CN112266389A - Benzimidazole organic compound and preparation method thereof - Google Patents

Benzimidazole organic compound and preparation method thereof Download PDF

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CN112266389A
CN112266389A CN202011125429.5A CN202011125429A CN112266389A CN 112266389 A CN112266389 A CN 112266389A CN 202011125429 A CN202011125429 A CN 202011125429A CN 112266389 A CN112266389 A CN 112266389A
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CN112266389B (en
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王进政
张鹤
黄悦
张雪
汪康
马晓宇
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The invention discloses an benzimidazole organic compound and a preparation method thereof, belonging to the technical field of semiconductors, wherein the preparation method of the compound provided by the invention comprises the following steps: 1) sequentially adding halogenated diphenylamine compound A, aldehyde compound B and sodium pyrosulfite into a DMF solution, and reacting to obtain an intermediate C; 2) sequentially adding the intermediate C, the compound D and bis (hexafluoroantimonic acid) triethylenenitrile (pentamethylcyclopentadienyl) rhodium (III) into o-dichloroethane to react to obtain an intermediate E; 3) sequentially adding the intermediate E, the compound F, palladium chloride and potassium acetate into 1, 4-dioxane to react to obtain an intermediate G; 4) and sequentially adding the intermediate G, the compound H, potassium carbonate and tetratriphenylphosphine palladium into a solvent for reaction to obtain the general formula (1). The compound provided by the invention can obviously reduce the driving voltage of the organic electroluminescent device, improve the luminous efficiency and prolong the service life of the organic electroluminescent device, thereby improving the practicability of the organic electroluminescent device.

Description

Benzimidazole organic compound and preparation method thereof
Technical Field
The invention relates to the technical field of semiconductors, in particular to a benzimidazole organic compound and a preparation method thereof.
Background
The organic electroluminescent (OLED) device technology can be used for manufacturing novel display products and novel lighting products, is expected to replace the existing liquid crystal display and fluorescent lamp lighting, and has wide application prospect. The OLED light-emitting device comprises electrode materials and organic functional materials clamped between different electrodes, and various different functional materials are mutually overlapped together according to the application to form the OLED light-emitting device. When voltage is applied to the electrodes at the two ends of the organic electroluminescent device and positive and negative charges in the functional material layer of the organic layer are acted by an electric field, the positive and negative charges are further compounded in the light-emitting layer, and the OLED electroluminescent device is generated.
In order to fabricate a high-performance OLED light-emitting device, various organic functional materials are required to have good photoelectric properties, for example, as a charge transport material, good carrier mobility, high glass transition temperature, etc. are required, and as a host material of a light-emitting layer, good bipolar property, appropriate HOMO/LUMO energy level, etc. are required.
The OLED photoelectric functional material film layer for forming the OLED device at least comprises more than two layers of structures, and the material types and the matching forms have the characteristics of richness and diversity. In addition, the photoelectric functional material has stronger selectivity, and the performance performances of the same material in devices with different structures can be completely different.
Therefore, how to provide a new organic compound and its application in an OLED device is a problem that needs to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention provides an organic benzimidazole compound and a preparation method thereof. The compound provided by the invention contains a benzimidazole structure, has higher glass transition temperature and molecular thermal stability, and proper HOMO, LUMO energy levels and Eg, and the photoelectric property and the service life of an OLED device can be effectively improved by applying the organic compound taking benzimidazole as a core in an organic electroluminescent device.
In order to achieve the purpose, the invention adopts the following technical scheme:
a benzimidazole organic compound, which is characterized in that the structure of the organic compound is shown as a general formula (1):
Figure BDA0002733458170000021
wherein, R is1And R2Independently represent: hydrogen, isotopes of hydrogen, halogen, cyano, nitro, hydroxy, amino, sulfonic, sulfonyl, phosphate, or phosphoryl; substituted or unsubstituted silyl, boryl or phosphoxy, substituted or unsubstituted C1～C60Alkyl of (C)3～C60Cycloalkyl, alkoxy, alkylamino, alkylmercapto; substituted or unsubstituted C2～C60Alkenyl of, C3～C60Cycloalkenyl group of (1), substituted or unsubstituted C3～C60Alkynyl of (A), C3～C60Cycloalkynyl group of (1), substituted or unsubstituted C6～C60An aryl group; 5-10 membered heterocyclic group, substituted or unsubstituted C10～C60Condensed ring group of (1), substituted or unsubstituted C10～C60Spiro ring group of (a) or monocyclic ring formed by linking to adjacent substituents, C3～C30An aliphatic ring or a 5-to 30-membered aromatic ring;
both m and n are 0 or 1, and when m is 1, n is 0; when n is 1, m is 0;
said L1、L2Each independently selected from the group consisting of a bond, substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, or substituted or unsubstituted C10～C60Any one of the condensed ring groups of (1);
ar is1、Ar2Each independently selected from substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C6-C30Arylamino of (a);
a is described1Is substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted 3-to 30-membered heteroaryl;
a is described2Is substituted or unsubstituted C2～C60A heterocyclic group.
Preferably, the heteroaryl is C3～C30Cycloalkyl, 3-to 10-membered heterocycloalkyl, or monocyclic ring formed by linking to an adjacent substituent, C3～C30An aliphatic ring or a 5-to 30-membered aromatic ring.
Wherein "heterocyclyl" refers to and includes aromatic and non-aromatic cyclic groups containing at least one heteroatom. Optionally, the at least one heteroatom is selected from O, S, N, P, B, Si and Se, preferably O, S or N. Preferred non-aromatic heterocyclic groups are heterocyclic groups containing 3 to 7 ring atoms including at least one heteroatom and include cyclic amines such as morpholinyl, piperidinyl, pyrrolidinyl and the like, and cyclic ethers/thioethers such as tetrahydrofuran, tetrahydropyran, tetrahydrothiophene and the like. In addition, the heterocyclic group may be optionally substituted. The heterocyclic group is not particularly limited, but the number of carbon atoms is preferably 2 to 60. According to one embodiment, the number of carbon atoms of the heterocyclic group is from 2 to 30. Examples of the heterocyclic group may include pyridyl, pyrrolyl, pyrimidinyl, pyridazinyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, pyrazinyl, oxazinyl, dioxanyl, triazinyl, tetrazinyl, quinolyl, isoquinolyl, quinolyl, quinazolinyl, quinoxalinyl, naphthyridinyl, acridinyl, xanthenyl, phenanthridinyl, naphthyridinyl, triazindenyl, indolyl, indolinyl, indolizinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, pyrazinopyrazinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothienyl, benzofuranyl, dibenzothienyl, dibenzofuranyl, dibenzocarbazolyl, benzocarbazolyl, Dibenzocarbazolyl, indolocarbazolyl, indenocarbazolyl, phenazinyl, imidazopyridinyl, phenoxazinyl, phenanthridinyl, phenanthrolinyl, phenothiazinyl, imidazopyridinyl, imidazophenanthridinyl, benzimidazoloquinazolinyl, naphthobenzofuranyl, naphthobenzothienyl, benzimidazolophenyl and the like, but is not limited thereto.
The term "substituted or unsubstituted" means substituted with one, two or more substituents selected from the group consisting of: deuterium; a halogen group; a nitrile group; a hydroxyl group; a carbonyl group; an ester group; a silyl group; a boron group; substituted or unsubstituted alkyl; substituted or unsubstituted cycloalkyl; substituted or unsubstituted alkoxy; substituted or unsubstituted alkenyl; substituted or unsubstituted alkylamino; a substituted or unsubstituted heterocyclylamino group; a substituted or unsubstituted arylamine group; substituted or unsubstituted aryl; and a substituted or unsubstituted heterocyclic group, or a substituent connected by two or more substituents among the substituents shown above, or no substituent. For example, "a substituent in which two or more substituents are linked" may include a biphenyl group. In other words, biphenyl can be an aryl group, or can be interpreted as a substituent with two phenyl groups attached.
The formula 1 can be represented by the following structure
Figure BDA0002733458170000041
Wherein A is3Represents substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted 3-to 30-membered heteroaryl;
x, Y, Z are independently selected from chemical bond, O, S, Si (R)5R6)，C(R7R8)，NR9；R5～R9Each independently selected from hydrogen, substituted or unsubstituted C1～C30Alkyl, substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, substituted or unsubstituted C1～C30Alkoxy, substituted or unsubstituted C1～C30Alkanemercapto, substituted or unsubstituted C6～C30An arylamino group.
R1-R4Ranges and above R1、R2The ranges are the same;
Ar1、Ar2、A1、L1、L2the ranges are the same as above;
preferably, the specific compound is represented by:
Figure BDA0002733458170000051
Figure BDA0002733458170000061
Figure BDA0002733458170000071
a preparation method of the benzimidazole organic compound is characterized by comprising the following steps:
(1) sequentially adding a halogenated diphenylamine compound A, an aldehyde compound B and sodium pyrosulfite into a DMF solution to form a solution 1, stirring at the temperature of 140 ℃ and 160 ℃ for reaction for 1.5-2.5h, cooling to room temperature, gradually adding water into the reaction solution until a large amount of solids are separated out, continuing stirring for 5-7h, and performing suction filtration, washing and drying to obtain an intermediate C;
(2) under the protection of inert gas, adding the intermediate C and the compound D into o-dichloroethane, adding a catalyst of bis (hexafluoroantimonate) triethylenenitrile (pentamethylcyclopentadienyl) rhodium (III) to form a solution 2, monitoring by using a thin-layer plate at 70-90 ℃ until a raw material point disappears, namely representing the end of reaction, then cooling to room temperature, carrying out suction filtration, washing, carrying out rotary evaporation to remove the solvent, and purifying to obtain an intermediate E;
(3) under the protection of inert gas, sequentially adding the intermediate E, the compound F, palladium chloride and potassium acetate into 1, 4-dioxane, uniformly mixing to form a solution 3, reacting at the temperature of 100-120 ℃ for 9-11h, cooling to room temperature after the reaction is finished, carrying out suction filtration, retaining a filtrate, removing the solvent from the filtrate, and purifying to obtain an intermediate G;
(4) under the protection of inert gas, sequentially adding the intermediate G, the compound H, potassium carbonate and tetratriphenylphosphine palladium into a solvent, uniformly mixing to form a solution 4, reacting at 80-100 ℃ for 9-11H, cooling to room temperature after the reaction is finished, separating, extracting, removing the solvent by a rotary evaporator, and purifying to obtain a compound shown in a general formula (1);
preferably, the reaction scheme of chemical formula 1-1 is as follows:
Figure BDA0002733458170000081
the reaction scheme of chemical formula 1-2 is as follows:
Figure BDA0002733458170000091
preferably, the molar concentration of each raw material in the solution 1 in the step (1) is as follows: 0.30-0.35mol/L of halogenated diphenylamine compound A, 0.30-0.35mol/L of aldehyde compound B and 0.38-0.42mol/L of sodium metabisulfite;
the washing is to wash the solid with water, ethanol, petroleum ether in sequence.
Preferably, the concentration of each substance in the solution 2 in the step (2) is as follows: 0.24-0.27mol/L of intermediate C, 0.02-0.04mol/L of compound D, 0.011-0.014mol/L of catalyst bis (hexafluoroantimonate) triethylenenitrile (pentamethylcyclopentadienyl) rhodium (III);
the washing is washing by using distilled water; the purification is performed by utilizing column chromatography, an eluent of the column chromatography is a mixed solvent of dichloromethane and petroleum ether, and the mass ratio of the dichloromethane to the petroleum ether is 1 (4-6).
Preferably, the concentration of each substance in the solution 3 in the step (3) is as follows: 0.15-0.17mol/L of intermediate E, 0.18-0.20mol/L of compound F, 0.0030-0.0035mol/L of palladium chloride and 0.30-0.35mol/L of potassium acetate;
the purification is to add petroleum ether and stir to separate out white solid.
Preferably, the concentration of each substance in the solution 4 in the step (4) is as follows: 0.05-0.15mol/L of intermediate G, 0.05-0.15mol/L of compound H, 0.20-0.25mol/L of potassium carbonate and 0.005-0.006mol/L of palladium tetratriphenylphosphine;
the solvent is a mixed solvent of toluene/ethanol/water, and the volume ratio of the toluene to the ethanol to the water is 3:1: 1;
the purification is that the crude product obtained after the solvent is removed is added into toluene, the mixture is stirred for 11 to 13 hours at the temperature of between 90 and 110 ℃ and then is filtered when the mixture is hot, the filter residue is washed by ethanol, and finally the drying is carried out.
An organic electroluminescent device comprising: the organic light-emitting diode comprises a first electrode, a second electrode and an organic layer arranged between the two electrodes, wherein the organic layer comprises a hole injection layer, a hole transport layer, a light-emitting layer and a light-emitting auxiliary layer, and preferably further comprises an electron transport layer, an electron injection layer, a hole blocking layer and an electron blocking layer;
wherein the light-emitting layer comprises benzimidazole organic compounds, and the doping material of the light-emitting layer can be selected from compounds containing iridium, such as tris (2-phenylpyridine) iridium (Ir (ppy)3)。
The organic electroluminescent device in the present invention is of a top emission type, a bottom emission type, or a double-sided emission type depending on the material used. In addition, the organic light emitting compound provided by the embodiment of the present invention may be used in organic electronic devices, such as organic solar cells, organic photoconductors, organic transistors, etc., using a principle similar to that of organic electroluminescent devices.
Compared with the prior art, the invention uses the luminescent main body compound as the main body material of the luminescent layer of the organic electroluminescent device, and compared with the existing CBP used as the main body material, the invention can remarkably reduce the driving voltage of the organic electroluminescent device, improve the luminescent efficiency and prolong the service life of the organic electroluminescent device, thereby improving the practicability of the organic electroluminescent device.
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.
The embodiment of the invention discloses an imidazole organic compound, which has a structure shown in a general formula (1):
Figure BDA0002733458170000111
wherein R is1And R2Independently represent: hydrogen, isotopes of hydrogen, halogen, cyano, nitro, hydroxy, amino, sulfonic, sulfonyl, phosphate, or phosphoryl; substituted or unsubstituted silyl, boryl or phosphoxy, substituted or unsubstituted C1～C60Alkyl of (C)3～C60Cycloalkyl, alkoxy, alkylamino, alkylmercapto; substituted or unsubstituted C2～C60Alkenyl of, C3～C60Cycloalkenyl group of (1), substituted or unsubstituted C3～C60Alkynyl of (A), C3～C60Cycloalkynyl, substituted or unsubstituted C6～C60An aryl group; 5-10 membered heterocyclic group, substituted or unsubstituted C10～C60Condensed ring group of (A) or substituted or unsubstituted C10～C60Spiro ring groups of (a) or linked to adjacent substituents to form monocyclic or polycyclic C3～C30An aliphatic ring or a 5-to 30-membered aromatic ring;
m and n are both 0 or 1, and when m is 1, n is 0; when n is 1, m is 0.
To further optimize the above technical solution, L1、L2Each independently selected from the group consisting of a bond, substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, or substituted or unsubstituted C10～C60Any one of the fused ring groups of (1).
Further, Ar1、Ar2Each independently selected from substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C6-C30An arylamino group. Heteroaryl may be monocyclic or fused polycyclic system, C3～C30Cycloalkyl, 3-to 10-membered heterocycloalkyl, or a linkage with an adjacent substituent to form a monocyclic or polycyclic C3～C30An aliphatic ring or a 5-to 30-membered aromatic ring.
Further, A1Is substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted 3-to 30-membered heteroaryl;
A2is substituted or unsubstituted C2～C60A heterocyclic group.
The embodiment of the invention also provides a preparation method of the benzimidazole organic compound, which comprises the following steps:
(1) sequentially adding a halogenated diphenylamine compound A, an aldehyde compound B and sodium pyrosulfite into a DMF solution to form a solution 1, stirring at the temperature of 140 ℃ and 160 ℃ for reaction for 1.5-2.5h, cooling to room temperature, gradually adding water into the reaction solution until a large amount of solids are separated out, continuing stirring for 5-7h, and performing suction filtration, washing and drying to obtain an intermediate C;
(2) under the protection of inert gas, adding the intermediate C and the compound D into o-dichloroethane, adding a catalyst bis (hexafluoroantimonate) triethylenenitrile (pentamethylcyclopentadienyl) rhodium (III) to form a solution 2, after the reaction is finished at 70-90 ℃, cooling to room temperature, carrying out suction filtration and washing, carrying out rotary evaporation to remove the solvent, and purifying to obtain an intermediate E;
(3) under the protection of inert gas, sequentially adding the intermediate E, the compound F, palladium chloride and potassium acetate into 1, 4-dioxane, uniformly mixing to form a solution 3, reacting at the temperature of 100-120 ℃ for 9-11h, cooling to room temperature after the reaction is finished, carrying out suction filtration, retaining the filtrate, removing the solvent from the filtrate, and purifying to obtain an intermediate G;
(4) under the protection of inert gas, sequentially adding the intermediate G, the compound H, potassium carbonate and tetratriphenylphosphine palladium into a solvent, uniformly mixing to form a solution 4, reacting at 80-100 ℃ for 9-11H, cooling to room temperature after the reaction is finished, separating, extracting, removing the solvent by a rotary evaporator, and purifying to obtain a compound shown in a general formula (1);
in order to further optimize the technical scheme, the molar concentration of each raw material in the solution 1 in the step (1) is as follows: 0.30-0.35mol/L of halogenated diphenylamine compound A, 0.30-0.35mol/L of aldehyde compound B and 0.38-0.42mol/L of sodium metabisulfite;
the washing is to wash the solid with water, ethanol, petroleum ether in sequence.
Further, the concentration of each substance in the solution 2 in the step (2) is as follows: 0.24-0.27mol/L of intermediate C, 0.02-0.04mol/L of compound D, 0.011-0.014mol/L of catalyst bis (hexafluoroantimonate) triethylenenitrile (pentamethylcyclopentadienyl) rhodium (III);
the washing is washing by using distilled water; the purification is performed by utilizing column chromatography, an eluent of the column chromatography is a mixed solvent of dichloromethane and petroleum ether, and the mass ratio of the dichloromethane to the petroleum ether is 1 (4-6).
Further, the concentration of each substance in the solution 3 in the step (3) is as follows: 0.15-0.17mol/L of intermediate E, 0.18-0.20mol/L of compound F, 0.0030-0.0035mol/L of palladium chloride and 0.30-0.35mol/L of potassium acetate;
the purification is to add petroleum ether and stir to separate out white solid.
Further, the concentration of each substance in the solution 4 in the step (4) is as follows: 0.05-0.15mol/L of intermediate G, 0.05-0.15mol/L of compound H, 0.20-0.25mol/L of potassium carbonate and 0.005-0.006mol/L of palladium tetratriphenylphosphine;
the solvent is a mixed solvent of toluene/ethanol/water, and the volume ratio of the toluene to the ethanol to the water is 3:1: 1;
the purification is that the crude product obtained after the solvent is removed is added into toluene, the mixture is stirred for 11 to 13 hours at the temperature of between 90 and 110 ℃ and then is filtered when the mixture is hot, the filter residue is washed by ethanol, and finally the drying is carried out.
An embodiment of the present invention further provides an organic electroluminescent device, including: the organic light emitting diode comprises a first electrode, a second electrode and an organic layer arranged between the two electrodes, wherein the organic layer comprises a light emitting layer.
The invention is further illustrated by the following specific examples.
Example 1:
a preparation of a benzimidazole organic compound (compound 1), comprising the steps of:
the reaction process is as follows:
Figure BDA0002733458170000131
1. raw materials A-1(100mmol) and B-1(100mmol) are added into a DMF (300ml) solution, sodium metabisulfite (120mmol) is added, the temperature is raised to 150 ℃, and the reaction is stirred for 2 h. After the reaction was completed, the temperature was lowered to room temperature, and water (100ml) was gradually added until a large amount of solid was precipitated. Stirring for 6h, suction filtering directly to obtain white solid, washing with water (50ml), ethanol (50ml), petroleum ether (50ml) in sequence, and drying to obtain the target product C-1(31.8g yield 95.2). MW: 334.05.
2. Intermediate C-1(90mmol) and D-1 (vinylene carbonate, 180mmol) were added to o-dichloroethane (350ml), the air was replaced with nitrogen, and the catalyst bis (hexafluoroantimonate) triethylenenitrile (pentamethylcyclopentadienyl) rhodium (III) (4.5mmol) was added under nitrogen protection. The reaction was heated to 80 ℃ and reacted for 20h, after completion of the reaction, cooled to room temperature, the solvent was filtered off with suction, washed with water (50ml), the solvent was removed using a rotary evaporator, and the product was purified using column chromatography (dichloromethane: petroleum ether ═ 1:5) to give intermediate E-1(24.1g yield 74.4%). MW: 360.11.
3. Intermediate E-1(65mmol) and pinacol diboron (78mmol) were added to 1, 4-dioxane (400ml), followed by palladium chloride (1.3mmol) and potassium acetate (130mmol), respectively, and the atmosphere was replaced with nitrogen. The reaction solution is heated to 110 ℃ and reacted for 10 h. After the reaction, the temperature was reduced to room temperature, the reaction mixture was directly filtered by suction, the filtrate was retained, the solvent was removed to give a black oily substance, which was added dropwise to petroleum ether (200ml) and stirred to precipitate a white solid, which was then filtered by suction and dried to give intermediate G-1(21.8G, yield 74.17%). MW: 452.13.
4. Intermediate G-1(45mmol) and H-1(45mmol) were added to a toluene/ethanol/water mixed solvent (V toluene: V ethanol: V water 240ml:80ml:80ml), air was replaced with nitrogen, potassium carbonate (90mmol) and tetrakistriphenylphosphine palladium (2.25mmol) were added, and the mixture was heated to 90 ℃ for 10 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, separated, and the aqueous phase was extracted with dichloromethane. The solvent was removed using a rotary evaporator and the resulting crude product was added to 100ml of toluene and stirred at 100 ℃ for 12 h. This was filtered with suction while hot, washed with ethanol (30ml), and dried to give compound 1(22.3g, yield 76.9%). MW: 645.27.
Example 2:
a preparation of a benzimidazole organic compound (compound 6), comprising the steps of:
the reaction process is as follows:
Figure BDA0002733458170000151
1. the raw materials A-6(100mmol) and B-6(100mmol) are added into a DMF (300ml) solution, sodium metabisulfite (120mmol) is added, the temperature is raised to 150 ℃, and the reaction is stirred for 2 h. After the reaction was completed, the temperature was lowered to room temperature, and water (100ml) was gradually added until a large amount of solid was precipitated. Stirring for 6h, suction filtration directly gave a white solid which was washed successively with water (50ml), ethanol (50ml), petroleum ether (50ml) and dried to give the desired product C-6(41.1g yield 90.9%). MW: 452.15.
2. Intermediate C-6(90mmol) and D-6 (vinylene carbonate, 180mmol) were added to o-dichloroethane (350ml), the air was replaced with nitrogen, and the catalyst bis (hexafluoroantimonate) triethylenenitrile (pentamethylcyclopentadienyl) rhodium (III) (4.5mmol) was added under nitrogen protection. The reaction was heated to 80 ℃ and reacted for 20h, after completion of the reaction, cooled to room temperature, the solvent was filtered off with suction, washed with water (50ml), the solvent was removed using a rotary evaporator, and the product was purified using column chromatography (dichloromethane: petroleum ether ═ 1:5) to give intermediate E-6(35.0g yield 76.3%). MW: 510.12.
3. Intermediate E-6(65mmol) and pinacol diboron (78mmol) were added to 1, 4-dioxane (400ml), followed by palladium chloride (1.3mmol) and potassium acetate (130mmol), respectively, and the atmosphere was replaced with nitrogen. The reaction solution is heated to 110 ℃ and reacted for 10 h. After the reaction, the temperature is reduced to room temperature, the reaction solution is directly filtered, the filtrate is reserved, the solvent is removed, a black oily substance is obtained, the black oily substance is dropwise added into petroleum ether (200ml) and stirred to separate out a white solid, and the white solid is filtered, filtered and dried to obtain an intermediate G-6(29.0G, the yield is 74.2%). MW: 602.23.
4. Intermediate G-6(45mmol) and H-6(45mmol) were added to a toluene/ethanol/water mixed solvent (V toluene: V ethanol: V water 240ml:80ml:80ml), air was replaced with nitrogen, potassium carbonate (90mmol) and tetrakistriphenylphosphine palladium (2.25mmol) were added, and the mixture was heated to 90 ℃ for 10 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, separated, and the aqueous phase was extracted with dichloromethane. The solvent was removed using a rotary evaporator and the resulting crude product was added to 100ml of toluene and stirred at 100 ℃ for 12 h. This was filtered with suction while hot, washed with ethanol (30ml), and dried to give compound 6(28.0g, yield 79.5%). MW: 783.26.
Example 3:
a preparation of a benzimidazole organic compound (compound 19) comprising the steps of:
the reaction process is as follows:
Figure BDA0002733458170000161
Figure BDA0002733458170000171
1. the raw materials A-19(100mmol) and B-19(100mmol) are added into DMF (300ml) solution, sodium metabisulfite (120mmol) is added, the temperature is raised to 150 ℃, and the reaction is stirred for 2 h. After the reaction was completed, the temperature was lowered to room temperature, and water (100ml) was gradually added until a large amount of solid was precipitated. Stirring for 6h, suction filtration directly gave a white solid which was washed successively with water (50ml), ethanol (50ml), petroleum ether (50ml) and dried to give the desired product C-19(31.1g yield 93.1%). MW: 334.05.
2. Intermediate C-19(90mmol) and D-19 (vinylene carbonate, 180mmol) were charged to o-dichloroethane (350ml), the air was replaced with nitrogen, and the catalyst bis (hexafluoroantimonate) triethylenenitrile (pentamethylcyclopentadienyl) rhodium (III) (4.5mmol) was added under nitrogen protection. The reaction was heated to 80 ℃ and reacted for 20h, after completion of the reaction, cooled to room temperature, the solvent was filtered off with suction, washed with water (50ml), the solvent was removed using a rotary evaporator, and the product was purified using column chromatography (dichloromethane: petroleum ether ═ 1:5) to give intermediate E-19(25.8g, yield 89.3%). MW: 386.07.
3. Intermediate E-19(65mmol) and pinacol diboron (78mmol) were added to 1, 4-dioxane (400ml), followed by palladium chloride (1.3mmol) and potassium acetate (130mmol), respectively, and the atmosphere was replaced with nitrogen. The reaction solution is heated to 110 ℃ and reacted for 10 h. After the reaction, the temperature is reduced to room temperature, the reaction solution is directly filtered, the filtrate is reserved, the solvent is removed, a black oily substance is obtained, the black oily substance is dropwise added into petroleum ether (200ml) and stirred to separate out a white solid, and the white solid is filtered, filtered and dried to obtain an intermediate G-19(23.3G, the yield is 74.9%). MW: 478.20.
4. Intermediate G-19(45mmol) and H-19(45mmol) were added to a toluene/ethanol/water mixed solvent (V toluene: V ethanol: V water 240ml:80ml:80ml), air was replaced with nitrogen, potassium carbonate (90mmol) and tetrakistriphenylphosphine palladium (2.25mmol) were added, and the mixture was heated to 90 ℃ for 10 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, separated, and the aqueous phase was extracted with dichloromethane. The solvent was removed using a rotary evaporator and the resulting crude product was added to 100ml of toluene and stirred at 100 ℃ for 12 h. Suction filtration was performed while hot, and the filtrate was washed with ethanol (30ml) and dried to obtain compound 19(23.5g, yield 84.2%). MW: 620.25.
Example 4:
a preparation of a benzimidazole organic compound (compound 27), comprising the steps of:
the reaction process is as follows:
Figure BDA0002733458170000181
1. the raw materials A-27(100mmol) and B-27(100mmol) were added to a DMF (300ml) solution, sodium metabisulfite (120mmol) was added, the temperature was raised to 150 ℃ and the reaction was stirred for 2 h. After the reaction was completed, the temperature was lowered to room temperature, and water (100ml) was gradually added until a large amount of solid was precipitated. After stirring for 6h, suction filtration directly gave a white solid which was washed successively with water (50ml), ethanol (50ml), petroleum ether (50ml) and dried to give the desired product C-27(31.61g yield 91.6%). MW: 345.12.
2. Intermediate C-27(90mmol) and D-27 (vinylene carbonate, 180mmol) were charged to o-dichloroethane (350ml), the air was replaced with nitrogen, and the catalyst bis (hexafluoroantimonate) triethylenenitrile (pentamethylcyclopentadienyl) rhodium (III) (4.5mmol) was added under nitrogen protection. The reaction was heated to 80 ℃ and reacted for 20h, after completion of the reaction, cooled to room temperature, the solvent was filtered off with suction, washed with water (50ml), the solvent was removed using a rotary evaporator, and the product was purified using column chromatography (dichloromethane: petroleum ether ═ 1:5) to give intermediate E-27(341.1g, yield 92.4%). MW: 521.13.
3. Intermediate E-27(65mmol) and pinacol diboron (78mmol) were added to 1, 4-dioxane (400ml), followed by palladium chloride (1.3mmol) and potassium acetate (130mmol), respectively, and the atmosphere was replaced with nitrogen. The reaction solution is heated to 110 ℃ and reacted for 10 h. After the reaction, the temperature is reduced to room temperature, the reaction solution is directly filtered, the filtrate is reserved, the solvent is removed, a black oily substance is obtained, the black oily substance is dropwise added into petroleum ether (200ml) and stirred to separate out a white solid, and the white solid is filtered, filtered and dried to obtain an intermediate G-27(27.9G, the yield is 70.0%). MW: 613.33.
4. Intermediate G-27(45mmol) and H-27(45mmol) were added to a toluene/ethanol/water mixed solvent (V toluene: V ethanol: V water 240ml:80ml:80ml), air was replaced with nitrogen, potassium carbonate (90mmol) and tetrakistriphenylphosphine palladium (2.25mmol) were added, and the mixture was heated to 90 ℃ for 10 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, separated, and the aqueous phase was extracted with dichloromethane. The solvent was removed using a rotary evaporator and the resulting crude product was added to 100ml of toluene and stirred at 100 ℃ for 12 h. Suction filtration was performed while hot, and the residue was washed with ethanol (30ml) and dried to obtain compound 27(24.3g, yield 78.1%). MW: 669.28.
Example 5
A benzimidazole organic compound (compound 8) was prepared, which was synthesized by the following specific steps:
(1) in the step 1, raw material raw materials A-1(100mmol) and B-1 are replaced by A-8 and B-8 to finally obtain an intermediate C-8;
(2) replacing the intermediates C-1 and D-1 with the intermediates C-8 and D-8 in the step 2 to finally obtain an intermediate E-8;
(3) replacing the intermediate E-1 with an intermediate E-8 in the step 3 to finally obtain an intermediate G-8;
(4) in the step 4, the intermediate G-1 is replaced by the intermediate G-8, and finally the compound 8 is obtained.
Example 6
A benzimidazole organic compound (compound 13) was prepared, which was synthesized by the following specific steps:
(1) in the step 1, raw material raw materials A-1(100mmol) and B-1 are replaced by A-13 and B-13, and an intermediate C-13 is finally obtained;
(2) replacing the intermediates C-1 and D-1 with the intermediates C-13 and D-13 in the step 2 to finally obtain an intermediate E-13;
(3) replacing the intermediate E-1 with an intermediate E-13 in the step 3 to finally obtain an intermediate G-13;
(4) in the step 4, the intermediate G-1 is replaced by the intermediate G-13, and finally the compound 13 is obtained.
Example 7
A benzimidazole organic compound (compound 24) was prepared, which was synthesized by the following specific steps:
(1) in the step 1, raw material raw materials A-1(100mmol) and B-1 are replaced by A-24 and B-24 to finally obtain an intermediate C-24;
(2) replacing the intermediates C-1 and D-1 with the intermediates C-24 and D-24 in the step 2 to finally obtain an intermediate E-24;
(3) replacing the intermediate E-1 with an intermediate E-24 in the step 3 to finally obtain an intermediate G-24;
(4) in step 4, intermediate G-1 is replaced by intermediate G-24 to finally obtain compound 24.
Example 8
A benzimidazole organic compound (compound 31) was prepared, which was synthesized by the following specific steps:
(1) in the step 1, raw material raw materials A-1(100mmol) and B-1 are replaced by A-31 and B-31 to finally obtain an intermediate C-31;
(2) replacing the intermediates C-1 and D-1 with the intermediates C-31 and D-31 in the step 2 to finally obtain an intermediate E-31;
(3) replacing the intermediate E-1 with an intermediate E-31 in the step 3 to finally obtain an intermediate G-31;
(4) in step 4, intermediate G-1 is replaced by intermediate G-31 to finally obtain compound 31.
Example 9
A benzimidazole organic compound (compound 42) was prepared, which was synthesized by the following specific steps:
(1) in the step 1, raw material raw materials A-1(100mmol) and B-1 are replaced by A-42 and B-42 to finally obtain an intermediate C-42;
(2) replacing the intermediates C-1 and D-1 with the intermediates C-42 and D-42 in the step 2 to finally obtain an intermediate E-42;
(3) replacing the intermediate E-1 with an intermediate E-42 in the step 3 to finally obtain an intermediate G-42;
(4) in step 4, intermediate G-1 is replaced by intermediate G-42 to finally obtain compound 42.
The compounds obtained in examples 5 to 9 have the mass spectrometric test values and the molecular formulae shown in Table 1 below.
Table 1:
structural formula of compound Molecular formula Theoretical value of mass spectrum Mass spectrometric test values
Example 5 C43H27N3 585.22 584.79
Example 6 C41H26N2O 562.20 562.03
Example 7 C35H22F2N2 508.18 508.29
Example 8 C44H29N3S 631.21 631.43
Example 9 C54H35N3 725.28 725.39
Example 10
A preparation method of an organic electroluminescent device comprises the following steps:
(1) coating thickness of Fisher company of
Figure BDA0002733458170000211
The ITO glass substrate is placed in distilled water for cleaning for 2 times, ultrasonic cleaning is carried out for 30min, the ITO glass substrate is repeatedly cleaned for 2 times by distilled water and is ultrasonically cleaned for 10min, after the cleaning by distilled water is finished, the ITO glass substrate is sequentially ultrasonically cleaned by solvents such as isopropanol, acetone, methanol and the like, then dried, transferred into a plasma cleaning machine, and cleaned for 5min to obtain an ITO transparent electrode which is used as an anode and sent into an evaporation machine.
(2) Sequentially evaporating CuPc on the prepared ITO transparent electrode
Figure BDA0002733458170000212
N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB,
Figure BDA0002733458170000213
) Compound 1 prepared in example 1 and doping Material Ir (ppy)3Mixture mixed according to the weight ratio of 95:5
Figure BDA0002733458170000214
Tris (8-hydroxyquinoline) aluminum electron transport layer (Alq)3，
Figure BDA0002733458170000215
)、LiF
Figure BDA0002733458170000216
Cathode Al
Figure BDA0002733458170000217
And obtaining the organic electroluminescent device.
Examples 11 to 18
A method for producing an organic electroluminescent device, which is different from embodiment 10: examples 11 to 18 were carried out by using, in order, the compound 1 prepared in the alternative example 1 of the compound 6, the compound 8, the compound 13, the compound 19, the compound 24, the compound 27, the compound 31 and the compound 42 as the host material and the dopant material Ir (ppy)3And carrying out mixed evaporation according to the weight ratio of 98:2, and preparing the corresponding organic electroluminescent device.
Comparative example 1
An organic electroluminescent device, which is manufactured by the method different from that of example 10, is: CBP is adopted to replace the compound 1 as a main material and a doping material Ir (ppy)3And mixed evaporation is carried out according to the weight ratio of 95: 5. Wherein, the structural formula of CBP is:
Figure BDA0002733458170000221
the organic electroluminescent devices obtained in examples 10 to 18 and comparative example 1 were tested for driving voltage, luminous efficiency, and T95 lifetime using a KEITHLEY model 2400 source measuring unit and a CS-2000 spectroradiometer, respectively, and the test results are shown in table 2 below.
TABLE 2
Figure BDA0002733458170000222
Figure BDA0002733458170000231
As can be seen from table 2 above, compared with the organic electroluminescent device prepared in comparative example 1 using the conventional CBP as the host material of the light-emitting layer, the organic electroluminescent device prepared using the organic light-emitting compound provided by the embodiment of the present invention as the host material of the light-emitting layer has significantly reduced driving voltage, significantly improved light-emitting efficiency, and significantly improved lifetime.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (8)

1. A benzimidazole organic compound, which is characterized in that the structure of the organic compound is shown as a general formula (1):
Figure FDA0002733458160000011
wherein, R is1And R2Independently represent: hydrogen, isotopes of hydrogen, halogen, cyano, nitroA group, hydroxyl group, amino group, sulfonic group, sulfonyl group, phosphoric group or phosphoryl group; substituted or unsubstituted silyl, boryl or phosphoxy, substituted or unsubstituted C1～C60Alkyl of (C)3～C60Cycloalkyl, alkoxy, alkylamino, alkylmercapto; substituted or unsubstituted C2～C60Alkenyl of, C3～C60Cycloalkenyl group of (1), substituted or unsubstituted C3～C60Alkynyl of (A), C3～C60Cycloalkynyl group of (1), substituted or unsubstituted C6～C60An aryl group; 5-10 membered heterocyclic group, substituted or unsubstituted C10～C60Condensed ring group of (1), substituted or unsubstituted C10～C60Spiro ring group of (a) or monocyclic ring formed by linking to adjacent substituents, C3～C30An aliphatic ring or a 5-to 30-membered aromatic ring;
when m is 1, n is 0; when n is 1, m is 0;
said L1、L2Each independently selected from the group consisting of a bond, substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, or substituted or unsubstituted C10～C60Any one of the condensed ring groups of (1);
ar is1、Ar2Each independently selected from substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted C6～C60An arylamine group;
a is described1Is substituted or unsubstituted C6～C30Aryl, substituted or unsubstituted 3-to 30-membered heteroaryl;
a is described2Is substituted or unsubstituted C2～C60A heterocyclic group.
2. The benzimidazole organic compound of claim 1, wherein the heteroaryl is C3～C30Cycloalkyl, 3-to 10-membered heterocycloalkyl, or monocyclic ring formed by linking to an adjacent substituent, C3～C30An aliphatic ring or a 5-to 30-membered aromatic ring.
3. A preparation method of benzimidazole organic compounds is characterized by comprising the following steps:
(1) sequentially adding a halogenated diphenylamine compound A, an aldehyde compound B and sodium pyrosulfite into a DMF (dimethyl formamide) solvent to form a solution 1, stirring at the temperature of 140 ℃ and 160 ℃ for reaction for 1.5-2.5h, cooling to room temperature, gradually adding water into the reaction solution until solid is separated out, continuing stirring for 5-7h, and performing suction filtration, washing and drying to obtain an intermediate C;
(2) adding the intermediate C and the compound D into o-dichloroethane under inert gas, adding a catalyst bis (hexafluoroantimonate) triethylenenitrile (pentamethylcyclopentadienyl) rhodium (III) to form a solution 2, cooling to room temperature after the reaction is finished at 70-90 ℃, performing suction filtration and washing, performing rotary evaporation to remove the solvent, and purifying to obtain an intermediate E;
(3) under inert gas, sequentially adding the intermediate E, the compound F, palladium chloride and potassium acetate into 1, 4-dioxane, uniformly mixing to form a solution 3, reacting at the temperature of 100-120 ℃ for 9-11h, cooling to room temperature after the reaction is finished, carrying out suction filtration, retaining the filtrate, removing the solvent from the filtrate, and purifying to obtain an intermediate G;
(4) under inert gas, sequentially adding the intermediate G, the compound H, potassium carbonate and tetratriphenylphosphine palladium into a solvent, uniformly mixing to form a solution 4, reacting at 80-100 ℃ for 9-11H, cooling to room temperature after the reaction is finished, separating, extracting, removing the solvent by a rotary evaporator, and purifying to obtain the compound shown in the general formula (1).
4. The method for preparing benzimidazole organic compounds according to claim 3, wherein the molar concentration of each raw material in the solution 1 in the step (1) is as follows: 0.30-0.35mol/L of halogenated diphenylamine compound A, 0.30-0.35mol/L of aldehyde compound B and 0.38-0.42mol/L of sodium metabisulfite;
the washing is to wash the solid with water, ethanol, petroleum ether in sequence.
5. The method for preparing benzimidazole organic compounds according to claim 3, wherein the concentration of each substance in the solution 2 in the step (2) is as follows: 0.24-0.27mol/L of intermediate C, 0.02-0.04mol/L of compound D, 0.011-0.014mol/L of catalyst bis (hexafluoroantimonate) triethylenenitrile (pentamethylcyclopentadienyl) rhodium (III);
the washing is washing by using distilled water; the purification is performed by utilizing column chromatography, an eluent of the column chromatography is a mixed solvent of dichloromethane and petroleum ether, and the mass ratio of the dichloromethane to the petroleum ether is 1 (4-6).
6. The method for preparing benzimidazole organic compounds according to claim 3, wherein the concentration of each substance in the solution 3 in the step (3) is as follows: 0.15-0.17mol/L of intermediate E, 0.18-0.20mol/L of compound F, 0.0030-0.0035mol/L of palladium chloride and 0.30-0.35mol/L of potassium acetate;
the purification is to add petroleum ether and stir to separate out white solid.
7. The method for preparing benzimidazole organic compounds according to claim 3, wherein the concentration of each substance in the solution 4 in the step (4) is as follows: 0.05-0.15mol/L of intermediate G, 0.05-0.15mol/L of compound H, 0.20-0.25mol/L of potassium carbonate and 0.005-0.006mol/L of palladium tetratriphenylphosphine;
the solvent is a mixed solvent of toluene/ethanol/water, and the volume ratio of the toluene to the ethanol to the water is 3:1: 1;
the purification is that the crude product obtained after the solvent is removed is added into toluene, the mixture is stirred for 11 to 13 hours at the temperature of between 90 and 110 ℃ and then is filtered when the mixture is hot, the filter residue is washed by ethanol, and finally the drying is carried out.
8. An organic electroluminescent device comprising: the organic light emitting diode comprises a first electrode, a second electrode and an organic layer arranged between the two electrodes, and is characterized in that the organic layer comprises a light emitting layer, and the light emitting layer comprises the benzimidazole organic compound according to any one of claims 1 to 2 or the benzimidazole organic compound prepared by the preparation method according to any one of claims 3 to 7.
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CN115385909A (en) * 2022-09-23 2022-11-25 江苏师范大学 Method for synthesizing imidazophenanthridine compound under co-catalysis of palladium and copper

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