CN104592124B - A kind of naphthalene [1,2] and imidazoles bipolarity conjugated compound and preparation and application - Google Patents

A kind of naphthalene [1,2] and imidazoles bipolarity conjugated compound and preparation and application Download PDF

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CN104592124B
CN104592124B CN201510007140.6A CN201510007140A CN104592124B CN 104592124 B CN104592124 B CN 104592124B CN 201510007140 A CN201510007140 A CN 201510007140A CN 104592124 B CN104592124 B CN 104592124B
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imidazoles
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CN104592124A (en
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苏仕健
刘明
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South China University of Technology SCUT
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    • C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
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    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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    • C07—ORGANIC CHEMISTRY
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    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
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Abstract

The invention belongs to luminescent material technical field, discloses a kind of naphthalene [1,2] and imidazoles bipolarity conjugated compound and preparation and application.The compound has the general structure shown in (1) or (2), and R1 and R2 is the conjugate unit with electron that is identical or differing in formula.Its preparation method is：Adjacent nitro naphthols reacts with the conjugate unit after trifluoromethyl sulfonic acid anhydride reaction with amino substitution, nitro is reduced to amino again, the conjugate unit that amino substitutes with acyl chlorides or aldehyde radical again carries out condensation reaction, it is coupled finally by Suzuki, Buchwald Hartwig couplings or copper catalysis halogenated aryl hydrocarbon ammoxidation are reacted with active conjugate unit, obtain naphthalene [1,2] and imidazoles bipolarity conjugated compound.The compound of the present invention is advantageously implemented preferable carrier balance, so as to obtain high device efficiency.

Description

A kind of naphthalene [1,2] and imidazoles bipolarity conjugated compound and preparation and application
Technical field
The invention belongs to luminescent material technical field, and in particular to a kind of naphthalene [1,2] and imidazoles bipolarity conjugated compound And preparation and application.
Background technology
Organic electroluminescent LED (OLED) because with efficiently, low voltage drive, be easy to large area and prepare and panchromatic aobvious The advantages that showing has broad application prospects, and obtains the extensive concern of people.The research starts from the last century 50's, until Doctor Deng Qingyun of Kodak in 1987 waits and sandwich device architecture is used in patent US4356429, develops OLED luminosity under 10V direct voltage drives reaches 1000cd/m2, OLED is obtained epoch-making development. In past 20 years, using novel light-emitting body, the OLED of especially organic-heavy metal complex phosphorescent emitters obtains No small success.However, due to more difficult acquisition wide bandgap phosphor, it disclosure satisfy that efficient pure blue lights (yCIE at present< 0.15, yCIE+xCIE<0.30) phosphorescent emitters quantity is very rare, and relative to green and red phosphorescence material, Selection is directed to the material of main part with high triplet energy level of blue phosphorescent also with suitable challenge.In addition, blue phosphorescent Unstable on device lifetime also largely limits its practical application.Therefore, the blue-fluorescence of development efficiently, stable Illuminator is still very necessary.In view of many factors, using blue fluorescent material can make the full-color displays of OLED or The practical production of white-light illuminating reduces cost and simplifies manufacturing process.But in the past classical blue organic fluorescence materials from N-type molecule or p-type molecule can be divided on molecular structure, is dominated or they show as electronics in device work, Show as hole to dominate, thus be difficult to the balance of carrier, so as to cause device current efficiency and quantum efficiency relatively low. And Donor-Acceptor (D-A) type molecule is simply designed, although bipolar transmission may be realized, reach equilbrium carrier Purpose, but because the Intramolecular electron transfer between electron unit and electrophilic subelement acts on, the band of compound can be caused Gap narrows, and causes glow peak red shift, it is difficult to obtains preferable blue-light-emitting.Overcome this difficult, it is necessary to which selection has suitable Intensity to electrical donor and electrophilicity receptor combination into a molecule, Intramolecular electron transfer is controlled in certain degree It is interior, it could obtain that performance is good, the high blue organic fluorescence materials of excitation.
The content of the invention
In order to solve the shortcomings that above prior art and weak point, primary and foremost purpose of the invention is to provide a kind of naphthalene [1,2] and imidazoles bipolarity conjugated compound.
Another object of the present invention is to provide the preparation method of above-mentioned naphthalene [1,2] and imidazoles bipolarity conjugated compound.
It is still another object of the present invention to provide the application of above-mentioned naphthalene [1,2] and imidazoles bipolarity conjugated compound.
The object of the invention is achieved through the following technical solutions：
There is the structure shown in (1) or (2) to lead to for a kind of naphthalene [1,2] and imidazoles bipolarity conjugated compound, the compound Formula：
R1 and R2 is the conjugate unit with electron that is identical or differing.
The conjugate unit includes aromatic rings, the carbon nitrogen hydrogen atom that ethene support group, acetylene support group, hydrocarbon atom are formed and formed Aromatic heterocycle, carbon nitrogen oxygen hydrogen atom form aromatic heterocycle, carbon sulphur hydrogen atom form aromatic heterocycle, carbon silicon hydrogen atom form Aromatic heterocycle, C1~C24 alkyl, alkyl-substituted conjugate unit, the conjugate unit or alkyl and alcoxyl of alkoxy substitution The simultaneously-substituted conjugate unit of base.
The aromatic heterocycle that the aromatic rings or carbon nitrogen hydrogen atom that the preferred hydrocarbon atom of conjugate unit is formed are formed.
Above-mentioned naphthalene [1,2] and the preparation method of imidazoles bipolarity conjugated compound, including following preparation process：
(1) adjacent nitro naphthols reacts to obtain the triflated compound of nitronaphthalene with trifluoromethyl sulfonic acid anhydride；
(2) the triflated compound of nitronaphthalene and the conjugate unit of amino substitution react, and obtain conjugate unit substitution Adjacent nitro naphthylamines；
(3) nitro for the adjacent nitro naphthylamines that conjugate unit substitutes is reduced into amino；
(4) conjugate unit that the amino of step (3) compound substitutes with acyl chlorides or aldehyde radical carries out condensation reaction；
(5) compound of step (4) is coupled by Suzuki, Buchwald-Hartwig is coupled or copper catalysis halo virtue Hydrocarbon ammoxidation is reacted with active conjugate unit, obtains naphthalene [1,2] and imidazoles bipolarity conjugated compound；
Conjugate unit described in step (2) or step (4) at least one be halogen substitution conjugate unit.
The preferred bromine of described halogen.
Above-mentioned naphthalene [1,2] and imidazoles bipolarity conjugated compound are as luminescent layer or electron transport layer materials in organic photoelectric Application in device.
Above-mentioned application concretely comprises the following steps：Lead on the hole transmission layer or electron transfer layer on ito glass Cross vacuum evaporation or solution coating prepares the film containing naphthalene [1,2] and imidazoles bipolarity conjugated compound, then in the film Either solution painting is covered with electron transfer layer or hole transmission layer to upper evaporation, then evaporation metal electrode is prepared into device.
The compound and preparation method of the present invention has the following advantages that and beneficial effect：
(1) naphthalene [1,2] of the invention and imidazoles bipolarity conjugated compound structure novelty, there is high fluorescent quantum to produce Rate, and ambipolar structure is advantageously implemented preferable carrier balance, so as to obtain high device efficiency；
(2) tool for preparing naphthalene [1,2] and imidazoles bipolarity conjugated compound is efficiently synthesized present invention firstly provides one kind Body path；
(3) naphthalene [1,2] and imidazoles bipolarity conjugated compound structure of the invention are single, and molecular weight determines, have preferable Dissolubility and film forming, can be applicable to the luminescent layer and electric transmission in organic electro-optic device such as including Organic Light Emitting Diode Layer.
Brief description of the drawings
Fig. 1, Fig. 2 and Fig. 5 are respectively the naphthalene [1,2] of embodiment 2 and embodiment 8 and imidazoles bipolarity conjugated compound conduct Voltage-current density-the brightness relationship curve of Organic Light Emitting Diode (OLED) device of luminescent layer, luminance-current efficiency-work( Rate relationship between efficiency curve and electroluminescent light spectrogram；
Fig. 3, Fig. 4 and Fig. 6 are respectively the naphthalene [1,2] of embodiment 3 and embodiment 9 and imidazoles bipolarity conjugated compound conduct Voltage-current density-the brightness relationship curve of Organic Light Emitting Diode (OLED) device of luminescent layer, luminance-current efficiency-work( Rate relationship between efficiency curve and electroluminescent light spectrogram.
Embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited In this.
Embodiment 1
(1) preparation of 1- nitronaphthalenes -2- triflates, reaction equation are as follows：
In 1 liter of single-necked flask, 1- nitros-beta naphthal (0.20mol, 37.8g) is added in 500 milliliters of dichloromethane Stirring and dissolving, add 50 milliliters of triethylamine after be cooled to 0 DEG C, be then slowly dropped into trifluoromethyl sulfonic acid anhydride (0.25mol, 70.5g).It is warmed to room temperature, reacts 10 hours naturally after being added dropwise.Then mixed liquor is poured into 1L water, and uses dichloromethane Extract product.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, white solid is obtained with silica gel chromatographic column separating-purifying (59.1g, yield 92%).
(2) preparation of 1- nitros-N- benzene -2- naphthylamines, reaction equation are as follows：
In 250 milliliters of three-necked flasks, 1- nitronaphthalene -2- triflates (50mmol, 16.1g) are added to 100 Stirring and dissolving in milliliter toluene, then aniline (100mmol, 9.3g) is separately added into, Anhydrous potassium carbonate (200mmol, 27.6g), four (triphenyl phosphorus) He Palladium (0.5mmol, 0.58g).110 DEG C are heated under argon atmosphere, is reacted 12 hours.Then mixed liquor falls Enter in 200mL water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, solvent is removed after separation, with silica gel color Spectrum post separation purifies to obtain red solid (11.2g, yield 85%).
(3) preparation of the amido naphthalene of N '-benzene -1,2- bis-, reaction equation are as follows：
In 1 liter of single-necked flask, 1- nitro-N-phenyl -2- naphthylamines (0.1mol, 26.4g) is added to 500 milliliters of ethanol Middle stirring and dissolving, add anhydrous stannous chloride (0.4mol, 75.6g), heating reflux reaction 18 hours.Then mixed liquor is poured into In 2L water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, uses silica gel chromatographic column Separating-purifying obtains gray solid (19.2g, yield 82%).
(4) preparation of 2- (4- bromobenzenes) -3- benzene -3-H- naphthalenes [1,2] and imidazoles, reaction equation are as follows：
In 1 liter of single-necked flask, by the amido naphthalene (50mmol, 11.7g) of N '-benzene -1,2- bis- and parabromobenzoyl chloride (10.5g, 48mmol), which is added in 150mL dichloromethane, to be dissolved, and then adds 10 milliliters of triethylamine, and it is small to react 10 at room temperature When.Then the solid separated out in reaction is filtered out, eluted successively with a small amount of ethanol and acetone.By gained white solid through overdrying After dry, it is added in 250mL single-necked flask, being mixed and heated to 110 DEG C with 100mL acetic acid reacts 12 hours.Then will mixing Liquid is poured into 500mL water, and extracts product with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, uses silicon Glue chromatographic column separating-purifying obtains white solid (12.2g, two steps add up to yield 64%).
(5) compound 1-1-1 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 2- (4- bromobenzenes) -3- benzene -3-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) with diphenylamines (6mmol, 1.0g), 100 milliliters of toluene are as solvent, 60 milligrams of palladium, tri-tert phosphorus (0.5mmol, 0.11g), and 1.5 grams of potassium carbonate.It is heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into 200 In milliliter water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, uses silica gel chromatograph Post separation purifies to obtain faint yellow solid, and drying obtains high-purity product (1.3g, yield after sublimed under vacuum 54%).
Embodiment 2
(1)~(4) are the same as embodiment 1；
(5) compound 1-1-2 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 2- (4- bromobenzenes) -3- benzene -3-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) and N, N- diphenyl -4- (4,4,5,5- tetramethyls -1,3,2- dioxaborolan -2- bases) aniline (7mmol, 2.6g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, 20 milliliters of weight concentrations are added as 10% aqueous sodium carbonate, 50 milligram four (triphenyl phosphorus) closes palladium, is heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into 200 milliliters of water, and with two Chloromethanes extracts product.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, Huang is obtained with silica gel chromatographic column separating-purifying Color solid, drying obtain high-purity product (1.7g, yield 61%) after sublimed under vacuum.
Embodiment 3
(1)~(4) are the same as embodiment 1；
(5) compound 1-1-3 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 2- (4- bromobenzenes) -3- benzene -3-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) and N, N- diphenyl -4 '-(4,4,5,5- tetramethyl -1,3,2- dioxaborolan -2- bases)-biphenyl -4- amine (7mmol, 3.1g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, add the sodium carbonate that 20 milliliters of weight concentrations are 10% Solution, 50 milligram four (triphenyl phosphorus) closes palladium, is heated to reflux lower stirring reaction 24 hours, and after cooling, mixed liquor is poured into 200 millis Rise in water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, uses silica gel chromatographic column Separating-purifying obtains green solid, and drying obtains high-purity product (1.9g, yield 59%) after sublimed under vacuum.
Embodiment 4
(1)~(4) are the same as embodiment 1；
(5) compound 1-1-4 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 2- (4- bromobenzenes) -3- benzene -3-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) and N, N- diphenyl -4 "-(4,4,5,5- tetramethyl -1,3,2- dioxaborolan -2- bases)-[1,1 '：4 ', 1 "-three Biphenyl] -4- amine (7mmol, 3.7g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, 20 milliliters of weight concentrations are added as 10% Aqueous sodium carbonate, 50 milligram four (triphenyl phosphorus) close palladium, be heated to reflux lower stirring reaction 24 hours, after cooling, will mix Liquid is poured into 200 milliliters of water, and extracts product with dichloromethane.Anhydrous magnesium sulfate dries organic phase, and solvent is removed after separation, uses Silica gel chromatographic column separating-purifying obtains green solid, and drying obtains high-purity product (1.9g, production after sublimed under vacuum Rate 53%).
Embodiment 5
(1)~(4) are the same as embodiment 1；
(5) compound 1-1-5 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 2- (4- bromobenzenes) -3- benzene -3-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) with 9- phenyl -3- (4,4,5,5- tetramethyls -1,3,2- dioxaborolan -2- bases) carbazole (7mmol, 2.6g), 30 in the least Toluene and 15 milliliters of tetrahydrofurans are risen, add the aqueous sodium carbonate that 20 milliliters of weight concentrations are 10%, 50 milligram of four (triphen Base phosphorus) palladium is closed, it is heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into 200 milliliters of water, and use dichloromethane Alkane extracts product.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, obtaining yellow with silica gel chromatographic column separating-purifying consolidates Body, drying obtain high-purity product (1.7g, yield 61%) after sublimed under vacuum.
Embodiment 6
(1)~(4) are the same as embodiment 1；
(5) compound 1-1-6 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 2- (4- bromobenzenes) -3- benzene -3-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) make with 9- hydrogen -3-9 '-bis- carbazoles (6mmol, 2.0g), 20 milliliters of 1,3- dimethyl -3,4,5,6- tetrahydrochysene -2- pyrimidones For solvent, 0.2 gram of cuprous iodide, 0.1 gram of 18- crown- 6- ethers, and 1.5 grams of potassium carbonate.It is heated to reflux lower stirring reaction 24 hours, After cooling, mixed liquor is poured into 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, separation After remove solvent, obtain yellow solid with silica gel chromatographic column separating-purifying, drying obtains high-purity after sublimed under vacuum Spend product (2.5g, yield 70%).
Embodiment 7
(1) preparation of 2- nitronaphthalenes -1- triflates, reaction equation are as follows：
In 1 liter of single-necked flask, 2- nitro -1- naphthols (0.20mol, 37.8g) is added in 500 milliliters of dichloromethane Stirring and dissolving, add 50 milliliters of triethylamine after be cooled to 0 DEG C, be then slowly dropped into trifluoromethyl sulfonic acid anhydride (0.25mol, 70.5g).It is warmed to room temperature, reacts 10 hours naturally after being added dropwise.Then mixed liquor is poured into 1L water, and uses dichloromethane Extract product.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, white solid is obtained with silica gel chromatographic column separating-purifying (59.1g, yield 92%).
(2) preparation of 2- nitros-N- benzene-naphthalidine, reaction equation are as follows：
In 250 milliliters of three-necked flasks, 2- nitronaphthalene -1- triflates (50mmol, 16.1g) are added to 100 Stirring and dissolving in milliliter toluene, then aniline (100mmol, 9.3g) is separately added into, Anhydrous potassium carbonate (200mmol, 27.6g), four (triphenyl phosphorus) He Palladium (0.5mmol, 0.58g).110 DEG C are heated under argon atmosphere, is reacted 12 hours.Then mixed liquor falls Enter in 200mL water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, solvent is removed after separation, with silica gel color Spectrum post separation purifies to obtain red solid (10.8g, yield 82%).
(3) preparation of the amido naphthalene of N- phenyl -1,2- bis-, reaction equation are as follows：
In 1 liter of single-necked flask, 2- nitros-N- benzene-naphthalidine (0.1mol, 26.4g) is added in 500 milliliters of ethanol Stirring and dissolving, add anhydrous stannous chloride (0.4mol, 75.6g), heating reflux reaction 18 hours.Then mixed liquor is poured into 2L In water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, and solvent is removed after separation, with silica gel chromatographic column point Gray solid (20.3g, yield 89%) is obtained from purification.
(4) preparation of 2- (4- bromobenzenes) -1- benzene -1-H- naphthalenes [1,2] and imidazoles, reaction equation are as follows：
In 1 liter of single-necked flask, by the amido naphthalene (50mmol, 11.7g) of N- phenyl -1,2- bis- and parabromobenzoyl chloride (10.5g, 48mmol), which is added in 150mL dichloromethane, to be dissolved, and then adds 10 milliliters of triethylamine, and it is small to react 10 at room temperature When.Then the solid separated out in reaction is filtered out, eluted successively with a small amount of ethanol and acetone.Gained white solid passes through drying Afterwards, it is added in 250mL single-necked flask, being mixed and heated to 110 DEG C with 100mL acetic acid reacts 12 hours.Then by mixed liquor Pour into 500mL water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, uses silica gel Chromatographic column separating-purifying obtains white solid (11.5g, two steps add up to yield 60%).
(5) compound 2-1-1 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 2- (4- bromobenzenes) -1- benzene -1-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) with diphenylamines (6mmol, 1.0g), 100 milliliters of toluene are as solvent, 60 milligrams of palladium, tri-tert phosphorus (0.5mmol, 0.11g), and 1.5 grams of potassium carbonate.It is heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into 200 In milliliter water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, uses silica gel chromatograph Post separation purifies to obtain white solid, and drying obtains high-purity product (1.1g, yield 46%) after sublimed under vacuum.
Embodiment 8
(1)~(4) are the same as embodiment 7；
(5) compound 2-1-2 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 2- (4- bromobenzenes) -1- benzene -1-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) and N, N- diphenyl -4- (4,4,5,5- tetramethyls -1,3,2- dioxaborolan -2- bases) aniline (7mmol, 2.6g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, 20 milliliters of weight concentrations are added as 10% aqueous sodium carbonate, 50 milligram four (triphenyl phosphorus) closes palladium, is heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into 200 milliliters of water, and with two Chloromethanes extracts product.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, Huang is obtained with silica gel chromatographic column separating-purifying Color solid, drying obtain high-purity product (1.5g, yield 54%) after sublimed under vacuum.
Embodiment 9
(1)~(4) are the same as embodiment 7；
(5) compound 2-1-3 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 2- (4- bromobenzenes) -1- benzene -1-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) and N, N- diphenyl -4 '-(4,4,5,5- tetramethyl -1,3,2- dioxaborolan -2- bases)-biphenyl -4- amine (7mmol, 3.1g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, add the sodium carbonate that 20 milliliters of weight concentrations are 10% Solution, 50 milligram four (triphenyl phosphorus) closes palladium, is heated to reflux lower stirring reaction 24 hours, and after cooling, mixed liquor is poured into 200 millis Rise in water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, uses silica gel chromatographic column Separating-purifying obtains green-yellow solid, and drying obtains high-purity product (1.9g, yield 59%) after sublimed under vacuum.
Embodiment 10
(1)~(4) are the same as embodiment 7；
(5) compound 2-1-4 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 2- (4- bromobenzenes) -1- benzene -1-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) and N, N- diphenyl -4 "-(4,4,5,5- tetramethyl -1,3,2- dioxaborolan -2- bases)-[1,1 '：4 ', 1 "-three Biphenyl] -4- amine (7mmol, 3.7g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, 20 milliliters of weight concentrations are added as 10% Aqueous sodium carbonate, 50 milligram four (triphenyl phosphorus) close palladium, be heated to reflux lower stirring reaction 24 hours, after cooling, will mix Liquid is poured into 200 milliliters of water, and extracts product with dichloromethane.Anhydrous magnesium sulfate dries organic phase, and solvent is removed after separation, uses Silica gel chromatographic column separating-purifying obtains green solid, and drying obtains high-purity product (1.7g, production after sublimed under vacuum Rate 48%).
Embodiment 11
(1)~(4) are the same as embodiment 7；
(5) compound 2-1-5 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 2- (4- bromobenzenes) -1- benzene -1-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) with 9- phenyl -3- (4,4,5,5- tetramethyls -1,3,2- dioxaborolan -2- bases) carbazole (7mmol, 2.6g), 30 in the least Toluene and 15 milliliters of tetrahydrofurans are risen, add the aqueous sodium carbonate that 20 milliliters of weight concentrations are 10%, 50 milligram of four (triphen Base phosphorus) palladium is closed, it is heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into 200 milliliters of water, and use dichloromethane Alkane extracts product.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, obtaining yellow with silica gel chromatographic column separating-purifying consolidates Body, drying obtain high-purity product (1.5g, yield 53%) after sublimed under vacuum.
Embodiment 12
(1)~(4) are the same as embodiment 7；
(5) compound 2-1-6 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 2- (4- bromobenzenes) -1- benzene -1-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) make with 9- hydrogen -3-9 '-bis- carbazoles (6mmol, 2.0g), 20 milliliters of 1,3- dimethyl -3,4,5,6- tetrahydrochysene -2- pyrimidones For solvent, 0.2 gram of cuprous iodide, 18 0.1 gram of 6 ethers of hat, and 1.5 grams of potassium carbonate.It is heated to reflux lower stirring reaction 24 hours, cools down Afterwards, mixed liquor is poured into 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, is gone after separation Except solvent, yellow solid is obtained with silica gel chromatographic column separating-purifying, drying obtains high-purity production after sublimed under vacuum Thing (2.2g, yield 61%).
Embodiment 13
(1) with embodiment 1；
(2) preparation of 1- nitros-N- (4- cyano group benzene) -2- naphthylamines, reaction equation are as follows：
In 250 milliliters of three-necked flasks, 1- nitronaphthalene -2- triflates (50mmol, 16.1g) are added to 100 Stirring and dissolving in milliliter toluene, then 4- anthranilo nitriles (60mmol, 7.1g) are separately added into, Anhydrous potassium carbonate (200mmol, 27.6g), four (triphenyl phosphorus) He Palladium (0.5mmol, 0.58g).110 DEG C are heated under argon atmosphere, is reacted 12 hours.So Mixed liquor is poured into 200mL water afterwards, and extracts product with dichloromethane.Anhydrous magnesium sulfate dries organic phase, is removed after separation molten Agent, red solid (12.7g, yield 88%) is obtained with silica gel chromatographic column separating-purifying.
(3) preparation of N '-amido naphthalenes of (4- cyano group benzene) -1,2- bis-, reaction equation are as follows：
In 1 liter of single-necked flask, 1- nitros-N- (4- cyano group benzene) -2- naphthylamines (0.1mol, 28.9g) is added to 500 millis Stirring and dissolving in ethanol is risen, adds anhydrous stannous chloride (0.4mol, 75.6g), heating reflux reaction 18 hours.Then will mixing Liquid is poured into 2L water, and extracts product with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, uses silica gel Chromatographic column separating-purifying obtains gray solid (20.4g, yield 79%).
(4) preparation of 2- (4- bromobenzenes) -3- (4- cyano group benzene) -3-H- naphthalenes [1,2] and imidazoles, reaction equation are as follows：
In 1 liter of single-necked flask, by N '-amido naphthalenes (50mmol, 13.0g) of (4- cyano group benzene) -1,2- bis- and to bromobenzene first Acyl chlorides (10.5g, 48mmol), which is added in 150mL dichloromethane, to be dissolved, and is then added 10 milliliters of triethylamine, is reacted at room temperature 10 hours.Then the solid separated out in reaction is filtered out, is eluted successively with a small amount of ethanol and acetone.Gained white solid is through overdrying After dry, it is added in 250mL single-necked flask, being mixed and heated to 110 DEG C with 100mL acetic acid reacts 12 hours.Then will mixing Liquid is poured into 500mL water, and extracts product with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, uses silicon Glue chromatographic column separating-purifying obtains white solid (13.8g, two steps add up to yield 68%).
(5) compound 1-2-1 preparation, reaction equation are as follows：
2- (4- bromobenzenes) -3- (4- cyano group benzene) -3-H- naphthalenes [1,2] and imidazoles are added into reaction bulb under an argon atmosphere (5mmol, 2.1g) and diphenylamines (6mmol, 1.0g), 100 milliliters of toluene are as solvent, 60 milligrams of palladium, tri-tert phosphorus (0.5mmol, 0.11g), and 1.5 grams of potassium carbonate.It is heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into 200 In milliliter water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, uses silica gel chromatograph Post separation purifies to obtain faint yellow solid, and drying obtains high-purity product (1.6g, yield after sublimed under vacuum 62%).
Embodiment 14
(1)~(4) are the same as embodiment 13；
(5) compound 1-2-2 preparation, reaction equation are as follows：
2- (4- bromobenzenes) -3- (4- cyano group benzene) -3-H- naphthalenes [1,2] and imidazoles are added into reaction bulb under an argon atmosphere (5mmol, 2.1g) and N, N- diphenyl -4- (4,4,5,5- tetramethyls -1,3,2- dioxaborolan -2- bases) aniline (7mmol, 2.6g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, add the sodium carbonate that 20 milliliters of weight concentrations are 10% Solution, 50 milligram four (triphenyl phosphorus) closes palladium, is heated to reflux lower stirring reaction 24 hours, and after cooling, mixed liquor is poured into 200 millis Rise in water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, uses silica gel chromatographic column Separating-purifying obtains green solid, and drying obtains high-purity product (2.1g, yield 72%) after sublimed under vacuum.
Embodiment 15
(1)~(4) are the same as embodiment 13；
(5) compound 1-2-3 preparation, reaction equation are as follows：
2- (4- bromobenzenes) -3- (4- cyano group benzene) -3-H- naphthalenes [1,2] and imidazoles are added into reaction bulb under an argon atmosphere (5mmol, 2.1g) and N, N- diphenyl -4 '-(4,4,5,5- tetramethyls -1,3,2- dioxaborolan -2- bases)-biphenyl - 4- amine (7mmol, 3.1g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, add the carbonic acid that 20 milliliters of weight concentrations are 10% Sodium water solution, 50 milligram four (triphenyl phosphorus) close palladium, are heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into In 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, solvent is removed after separation, with silica gel color Spectrum post separation purifies to obtain green solid, and drying obtains high-purity product (2.4g, yield after sublimed under vacuum 72%).
Embodiment 16
(1)~(4) are the same as embodiment 13；
(5) compound 1-2-4 preparation, reaction equation are as follows：
2- (4- bromobenzenes) -3- (4- cyano group benzene) -3-H- naphthalenes [1,2] and imidazoles are added into reaction bulb under an argon atmosphere (5mmol, 2.1g) and N, N- diphenyl -4 "-(4,4,5,5- tetramethyls -1,3,2- dioxaborolan -2- bases)-[1,1 '： 4 ', 1 "-terphenyl] -4- amine (7mmol, 3.7g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, it is dense to add 20 milliliters of weight The aqueous sodium carbonate for 10% is spent, 50 milligram four (triphenyl phosphorus) closes palladium, be heated to reflux lower stirring reaction 24 hours, cool down Afterwards, mixed liquor is poured into 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, is gone after separation Except solvent, yellow solid is obtained with silica gel chromatographic column separating-purifying, drying obtains high-purity production after sublimed under vacuum Thing (2.2g, yield 59%).
Embodiment 17
(1)~(4) are the same as embodiment 13；
(5) compound 1-2-5 preparation, reaction equation are as follows：
2- (4- bromobenzenes) -3- (4- cyano group benzene) -3-H- naphthalenes [1,2] and imidazoles are added into reaction bulb under an argon atmosphere (5mmol, 2.1g) and 9- phenyl -3- (4,4,5,5- tetramethyls -1,3,2- dioxaborolan -2- bases) carbazole (7mmol, 2.6g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, 20 milliliters of weight concentrations are added as 10% aqueous sodium carbonate, 50 Four (triphenyl phosphorus) of milligram close palladium, are heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into 200 milliliters of water, And extract product with dichloromethane.Anhydrous magnesium sulfate dries organic phase, solvent is removed after separation, with silica gel chromatographic column separating-purifying Faint yellow solid is obtained, drying obtains high-purity product (2.3g, yield 77%) after sublimed under vacuum.
Embodiment 18
(1)~(4) are the same as embodiment 13；
(5) compound 1-2-6 preparation, reaction equation are as follows：
2- (4- bromobenzenes) -3- (4- cyano group benzene) -3-H- naphthalenes [1,2] and imidazoles are added into reaction bulb under an argon atmosphere (5mmol, 2.1g) and 9- hydrogen -3-9 '-bis- carbazoles (6mmol, 2.0g), 20 milliliters of 1,3- dimethyl -3,4,5,6- tetrahydrochysene -2- are phonetic Pyridine ketone is as solvent, 0.2 gram of cuprous iodide, 18 0.1 gram of 6 ethers of hat, and 1.5 grams of potassium carbonate.It is small to be heated to reflux lower stirring reaction 24 When, after cooling, mixed liquor is poured into 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, Solvent is removed after separation, obtains faint yellow solid with silica gel chromatographic column separating-purifying, drying obtains after sublimed under vacuum To high-purity product (2.4g, yield 68%).
Embodiment 19
(1) with embodiment 7；
(2) preparation of 2- nitros-N- (4- cyano group benzene)-naphthalidine, reaction equation are as follows：
In 250 milliliters of three-necked flasks, 2- nitronaphthalene -1- triflates (50mmol, 16.1g) are added to 100 Stirring and dissolving in milliliter toluene, then 4- anthranilo nitriles (60mmol, 7.1g) are separately added into, Anhydrous potassium carbonate (200mmol, 27.6g), four (triphenyl phosphorus) He Palladium (0.5mmol, 0.58g).110 DEG C are heated under argon atmosphere, is reacted 12 hours.So Mixed liquor is poured into 200mL water afterwards, and extracts product with dichloromethane.Anhydrous magnesium sulfate dries organic phase, is removed after separation molten Agent, red solid (11.7g, yield 81%) is obtained with silica gel chromatographic column separating-purifying.
(3) preparation of the amido naphthalenes of N- (4- cyano group benzene) -1,2- bis-, reaction equation are as follows：
In 1 liter of single-necked flask, 2- nitros-N- (4- cyano group benzene)-naphthalidine (0.1mol, 28.9g) is added to 500 millis Stirring and dissolving in ethanol is risen, adds anhydrous stannous chloride (0.4mol, 75.6g), heating reflux reaction 18 hours.Then will mixing Liquid is poured into 2L water, and extracts product with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, uses silica gel Chromatographic column separating-purifying obtains yellow solid (20.0g, yield 77%).
(4) preparation of 2- (4- bromobenzenes) -1- (4- cyano group benzene) -1-H- naphthalenes [1,2] and imidazoles, reaction equation are as follows：
In 1 liter of single-necked flask, by the amido naphthalenes (50mmol, 13.0g) of N- (4- cyano group benzene) -1,2- bis- and to Bromophenacyl Chlorine (10.5g, 48mmol), which is added in 150mL dichloromethane, to be dissolved, and is then added 10 milliliters of triethylamine, is reacted 10 at room temperature Hour.Then the solid separated out in reaction is filtered out, is eluted successively with a small amount of ethanol and acetone.Gained white solid passes through drying Afterwards, it is added in 250mL single-necked flask, being mixed and heated to 110 DEG C with 100mL acetic acid reacts 12 hours.Then by mixed liquor Pour into 500mL water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, uses silica gel Chromatographic column separating-purifying obtains white solid (12.0g, two steps add up to yield 59%).
(5) compound 2-2-1 preparation, reaction equation are as follows：
2- (4- bromobenzenes) -1- (4- cyano group benzene) -1-H- naphthalenes [1,2] and imidazoles are added into reaction bulb under an argon atmosphere (5mmol, 2.1g) and diphenylamines (6mmol, 1.0g), 100 milliliters of toluene are as solvent, 60 milligrams of palladium, tri-tert phosphorus (0.5mmol, 0.11g), and 1.5 grams of potassium carbonate.It is heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into 200 In milliliter water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, uses silica gel chromatograph Post separation purifies to obtain faint yellow solid, and drying obtains high-purity product (1.4g, yield after sublimed under vacuum 54%).
Embodiment 20
(1)~(4) are the same as embodiment 19；
(5) compound 2-2-2 preparation, reaction equation are as follows：
2- (4- bromobenzenes) -1- (4- cyano group benzene) -1-H- naphthalenes [1,2] and imidazoles are added into reaction bulb under an argon atmosphere (5mmol, 2.1g) and N, N- diphenyl -4- (4,4,5,5- tetramethyls -1,3,2- dioxaborolan -2- bases) aniline (7mmol, 2.6g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, add the sodium carbonate that 20 milliliters of weight concentrations are 10% Solution, 50 milligram four (triphenyl phosphorus) closes palladium, is heated to reflux lower stirring reaction 24 hours, and after cooling, mixed liquor is poured into 200 millis Rise in water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, uses silica gel chromatographic column Separating-purifying obtains yellow solid, and drying obtains high-purity product (1.7g, yield 59%) after sublimed under vacuum.
Embodiment 21
(1)~(4) are the same as embodiment 19；
(5) compound 2-2-3 preparation, reaction equation are as follows：
2- (4- bromobenzenes) -1- (4- cyano group benzene) -1-H- naphthalenes [1,2] and imidazoles are added into reaction bulb under an argon atmosphere (5mmol, 2.1g) and N, N- diphenyl -4 '-(4,4,5,5- tetramethyls -1,3,2- dioxaborolan -2- bases)-biphenyl - 4- amine (7mmol, 3.1g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, add the carbonic acid that 20 milliliters of weight concentrations are 10% Sodium water solution, 50 milligram four (triphenyl phosphorus) close palladium, are heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into In 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, solvent is removed after separation, with silica gel color Spectrum post separation purifies to obtain green solid, and drying obtains high-purity product (2.3g, yield after sublimed under vacuum 69%).
Embodiment 22
(1)~(4) are the same as embodiment 19；
(5) compound 2-2-4 preparation, reaction equation are as follows：
2- (4- bromobenzenes) -1- (4- cyano group benzene) -1-H- naphthalenes [1,2] and imidazoles are added into reaction bulb under an argon atmosphere (5mmol, 2.1g) and N, N- diphenyl -4 "-(4,4,5,5- tetramethyls -1,3,2- dioxaborolan -2- bases)-[1,1 '： 4 ', 1 "-terphenyl] -4- amine (7mmol, 3.7g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, it is dense to add 20 milliliters of weight The aqueous sodium carbonate for 10% is spent, 50 milligram four (triphenyl phosphorus) closes palladium, be heated to reflux lower stirring reaction 24 hours, cool down Afterwards, mixed liquor is poured into 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, is gone after separation Except solvent, yellow solid is obtained with silica gel chromatographic column separating-purifying, drying obtains high-purity production after sublimed under vacuum Thing (1.9g, yield 51%).
Embodiment 23
(1)~(4) are the same as embodiment 19；
(5) compound 2-2-5 preparation, reaction equation are as follows：
2- (4- bromobenzenes) -1- (4- cyano group benzene) -1-H- naphthalenes [1,2] and imidazoles are added into reaction bulb under an argon atmosphere (5mmol, 2.1g) and 9- phenyl -3- (4,4,5,5- tetramethyls -1,3,2- dioxaborolan -2- bases) carbazole (7mmol, 2.6g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, 20 milliliters of weight concentrations are added as 10% aqueous sodium carbonate, 50 Four (triphenyl phosphorus) of milligram close palladium, are heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into 200 milliliters of water, And extract product with dichloromethane.Anhydrous magnesium sulfate dries organic phase, solvent is removed after separation, with silica gel chromatographic column separating-purifying Faint yellow solid is obtained, drying obtains high-purity product (2.0g, yield 69%) after sublimed under vacuum.
Embodiment 24
(1)~(4) are the same as embodiment 19；
(5) compound 2-2-6 preparation, reaction equation are as follows：
2- (4- bromobenzenes) -1- (4- cyano group benzene) -1-H- naphthalenes [1,2] and imidazoles are added into reaction bulb under an argon atmosphere (5mmol, 2.1g) and 9- hydrogen -3-9 '-bis- carbazoles (6mmol, 2.0g), 20 milliliters of 1,3- dimethyl -3,4,5,6- tetrahydrochysene -2- are phonetic Pyridine ketone is as solvent, 0.2 gram of cuprous iodide, 18 0.1 gram of 6 ethers of hat, and 1.5 grams of potassium carbonate.It is small to be heated to reflux lower stirring reaction 24 When, after cooling, mixed liquor is poured into 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, Solvent is removed after separation, obtains faint yellow solid with silica gel chromatographic column separating-purifying, drying obtains after sublimed under vacuum To high-purity product (2.5g, yield 67%).
Embodiment 25
(1) with embodiment 1；
(2) preparation of 1- nitros-N- (4- bromobenzenes) -2- naphthylamines, reaction equation are as follows：
In 250 milliliters of three-necked flasks, 1- nitronaphthalene -2- triflates (50mmol, 16.1g) are added to 100 Stirring and dissolving in milliliter toluene, then 4- bromanilines (60mmol, 10.3g) are separately added into, Anhydrous potassium carbonate (200mmol, 27.6g), four (triphenyl phosphorus) He Palladium (0.5mmol, 0.58g).110 DEG C are heated under argon atmosphere, is reacted 12 hours.So Mixed liquor is poured into 200mL water afterwards, and extracts product with dichloromethane.Anhydrous magnesium sulfate dries organic phase, is removed after separation molten Agent, red solid (13.7g, yield 80%) is obtained with silica gel chromatographic column separating-purifying.
(3) preparation of N '-amido naphthalenes of (4- bromobenzenes) -1,2- bis-, reaction equation are as follows：
In 1 liter of single-necked flask, 1- nitros-N- (4- bromobenzenes) -2- naphthylamines (0.1mol, 34.3g) is added to 500 milliliters Stirring and dissolving in ethanol, add anhydrous stannous chloride (0.4mol, 75.6g), heating reflux reaction 18 hours.Then by mixed liquor Pour into 2L water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, solvent is removed after separation, with silica gel color Spectrum post separation purifies to obtain gray solid (25.3g, yield 81%).
(4) preparation of 3- (4- bromobenzenes) -2- benzene -3-H- naphthalenes [1,2] and imidazoles, reaction equation are as follows：
In 1 liter of single-necked flask, by N '-amido naphthalenes (50mmol, 15.6g) of (4- bromobenzenes) -1,2- bis- and chlorobenzoyl chloride (6.7g, 48mmol), which is added in 150mL dichloromethane, to be dissolved, and adds 10 milliliters of triethylamine, is reacted 10 hours at room temperature. Then the solid separated out in reaction is filtered out, is eluted successively with a small amount of ethanol and acetone.Gained white solid adds after drying Enter into 250mL single-necked flask, being mixed and heated to 110 DEG C with 100mL acetic acid reacts 12 hours.Then mixed liquor is poured into In 500mL water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, uses silica gel chromatograph Post separation purifies to obtain white solid (13.4g, two steps add up to yield 70%).
(5) compound 1-3-1 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 3- (4- bromobenzenes) -2- benzene -3-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) with diphenylamines (6mmol, 1.0g), 100 milliliters of toluene are as solvent, 60 milligrams of palladium, tri-tert phosphorus (0.5mmol, 0.11g), and 1.5 grams of potassium carbonate.It is heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into 200 In milliliter water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, uses silica gel chromatograph Post separation purifies to obtain white solid, and drying obtains high-purity product (1.2g, yield 49%) after sublimed under vacuum.
Embodiment 26
(1)~(4) are the same as embodiment 25；
(5) compound 1-3-2 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 3- (4- bromobenzenes) -2- benzene -3-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) and N, N- diphenyl -4- (4,4,5,5- tetramethyls -1,3,2- dioxaborolan -2- bases) aniline (7mmol, 2.6g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, 20 milliliters of weight concentrations are added as 10% aqueous sodium carbonate, 50 milligram four (triphenyl phosphorus) closes palladium, is heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into 200 milliliters of water, and with two Chloromethanes extracts product.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, is obtained with silica gel chromatographic column separating-purifying light Yellow solid, drying obtain high-purity product (1.8g, yield 63%) after sublimed under vacuum.
Embodiment 27
(1)~(4) are the same as embodiment 25；
(5) compound 1-3-3 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 3- (4- bromobenzenes) -2- benzene -3-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) and N, N- diphenyl -4 '-(4,4,5,5- tetramethyl -1,3,2- dioxaborolan -2- bases)-biphenyl -4- amine (7mmol, 3.1g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, add the sodium carbonate that 20 milliliters of weight concentrations are 10% Solution, 50 milligram four (triphenyl phosphorus) closes palladium, is heated to reflux lower stirring reaction 24 hours, and after cooling, mixed liquor is poured into 200 millis Rise in water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, uses silica gel chromatographic column Separating-purifying obtains faint yellow solid, and drying obtains high-purity product (2.1g, yield 65%) after sublimed under vacuum.
Embodiment 28
(1)~(4) are the same as embodiment 25；
(5) compound 1-3-4 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 3- (4- bromobenzenes) -2- benzene -3-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) and N, N- diphenyl -4 "-(4,4,5,5- tetramethyl -1,3,2- dioxaborolan -2- bases)-[1,1 '：4 ', 1 "-three Biphenyl] -4- amine (7mmol, 3.7g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, 20 milliliters of weight concentrations are added as 10% Aqueous sodium carbonate, 50 milligram four (triphenyl phosphorus) close palladium, be heated to reflux lower stirring reaction 24 hours, after cooling, will mix Liquid is poured into 200 milliliters of water, and extracts product with dichloromethane.Anhydrous magnesium sulfate dries organic phase, and solvent is removed after separation, uses Silica gel chromatographic column separating-purifying obtains faint yellow solid, drying after sublimed under vacuum obtain high-purity product (1.7g, Yield 48%).
Embodiment 29
(1)~(4) are the same as embodiment 25；
(5) compound 1-3-5 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 3- (4- bromobenzenes) -2- benzene -3-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) and N, N- diphenyl -4- (4,4,5,5- tetramethyls -1,3,2- dioxaborolan -2- bases) aniline (7mmol, 2.6g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, 20 milliliters of weight concentrations are added as 10% aqueous sodium carbonate, 50 milligram four (triphenyl phosphorus) closes palladium, is heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into 200 milliliters of water, and with two Chloromethanes extracts product.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, Huang is obtained with silica gel chromatographic column separating-purifying Color solid, drying obtain high-purity product (1.9g, yield 69%) after sublimed under vacuum.
Embodiment 30
(1)~(4) are the same as embodiment 25；
(5) compound 1-3-6 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 3- (4- bromobenzenes) -2- benzene -3-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) make with 9- hydrogen -3-9 '-bis- carbazoles (6mmol, 2.0g), 20 milliliters of 1,3- dimethyl -3,4,5,6- tetrahydrochysene -2- pyrimidones For solvent, 0.2 gram of cuprous iodide, 18 0.1 gram of 6 ethers of hat, and 1.5 grams of potassium carbonate.It is heated to reflux lower stirring reaction 24 hours, cools down Afterwards, mixed liquor is poured into 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, is gone after separation Except solvent, faint yellow solid is obtained with silica gel chromatographic column separating-purifying, drying obtains high-purity after sublimed under vacuum Product (2.2g, yield 66%).
Embodiment 31
(1) with embodiment 7；
(2) preparation of 2- nitros-N- (4- bromobenzenes)-naphthalidine, reaction equation are as follows：
In 250 milliliters of three-necked flasks, 2- nitronaphthalene -1- triflates (50mmol, 16.1g) are added to 100 Stirring and dissolving in milliliter toluene, then 4- bromanilines (60mmol, 10.3g) are separately added into, Anhydrous potassium carbonate (200mmol, 27.6g), four (triphenyl phosphorus) He Palladium (0.5mmol, 0.58g).110 DEG C are heated under argon atmosphere, is reacted 12 hours.So Mixed liquor is poured into 200mL water afterwards, and extracts product with dichloromethane.Anhydrous magnesium sulfate dries organic phase, is removed after separation molten Agent, dark red solid (15.4g, yield 90%) is obtained with silica gel chromatographic column separating-purifying.
(3) preparation of the amido naphthalenes of N- (4- bromobenzenes) -1,2- bis-, reaction equation are as follows：
In 1 liter of single-necked flask, 2- nitros-N- (4- bromobenzenes)-naphthalidines (0.1mol, 34.3g) are added to 500 milliliters Stirring and dissolving in ethanol, add anhydrous stannous chloride (0.4mol, 75.6g), heating reflux reaction 18 hours.Then by mixed liquor Pour into 2L water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, solvent is removed after separation, with silica gel color Spectrum post separation purifies to obtain gray solid (25.9g, yield 83%).
(4) preparation of 1- (4- bromobenzenes) -2- benzene -1-H- naphthalenes [1,2] and imidazoles, reaction equation are as follows：
In 1 liter of single-necked flask, by the amido naphthalenes (50mmol, 15.6g) of N- (4- bromobenzenes) -1,2- bis- and chlorobenzoyl chloride (6.7g, 48mmol), which is added in 150mL dichloromethane, to be dissolved, and adds 10 milliliters of triethylamine, is reacted 10 hours at room temperature. Then the solid separated out in reaction is filtered out, is eluted successively with a small amount of ethanol and acetone.Gained white solid adds after drying Enter into 250mL single-necked flask, being mixed and heated to 110 DEG C with 100mL acetic acid reacts 12 hours.Then mixed liquor is poured into In 500mL water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, uses silica gel chromatograph Post separation purifies to obtain white solid (12.4g, two steps add up to yield 63%).
(5) compound 2-3-1 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 1- (4- bromobenzenes) -2- benzene -1-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) with diphenylamines (6mmol, 1.0g), 100 milliliters of toluene are as solvent, 60 milligrams of palladium, tri-tert phosphorus (0.5mmol, 0.11g), and 1.5 grams of potassium carbonate.It is heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into 200 In milliliter water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, uses silica gel chromatograph Post separation purifies to obtain white solid, and drying obtains high-purity product (1.1g, yield 45%) after sublimed under vacuum.
Embodiment 32
(1)~(4) are the same as embodiment 31；
(5) compound 2-3-2 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 1- (4- bromobenzenes) -2- benzene -1-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) and N, N- diphenyl -4- (4,4,5,5- tetramethyls -1,3,2- dioxaborolan -2- bases) aniline (7mmol, 2.6g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, 20 milliliters of weight concentrations are added as 10% aqueous sodium carbonate, 50 milligram four (triphenyl phosphorus) closes palladium, is heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into 200 milliliters of water, and with two Chloromethanes extracts product.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, is obtained with silica gel chromatographic column separating-purifying light Yellow solid, drying obtain high-purity product (1.7g, yield 60%) after sublimed under vacuum.
Embodiment 33
(1)~(4) are the same as embodiment 31；
(5) compound 2-3-3 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 1- (4- bromobenzenes) -2- benzene -1-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) and N, N- diphenyl -4 '-(4,4,5,5- tetramethyl -1,3,2- dioxaborolan -2- bases)-biphenyl -4- amine (7mmol, 3.1g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, add the sodium carbonate that 20 milliliters of weight concentrations are 10% Solution, 50 milligram four (triphenyl phosphorus) closes palladium, is heated to reflux lower stirring reaction 24 hours, and after cooling, mixed liquor is poured into 200 millis Rise in water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, uses silica gel chromatographic column Separating-purifying obtains faint yellow solid, and drying obtains high-purity product (1.8g, yield 56%) after sublimed under vacuum.
Embodiment 34
(1)~(4) are the same as embodiment 31；
(5) compound 2-3-4 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 1- (4- bromobenzenes) -2- benzene -1-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) and N, N- diphenyl -4 "-(4,4,5,5- tetramethyl -1,3,2- dioxaborolan -2- bases)-[1,1 '：4 ', 1 "-three Biphenyl] -4- amine (7mmol, 3.7g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, 20 milliliters of weight concentrations are added as 10% Aqueous sodium carbonate, 50 milligram four (triphenyl phosphorus) close palladium, be heated to reflux lower stirring reaction 24 hours, after cooling, will mix Liquid is poured into 200 milliliters of water, and extracts product with dichloromethane.Anhydrous magnesium sulfate dries organic phase, and solvent is removed after separation, uses Silica gel chromatographic column separating-purifying obtains faint yellow solid, drying after sublimed under vacuum obtain high-purity product (1.6g, Yield 45%).
Embodiment 35
(1)~(4) are the same as embodiment 31；
(5) compound 2-3-5 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 1- (4- bromobenzenes) -2- benzene -1-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) and N, N- diphenyl -4- (4,4,5,5- tetramethyls -1,3,2- dioxaborolan -2- bases) aniline (7mmol, 2.6g), 30 milliliters of toluene and 15 milliliters of tetrahydrofurans, 20 milliliters of weight concentrations are added as 10% aqueous sodium carbonate, 50 milligram four (triphenyl phosphorus) closes palladium, is heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into 200 milliliters of water, and with two Chloromethanes extracts product.Anhydrous magnesium sulfate dries organic phase, removes solvent after separation, Huang is obtained with silica gel chromatographic column separating-purifying Color solid, drying obtain high-purity product (1.6g, yield 58%) after sublimed under vacuum.
Embodiment 36
(1)~(4) are the same as embodiment 31；
(5) compound 2-3-6 preparation, reaction equation are as follows：
Added under an argon atmosphere into reaction bulb 1- (4- bromobenzenes) -2- benzene -1-H- naphthalenes [1,2] and imidazoles (5mmol, 2.0g) make with 9- hydrogen -3-9 '-bis- carbazoles (6mmol, 2.0g), 20 milliliters of 1,3- dimethyl -3,4,5,6- tetrahydrochysene -2- pyrimidones For solvent, 0.2 gram of cuprous iodide, 18 0.1 gram of 6 ethers of hat, and 1.5 grams of potassium carbonate.It is heated to reflux lower stirring reaction 24 hours, cools down Afterwards, mixed liquor is poured into 200 milliliters of water, and product is extracted with dichloromethane.Anhydrous magnesium sulfate dries organic phase, is gone after separation Except solvent, faint yellow solid is obtained with silica gel chromatographic column separating-purifying, drying obtains high-purity after sublimed under vacuum Product (2.5g, yield 69%).
The naphthalene [1,2] and imidazoles bipolarity conjugated compound that embodiment 2, embodiment 3, embodiment 8, embodiment 9 obtain are used In the performance test for preparing Organic Light Emitting Diode (OLED) device：
Indium tin oxide-coated glass (ITO) is handled after ultrasonic wave cleans with oxygen-Plasma, the square electricity of ito glass Hinder for 10 Ω/cm2.Hole injection layer polymer is poly- (3,4- ethylenedioxythiophene) (PEDOT), hole transmission layer N, Embodiment 2, embodiment is respectively adopted in N'- diphenyl-N, N'- (1- naphthyls) -1,1'- biphenyl -4,4'- diamines (NPB), luminescent layer 3rd, embodiment 8, the naphthalene [1,2] prepared by embodiment 9 and imidazoles bipolarity conjugated compound, electron transfer layer use 1,3,5- tri- (1- phenyl -1-H- benzo [d] imidazoles -2-) benzene (TPBI)；Cathode electrode uses LiF/Al metals.Applied between ITO and metal electrode Add positive bias, the characteristic of device is tested under different electric currents, it is as a result as shown in the table.
Wherein CE represents luminous efficiency, and EQE represents external quantum efficiency, and PE is power efficiency, and CIE is chromaticity coordinates.
The organic light emission two of the naphthalene of embodiment 2 and embodiment 8 [1,2] and imidazoles bipolarity conjugated compound as luminescent layer Voltage-current density-the brightness relationship curve of pole pipe (OLED) device is as shown in Figure 1；Its luminance-current efficiency-power efficiency Relation curve is as shown in Figure 2；Its electroluminescent spectrum is as shown in Figure 5.
The organic light emission two of the naphthalene of embodiment 3 and embodiment 9 [1,2] and imidazoles bipolarity conjugated compound as luminescent layer Voltage-current density-the brightness relationship curve of pole pipe (OLED) device is as shown in Figure 3；Its luminance-current efficiency-power efficiency Relation curve is as shown in Figure 4；Its electroluminescent spectrum is as shown in Figure 6.
The naphthalene [1,2] and imidazoles bipolarity conjugated compound of the present invention has it can be seen from the result in upper table and figure Higher fluorescence quantum yield, there is higher luminous efficiency using its Organic Light Emitting Diode (OLED) device as luminescent layer.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (2)

1. a kind of naphthalene [1,2] and imidazoles bipolarity conjugated compound, it is characterised in that：The compound has any one of following institute The structural formula stated：
2. the naphthalene [1,2] and imidazoles bipolarity conjugated compound described in claim 1 are as emitting layer material in organic photoelectric device Application in part, it is characterised in that the application concretely comprises the following steps：In the hole transmission layer or electronics on ito glass The film containing naphthalene [1,2] and imidazoles bipolarity conjugated compound is prepared by vacuum evaporation or solution coating on transport layer, Then either solution painting is covered with electron transfer layer or hole transmission layer to evaporation on the thin film, then evaporation metal electrode is prepared into Organic electro-optic device.
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