene, oxygen and stirring for reaction for 8 hours at the temperature of 110 ℃ are added, cooling to room temperature, filtering, washing a filter cake with petroleum ether, and recrystallizing with ethanol to obtain yellow solid Int-1, wherein the yield is 81%.
And a second step of: preparation of intermediate Int-2
Figure BDA0002649260220000182
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109.4mmol of methoxymethyl triphenyl phosphorus chloride is dispersed in 500mL of anhydrous tetrahydrofuran, the temperature is reduced to minus 78 ℃ by liquid nitrogen under the protection of nitrogen, 12.3g (109.4 mmol) of potassium tert-butoxide is added in batches, the temperature is reduced to minus 78 ℃ after stirring reaction is carried out for 30 minutes at room temperature, 91.2mmol of raw material Int-1 is added dropwise in solution in tetrahydrofuran, after the addition, the reaction is carried out for 1 hour by heat preservation and stirring, the reaction is carried out overnight at room temperature, 150mL of saturated ammonium chloride aqueous solution is added, the ethyl acetate is used for extraction, the organic phase is dried, filtered, concentrated to dryness at reduced pressure, and the yellow solid is obtained after separation and purification by a silica gel column, the yield: 65%.
And a third step of: preparation of intermediate Int-3
Figure BDA0002649260220000183
20.0mmol of intermediate Int-2 is dissolved in 160mL of acetone and 40mL of water, 25mL of 48% hydrobromic acid aqueous solution is added for stirring reaction for 24 hours, ethyl acetate is used for extraction, an organic phase is dried and filtered, filtrate is concentrated to dryness under reduced pressure, silica gel is used for separation and purification, ethanol is used for recrystallization, and yellow solid Int-3 is obtained with the yield of 94%.
Fourth step: preparation of intermediate Int-4
Figure BDA0002649260220000191
18.0mmol of intermediate Int-3 is dissolved in 80mL of acetonitrile, 2.7mmol of N-hydroxyphthalimide is added, oxygen is introduced, the temperature is raised to 80 ℃ and the mixture is stirred for reaction for 24 hours, the mixture is cooled to room temperature and concentrated to dryness under reduced pressure, and a brown solid Int-4 is obtained by separation and purification by a silica gel column, wherein the yield is 92%.
Fifth step: preparation of intermediate Int-5
Figure BDA0002649260220000192
15.0mmol of intermediate Int-4 is dissolved in 100mL of dichloromethane, 15.0mL of trifluoromethanesulfonic acid is added, the mixture is heated, refluxed and stirred for reaction for 24 hours, cooled to room temperature, concentrated to dryness under reduced pressure, added with ice water and stirred for 1 hour, filtered, the filter cake is washed with water, separated and purified by a silica gel column, and recrystallized by ethanol to obtain yellow solid Int-5 with the yield of 77 percent.
Sixth step: preparation of Compound CJH-P55
Figure BDA0002649260220000193
12.0mmol of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine is dissolved in 80mL of dry tetrahydrofuran, the temperature is reduced to minus 78 ℃ by liquid nitrogen under the protection of nitrogen, 4.8mL of 2.5M butyl lithium n-hexane solution is added dropwise, stirring reaction is carried out for 1 hour, 10.0mmol of intermediate Int-5 is added dropwise in the solution of dry tetrahydrofuran, stirring reaction is carried out for 1 hour at room temperature, 20mL of concentrated hydrochloric acid is added dropwise, stirring reaction is carried out for 1 hour, extraction is carried out by ethyl acetate, the organic phase is collected, drying, filtration and concentration drying under reduced pressure are carried out, separation and purification are carried out by using a silica gel column, and then, the product CJH-P55 is obtained by recrystallization by using dichloromethane/ethanol, and the yield is 92%. MS (MALDI-TOF): m/z 628.2519[ M+H ] +;1HNMR (delta, CDCl 3): 8.82 (1H, s); 8.34 to 8.31 (4H, m); 8.11 to 8.09 (1H, m); 7.98 to 7.91 (4H, m); 7.85 to 7.78 (2H, m); 7.68 to 7.56 (3H, m); 7.49 to 7.24 (14H, m).
Example 2
Referring to the synthesis method of example 1, the following compounds were prepared, namely, the steps of the method were the same as those of example 1 except that according to the desired product, N-phenylbenzamidine in the first step of example 1 was replaced with a different compound according to actual needs, 2-chloro-4, 6-diphenyl-1, 3, 5-triazine in the fourth step of example 1 was replaced, and the mass amounts of the compounds were changed according to the molar amounts to prepare the compounds numbered CJH-P24, CJH-P25, CJH-P27, CJH-P40 to CJH-P42, CJH-P46, CJH-P48, CJH-P53, CJH-P54, CJH-P56 to CJH-P61, CJH-P113, CJH-P116 to CJH-P118.
Example 3
The preparation of the compound CJH-P03 comprises the following steps:
the first step: preparation of intermediate Int-6
Figure BDA0002649260220000201
Synthetic procedure referring to the first step of example 1, the substitution of SM-1 for SM-3 in the first step of example 1 produced intermediate Int-6 as a yellow solid in 88% yield.
And a second step of: preparation of intermediate Int-7
Figure BDA0002649260220000202
Synthesis procedure referring to the second step of example 1, intermediate Int-7 was prepared in 62% yield as yellow solid by substituting intermediate Int-1 of the second step of example 1 with intermediate Int-6.
And a third step of: preparation of intermediate Int-8
Figure BDA0002649260220000203
Synthesis procedure referring to the third step of example 1, intermediate Int-8 was prepared in 97% yield as yellow solid by substituting intermediate Int-2 of the third step of example 1 with intermediate Int-7.
Fourth step: preparation of intermediate Int-9
Figure BDA0002649260220000211
Synthesis procedure referring to the fourth step of example 1, intermediate Int-9 was prepared as a yellow solid in 90% yield by substituting intermediate Int-3 of the fourth step of example 1 with intermediate Int-8.
Fifth step: preparation of intermediate Int-10
Figure BDA0002649260220000212
Synthesis procedure with reference to the fifth step of example 1, intermediate Int-10 was prepared in 82% yield as yellow solid by substituting intermediate Int-4 of the fifth step of example 1 with intermediate Int-9.
Sixth step: preparation of intermediate Int-11
Figure BDA0002649260220000213
Synthesis procedure referring to the sixth step of example 1, intermediate Int-11 was prepared in 87% yield as yellow solid by substituting intermediate Int-5 of the sixth step of example 1 with intermediate Int-10.
Seventh step: preparation of Compound CJH-P03
Figure BDA0002649260220000214
9.5mmol of (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) boric acid, 8.6mmol of Int-11, 3.7g (34.9 mmol) of sodium carbonate and 5mg of Pd (PPh 3) 4 as catalyst are added, 40mL of toluene and 10mL of ethanol and 5mL of water are added, the mixture is heated, refluxed and stirred for reaction for 12 hours, cooled to room temperature, extracted with ethyl acetate, the organic phase is dried, filtered, the filtrate is concentrated under reduced pressure to dryness, separated and purified by a silica gel column, heated to boiling with ethanol and filtered while hot, to obtain 4.9g of a product CJH-P03, and the yield is 73%. MS (MALDI-TOF): m/z 781.3097[ M+H ] +;1HNMR (delta, CDCl 3): 9.11 (1H, s); 8.81 to 8.78 (4H, m); 8.61 to 8.59 (1H, m); 8.39 to 8.27 (4H, m); 8.06-7.87 (10H, m); 7.78 to 7.74 (2H, m); 7.69 to 7.61 (7H, m); 7.42 to 7.27 (7H, m).
Example 4
Referring to the synthetic method of example 3, the following compounds were prepared, namely, the method steps were the same as example 3 except that according to the desired product, different compounds were used instead of N-phenylbenzamidine in the first step of example 3, according to actual needs, instead of (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) boric acid in the seventh step of example 3, and the mass amounts of the compounds were changed according to the molar amounts, to prepare the compounds having the numbers CJH-P01, CJH-P02, CJH-P04-CJH-P23, CJH-P26, CJH-P28-CJH-P31, CJH-P33-CJH-P39, CJH-P43-CJH-P45, CJH-P47, CJH-P49-CJH-P52, CJH-P62-CJH-P112, CJH-P114, CJH-P115, CJH-P119, CJH-P120.
Example 5
The preparation of the compound CJH-P32 comprises the following steps:
the first step: preparation of intermediate Int-12
Figure BDA0002649260220000221
Synthesis procedure referring to the sixth step of example 1, intermediate Int-12 was prepared in 85% yield as yellow solid by substituting intermediate Int-5 of the sixth step of example 1 with intermediate Int-10.
And a second step of: preparation of intermediate Int-13
Figure BDA0002649260220000222
15.0mmol of intermediate Int-12 is dissolved in 80mL of dry tetrahydrofuran, the temperature is reduced to minus 78 ℃ by liquid nitrogen under the protection of nitrogen, 7.2mL of 2.5M butyl lithium n-hexane solution is added dropwise, the mixture is stirred and reacted for 1 hour, 18.0mmol of diphenyl phosphorus chloride solution dissolved in the dry tetrahydrofuran is added dropwise, the mixture is stirred and reacted for 1 hour at room temperature, 20mL of saturated ammonium chloride aqueous solution is added dropwise, the mixture is stirred and reacted for 1 hour, ethyl acetate is used for extraction, an organic phase is collected, the organic phase is dried and filtered, the filtrate is concentrated to dryness under reduced pressure, and the white solid Int-13 is obtained by separating and purifying by a silica gel column, and the yield is 82%.
And a third step of: preparation of Compound CJH-P32
Figure BDA0002649260220000231
10.0mmol of intermediate Int-13 is dissolved in 60mL of dichloromethane, 5mL of 35% hydrogen peroxide is added, the temperature is raised, the reflux and the stirring are carried out for 12 hours, the reaction is cooled to room temperature, the water washing is carried out, the organic phase is further washed by saturated sodium bisulfite aqueous solution, the water washing is carried out, the organic phase is dried, the filtration is carried out, the filtrate is concentrated to dryness under reduced pressure, the separation and the purification are carried out by a silica gel column, the ethyl acetate is further heated to boiling, the filtration is carried out while the product CJH-P32 is hot, and the yield is 93%. MS (MALDI-TOF): m/z 828.2906[ M+H ] +;1HNMR (delta, CDCl 3): 8.81 to 8.78 (4H, m); 8.46 to 8.41 (3H, m); 8.09-8.07 (2H, m); 7.94-7.90 (2H, m); 7.76 to 7.65 (9H, m); 7.57 to 7.32 (18H, m).
Example 6
The preparation of the compound CJH-P126 comprises the following steps:
the first step: preparation of intermediate Int-14
Figure BDA0002649260220000232
122.0mg of anhydrous ferric trichloride and 480.0mg of anhydrous methanol are added into 80mL of 1, 2-dichloroethane under the protection of nitrogen, the mixture is stirred and reacted for 30 minutes at room temperature, 15.0mmol of intermediate Int-7 prepared in the second step of example 3 is added, the temperature is raised to 80 ℃, the mixture is stirred and reacted for 8 hours, the mixture is concentrated to dryness under reduced pressure, and the mixture is separated and purified by a silica gel column to obtain intermediate Int-14, wherein the yield is 82%.
And a second step of: preparation of Compound CJH-P126
Figure BDA0002649260220000233
10.0mmol of (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) boric acid, 8.3mmol of Int-14, 3.5g (33.2 mmol) of sodium carbonate and 5mg of Pd (PPh 3) 4 catalyst are added, 40mL of toluene and 10mL of ethanol and 5mL of water are added, the mixture is heated, refluxed and stirred for reaction for 12 hours, cooled to room temperature, extracted with ethyl acetate, the organic phase is dried, filtered, the filtrate is concentrated under reduced pressure to dryness, separated and purified by a silica gel column, heated to boiling with ethanol, filtered while hot, to obtain the product CJH-P126, and the yield is 76%. MS (MALDI-TOF): m/z704.2828[ M+H ] +;1HNMR (delta, CDCl 3): 8.80 to 8.78 (4H, m); 8.49 to 8.48 (1H, m); 8.38 to 8.35 (2H, m); 8.09-8.08 (1H, m); 7.91 to 7.72 (10H, m); 7.66 to 7.43 (9H, m); 7.35 to 7.22 (6H, m).
Example 7
Referring to the synthetic method of example 6, the following compounds were prepared, namely, the method steps were the same as example 6 except that the chalcone in the first step of example 3 was replaced with a different compound according to actual needs, the (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) boronic acid in the second step of example 6 was replaced with a different compound according to actual needs, and the mass amounts of the compounds were changed according to molar amounts, to prepare the compounds of numbers CJH-P121 to CJH-P125, CJH-P127 to CJH-P130.
Example 8
The preparation of the compound CJH-P132 comprises the following steps:
the first step: preparation of intermediate Int-15
Figure BDA0002649260220000241
Under the protection of nitrogen, 5mL of DAST (diethylaminosulfur trifluoride) is added into 80mL of dichloromethane, the temperature is reduced to minus 40 ℃ by liquid nitrogen, 15.0mmol of intermediate Int-10 prepared in the fifth step of the example 3 is added, stirring is carried out for 2 hours, 20mL of saturated brine is added dropwise, the dichloromethane is used for extraction, an organic phase is collected, drying and filtration are carried out, the filtrate is concentrated under reduced pressure and dried, and the intermediate Int-15 is obtained by separation and purification by a silica gel column, wherein the yield is 96%.
And a second step of: preparation of Compound CJH-P132
Figure BDA0002649260220000242
10.0mmol of intermediate Int-15, 12.0mmol of para-nitrilophenylboronic acid, 3.7g (35.0 mmol) of sodium carbonate and 58.0mg of Pd (PPh 3) 4 as catalyst, 60mL of toluene and 30mL of ethanol and 20mL of water are added, the mixture is heated, refluxed and stirred for reaction for 12 hours, cooled to room temperature, extracted with ethyl acetate, the organic phase is dried, filtered, the filtrate is concentrated to dryness under reduced pressure, separated and purified by a silica gel column, and recrystallized by dichloromethane-ethanol to obtain the product CJH-P132 with the yield of 83 percent. MS (MALDI-TOF): m/z 516.1892[ M+H ] +;1HNMR (delta, CDCl 3): 8.12 to 8.10 (2H, m); 7.87 to 7.84 (2H, m); 7.78 to 7.74 (3H, m); 7.69 to 7.65 (3H, m); 7.60 to 7.53 (6H, m); 7.49 to 7.45 (2H, m); 7.41 to 7.32 (3H, m); 7.26 to 7.22 (1H, m).
Example 9
Referring to the synthesis method of example 8, the following compounds were prepared, namely, the method steps were the same as those of example 8 except that the P-nitrilophenylboronic acid in the second step of example 8 was replaced with a different compound according to actual needs depending on the desired product, and the mass amounts of the compounds were changed according to molar amounts, to prepare compounds numbered CJH-P131 and CJH-P133.
Example 10
The preparation of the compound CJH-P136 comprises the following steps:
the first step: preparation of intermediate Int-16
Figure BDA0002649260220000251
Under the protection of nitrogen, 10.0mmol of intermediate Int-10 prepared in the fifth step of the example 3 is dissolved in 60mL of dichloromethane, 0.25mmol of zinc iodide is added, the temperature is reduced to 0 ℃ by using an ice water bath, 12.0mmol of trimethylcyanogen is added dropwise, the mixture is stirred and reacted for 2 hours, the mixture is stirred and reacted for 12 hours at room temperature, 20mL of concentrated hydrochloric acid is added, the mixture is stirred and reacted for 1 hour at room temperature, dichloromethane is used for extraction, an organic phase is collected, dried, filtered, the filtrate is concentrated to dryness under reduced pressure, and the mixture is separated and purified by using a silica gel column to obtain the intermediate Int-16, and the yield is 95%.
And a second step of: preparation of Compound CJH-P136
Figure BDA0002649260220000252
10.0mmol of intermediate Int-16, 12.0mmol of (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) boric acid, 3.7g (35.0 mmol) of sodium carbonate and 58.0mg of Pd (PPh 3) 4 catalyst are added, 60mL of toluene and 30mL of ethanol and 20mL of water are added, the mixture is stirred for reaction for 12 hours at a temperature rising reflux, cooled to room temperature, extracted with ethyl acetate, the organic phase is dried, filtered, the filtrate is concentrated to dryness under reduced pressure, and the mixture is separated and purified by a silica gel column and recrystallized by methylene dichloride/methanol to obtain a product CJH-P136 with the yield of 85 percent. MS (MALDI-TOF): m/z 729.2784[ M+H ] +;1HNMR (delta, CDCl 3): 8.71 to 8.69 (4H, m); 8.47 to 8.44 (2H, m); 8.28 to 8.25 (2H, m); 8.08 to 8.06 (2H, m); 7.89-7.78 (6H, m); 7.71 to 7.66 (4H, m); 7.58 to 7.51 (6H, m); 7.46 to 7.36 (6H, m).
Example 11
Referring to the synthesis method of example 10, the following compounds were prepared, namely, the steps of the method were the same as those of example 10 except that the (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) boronic acid in the second step of example 10 was replaced with different compounds according to practical needs depending on the desired products, and the mass usage of the compounds was changed according to the molar amounts, so as to prepare the compounds of numbers CJH-P134 and CJH-P135.
Example 12
An organic electroluminescent device, which is a bottom emission light device, having a structure as shown in fig. 1, comprising a substrate 1, an anode layer 2 provided on the substrate 1, a hole injection layer 3 provided on the anode layer 2, a hole transport layer 4 provided on the hole injection layer 3, an organic light emitting layer 5 provided on the hole transport layer 4, an electron transport layer 6 provided on the organic light emitting layer 5, an electron injection layer 7 provided on the electron transport layer 6, and a cathode layer 8 provided on the electron injection layer 7, is prepared by the steps of:
1) The glass substrate coated with the ITO conductive layer is subjected to ultrasonic treatment in a cleaning agent for 30 minutes, rinsed in deionized water, subjected to ultrasonic treatment in an acetone/ethanol mixed solvent for 30 minutes, baked in a clean environment until completely dried, irradiated by an ultraviolet light cleaning machine for 10 minutes, and bombarded on the surface by a low-energy cation beam.
2) Placing the above ITO glass substrate in vacuum chamber, and vacuumizing to 1×10 -5 ～9×10 -3 Pa, vapor-depositing 2-TNATA as a hole injection layer on the anode layer film, the vapor-deposited film thickness being
Figure BDA0002649260220000261
3) Continuously evaporating NPB as a hole transport layer on the hole injection layer, wherein the evaporating film thickness is as follows
Figure BDA0002649260220000262
/>
4) Continuously evaporating CzSi as a main material and Ir (mppy) 3 as a doping material on the hole transport layer, wherein the mass ratio of CzSi to Ir (mppy) 3 is 90:10, and the film thickness of the organic light-emitting layer obtained by evaporation is as the organic light-emitting layer of the device
Figure BDA0002649260220000263
5) Continuously evaporating a layer of the compound (formula I) as a main material and LiQ as a doping material on the organic light-emitting layer, wherein the mass ratio of the compound (formula I) to the LiQ is 50:50, and the compound is used as an electron transport layer of a device, and the evaporating film thickness is
Figure BDA0002649260220000264
6) Continuously evaporating a LiF layer on the electron transport layer to form an electron injection layer with an evaporating film thickness of
Figure BDA0002649260220000265
7) Evaporating a magnesium/silver alloy layer on the electron injection layer to obtain a cathode layer with a thickness of
Figure BDA0002649260220000266
The mass ratio of magnesium to silver is 1:9, and the OLED device provided by the invention is obtained.
Example 13
An organic electroluminescent device is a bottom emission light device, and has a structure shown in fig. 2, and comprises a substrate 1, an anode layer 2 arranged on the substrate 1, a hole injection layer 3 arranged on the anode layer 2, an electron blocking layer 4 arranged on the hole injection layer 3, an organic luminescent layer 5 arranged on the electron blocking layer 4, a hole blocking layer 6 arranged on the organic luminescent layer 5, an electron injection layer 7 arranged on the hole blocking layer 6, and a cathode layer 8 arranged on the electron injection layer 7.
Example 14
According to the same procedure as in example 12, the compound (formula I) in step 5) was selected as CJH-P03 to obtain the device OLED-1 provided by the present invention;
example 15
According to the same procedure as in example 12, the compound (formula I) in step 5) was selected as CJH-P36 to obtain the device OLED-2 provided by the present invention;
example 16
According to the same procedure as in example 12, the compound (formula I) in step 5) was selected as CJH-P55 to obtain the device OLED-3 provided by the present invention;
example 17
According to the same procedure as in example 12, the compound (formula I) in step 5) was selected as CJH-P69 to obtain the device OLED-4 provided by the present invention;
example 18
According to the same procedure as in example 12, the compound (formula I) in step 5) was selected as CJH-P87 to obtain the device OLED-5 provided by the present invention;
example 19
According to the same procedure as in example 12, the compound (formula I) in step 5) was selected as CJH-P136 to obtain the device OLED-6 provided by the present invention;
example 20
By following the same procedure as in example 12, substituting the compound (formula I) in step 5) with Alq3, a comparative device OLED-7 was obtained;
the results of the performance measurements of the resulting devices are set forth in Table 1, wherein the drive voltage, current efficiency, color coordinates (1931 CIE), full width at half maximum (FWHM), and External Quantum Efficiency (EQE) are at a current density of 10mA/cm for the devices 2 Under the condition that the LT95% lifetime of the device is 10000cd/m at the initial brightness, and the data normalization processing is carried out compared with the reference device 2 And data normalization is performed as compared to the reference device.
TABLE 1 results of Performance test of OLED-1 to OLED-7
Figure BDA0002649260220000271
From the above, the device prepared from the organic material has low driving voltage, current efficiency and quantum efficiency which are obviously higher than those of Alq3 serving as an electron transport layer under the same current density condition, and the LT95% service life of the device is much better.
While the invention has been described in detail in the foregoing general description, embodiments and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.

Claims (5)

1. An imidazole derivative, characterized in that the structural formula of the imidazole derivative is any one of the following:
Figure FDA0004208728280000011
Figure FDA0004208728280000021
Figure FDA0004208728280000031
Figure FDA0004208728280000041
Figure FDA0004208728280000051
Figure FDA0004208728280000061
Figure FDA0004208728280000071
2. an organic electroluminescent material, characterized in that a raw material of the organic electroluminescent material comprises the imidazole derivative according to claim 1.
3. An organic electroluminescent device, comprising a first electrode, a second electrode, and one or more organic layers disposed between the first electrode and the second electrode; the material of at least one of the organic layers comprises the imidazole derivative of claim 1.
4. The organic electroluminescent device of claim 3, wherein the organic layer comprises a hole injection layer, a hole transport layer, a hole blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, or an electron blocking layer.
5. Use of the imidazole derivative according to claim 1 for the preparation of an organic electroluminescent device.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101218208A (en) * 2005-07-11 2008-07-09 出光兴产株式会社 Nitrogen-containing heterocyclic derivative and organic electroluminescent element using same
CN107129469A (en) * 2017-06-08 2017-09-05 吉林大学 A kind of pyrene benzimidazole derivative and its preparation method and application
CN107556310A (en) * 2017-09-20 2018-01-09 石家庄诚志永华显示材料有限公司 Imdazole derivatives, material and organic electroluminescence device comprising the imdazole derivatives
CN108218787A (en) * 2018-04-04 2018-06-29 长春海谱润斯科技有限公司 A kind of pyrene compound and its organic luminescent device
CN108484507A (en) * 2018-04-04 2018-09-04 长春海谱润斯科技有限公司 A kind of pyrene analog derivative and its organic luminescent device
CN108516960A (en) * 2018-04-04 2018-09-11 长春海谱润斯科技有限公司 A kind of glyoxaline compound and its organic luminescent device
CN108558768A (en) * 2018-04-04 2018-09-21 长春海谱润斯科技有限公司 A kind of class compound in the wrong and its organic luminescent device containing glyoxaline structure
US20190148645A1 (en) * 2016-04-08 2019-05-16 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compound and organic electroluminescent device comprising the same
CN110878054A (en) * 2018-09-06 2020-03-13 北京鼎材科技有限公司 Imidazole compound and application thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101218208A (en) * 2005-07-11 2008-07-09 出光兴产株式会社 Nitrogen-containing heterocyclic derivative and organic electroluminescent element using same
US20190148645A1 (en) * 2016-04-08 2019-05-16 Rohm And Haas Electronic Materials Korea Ltd. Organic electroluminescent compound and organic electroluminescent device comprising the same
CN107129469A (en) * 2017-06-08 2017-09-05 吉林大学 A kind of pyrene benzimidazole derivative and its preparation method and application
CN107556310A (en) * 2017-09-20 2018-01-09 石家庄诚志永华显示材料有限公司 Imdazole derivatives, material and organic electroluminescence device comprising the imdazole derivatives
CN108218787A (en) * 2018-04-04 2018-06-29 长春海谱润斯科技有限公司 A kind of pyrene compound and its organic luminescent device
CN108484507A (en) * 2018-04-04 2018-09-04 长春海谱润斯科技有限公司 A kind of pyrene analog derivative and its organic luminescent device
CN108516960A (en) * 2018-04-04 2018-09-11 长春海谱润斯科技有限公司 A kind of glyoxaline compound and its organic luminescent device
CN108558768A (en) * 2018-04-04 2018-09-21 长春海谱润斯科技有限公司 A kind of class compound in the wrong and its organic luminescent device containing glyoxaline structure
CN110878054A (en) * 2018-09-06 2020-03-13 北京鼎材科技有限公司 Imidazole compound and application thereof

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