CN109535011B - Organic electroluminescent material and organic electroluminescent device comprising same - Google Patents
Organic electroluminescent material and organic electroluminescent device comprising same Download PDFInfo
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- CN109535011B CN109535011B CN201811581714.0A CN201811581714A CN109535011B CN 109535011 B CN109535011 B CN 109535011B CN 201811581714 A CN201811581714 A CN 201811581714A CN 109535011 B CN109535011 B CN 109535011B
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- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 125000005017 substituted alkenyl group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000004426 substituted alkynyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000005346 substituted cycloalkyl group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229940045860 white wax Drugs 0.000 description 1
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Abstract
The invention provides an organic electroluminescent material and an organic electroluminescent device comprising the same, belonging to the technical field of electroluminescence. Based on the structure of triarylamine, a second core group taking adamantane as a center is introduced; wherein triarylamine has excellent hole transport property, which is the basis of the material as a hole transport layer; the adamantane has a structure with larger steric hindrance and firm rigidity, so that the molecular crystallinity is reduced, the film-forming property of the material is improved, and the energy loss caused by the self vibration relaxation of the molecules is reduced; the compound containing the adamantyl group has excellent hole transport performance, can be used for manufacturing organic electroluminescent devices, particularly used as a hole transport layer material in the organic electroluminescent devices, and can effectively improve the luminous efficiency and prolong the service life of the organic electroluminescent devices.
Description
Technical Field
The invention relates to an organic electroluminescent material and application thereof as a hole transport layer material in an organic electroluminescent device, in particular to an organic electroluminescent material and an organic electroluminescent device comprising the same, belonging to the field of electroluminescence.
Background
Electroluminescence (EL) is a physical phenomenon in which an electric field is generated by a voltage applied to two electrodes, electrons excited by the electric field collide with a luminescence center, and the electrons undergo transition, change, and recombination between energy levels to emit light. In recent years, Organic electroluminescent devices (OLEDs) have been gradually introduced into the human field of vision as a new generation of display technology. An OLED is an electroluminescent device formed of a multi-layered organic thin film structure in which an organic thin film is a film of an organic light emitting material formed on a substrate using an evaporation, or spin coating process. Compared with the traditional display technology, the display technology has the advantages of voltage characteristic, light-emitting brightness, light-emitting efficiency, color quality, response speed, viewing angle and the like, and has low cost, thereby having wide market prospect.
In order to improve the luminance, efficiency and lifetime of organic electroluminescent devices, a multilayer structure is generally used in the devices. These multilayer structures include: the organic layers have the functions of improving the injection efficiency of carriers (holes and electrons) between the interfaces of each layer, balancing the capability of the carriers to be transmitted between each layer, and thus improving the brightness and the efficiency of the device.
At present, although a large number of organic electroluminescent materials with excellent performance have been developed, the technology still has many problems, and how to design new materials with better performance to adjust, so that all devices can achieve the effects of reducing voltage, improving efficiency and prolonging life, is a problem to be solved by those skilled in the art.
Disclosure of Invention
The purpose of the present invention is to provide an organic electroluminescent material which has high heat resistance and excellent chemical stability and can be used as a material for a hole injection layer, a hole transport layer, an electron blocking layer, or the like.
Another object of the present invention is to provide an organic light emitting device including the organic electroluminescent material, which has a lower driving voltage, higher light emitting efficiency and a longer service life.
In order to achieve the purpose, the technical scheme of the invention is as follows:
an organic electroluminescent material having a structure represented by chemical formula 1:
R1、Ar1and Ar2The same or different, each is independently selected from one of substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 40 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 32 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 40 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 40 carbon atoms, substituted or unsubstituted heteroaralkyl group having 2 to 40 carbon atoms, substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and substituted or unsubstituted heteroaryl group having 1 to 40 carbon atoms;
Ar3selected from single bonds, substituted or unsubstituted carbonsAn alkylene group having 1 to 40 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 40 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 32 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 40 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 40 carbon atoms, a substituted or unsubstituted aralkylene group having 7 to 40 carbon atoms, one of a substituted or unsubstituted heteroarylene group having 1 to 40 carbon atoms, a substituted or unsubstituted arylene group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 40 carbon atoms, a substituted or unsubstituted cycloalkenylene group having 3 to 15 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 2 to 32 carbon atoms, and a substituted or unsubstituted heteroalkenylene group having 2 to 15 carbon atoms.
In a further development of the invention, the R is1、Ar1、Ar2And Ar3The substituents (B) are the same or different and each is independently selected from deuterium, a cyano group, a nitro group, a halogen, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 40 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 32 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 40 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 40 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 2 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 40 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 40 carbon atoms, a substituted or unsubstituted alkylamino group having a carbon atom number of 1 to 40, a substituted or unsubstituted heteroaryl group having a carbon atom number of 2 to 32 carbon atoms, a substituted or unsubstituted heteroaryl group having a carbon atom number of 2 to 40, One of a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 40 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 1 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 45 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms.
In a further development of the invention, the R is1、Ar1And Ar2The same or different, each independently selected from a substituted or unsubstituted aralkyl group having 7 to 40 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 2 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 1 to 40 carbon atoms.
In a further development of the invention, Ar is3And one selected from substituted or unsubstituted phenyl, biphenyl, naphthyl, dimethyl fluorenyl, dibenzofuranyl and dibenzothienyl.
In a further improvement of the present invention, the chemical formula 1 is one of the following compounds:
in a further development of the invention, Ar is3And (b) one selected from the group consisting of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted dimethylfluorenyl group, a substituted or unsubstituted dibenzofuranyl group, and a substituted or unsubstituted dibenzothiophenyl group.
An organic electroluminescent device comprising a cathode, an anode, and one or more organic layers between the cathode and the anode, at least one of the one or more organic layers between the cathode and the anode comprising the organic electroluminescent material of claim 1.
In a further development of the invention, the organic layer is selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer.
In a further development of the invention, the organic layer comprising the organic electroluminescent material as claimed in claim 1 is a hole-transport layer.
Compared with the prior art, the invention has the following beneficial effects: the compound is characterized in that a second core group taking adamantane as a center is introduced based on the structure of triarylamine; wherein triarylamine has excellent hole transport property, which is the basis of the material as a hole transport layer; the adamantane has a structure with larger steric hindrance and firm rigidity, so that the molecular crystallinity is reduced, the film-forming property of the material is improved, and the energy loss caused by the self vibration relaxation of the molecules is reduced;
on the basis of the two core functional groups, the structure introduces another aryl group on adamantane, and the aryl group mainly has the following functions:
1. on the premise of not influencing the physical properties of adamantane, an energy transmission path between intermolecular triarylamine core groups is increased, and the hole conductivity of the material is further improved;
2. the adamantane core group is protected to a certain extent, and isomerization/dehydrogenation reaction of the adamantane core group is inhibited at high temperature, so that the purity of the material and the performance of a device are improved.
The compound containing the adamantyl group has excellent hole transport performance, can be used for manufacturing organic electroluminescent devices, particularly used as a hole transport layer material in the organic electroluminescent devices, and can effectively improve the luminous efficiency and prolong the service life of the organic electroluminescent devices.
Drawings
FIG. 1 is a schematic structural diagram of an organic electroluminescent material according to the present invention.
Detailed Description
The present invention will be described in further detail below with reference to examples. However, the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Referring to fig. 1, an organic electroluminescent material according to the present invention has a structure shown in chemical formula 1:
R1、Ar1and Ar2The same or different, each is independently selected from one of substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 40 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 32 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, substituted or unsubstituted heterocycloalkyl group having 2 to 40 carbon atoms, substituted or unsubstituted aralkyl group having 7 to 40 carbon atoms, substituted or unsubstituted heteroaralkyl group having 2 to 40 carbon atoms, substituted or unsubstituted aryl group having 6 to 40 carbon atoms, and substituted or unsubstituted heteroaryl group having 1 to 40 carbon atoms;
Ar3selected from the group consisting of a single bond, a substituted or unsubstituted alkylene group having 1 to 40 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 40 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 32 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 40 carbon atoms, a substituted or unsubstituted heterocycloalkylene group having 2 to 40 carbon atoms, a substituted or unsubstituted aralkylene group having 7 to 40 carbon atoms, one of a substituted or unsubstituted heteroarylene group having 1 to 40 carbon atoms, a substituted or unsubstituted arylene group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 40 carbon atoms, a substituted or unsubstituted cycloalkenylene group having 3 to 15 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 2 to 32 carbon atoms, and a substituted or unsubstituted heteroalkenylene group having 2 to 15 carbon atoms;
the R is1、Ar1、Ar2And Ar3The substituents (B) are the same or different and each is independently selected from deuterium, a cyano group, a nitro group, a halogen, a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 40 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 32 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 2 to 40 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 40 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 2 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 40 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 40 carbon atoms, a substituted or unsubstituted alkylamino group having a carbon atom number of 1 to 40, a substituted or unsubstituted heteroaryl group having a carbon atom number of 2 to 32 carbon atoms, a substituted or unsubstituted heteroaryl group having a carbon atom number of 2 to 40, One of a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 40 carbon atoms, a substituted or unsubstituted aralkylamino group having 7 to 30 carbon atoms, a substituted or unsubstituted heteroarylamino group having 1 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 45 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 50 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, and a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms.
Specifically, the R is1、Ar1And Ar2The same or different, each is independently selected from the group consisting of a substituted or unsubstituted aralkyl group having 7 to 40 carbon atoms, a substituted or unsubstituted heteroaralkyl group having 2 to 40 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 1 to 40 carbon atoms.
Specifically, Ar is3One member selected from the group consisting of a substituted or unsubstituted arylene group having 6 to 40 carbon atoms, a substituted or unsubstituted heteroarylene group having 1 to 40 carbon atoms, a substituted or unsubstituted aralkylene group having 7 to 40 carbon atoms, and a substituted or unsubstituted heteroaralkylene group having 2 to 40 carbon atoms.
Specifically, the chemical formula 1 is one of the following compounds:
ar in the invention3And (b) one selected from the group consisting of a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted dimethylfluorenyl group, a substituted or unsubstituted dibenzofuranyl group, and a substituted or unsubstituted dibenzothiophenyl group.
An organic electroluminescent device based on the organic electroluminescent material comprises a cathode, an anode and more than one organic layers arranged between the cathode and the anode, wherein at least one of the more than one organic layers comprises the organic electroluminescent material.
The organic layer is selected from a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.
The organic layer comprising the organic electroluminescent material is a hole transport layer.
The unsubstituted alkyl group in the present invention means a linear alkyl group having 1 to 40 carbon atoms or a branched alkyl group having 1 to 13 carbon atoms. For example, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, isopentyl, hexyl and the like. The substituted alkyl group having 1 to 40 carbon atoms means that at least one hydrogen atom is substituted with deuterium atom, F, Cl, I, CN, hydroxyl group, nitro group, amino group, or the like.
The unsubstituted alkenyl group in the present invention refers to an alkenyl group having 2 to 40 carbon atoms, a straight-chain alkenyl group having 2 to 40 carbon atoms containing a carbon-carbon double bond, or a branched-chain alkenyl group having 1 to 13 carbon atoms. For example: vinyl, propenyl, allyl, isopropenyl, 2-butenyl, and the like. The substituted alkenyl group having 2 to 40 carbon atoms means that at least one hydrogen atom is substituted with deuterium atom, F, Cl, I, CN, hydroxyl group, nitro group, amino group or the like.
The unsubstituted alkynyl group in the present invention refers to an alkynyl group having 2 to 32 carbon atoms, a straight-chain alkynyl group having 2 to 32 carbon atoms containing a carbon-carbon triple bond, or a branched-chain alkynyl group having 1 to 10 carbon atoms. For example: ethynyl, 2-propynyl, and the like. The substituted alkynyl group having 2 to 32 carbon atoms means that at least one hydrogen atom is substituted with deuterium atom, F, Cl, I, CN, hydroxyl group, nitro group, amino group or the like.
The unsubstituted aryl group in the present invention means an aryl group having 6 to 40 carbon atoms. For example: phenyl, naphthyl, pyrenyl, dimethylfluorenyl, anthracenyl, phenanthrenyl,
Mesityl, azunyl, acenaphthenyl, biphenyl, benzanthryl, spirobifluorenyl, perylenyl, indenyl, and the like. The substituted aryl group having 6 to 40 carbon atoms means that at least one hydrogen atom is substituted with deuterium atom, F, Cl, I, CN, hydroxyl group, nitro group, amino group, or the like.
The unsubstituted aralkyl group in the present invention means an aralkyl group having 7 to 30 carbon atoms. For example: tolyl, dimethylfluorenyl, and the like. The substituted aralkyl group having 7 to 30 carbon atoms means that at least one hydrogen atom is substituted with deuterium atom, F, Cl, I, CN, hydroxyl group, nitro group, amino group, or the like.
The unsubstituted heteroaryl group in the present invention means a heteroaryl group having 2 to 40 carbon atoms. For example: pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, quinolinyl, indolyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, dibenzoselenophenyl, and the like. Substituted heteroaryl having 2 to 40 carbon atoms means that at least one hydrogen atom is substituted with deuterium atom, F, Cl, I, CN, hydroxyl, nitro, amino, or the like.
The unsubstituted cycloalkyl group in the present invention means a cycloalkyl group having 3 to 40 carbon atoms. For example: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl and the like. The substituted cycloalkyl group having 3 to 40 carbon atoms means that at least one hydrogen atom is substituted with deuterium atom, F, Cl, I, CN, hydroxyl group, nitro group, amino group or the like.
The following description will be made by way of specific examples.
Synthesis of Compound 1
Bromobenzene (10.0g,63.7mmol) is dissolved in tetrahydrofuran (20mL), under the protection of nitrogen at 0 ℃, the bromobenzene is slowly dropped into the tetrahydrofuran (20mL) solution containing magnesium strips (1.9g,76.2mmol) and 1, 2-dibromoethane (0.1g), the reaction naturally rises to room temperature after the dropping is finished, and the stirring is kept for 3 hours; transferring the reaction solution to another container to remove residual magnesium strips, removing tetrahydrofuran under reduced pressure, and adding dichloromethane (30mL) to dilute the solid; then slowly dropwise adding a dichloromethane (50mL) solution dissolved with 1-bromoadamantane (13.7g,76.4mmol) at room temperature under the protection of nitrogen, heating to reflux, and keeping stirring for 2 hours; after cooling, pouring the reaction solution into 2mol/L hydrochloric acid at 0 ℃, separating an organic phase, and extracting a water phase by using n-heptane; the combined organic phases were washed with water, dried over magnesium sulfate, filtered and the solvent was removed under reduced pressure; purification of the crude product by silica gel column chromatography using n-heptane as the mobile phase gave 8.5g of intermediate 1-A-I as a colorless oil in 58% yield.
Intermediate 1-A-I (8.5g,40.0mmol) was added portionwise to a mixed solution of acetic acid (60mL) and acetic anhydride (60mL) in which chromium trioxide (12.0g,120.1mmol) was dissolved at 0 ℃ and then allowed to warm to room temperature naturally, followed by stirring for 12 hours. Adding water and dichloromethane into the reaction solution, stirring for 0.5h, separating liquid, extracting the water phase with dichloromethane, combining organic phases, adding magnesium sulfate, drying, filtering, and removing the solvent under reduced pressure; obtaining a crude product of yellow oily matter; adding 2mol/L sodium hydroxide aqueous solution (60mL) into the crude product, stirring at room temperature for 8h, and filtering to obtain a solid; the crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as the mobile phase to give 4.1g of intermediate 1-A-II as a white solid with a yield of 45%.
Intermediate 1-a-II (4.1g,18.0mmol) and bromobenzene (2.8g,18.0mmol) were dissolved in dichloromethane (30mL), trifluoromethanesulfonic acid (3.2g,21.5mmol) was slowly added dropwise under nitrogen protection at-40 ℃, the temperature was raised to 0 ℃ after stirring for 4h with constant temperature, and 2mol/L aqueous sodium hydroxide solution was added dropwise to the reaction solution so that the pH of the reaction solution became 7. Then, liquid separation is carried out, the organic phase is washed by water, magnesium sulfate is added for drying, and the solvent is removed under reduced pressure; the crude product was purified by silica gel column chromatography using n-heptane as the mobile phase to give 4.5g of intermediate 1-A as a white solid in a yield of 68%.
Adding 2-bromo-9, 9-dimethylfluorene (10.0g,36.6mmol), 2-amino-9, 9-dimethylfluorene (8.4g,0.3mmol), tris (dibenzylideneacetone) dipalladium (0.7g,0.7mmol), 2-dicyclohexyl-phosphorus-2, 4, 6-triisopropylbiphenyl (0.7g,1.5mmol) and sodium tert-butoxide (5.3g,54.9mmol) into toluene (100mL), heating to reflux temperature under nitrogen protection, stirring for 2h and then cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate for drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/n-heptane system to give 12.3g of intermediate 1-B as a pale yellow solid in 84% yield.
Intermediate 1-A (4.5g,12.3mmol), 1-B (4.9g,12.3mmol), tris (dibenzylideneacetone) dipalladium (0.2g,0.2mmol), 2-dicyclohexylphosphonium-2, 6-dimethoxybiphenyl (0.2g,0.5mmol) and sodium tert-butoxide (1.8g,18.4mmol)Adding into toluene (50mL), heating to reflux temperature under the protection of nitrogen, and stirring for 8 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/n-heptane system to yield 5.8g of compound 1 as a white solid in 69%). Mass spectrum M/z 688.4(M + H)+)。
Synthesis of Compound 2
Intermediate 1-a-II (5.0g,21.9mmol) and 4-bromobiphenyl (5.1g,21.9mmol) were dissolved in dichloromethane (35mL), trifluoromethanesulfonic acid (3.9g,26.3mmol) was slowly added dropwise under a nitrogen protection condition at-20 ℃, stirred for 2h with heat preservation, then warmed to 0 ℃, and 2mol/L aqueous sodium hydroxide solution was added dropwise to the reaction solution so that the pH of the reaction solution became 7. Then, liquid separation is carried out, the organic phase is washed by water, magnesium sulfate is added for drying, and the solvent is removed under reduced pressure; the crude product was purified by silica gel column chromatography using n-heptane as the mobile phase to give 5.5g of intermediate 2-A as a white solid with a yield of 57%.
4-bromobiphenyl (10.0g,42.9mmol), 4-aminobiphenyl (8.0g,47.2mmol), tris (dibenzylideneacetone) dipalladium (0.8g,0.9mmol), 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (0.8g,1.7mmol) and sodium tert-butoxide (6.2g,64.3mmol) were added to toluene (100mL), heated to reflux temperature under nitrogen protection and stirred for 1 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/ethanol system to give 10.4g of light yellow solid intermediate 2-B in a yield of 75%.
Adding the intermediate 2-A (5.5g,12.4mmol), the intermediate 2-B (4.0g,12.4mmol), tris (dibenzylideneacetone) dipalladium (0.2g,0.2mmol), 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.2g,0.5mmol) and sodium tert-butoxide (1.8g,18.6mmol) into toluene (60mL), heating to reflux temperature under nitrogen protection, and stirring for 6 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/n-heptane system to give 5.1g of compound 2 as a white solid in a yield of 60%. Mass spectrum M/z 684.4(M + H)+)。
Synthesis of Compound 3
Dissolving 2-bromonaphthalene (15.0g,72.4mmol) in tetrahydrofuran (30mL), slowly dropping the solution into the tetrahydrofuran (30mL) solution containing magnesium strips (2.1g,87.5mmol) and 1, 2-dibromoethane (0.1g) under the protection of nitrogen at 0 ℃, naturally raising the temperature to room temperature after dropping, and keeping stirring for 2 hours; the reaction solution was transferred to another vessel to remove residual magnesium strips, tetrahydrofuran was removed under reduced pressure, and the solid was diluted with dichloromethane (30 mL); then slowly dropwise adding a dichloromethane (60mL) solution dissolved with 1-bromoadamantane (15.6g,72.4mmol) at room temperature under the protection of nitrogen, heating to reflux, and keeping stirring for 3 hours; after cooling, pouring the reaction solution into 2mol/L hydrochloric acid at 0 ℃, separating an organic phase, and extracting a water phase by using dichloromethane; the combined organic phases were washed with water, dried over magnesium sulfate, filtered and the solvent was removed under reduced pressure; the crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as the mobile phase to give 9.7g of intermediate 3-A-I as a white solid with a yield of 59%.
Intermediate 3-A-I (9.7g,37.0mmol) was added portionwise to a mixed solution of acetic acid (60mL) and acetic anhydride (60mL) in which chromium trioxide (11.1g,110.9mmol) was dissolved at 0 ℃ and then allowed to warm to room temperature naturally, followed by stirring for 10 hours. Adding water and dichloromethane into the reaction solution, stirring for 0.5h, separating liquid, extracting the water phase with dichloromethane, combining organic phases, adding magnesium sulfate, drying, filtering, and removing the solvent under reduced pressure; obtaining a yellow solid crude product; adding 2mol/L sodium hydroxide aqueous solution (60mL) into the crude product, stirring for 6h at room temperature, and filtering to obtain a solid; the crude product was purified by silica gel column chromatography using methylene chloride/n-heptane as a mobile phase to give 5.2g of intermediate 3-A-II as a white solid with a yield of 51%.
Intermediate 3-a-II (5.2g,18.7mmol) and bromobenzene (2.9g,18.7mmol) were dissolved in dichloromethane (40mL), trifluoromethanesulfonic acid (3.4g,22.4mmol) was slowly added dropwise under nitrogen protection at-40 ℃, the temperature was raised to 0 ℃ after stirring for 3h with constant temperature, and 2mol/L aqueous sodium hydroxide solution was added dropwise to the reaction solution so that the pH of the reaction solution became 7. Then, liquid separation is carried out, the organic phase is washed by water, magnesium sulfate is added for drying, and the solvent is removed under reduced pressure; the crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as the mobile phase to give 4.6g of intermediate 3-A as a white solid in 59% yield.
Adding 2-bromo-9, 9-dimethylfluorene (10.0g,36.6mmol), 4-aminobiphenyl (6.8g,40.3mmol), tris (dibenzylideneacetone) dipalladium (0.7g,0.7mmol), 2-dicyclohexyl-phosphorus-2, 4, 6-triisopropylbiphenyl (0.7g,1.5mmol) and sodium tert-butoxide (5.3g,54.9mmol) into toluene (100mL), heating to reflux temperature under nitrogen protection, stirring for 2 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/ethanol system to give 9.8g of intermediate 3-B as a white solid in 83% yield.
Adding the intermediate 3-A (4.6g,11.0mmol), 3-B (4.0g,11.0mmol), tris (dibenzylideneacetone) dipalladium (0.2g,0.2mmol), 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.2g,0.4mmol) and sodium tert-butoxide (1.6g,16.5mmol) into toluene (50mL), heating to reflux temperature under nitrogen protection, and stirring for 12 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/ethyl acetate system to give 4.3g of compound 3 as a white solid in 56% yield. Mass spectrum M/z 698.4(M + H)+)。
Synthesis of Compound 4
Intermediate 1-a-II (4.0g,17.5mmol) and 2-bromo-9, 9-dimethylfluorene (4.8g,17.5mmol) were dissolved in dichloromethane (30mL), trifluoromethanesulfonic acid (3.2g,21.0mmol) was slowly added dropwise under a nitrogen protection condition at-30 ℃, stirred for 4h with heat preservation, then warmed to 0 ℃, and 2mol/L aqueous sodium hydroxide solution was added dropwise to the reaction solution so that the pH of the reaction solution became 7. Then, liquid separation is carried out, the organic phase is washed by water, magnesium sulfate is added for drying, and the solvent is removed under reduced pressure; the crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as the mobile phase to give 4.8g of intermediate 4-A as a white solid in a yield of 57%.
Adding 2-bromonaphthalene (10.0g,48.3mmol), 4-aminobiphenyl (9.0g,53.1mmol), tris (dibenzylideneacetone) dipalladium (0.9g,1.0mmol), 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (0.9g,1.9mmol) and sodium tert-butoxide (7.0g,72.4mmol) into toluene (100mL), heating to reflux temperature under nitrogen protection, stirring for 1 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; purification of the crude product by recrystallization using a dichloromethane/n-heptane system gave 11.9g of intermediate 4-B as a white solid in 77% yield.
Adding the intermediate 4-A (4.8g,9.9mmol), 4-B (2.9g,9.9mmol), tris (dibenzylideneacetone) dipalladium (0.2g,0.2mmol), 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.2g,0.4mmol) and sodium tert-butoxide (1.4g,14.9mmol) into toluene (50mL), heating to reflux temperature under nitrogen protection, and stirring for 12 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/n-heptane system to give 4.7g of compound 4 as a white solid in 68% yield. Mass spectrum M/z 698.4(M + H)+)。
Synthesis of Compound 5
Intermediate 1-a-II (5.0g,17.5mmol) and 2-bromonaphthalene (3.6g,17.5mmol) were dissolved in dichloromethane (30mL), trifluoromethanesulfonic acid (3.2g,21.0mmol) was slowly added dropwise under nitrogen protection at-40 ℃, stirred for 2h with constant temperature, warmed to 0 ℃, and 2mol/L aqueous sodium hydroxide solution was added dropwise to the reaction solution to adjust the pH of the reaction solution to 7. Then, liquid separation is carried out, the organic phase is washed by water, magnesium sulfate is added for drying, and the solvent is removed under reduced pressure; the crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as the mobile phase to give 4.5g of intermediate 5-A as a white solid in 62% yield.
Adding 2-bromo-9, 9-dimethylfluorene (10.0g,36.6mmol), 2-aminobiphenyl (6.8g,40.3mmol), tris (dibenzylideneacetone) dipalladium (0.7g,0.7mmol), 2-dicyclohexyl-phosphorus-2, 4, 6-triisopropylbiphenyl (0.7g,1.5mmol) and sodium tert-butoxide (5.3g,54.9mmol) into toluene (100mL), heating to reflux temperature under nitrogen protection, stirring for 3 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/ethanol system to give 11.0g of intermediate 5-B as a pale yellow solid in 83% yield.
Adding the intermediate 5-A (4.5g,10.8mmol), 5-B (3.9g,10.8mmol), tris (dibenzylideneacetone) dipalladium (0.2g,0.2mmol), 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.2g,0.4mmol) and sodium tert-butoxide (1.6g,16.2mmol) into toluene (50mL), heating to reflux temperature under nitrogen protection, and stirring for 12 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/n-heptane system to give 5.0g of compound 5 as a white solid in 66% yield. Mass spectrum M/z 698.4(M + H)+)。
Synthesis of Compound 6
Intermediate 1-a-II (4.0g,17.5mmol) and 2-bromodibenzofuran (4.3g,17.5mmol) were dissolved in dichloromethane (30mL), trifluoromethanesulfonic acid (3.2g,21.0mmol) was slowly added dropwise under nitrogen protection at-40 ℃, stirred for 4h at constant temperature, then raised to 0 ℃, and 2mol/L aqueous sodium hydroxide solution was added dropwise to the reaction solution to adjust the pH of the reaction solution to 7. Then, liquid separation is carried out, the organic phase is washed by water, magnesium sulfate is added for drying, and the solvent is removed under reduced pressure; the crude product was purified by silica gel column chromatography using n-heptane as the mobile phase to give 5.1g of intermediate 6-A as a white solid with a yield of 64%.
4-bromobiphenyl (10.0g,42.9mmol), aniline (4.4g,47.2mmol), tris (dibenzylideneacetone) dipalladium (0.8g,0.9mmol), 2-dicyclohexylphosphonium-2, 4, 6-triisopropylbiphenyl (0.8g,1.7mmol) and sodium tert-butoxide (6.2g,64.3mmol) were added to toluene (100mL), heated to reflux temperature under nitrogen and stirred for 1 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/ethanol system to give 8.3g of the intermediate 6-B as a pale brown solid with a yield of 79%.
Adding the intermediate 6-A (5.1g,11.1mmol), 6-B (2.7g,11.1mmol), tris (dibenzylideneacetone) dipalladium (0.2g,0.2mmol), 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.2g,0.4mmol) and sodium tert-butoxide (1.6g,16.7mmol) into toluene (50mL), heating to reflux temperature under nitrogen protection, and stirring for 6 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/n-heptane system to give 4.2g of compound 6 as a white solid in 61% yield. Mass spectrum M/z 622.3(M + H)+)。
Synthesis of Compound 7
Dissolving 4-bromobiphenyl (15.0g,64.3mmol) in tetrahydrofuran (35mL), slowly dropping the solution into tetrahydrofuran (30mL) solution containing magnesium strips (1.9g,77.2mmol) and 1, 2-dibromoethane (0.1g) under the protection of nitrogen at 0 ℃, naturally raising the temperature to room temperature after dropping, and keeping stirring for 3 hours; the reaction solution was transferred to another vessel to remove residual magnesium strips, tetrahydrofuran was removed under reduced pressure, and the solid was diluted with dichloromethane (30 mL); then slowly dropwise adding a dichloromethane (50mL) solution dissolved with 1-bromoadamantane (13.8g,64.3mmol) at room temperature under the protection of nitrogen, heating to reflux, and keeping stirring for 3 hours; after cooling, pouring the reaction solution into 2mol/L hydrochloric acid at 0 ℃, separating an organic phase, and extracting a water phase by using dichloromethane; the combined organic phases were washed with water, dried over magnesium sulfate, filtered and the solvent was removed under reduced pressure; the crude product was purified by silica gel column chromatography using n-heptane as the mobile phase to give 8.0g of intermediate 7-A-I as a white solid with a yield of 41%.
Intermediate 7-A-I (8.0g,27.7mmol) was added portionwise to a mixed solution of acetic acid (50mL) and acetic anhydride (50mL) in which chromium trioxide (8.3g,83.2mmol) was dissolved at 0 ℃ and then allowed to warm to room temperature naturally, followed by stirring for 10 hours. Adding water and dichloromethane into the reaction solution, stirring for 0.5h, separating liquid, extracting the water phase with dichloromethane, combining organic phases, adding magnesium sulfate, drying, filtering, and removing the solvent under reduced pressure; obtaining a yellow solid crude product; adding 2mol/L sodium hydroxide aqueous solution (50mL) into the crude product, stirring for 8h at room temperature, and filtering to obtain a solid; the crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as the mobile phase to give 4.4g of intermediate 7-A-II as a white solid with a yield of 52%.
Intermediate 7-a-II (4.4g,14.5mmol) and bromobenzene (2.3g,14.5mmol) were dissolved in dichloromethane (30mL), trifluoromethanesulfonic acid (2.6g,17.3mmol) was slowly added dropwise under nitrogen protection at-30 ℃, the temperature was raised to 0 ℃ after stirring for 6h with constant temperature, and 2mol/L aqueous sodium hydroxide solution was added dropwise to the reaction solution so that the pH of the reaction solution became 7. Then, liquid separation is carried out, the organic phase is washed by water, magnesium sulfate is added for drying, and the solvent is removed under reduced pressure; the crude product was purified by silica gel column chromatography using n-heptane as the mobile phase to give 4.3g of intermediate 7-A as a white solid with a yield of 65%.
2-bromodibenzofuran (10.0g,40.5mmol), 2-amino-9, 9-dimethylfluorene (9.3g,44.5mmol), tris (dibenzylideneacetone) dipalladium (0.7g,0.8mmol), 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl (0.8g,1.6mmol) and sodium tert-butoxide (5.8g,60.7mmol) were added to toluene (100mL), heated to reflux temperature under nitrogen and stirred for 4 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/n-heptane system to yield 12.9g of intermediate 7-B as a white solid in 85% yield.
Adding the intermediate 7-A (4.3g,9.7mmol), 7-B (3.6g,9.7mmol), tris (dibenzylideneacetone) dipalladium (0.2g,0.2mmol), 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.2g,0.4mmol) and sodium tert-butoxide (1.4g,14.5mmol) into toluene (40mL), heating to reflux temperature under nitrogen protection, and stirring for 10 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/ethyl acetate system to give 4.6g of compound 7 as a white solid in 64% yield. Mass spectrum M/z 738.4(M + H)+)
Synthesis of Compound 8
Dissolving 3-bromobiphenyl (10.0g,42.9mmol) in tetrahydrofuran (15mL), slowly dropping the solution into tetrahydrofuran (25mL) solution containing magnesium strips (1.3g,54.2mmol) and 1, 2-dibromoethane (0.1g) under the protection of nitrogen at 0 ℃, naturally raising the temperature to room temperature after dropping, and keeping stirring for 3 hours; the reaction solution was transferred to another vessel to remove residual magnesium strips, tetrahydrofuran was removed under reduced pressure, and the solid was diluted with dichloromethane (20 mL); then slowly dropwise adding a dichloromethane (40mL) solution dissolved with 1-bromoadamantane (9.2g,42.9mmol) at room temperature under the protection of nitrogen, heating to reflux, and keeping stirring for 4 hours; after cooling, pouring the reaction solution into 2mol/L hydrochloric acid at 0 ℃, separating an organic phase, and extracting a water phase by using n-heptane; the combined organic phases were washed with water, dried over magnesium sulfate, filtered and the solvent was removed under reduced pressure; the crude product was purified by silica gel column chromatography using n-heptane as the mobile phase to give 6.5g of intermediate 8-A-I as a colorless oil in 66% yield.
Intermediate 8-A-I (6.5g,22.5mmol) was added portionwise to a mixed solution of acetic acid (40mL) and acetic anhydride (40mL) in which chromium trioxide (6.8g,67.6mmol) was dissolved at 0 ℃ and then allowed to warm to room temperature naturally, followed by stirring for 16 h. Adding water and dichloromethane into the reaction solution, stirring for 0.5h, separating liquid, extracting the water phase with dichloromethane, combining organic phases, adding magnesium sulfate, drying, filtering, and removing the solvent under reduced pressure; obtaining a crude product of yellow oily matter; adding 2mol/L sodium hydroxide aqueous solution (40mL) into the crude product, stirring for 10h at room temperature, and filtering to obtain a solid; the crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as the mobile phase to give 4.1g of intermediate 8-A-II as a white solid with a yield of 60%.
Intermediate 8-a-II (4.1g,13.5mmol) and bromobenzene (2.1g,13.5mmol) were dissolved in dichloromethane (30mL), trifluoromethanesulfonic acid (2.4g,16.2mmol) was slowly added dropwise under nitrogen protection at-30 ℃, the temperature was raised to 0 ℃ after stirring for 5 hours with constant temperature, and a 2mol/L aqueous solution of sodium hydroxide was added dropwise to the reaction solution so that the pH of the reaction solution became 7. Then, liquid separation is carried out, the organic phase is washed by water, magnesium sulfate is added for drying, and the solvent is removed under reduced pressure; the crude product was purified by silica gel column chromatography using n-heptane as the mobile phase to give 3.9g of intermediate 8-A as a white solid with a yield of 63%.
Adding 3-bromo-N-phenylcarbazole (10g,31.0mmol), 2-amino-9, 9-dimethylfluorene (7.1g,34.1mmol), tris (dibenzylideneacetone) dipalladium (0.6g,0.6mmol), 2-dicyclohexyl-phosphorus-2, 4, 6-triisopropylbiphenyl (0.6g,1.2mmol) and sodium tert-butoxide (4.5g,46.6mmol) into toluene (100mL), heating to reflux temperature under nitrogen protection, and stirring for 3 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/n-heptane system to yield 10.4g of intermediate 8-B as a white solid in 74% yield.
Adding the intermediate 8-A (3.9g,8.8mmol), 8-B (4.0g,8.8mmol), tris (dibenzylideneacetone) dipalladium (0.2g,0.2mmol), 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.1g,0.4mmol) and sodium tert-butoxide (1.3g,13.2mmol) into toluene (40mL), heating to reflux temperature under nitrogen protection, and stirring for 8 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/ethyl acetate system to give 4.1g of compound 8 as a white solid in a yield of 57%. Mass spectrum M/z 813.4(M + H)+)
Synthesis of Compound 9
Dissolving 3-bromo-N-phenylcarbazole (20g,62.1mmol) in tetrahydrofuran (35mL), slowly dropping the solution into a tetrahydrofuran (30mL) solution containing magnesium strips (1.8g,74.5mmol) and 1, 2-dibromoethane (0.1g) under the protection of nitrogen at 0 ℃, naturally heating to room temperature after dropping, and keeping stirring for 5 hours; the reaction solution was transferred to another vessel to remove residual magnesium strips, tetrahydrofuran was removed under reduced pressure, and the solid was diluted with dichloromethane (40 mL); then slowly dropwise adding a dichloromethane (40mL) solution dissolved with 1-bromoadamantane (13.4g,62.3mmol) at room temperature under the protection of nitrogen, heating to reflux, and keeping stirring for 2 hours; after cooling, pouring the reaction solution into 2mol/L hydrochloric acid at 0 ℃, separating an organic phase, and extracting a water phase by using dichloromethane; the combined organic phases were washed with water, dried over magnesium sulfate, filtered and the solvent was removed under reduced pressure; the crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as the mobile phase to give 7.0g of intermediate 9-A-I as a white solid in 49% yield.
Intermediate 9-A-I (7.0g,18.5mmol) was added portionwise to a mixed solution of acetic acid (50mL) and acetic anhydride (50mL) in which chromium trioxide (5.6g,55.6mmol) was dissolved at 0 ℃ and then allowed to warm to room temperature naturally, followed by stirring for 12 hours. Adding water and dichloromethane into the reaction solution, stirring for 0.5h, separating liquid, extracting the water phase with dichloromethane, combining organic phases, adding magnesium sulfate, drying, filtering, and removing the solvent under reduced pressure; obtaining a yellow solid crude product; adding 2mol/L sodium hydroxide aqueous solution (50mL) into the crude product, stirring for 8h at room temperature, and filtering to obtain a solid; the crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as the mobile phase to give 4.7g of intermediate 9-A-II as a white solid with a yield of 64%.
Intermediate 9-a-II (4.7g,11.9mmol) and bromobenzene (1.9g,11.9mmol) were dissolved in dichloromethane (30mL), trifluoromethanesulfonic acid (2.2g,14.3mmol) was slowly added dropwise under nitrogen protection at-30 ℃, the temperature was raised to 0 ℃ after stirring for 5h with constant temperature, and a 2mol/L aqueous solution of sodium hydroxide was added dropwise to the reaction solution so that the pH of the reaction solution became 7. Then, liquid separation is carried out, the organic phase is washed by water, magnesium sulfate is added for drying, and the solvent is removed under reduced pressure; the crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as the mobile phase to give 4.0g of intermediate 9-A as a white solid in 63% yield.
Adding the intermediate 9-A (4.0g,7.5mmol), diphenylamine (1.3g,7.5mmol), tris (dibenzylideneacetone) dipalladium (0.1g,0.2mmol), 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.1g,0.3mmol) and sodium tert-butoxide (1.1g,11.3mmol) into toluene (40mL), heating to reflux temperature under nitrogen protection, and stirring for 8 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/n-heptane system to give 3.3g of compound 9 as a white solid in 71% yield. Mass spectrum M/z 621.3(M + H)+)
Synthesis of Compound 10
Dissolving 2-bromo-9, 9-dimethylfluorene (15.0g,54.9mmol) in tetrahydrofuran (25mL), slowly dropping the solution into a tetrahydrofuran (25mL) solution containing magnesium strips (1.6g,65.9mmol) and 1, 2-dibromoethane (0.1g) under the protection of nitrogen at 0 ℃, naturally raising the temperature to room temperature after dropping, and keeping stirring for 4 hours; the reaction solution was transferred to another vessel to remove residual magnesium strips, tetrahydrofuran was removed under reduced pressure, and the solid was diluted with dichloromethane (30 mL); then slowly dropwise adding a dichloromethane (40mL) solution dissolved with 1-bromoadamantane (11.8g,54.9mmol) at room temperature under the protection of nitrogen, heating to reflux, and keeping stirring for 3 hours; after cooling, pouring the reaction solution into 2mol/L hydrochloric acid at 0 ℃, separating an organic phase, and extracting a water phase by using n-heptane; the combined organic phases were washed with water, dried over magnesium sulfate, filtered and the solvent was removed under reduced pressure; the crude product was purified by silica gel column chromatography using n-heptane as the mobile phase to give 5.9g of the intermediate 10-A-I as a white wax in 47% yield.
Intermediate 10-A-I (5.9g,18.0mmol) was added portionwise to a mixed solution of acetic acid (40mL) and acetic anhydride (40mL) in which chromium trioxide (5.4g,53.9mmol) was dissolved at 0 ℃ and then allowed to warm to room temperature naturally, followed by stirring for 10 hours. Adding water and dichloromethane into the reaction solution, stirring for 0.5h, separating liquid, extracting the water phase with dichloromethane, combining organic phases, adding magnesium sulfate, drying, filtering, and removing the solvent under reduced pressure; obtaining a yellow solid crude product; adding 2mol/L sodium hydroxide aqueous solution (40mL) into the crude product, stirring at room temperature for 6h, and filtering to obtain a solid; the crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as the mobile phase to give 3.9g of intermediate 10-A-II as a white solid with a yield of 63%.
Intermediate 10-a-II (3.9g,11.3mmol) and bromobenzene (1.8g,11.3mmol) were dissolved in dichloromethane (30mL), trifluoromethanesulfonic acid (2.0g,13.6mmol) was slowly added dropwise under nitrogen protection at-30 ℃, the temperature was maintained and stirred for 6h, then the temperature was raised to 0 ℃, and 2mol/L aqueous sodium hydroxide solution was added dropwise to the reaction solution so that the pH of the reaction solution became 7. Then, liquid separation is carried out, the organic phase is washed by water, magnesium sulfate is added for drying, and the solvent is removed under reduced pressure; the crude product was purified by silica gel column chromatography using dichloromethane/n-heptane as the mobile phase to give 4.1g of intermediate 10-A as a white solid in a yield of 75%.
Adding 2-bromonaphthalene (10g,48.3mmol), aniline (4.9g,53.1mmol), tris (dibenzylideneacetone) dipalladium (0.9g,1.0mmol), 2-dicyclohexylphosphonium-2, 4, 6-triisopropylbiphenyl (0.9g,1.9mmol) and sodium tert-butoxide (7.0g,72.4mmol) into toluene (100mL), heating to reflux temperature under nitrogen protection, stirring for 1 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/ethanol system to give 8.2g of a light brown solid intermediate 10-B in 77% yield.
Adding the intermediate 10-A (4.1g,8.5mmol), 10-B (1.9g,8.5mmol), tris (dibenzylideneacetone) dipalladium (0.2g,0.2mmol), 2-dicyclohexyl phosphorus-2, 6-dimethoxy-biphenyl (0.1g,0.3mmol) and sodium tert-butoxide (1.2g,12.7mmol) into toluene (40mL), heating to reflux temperature under nitrogen protection, and stirring for 6 h; cooling to room temperature, washing the reaction solution with water, adding magnesium sulfate, drying, filtering, passing the filtrate through a short silica gel column, and removing the solvent under reduced pressure; the crude product was purified by recrystallization using a dichloromethane/n-heptane system to give 3.3g of compound 10 as a white solid in 63% yield. Mass spectrum M/z 622.4(M + H)+)。
Example 1: fabrication of organic electroluminescent device
The anode was prepared by the following procedure: will have a thickness of
The ITO substrate (manufactured by Corning) of (1) was cut into a size of 40mm × 40mm × 0.7mm, prepared into an experimental substrate having a pattern of cathode and anode regions and an insulating layer using a photolithography process, using violetExternal ozone and O2:N2The plasma was surface treated to increase the work function of the anode (experimental substrate) and to remove scum.
On a glass experimental substrate (anode), m-MTDATA was vacuum-evaporated to form a Hole Injection Layer (HIL) having a thickness, and on the hole injection layer, Compound 1 was vacuum-evaporated to form a Hole Injection Layer (HIL) having a thickness
A Hole Transport Layer (HTL).
Depositing TCTA on the hole transport layer to a thickness of
Electron Blocking Layer (EBL).
Using alpha, beta-AND as main body, simultaneously doping 4,4' - (3, 8-diphenylpyrene-1, 6-diylbis (N, N-diphenylaniline) to form a layer with thickness of
The light emitting layer (EML).
DBimiBphen and LiQ are mixed according to the weight ratio of 1:1 and evaporated to form
A thick Electron Transport Layer (ETL), and depositing LiQ on the electron transport layer to form a layer with a thickness of
And then magnesium (Mg) and silver (Ag) were mixed at a ratio of 9: 1, vacuum-evaporating on the electron injection layer to a thickness of
The cathode of (1).
Further, N- (4- (9H-carbazol-9-yl) phenyl) -4'- (9H-carbazol-9-yl) -N-phenyl- [1,1' -biphenyl ] -4-amine having a thickness of 65nm was deposited on the cathode to form a capping layer (CPL), thereby completing the production of an organic light-emitting device.
Examples 2 to 10
Organic electroluminescent devices were produced in the same manner as in example 1, except that the compounds shown in table 1 were each used in forming the hole transport layer.
That is, the compound 2 was used in example 2 to fabricate an organic electroluminescent device, the compound 3 was used in example 3 to fabricate an organic electroluminescent device, and the corresponding compounds 4 to 10 were used in examples 4 to 10 to fabricate an organic electroluminescent device, respectively, and the device properties are shown in table 1.
Comparative example 1 to comparative example 3
In the above example 1, an organic electroluminescent device was manufactured in the same manner as in example 1, except that NPB, compound a, and compound B were used as the hole transport layer instead of compound 1.
Namely, comparative example 1 produced an organic electroluminescent device using NPB, comparative example 2 produced an organic electroluminescent device using compound a, and comparative example 3 produced an organic electroluminescent device using compound B, and the device properties are shown in table 1.
For the organic electroluminescent device prepared as above, at 10mA/cm2The device performance was analyzed under the conditions of (1), and the results are shown in table 1 below.
TABLE 1 device Performance
Referring to Table 1, in the case of examples 1 to 10 using the compound of the present invention as a hole transport layer, the voltage (V), the current efficiency (Cd/A), the luminance (Cd/m) were compared with those of comparative examples 1 to 32) And External Quantum Efficiency (EQE) and half-life (T50) exhibit better characteristics. Therefore, the device manufactured by using the compound of the invention has the characteristics of reducing the driving voltage, improving the luminous efficiency and prolonging the service life.
In conclusion, the compound of the present invention is used as a hole transport layer of an organic electroluminescent device, so that the organic electroluminescent device comprising the compound has lower driving voltage, higher luminous efficiency and better lifetime.
As can be seen from table 1 of the results of the organic electroluminescent device of the example, the compound of the present invention further improves the hole conductivity of the material when adamantane is used as a hole transport material after introducing an aryl group thereto. Therefore, an organic electroluminescent device having excellent characteristics such as driving voltage, luminous efficiency, external quantum efficiency, and half-life can be manufactured.
The above examples are merely further illustrative of the compounds of the present invention and the scope of the invention as claimed is not limited thereto. It will be apparent to those skilled in the art that various additions and modifications can be made to the present invention without departing from the scope of the technical idea of the present invention as set forth in the claims of the present invention.
Claims (5)
1. An organic electroluminescent material, wherein the structure of the material is shown in chemical formula 1:
R1、Ar1and Ar2Each independently selected from phenyl, naphthyl, biphenyl, dimethylfluorenyl, dibenzofuranyl, substituted or unsubstituted carbazolyl;
R1、Ar1and Ar2The substituents of (a) are each independently selected from aryl groups having 6 carbon atoms;
Ar3selected from the group consisting of phenylene, naphthylene, biphenylene, dimethylfluorenyl, dibenzofuranylene.
2. The organic electroluminescent material of claim 1, wherein the chemical formula 1 is one of the compounds of the following structures:
3. an organic electroluminescent device comprising a cathode, an anode and one or more organic layers between the cathode and the anode, wherein at least one of the one or more organic layers between the cathode and the anode comprises the organic electroluminescent material of claim 1.
4. The organic electroluminescent device according to claim 3, wherein the organic layer comprises a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer.
5. The organic electroluminescent device according to claim 3, wherein the organic layer containing the organic electroluminescent material according to claim 1 is a hole transport layer.
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| CN110183333B (en) * | 2019-06-19 | 2020-06-30 | 陕西莱特光电材料股份有限公司 | Organic electroluminescent material and organic electroluminescent device containing same |
| CN110240546B (en) * | 2019-06-24 | 2020-04-17 | 陕西莱特光电材料股份有限公司 | Preparation method of adamantyl-containing triphenylamine derivative |
| CN110289361B (en) * | 2019-06-24 | 2022-06-10 | 陕西莱特光电材料股份有限公司 | Organic electroluminescent device |
| CN110317141A (en) * | 2019-07-01 | 2019-10-11 | 陕西莱特光电材料股份有限公司 | A kind of electroluminescent organic material and its synthetic method and application |
| CN110518133A (en) * | 2019-08-15 | 2019-11-29 | 陕西莱特光电材料股份有限公司 | Organic electroluminescence device and electronic device |
| CN110563647B (en) * | 2019-08-27 | 2021-02-12 | 陕西莱特光电材料股份有限公司 | Nitrogen-containing compound, organic electroluminescent device, and photoelectric conversion device |
| CN110615759B (en) * | 2019-09-25 | 2020-08-11 | 陕西莱特光电材料股份有限公司 | Compound, photoelectric conversion device, and electronic device |
| KR102718974B1 (en) * | 2019-10-18 | 2024-10-16 | 주식회사 엘지화학 | Novel compound and organic light emitting device comprising the same |
| KR102718973B1 (en) * | 2019-10-18 | 2024-10-17 | 주식회사 엘지화학 | Novel compound and organic light emitting device comprising the same |
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| CN112952010B (en) * | 2019-11-22 | 2022-11-18 | 陕西莱特光电材料股份有限公司 | Light emitting device and electronic apparatus |
| CN112209840B (en) * | 2020-03-13 | 2022-01-28 | 陕西莱特光电材料股份有限公司 | Nitrogen-containing compound, electronic component, and electronic device |
| CN112110825B (en) * | 2020-04-20 | 2022-02-11 | 陕西莱特光电材料股份有限公司 | Arylamine compound, electronic element using arylamine compound and electronic device |
| CN114149461B (en) * | 2020-09-08 | 2024-05-31 | 材料科学有限公司 | Organic compound and organic electroluminescent element comprising same |
| CN113636944B (en) * | 2021-05-07 | 2023-11-03 | 陕西莱特光电材料股份有限公司 | Organic compound, electronic element comprising same and electronic device |
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