CN102649766B - Alcohol-soluble hole-transporting molecular material and preparation method thereof - Google Patents
Alcohol-soluble hole-transporting molecular material and preparation method thereof Download PDFInfo
- Publication number
- CN102649766B CN102649766B CN201210127043.7A CN201210127043A CN102649766B CN 102649766 B CN102649766 B CN 102649766B CN 201210127043 A CN201210127043 A CN 201210127043A CN 102649766 B CN102649766 B CN 102649766B
- Authority
- CN
- China
- Prior art keywords
- reaction
- molecular material
- reactant
- preparation
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an alcohol-soluble hole-transporting molecular material and a preparation method thereof. A plurality of hydroxyl groups are introduced into aromatic amine molecules, so that the prepared material has excellent hot-transporting performance and alcohol solubility, and is insoluble in other types of solvents such as toluene, chlorobenzene, dichloromethane, chloroform and the like. During the preparation, the alcohol-soluble hole-transporting molecular material is prepared by the following steps: protecting the hydroxyl groups of alkane, aromatic hydrocarbon, alkane derivative or aromatic hydrocarbon derivative containing the hydroxyl groups through dihydropyran; obtaining an aromatic amino precursor through reaction such as Suzuki coupling, Ullmann coupling, Stille coupling and the like; and finally removing the protective groups to obtain the target product. The material can perform film formation in alcohol solution, can resist corrosion by other solvents such as toluene, chlorobenzene, dichloromethane, chloroform and the like, and has application prospect in solution processing of multi-layer organic photoelectric devices.
Description
Technical field
The present invention relates to hole transport molecular material, particularly alcohol dissolubility hole transport molecular material and preparation method thereof.
Background technology
1987, prepared by Tang and VanSlyke usings small molecules organometallic complex 8-hydroxyquinoline aluminum as the multilayer film electroluminescent device of electric transmission and luminescent layer material, has made initiative work in the design of Organic Light Emitting Diode (OLED).Nineteen ninety, scientist's reported first of univ cambridge uk the polymer electroluminescent device of being prepared by soluble precursor; 1991, Heeger and Braun reported the Polymer Thin Film Electroluminescent Devices of preparing by the spin coating method of macromolecular solution.Current, the small molecules electroluminescent device based on vacuum thermal evaporation film-forming technology has been successfully applied to the display screen of some consumption electronic products, end of the year 2007 particularly, 11 inches of OLED color TV display screens that Sony is released.And take solution processed-type electroluminescent material as basic electroluminescent device, and it is believed that to have great advantage at tool aspect low cost, big area and flexible demonstration, just making great efforts to develop towards applicationization.
In recent years, the research for solution processed-type molecule-type organic photoelectrical material comes into one's own day by day.On the one hand, the advantage such as organic molecule material has that molecular structure is clearly fixed, single, the easy purifying of molecular weight, performance are easy to control, and comparatively definite molecular structure-property relationship can be provided, for further molecule, device design provide foundation.In addition on the one hand, nearest research shows, small molecule material also can, as polymkeric substance, can adopt printing technique to carry out wet processes.Thereby solution processable organic electroluminescence molecular luminescence material, provides new optional approach for preparing low cost, big area and flexible el device.
Based on solution processed-type organic electroluminescent molecular material, further investigation electroluminescent device is integrated, for example, synthesize the solution processed-type organic molecule charge transfer material that performance is controlled, match, for realizing controlled " whole soln processed-type " electroluminescent device of performance, have very important significance.
The solution processing of multilayer device, must overcome the etching problem of solvent to subsurface material.Existing device architecture is generally spin coating hole injection/transport material on conductive glass, then spin coating luminescent material layer by layer thereon.Generally, luminescent material need to be from the weak polar solvents such as toluene, dimethylbenzene or chlorobenzene film forming.This just requires hole injection/transport material not only to need good hole injection/transmission performance, and can effectively overcome the erosion of these solvents.Existing terms of settlement, is used PEDOT:PSS as hole injection/transport layer, film forming from water conventionally.Because it has good electroconductibility and can resist multi-solvents corrosion, be widely used in the research work of organic electro-optic device.But as a kind of highly acid polymer materials, it also has the shortcoming that himself is difficult to overcome.On the one hand, strongly-acid is understood corroding metal oxide anode material, thereby affects the stability of device; On the other hand, polymkeric substance itself is due to the uncertainty of its structure, such as the polymolecularity of molecular weight, causes device performance to be difficult to control.
Summary of the invention
The object of the invention is that the above-mentioned shortcoming that overcomes prior art, with not enough, provides a class alcohol dissolubility hole transport molecular material, and its solvability has good solvent selectivity.Another object of the present invention is to provide the preparation method of above-mentioned alcohol dissolubility hole transport molecular material.
Object of the present invention is achieved through the following technical solutions:
Alcohol dissolubility hole transport molecular material, has suc as formula (I) or molecular structure (II):
Wherein, Ar
1for any one in aromatic hydrocarbons, condensed-nuclei aromatics, arene derivatives or condensed-nuclei aromatics derivative; Ar
2for any one in aromatic hydrocarbons, condensed-nuclei aromatics, arene derivatives or condensed-nuclei aromatics derivative; Ar
3for any one in aromatic hydrocarbons, condensed-nuclei aromatics, arene derivatives or condensed-nuclei aromatics derivative; Ar wherein
1, Ar
2, Ar
3in three groups, has one at least with hydroxyl.
Described Ar
1for comprising the group of any structural unit in structural unit (1)～(4); Ar
2for comprising the group of any structural unit in structural unit (1)～(4); Ar
3for comprising the group of any structural unit in structural unit (1)～(4);
Wherein, R
1～R
6in have at least one to comprise that containing carbon number be 1～20 and end group be hydroxyl alkyl chain or oxyalkyl chain.
The group of described Ar1 for comprising any structural unit in structural unit (5)～(12); Described Ar
2for comprising the group of any structural unit in structural unit (5)～(12); Described Ar
3for comprising the group of any structural unit in structural unit (5)～(12);
The preparation method of above-mentioned alcohol dissolubility hole transport molecular material, comprises the following steps:
(1) in alkane, aromatic hydrocarbons, alkane derivatives or the arene derivatives of hydroxyl group, add catalyzer and dihydropyrane, obtain the hydroxy reaction with tetrahydropyrans blocking group;
(2) hydroxy reaction with tetrahydropyrans blocking group step (1) being obtained generates the intermediate product with tetrahydropyrans blocking group by cross-coupling reaction;
(3) intermediate product with tetrahydropyrans blocking group step (2) being obtained is dissolved in methylene dichloride, adds ethanol and catalyzer, and stirring at normal temperature is sloughed tetrahydropyrans blocking group, obtains alcohol dissolubility hole transport molecular material.
Described in step (1), catalyzer is the hydrochloric acid of concentration 12mol/L, and the mol ratio of the contained hydroxyl value of hydroxyl reactant, an acidic catalyst, dihydropyrane is 1: 0.03: 1.5～1: 0.06: 2.
In step (3), described catalyzer is that concentration is the hydrochloric acid of 12mol/L, and the contained blocking group number of hydroxyl reactant, the mol ratio of an acidic catalyst are 1: 3～1: 6.
Described cross-coupling reaction comprises Suzuki linked reaction, and concrete reaction conditions is:
Reactant is under protection of inert gas; temperature of reaction is 70～110 ℃; reaction times is 8～36h; use four (triphenyl is seen) to close palladium as catalyzer, wherein four (triphenyl is seen) to close palladium be 1: 100～4: 100 with the mol ratio of the active group of reactant with tetrahydropyrans group.
The described cross-coupling reaction of step (2) comprises Ullmann linked reaction, and reaction conditions is:
Reactant, under protection of inert gas, is used cuprous iodide as catalyzer, and temperature of reaction is 100～150 ℃, and the reaction times is 8～72h, and wherein cuprous iodide is 1: 100～3: 100 with the mol ratio of the active group of reactant with tetrahydropyrans group.
The described cross-coupling reaction of step (2) comprises Stille linked reaction, and reaction conditions is specially:
Reactant is under protection of inert gas; use four (triphenyl is seen) to close palladium as catalyzer; temperature of reaction is 110 ℃, and the reaction times is 12h, wherein four (triphenyl is seen) to close palladium be 4: 100 with the mol ratio of active group with the reactant of tetrahydropyrans group.
The reaction conditions of the described alkylated reaction of step (2) is specially:
Under alkaline condition, in atmosphere of inert gases, carry out alkylated reaction, temperature of reaction is at 0～50 ℃, and the reaction times is 8～36h.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) the present invention introduces a plurality of hydroxyls in aromatic amine molecule, make prepared material there is good hole transport performance and alcohol dissolubility (as methyl alcohol), and be insoluble in other types solvent, as toluene, chlorobenzene, methylene dichloride, chloroform etc., for the solution of multilayer device is provided by a kind of new approach that provides.
(2) alcohol dissolubility poly-hydroxy hole transport molecular material of the present invention has higher film morphology stability: by there is stronger Intermolecular Forces between aromatic hydrocarbons and hydroxyl, make the material to there is higher thermostability and second-order transition temperature, avoided material crystallization and affect performance and the life-span of device in life-time service process.
(3) with respect to conventional hole injection layer PEDOT:PSS, use the organic electroluminescence device of alcohol dissolubility poly-hydroxy hole transport molecular material of the present invention to show better properties, and to ito glass non-corrosiveness.
(4) alcohol dissolubility poly-hydroxy hole transport molecular material of the present invention is synthetic simply, purification is convenient.
Accompanying drawing explanation
Fig. 1 is the current density-voltage-luminosity response of the electroluminescent device of the hole transport molecular material material that is respectively embodiment 1 preparation, traditional PEDOT:PSS.
Fig. 2 is current efficiency-current density rational curve of the electroluminescent device of the hole transport molecular material material that is respectively embodiment 1 preparation, traditional PEDOT:PSS.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
Be shown below, the preparation process of the alcohol dissolubility hole transport molecular material of the present embodiment is as follows:
Step 1: ethylene bromohyrin (50g, 0.4mol) is slowly poured in the dihydropyrane (67g, 0.8mol) stirring in flask, and cooling with ice-water bath, after being finished down, then add concentrated hydrochloric acid (12mol/L, 2mL), after 8h, reaction solution becomes black.Through underpressure distillation, obtain colourless oil liquid 1.
Step 2: 2,7-dibromo fluorenes (3.24g, 10mmol) is poured in flask; add dimethyl sulfoxide (DMSO) (30mL) stirring to be vented to solid and all dissolve, then add KOH (5.8g, 104.1mmol); under nitrogen protection, react 1h, solution gradually becomes reddish-brown.Then by 1 (4.6g, 22mmol), be slowly added drop-wise in reaction flask, in ice-water bath, react 8h.Mixture, through extraction, column chromatography, obtains white solid 2.
Step 3: 2 (11.6g, 20mmol) are dissolved in dry tetrahydrofuran (THF) (60mL), and nitrogen protection, is cooled to-78 ℃.Slowly drip n-BuLi (1.6M, 27.5mL, 44mmol) in reaction flask, mixture from colourless become brown.After dropwising, at-78 ℃, 1h is stirred in lower continuation, then with syringe, adds 4,4,5,5-tetramethyl--1, and 3,2-Virahol ylboronic acid ester (8.2g, 44mmol), is then naturally warmed up to room temperature and stirs 24h.Mixture is with after ethanol termination reaction, and rotary distillation is removed ethanol and tetrahydrofuran (THF), and remaining solid obtains 3 through extraction, column chromatography.
Step 4: 2-bromine fluorenes (2.45g, 10mmol) is poured in flask, added dimethyl sulfoxide (DMSO) (30mL) stirring to be vented to solid and all dissolve; add again KOH (5.8g; 104.1mmol), under nitrogen protection, react 1h, solution gradually becomes reddish-brown.Then by 1 (4.6g, 22mmol), be slowly added drop-wise in reaction flask, in ice-water bath, react 8h.Mixture, through extraction, column chromatography, obtains white solid 4.
Step 5: 4 (10g, 20mmol) are dissolved in dry tetrahydrofuran (THF) (60mL), and nitrogen protection, is cooled to-78 ℃.The n-BuLi (1.6M, 13.5mL, 21.6mmol) slowly dripping in reaction flask, mixture from colourless become brown.After dropwising, at-78 ℃, continue to stir 1h.Iodine grain (5.5g, 21.6mmol) is dissolved in dry tetrahydrofuran (THF) (20mL), and with injection, solution is splashed in reaction flask, be then naturally warmed up to room temperature and stir 24h.Mixture is with after the aqueous solution termination reaction of sodium bisulfite, and rotary distillation is removed tetrahydrofuran (THF), through extraction, column chromatography, obtains faint yellow solid 5.
Step 6 is 5 (2.3g, 4.2mmol), para-bromoaniline (344mg, 2mmol), and potassium hydroxide (1.68g, 30mmol) and dry toluene (50mL) join in reaction flask, logical nitrogen bubble exhaust 30min.By the cuprous iodide (20mg, 0.1mmol) and 1 of catalytic amount, luxuriant and rich with fragrance Lorraine of 10-(36mg, 0.2mmol) joins rapidly in reaction flask, to 110 ℃ of back flow reaction 48h.After mixture is cooling, through extraction, column chromatography, obtain light yellow solid 6.
Step 7: by 3 (0.67g, 1mmol), 6 (2.1g, 2.1mmol) and toluene (40mL), ethanol (20mL), aqueous sodium carbonate (2M, 20mL) join in reaction flask, logical nitrogen bubble exhaust 30min.By the Pd (PPh of catalytic amount
3)
4(12mg, 0.01mmol) joins rapidly in reaction flask, is then heated to 110 ℃ of back flow reaction 8h.Mixture is cooling obtains yellow-green colour solid 7 by extraction, column chromatography.
Step 8: 7 (0.5g, 0.5mmol) are dissolved in to methylene dichloride (20mL), are adding wherein ethanol (5mL) and concentrated hydrochloric acid (12mol/L, 0.13mL), stirring at normal temperature 24h.Mixture evaporate to dryness, and with the mixed solvent recrystallization of tetrahydrofuran (THF)/methylene dichloride, obtain yellowish green solid C1, i.e. the target product of the present embodiment.
Adopt the present embodiment C1 to prepare electroluminescent diode [ITO/PEDOT:PSS (40nm) or C1 (40nm)/P-PPV (80nm)/CsF (1.5nm)/Al (80nm)], detailed process is as follows:
By resistance be tin indium oxide (ITO) the conductive glass substrate of 10-20 Ω/mouth successively through deionized water, acetone, washing composition, deionized water and Virahol ultrasonic cleaning, after oven for drying, with PLASMA (oxygen plasma), process 4 minutes.Glove box (Vacuum Atmosphere Co.) at nitrogen atmosphere is inner, on the ito glass substrate of above-mentioned processing, is coated with one deck hole mobile material film from alcoholic solution, and thickness is about 40nm, and then spin coating luminescent layer.Then be 3 * 10
-4under the vacuum of Pa, evaporation metal CsF (1.5nm)/Al (80nm) negative electrode.Device efficient lighting area is 0.19cm
2.Film thickness is measured with Veeco Dektak150 step instrument.The sedimentation rate of metal electrode evaporation and thickness thereof are measured with thickness/speed instrument STM-100 of Sycon Instrument.
Current density-voltage-the brightness of electroluminescent device and current efficiency-current density rational curve, as shown in Figure 1 and Figure 2.Related data is listed in table 1.Can find out, than PEDOT:PSS, the electroluminescent diode of the alcohol dissolubility hole transport molecular material of preparing based on the present embodiment, has good electroluminescent properties.
The electroluminescent properties of electroluminescent diode prepared by table 1 the present embodiment
Embodiment 2
Be shown below, the preparation process of the alcohol dissolubility hole transport molecular material of the present embodiment is as follows:
Step 1: preparation 6, the present embodiment is prepared 6 process and embodiment 1 together, does not repeat them here.
Step 2: 6 (1.6g, 1.6mmol) are dissolved in dry tetrahydrofuran (THF) (60mL), and nitrogen protection, is cooled to-78 ℃.Slowly drip n-BuLi (1.6M, 1mL, 1.6mmol) in reaction flask.After dropwising, at-78 ℃, continue to stir 1h, then with syringe, add 4,4,5,5-tetramethyl--1,3,2-Virahol ylboronic acid ester (0.3mg, 1.6mmo), is then naturally warmed up to room temperature and stirs 24h.Mixture is with after ethanol termination reaction, and rotary distillation is removed ethanol and tetrahydrofuran (THF), and remaining solid obtains yellow solid 8 through extraction, column chromatography.
Step 3: by 6 (0.5g, 0.5mmol), 8 (0.5g, 0.5mmol) and toluene (40mL), ethanol (20mL), aqueous sodium carbonate (2M, 20mL) join in reaction flask, logical nitrogen bubble exhaust 30min.By the Pd (PPh of catalytic amount
3)
4(23mg, 0.02mmol) joins rapidly in reaction flask, is then heated to 90 ℃ of back flow reaction 12h.Mixture is cooling obtains white solid 9 by extraction, column chromatography.
Step 4: 9 (0.5g, 0.5mmol) are dissolved in to methylene dichloride (20mL), are adding wherein ethanol (5mL) and concentrated hydrochloric acid (12mol/L, 0.13mL), stirring at normal temperature 24h.Mixture evaporate to dryness, and with the mixed solvent recrystallization of tetrahydrofuran (THF)/methylene dichloride, obtain white solid C2, i.e. the target product of the present embodiment.
Embodiment 3
Be shown below, the preparation process of the alcohol dissolubility hole transport molecular material of the present embodiment is as follows:
Step 1: 6-is bromo-1, and 2-hexylene glycol (50g, 254mmol) is slowly poured in the dihydropyrane (64g, 760mmol) stirring in flask, and cooling with ice-water bath, after being finished down, then adds concentrated hydrochloric acid (0.63mL, 12mol/L), after 8h.Through underpressure distillation, obtain colourless oil liquid 10.
Step 2: 2,7-dibromo fluorenes (1.62g, 5mmol) is poured in flask; add dimethyl sulfoxide (DMSO) (30mL) stirring to be vented to solid and all dissolve, then add KOH (2.8g, 50mmol); under nitrogen protection, react 1h, solution gradually becomes reddish-brown.Then by 1 (4.0g, 11mmol), be slowly added drop-wise in reaction flask, in 50 ℃ of water-baths, react 36h.Mixture obtains colorless oil 11 through extraction, column chromatography.
Step 3: 11 (3.25g, 4mmol) are dissolved in dry tetrahydrofuran (THF) (60mL), and nitrogen protection, is cooled to-78 ℃.Slowly drip n-BuLi (1.6M, 3mL, 4.8mmol) in reaction flask, mixture from colourless become brown.After dropwising, at-78 ℃, continue to stir 1h, then with syringe, add 4,4,5,5-tetramethyl--1,3,2-Virahol ylboronic acid ester (0.9g, 4.9mmol), is then naturally warmed up to room temperature and stirs 24h.Mixture is with after ethanol termination reaction, and rotary distillation is removed ethanol and tetrahydrofuran (THF), and remaining solid obtains white solid 12 through extraction, column chromatography.
Step 4: preparation 6, the present embodiment is prepared 6 process and embodiment 1 together, does not repeat them here.
Step 5: by 6 (1.0g, 1mmol), 12 (0.94g, 1.1mmol) and toluene (40mL), ethanol (20mL), aqueous sodium carbonate (2M, 20mL) join in reaction flask, logical nitrogen bubble exhaust 30min.By the Pd (PPh of catalytic amount
3)
4(35mg, 0.03mmol) joins rapidly in reaction flask, is then heated to 90 ℃ of back flow reaction 12h.Mixture is cooling obtains white solid 13 by extraction, column chromatography.
Step 6: 13 (0.83g, 0.5mmol) are dissolved in to methylene dichloride (20mL), are adding wherein ethanol (5mL) and concentrated hydrochloric acid (12mol/L, 1mL), stirring at normal temperature 24h.Mixture evaporate to dryness, and with the mixed solvent recrystallization of tetrahydrofuran (THF)/methylene dichloride, obtain white solid C3, i.e. the target product of the present embodiment.
Embodiment 4
Be shown below, the preparation process of the alcohol dissolubility hole transport molecular material of the present embodiment is as follows:
Step 1: preparation 1, the present embodiment is prepared 1 process and embodiment 1 together, does not repeat them here.
Step 2: bromophenol (8.6g, 50mmol) is poured in flask, added ethanol (50mL) stirring to be vented to solid and all dissolve, then add KOH (2.8g, 50mmol), react 2h under nitrogen protection.Then by 1 (13.6g, 65mmol), be slowly added drop-wise in reaction flask, in ice-water bath, react 8h.Mixture obtains colourless viscous liquid 14 through extraction, column chromatography.
Step 3: 14 (3g, 10mmol) are dissolved in dry tetrahydrofuran (THF) (60mL), and nitrogen protection, is cooled to-78 ℃.Slowly drip n-BuLi (1.6M, 7mL, 11mmol) in reaction flask, mixture from colourless become brown.After dropwising, at-78 ℃, continue to stir 1h, then with syringe, add 4,4,5,5-tetramethyl--1,3,2-Virahol ylboronic acid ester (2.3mL, 11mmol), is then naturally warmed up to room temperature and stirs 24h.Mixture is with after ethanol termination reaction, and rotary distillation is removed ethanol and tetrahydrofuran (THF), and remaining solid obtains thick liquid 15 through extraction, column chromatography.
Step 4: 1,3,5-tribromo-benzene (0.62g, 2mmol), 15 (1.45g, 4mmol) and toluene (40mL), ethanol (20mL), aqueous sodium carbonate (2M, 20mL) join in reaction flask, logical nitrogen bubble exhaust 30min.By the Pd (PPh of catalytic amount
3)
4(140mg, 0.12mmol) joins rapidly in reaction flask, is then heated to 90 ℃ of back flow reaction 18h.Mixture is cooling obtains white solid 16 by extraction, column chromatography.
Step 4: 16 (428mg, 1mmol) are dissolved in dry tetrahydrofuran (THF) (30mL), and nitrogen protection, is cooled to-78 ℃.The n-BuLi (1.6M, 1mL, 1.6mmol) slowly dripping is in reaction flask.After dropwising, at-78 ℃, continue to stir 1h, then with syringe, add 4,4,5,5-tetramethyl--1,3,2-Virahol ylboronic acid ester (300mg, 1.6mmol), is then naturally warmed up to room temperature and stirs 24h.Mixture is with after ethanol termination reaction, and rotary distillation is removed ethanol and tetrahydrofuran (THF), and remaining solid obtains thick liquid 17 through extraction, column chromatography.
Step 5: preparation 6, the present embodiment is prepared 6 process and embodiment 1 together, does not repeat them here.
Step 6: by 6 (0.5g, 0.5mmol), 17 (0.24g, 0.5mmol) and toluene (40mL), ethanol (20mL), aqueous sodium carbonate (2M, 20mL) join in reaction flask, logical nitrogen bubble exhaust 30min.By the Pd (PPh of catalytic amount
3)
4(23mg, 0.02mmol) joins rapidly in reaction flask, is then heated to 90 ℃ of back flow reaction 8h.Mixture is cooling obtains white solid 18 by extraction, column chromatography.
Step 7: 18 (290mg, 0.2mmol) are dissolved in to methylene dichloride (20mL), are adding wherein ethanol (2mL) and concentrated hydrochloric acid (12mol/L, 0.1mL), stirring at normal temperature 24h.Mixture evaporate to dryness, and with the mixed solvent recrystallization of tetrahydrofuran (THF)/methylene dichloride, obtain white solid C4, i.e. the target product of the present embodiment.
Embodiment 5
Be shown below, the preparation process of the alcohol dissolubility hole transport molecular material of the present embodiment is as follows:
Step 1: 4-bromobutanol (76g, 0.50mol) is slowly poured in the dihydropyrane (60g, 0.71mol) stirring in flask, and cooling with ice-water bath, after being finished down, then add concentrated hydrochloric acid (12mol/L, 2mL), after 8h.Through underpressure distillation, obtain colourless oil liquid 19.
Step 2: 2-bromine carbazole (2.45g, 10mmol) is poured in flask, added acetone (50mL) stirring to be vented to solid and all dissolve, then add KOH (1.12g, 20mmol), react 1h under nitrogen protection.Then by 19 (3.54g, 15mmol), be slowly added drop-wise in reaction flask heating reflux reaction 2h.Mixture is after methylene dichloride and washing.Through column chromatography, obtain white solid 20.
Step 3: 20 (4.01g, 10mmol) are dissolved in dry tetrahydrofuran (THF) (60mL), and nitrogen protection, is cooled to-78 ℃.Slowly drip n-BuLi (1.6M, 7mL, 11mmol) in reaction flask, mixture from colourless become brown.After dropwising, at-78 ℃, continue to stir 1h, then with syringe, add 4,4,5,5-tetramethyl--1,3,2-Virahol ylboronic acid ester (2.3mL, 11mmol), is then naturally warmed up to room temperature and stirs 24h.Mixture is with after ethanol termination reaction, and rotary distillation is removed ethanol and tetrahydrofuran (THF), and remaining solid obtains white solid 21 through extraction, column chromatography.
Step 4: by 3,6-dibromo carbazole (1.3g, 4mmol), 21 (3.95g, 8.8mmol) and toluene (60mL), ethanol (30mL), aqueous sodium carbonate (2M, 30mL) join in reaction flask, logical nitrogen bubble exhaust 30min.By the Pd (PPh of catalytic amount
3)
4(300mg, 0.08mmol) joins rapidly in reaction flask, is then heated to 70 ℃ of reaction 36h.Mixture is cooling obtains yellow solid 22 by extraction, column chromatography.
Step 5: preparation 2, the present embodiment is prepared 2 process and embodiment 1 together, does not repeat them here.
Step 6: by 22 (2.4g, 3mmol), 2 (1.8mg, 3.1mmol), salt of wormwood (1.66g, 12mmol), 18-hat-6-ether (40mg, 0.15mmol) and 1,3-dimethyl-3,4,5,6-tetrahydrochysene-2-pyrimidone (1mL) joins in reaction flask, logical nitrogen bubble exhaust 30min.The cuprous iodide (6mg, 0.03mmol) of catalytic amount is joined rapidly in reaction flask, to 150 ℃ of reaction 8h.After mixture is cooling, through extraction, column chromatography, obtain yellow solid 23.
Step 7: 23 (1.96g, 1.5mmol) are dissolved in dry tetrahydrofuran (THF) (60mL), and nitrogen protection, is cooled to-78 ℃.Slowly drip n-BuLi (1.6M, 1mL, 16mmol) in reaction flask, mixture from colourless become brown.After dropwising, at-78 ℃, continue to stir 1h, then with syringe, add 4,4,5,5-tetramethyl--1,3,2-Virahol ylboronic acid ester (300mg, 1.6mmol), is then naturally warmed up to room temperature and stirs 24h.Mixture is with after ethanol termination reaction, and rotary distillation is removed ethanol and tetrahydrofuran (THF), and remaining solid obtains yellow solid 24 through extraction, column chromatography.
Step 8: preparation 10, the present embodiment is prepared 10 process and embodiment 3 together, does not repeat them here.
Step 9: the bromo-Resorcinol of 5-(4.7g, 25mmol) is poured in flask, added ethanol (50mL) stirring to be vented to solid and all dissolve, then add KOH (2.8g, 50mmol), react 2h under nitrogen protection.Then by 10 (23.7g, 65mmol), be slowly added drop-wise in reaction flask, in ice-water bath, react 12h.Mixture obtains colourless viscous liquid 25 through extraction, column chromatography.
Step 10: 25 (7.56g, 10mmol) are dissolved in dry tetrahydrofuran (THF) (60mL), and nitrogen protection, is cooled to-78 ℃.Slowly drip n-BuLi (1.6M, 7mL, 11mmol) in reaction flask, mixture from colourless become brown.After dropwising, at-78 ℃, continue to stir 1h, then with syringe, add 4,4,5,5-tetramethyl--1,3,2-Virahol ylboronic acid ester (2.3mL, 11mmol), is then naturally warmed up to room temperature and stirs 24h.Mixture is with after ethanol termination reaction, and rotary distillation is removed ethanol and tetrahydrofuran (THF), and remaining solid obtains thick liquid 26 through extraction, column chromatography.
Step 11: preparation 1, the present embodiment is prepared 1 process and embodiment 1 together, does not repeat them here.
The bromo-beta naphthal of step 12: 6-(11.1g, 50mmol) is poured in flask, adds ethanol (100mL) stirring to be vented to solid and all dissolves, then add KOH (2.8g, 50mmol), under nitrogen protection, reacts 2h.Then by 1 (13.6g, 65mmol), be slowly added drop-wise in reaction flask, in ice-water bath, react 12h.Mixture obtains colourless viscous liquid 27 through extraction, column chromatography.
Step 13: 27 (7.63g, 25mmol) are dissolved in the tetrahydrofuran (THF) that 60mL is dry, and nitrogen protection, is cooled to-78 ℃.Slowly drip n-BuLi (1.6M, 17mL, 27.5mmol) in reaction flask, mixture from colourless become brown.After dropwising, at-78 ℃, continue to stir 1h, then with syringe, add 4,4,5,5-tetramethyl--1,3,2-Virahol ylboronic acid ester (5.1g, 27.5mmol), is then naturally warmed up to room temperature and stirs 24h.Mixture is with after ethanol termination reaction, and rotary distillation is removed ethanol and tetrahydrofuran (THF), and remaining solid obtains thick liquid 28 through extraction, column chromatography.
Step 14: by 1,3,5-tribromo-benzene (3.12g, 10mmol), 28 (3.94g, 9.9mmol) and toluene (60mL), ethanol (30mL), aqueous sodium carbonate (2M, 30mL) join in reaction flask logical nitrogen bubble exhaust 30min.By the Pd (PPh of catalytic amount
3)
4(346mg, 0.32mmol) joins rapidly in reaction flask, is then heated to 90 ℃ of back flow reaction 18h.Mixture is cooling obtains thick liquid 29 by extraction, column chromatography.
Step 15: by 26 (4.1g, 5.1mmol), 29 (2.52g, 5mmol) and toluene (30mL), ethanol (15mL), aqueous sodium carbonate (2M, 15mL) join in reaction flask, logical nitrogen bubble exhaust 30min.By the Pd (PPh of catalytic amount
3)
4(288mg, 0.15mmol) joins rapidly in reaction flask, is then heated to 90 ℃ of back flow reaction 18h.Mixture is cooling obtains thick liquid 30 by extraction, column chromatography.
Step 10 six: by 24 (678mg, 0.5mmol), 30 (551mg, 0.5mmol) and toluene (20mL), ethanol (10mL), aqueous sodium carbonate (2M, 10mL) join in reaction flask, logical nitrogen bubble exhaust 30min.By the Pd (PPh of catalytic amount
3)
4(30mg, 0.015mmol) joins rapidly in reaction flask, is then heated to 90 ℃ of back flow reaction 18h.Mixture is cooling obtains brown color solid 31 by extraction, column chromatography.
Step 10 seven: 31 (676mg, 0.2mmol) are dissolved in to methylene dichloride (20mL), are adding wherein ethanol (2mL) and concentrated hydrochloric acid (12mol/L, 0.05mL), stirring at normal temperature 24h.Mixture evaporate to dryness, and with the mixed solvent recrystallization of tetrahydrofuran (THF)/methylene dichloride, obtain brown color solid C5, i.e. the target product of the present embodiment.
Embodiment 6
Be shown below, the preparation process of the alcohol dissolubility hole transport molecular material of the present embodiment is as follows:
Step 1: preparation 1, the present embodiment is prepared 1 process and embodiment 1 together, does not repeat them here.
The bromo-1-naphthols of step 2: 4-(11.1g, 50mmol) is poured in flask, adds ethanol (100mL) stirring to be vented to solid and all dissolves, then add KOH (2.8g, 50mmol), under nitrogen protection, reacts 2h.Then by 1 (13.6g, 65mmol), be slowly added drop-wise in reaction flask, in ice-water bath, react 12h.Mixture obtains colourless viscous liquid 32 through extraction, column chromatography.
Step 3: 32 (7.02g, 20mmol) are dissolved in dry tetrahydrofuran (THF) (60mL), and nitrogen protection, is cooled to-78 ℃.Slowly drip n-BuLi (1.6M, 14mL, 22mmol) in reaction flask, mixture from colourless become brown.After dropwising, at-78 ℃, continue to stir 1h, then with syringe, add 4,4,5,5-tetramethyl--1,3,2-Virahol ylboronic acid ester (4.1g, 22mmol), is then naturally warmed up to room temperature and stirs 24h.Mixture is with after ethanol termination reaction, and rotary distillation is removed ethanol and tetrahydrofuran (THF), and remaining solid obtains colorless oil 33 through extraction, column chromatography.
Step 4: 3 bromo thiophene (1.8g, 11mmol), 33 (3.98g, 10mmol) and toluene (40mL), ethanol (20mL), aqueous sodium carbonate (2M, 20mL) join in reaction flask, logical nitrogen bubble exhaust 30min.By the Pd (PPh of catalytic amount
3)
4(35mg, 0.03mmol) joins rapidly in reaction flask, is then heated to 90 ℃ of back flow reaction 12h.Mixture is cooling obtains brown oil 34 by extraction, column chromatography.
Step 5: 34 (2.12g, 6mmol) are dissolved in DMF (50mL), and under ice bath, lucifuge is stirred to solid matter and dissolves completely.Divide and will in N-bromo-succinimide (1.08g, 6.06mmol) input reaction flask, react 4h three times.Mixture obtains brown oil 35 with distillation washing by extraction, column chromatography.
Step 6: the bromo-1-3-naphthalenediol of 5-is dissolved in to (18.9g, 100mmol) and pours in flask, add ethanol (200mL) stirring to be vented to solid and all dissolve, then add KOH (5.6g, 100mmol), react 2h under nitrogen protection.Then by 1 (8.65g, 130mmol), be slowly added drop-wise in reaction flask, in ice-water bath, react 12h.Mixture obtains colourless viscous liquid 36 through extraction, column chromatography.
Step 7: 36 (8.9g, 20mmol) are dissolved in dry tetrahydrofuran (THF) (60mL), and nitrogen protection, is cooled to-78 ℃.Slowly drip n-BuLi (1.6M, 14mL, 22mmol) in reaction flask, mixture from colourless become brown.After dropwising, at-78 ℃, continue to stir 1h, then with syringe, add 4,4,5,5-tetramethyl--1,3,2-Virahol ylboronic acid ester (4.1g, 22mmol), is then naturally warmed up to room temperature and stirs 24h.Mixture is with after ethanol termination reaction, and rotary distillation is removed ethanol and tetrahydrofuran (THF), and remaining solid obtains colorless oil 37 through extraction, column chromatography.
Step 8: 35 (2.6g, 6mmol), 37 (3.0g, 6mmol) and toluene (20mL), ethanol (10mL), aqueous sodium carbonate (2M, 10mL) join in reaction flask, logical nitrogen bubble exhaust 30min.By the Pd (PPh of catalytic amount
3)
4(208mg, 0.18mmol) joins rapidly in reaction flask, is then heated to 90 ℃ of back flow reaction 12h.Mixture is cooling obtains brown solid 38 by extraction, column chromatography.
Step 9: 38 (3.6g, 5mmol) are dissolved in DMF (70mL), and under ice bath, lucifuge is stirred to solid matter and dissolves completely.Divide and will in N-bromo-succinimide (0.9g, 5.05mmol) input reaction flask, react 4h three times.Mixture obtains brown solid 39 through extraction, column chromatography.
Step 10: 2-bromothiophene (0.81g, 5mmol), Mg powder (120mg, 5mmo) are added in anhydrous THF (50mL) to N
2protection.Add 1 of iodine grain, heating.After 2h, reaction solution is slowly splashed into 39 (3.19g, 4mmol), NidpppCl
2(30mg) in anhydrous THF (30mL) solution, stirring and refluxing logical N
2.After reaction 2d, cool to room temperature.With distillation washing, by extraction, column chromatography, obtain brown solid 40.
Step 11: 40 (4.0g, 5mmol) are dissolved in dry tetrahydrofuran (THF) (60mL), and nitrogen protection, is cooled to-78 ℃.Slowly drip n-BuLi (1.6M, 0.35mL, 5.5mmol) in reaction flask.After dropwising, at-78 ℃, continue to stir 1h, then with syringe, add tributyltin chloride (1.8g, 5.5mmol), be then naturally warmed up to room temperature and stir 24h.Mixture is with after ethanol termination reaction, and rotary distillation is removed ethanol and tetrahydrofuran (THF), and remaining solid obtains brown solid 41 through extraction, column chromatography.
Step 12: preparation 22, the present embodiment is prepared 22 process and embodiment 5 together, does not repeat them here.
Step 13: by 22 (2.4g, 3mmol), to bromo-iodobenzene (877mg, 3.1mmol), salt of wormwood (1.66g, 12mmol), 18-hat-6-ether (40mg, 0.15mmol) and 1,3-dimethyl-3,4,5,6-tetrahydrochysene-2-pyrimidone (1mL) joins in reaction flask, logical nitrogen bubble exhaust 30min.The cuprous iodide (226mg, 1.2mmol) of catalytic amount is joined rapidly in reaction flask, to 170 ℃ of reaction 24h.Mixture obtains yellow solid 42 through extraction, column chromatography.
Step 14: 42 (963mg, 1mmol), 41 (1.09g, 1mmol) and toluene (30mL) join in reaction flask, logical nitrogen bubble exhaust 30min.By the Pd (PPh of catalytic amount
3)
4(46mg, 0.04mmol) joins rapidly in reaction flask, is then heated to 110 ℃ of back flow reaction 12h.Mixture is cooling obtains reddish-brown solid 43 with distillation washing by extraction, column chromatography afterwards.
Step 15: 43 (506mg, 0.3mmol) are dissolved in to methylene dichloride (20mL), are adding wherein ethanol (2mL) and concentrated hydrochloric acid (12mol/L, 0.15mL), stirring at normal temperature 24h.Mixture evaporate to dryness, and with the mixed solvent recrystallization of tetrahydrofuran (THF)/methylene dichloride, obtain the solid C6 of reddish-brown, i.e. the target product of the present embodiment.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not limited by the examples; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (5)
1. alcohol dissolubility hole transport molecular material, is characterized in that, has following molecular structure:
2. the preparation method of alcohol dissolubility hole transport molecular material, is characterized in that, comprises the following steps:
(1) in alkane, aromatic hydrocarbons, alkane derivatives or the arene derivatives of hydroxyl group, add catalyzer and dihydropyrane, obtain the hydroxy reaction with tetrahydropyrans blocking group;
(2) hydroxy reaction with tetrahydropyrans blocking group step (1) being obtained generates the intermediate product with tetrahydropyrans blocking group by cross-coupling reaction;
(3) intermediate product with tetrahydropyrans blocking group step (2) being obtained is dissolved in methylene dichloride, adds ethanol and catalyzer, and stirring at normal temperature is sloughed tetrahydropyrans blocking group, obtains alcohol dissolubility hole transport molecular material;
Described cross-coupling reaction comprises Suzuki linked reaction, and concrete reaction conditions is:
Reactant is under protection of inert gas, use four (triphenyl is seen) to close palladium as catalyzer, temperature of reaction is 70～110 ℃, and the reaction times is 8～36h, and wherein to see and close palladium be 1:100～4:100 with the mol ratio of active group with the reactant of tetrahydropyrans group to four triphenyls;
Or described cross-coupling reaction comprises Ullmann linked reaction, reaction conditions is:
Reactant, under protection of inert gas, is used cuprous iodide as catalyzer, and temperature of reaction is 100～150 ℃, and the reaction times is 8～72h, and wherein cuprous iodide is 1:100～3:100 with the mol ratio of the active group of reactant with tetrapyran group;
Or described cross-coupling reaction comprises Stille linked reaction, reaction conditions is specially:
Reactant is under protection of inert gas; use four (triphenyl is seen) to close palladium as catalyzer; temperature of reaction is 110 ℃, and the reaction times is 12h, wherein four (triphenyl is seen) to close palladium be 4:100 with the mol ratio of active group with the reactant of tetrahydropyrans group.
3. the preparation method of alcohol dissolubility hole transport molecular material according to claim 2, it is characterized in that, described in step (1), catalyzer is the hydrochloric acid of concentration 12mol/L, and the mol ratio of the contained hydroxyl value of hydroxyl reactant, an acidic catalyst, dihydropyrane is 1:0.03:1.5～1:0.06:2.
4. the preparation method of alcohol dissolubility hole transport molecular material according to claim 2; it is characterized in that; in step (3), described catalyzer is the hydrochloric acid of concentration 12mol/L, and the contained blocking group number of hydroxyl reactant, the mol ratio of an acidic catalyst are 1:3～1:6.
5. the preparation method of alcohol dissolubility hole transport molecular material according to claim 2, it is characterized in that, the reaction conditions of the described alkylated reaction of step (2) is specially: under alkaline condition, in atmosphere of inert gases, carry out alkylated reaction, temperature of reaction is at 0～50 ℃, and the reaction times is 8～36h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210127043.7A CN102649766B (en) | 2012-04-26 | 2012-04-26 | Alcohol-soluble hole-transporting molecular material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210127043.7A CN102649766B (en) | 2012-04-26 | 2012-04-26 | Alcohol-soluble hole-transporting molecular material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102649766A CN102649766A (en) | 2012-08-29 |
| CN102649766B true CN102649766B (en) | 2014-10-08 |
Family
ID=46691896
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210127043.7A Expired - Fee Related CN102649766B (en) | 2012-04-26 | 2012-04-26 | Alcohol-soluble hole-transporting molecular material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102649766B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7068561B1 (en) * | 2020-07-28 | 2022-05-16 | 三井化学株式会社 | Compounds, resins, polycarbonate resins, and optical moldings |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174037A (en) * | 2011-02-28 | 2011-09-07 | 东莞彩显有机发光科技有限公司 | Phosphorescent host material with bipolar carrier transmitting capacity |
| CN102382105A (en) * | 2011-09-21 | 2012-03-21 | 东莞彩显有机发光科技有限公司 | Bipolar host material used for blue emitting phosphor |
-
2012
- 2012-04-26 CN CN201210127043.7A patent/CN102649766B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102174037A (en) * | 2011-02-28 | 2011-09-07 | 东莞彩显有机发光科技有限公司 | Phosphorescent host material with bipolar carrier transmitting capacity |
| CN102382105A (en) * | 2011-09-21 | 2012-03-21 | 东莞彩显有机发光科技有限公司 | Bipolar host material used for blue emitting phosphor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102649766A (en) | 2012-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101024633B (en) | Tricyclic arylamine monomer and polymers and devices thereof | |
| CN102131843B (en) | Phenoxazine system macromolecular compound and the luminous element using it | |
| CN107722062B (en) | Metal iridium or platinum complex and organic electroluminescent device containing metal iridium or platinum complex | |
| CN103270111A (en) | Composition and block copolymer | |
| JP5387935B2 (en) | π-conjugated polymer | |
| CN101535324A (en) | Organic iridium compositions and their use in electronic devices | |
| CN109476827A (en) | Organic electronic material and its utilization | |
| CN101392174B (en) | Soluble electro-green light organic molecule glass material and preparation method and use thereof | |
| CN101898996A (en) | Organic material and application thereof to organic electroluminescent devices | |
| CN101663272B (en) | Cbp compound | |
| CN102649766B (en) | Alcohol-soluble hole-transporting molecular material and preparation method thereof | |
| CN107759774B (en) | D-A type polymer with main chain containing S, S-dioxo-dibenzothiophene as well as preparation method and application thereof | |
| CN103547611B (en) | The light-emitting component of macromolecular compound and its formation of use | |
| CN105294781B (en) | Heterogeneous multi-nuclear metal complexes of iridium-europium and its preparation method and application | |
| CN103113413A (en) | Bicyclo-iridium complex, preparation method of complex, organic light emitting diode (OLED) and preparation method of OLED | |
| CN108503800B (en) | Polymer containing S, S-dioxo-dibenzothiophene macrocyclic unit, preparation method and application thereof | |
| Huang et al. | Synthesis, characterization, and photophysics of electroluminescent fluorene/dibenzothiophene-and fluorene/dibenzothiophene-S, S-dioxide-based main-chain copolymers bearing benzimidazole-based iridium complexes as backbones or dopants | |
| CN101775122B (en) | Red light conjugated polymer of side-chain quinoline ligand-containing iridium compound and light-emitting device | |
| CN100372910C (en) | Conjugate light-emitting polymer with antioxidant group in the side chain and its application | |
| JP2019176093A (en) | Organic electroluminescence element | |
| CN110951049A (en) | Light-emitting polymer, preparation method thereof and application thereof in preparing light-emitting diode | |
| CN108276558A (en) | A kind of electroluminescent polymer and the preparation method and application thereof | |
| CN108070073A (en) | Poly- spiro fluorene and organic electroluminescence device | |
| CN103012055A (en) | Water-solubility and alcohol solubility multi-armed structural material and preparation and application method thereof | |
| CN100554365C (en) | Electroluminescent polymer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20141008 Termination date: 20210426 |