WO2017035972A1 - Aromatic amine compound and preparation and application thereof - Google Patents

Aromatic amine compound and preparation and application thereof Download PDF

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WO2017035972A1
WO2017035972A1 PCT/CN2015/096450 CN2015096450W WO2017035972A1 WO 2017035972 A1 WO2017035972 A1 WO 2017035972A1 CN 2015096450 W CN2015096450 W CN 2015096450W WO 2017035972 A1 WO2017035972 A1 WO 2017035972A1
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carbon atoms
substituted
unsubstituted
group
aromatic amine
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PCT/CN2015/096450
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French (fr)
Chinese (zh)
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高春吉
孙向男
王贺
王永光
崔敦洙
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吉林奥来德光电材料股份有限公司
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Publication of WO2017035972A1 publication Critical patent/WO2017035972A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
    • C07D221/08—Aza-anthracenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom

Definitions

  • the invention relates to the technical field of organic photoelectric materials, in particular to an aromatic amine compound and a preparation method and application thereof.
  • the host material in the electroluminescent device mainly has two types of small molecule host materials and polymer host materials.
  • Many high-efficiency electroluminescent devices have been prepared by doping a phosphorescent complex with a small molecule host material as a light-emitting layer.
  • the preparation of electroluminescent devices by doping various phosphorescent complex guest bodies with a polymer host material as a light-emitting layer has received much attention. Due to the rapid development of optoelectronic communication and multimedia in recent years, organic optoelectronic materials have become the core of the modern social information and electronics industry.
  • Organic electroluminescent device is a new type of flat display device. Compared with small molecule electroluminescent devices, it has energy saving, fast response, stable color, strong environmental adaptability, no radiation, long life and light weight. Thin thickness and other characteristics.
  • An organic electroluminescent device generally consists of two opposing electrodes and at least one layer of an organic luminescent compound interposed between the two electrodes. Charge is injected into the organic layer formed between the anode and the cathode to form electron and hole pairs, causing light emission of an organic compound having fluorescent or phosphorescent properties.
  • a voltage is applied between the anode and the cathode, and holes are injected from the anode through the hole transport layer into the light-emitting layer, while electrons are injected from the cathode through the electron transport layer into the light-emitting layer.
  • carriers are rearranged to form excitons.
  • the excited exciton transitions to the ground state, causing the luminescent layer molecules to emit light, and the image is thus formed.
  • the luminous efficiency of these materials is generally low, and the requirements for the luminous efficiency of the organic electroluminescent device cannot be satisfied.
  • the light-emitting device prepared by the aromatic amine compound provided by the present invention has an average luminous efficiency of 167% of the prior art.
  • R 1 , R 2 and R 3 are independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 50 carbon atoms, a substitution or An unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted aromatic amine group having 5 to 40 carbon atoms;
  • R 4 and R 5 are independently selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted An aromatic amine group having 5 to 40 carbon atoms, an aryloxy group having 6 to 50 carbon atoms or an arylsulfonyl group.
  • R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from the following chemical formulas, as defined in claim 1:
  • X and Y are independently selected from a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, A substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkaryloxy group having 7 to 30 carbon atoms a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 carbon atoms And one of a substituted or unsubstituted aromatic amine having 6 to 30 carbon atoms.
  • the formula I is specifically:
  • the invention provides a preparation method of an aromatic amine compound, comprising the following steps:
  • the reactant 1 was dissolved in anhydrous diethyl ether, and butyllithium was added in a dry ice bath at -75 to -80 ° C under oxygen atmosphere. After 1 to 3 hours, dimethyl phthalate was added, and the reaction was heated to 15 after 1 to 3 hours. ⁇ 25 ° C, adding water to terminate the reaction, to obtain product 1;
  • the product 1 is dissolved in tetrahydrofuran, lowered to 0 ° C, added to the mixture LTMP and reacted at 0 ° C for 1-3 hours to obtain the product 2;
  • the product 2 is dissolved in acetonitrile, then the halogen-containing reactant is added, the temperature is raised to 55-65 ° C, and the reaction is carried out for 4-6 hours to obtain the product 3;
  • the product 3 the reactant 2, the tetrakistriphenylphosphine palladium are dissolved in a mixture of toluene, ethanol and water in a volume ratio of (1 to 3): (0.5 to 1): (0.5 to 1), in which oxygen is isolated. Under the conditions, the temperature is raised to 100 to 120 ° C for 20 to 28 hours to obtain an aromatic amine compound having the structure of formula I;
  • Reactant 1 is a halogenated pyridine derivative having the structure shown in Formula II;
  • the reactant 2 is YR 4 or YR 5 ;
  • the halogen-containing reactant is one of phosphorus oxychloride, phosphorus oxybromide and phosphorus oxyiodide;
  • the mixed liquid LTMP is prepared by dissolving 0.13 mol of butyl lithium and 0.14 mol of 2,2,6,6-tetramethylpiperidine at 0 ° C in 500 mL of tetrahydrofuran;
  • R 1 , R 2 and R 3 are independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 50 carbon atoms, a substitution or An unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted aromatic amine group having 5 to 40 carbon atoms;
  • R 4 and R 5 are independently selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted An aromatic amine group having 5 to 40 carbon atoms, an aryloxy group having 6 to 50 carbon atoms or an arylsulfonyl group;
  • X 1 is I, Cl or Br
  • Y is B(OH) 2 .
  • the reactant 1 is with One of them.
  • the reactant 2 is with One of them.
  • the molar ratio of the reactant 1 to dimethyl phthalate is (1 to 1.2):1.
  • the molar ratio of the halogen atom to the product 2 in the halogen-containing reactant is (1-8):1.
  • the molar ratio of the product 3 to the reactant 2 is (1 to 3): 1.
  • the present invention provides the use of the aromatic amine compound of the above technical solution or the aromatic amine compound obtained by the preparation method of the above technical solution in an organic electroluminescent device, wherein the aromatic amine compound is used as a hole transport Material or hole blocking material.
  • the aromatic amine compound having the skeleton structure represented by Formula I provided by the present invention can be applied to an organic electroluminescence device, and the obtained organic electroluminescence device has markedly improved luminous efficiency and lifetime, and the average luminous efficiency is present. There is a technology of 167%, and the average life expectancy is 209% of the prior art, which can meet the requirements of OLED use. Further, the aromatic amine compound provided by the present application also has excellent film forming properties and heat resistance.
  • the present invention provides an aromatic amine compound having the structure of Formula I:
  • R 1 , R 2 and R 3 are independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 50 carbon atoms, a substitution or An unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted aromatic amine group having 5 to 40 carbon atoms;
  • R 4 and R 5 are independently selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted An aromatic amine group having 5 to 40 carbon atoms, an aryloxy group having 6 to 50 carbon atoms or an arylsulfonyl group.
  • the structure of the aromatic amine compound having a structure represented by Formula I provided by the present invention includes R 1 , R 2 , R 3 , R 4 and R 5 .
  • the R 1 , R 2 and R 3 are preferably independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 10 to 20 carbon atoms, and a substituted or unsubstituted carbon atom number of 25
  • R 1 , R 2 , R 3 , R 4 and R 5 in the formula I may preferably be independently selected from any one of the following chemical formulas:
  • X and Y may independently be selected from a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms.
  • a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms a substituted or unsubstituted alkylaryl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkylaryloxy group having 7 to 30 carbon atoms a substituted, unsubstituted or substituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic ring having 5 to 30 carbon atoms And a substituted or unsubstituted aromatic amine having 6 to 30 carbon atoms.
  • the X and Y are preferably independently selected from a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 10 to 20 carbon atoms, and a substituted or unsubstituted carbon number.
  • a 10 to 20 alkoxy group a substituted or unsubstituted alkenyl group having 10 to 20 carbon atoms, a substituted or unsubstituted alkylaryl group having 15 to 25 carbon atoms, a substituted or unsubstituted carbon number
  • a substituted or unsubstituted aryl group having 15 to 25 carbon atoms
  • substituted or unsubstituted aryloxy group having 15 to 25 carbon atoms
  • substituted or unsubstituted carbon atom It is one of 15 to 25 heterocyclic groups and a substituted or unsubstituted aromatic amine having 15 to 25 carbon atoms.
  • the aromatic amine compound is preferably
  • the invention provides a preparation method of an aromatic amine compound, comprising the following steps:
  • the reactant 1 was dissolved in anhydrous diethyl ether, and butyllithium was added in a dry ice bath at -75 to -80 ° C under oxygen atmosphere. After 1 to 3 hours, dimethyl phthalate was added, and the reaction was heated to 15 after 1 to 3 hours. ⁇ 25 ° C, adding water to terminate the reaction, to obtain product 1;
  • the product 1 is dissolved in tetrahydrofuran, lowered to 0 ° C, added to the mixture LTMP and reacted at 0 ° C for 1-3 hours to obtain the product 2;
  • the product 2 is dissolved in acetonitrile, then the halogen-containing reactant is added, the temperature is raised to 55-65 ° C, and the reaction is carried out for 4-6 hours to obtain the product 3;
  • the product 3 the reactant 2, the tetrakistriphenylphosphine palladium are dissolved in a mixture of toluene, ethanol and water in a volume ratio of (1 to 3): (0.5 to 1): (0.5 to 1), in which oxygen is isolated. Under the conditions, the temperature is raised to 100 to 120 ° C for 20 to 28 hours to obtain an aromatic amine compound having the structure of formula I;
  • Reactant 1 is a halogenated pyridine derivative having the structure shown in Formula II;
  • the reactant 2 is YR 4 or YR 5 ;
  • the halogen-containing reactant is one of phosphorus oxychloride, phosphorus oxybromide and phosphorus oxyiodide;
  • the mixed liquid LTMP is prepared by dissolving 0.13 mol of butyl lithium and 0.14 mol of 2,2,6,6-tetramethylpiperidine at 0 ° C in 500 mL of tetrahydrofuran;
  • R 1 , R 2 and R 3 are independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 50 carbon atoms, a substitution or An unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted aromatic amine group having 5 to 40 carbon atoms;
  • R 4 and R 5 are independently selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted An aromatic amine group having 5 to 40 carbon atoms;
  • X 1 is I, Cl or Br
  • Y is B(OH) 2 .
  • the reactant 1 is dissolved in anhydrous diethyl ether, and butyllithium is added in a dry ice bath at -75 to -80 ° C under the condition of isolating oxygen. After reacting for 1 to 3 hours, dimethyl phthalate is added.
  • the above dry ice bath temperature is preferably -78 °C.
  • the present invention has no specific requirements for the specific manner of isolating the above oxygen.
  • nitrogen is introduced to isolate oxygen.
  • the reaction time of the reactant 1 with butyl lithium may specifically be 1 h, 2 h or 3 h.
  • the molar ratio of the reactant 1 to dimethyl phthalate is preferably (1 to 1.2): 1, and may be specifically 1:1, 1.1:1 or 1.2:1 in the embodiment of the present invention.
  • the volume ratio of the amount of the reactant 1 to the anhydrous diethyl ether is preferably 1 mol: (2.5 to 4.5) L, specifically the amount of the reactant 1 in the embodiment of the present invention.
  • the volume ratio of anhydrous diethyl ether was 1 mol: 2.5 L, 1 mol: 3 L, 1 mol: 3.5 L, 1 mol: 4 L or 1 mol: 4.5 L.
  • the volume ratio of the substance of the reactant 1 to the butyl lithium is preferably 1 mol: (0.4 to 0.5) L, specifically the amount of the substance of the reactant 1 in the embodiment of the present invention.
  • the volume ratio of anhydrous diethyl ether was 1 mol: 0.4 L, 1 mol: 0.42 L, 1 mol: 0.44 L, 1 mol: 0.46 L, 1 mol: 0.48 L or 1 mol: 0.5 L.
  • a butyl lithium solution is preferably added, and the molar concentration of the butyl lithium solution is preferably 1.5 to 3.5 M, and specifically, the concentration of the butyl lithium in the embodiment of the present invention is 1.5 M. 2.0M, 2.5M, 3.0M or 3.5M.
  • butyllithium in a dry ice bath at -75 to -80 ° C under the condition of isolating oxygen, and then reacting for 1 to 3 hours under stirring to add dimethyl phthalate.
  • the present invention is heated to 15 to 25 ° C after adding dimethyl phthalate for 1 to 3 hours, and the reaction is terminated by adding water to obtain the product 1.
  • the present invention has no specific requirements for the above reaction time, and specifically may be 1 h, 2 h or 3 h.
  • the present invention has no specific requirement for the temperature after the above temperature rise, and specifically may be 15 ° C, 17 ° C, 19 ° C, 21 ° C, 23 ° C or 25 ° C.
  • the volume ratio of the anhydrous diethyl ether to water is preferably 6: (3 to 7), and specifically, in the embodiment of the present invention, the volume ratio of the anhydrous diethyl ether to water is 6:3, 6: 4, 6:5, 6:6 or 6:7.
  • the reactant 1 is preferably with One of them.
  • the product 1 is preferably with One of them.
  • the product 1 is dissolved in tetrahydrofuran and lowered to 0 ° C. After the mixture LTMP is added, the reaction is carried out at 0 ° C for 1 to 3 hours to obtain the product 2.
  • the present invention has no specific requirements for the above reaction time, and specifically may be 1 h, 2 h or 3 h.
  • the volume ratio of the amount of the product of the product 1 to the tetrahydrofuran is preferably 1 g: (25 to 45) ml, specifically, the ratio of the amount of the product of the product 1 to the volume ratio of tetrahydrofuran in the examples of the present invention. It is 1 g: 25 ml, 1 g: 30 ml, 1 g: 35 ml, 1 g: 45 ml or 1 g: 55 ml.
  • the volume ratio of the tetrahydrofuran to water is preferably 6: (3 to 7), and specifically, in the embodiment of the present invention, the volume ratio of the tetrahydrofuran to water is 6:3, 6:4, 6: 5, 6:6 or 6:7.
  • the obtained reaction product after the reaction is terminated by adding water.
  • the product 2 is preferably with One of them.
  • the product 2 is dissolved in acetonitrile, and then the halogen-containing reactant is added, the temperature is raised to 55 to 65 ° C, and the reaction is carried out for 4 to 6 hours to obtain the product 3.
  • the reaction temperature is specifically 56 ° C, 58 ° C, 60 ° C, 62 ° C or 64 ° C; the above reaction time is specifically 4 h, 5 h or 6 h.
  • the molar ratio of the halogen atom to the product 2 in the halogen-containing reactant is (1 to 8): 1, which may be specifically 1:1, 2:1, 3:1 in the embodiment of the present invention. , 4:1, 5:1, 6:1, 7:1 or 8:1.
  • the mass ratio of the product 2 to the acetonitrile is preferably 1 g: (15 to 40) ml, and specifically the volume ratio of the product 2 to the acetonitrile in the embodiment of the present invention is 1 g: 15 ml, 1 g: 20 ml, 1 g: 25 ml, 1 g: 30 ml, 1 g: 35 ml or 1 g: 40 ml.
  • the halogen-containing reactant is preferably one of phosphorus oxychloride, phosphorus oxybromide and phosphorus oxyiodate.
  • the mass ratio of the product 2 to the halogen reactant is preferably 2: (5 to 7).
  • the mass ratio of the amount of the product of the product 2 to the acetonitrile is 2: 5, 2:6 or 2:7.
  • the obtained reaction product it is preferred to subject the obtained reaction product to post-treatment after completion of the reaction.
  • water is added to remove, and the sodium carbonate saturated solution is added to adjust the pH to 7-8, and then dichloromethane is added, extracted three times, and the product 3 is purified by spin-drying.
  • the product 3 is preferably with One of them.
  • the product 3, the reactant 2, the tetrakistriphenylphosphine palladium are dissolved in a mixture of toluene, ethanol and water in a volume ratio of (1 to 3): (0.5 to 1): (0.5 to 1), which is isolated.
  • the above aromatic aromatic compound is obtained by raising the temperature to 100 to 120 ° C for 20 to 28 hours under oxygen conditions.
  • the present invention has no specific requirements for the above reaction temperature, and may specifically be 105 ° C, 110 ° C, 115 ° C, or 118 ° C.
  • the present invention has no specific requirements for the above reaction time, and specifically may be 22h, 24h or 26h.
  • the molar ratio of the product 3 to the reactant 2 is (1 to 3): 1, and may be specifically 1:1, 2:1 or 3:1 in the embodiment of the present invention.
  • the mass ratio of the product 3 to tetrakistriphenylphosphine palladium is preferably 15: (3 to 5), specifically the mass of the product 3 and tetrakistriphenylphosphine palladium in the examples of the present invention.
  • the ratio is 15:3, 15:4 or 15:5.
  • the volume ratio of the substance of the product 3 to the mixed liquid of toluene, ethanol and water is preferably 1 g: (30 to 50) ml, specifically the substance of the product 2 in the embodiment of the present invention.
  • the volume ratio to the acetonitrile is 1 g: 30 ml, 1 g: 35 ml, 1 g: 40 ml, 1 g: 45 ml or 1 g: 50 ml.
  • the volume ratio of toluene, ethanol and water is preferably 2:1:1.
  • the reactant 2 is preferably with One of them.
  • the present invention provides the use of the aromatic amine compound of the above technical solution or the aromatic amine compound obtained by the preparation method of the above technical solution in an organic electroluminescent device, wherein the aromatic amine compound is used as a hole transport Material or hole blocking material.
  • the present invention has no special requirements on the structure of the organic electroluminescent device, and a conventional organic electroluminescent device can be used.
  • the organic electroluminescent device can be specifically an organic light emitting device, an organic solar cell, Electronic paper, organic photoreceptor and organic thin film transistor.
  • the organic electroluminescent device preferably includes a first electrode, a second electrode, and one or more organic layer disposed between the two electrodes; more preferably at least one organic layer in the organic layer
  • An aromatic amine compound obtained by the above-described method of the aromatic amine compound or the above-described technical solution, and at least one organic layer in the organic layer contains the aromatic amine compound as described in the above technical solution or The aromatic amine compound and other substances obtained by the preparation method described in the above technical scheme.
  • the present invention has no special requirements on the organic layer of the organic electroluminescent device, and may be disposed in accordance with an organic layer of a conventional organic electroluminescent device.
  • the organic layer preferably includes at least a hole injection layer, a hole transport layer, and both a hole injection and a hole.
  • At least one of the three layers of the hole injection layer, the hole transport layer, and the injection layer having the hole injection technique and the hole transporting ability contains a conventional hole injecting substance and a hole transporting substance, and has an empty space.
  • the hole is injected with a substance having a hole transporting skill or a substance generated by an electron transporting substance.
  • the organic layer is preferably a light-emitting layer; more preferably, the light-emitting layer comprises one or more of a phosphorescent host, a fluorescent host, phosphorescent doping, and fluorescent doping.
  • Will Fisher's coating thickness is The ITO glass substrate was washed twice in distilled water, ultrasonically washed for 30 minutes, washed in the order of isopropanol, acetone, and methanol for 30 minutes, washed twice with distilled water, ultrasonically washed for 10 minutes, dried, and transferred to a plasma. In the washing machine, the substrate was washed for 5 minutes and sent to a vapor deposition machine.
  • the organic light-emitting device prepared by using the aromatic amine compound obtained by the present invention has greatly improved luminous efficiency and lifetime of the organic light-emitting device prepared by the general organic matter.
  • the average luminous efficiency is 167% of the prior art, and the average life is 209% of the prior art.
  • the aromatic amine compound having the skeleton structure represented by Formula I provided by the present invention can be applied to an organic electroluminescence device, and the obtained organic electroluminescence device has markedly improved luminous efficiency and lifetime, and the average luminous efficiency is present. There is a technology of 167%, and the average life expectancy is 209% of the prior art, which can meet the requirements of OLED use. Further, the aromatic amine compound provided by the present application also has excellent film forming properties and heat resistance.

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Abstract

Provided in the present invention are an aromatic amine compound and the preparation and application thereof. The aromatic amine compound having the skeletal structure shown in formula I provided in the present invention can be used in organic electroluminescent devices, the light-emitting efficiency and service life of the obtained organic electroluminescent devices both being significantly improved, the average light-emitting efficiency being 167% of that in the prior art and the average service life being 209% of that in the prior art, meeting the usage requirements for OLEDs. In addition, the aromatic amine compound provided in the present application has excellent film-forming properties and heat resistance.

Description

一种芳香族胺类化合物及其制备方法和应用Aromatic amine compound and preparation method and application thereof
本申请要求于2015年08月31日提交中国专利局、申请号为201510546032.6、发明名称为“一种芳香族胺类化合物及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims priority to Chinese Patent Application No. 201510546032.6, entitled "Aromatic Amine Compounds and Preparation Methods and Applications", filed on August 31, 2015, the entire contents of which are incorporated by reference. The citations are incorporated herein by reference.
技术领域Technical field
本发明涉及有机光电材料技术领域，尤其涉及一种芳香族胺类化合物及其制备方法和应用。The invention relates to the technical field of organic photoelectric materials, in particular to an aromatic amine compound and a preparation method and application thereof.
背景技术Background technique
电致发光器件中的主体材料主要有小分子主体材料和聚合物主体材料两类。利用小分子主体材料掺杂磷光配合物做为发光层已经制备了许多高效的电致发光器件。近年来，利用聚合物主体材料掺杂各种磷光配合物客体作为发光层制备电致发光器件受到了较多的关注。由于近几年光电通讯和多媒体领域的迅速发展，有机光电子材料已成为现代社会信息和电子产业的核心。The host material in the electroluminescent device mainly has two types of small molecule host materials and polymer host materials. Many high-efficiency electroluminescent devices have been prepared by doping a phosphorescent complex with a small molecule host material as a light-emitting layer. In recent years, the preparation of electroluminescent devices by doping various phosphorescent complex guest bodies with a polymer host material as a light-emitting layer has received much attention. Due to the rapid development of optoelectronic communication and multimedia in recent years, organic optoelectronic materials have become the core of the modern social information and electronics industry.
有机电致发光器件(OLED)是一种新型的平面显示器件，与小分子电致发光器件相比具有节能、响应速度快、颜色稳定、环境适应性强、无辐射、寿命长、质量轻、厚度薄等特点。有机电致发光器件，一般由两个对置的电极和插入在该两个电极之间的至少一层有机发光化合物组成。电荷被注入到在阳极和阴极之间形成的有机层中，以形成电子和空穴对，使具有荧光或磷光特性的有机化合物产生了光发射。在阳极和阴极之间施加电压，空穴就从阳极通过空穴传输层注入到发光层中，同时，电子从阴极通过电子传输层注入到发光层中。在发光层区域，载流子重排形成激子。激发态激子转变到基态，引起发光层分子发光，图象因此形成。Organic electroluminescent device (OLED) is a new type of flat display device. Compared with small molecule electroluminescent devices, it has energy saving, fast response, stable color, strong environmental adaptability, no radiation, long life and light weight. Thin thickness and other characteristics. An organic electroluminescent device generally consists of two opposing electrodes and at least one layer of an organic luminescent compound interposed between the two electrodes. Charge is injected into the organic layer formed between the anode and the cathode to form electron and hole pairs, causing light emission of an organic compound having fluorescent or phosphorescent properties. A voltage is applied between the anode and the cathode, and holes are injected from the anode through the hole transport layer into the light-emitting layer, while electrons are injected from the cathode through the electron transport layer into the light-emitting layer. In the region of the light-emitting layer, carriers are rearranged to form excitons. The excited exciton transitions to the ground state, causing the luminescent layer molecules to emit light, and the image is thus formed.
目前有机电致器件中空穴传输材料(Electron Transport Layer)的代表物质如下： The representative materials of the current Electro Transport Layer in organic electro-optical devices are as follows:
Figure PCTCN2015096450-appb-000001
Figure PCTCN2015096450-appb-000001
但这些材料发光效率普遍较低，不能够满足有机电致发光器件对发光效率的要求。However, the luminous efficiency of these materials is generally low, and the requirements for the luminous efficiency of the organic electroluminescent device cannot be satisfied.
发明内容Summary of the invention
本发明的目的在于提供一种芳香族胺类化合物及其制备方法和应用，旨在提供一种新的高效的有机电致发光材料。与现有技术相比，本发明提供的芳香族胺类化合物制备得到的发光器件，平均发光效率为现有技术的167％。It is an object of the present invention to provide an aromatic amine compound, a preparation method and application thereof, and to provide a novel and highly efficient organic electroluminescent material. Compared with the prior art, the light-emitting device prepared by the aromatic amine compound provided by the present invention has an average luminous efficiency of 167% of the prior art.
本发明的技术方案如下：The technical solution of the present invention is as follows:
一种芳香族胺类化合物，具有式I所示结构：An aromatic amine compound having the structure of formula I:
Figure PCTCN2015096450-appb-000002
Figure PCTCN2015096450-appb-000002
式I中，In formula I,
R1、R2和R3独立地选自氢原子、取代或未取代的碳原子数为1～30的烷基、取代或未取代的碳原子数为7～50的烷芳基、取代或未取代的碳原子数为6～50的芳基、取代或未取代的碳原子数为5～50的杂环基、取代或未取代的碳原子数为5～40的芳香族胺基； R 1 , R 2 and R 3 are independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 50 carbon atoms, a substitution or An unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted aromatic amine group having 5 to 40 carbon atoms;
R4和R5独立地选自氢原子、取代或未取代的碳原子数为6～50的芳基、取代或未取代的碳原子数为5～50的杂环基、取代或未取代的碳原子数为5～40的芳香族胺基、碳原子数6～50的芳氧基或芳巯基。优选的，所述式I中R1、R2、R3、R4和R5在满足权利要求1中所述限定下，独立的选自下面化学式中任意一个：R 4 and R 5 are independently selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted An aromatic amine group having 5 to 40 carbon atoms, an aryloxy group having 6 to 50 carbon atoms or an arylsulfonyl group. Preferably, in the formula I, R 1 , R 2 , R 3 , R 4 and R 5 are each independently selected from the following chemical formulas, as defined in claim 1:
Figure PCTCN2015096450-appb-000003
Figure PCTCN2015096450-appb-000003
Figure PCTCN2015096450-appb-000004
Figure PCTCN2015096450-appb-000004
其中X和Y独立的选自氢原子、卤素原子、氰基、取代或未取代的碳原子数为1～30的烷基、取代或未取代的碳原子数为1～30的烷氧基、取代或未取代的碳原子数为2～30的烯基、取代或未取代的碳原子数为7～30的烷芳基、取代或未取代的碳原子数为7～30的烷芳氧基、取代或未取代的碳原子数为6～30的芳香基、取代或未取代的碳原子数为6～30的芳氧基、取代或未取代的碳原子数为5～30的杂环基和取代或未取代的碳原子数为6～30的芳香族胺中的一种。Wherein X and Y are independently selected from a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, A substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkaryloxy group having 7 to 30 carbon atoms a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 carbon atoms And one of a substituted or unsubstituted aromatic amine having 6 to 30 carbon atoms.
优选的，所述式I具体为：Preferably, the formula I is specifically:
Figure PCTCN2015096450-appb-000005
Figure PCTCN2015096450-appb-000005
Figure PCTCN2015096450-appb-000006
Figure PCTCN2015096450-appb-000006
Figure PCTCN2015096450-appb-000007
Figure PCTCN2015096450-appb-000007
本发明提供了一种芳香族胺类化合物的制备方法，包括以下步骤：The invention provides a preparation method of an aromatic amine compound, comprising the following steps:
将反应物1溶于无水乙醚，在干冰浴-75～-80℃、隔绝氧气的条件下加入丁基锂，反应1～3h后加入酞酸二甲酯，反应1～3h后升温至15～25℃，加入水终止反应，得到产物1；The reactant 1 was dissolved in anhydrous diethyl ether, and butyllithium was added in a dry ice bath at -75 to -80 ° C under oxygen atmosphere. After 1 to 3 hours, dimethyl phthalate was added, and the reaction was heated to 15 after 1 to 3 hours. ～25 ° C, adding water to terminate the reaction, to obtain product 1;
将产物1溶于四氢呋喃中，降至0℃，加入混合液LTMP后在0℃下反应1～3小时得到产物2；The product 1 is dissolved in tetrahydrofuran, lowered to 0 ° C, added to the mixture LTMP and reacted at 0 ° C for 1-3 hours to obtain the product 2;
将产物2溶于乙腈中，然后添加含卤反应物，升温到55～65℃，反应4～6h，得到产物3；The product 2 is dissolved in acetonitrile, then the halogen-containing reactant is added, the temperature is raised to 55-65 ° C, and the reaction is carried out for 4-6 hours to obtain the product 3;
将产物3、反应物2、四三苯基膦钯溶于甲苯、乙醇和水体积比为(1～3):(0.5～1):(0.5～1)的混合液中，在隔绝氧气的条件下，升温至100～120℃反应20～28小时，得到具有式I结构所示的芳香族胺类化合物；The product 3, the reactant 2, the tetrakistriphenylphosphine palladium are dissolved in a mixture of toluene, ethanol and water in a volume ratio of (1 to 3): (0.5 to 1): (0.5 to 1), in which oxygen is isolated. Under the conditions, the temperature is raised to 100 to 120 ° C for 20 to 28 hours to obtain an aromatic amine compound having the structure of formula I;
Figure PCTCN2015096450-appb-000008
Figure PCTCN2015096450-appb-000008
其中， among them,
反应物1为具有式Ⅱ结构所示的卤代吡啶类衍生物；Reactant 1 is a halogenated pyridine derivative having the structure shown in Formula II;
Figure PCTCN2015096450-appb-000009
Figure PCTCN2015096450-appb-000009
所述反应物2为Y-R4或Y-R5；The reactant 2 is YR 4 or YR 5 ;
所述含卤反应物为三氯氧磷、三溴氧磷和三碘氧磷中的一种；The halogen-containing reactant is one of phosphorus oxychloride, phosphorus oxybromide and phosphorus oxyiodide;
所述混合液LTMP的制备方法为：500mL的四氢呋喃在0℃下溶解0.13mol丁基锂和0.14mol的2,2,6,6-四甲基哌啶；The mixed liquid LTMP is prepared by dissolving 0.13 mol of butyl lithium and 0.14 mol of 2,2,6,6-tetramethylpiperidine at 0 ° C in 500 mL of tetrahydrofuran;
其中，在式I、式Ⅱ和反应物2中：Wherein, in Formula I, Formula II and Reactant 2:
R1、R2和R3独立地选自氢原子、取代或未取代的碳原子数为1～30的烷基、取代或未取代的碳原子数为7～50的烷芳基、取代或未取代的碳原子数为6～50的芳基、取代或未取代的碳原子数为5～50的杂环基、取代或未取代的碳原子数为5～40的芳香族胺基；R 1 , R 2 and R 3 are independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 50 carbon atoms, a substitution or An unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted aromatic amine group having 5 to 40 carbon atoms;
R4和R5独立地选自氢原子、取代或未取代的碳原子数为6～50的芳基、取代或未取代的碳原子数为5～50的杂环基、取代或未取代的碳原子数为5～40的芳香族胺基、碳原子数6～50的芳氧基或芳巯基；R 4 and R 5 are independently selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted An aromatic amine group having 5 to 40 carbon atoms, an aryloxy group having 6 to 50 carbon atoms or an arylsulfonyl group;
X1为I、Cl或Br；X 1 is I, Cl or Br;
Y为B(OH)2。Y is B(OH) 2 .
优选的，所述反应物1为
Figure PCTCN2015096450-appb-000010
Figure PCTCN2015096450-appb-000011
和
Figure PCTCN2015096450-appb-000012
中的一种。Preferably, the reactant 1 is
Figure PCTCN2015096450-appb-000010
Figure PCTCN2015096450-appb-000011
with
Figure PCTCN2015096450-appb-000012
One of them.
优选的，所述反应物2为
Figure PCTCN2015096450-appb-000013
Figure PCTCN2015096450-appb-000015
和
Figure PCTCN2015096450-appb-000016
中的一种。Preferably, the reactant 2 is
Figure PCTCN2015096450-appb-000013
Figure PCTCN2015096450-appb-000015
with
Figure PCTCN2015096450-appb-000016
One of them.
优选的，所述反应物1与酞酸二甲酯的摩尔比为(1～1.2):1。Preferably, the molar ratio of the reactant 1 to dimethyl phthalate is (1 to 1.2):1.
优选的，所述含卤反应物中卤素原子与产物2的摩尔比为(1～8):1。Preferably, the molar ratio of the halogen atom to the product 2 in the halogen-containing reactant is (1-8):1.
优选的，所述产物3与反应物2的摩尔比为(1～3):1。Preferably, the molar ratio of the product 3 to the reactant 2 is (1 to 3): 1.
本发明提供了上述技术方案所述芳香族胺类化合物或上述技术方案所述制备方法得到的芳香族胺类化合物在有机电致发光器件中的应用，所述芳香族胺类化合物作为空穴传输材料或空穴阻挡材料。The present invention provides the use of the aromatic amine compound of the above technical solution or the aromatic amine compound obtained by the preparation method of the above technical solution in an organic electroluminescent device, wherein the aromatic amine compound is used as a hole transport Material or hole blocking material.
本发明的有益效果是：The beneficial effects of the invention are:
本发明提供的具有式I所示骨架结构的芳香族胺类化合物可以应用到有机电致发光器件中，得到的有机电致发光器件的发光效率及寿命均有显著的提高，平均发光效率为现有技术的167％，平均寿命为现有技术的209％，能够满足OLED的使用要求。此外，本申请提供的芳香族胺类化合物还具有优良的成膜性能和耐热性。The aromatic amine compound having the skeleton structure represented by Formula I provided by the present invention can be applied to an organic electroluminescence device, and the obtained organic electroluminescence device has markedly improved luminous efficiency and lifetime, and the average luminous efficiency is present. There is a technology of 167%, and the average life expectancy is 209% of the prior art, which can meet the requirements of OLED use. Further, the aromatic amine compound provided by the present application also has excellent film forming properties and heat resistance.
具体实施方式detailed description
本发明提供了一种芳香族胺类化合物，具有式I所示结构：The present invention provides an aromatic amine compound having the structure of Formula I:
Figure PCTCN2015096450-appb-000017
Figure PCTCN2015096450-appb-000017
式I中，In formula I,
R1、R2和R3独立地选自氢原子、取代或未取代的碳原子数为1～30的烷基、取代或未取代的碳原子数为7～50的烷芳基、取代或未取代的碳原子数为6～50的芳基、取代或未取代的碳原子数为5～50的杂环基、取代或未取代的碳原子数为5～40的芳香族胺基； R 1 , R 2 and R 3 are independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 50 carbon atoms, a substitution or An unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted aromatic amine group having 5 to 40 carbon atoms;
R4和R5独立地选自氢原子、取代或未取代的碳原子数为6～50的芳基、取代或未取代的碳原子数为5～50的杂环基、取代或未取代的碳原子数为5～40的芳香族胺基、碳原子数6～50的芳氧基或芳巯基。R 4 and R 5 are independently selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted An aromatic amine group having 5 to 40 carbon atoms, an aryloxy group having 6 to 50 carbon atoms or an arylsulfonyl group.
本发明提供的具有式I所示结构的芳香族胺类化合物的结构中包含R1、R2、R3、R4和R5。在本发明中，所述R1、R2和R3优选的独立地选自氢原子、取代或未取代的碳原子数为10～20的烷基、取代或未取代的碳原子数为25～35的烷芳基、取代或未取代的碳原子数为15～35的芳基、取代或未取代的碳原子数为15～35的杂环基、取代或未取代的碳原子数为15～30的芳香族胺基；所述R4和R5优选的独立地选自氢原子、取代或未取代的碳原子数为6～50的芳基、取代或未取代的碳原子数为5～50的杂环基、取代或未取代的碳原子数为5～40的芳香族胺基。The structure of the aromatic amine compound having a structure represented by Formula I provided by the present invention includes R 1 , R 2 , R 3 , R 4 and R 5 . In the present invention, the R 1 , R 2 and R 3 are preferably independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 10 to 20 carbon atoms, and a substituted or unsubstituted carbon atom number of 25 An alkylaryl group of ～35, a substituted or unsubstituted aryl group having 15 to 35 carbon atoms, a substituted or unsubstituted heterocyclic group having 15 to 35 carbon atoms, and a substituted or unsubstituted carbon atom number of 15 An aromatic amine group of ～30; wherein R 4 and R 5 are preferably independently selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, and a substituted or unsubstituted carbon atom number of 5 A heterocyclic group of ～50, a substituted or unsubstituted aromatic amine group having 5 to 40 carbon atoms.
在本发明中，所述式I中R1、R2、R3、R4和R5优选的可以独立的选自下面化学式中任意一个：In the present invention, R 1 , R 2 , R 3 , R 4 and R 5 in the formula I may preferably be independently selected from any one of the following chemical formulas:
Figure PCTCN2015096450-appb-000018
Figure PCTCN2015096450-appb-000018
Figure PCTCN2015096450-appb-000019
Figure PCTCN2015096450-appb-000019
其中X和Y可以独立的选自氢原子、卤素原子、氰基、取代或未取代的碳原子数为1～30的烷基、取代或未取代的碳原子数为1～30的烷氧基、取代或未取代的碳原子数为2～30的烯基、取代或未取代的碳原子数为7～30的烷芳基、取代或未取代的碳原子数为7～30的烷芳氧基、取代或未取代的碳原子数为6～30的芳香基、取代或未取代的碳原子数为6～30的芳氧基、取代或未取代的碳原子数为5～30的杂环基和取代或未取代的碳原子数为6～30的芳香族胺中的一种。Wherein X and Y may independently be selected from a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms. a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkylaryloxy group having 7 to 30 carbon atoms a substituted, unsubstituted or substituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic ring having 5 to 30 carbon atoms And a substituted or unsubstituted aromatic amine having 6 to 30 carbon atoms.
在本发明中，所述X和Y优选的可以独立的选自氢原子、卤素原子、氰基、取代或未取代的碳原子数为10～20的烷基、取代或未取代的碳原子数为10～20的烷氧基、取代或未取代的碳原子数为10～20的烯基、取代或未取代的碳原子数为15～25的烷芳基、取代或未取代的碳原子数为 15～25的烷芳氧基、取代或未取代的碳原子数为15～25的芳香基、取代或未取代的碳原子数为15～25的芳氧基、取代或未取代的碳原子数为15～25的杂环基和取代或未取代的碳原子数为15～25的芳香族胺中的一种。In the present invention, the X and Y are preferably independently selected from a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 10 to 20 carbon atoms, and a substituted or unsubstituted carbon number. a 10 to 20 alkoxy group, a substituted or unsubstituted alkenyl group having 10 to 20 carbon atoms, a substituted or unsubstituted alkylaryl group having 15 to 25 carbon atoms, a substituted or unsubstituted carbon number For 15 to 25 alkaryloxy group, substituted or unsubstituted aryl group having 15 to 25 carbon atoms, substituted or unsubstituted aryloxy group having 15 to 25 carbon atoms, substituted or unsubstituted carbon atom It is one of 15 to 25 heterocyclic groups and a substituted or unsubstituted aromatic amine having 15 to 25 carbon atoms.
在本发明中，所述芳香族胺类化合物优选为
Figure PCTCN2015096450-appb-000020
Figure PCTCN2015096450-appb-000021
In the present invention, the aromatic amine compound is preferably
Figure PCTCN2015096450-appb-000020
Figure PCTCN2015096450-appb-000021
Figure PCTCN2015096450-appb-000022
Figure PCTCN2015096450-appb-000022
本发明提供了一种芳香族胺类化合物的制备方法，包括以下步骤：The invention provides a preparation method of an aromatic amine compound, comprising the following steps:
将反应物1溶于无水乙醚，在干冰浴-75～-80℃、隔绝氧气的条件下加入丁基锂，反应1～3h后加入酞酸二甲酯，反应1～3h后升温至15～25℃，加入水终止反应，得到产物1； The reactant 1 was dissolved in anhydrous diethyl ether, and butyllithium was added in a dry ice bath at -75 to -80 ° C under oxygen atmosphere. After 1 to 3 hours, dimethyl phthalate was added, and the reaction was heated to 15 after 1 to 3 hours. ～25 ° C, adding water to terminate the reaction, to obtain product 1;
将产物1溶于四氢呋喃中，降至0℃，加入混合液LTMP后在0℃下反应1～3小时得到产物2；The product 1 is dissolved in tetrahydrofuran, lowered to 0 ° C, added to the mixture LTMP and reacted at 0 ° C for 1-3 hours to obtain the product 2;
将产物2溶于乙腈中，然后添加含卤反应物，升温到55～65℃，反应4～6h，得到产物3；The product 2 is dissolved in acetonitrile, then the halogen-containing reactant is added, the temperature is raised to 55-65 ° C, and the reaction is carried out for 4-6 hours to obtain the product 3;
将产物3、反应物2、四三苯基膦钯溶于甲苯、乙醇和水体积比为(1～3):(0.5～1):(0.5～1)的混合液中，在隔绝氧气的条件下，升温至100～120℃反应20～28小时，得到具有式I结构所示的芳香族胺类化合物；The product 3, the reactant 2, the tetrakistriphenylphosphine palladium are dissolved in a mixture of toluene, ethanol and water in a volume ratio of (1 to 3): (0.5 to 1): (0.5 to 1), in which oxygen is isolated. Under the conditions, the temperature is raised to 100 to 120 ° C for 20 to 28 hours to obtain an aromatic amine compound having the structure of formula I;
Figure PCTCN2015096450-appb-000023
Figure PCTCN2015096450-appb-000023
其中，among them,
反应物1为具有式Ⅱ结构所示的卤代吡啶类衍生物；Reactant 1 is a halogenated pyridine derivative having the structure shown in Formula II;
Figure PCTCN2015096450-appb-000024
Figure PCTCN2015096450-appb-000024
所述反应物2为Y-R4或Y-R5；The reactant 2 is YR 4 or YR 5 ;
所述含卤反应物为三氯氧磷、三溴氧磷和三碘氧磷中的一种；The halogen-containing reactant is one of phosphorus oxychloride, phosphorus oxybromide and phosphorus oxyiodide;
所述混合液LTMP的制备方法为：500mL的四氢呋喃在0℃下溶解0.13mol丁基锂和0.14mol的2,2,6,6-四甲基哌啶；The mixed liquid LTMP is prepared by dissolving 0.13 mol of butyl lithium and 0.14 mol of 2,2,6,6-tetramethylpiperidine at 0 ° C in 500 mL of tetrahydrofuran;
其中，在式I、式Ⅱ和反应物2中：Wherein, in Formula I, Formula II and Reactant 2:
R1、R2和R3独立地选自氢原子、取代或未取代的碳原子数为1～30的烷基、取代或未取代的碳原子数为7～50的烷芳基、取代或未取代的碳原子数为6～50的芳基、取代或未取代的碳原子数为5～50的杂环基、取代或未取代的碳原子数为5～40的芳香族胺基；R 1 , R 2 and R 3 are independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 50 carbon atoms, a substitution or An unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted aromatic amine group having 5 to 40 carbon atoms;
R4和R5独立地选自氢原子、取代或未取代的碳原子数为6～50的芳基、取代或未取代的碳原子数为5～50的杂环基、取代或未取代的碳原子数为5～40的芳香族胺基；R 4 and R 5 are independently selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted An aromatic amine group having 5 to 40 carbon atoms;
X1为I、Cl或Br；X 1 is I, Cl or Br;
Y为B(OH)2。 Y is B(OH) 2 .
本发明将反应物1溶于无水乙醚，在干冰浴-75～-80℃、隔绝氧气的条件下加入丁基锂，反应1～3h后加入酞酸二甲酯。在本发明中，上述干冰浴温度优选为-78℃。本发明对上述隔绝氧气的具体方式没有具体要求，在本发明实施例中，具体为通入氮气来隔绝氧气。在本发明的实施例中，所述反应物1与丁基锂的反应时间具体的可以为1h、2h或3h。In the present invention, the reactant 1 is dissolved in anhydrous diethyl ether, and butyllithium is added in a dry ice bath at -75 to -80 ° C under the condition of isolating oxygen. After reacting for 1 to 3 hours, dimethyl phthalate is added. In the present invention, the above dry ice bath temperature is preferably -78 °C. The present invention has no specific requirements for the specific manner of isolating the above oxygen. In the embodiment of the present invention, specifically, nitrogen is introduced to isolate oxygen. In an embodiment of the invention, the reaction time of the reactant 1 with butyl lithium may specifically be 1 h, 2 h or 3 h.
在本发明中，所述反应物1与酞酸二甲酯的摩尔比优选为(1～1.2):1，在本发明的实施例中可具体为1:1、1.1:1或1.2:1。本发明中，所述反应物1的物质的量与无水乙醚的体积比优选为1mol:(2.5～4.5)L，具体的在本发明的实施例中所述反应物1的物质的量与无水乙醚的体积比为1mol:2.5L、1mol:3L、1mol:3.5L、1mol:4L或1mol:4.5L。In the present invention, the molar ratio of the reactant 1 to dimethyl phthalate is preferably (1 to 1.2): 1, and may be specifically 1:1, 1.1:1 or 1.2:1 in the embodiment of the present invention. . In the present invention, the volume ratio of the amount of the reactant 1 to the anhydrous diethyl ether is preferably 1 mol: (2.5 to 4.5) L, specifically the amount of the reactant 1 in the embodiment of the present invention. The volume ratio of anhydrous diethyl ether was 1 mol: 2.5 L, 1 mol: 3 L, 1 mol: 3.5 L, 1 mol: 4 L or 1 mol: 4.5 L.
本发明中，所述反应物1的物质的量与丁基锂的体积比优选为1mol:(0.4～0.5)L，具体的在本发明的实施例中所述反应物1的物质的量与无水乙醚的体积比为1mol:0.4L、1mol:0.42L、1mol:0.44L、1mol:0.46L、1mol:0.48L或1mol:0.5L。在本发明中，优选加入的是丁基锂溶液，所述丁基锂溶液的摩尔浓度优选为1.5～3.5M，具体的在本发明的实施例中所述丁基锂的浓度为1.5M、2.0M、2.5M、3.0M或3.5M。In the present invention, the volume ratio of the substance of the reactant 1 to the butyl lithium is preferably 1 mol: (0.4 to 0.5) L, specifically the amount of the substance of the reactant 1 in the embodiment of the present invention. The volume ratio of anhydrous diethyl ether was 1 mol: 0.4 L, 1 mol: 0.42 L, 1 mol: 0.44 L, 1 mol: 0.46 L, 1 mol: 0.48 L or 1 mol: 0.5 L. In the present invention, a butyl lithium solution is preferably added, and the molar concentration of the butyl lithium solution is preferably 1.5 to 3.5 M, and specifically, the concentration of the butyl lithium in the embodiment of the present invention is 1.5 M. 2.0M, 2.5M, 3.0M or 3.5M.
本发明优选在干冰浴-75～-80℃、隔绝氧气的条件下加入丁基锂后，在搅拌条件下反应1～3h后加入酞酸二甲酯。In the present invention, it is preferred to add butyllithium in a dry ice bath at -75 to -80 ° C under the condition of isolating oxygen, and then reacting for 1 to 3 hours under stirring to add dimethyl phthalate.
本发明在加入酞酸二甲酯反应1～3h后升温至15～25℃，加入水终止反应，得到产物1。本发明对上述反应时间没有具体要求，具体的可以为1h、2h或3h。本发明对上述升温后的温度没有具体要求，具体的可以为15℃、17℃、19℃、21℃、23℃或25℃。The present invention is heated to 15 to 25 ° C after adding dimethyl phthalate for 1 to 3 hours, and the reaction is terminated by adding water to obtain the product 1. The present invention has no specific requirements for the above reaction time, and specifically may be 1 h, 2 h or 3 h. The present invention has no specific requirement for the temperature after the above temperature rise, and specifically may be 15 ° C, 17 ° C, 19 ° C, 21 ° C, 23 ° C or 25 ° C.
本发明中，所述无水乙醚与水的体积比优选为6:(3～7)，具体的在本发明的实施例中所述无水乙醚与水的体积比为6:3、6:4、6:5、6:6或6:7。In the present invention, the volume ratio of the anhydrous diethyl ether to water is preferably 6: (3 to 7), and specifically, in the embodiment of the present invention, the volume ratio of the anhydrous diethyl ether to water is 6:3, 6: 4, 6:5, 6:6 or 6:7.
本发明优选在加水终止反应后对得到的反应产物进行后处理。在本发明中，具体为对反应产物统一进行分液，分去水层，水层用乙酸乙酯萃取一遍，旋干有机溶剂，用二氯甲烷:聚乙烯＝(7～11):1(体积比)过柱分离，得到纯净的产物1。 In the present invention, it is preferred to post-treat the obtained reaction product after the reaction is terminated by adding water. In the present invention, the reaction product is specifically subjected to liquid separation, the aqueous layer is separated, the aqueous layer is extracted once with ethyl acetate, and the organic solvent is spin-dried with dichloromethane: polyethylene = (7 to 11): 1 ( The volume ratio) was separated by column to give pure product 1.
在本发明中，所述所述反应物1优选为
Figure PCTCN2015096450-appb-000025
Figure PCTCN2015096450-appb-000026
Figure PCTCN2015096450-appb-000027
和
Figure PCTCN2015096450-appb-000028
中的一种。In the present invention, the reactant 1 is preferably
Figure PCTCN2015096450-appb-000025
Figure PCTCN2015096450-appb-000026
Figure PCTCN2015096450-appb-000027
with
Figure PCTCN2015096450-appb-000028
One of them.
在本发明中，所述所述产物1优选为
Figure PCTCN2015096450-appb-000029
Figure PCTCN2015096450-appb-000030
Figure PCTCN2015096450-appb-000031
和
Figure PCTCN2015096450-appb-000032
中的一种。In the present invention, the product 1 is preferably
Figure PCTCN2015096450-appb-000029
Figure PCTCN2015096450-appb-000030
Figure PCTCN2015096450-appb-000031
with
Figure PCTCN2015096450-appb-000032
One of them.
本发明在得到将产物1后，将产物1溶于四氢呋喃中，降至0℃，加入混合液LTMP后在0℃下反应1～3小时得到产物2。本发明对上述反应时间没有具体要求，具体的可以为1h、2h或3h。In the present invention, after the product 1 is obtained, the product 1 is dissolved in tetrahydrofuran and lowered to 0 ° C. After the mixture LTMP is added, the reaction is carried out at 0 ° C for 1 to 3 hours to obtain the product 2. The present invention has no specific requirements for the above reaction time, and specifically may be 1 h, 2 h or 3 h.
本发明中，所述产物1的物质的量与四氢呋喃的体积比优选为1g:(25～45)ml，具体的在本发明的实施例中所述产物1的物质的量与四氢呋喃的体积比为1g:25ml、1g:30ml、1g:35ml、1g:45ml或1g:55ml。 In the present invention, the volume ratio of the amount of the product of the product 1 to the tetrahydrofuran is preferably 1 g: (25 to 45) ml, specifically, the ratio of the amount of the product of the product 1 to the volume ratio of tetrahydrofuran in the examples of the present invention. It is 1 g: 25 ml, 1 g: 30 ml, 1 g: 35 ml, 1 g: 45 ml or 1 g: 55 ml.
本发明中，所述四氢呋喃与水的体积比优选为6:(3～7)，具体的在本发明的实施例中所述四氢呋喃与水的体积比为6:3、6:4、6:5、6:6或6:7。In the present invention, the volume ratio of the tetrahydrofuran to water is preferably 6: (3 to 7), and specifically, in the embodiment of the present invention, the volume ratio of the tetrahydrofuran to water is 6:3, 6:4, 6: 5, 6:6 or 6:7.
本发明在加入混合液LTMP后优选在0℃及搅拌条件下反应1～3小时得到产物2。In the present invention, after the addition of the mixed solution LTMP, it is preferred to carry out the reaction at 0 ° C under stirring for 1 to 3 hours to obtain the product 2.
本发明优选在加水终止反应后对得到的反应产物进行后处理。在本发明中，具体为分去水层，将有机层旋干，用二氯甲烷:石油醚＝10:1过柱分离，得纯净的产物2。In the present invention, it is preferred to post-treat the obtained reaction product after the reaction is terminated by adding water. In the present invention, specifically, the aqueous layer is separated, and the organic layer is spin-dried and separated by a dichloromethane: petroleum ether = 10:1 to obtain a pure product 2.
在本发明中，所述所述产物2优选为
Figure PCTCN2015096450-appb-000033
Figure PCTCN2015096450-appb-000034
Figure PCTCN2015096450-appb-000035
和
Figure PCTCN2015096450-appb-000036
中的一种。In the present invention, the product 2 is preferably
Figure PCTCN2015096450-appb-000033
Figure PCTCN2015096450-appb-000034
Figure PCTCN2015096450-appb-000035
with
Figure PCTCN2015096450-appb-000036
One of them.
本发明将产物2溶于乙腈中，然后添加含卤反应物，升温到55～65℃，反应4～6h，得到产物3。在本发明实施例中，上述反应温度具体为56℃、58℃、60℃、62℃或64℃；上述反应时间具体为4h、5h或6h。In the present invention, the product 2 is dissolved in acetonitrile, and then the halogen-containing reactant is added, the temperature is raised to 55 to 65 ° C, and the reaction is carried out for 4 to 6 hours to obtain the product 3. In the embodiment of the present invention, the reaction temperature is specifically 56 ° C, 58 ° C, 60 ° C, 62 ° C or 64 ° C; the above reaction time is specifically 4 h, 5 h or 6 h.
在本发明中，所述含卤反应物中卤素原子与产物2的摩尔比为(1～8):1，在本发明的实施例中可具体为1:1、2:1、3:1、4:1、5:1、6:1、7:1或8:1。In the present invention, the molar ratio of the halogen atom to the product 2 in the halogen-containing reactant is (1 to 8): 1, which may be specifically 1:1, 2:1, 3:1 in the embodiment of the present invention. , 4:1, 5:1, 6:1, 7:1 or 8:1.
本发明中，所述产物2的质量与乙腈的体积比优选为1g:(15～40)ml，具体的在本发明的实施例中所述产物2的质量与乙腈的体积比为 1g:15ml、1g:20ml、1g:25ml、1g:30ml、1g:35ml或1g:40ml。In the present invention, the mass ratio of the product 2 to the acetonitrile is preferably 1 g: (15 to 40) ml, and specifically the volume ratio of the product 2 to the acetonitrile in the embodiment of the present invention is 1 g: 15 ml, 1 g: 20 ml, 1 g: 25 ml, 1 g: 30 ml, 1 g: 35 ml or 1 g: 40 ml.
在本发明中，所述含卤反应物优选为三氯氧磷、三溴氧磷和三碘氧磷中的一种。本发明中，所述产物2与卤反应物的质量比优选为2:(5～7)，具体的在本发明的实施例中所述产物2的物质的量与乙腈的质量比为2:5、2:6或2:7。In the present invention, the halogen-containing reactant is preferably one of phosphorus oxychloride, phosphorus oxybromide and phosphorus oxyiodate. In the present invention, the mass ratio of the product 2 to the halogen reactant is preferably 2: (5 to 7). Specifically, in the embodiment of the present invention, the mass ratio of the amount of the product of the product 2 to the acetonitrile is 2: 5, 2:6 or 2:7.
本发明优选在反应结束后对得到的反应产物进行后处理。在本发明中，具体为反应完毕后，加入水萃灭，再加碳酸钠饱合溶液调节pH值为7-8，再加入二氯甲烷，萃取三次，旋干得纯净的产物3。In the present invention, it is preferred to subject the obtained reaction product to post-treatment after completion of the reaction. In the present invention, specifically, after completion of the reaction, water is added to remove, and the sodium carbonate saturated solution is added to adjust the pH to 7-8, and then dichloromethane is added, extracted three times, and the product 3 is purified by spin-drying.
在本发明中，所述产物3优选为
Figure PCTCN2015096450-appb-000037
Figure PCTCN2015096450-appb-000038
Figure PCTCN2015096450-appb-000039
和
Figure PCTCN2015096450-appb-000040
中的一种。In the present invention, the product 3 is preferably
Figure PCTCN2015096450-appb-000037
Figure PCTCN2015096450-appb-000038
Figure PCTCN2015096450-appb-000039
with
Figure PCTCN2015096450-appb-000040
One of them.
本发明将产物3、反应物2、四三苯基膦钯溶于甲苯、乙醇和水体积比为(1～3):(0.5～1):(0.5～1)的混合液中，在隔绝氧气的条件下，升温至100～120℃反应20～28小时即得到上述芳香族胺类化合物。本发明对上述反应温度没有具体要求，具体的可以为105℃、110℃、115℃、或118℃。本发明对上述反应时间没有具体要求，具体的可以为22h、24h或26h。In the present invention, the product 3, the reactant 2, the tetrakistriphenylphosphine palladium are dissolved in a mixture of toluene, ethanol and water in a volume ratio of (1 to 3): (0.5 to 1): (0.5 to 1), which is isolated. The above aromatic aromatic compound is obtained by raising the temperature to 100 to 120 ° C for 20 to 28 hours under oxygen conditions. The present invention has no specific requirements for the above reaction temperature, and may specifically be 105 ° C, 110 ° C, 115 ° C, or 118 ° C. The present invention has no specific requirements for the above reaction time, and specifically may be 22h, 24h or 26h.
在本发明中，所述产物3与反应物2的摩尔比为(1～3):1，在本发明的实施例中可具体为1:1、2:1或3:1。 In the present invention, the molar ratio of the product 3 to the reactant 2 is (1 to 3): 1, and may be specifically 1:1, 2:1 or 3:1 in the embodiment of the present invention.
本发明中，所述产物3与四三苯基膦钯的质量比优选为15:(3～5)，具体的在本发明的实施例中所述产物3与四三苯基膦钯的质量比为15:3、15:4或15:5。In the present invention, the mass ratio of the product 3 to tetrakistriphenylphosphine palladium is preferably 15: (3 to 5), specifically the mass of the product 3 and tetrakistriphenylphosphine palladium in the examples of the present invention. The ratio is 15:3, 15:4 or 15:5.
本发明中，所述产物3的物质的量与甲苯、乙醇和水的混合液的体积比优选为1g:(30～50)ml，具体的在本发明的实施例中所述产物2的物质的量与乙腈的体积比为1g:30ml、1g:35ml、1g:40ml、1g:45ml或1g:50ml。In the present invention, the volume ratio of the substance of the product 3 to the mixed liquid of toluene, ethanol and water is preferably 1 g: (30 to 50) ml, specifically the substance of the product 2 in the embodiment of the present invention. The volume ratio to the acetonitrile is 1 g: 30 ml, 1 g: 35 ml, 1 g: 40 ml, 1 g: 45 ml or 1 g: 50 ml.
本发明优选在加入15g产物3时加入600ml甲苯、乙醇和水的混合液。在本发明中，所述甲苯、乙醇和水体积比优选为2:1:1。In the present invention, it is preferred to add 600 ml of a mixture of toluene, ethanol and water at the time of adding 15 g of the product 3. In the present invention, the volume ratio of toluene, ethanol and water is preferably 2:1:1.
在本发明中，所述反应物2优选为
Figure PCTCN2015096450-appb-000041
Figure PCTCN2015096450-appb-000042
Figure PCTCN2015096450-appb-000043
和
Figure PCTCN2015096450-appb-000044
中的一种。In the present invention, the reactant 2 is preferably
Figure PCTCN2015096450-appb-000041
Figure PCTCN2015096450-appb-000042
Figure PCTCN2015096450-appb-000043
with
Figure PCTCN2015096450-appb-000044
One of them.
本发明提供了上述技术方案所述芳香族胺类化合物或上述技术方案所述制备方法得到的芳香族胺类化合物在有机电致发光器件中的应用，所述芳香族胺类化合物作为空穴传输材料或空穴阻挡材料。The present invention provides the use of the aromatic amine compound of the above technical solution or the aromatic amine compound obtained by the preparation method of the above technical solution in an organic electroluminescent device, wherein the aromatic amine compound is used as a hole transport Material or hole blocking material.
本发明对所述有机电致发光器件的结构没有特殊要求，采用常规的有机电致发光器件即可，在本发明中，所述有机电致发光器件可具体为有机发光器件、有机太阳电池、电子纸、有机感光体和有机薄膜晶体管。在本发明中，所述有机电致发光器件优选包括第一电极、第二电极和置于所述两电极之间的一个或多个有机物层；更优选的所述有机物层中至少一个有机物层包含如上述技术方案所述芳香族胺类化合物或上述技术方案所述制备方法得到的芳香族胺类化合物且所述有机物层中至少一个有机物层包含如上述技术方案所述芳香族胺类化合物或上述技术方案所述制备方法得到的芳香族胺类化合物和其他物质。The present invention has no special requirements on the structure of the organic electroluminescent device, and a conventional organic electroluminescent device can be used. In the present invention, the organic electroluminescent device can be specifically an organic light emitting device, an organic solar cell, Electronic paper, organic photoreceptor and organic thin film transistor. In the present invention, the organic electroluminescent device preferably includes a first electrode, a second electrode, and one or more organic layer disposed between the two electrodes; more preferably at least one organic layer in the organic layer An aromatic amine compound obtained by the above-described method of the aromatic amine compound or the above-described technical solution, and at least one organic layer in the organic layer contains the aromatic amine compound as described in the above technical solution or The aromatic amine compound and other substances obtained by the preparation method described in the above technical scheme.
本发明对所述有机电致发光器件的有机物层没有特殊要求，按照常规的有机电致发光器件的有机物层进行设置即可。在本发明中，所述有机物层优选的至少包括空穴注入层、空穴传输层、既具备空穴注入又具备空穴 传输技能的注传层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层和既具备电子传输又具备电子注入技能的传注层中的一种；更优选的，所述空穴注入层、空穴传输层、既具备空穴注入又具备空穴传输技能的注传层这三层中至少一层是含有常规的空穴注入物质、空穴传输物质、既具备空穴注入又具备空穴传输技能的物质或电子传输物质生成的物质。The present invention has no special requirements on the organic layer of the organic electroluminescent device, and may be disposed in accordance with an organic layer of a conventional organic electroluminescent device. In the present invention, the organic layer preferably includes at least a hole injection layer, a hole transport layer, and both a hole injection and a hole. a transmission transmission layer, an electron blocking layer, a light-emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a transfer layer having both electron transport and electron injection skills; more preferably, At least one of the three layers of the hole injection layer, the hole transport layer, and the injection layer having the hole injection technique and the hole transporting ability contains a conventional hole injecting substance and a hole transporting substance, and has an empty space. The hole is injected with a substance having a hole transporting skill or a substance generated by an electron transporting substance.
在本发明中，所述有机物层中优选的至少一层为发光层；更优选的，所述发光层包括磷光主体、荧光主体、磷光掺杂及荧光掺杂中的一种或多种。In the present invention, at least one of the organic layer is preferably a light-emitting layer; more preferably, the light-emitting layer comprises one or more of a phosphorescent host, a fluorescent host, phosphorescent doping, and fluorescent doping.
下面将结合本发明中的实施例，对本发明中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. It is apparent that the described embodiments are only a part of the embodiments of the invention, and not all of the embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative efforts are within the scope of the present invention.
在下述实施例中，原料均为市售商品。In the following examples, the raw materials were all commercially available.
实施例1：中间体的合成Example 1: Synthesis of intermediates
中间体2-(吡啶-2-羰基)苯甲酸甲酯(B-1)的合成：Synthesis of intermediate 2-(pyridine-2-carbonyl)benzoic acid methyl ester (B-1):
Figure PCTCN2015096450-appb-000045
Figure PCTCN2015096450-appb-000045
合成方法：将3-溴吡啶(15.9g，0.1mol)溶于300mL无水乙醚中，干冰浴-78℃，在隔绝氧气的条件下，加入44mL的丁基锂(2.5M)，搅拌反应1小时，再加入酞酸二甲酯(19.5g，0.1mol)，反应2小时，后逐渐升到15～25℃，加入水终止反应。Synthetic method: 3-bromopyridine (15.9 g, 0.1 mol) was dissolved in 300 mL of anhydrous diethyl ether, and dried in an ice bath at -78 ° C. Under the condition of isolating oxygen, 44 mL of butyl lithium (2.5 M) was added, and the reaction was stirred. After an additional hour, dimethyl decanoate (19.5 g, 0.1 mol) was added, and the reaction was allowed to proceed for 2 hours, then gradually increased to 15 to 25 ° C, and water was added to terminate the reaction.
后处理过程：对反应产物进行分液，分去水层，水层用乙酸乙酯萃取一遍，旋干有机溶剂，用二氯甲烷:聚乙烯＝9:1(体积比)过柱分离，得白色固体B-1(12.3g，产率为51％)。Post-treatment process: the reaction product was separated, the aqueous layer was separated, the aqueous layer was extracted with ethyl acetate, and the organic solvent was spun and separated by dichloromethane: polyethylene = 9:1 (volume ratio). White solid B-1 (12.3 g, yield 51%).
中间体B-2～B-11的合成Synthesis of Intermediates B-2 to B-11
按照上述中间体B-1的合成方法得到中间体B-2～B-11:Intermediates B-2 to B-11 were obtained according to the above-mentioned intermediate B-1:
表3中间体B-2～B-11的制备原料、结构及产率明细 Table 3 Preparation of intermediates B-2 to B-11 Raw materials, structures and yield details
Figure PCTCN2015096450-appb-000046
Figure PCTCN2015096450-appb-000046
Figure PCTCN2015096450-appb-000047
Figure PCTCN2015096450-appb-000047
中间体苯并[g]喹啉-5-二酮(C-1)的合成Synthesis of Intermediate Benzo[g]quinolin-5-dione (C-1)
Figure PCTCN2015096450-appb-000048
Figure PCTCN2015096450-appb-000048
合成方法：将B-1(10g,41.5mmol)溶解于300mL的四氢呋喃中，降温至0℃，加入混合液LTMP后在0℃下搅拌反应2小时。Synthetic method: B-1 (10 g, 41.5 mmol) was dissolved in 300 mL of tetrahydrofuran, and the temperature was lowered to 0 ° C. After the mixture was added LTMP, the reaction was stirred at 0 ° C for 2 hours.
LTMP的合成：500mL的四氢呋喃在0℃下溶解0.13mol丁基锂和0.14mol的2,2,6,6-四甲基哌啶。Synthesis of LTMP: 500 mL of tetrahydrofuran dissolved 0.13 mol of butyllithium and 0.14 mol of 2,2,6,6-tetramethylpiperidine at 0 °C.
后处理过程：加入200mL水终止反应，分去水层，将有机层旋干，用二氯甲烷:石油醚＝10:1过柱分离，得固体(C-1)(20.8mmol，产率为40％)。After-treatment: the reaction was terminated by adding 200 mL of water, and the aqueous layer was separated, and the organic layer was dried with methylene chloride: petroleum ether = 10:1 to give a solid (C-1) (20.8 mmol, yield 40%).
中间体C-2～C-11的合成：Synthesis of intermediates C-2 to C-11:
按照上述中间体C-1的合成方法得到中间体C-2～C-11:Intermediate C-2 to C-11 were obtained according to the above-mentioned intermediate C-1:
表4中间体C-2～C-11的制备原料、结构及产率明细 Table 4 Preparation of intermediates C-2 to C-11 Preparation of raw materials, structures and yields
Figure PCTCN2015096450-appb-000049
Figure PCTCN2015096450-appb-000049
Figure PCTCN2015096450-appb-000050
Figure PCTCN2015096450-appb-000050
中间体5,10-二氯苯并[g]喹啉(D-1)的合成Synthesis of Intermediate 5,10-Dichlorobenzo[g]quinoline (D-1)
Figure PCTCN2015096450-appb-000051
Figure PCTCN2015096450-appb-000051
合成方法：将C-1(10g，47.8mmol)加入到反应瓶中，加入200mL乙腈，再称取30g三氯氧磷缓慢滴加到反应瓶中，滴加完毕后缓慢升温到60℃，反应时间为5小时。Synthetic method: C-1 (10g, 47.8mmol) was added to the reaction flask, 200mL acetonitrile was added, and 30g of phosphorus oxychloride was weighed and slowly added to the reaction flask. After the addition was completed, the temperature was slowly raised to 60 ° C. The time is 5 hours.
后处理过程：反应完毕后，加入水小心萃灭，再加放大量的碳酸钠饱合溶液调节PH值为7-8，再加入二氯甲烷，萃取三次，旋干得固体D-1(7.2g，产率为61％)。Post-treatment: After the reaction is completed, add water to carefully extract, and add a large amount of sodium carbonate saturation solution to adjust the pH value of 7-8, then add dichloromethane, extract three times, and spin dry to obtain solid D-1 (7.2 g, yield 61%).
中间体D-2～D-11的合成：Synthesis of intermediates D-2 to D-11:
按照上述中间体D-1的合成方法得到中间体D-2～D-11:Intermediate D-2 to D-11 were obtained according to the above-mentioned intermediate D-1:
表5中间体D-2～D-11的制备原料、结构及产率明细Table 5 Preparation of intermediates D-2 to D-11 Raw materials, structures and yield details
Figure PCTCN2015096450-appb-000052
Figure PCTCN2015096450-appb-000052
Figure PCTCN2015096450-appb-000053
Figure PCTCN2015096450-appb-000053
Figure PCTCN2015096450-appb-000054
Figure PCTCN2015096450-appb-000054
实施例2：芳香族胺类化合物的合成Example 2: Synthesis of aromatic amine compounds
5,10-二苯基苯并[g]喹啉(E-1)即式I-1的合成Synthesis of 5,10-diphenylbenzo[g]quinoline (E-1), formula I-1
Figure PCTCN2015096450-appb-000055
Figure PCTCN2015096450-appb-000055
合成方法：将D-1(15g,0.6mmol)、苯硼酸(18g,0.146mmol)、四三苯基膦钯4g加入到反应瓶中，再加入甲苯、乙醇和水体积比为2:1:1的混合液共计600mL，在隔绝氧气的条件下，搅拌升温至110℃反应24小时。Synthesis method: D-1 (15g, 0.6mmol), phenylboronic acid (18g, 0.146mmol), tetrakistriphenylphosphine palladium 4g was added to the reaction flask, and then added toluene, ethanol and water volume ratio of 2:1: The total amount of the mixed solution of 1 was 600 mL, and the reaction was heated to 110 ° C for 24 hours while stirring under oxygen.
后处理过程：把反应产物降至15～25℃，加入乙酸乙酯分液，萃取两次，使用旋转蒸发仪旋干甲苯。加入二氯甲烷溶解固体，使用组分为石油醚:乙酸乙酯＝2:1的洗脱液冲洗，得固体E-1(12.4g，产率为62％)。Post-treatment: The reaction product was lowered to 15 to 25 ° C, and ethyl acetate was added for liquid separation, extracted twice, and toluene was spin-dried using a rotary evaporator. Dichloromethane was added to dissolve the solid, which was washed with ethyl ether: ethyl ether = 2:1 to give solid E-1 (12.4 g, yield 62%).
化合物E-2～E-22的合成：Synthesis of compounds E-2 to E-22:
按照上述制备E-1的合成方法得到化合物E-2～E-22:Compounds E-2 to E-22 were obtained according to the above synthetic method for the preparation of E-1:
表6化合物E-2～E-22的制备原料、结构及产率明细Table 6 Preparation of compounds E-2 to E-22 raw materials, structure and yield details
Figure PCTCN2015096450-appb-000056
Figure PCTCN2015096450-appb-000056
Figure PCTCN2015096450-appb-000057
Figure PCTCN2015096450-appb-000057
Figure PCTCN2015096450-appb-000058
Figure PCTCN2015096450-appb-000058
Figure PCTCN2015096450-appb-000059
Figure PCTCN2015096450-appb-000059
5-溴-10-(2-萘基)苯并[g]喹啉(E-23-1)的合成： Synthesis of 5-bromo-10-(2-naphthyl)benzo[g]quinoline (E-23-1):
Figure PCTCN2015096450-appb-000060
Figure PCTCN2015096450-appb-000060
合成方法：参考E-1的合成，投入5,10-二溴苯并[g]喹啉(6.0g,17.8mmol)和2-萘硼酸(3.4g，19.6mmol)，得固体5-溴-10-(2-萘基)苯并[g]喹啉约(3.2g，产率为48％)。Synthetic method: With reference to the synthesis of E-1, 5,10-dibromobenzo[g]quinoline (6.0 g, 17.8 mmol) and 2-naphthaleneboronic acid (3.4 g, 19.6 mmol) were added to give a solid 5-bromo- 10-(2-Naphthyl)benzo[g]quinoline (3.2 g, yield 48%).
E-23即式I-23的合成：E-23 is the synthesis of formula I-23:
Figure PCTCN2015096450-appb-000061
Figure PCTCN2015096450-appb-000061
合成方法：参考E-1的合成，投入5-溴-10-(2-萘基)苯并[g]喹啉(3.3g，8.7mmol)和1-萘硼酸(1.65g，9.6mmol)，得固体E-23(1.8g，产率为48％)。Synthesis method: With reference to the synthesis of E-1, 5-bromo-10-(2-naphthyl)benzo[g]quinoline (3.3 g, 8.7 mmol) and 1-naphthaleneboronic acid (1.65 g, 9.6 mmol) were charged. Solid E-23 (1.8 g, yield 48%) was obtained.
E-24即式I-24的合成：E-24 is the synthesis of formula I-24:
Figure PCTCN2015096450-appb-000062
Figure PCTCN2015096450-appb-000062
合成方法：将二苯胺(24mmol)和叔丁醇钠(28g，0.30mol)，甲苯400mL加入到反应瓶中，搅拌30分钟，氮气保护，然后加入5,10-二氯苯并[g]喹啉(24mmol)、三(二亚卞基丙酮)二钯1.5g，最后加入三叔丁基膦4g，升温到100℃反应24小时。体系降温，加入水终止反应。Synthesis method: diphenylamine (24 mmol) and sodium t-butoxide (28 g, 0.30 mol), 400 mL of toluene were added to the reaction flask, stirred for 30 minutes, protected with nitrogen, and then added with 5,10-dichlorobenzo[g]quina 1.5 g of porphyrin (24 mmol) and tris(dipyridinylacetone) dipalladium, and finally 4 g of tri-tert-butylphosphine, and the mixture was heated to 100 ° C for 24 hours. The system was cooled and water was added to terminate the reaction.
后处理过程：对反应产物进行过滤，滤液分液，旋干甲苯，加入少量二氯甲烷溶解固体，石油醚:二氯甲烷＝3:1(体积比)过柱分离，得E-24(6.17g，y＝50％)。After-treatment: the reaction product was filtered, the filtrate was separated, the toluene was spun, and a small amount of dichloromethane was added to dissolve the solid. Petroleum ether: dichloromethane = 3:1 (volume ratio) was separated by column to obtain E-24 (6.17). g, y = 50%).
E-25即式I-25的合成：E-25 is the synthesis of formula I-25:
Figure PCTCN2015096450-appb-000063
Figure PCTCN2015096450-appb-000063
合成方法：取1-羟基萘(14g,0.1mol)溶于100mL无水四氢呋喃中，搅拌，称量NaH(0.96g,0.4mol)加到反应瓶中，再加入5,10-二氯苯并[g]喹啉(27.50g，0.11mol)，在15～25℃温度下反应8～14h。 Synthetic method: 1-hydroxynaphthalene (14 g, 0.1 mol) was dissolved in 100 mL of anhydrous tetrahydrofuran, stirred, and NaH (0.96 g, 0.4 mol) was weighed into a reaction flask, and then 5,10-dichlorobenzene was added. [g] Quinoline (27.50 g, 0.11 mol), reacted at a temperature of 15 to 25 ° C for 8 to 14 h.
后处理过程：对反应产物进行过滤，除去固体物质，滤液旋干，加入二氯甲烷溶解，过柱用石油醚：乙酸乙酯＝1：5(体积比)冲柱，得固体E-25(23.20g，y＝50％)。After-treatment: the reaction product was filtered, the solid matter was removed, the filtrate was spun dry, dissolved in dichloromethane, and the column was washed with petroleum ether: ethyl acetate = 1:5 (volume ratio) to obtain a solid E-25 ( 23.20g, y=50%).
E-26即式I-26的合成：E-26 is the synthesis of formula I-26:
Figure PCTCN2015096450-appb-000064
Figure PCTCN2015096450-appb-000064
合成方法：将1-萘硫醇(1.6g，10mmol)，5,10-二氯苯并[g]喹啉(2.48g，10mmol)，氢氧化钾(840mg，15mmol)，mPANI/pFe3O4(2.5g，5mol％)，H2O(30mL)混合，反应8小时。Synthetic method: 1-naphthyl mercaptan (1.6 g, 10 mmol), 5,10-dichlorobenzo[g]quinoline (2.48 g, 10 mmol), potassium hydroxide (840 mg, 15 mmol), mPANI/pFe3O4 (2.5 g, 5 mol%), H2O (30 mL) was mixed and reacted for 8 hours.
后处理过程：将反应产物通过乙酸乙酯萃取有机相，并采用乙酸乙酯：石油醚＝4:1(体积比)过柱分离，得白色固体(E-25)(1.89g，y＝38％)。Post-treatment: The reaction product was extracted with EtOAc (EtOAc):EtOAc (EtOAc:EtOAc:EtOAc %).
实施例3：有机电致发光器件的制备Example 3: Preparation of organic electroluminescent device
将费希尔公司涂层厚度为
Figure PCTCN2015096450-appb-000065
的ITO玻璃基板放在蒸馏水中清洗2次，超声波洗涤30分钟，按异丙醇、丙酮、甲醇按顺序共洗涤30分钟，用蒸馏水反复清洗2次，超声波洗涤10分钟，干燥，转移到等离子体清洗机里，将上述基板洗涤5分钟，送到蒸镀机里。将已经准备好的ITO透明电极上蒸镀空穴注入层2-TNATA蒸镀
Figure PCTCN2015096450-appb-000066
空穴传输层a-NPD蒸镀
Figure PCTCN2015096450-appb-000067
青色主体AND/掺杂5％的TPPDA蒸镀
Figure PCTCN2015096450-appb-000068
空穴阻挡层及空穴传输层TPBi或本发明实施例2中得到的芳香族胺类化合物蒸镀
Figure PCTCN2015096450-appb-000069
Figure PCTCN2015096450-appb-000070
阴极
Figure PCTCN2015096450-appb-000071
上述过程有机物蒸镀速度是保持
Figure PCTCN2015096450-appb-000072
/sec、LiF是
Figure PCTCN2015096450-appb-000073
/sec,Al是
Figure PCTCN2015096450-appb-000074
/sec。 Will Fisher's coating thickness is
Figure PCTCN2015096450-appb-000065
The ITO glass substrate was washed twice in distilled water, ultrasonically washed for 30 minutes, washed in the order of isopropanol, acetone, and methanol for 30 minutes, washed twice with distilled water, ultrasonically washed for 10 minutes, dried, and transferred to a plasma. In the washing machine, the substrate was washed for 5 minutes and sent to a vapor deposition machine. Evaporation of the hole injection layer 2-TNATA on the prepared ITO transparent electrode
Figure PCTCN2015096450-appb-000066
Hole transport layer a-NPD evaporation
Figure PCTCN2015096450-appb-000067
Cyan body AND/doped 5% TPPDA evaporation
Figure PCTCN2015096450-appb-000068
The hole blocking layer and the hole transport layer TPBi or the aromatic amine compound obtained in the second embodiment of the present invention are vapor-deposited
Figure PCTCN2015096450-appb-000069
Figure PCTCN2015096450-appb-000070
cathode
Figure PCTCN2015096450-appb-000071
The above process organic evaporation rate is maintained
Figure PCTCN2015096450-appb-000072
/sec, LiF is
Figure PCTCN2015096450-appb-000073
/sec, Al is
Figure PCTCN2015096450-appb-000074
/sec.
Figure PCTCN2015096450-appb-000075
Figure PCTCN2015096450-appb-000075
上述方法制造的有机发光器件的电子发光特性在表7中表示。The electron emission characteristics of the organic light-emitting device manufactured by the above method are shown in Table 7.
表7有机发光器件电子发光特性记录表Table 7 Electroluminescence characteristics of organic light-emitting devices
Figure PCTCN2015096450-appb-000076
Figure PCTCN2015096450-appb-000076
由表3可以看出，用本发明得到的芳香族胺类化合物制备的有机发光器件较一般有机物制备的有机发光器件的发光效率和寿命均大大提高。其中，平均发光效率为现有技术的167％，平均寿命为现有技术的209％。 It can be seen from Table 3 that the organic light-emitting device prepared by using the aromatic amine compound obtained by the present invention has greatly improved luminous efficiency and lifetime of the organic light-emitting device prepared by the general organic matter. Among them, the average luminous efficiency is 167% of the prior art, and the average life is 209% of the prior art.
本发明提供的具有式I所示骨架结构的芳香族胺类化合物可以应用到有机电致发光器件中，得到的有机电致发光器件的发光效率及寿命均有显著的提高，平均发光效率为现有技术的167％，平均寿命为现有技术的209％，能够满足OLED的使用要求。此外，本申请提供的芳香族胺类化合物还具有优良的成膜性能和耐热性。The aromatic amine compound having the skeleton structure represented by Formula I provided by the present invention can be applied to an organic electroluminescence device, and the obtained organic electroluminescence device has markedly improved luminous efficiency and lifetime, and the average luminous efficiency is present. There is a technology of 167%, and the average life expectancy is 209% of the prior art, which can meet the requirements of OLED use. Further, the aromatic amine compound provided by the present application also has excellent film forming properties and heat resistance.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。 The above description is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can also make several improvements and retouchings without departing from the principles of the present invention. It should be considered as the scope of protection of the present invention.

Claims (10)

  1. 一种芳香族胺类化合物，具有式I所示结构：An aromatic amine compound having the structure of formula I:
    Figure PCTCN2015096450-appb-100001
    Figure PCTCN2015096450-appb-100001
    式I中，In formula I,
    R1、R2和R3独立地选自氢原子、取代或未取代的碳原子数为1～30的烷基、取代或未取代的碳原子数为7～50的烷芳基、取代或未取代的碳原子数为6～50的芳基、取代或未取代的碳原子数为5～50的杂环基、取代或未取代的碳原子数为5～40的芳香族胺基；R 1 , R 2 and R 3 are independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 50 carbon atoms, a substitution or An unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted aromatic amine group having 5 to 40 carbon atoms;
    R4和R5独立地选自氢原子、取代或未取代的碳原子数为6～50的芳基、取代或未取代的碳原子数为5～50的杂环基、取代或未取代的碳原子数为5～40的芳香族胺基、碳原子数6～50的芳氧基或芳巯基。R 4 and R 5 are independently selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted An aromatic amine group having 5 to 40 carbon atoms, an aryloxy group having 6 to 50 carbon atoms or an arylsulfonyl group.
  2. 根据权利要求1所述的芳香族胺类化合物，其特征在于，所述式I中R1、R2、R3、R4和R5独立的选自下面化学式中任意一个：The aromatic amine compound according to claim 1, wherein R 1 , R 2 , R 3 , R 4 and R 5 in the formula I are independently selected from any one of the following chemical formulae:
    Figure PCTCN2015096450-appb-100002
    Figure PCTCN2015096450-appb-100002
    Figure PCTCN2015096450-appb-100003
    Figure PCTCN2015096450-appb-100003
    其中X和Y独立的选自氢原子、卤素原子、氰基、取代或未取代的碳原子数为1～30的烷基、取代或未取代的碳原子数为1～30的烷氧基、取代或未取代的碳原子数为2～30的烯基、取代或未取代的碳原子数为7～30的烷芳基、取代或未取代的碳原子数为7～30的烷芳氧基、取代或未取代的碳原子数为6～30的芳香基、取代或未取代的碳原子数为6～30的芳氧基、取代或未取代的碳原子数为5～30的杂环基和取代或未取代的碳原子数为6～30的芳香族胺中的一种。Wherein X and Y are independently selected from a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, A substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 30 carbon atoms, a substituted or unsubstituted alkaryloxy group having 7 to 30 carbon atoms a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 carbon atoms And one of a substituted or unsubstituted aromatic amine having 6 to 30 carbon atoms.
  3. 根据权利要求1所述的芳香族胺类化合物，其特征在于，所述式I具体为： The aromatic amine compound according to claim 1, wherein the formula I is specifically:
    Figure PCTCN2015096450-appb-100004
    Figure PCTCN2015096450-appb-100004
    Figure PCTCN2015096450-appb-100005
    Figure PCTCN2015096450-appb-100005
  4. 一种权利要求1～3任意一项所述的芳香族胺类化合物的制备方法，包括以下步骤：A method for producing an aromatic amine compound according to any one of claims 1 to 3, comprising the steps of:
    将反应物1溶于无水乙醚，在干冰浴-75～-80℃、隔绝氧气的条件下加入丁基锂，反应1～3h后加入酞酸二甲酯，反应1～3h后升温至15～25℃，加入水终止反应，得到产物1；The reactant 1 was dissolved in anhydrous diethyl ether, and butyllithium was added in a dry ice bath at -75 to -80 ° C under oxygen atmosphere. After 1 to 3 hours, dimethyl phthalate was added, and the reaction was heated to 15 after 1 to 3 hours. ～25 ° C, adding water to terminate the reaction, to obtain product 1;
    将产物1溶于四氢呋喃中，降至0℃，加入混合液LTMP后在0℃下反应1～3小时得到产物2；The product 1 is dissolved in tetrahydrofuran, lowered to 0 ° C, added to the mixture LTMP and reacted at 0 ° C for 1-3 hours to obtain the product 2;
    将产物2溶于乙腈中，然后添加含卤反应物，升温到55～65℃，反应4～6h，得到产物3；The product 2 is dissolved in acetonitrile, then the halogen-containing reactant is added, the temperature is raised to 55-65 ° C, and the reaction is carried out for 4-6 hours to obtain the product 3;
    将产物3、反应物2、四三苯基膦钯溶于甲苯、乙醇和水体积比为(1～3):(0.5～1):(0.5～1)的混合液中，在隔绝氧气的条件下，升温至100～120℃反应20～28小时，得到具有式I结构所示的芳香族胺类化合物； The product 3, the reactant 2, the tetrakistriphenylphosphine palladium are dissolved in a mixture of toluene, ethanol and water in a volume ratio of (1 to 3): (0.5 to 1): (0.5 to 1), in which oxygen is isolated. Under the conditions, the temperature is raised to 100 to 120 ° C for 20 to 28 hours to obtain an aromatic amine compound having the structure of formula I;
    Figure PCTCN2015096450-appb-100006
    Figure PCTCN2015096450-appb-100006
    其中，among them,
    反应物1为具有式Ⅱ结构所示的卤代吡啶类衍生物；Reactant 1 is a halogenated pyridine derivative having the structure shown in Formula II;
    Figure PCTCN2015096450-appb-100007
    Figure PCTCN2015096450-appb-100007
    所述反应物2为Y-R4或Y-R5；The reactant 2 is YR 4 or YR 5 ;
    所述含卤反应物为三氯氧磷、三溴氧磷和三碘氧磷中的一种；The halogen-containing reactant is one of phosphorus oxychloride, phosphorus oxybromide and phosphorus oxyiodide;
    所述混合液LTMP的制备方法为：500mL的四氢呋喃在0℃下溶解0.13mol丁基锂和0.14mol的2,2,6,6-四甲基哌啶；The mixed liquid LTMP is prepared by dissolving 0.13 mol of butyl lithium and 0.14 mol of 2,2,6,6-tetramethylpiperidine at 0 ° C in 500 mL of tetrahydrofuran;
    其中，在式I、式Ⅱ和反应物2中：Wherein, in Formula I, Formula II and Reactant 2:
    R1、R2和R3独立地选自氢原子、取代或未取代的碳原子数为1～30的烷基、取代或未取代的碳原子数为7～50的烷芳基、取代或未取代的碳原子数为6～50的芳基、取代或未取代的碳原子数为5～50的杂环基、取代或未取代的碳原子数为5～40的芳香族胺基；R 1 , R 2 and R 3 are independently selected from a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylaryl group having 7 to 50 carbon atoms, a substitution or An unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted aromatic amine group having 5 to 40 carbon atoms;
    R4和R5独立地选自氢原子、取代或未取代的碳原子数为6～50的芳基、取代或未取代的碳原子数为5～50的杂环基、取代或未取代的碳原子数为5～40的芳香族胺基；R 4 and R 5 are independently selected from a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted An aromatic amine group having 5 to 40 carbon atoms;
    X1为I、Cl或Br；X 1 is I, Cl or Br;
    Y为B(OH)2。Y is B(OH) 2 .
  5. 根据权利要求4所述的制备方法，其特征在于，所述反应物1为The preparation method according to claim 4, wherein the reactant 1 is
    Figure PCTCN2015096450-appb-100008
    Figure PCTCN2015096450-appb-100008
    Figure PCTCN2015096450-appb-100009
    中的一种。
    Figure PCTCN2015096450-appb-100009
    One of them.
  6. 根据权利要求4所述的制备方法，其特征在于，所述反应物2为The preparation method according to claim 4, wherein the reactant 2 is
    Figure PCTCN2015096450-appb-100010
    Figure PCTCN2015096450-appb-100011
    中的一种。
    Figure PCTCN2015096450-appb-100010
    Figure PCTCN2015096450-appb-100011
    One of them.
  7. 根据权利要求4所述的制备方法，其特征在于，所述反应物1与酞酸二甲酯的摩尔比为(1～1.2):1。The preparation method according to claim 4, wherein the molar ratio of the reactant 1 to dimethyl phthalate is (1 to 1.2):1.
  8. 根据权利要求4所述的制备方法，其特征在于，所述含卤反应物中卤素原子与产物2的摩尔比为(1～8):1。The method according to claim 4, wherein the molar ratio of the halogen atom to the product 2 in the halogen-containing reactant is (1 to 8):1.
  9. 根据权利要求4所述的制备方法，其特征在于，所述产物3与反应物2的摩尔比为(1～3):1。The method according to claim 4, wherein the molar ratio of the product 3 to the reactant 2 is (1 to 3):1.
  10. 权利要求1～3任意一项所述芳香族胺类化合物或权利要求4～9任意一项所述制备方法得到的芳香族胺类化合物在制备有机电致发光器件中的应用，所述芳香族胺类化合物作为空穴传输材料或空穴阻挡材料。 The use of the aromatic amine compound according to any one of claims 1 to 3 or the aromatic amine compound obtained by the production method according to any one of claims 4 to 9, for producing an organic electroluminescence device, the aromatic The amine compound acts as a hole transport material or a hole blocking material.
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