CN104892579A - Aromatic heterocyclic compound and preparation method thereof, and organic electroluminescent device - Google Patents

Aromatic heterocyclic compound and preparation method thereof, and organic electroluminescent device Download PDF

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CN104892579A
CN104892579A CN201510295908.4A CN201510295908A CN104892579A CN 104892579 A CN104892579 A CN 104892579A CN 201510295908 A CN201510295908 A CN 201510295908A CN 104892579 A CN104892579 A CN 104892579A
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carbonatoms
unsubstituted carbonatoms
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高春吉
崔敦洙
王贺
李文军
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Jilin Optical and Electronic Materials Co Ltd
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Priority to PCT/CN2015/095266 priority patent/WO2016192329A1/en
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Abstract

The invention provides an aromatic heterocyclic compound which has a structure as shown in a formula (I) in the specification. The benzo[g]phthalazine-containing aromatic heterocyclic compound provided by the invention is prepared by introducing Q1, Q2, Ar1, Ar2, Ar3 and Ar4 groups into a benzo[g]phthalazine compound, so that the electronic density and skill can be improved; the property of the aromatic heterocyclic compound can be improved by changing the variety of R1 and R2 of benzo[g]phthalazine, so that an organic electroluminescent device manufactured by the aromatic heterocyclic compound as shown in the formula (I) has high relatively luminous efficiency, long service life, relatively high brightness and excellent heat resistance. In addition, a new preparation method of the aromatic heterocyclic compound provided by the invention is simple and easy for industrialization.

Description

A kind of heteroaromatic compounds and preparation method thereof and organic electroluminescence device
Technical field
The present invention relates to technical field of organic luminescence materials, particularly relate to a kind of heteroaromatic compounds and preparation method thereof.
Background technology
Luminescent material refers to material that can be luminous under various forms energy excitation.Many materials of occurring in nature, comprise mineral compound and organic compound, more or less all can be luminous.Luminescent material is a kind of meticulous hi-tech industry, is widely used in industry, medical science, traffic and military field.Luminescent material can be divided into phosphor and luminous organic material by its component.
And in numerous luminescent material, of a great variety due to organic compound, adjustability is good, rich color, and purity of color is high, and molecular designing is relatively flexible, and on luminescence mechanism, physical and chemical performance, or respective feature is had in application.Thus, the research of organic materials is subject to people's attention day by day, and this is wherein according to different molecular structures, and luminous organic material can be divided into: organic molecule luminescent material, organic polymer luminescent material and organic coordination compound luminescent material.And this wherein organic molecule luminescent material is of a great variety, their multi-bands have conjugation heterocycle and various chromophore, structure is easy to adjustment, changes its conjugate length, thus compound optoelectronic character is changed by the introducing unsaturated group such as ethylene linkage, phenyl ring and various chromophore.Thus, obtain numerous researchers and be devoted to micromolecular research, as oxadiazoles and compounds thereof on the one hand, triazole and compounds thereof, rhodamine and compounds thereof, coumarin kind compound, 1,8-naphthoyl imide compounds, pyrazoline compounds, triphenylamine compound, porphyrins, carbazole, pyrazine, thiazole compound ， perylene compounds etc.They are widely used in the aspects such as optical electron device, DNA diagnosis, Optochemical sensor, dyestuff, white dyes, fluorescent coating, laser dyes, organic electroluminescence device (OLED).
This wherein, organic electroluminescence device typically refers to and is made up of two opposed electrodes and at least one deck organic luminescent compounds be inserted between these two electrodes.Electric charge is injected in the organic layer formed between the anode and cathode, to form electronics and hole pair, makes the organic compound with fluorescence or phosphorescent characteristics create light emission.It is a kind of novel flat panel display device, has the plurality of advantages such as energy-conservation, fast response time, colour stable, environmental compatibility are strong, radiationless, quality is light, thickness is thin.And developing rapidly along with photoelectric communication in recent years and MultiMedia Field, organic optoelectronic material has become the core of modern society's information and electronic industry.Therefore, along with the high speed development in field, higher requirement be it is also proposed in performance to luminous organic material.
In view of this, how to find a kind of luminous organic material with better performance, improve luminous efficiency and the work-ing life of luminescent device, be this area researchist's problem demanding prompt solution always.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of heteroaromatic compounds and preparation method thereof, and organic electroluminescence device, especially for the heteroaromatic compounds of one containing benzo [g] phthalazines.Heteroaromatic compounds provided by the invention, has better properties, can improve luminous efficiency and the work-ing life of luminescent device.
The invention provides a kind of heteroaromatic compounds, there is structure shown in formula (I):
Wherein,
L 1, L 2, L 3, L 4independently selected from 0 or 1;
Q 1and Q 2independently selected from nitrogen, oxygen, sulphur, carbonatoms be 6 ~ 30 aryl or carbonatoms be 1 ~ 30 heterocyclic radical;
R 1and R 2independently selected from hydrogen atom, cyano group, the substituted or unsubstituted carbonatoms aryl that is 6 ~ 50, the substituted or unsubstituted carbonatoms heterocyclic radical that is 5 ~ 50, the substituted or unsubstituted carbonatoms aromatic series amido that is 7 ~ 30, the substituted or unsubstituted carbonatoms aralkoxy that is 7 ~ 30, substituted or unsubstituted carbonatoms be 7 ~ 30 aralkyl sulfydryl or carbonatoms be 1 ~ 30 alkyl;
Ar 1, Ar 2, Ar 3and Ar 4independently selected from hydrogen atom, the substituted or unsubstituted carbonatoms aralkyl that is 7 ~ 50, the substituted or unsubstituted carbonatoms aralkoxy that is 7 ~ 50, the substituted or unsubstituted carbonatoms aralkyl sulfydryl that is 7 ~ 50, the carbonatoms aryl that is 6 ~ 50, substituted or unsubstituted carbonatoms be 5 ~ 50 heterocyclic radical or substituted or unsubstituted carbonatoms be 7 ~ 30 aromatic series amido.
Preferably, described heteroaromatic compounds has following structure:
Wherein,
Z 1~ Z 16independently selected from CH, C or N;
L 3and L 4independently selected from 0 or 1;
R 1and R 2independently selected from hydrogen atom, cyano group, the substituted or unsubstituted carbonatoms aryl that is 6 ~ 50, the substituted or unsubstituted carbonatoms heterocyclic radical that is 5 ~ 50, substituted or unsubstituted carbonatoms be the aromatic series amido of 7 ~ 30, substituted or unsubstituted carbonatoms be 7 ~ 30 aralkoxy or replacement, unsubstituted carbonatoms be 7 ~ 30 aralkyl sulfydryl or carbonatoms be 1 ~ 30 alkyl;
Ar 1, Ar 2, Ar 3and Ar 4independently selected from the aromatic series amido of the aralkyl sulfydryl of the aralkoxy of the aralkyl of hydrogen atom, substituted or unsubstituted carbonatoms 7 ~ 50, substituted or unsubstituted carbonatoms 7 ~ 50, substituted or unsubstituted carbonatoms 7 ~ 50, the aryl of carbonatoms 6 ~ 50, the heterocyclic radical of substituted or unsubstituted carbonatoms 5 ~ 50 or substituted or unsubstituted carbonatoms 7 ~ 30.
Preferably, described heteroaromatic compounds has following structure:
Wherein,
Z 1~ Z 8independently selected from C, CH or N; L 3with L 4be 0 or 1 independently;
Q 1and Q 2independently selected from nitrogen, oxygen, sulphur, carbonatoms be 6 ~ 30 aryl or carbonatoms be 1 ~ 30 heterocyclic radical;
Ar 1, Ar 2, Ar 3and Ar 4independently selected from hydrogen atom, the substituted or unsubstituted carbonatoms aralkyl that is 7 ~ 50, the substituted or unsubstituted carbonatoms aralkoxy that is 7 ~ 50, the substituted or unsubstituted carbonatoms aralkyl sulfydryl that is 7 ~ 50, the carbonatoms aryl that is 6 ~ 50, substituted or unsubstituted carbonatoms be 5 ~ 50 heterocyclic radical or substituted or unsubstituted carbonatoms be 7 ~ 30 aromatic series amido;
R 2, R 1' and R 2' independently selected from carbonatoms be the aryl of 6 ~ 50, substituted or unsubstituted carbonatoms be 5 ~ 50 heterocyclic radical or carbonatoms be 1 ~ 30 alkyl.
Preferably, described heteroaromatic compounds has following structure:
Wherein,
Z 1~ Z 16independently selected from C, CH or N; L 3with L 4be 0 or 1 independently;
Q 1and Q 2independently selected from nitrogen, oxygen, sulphur, carbonatoms be 6 ~ 30 aryl or carbonatoms be 1 ~ 30 heterocyclic radical;
Ar 1, Ar 2, Ar 3and Ar 4independently selected from hydrogen atom, the substituted or unsubstituted carbonatoms aralkyl that is 7 ~ 50, the substituted or unsubstituted carbonatoms aralkoxy that is 7 ~ 50, the substituted or unsubstituted carbonatoms aralkyl sulfydryl that is 7 ~ 50, the carbonatoms aryl that is 6 ~ 50, substituted or unsubstituted carbonatoms be 5 ~ 50 heterocyclic radical or substituted or unsubstituted carbonatoms be 7 ~ 30 aromatic series amido.
Preferably, in described heteroaromatic compounds ,-Ar 1,-Ar 2,-Ar 3with-Ar 4independently selected from structure following formula (1) ~ formula (35) Suo Shi:
Wherein,
X and Y is independently selected from hydrogen atom, halogen atom, cyano group, substituted or unsubstituted carbonatoms is the alkyl of 1 ~ 30, substituted or unsubstituted carbonatoms is the alkoxyl group of 1 ~ 30, substituted or unsubstituted carbonatoms is the thiazolinyl of 2 ~ 30, substituted or unsubstituted carbonatoms is the aralkyl of 7 ~ 30, substituted or unsubstituted carbonatoms is the aralkoxy of 7 ~ 30, substituted or unsubstituted carbonatoms is the aryl of 6 ~ 30, substituted or unsubstituted carbonatoms is the aryloxy of 6 ~ 30, substituted or unsubstituted carbonatoms is the heterocyclic radical of 5 ~ 30, or substituted or unsubstituted carbonatoms is the aromatic series amido of 7 ~ 30.
Preferably, described Q 1and Q 2be phenyl, and R 1and R 2when being cyano group or phenyl, Ar 1and Ar 2independently selected from the aromatic series amido of the aryl of substituted or unsubstituted carbonatoms 7 ~ 50, the heterocyclic radical of substituted or unsubstituted carbonatoms 5 ~ 50 or substituted or unsubstituted carbonatoms 7 ~ 30;
Described L 1with L 2be asynchronously 0.
The invention provides a kind of preparation method of heteroaromatic compounds, comprising:
Compound shown in compound shown in formula (V) and formula (VI) and the compound shown in formula (VII) are reacted, obtains the heteroaromatic compounds shown in formula (I);
Wherein,
X ' is halogen atom, Y ' and Y 1' independently selected from B (OH) 2or H;
L 1, L 2, L 3, L 4independently selected from 0 or 1;
Q 1and Q 2independently selected from nitrogen, oxygen, sulphur, carbonatoms be 6 ~ 30 aryl or carbonatoms be 1 ~ 30 heterocyclic radical;
R 1and R 2independently selected from hydrogen atom, cyano group, the substituted or unsubstituted carbonatoms aryl that is 6 ~ 50, the substituted or unsubstituted carbonatoms heterocyclic radical that is 5 ~ 50, the substituted or unsubstituted carbonatoms aromatic series amido that is 7 ~ 30, the substituted or unsubstituted carbonatoms aralkoxy that is 7 ~ 30, substituted or unsubstituted carbonatoms be 7 ~ 30 aralkyl sulfydryl or carbonatoms be 1 ~ 30 alkyl;
Ar 1, Ar 2, Ar 3and Ar 4independently selected from hydrogen atom, the substituted or unsubstituted carbonatoms aralkyl that is 7 ~ 50, the substituted or unsubstituted carbonatoms aralkoxy that is 7 ~ 50, the substituted or unsubstituted carbonatoms aralkyl sulfydryl that is 7 ~ 50, the carbonatoms aryl that is 6 ~ 50, substituted or unsubstituted carbonatoms be 5 ~ 50 heterocyclic radical or substituted or unsubstituted carbonatoms be 7 ~ 30 aromatic series amido.
The invention provides a kind of organic electroluminescence device, comprise heteroaromatic compounds prepared by the heteroaromatic compounds described in above-mentioned any one technical scheme or the preparation method described in technique scheme.
Preferably, the organic matter layer comprising the first electrode, the second electrode and be arranged between described first electrode and the second electrode;
Described organic matter layer comprises heteroaromatic compounds prepared by the heteroaromatic compounds described in above-mentioned any one technical scheme or the preparation method described in technique scheme.
The invention provides a kind of organic photoelectrical material, it is characterized in that, comprise heteroaromatic compounds prepared by the heteroaromatic compounds described in above-mentioned any one technical scheme or the preparation method described in technique scheme;
Described organic photoelectrical material comprises organic photovoltaic cell, Electronic Paper, Organophotoreceptor or organic transistor.
The invention provides a kind of heteroaromatic compounds containing benzo [g] phthalazines, there is structure shown in formula I, wherein, L 1, L 2, L 3, L 4independently selected from 0 or 1; Q 1and Q 2independently selected from nitrogen, oxygen, sulphur, carbonatoms be 6 ~ 30 aryl or carbonatoms be 1 ~ 30 heterocyclic radical; R 1and R 2independently selected from hydrogen atom, cyano group, the substituted or unsubstituted carbonatoms aryl that is 6 ~ 50, the substituted or unsubstituted carbonatoms heterocyclic radical that is 5 ~ 50, the substituted or unsubstituted carbonatoms aromatic series amido that is 7 ~ 30, the substituted or unsubstituted carbonatoms aralkoxy that is 7 ~ 30, substituted or unsubstituted carbonatoms be 7 ~ 30 aralkyl sulfydryl or carbonatoms be 1 ~ 30 alkyl; Ar 1, Ar 2, Ar 3and Ar 4independently selected from hydrogen atom, the substituted or unsubstituted carbonatoms aralkyl that is 7 ~ 50, the substituted or unsubstituted carbonatoms aralkoxy that is 7 ~ 50, the substituted or unsubstituted carbonatoms aralkyl sulfydryl that is 7 ~ 50, the carbonatoms aryl that is 6 ~ 50, substituted or unsubstituted carbonatoms be 5 ~ 50 heterocyclic radical or substituted or unsubstituted carbonatoms be 7 ~ 30 aromatic series amido.Compared with prior art, the heteroaromatic compounds with structure shown in formula (I) provided by the invention introduces Q in benzo [g] phthalazine compound 1, Q 2, Ar 1, Ar 2, Ar 3with Ar 4group, can improve electronics intensity and technical ability; And change the R of benzo [g] phthalazines 1and R 2kind can improve the performance of heteroaromatic compounds, the organic electroluminescence device of the heteroaromatic compounds manufacture shown in contained (I) disclosed in this invention is made to have higher photoluminescence efficiency and work-ing life, and higher brightness and outstanding thermotolerance.In addition, the method for making of new heteroaromatic compounds provided by the invention is simple, is easy to industrialization.Experimental result shows, the organic electroluminescence device of heteroaromatic compounds provided by the invention and preparation, has good optical property, can improve luminous efficiency and the work-ing life of luminescent device.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The invention provides a kind of heteroaromatic compounds, there is structure shown in formula (I):
Wherein,
L 1, L 2, L 3, L 4independently selected from 0 or 1, be more preferably L 1with L 2be asynchronously 0;
Q 1and Q 2independently selected from nitrogen, oxygen, sulphur, carbonatoms be 6 ~ 30 aryl or carbonatoms be 1 ~ 30 heterocyclic radical, more preferably be selected from nitrogen, oxygen, sulphur, carbonatoms be 6 ~ 24 aryl or carbonatoms be 1 ~ 24 heterocyclic radical, be more preferably selected from nitrogen, oxygen, sulphur, carbonatoms be 6 ~ 14 aryl or carbonatoms be 1 ~ 14 heterocyclic radical.
Described heteroaromatic compounds is at Q 1and Q 2on more specifically preferred such as formula shown in any structure of (II-1) ~ formula (II-9):
Wherein, Z 1~ Z 16be selected from C, CH or N independently of one another; L 3and L 4independently selected from 0 or 1;
R in the present invention 1and R 2independently selected from hydrogen atom, cyano group, substituted or unsubstituted carbonatoms is the aryl of 6 ~ 50, substituted or unsubstituted carbonatoms is the heterocyclic radical of 5 ~ 50, substituted or unsubstituted carbonatoms is the aromatic series amido of 7 ~ 30, substituted or unsubstituted carbonatoms is aralkoxy or the replacement of 7 ~ 30, unsubstituted carbonatoms be 7 ~ 30 aralkyl sulfydryl or carbonatoms be 1 ~ 30 alkyl, be preferredly selected from hydrogen atom, cyano group, substituted or unsubstituted carbonatoms is the aryl of 6 ~ 30, substituted or unsubstituted carbonatoms is the heterocyclic radical of 5 ~ 30, substituted or unsubstituted carbonatoms is the aromatic series amido of 7 ~ 25, substituted or unsubstituted carbonatoms is aralkoxy or the replacement of 7 ~ 25, unsubstituted carbonatoms be 7 ~ 25 aralkyl sulfydryl or carbonatoms be 1 ~ 25 alkyl, be preferredly selected from hydrogen atom, cyano group, substituted or unsubstituted carbonatoms is the aryl of 10 ~ 20, substituted or unsubstituted carbonatoms is the heterocyclic radical of 8 ~ 20, substituted or unsubstituted carbonatoms is the aromatic series amido of 10 ~ 20, substituted or unsubstituted carbonatoms is aralkoxy or the replacement of 10 ~ 20, unsubstituted carbonatoms be 10 ~ 20 aralkyl sulfydryl or carbonatoms be 2 ~ 20 alkyl.
Described heteroaromatic compounds is at R 1and R 2on more specifically preferred such as formula shown in any structure of (III-1) ~ formula (III-7):
Wherein,
Z 1~ Z 8independently selected from C, CH or N; L 3with L 4be 0 or 1 independently;
Q 1and Q 2independently selected from nitrogen, oxygen, sulphur, carbonatoms be 6 ~ 30 aryl or carbonatoms be 1 ~ 30 heterocyclic radical, more preferably from nitrogen, oxygen, sulphur, carbonatoms be 7 ~ 25 aryl or carbonatoms be 2 ~ 25 heterocyclic radical, more preferably from nitrogen, oxygen, sulphur, carbonatoms be 10 ~ 20 aryl or carbonatoms be 5 ~ 20 heterocyclic radical;
R 2, R 1' and R 2' independently selected from carbonatoms be the aryl of 6 ~ 50, substituted or unsubstituted carbonatoms be 5 ~ 50 heterocyclic radical or carbonatoms be 1 ~ 30 alkyl, more preferably from carbonatoms be the aryl of 7 ~ 30, substituted or unsubstituted carbonatoms be 7 ~ 30 heterocyclic radical or carbonatoms be 7 ~ 25 alkyl, more preferably from carbonatoms be the aryl of 10 ~ 20, substituted or unsubstituted carbonatoms be 10 ~ 20 heterocyclic radical or carbonatoms be 10 ~ 20 alkyl.
Ar 1, Ar 2, Ar 3and Ar 4independently selected from hydrogen atom, substituted or unsubstituted carbonatoms is the aralkyl of 7 ~ 50, substituted or unsubstituted carbonatoms is the aralkoxy of 7 ~ 50, substituted or unsubstituted carbonatoms is the aralkyl sulfydryl of 7 ~ 50, carbonatoms is the aryl of 6 ~ 50, substituted or unsubstituted carbonatoms is the heterocyclic radical of 5 ~ 50, or substituted or unsubstituted carbonatoms is the aromatic series amido of 7 ~ 30, is more preferably selected from hydrogen atom, substituted or unsubstituted carbonatoms is the aralkyl of 10 ~ 30, substituted or unsubstituted carbonatoms is the aralkoxy of 10 ~ 30, substituted or unsubstituted carbonatoms is the aralkyl sulfydryl of 10 ~ 30, carbonatoms is the aryl of 8 ~ 30, substituted or unsubstituted carbonatoms is the heterocyclic radical of 7 ~ 30, or substituted or unsubstituted carbonatoms is the aromatic series amido of 10 ~ 25, is more preferably selected from hydrogen atom, substituted or unsubstituted carbonatoms is the aralkyl of 15 ~ 25, substituted or unsubstituted carbonatoms is the aralkoxy of 15 ~ 25, substituted or unsubstituted carbonatoms is the aralkyl sulfydryl of 15 ~ 25, carbonatoms is the aryl of 15 ~ 25, substituted or unsubstituted carbonatoms is the heterocyclic radical of 10 ~ 25, or substituted or unsubstituted carbonatoms is the aromatic series amido of 15 ~ 20.
Described heteroaromatic compounds, works as R 1and R 2when being all selected from hydrogen atom, at Q 1and Q 2on more specifically preferred such as formula shown in any structure of (IV-1) ~ formula (IV-10):
Wherein,
Z 1~ Z 16independently selected from C, CH or N; L 3with L 4be 0 or 1 independently;
Q 1and Q 2independently selected from nitrogen, oxygen, sulphur, carbonatoms be 6 ~ 30 aryl or carbonatoms be 1 ~ 30 heterocyclic radical, more preferably from nitrogen, oxygen, sulphur, carbonatoms be 7 ~ 25 aryl or carbonatoms be 2 ~ 25 heterocyclic radical, more preferably from nitrogen, oxygen, sulphur, carbonatoms be 10 ~ 20 aryl or carbonatoms be 5 ~ 20 heterocyclic radical;
Ar 1, Ar 2, Ar 3and Ar 4independently selected from hydrogen atom, substituted or unsubstituted carbonatoms is the aralkyl of 7 ~ 50, substituted or unsubstituted carbonatoms is the aralkoxy of 7 ~ 50, substituted or unsubstituted carbonatoms is the aralkyl sulfydryl of 7 ~ 50, carbonatoms is the aryl of 6 ~ 50, substituted or unsubstituted carbonatoms is the heterocyclic radical of 5 ~ 50, or substituted or unsubstituted carbonatoms is the aromatic series amido of 7 ~ 30, is more preferably selected from hydrogen atom, substituted or unsubstituted carbonatoms is the aralkyl of 10 ~ 30, substituted or unsubstituted carbonatoms is the aralkoxy of 10 ~ 30, substituted or unsubstituted carbonatoms is the aralkyl sulfydryl of 10 ~ 30, carbonatoms is the aryl of 8 ~ 30, substituted or unsubstituted carbonatoms is the heterocyclic radical of 7 ~ 30, or substituted or unsubstituted carbonatoms is the aromatic series amido of 10 ~ 25, is more preferably selected from hydrogen atom, substituted or unsubstituted carbonatoms is the aralkyl of 15 ~ 25, substituted or unsubstituted carbonatoms is the aralkoxy of 15 ~ 25, substituted or unsubstituted carbonatoms is the aralkyl sulfydryl of 15 ~ 25, carbonatoms is the aryl of 15 ~ 25, substituted or unsubstituted carbonatoms is the heterocyclic radical of 10 ~ 25, or substituted or unsubstituted carbonatoms is the aromatic series amido of 15 ~ 20.
In some specific embodiment, as described Q 1and Q 2be phenyl, and R 1and R 2when being cyano group or phenyl, Ar 1and Ar 2independently selected from the aromatic series amido of the aryl of substituted or unsubstituted carbonatoms 7 ~ 50, the heterocyclic radical of substituted or unsubstituted carbonatoms 5 ~ 50 or substituted or unsubstituted carbonatoms 7 ~ 30, Ar 1and Ar 2more preferably the aromatic series amido of the aryl of substituted or unsubstituted carbonatoms 10 ~ 30, the heterocyclic radical of substituted or unsubstituted carbonatoms 7 ~ 30 or substituted or unsubstituted carbonatoms 10 ~ 25 is selected from, Ar 1and Ar 2more preferably the aromatic series amido of the aryl of substituted or unsubstituted carbonatoms 15 ~ 20, the heterocyclic radical of substituted or unsubstituted carbonatoms 10 ~ 25 or substituted or unsubstituted carbonatoms 15 ~ 20 is selected from.
Described heteroaromatic compounds is at Ar 1~ Ar 4on more specifically preferred such as formula shown in any structure of (1) ~ formula (35):
Wherein,
X and Y is independently selected from hydrogen atom, halogen atom, cyano group, substituted or unsubstituted carbonatoms is the alkyl of 1 ~ 30, substituted or unsubstituted carbonatoms is the alkoxyl group of 1 ~ 30, substituted or unsubstituted carbonatoms is the thiazolinyl of 2 ~ 30, substituted or unsubstituted carbonatoms is the aralkyl of 7 ~ 30, substituted or unsubstituted carbonatoms is the aralkoxy of 7 ~ 30, substituted or unsubstituted carbonatoms is the aryl of 6 ~ 30, substituted or unsubstituted carbonatoms is the aryloxy of 6 ~ 30, substituted or unsubstituted carbonatoms is the heterocyclic radical of 5 ~ 30, or substituted or unsubstituted carbonatoms is the aromatic series amido of 7 ~ 30, more preferably from hydrogen atom, halogen atom, cyano group, substituted or unsubstituted carbonatoms is the alkyl of 2 ~ 25, substituted or unsubstituted carbonatoms is the alkoxyl group of 2 ~ 25, substituted or unsubstituted carbonatoms is the thiazolinyl of 3 ~ 25, substituted or unsubstituted carbonatoms is the aralkyl of 10 ~ 25, substituted or unsubstituted carbonatoms is the aralkoxy of 10 ~ 25, substituted or unsubstituted carbonatoms is the aryl of 8 ~ 25, substituted or unsubstituted carbonatoms is the aryloxy of 8 ~ 25, substituted or unsubstituted carbonatoms is the heterocyclic radical of 7 ~ 25, or substituted or unsubstituted carbonatoms is the aromatic series amido of 10 ~ 25, more preferably from hydrogen atom, halogen atom, cyano group, substituted or unsubstituted carbonatoms is the alkyl of 5 ~ 20, substituted or unsubstituted carbonatoms is the alkoxyl group of 5 ~ 20, substituted or unsubstituted carbonatoms is the thiazolinyl of 5 ~ 20, substituted or unsubstituted carbonatoms is the aralkyl of 15 ~ 20, substituted or unsubstituted carbonatoms is the aralkoxy of 15 ~ 20, substituted or unsubstituted carbonatoms is the aryl of 10 ~ 20, substituted or unsubstituted carbonatoms is the aryloxy of 10 ~ 20, substituted or unsubstituted carbonatoms is the heterocyclic radical of 10 ~ 20, or substituted or unsubstituted carbonatoms is the aromatic series amido of 15 ~ 20.
In the present invention, the aryl of above-mentioned replacement, the heterocyclic radical replaced, the aromatic series amido replaced, the aralkoxy replaced, the aralkyl sulfydryl replaced, the aralkyl replaced, the thiazolinyl replaced, replace aryloxy in, described replacement refer to that, containing substituent, described substituting group is preferably selected from halogen, the alkyl of C1 ~ C30, the thiazolinyl of C2 ~ C30, the alkynyl of C2 ~ C30, hydroxyl, the alkoxyl group of C1 ~ C30, amino, nitro, sulfydryl, thioether group, imido grpup, cyano group, amide group, phosphonate radical, phosphine, carboxyl, thiocarbonyl, alkylsulfonyl, sulfamyl, carbonyl, aldehyde radical, ester group, ethanoyl, acetoxyl group, formamyl, oxo base (=O), haloalkyl, the aminoacyl replaced and aminoalkyl group, cycloalkyl (can be monocycle, fused polycycle or the many rings of non-condensed), heterocyclic radical (can be monocycle, fused polycycle or the many rings of non-condensed), monocycle or condense or non-condensed polyaromatic (as phenyl, naphthyl, pyrryl, indyl, furyl, thienyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, triazolyl, tetrazyl, pyrazolyl, quinolyl, isoquinolyl, acridyl, pyrazinyl, pyridazinyl, pyrimidyl, benzimidazolyl-, benzothienyl or benzofuryl), amino, the alkyl of-O-C1 ~ C20, O-aryl, aryl, the alkyl of aryl-C1 ~ C20,-CO 2cH 3,-CONH 2,-OCH 2cONH 2,-NH 2,-SO 2nH 2,-OCHF 2,-CF 3,-OCF 3.The substituting group that these substituting groups are optionally selected from above-mentioned group further replaces.In the present invention, described substituting group is more preferably selected from the arbitrary substituting group in following formula 36 ~ 65:
Heteroaromatic compounds provided by the invention introduces Q in benzo [g] phthalazine compound 1, Q 2, Ar 1, Ar 2, Ar 3with Ar 4group, can improve electronics intensity and technical ability; And change the R of benzo [g] phthalazines 1and R 2kind can improve the performance of heteroaromatic compounds, the organic electroluminescence device of the heteroaromatic compounds manufacture shown in contained (I) disclosed in this invention is made to have higher photoluminescence efficiency and work-ing life, and higher brightness and outstanding thermotolerance.Experimental result shows, the organic electroluminescence device of heteroaromatic compounds provided by the invention and preparation, has good optical property, can improve luminous efficiency and the work-ing life of luminescent device.
The present invention also provides a kind of preparation method of heteroaromatic compounds, comprising:
Compound shown in compound shown in formula (V) and formula (VI) and the compound shown in formula (VII) are reacted, obtains the heteroaromatic compounds shown in formula (I);
Wherein,
X ' is halogen atom, Y ' and Y 1' independently selected from B (OH) 2or H;
L 1, L 2, L 3, L 4independently selected from 0 or 1;
Q 1and Q 2independently selected from nitrogen, oxygen, sulphur, carbonatoms be 6 ~ 30 aryl or carbonatoms be 1 ~ 30 heterocyclic radical;
R 1and R 2independently selected from hydrogen atom, cyano group, the substituted or unsubstituted carbonatoms aryl that is 6 ~ 50, the substituted or unsubstituted carbonatoms heterocyclic radical that is 5 ~ 50, the substituted or unsubstituted carbonatoms aromatic series amido that is 7 ~ 30, the substituted or unsubstituted carbonatoms aralkoxy that is 7 ~ 30, substituted or unsubstituted carbonatoms be 7 ~ 30 aralkyl sulfydryl or carbonatoms be 1 ~ 30 alkyl;
Ar 1, Ar 2, Ar 3and Ar 4independently selected from hydrogen atom, the substituted or unsubstituted carbonatoms aralkyl that is 7 ~ 50, the substituted or unsubstituted carbonatoms aralkoxy that is 7 ~ 50, the substituted or unsubstituted carbonatoms aralkyl sulfydryl that is 7 ~ 50, the carbonatoms aryl that is 6 ~ 50, substituted or unsubstituted carbonatoms be 5 ~ 50 heterocyclic radical or substituted or unsubstituted carbonatoms be 7 ~ 30 aromatic series amido.
Wherein, described L 1, L 2, L 3, L 4, Q 1, Q 2, Ar 1, Ar 2, Ar 3, Ar 4, R 1with R 2all same as above, do not repeat them here.
The present invention is raw materials used, is not particularly limited its source, commercially buy or prepare according to preparation method well known to those skilled in the art.
The raw materials used purity of the present invention is not particularly limited, and with the purity for this type of reaction well known to those skilled in the art, the present invention is preferably analytical pure and above rank.
Compound shown in formula described in the present invention (V) is preferably prepared in accordance with the following methods:
According to the present invention, work as Q 1or Q 2for the aryl of C6 ~ C30 or the heterocyclic radical of C1 ~ C30; Y ' or Y 1' be B (OH) 2compound shown in compound shown in formula (V) and formula (VI) or the compound shown in formula (VII) carry out C-C coupling reaction under catalyst action, described reaction conditions is reaction conditions well known to those skilled in the art, there is no special restriction.
As described Q 1or Q 2during for N, O or S, Y ' or Y 1' be H, now, the compound shown in the compound shown in formula (V) and formula (VI) or the compound shown in formula (VII) carry out replacement(metathesis)reaction; The condition of described replacement(metathesis)reaction is conditions of replacement reaction well known to those skilled in the art, there is no special restriction.
In above-mentioned reaction formula, described R 1, X ' is all same as above, do not repeat them here.
In the present invention, when Y ＇ is B (OH) 2time, the compound shown in described formula (VI) is preferably prepared in accordance with the following methods:
X ＂ is halogen atom.
Work as Y 1' be B (OH) 2time, the compound shown in formula (VII), preferably prepare in accordance with the following methods:
X ＂ is halogen atom.
In the present invention, as described L 1with L 2when being 0, by the compound shown in formula (IV) after reduction reaction, the compound shown in formula (I) can be obtained simultaneously.
From above-mentioned preparation process, can find out that heteroaromatic compounds preparation method provided by the invention is simple, be easy to industrialization.
The present invention also provides a kind of organic electroluminescence device, comprises heteroaromatic compounds prepared by heteroaromatic compounds described in above-mentioned any one technical scheme or any one preparation method.
The present invention's other conditions to described organic electroluminescence device are not particularly limited, with organic electroluminescence device well known to those skilled in the art, the organic matter layer that the present invention preferably includes the first electrode, the second electrode and is arranged between described first electrode and the second electrode; Described organic matter layer comprises above-mentioned heteroaromatic compounds.
According to the present invention, described organic matter layer preferably includes hole injection layer, hole transmission layer, not only possess hole injection but also possess hole transport technical ability layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer with not only possessed electric transmission but also possessed in electron injection technical ability layer one or more layers, more preferably the hole injection layer set gradually is comprised, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer and electron injecting layer or set gradually not only possess hole and inject but also possess hole transport technical ability layer, electronic barrier layer, luminescent layer, hole blocking layer with not only possess electric transmission but also possess electron injection technical ability layer.
When organic matter layer of the present invention comprise hole injection layer, hole transmission layer or not only possessed hole inject but also possess hole transport technical ability layer time, preferred described hole injection layer, hole transmission layer or not only possessed hole inject but also possess hole transport technical ability layer at least one deck comprise hole injecting material, hole transporting material or not only possessed the material injecting but also possess hole transport technical ability in hole.
When organic matter layer of the present invention is single layer structure, described organic matter layer is luminescent layer, and when described organic matter layer is multilayered structure, described organic matter layer comprises luminescent layer; Preferably include in described luminescent layer phosphorescence host, fluorescent host, phosphorescence dopant material and fluorescence adulterate in one or more; One or more in described phosphorescence host, fluorescent host, phosphorescence dopant material and fluorescence dopant material are the heteroaromatic compounds shown in formula (I).
Described luminescent layer also can be preferably red, yellow or cyan luminescent layer, and described heteroaromatic compounds is main body or the dopant of redness, yellow or cyan luminescent layer.As, when described luminescent layer is cyan luminescent layer, when the heteroaromatic compounds shown in described formula (I) is used in cyan main body or cyan doping purposes, high-level efficiency, high brightness, high resolving power and long-life organic luminescent device can be provided.
When described organic matter layer comprises electron transfer layer, described electron transfer layer can comprise the heteroaromatic compounds shown in formula (I) and/or metallic compound.Described metallic compound is the material for electric transmission well known to those skilled in the art, there is no special restriction.
When described organic matter layer comprises luminescent layer and electron transfer layer simultaneously, described luminescent layer and electron transfer layer can comprise the heteroaromatic compounds shown in the identical or not identical formula of structure (I).
Organic electroluminescence device provided by the invention utilizes the heteroaromatic compounds shown in formula (I) and conventional material to make the method preparation of organic electronic devices, there is no special restriction, the present invention preferably utilizes the methods such as film vapor deposition, electron beam evaporation or physical vapor deposition evaporation metal and have the oxide compound of electroconductibility and their alloy forms anode on substrate, then form organic matter layer and evaporation negative electrode thereon, obtain organic electroluminescence device.
Described organic matter layer can comprise above-mentioned hole injection layer simultaneously, hole transmission layer, luminescent layer, the multilayered structure of hole blocking layer and electron transfer layer, and these multilayered structures can according to above-mentioned film vapor deposition, the method such as electron beam evaporation or physical vapor deposition evaporation, also various macromolecular material solvent engineering can be used to substitute evaporation coating method, as spin-coating (spin-coating), strip shaping (tape-casting), scraping blade method (doctor-blading), silk screen printing (Screen-Printing), the method reduction layer numeral systems such as ink jet printing or thermal imaging (Thermal-Imaging) are made.
Luminescence before organic electroluminescence device provided by the invention also can be divided into according to the material used, back side illuminated or lighting at two sides.
Present invention also offers a kind of organic photoelectrical material, comprise the heteroaromatic compounds described in above-mentioned any one technical scheme, or heteroaromatic compounds prepared by the preparation method described in any one technical scheme; Described organic photoelectrical material comprises organic photovoltaic cell, Electronic Paper, Organophotoreceptor or organic transistor.
Based on the principle application that above-mentioned organic electroluminescence device is same, heteroaromatic compounds provided by the present invention is except at organic luminescent device (OLED), as thrown light on in OLED, flexible OLED, can also be applied in organic photovoltaic cell (OSC), Electronic Paper (e-paper), Organophotoreceptor (OPC) or OTFT (OTFT).
In order to further illustrate the present invention, below in conjunction with embodiment, heteroaromatic compounds provided by the invention and preparation method thereof and organic electroluminescence device are described in detail.
Embodiment 1
The synthesis of the chloro-5-phenyl pyrazines (A-1) of intermediate 2-:
By bromo-for 2-5-chloropyrazine (21.3g; 0.11mol); phenylo boric acid (12.2g; 0.10mol), four triphenyl phosphorus palladium 0.5g, join in 1000mL reaction flask; add toluene 400mL; aqueous sodium carbonate (2N, 150mL) nitrogen protection, oil bath 80 DEG C reaction 24 hours.Last handling process: reaction system is lowered the temperature, leave standstill 30 minutes separatory, retain organic layer, be spin-dried for toluene, solid adds a small amount of methylene dichloride and dissolves, and crosses post and is separated, with sherwood oil: methylene dichloride=1:1 (volume ratio) rushes post, obtain solid (A-1) (10.7g, y=56%).
Embodiment 2
The synthesis of intermediate A-2 ~ A-5:
According to the synthetic method of above-described embodiment 1 intermediate A-1, by same molar than preparing the compound shown in table 1, table 1 is the embodiment of the present invention 2 reactive material, generate material and productive rate gathers.
Table 1 embodiment 2 reactive material, generation material and productive rate gather
Embodiment 3
The synthesis of chloro-N, the N-diphenyl pyrazine of intermediate 5--2-amine (A-6):
By pentanoic (16.9g; 0.10mol) with sodium tert-butoxide (28g; 0.30mol); toluene 400mL joins in reaction flask, stirs 30 minutes, nitrogen protection; then the bromo-5-chloropyrazine of 2-(23.2g is added; 0.12mol), three (two sub-Bian benzylacetones) two palladium 1.5g, finally add tri-butyl phosphine 4g, be warmed up to 100 DEG C reaction 24 hours.Last handling process: system is lowered the temperature, and adds water termination reaction, filters, filtrate separatory, is spin-dried for toluene, adds a small amount of methylene dichloride dissolved solids, sherwood oil: methylene dichloride=3:1 (volume ratio) crosses post and is separated, and obtains solid (A-6) (14.1g, y=50%).
Embodiment 4
The synthesis of intermediate A-7 and A-8
According to the synthetic method of above-described embodiment 3 intermediate A-6, prepare compound shown in table 2 with same molar ratio, table 2 is the embodiment of the present invention 4 reactive material, generate material and productive rate and gather.
Table 2 embodiment of the present invention 4 reactive material, generation material and productive rate gather
Embodiment 5
The synthesis of chloro-2, the 3-diphenyl pyrazines (A-9) of intermediate 5-:
By phenylo boric acid (24.4g; 0.20mol); the bromo-5-chloroquinoline (27.3g, 0.10mol) of 2,3-bis-; tetra-triphenylphosphine palladium (7.0g; 3%) join in reaction flask, add toluene 600mL, aqueous sodium carbonate (2N250mL) nitrogen protection; oil bath 90 DEG C reaction, spends the night.Last handling process: system is lowered the temperature, separatory, is spin-dried for toluene, and residuum methylene dichloride is entirely molten, add the sherwood oil of equivalent again, cross silica gel funnel, and rinse with methylene dichloride: sherwood oil=1:2 (volume ratio), until product-free point flows out, collect filtrate, and be spin-dried for solvent, obtain dark solid (A-9) (21.3g, y=80%).
Embodiment 6
The synthesis of intermediate A-10 ~ A-12
According to the synthetic method of above-described embodiment 5 intermediate A-9, prepare compound shown in table 3 with same molar ratio, table 3 is the embodiment of the present invention 6 reactive material, generate material and productive rate and gather.
Table 3 embodiment of the present invention 6 reactive material, generation material and productive rate gather
Embodiment 7
The synthesis of intermediate 5-(4-pyridyl) pyrimidine-2-base boric acid (A-13):
Get 5-(4-pyridyl)-2-bromo pyrimi piperidine (10g; 42.4mmol) join in there-necked flask; add THF100mL; nitrogen protection ,-78 DEG C are stirred 30 minutes, then add n-Butyl Lithium (2.5M) 21mL; react 1 hour; add triisopropyl borate ester 14g again, low-temp reaction 1 hour, recovers room temperature gradually.Last handling process, adds 2M hydrochloric acid and makes solution pH value be 4-5 in system, leave standstill separatory, aqueous layer with ethyl acetate extracts one time, merges organic layer, is spin-dried for, obtains white solid (A-13) (6.8g, y=80%).
Embodiment 8
The synthesis of intermediate A-14 ~ A-18
According to the synthetic method of above-described embodiment 7 intermediate A-13, prepare compound shown in table 4 with same molar ratio, table 4 is the embodiment of the present invention 8 reactive material, generate material and productive rate and gather.
Table 4 embodiment of the present invention 8 reactive material, generation material and productive rate gather
Embodiment 9
The synthesis of intermediate 2-(pyrazine-2-carbonyl) methyl benzoate (B-1):
By 2-bromo-pyrazine (15.9g, 0.1mol) be dissolved in 300ml anhydrous diethyl ether, the dry ice bath-78 DEG C, nitrogen protection, add the BuLi (2.5M) of 44ml, stirring reaction 1 hour, add dimethyl phthalate (19.4g again, 0.1mol), react 2 hours, after be raised to room temperature gradually, be added to the water only reaction, last handling process: system separatory, branch vibration layer, aqueous layer with ethyl acetate extracts one time, merge organic layer and be spin-dried for organic solvent, with methylene dichloride: sherwood oil=9:1 crosses post and is separated, obtain white solid (B-1) (13.3g, Y=55%).
Embodiment 10
The synthesis of intermediate B-2 ~ B-14
According to the synthetic method of above-described embodiment 9 intermediate B-1, prepare compound shown in table 5 with same molar ratio, table 5 is the embodiment of the present invention 10 reactive material, generate material and productive rate and gather.
Table 5 embodiment of the present invention 10 reactive material, generation material and productive rate gather
Embodiment 11
The synthesis of intermediate benzo [g] quinoxaline-5,10-diketone (C-1):
B-1 (10g prepared by embodiment 9,41.3mmol) compound dissolution is in the THF of 300ml, cool to 0 DEG C, add the mixed solution LTMP (synthesis of LTMP: in the THF of 500ml, 0 DEG C is kept to dissolve 0.13mol BuLi, 2,2 of 0.14mol, 6,6-tetramethyl piperidine).0 DEG C of stirring reaction 2 hours, add 200ml water stopped reaction, branch vibration layer, organic layer is spin-dried for, with methylene dichloride: sherwood oil=10:1 crosses post and is separated, and obtains solid (C-1) (3.4g, y=40%).
Embodiment 12
The synthesis of intermediate C-2 ~ C-14:
According to the synthetic method of above-described embodiment 11 intermediate C-1, prepare compound shown in table 6 with same molar ratio, table 6 is the embodiment of the present invention 12 reactive material, generate material and productive rate and gather.
Table 6 embodiment of the present invention 12 reactive material, generation material and productive rate gather
Embodiment 13
The synthesis of intermediate 5,10-dichloro benzo [g] quinoxaline (D-1):
Take C-1 (10g, 47.6mmol) prepared by embodiment 11, join in reaction flask, add 200ml acetonitrile, then take 30g phosphorus oxychloride and be slowly added drop-wise in reaction flask, dropwise and be slowly warmed up to 60 DEG C afterwards, the reaction times is 5 hours.After completion of the reaction, add water and carefully extract and go out, the fuller solution that closes of the sodium carbonate adding amplification quantity adjusts pH value 7-8, then add methylene dichloride, extract three times, be spin-dried for obtain solid (D-1) (9.0g, y=75%).
Embodiment 14
The synthesis of intermediate D-2 ~ D14:
According to the synthetic method of above-described embodiment 13 intermediate D-1, prepare compound shown in table 7 with same molar ratio, table 7 is the embodiment of the present invention 14 reactive material, generate material and productive rate and gather.
Table 7 embodiment of the present invention 14 reactive material, generation material and productive rate gather
Embodiment 15
The synthesis of 5,10-bis-(4-pyridyl) benzo [g] quinoxaline (E-1):
D-1 (15.0g prepared by embodiment 13; 60mmol); 4-pyridine borate (18.0g; 146mmol), tetra-triphenylphosphine palladium 4g joins in reaction flask, then adds toluene 300mL; aqueous sodium carbonate (2N; 100ml), nitrogen protection, stirs and is warmed up to 110 DEG C of reactions 24 hours.Last handling process: cooling, separatory, is spin-dried for toluene.Add methylene dichloride dissolved solids, cross post, sherwood oil: ethyl acetate=2:1 (volume ratio) rinses, and obtains solid (E-1) (12g, y=60%).
Utilize nucleus magnetic resonance to analyze obtain in embodiment 15 5,10-bis-(4-pyridyl) benzo [g] quinoxaline (E-1), obtaining result is:
1H NMR(500MHz,Chloroform)δ8.97(s,1H),8.94(s,1H),8.71(s,2H),7.90(s,2H),7.47(s,1H)。Mass spectrum: 334.13.
Embodiment 16
The synthesis of E-2 ~ E-23:
According to the synthetic method of above-described embodiment 15 intermediate E-1, prepare compound shown in table 8 with same molar ratio, table 8 is the embodiment of the present invention 16 reactive material, generate material and productive rate and gather.
Table 8 embodiment of the present invention 16 reactive material, generation material and productive rate gather
Utilize nucleus magnetic resonance to analyze the E-2 obtained in embodiment 16, obtaining result is:
1H NMR(500MHz,Chloroform)δ8.97(s,1H),8.93(s,1H),8.37(s,1H),7.47(s,1H),7.38(s,1H),7.14(s,1H),6.90(s,1H)。
Embodiment 17
The synthesis of F-1 ~ F-9:
According to the synthetic method of above-described embodiment 15 intermediate E-1, the Compound D 2 ~ D9 prepared with embodiment 14, for raw material, prepares compound shown in table 9 with same molar ratio, and table 9 is the embodiment of the present invention 17 reactive material, generate material and productive rate gathers.
Table 9 embodiment of the present invention 17 reactive material, generation material and productive rate gather
Utilize nucleus magnetic resonance to analyze the F-1 obtained in embodiment 17, obtaining result is: 1h NMR (500MHz, Chloroform) δ 9.89 (s, 1H), 8.97 (s, 2H), 8.71 (s, 4H), 8.26 (s, 2H), 7.90 (s, 4H), 7.65 – 7.42 (m, 5H).
Embodiment 18
The synthesis of G-1 ~ G9:
According to the synthetic method of above-described embodiment 15 intermediate E-1, Compound D 10 ~ the D13 prepared with embodiment 14 is for raw material, prepare compound shown in table 10 with same molar ratio, table 10 is the embodiment of the present invention 18 reactive material, generate material and productive rate and gather.
Table 10 embodiment of the present invention 18 reactive material, generation material and productive rate gather
Utilize nucleus magnetic resonance to analyze the G-1 obtained in embodiment 18, the result obtained is: 1H NMR (500MHz, Chloroform) δ 8.97 (s, 1H), 8.71 (s, 1H), 8.03 (s, 1H), 7.90 (s, 1H), 7.59 (s, 1H), 7.47 (s, 1H), 7.32 (s, 1H).
Embodiment 19
The synthesis of N, N-phenylbenzene-10-(pyridin-4-yl oxygen base) benzo [g] quinoxaline-5-amine (H-1):
1) synthesis of 10-chloro-N, N-phenylbenzene benzo [g] quinoxaline-5-amine:
According to the synthetic method of A-6, add 5,10-dichloro benzo [g] quinoxaline (6.0g, 24mol), pentanoic (4.4g, 24mol), obtain solid 10-chloro-N, N-phenylbenzene benzo [g] quinoxaline-5-amine (5.04g, y=55%).
2) synthesis of N, N-phenylbenzene-10-(pyridin-4-yl oxygen base) benzo [g] quinoxaline-5-amine (H-1):
Disubstituted-4-hydroxy pyridine (10g, 0.1mol) is dissolved in 100mL anhydrous tetrahydro furan, stirs, precise NaH (0.96g, 0.4mol) be added in batches in reaction flask, too not fast, prevent too many bubble from producing, add rear solution and present yellow, at this moment 10-chloro-N, N-phenylbenzene benzo [g] quinoxaline-5-amine (42.0g, 0.11mol) is added again, also will add, room temperature reaction spends the night in batches.Last handling process: filter, removing solid matter, is spin-dried for, and adds methylene dichloride and dissolves, cross post sherwood oil: ethyl acetate=1:5 rushes post, obtains solid (H-1) (22.0g, y=50%).
Utilize nucleus magnetic resonance to analyze the H-1 obtained in embodiment 19, obtaining result is: 1h NMR (500MHz, Chloroform) δ 8.90 (d, J=9.3Hz, 2H), 8.39 (s, 2H), 8.12 (s, 1H), 8.00 (s, 1H), 7.68 (s, 1H), 7.50 (s, 1H), 7.24 (s, 4H), 7.08 (d, J=4.2Hz, 6H), 7.00 (s, 2H).
Embodiment 20
The synthesis of N, N-phenylbenzene-10-(pyridin-4-yl sulphur) benzo [g] quinoxaline-5-amine (H-2):
By 4-pyridine mercaptan (1.1g, 10m mol), N, N-phenylbenzene-10-(pyridin-4-yl oxygen base) benzo [g] quinoxaline-5-amine (3.8g, 10mmol), KOH (840mg, 15mmol), mPANI/pFe 3o 4(2.5g, 5mol%), H 2o (30mL) heats 8 hours.By extraction into ethyl acetate organic phase, and adopt (ethyl acetate: sherwood oil=4:1) to cross post separation, obtain white solid (H-2) (1.83g, y=40%).
Utilize nucleus magnetic resonance to analyze the H-2 obtained in embodiment 20, obtaining result is: 1h NMR (500MHz, Chloroform) δ 8.99 (s, 1H), 8.89 (d, J=7.2Hz, 3H), 8.12 (s, 1H), 7.84 (s, 1H), 7.55 – 7.40 (m, 4H), 7.24 (s, 4H), 7.08 (s, 4H), 7.00 (s, 2H).
Embodiment 21
The synthesis of 5,10-bis-(pyridin-4-yl oxygen base) benzo [g] quinoxaline (H-3):
The synthetic method of H-1 in reference example 19, drops into 10-chloro-N, N-phenylbenzene benzo [g] quinoxaline-5-amine (5.0g, 20mmol), 4-pyridone (4.0g, 42mmol), obtain solid (H-3) (3.4g, y=50%).
Utilize nucleus magnetic resonance to analyze the H-3 obtained in embodiment 21, obtaining result is: 1h NMR (500MHz, Chloroform) δ 8.90 (s, 2H), 8.39 (s, 4H), 8.00 (s, 2H), 7.68 (s, 2H), 7.06 (s, 4H).
Embodiment 22
The synthesis of 5,10-bis-(pyridin-4-yl sulphur) benzo [g] quinoxaline (H-4):
According to the synthetic method of H-2 in embodiment 20, add 4-pyridine mercaptan (2.2g, 20m mol), N, N-phenylbenzene-10-(pyridin-4-yl oxygen base) benzo [g] quinoxaline-5-amine (2.5g, 10mmol), KOH (840mg, 15mmol), mPANI/pFe 3o 4(2.5g, 5mol%), H 2o (30mL) heats 8 hours.By extraction into ethyl acetate organic phase, and adopt ethyl acetate: sherwood oil=4:1 crosses post and is separated, and obtains white solid (H-4) (1.4g, y=35%).
Utilize nucleus magnetic resonance to analyze the H-4 obtained in embodiment 22, obtaining result is: 1h NMR (500MHz, Chloroform) δ 8.98 (s, 2H), 8.88 (s, 4H), 7.84 (s, 2H), 7.47 (s, 2H), 7.43 (s, 4H).
Embodiment 23
By Fisher Co., Ltd's coat-thickness be ito glass substrate be placed in distilled water clean 2 times, ultrasonic washing 30 minutes, then 30 minutes are washed successively by the order of Virahol, acetone, methyl alcohol, 2 times are repeatedly cleaned with distilled water, ultrasonic washing 10 minutes, dry, transfer in plasma washing machine, aforesaid substrate is washed 5 minutes, deliver in evaporator.
By evaporation hole injection layer 2-TNATA evaporation on ready ito transparent electrode hole transmission layer a-NPD evaporation the TPPDA evaporation of cyan main body A DN/ doping 5% the material evaporation of hole blocking layer and hole transmission layer TPBi or embodiment E ~ H negative electrode said process organic matter vaporization plating speed keeps liF is al is
The electron luminescence characteristic of the organic luminescent device that aforesaid method obtains is in table 11.
The electron luminescence characteristic of hole blocking layer and hole transmission layer substance classes and organic electroluminescence device in table 11 embodiment 23
As can be seen from above-mentioned table 11, the luminous efficiency of the device of heteroaromatic compounds of the present invention and life characteristic is utilized all to increase significantly.
The present invention adopts the organic luminescent device of heteroaromatic compounds, can obtain luminous efficiency and life-span good experiment effect, therefore can be applicable to the OLED industry that practicality is high.Organic electroluminescence device of the present invention is equally applicable to the light source, display panel, mark etc. of flat panel display, planar illuminant, illumination face illuminating OLED twinkler, flexible twinkler, duplicating machine, printer, LCD backlight or weigher class.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.

Claims (10)

1. a heteroaromatic compounds, has structure shown in formula (I):
Wherein,
L 1, L 2, L 3, L 4independently selected from 0 or 1;
Q 1and Q 2independently selected from nitrogen, oxygen, sulphur, carbonatoms be 6 ~ 30 aryl or carbonatoms be 1 ~ 30 heterocyclic radical;
R 1and R 2independently selected from hydrogen atom, cyano group, the substituted or unsubstituted carbonatoms aryl that is 6 ~ 50, the substituted or unsubstituted carbonatoms heterocyclic radical that is 5 ~ 50, the substituted or unsubstituted carbonatoms aromatic series amido that is 7 ~ 30, the substituted or unsubstituted carbonatoms aralkoxy that is 7 ~ 30, substituted or unsubstituted carbonatoms be 7 ~ 30 aralkyl sulfydryl or carbonatoms be 1 ~ 30 alkyl;
Ar 1, Ar 2, Ar 3and Ar 4independently selected from hydrogen atom, the substituted or unsubstituted carbonatoms aralkyl that is 7 ~ 50, the substituted or unsubstituted carbonatoms aralkoxy that is 7 ~ 50, the substituted or unsubstituted carbonatoms aralkyl sulfydryl that is 7 ~ 50, the carbonatoms aryl that is 6 ~ 50, substituted or unsubstituted carbonatoms be 5 ~ 50 heterocyclic radical or substituted or unsubstituted carbonatoms be 7 ~ 30 aromatic series amido.
2. heteroaromatic compounds according to claim 1, is characterized in that, described heteroaromatic compounds has following structure:
Wherein,
Z 1~ Z 16independently selected from CH, C or N;
L 3and L 4independently selected from 0 or 1;
R 1and R 2independently selected from hydrogen atom, cyano group, the substituted or unsubstituted carbonatoms aryl that is 6 ~ 50, the substituted or unsubstituted carbonatoms heterocyclic radical that is 5 ~ 50, substituted or unsubstituted carbonatoms be the aromatic series amido of 7 ~ 30, substituted or unsubstituted carbonatoms be 7 ~ 30 aralkoxy or replacement, unsubstituted carbonatoms be 7 ~ 30 aralkyl sulfydryl or carbonatoms be 1 ~ 30 alkyl;
Ar 1, Ar 2, Ar 3and Ar 4independently selected from the aromatic series amido of the aralkyl sulfydryl of the aralkoxy of the aralkyl of hydrogen atom, substituted or unsubstituted carbonatoms 7 ~ 50, substituted or unsubstituted carbonatoms 7 ~ 50, substituted or unsubstituted carbonatoms 7 ~ 50, the aryl of carbonatoms 6 ~ 50, the heterocyclic radical of substituted or unsubstituted carbonatoms 5 ~ 50 or substituted or unsubstituted carbonatoms 7 ~ 30.
3. heteroaromatic compounds according to claim 1, is characterized in that, described heteroaromatic compounds has following structure:
Wherein,
Z 1~ Z 8independently selected from C, CH or N; L 3with L 4be 0 or 1 independently;
Q 1and Q 2independently selected from nitrogen, oxygen, sulphur, carbonatoms be 6 ~ 30 aryl or carbonatoms be 1 ~ 30 heterocyclic radical;
Ar 1, Ar 2, Ar 3and Ar 4independently selected from hydrogen atom, the substituted or unsubstituted carbonatoms aralkyl that is 7 ~ 50, the substituted or unsubstituted carbonatoms aralkoxy that is 7 ~ 50, the substituted or unsubstituted carbonatoms aralkyl sulfydryl that is 7 ~ 50, the carbonatoms aryl that is 6 ~ 50, substituted or unsubstituted carbonatoms be 5 ~ 50 heterocyclic radical or substituted or unsubstituted carbonatoms be 7 ~ 30 aromatic series amido;
R 2, R 1' and R 2' independently selected from carbonatoms be the aryl of 6 ~ 50, substituted or unsubstituted carbonatoms be 5 ~ 50 heterocyclic radical or carbonatoms be 1 ~ 30 alkyl.
4. heteroaromatic compounds according to claim 1, is characterized in that, described heteroaromatic compounds has following structure:
wherein,
Z 1~ Z 16independently selected from C, CH or N; L 3with L 4be 0 or 1 independently;
Q 1and Q 2independently selected from nitrogen, oxygen, sulphur, carbonatoms be 6 ~ 30 aryl or carbonatoms be 1 ~ 30 heterocyclic radical;
Ar 1, Ar 2, Ar 3and Ar 4independently selected from hydrogen atom, the substituted or unsubstituted carbonatoms aralkyl that is 7 ~ 50, the substituted or unsubstituted carbonatoms aralkoxy that is 7 ~ 50, the substituted or unsubstituted carbonatoms aralkyl sulfydryl that is 7 ~ 50, the carbonatoms aryl that is 6 ~ 50, substituted or unsubstituted carbonatoms be 5 ~ 50 heterocyclic radical or substituted or unsubstituted carbonatoms be 7 ~ 30 aromatic series amido.
5. the heteroaromatic compounds according to claims 1 to 3 any one, is characterized in that, in described heteroaromatic compounds, and-Ar 1,-Ar 2,-Ar 3with-Ar 4independently selected from structure following formula (1) ~ formula (35) Suo Shi:
Wherein,
X and Y is independently selected from hydrogen atom, halogen atom, cyano group, substituted or unsubstituted carbonatoms is the alkyl of 1 ~ 30, substituted or unsubstituted carbonatoms is the alkoxyl group of 1 ~ 30, substituted or unsubstituted carbonatoms is the thiazolinyl of 2 ~ 30, substituted or unsubstituted carbonatoms is the aralkyl of 7 ~ 30, substituted or unsubstituted carbonatoms is the aralkoxy of 7 ~ 30, substituted or unsubstituted carbonatoms is the aryl of 6 ~ 30, substituted or unsubstituted carbonatoms is the aryloxy of 6 ~ 30, substituted or unsubstituted carbonatoms is the heterocyclic radical of 5 ~ 30, or substituted or unsubstituted carbonatoms is the aromatic series amido of 7 ~ 30.
6. heteroaromatic compounds according to claim 1, is characterized in that, described Q 1and Q 2be phenyl, and R 1and R 2when being cyano group or phenyl, Ar 1and Ar 2independently selected from the aromatic series amido of the aryl of substituted or unsubstituted carbonatoms 7 ~ 50, the heterocyclic radical of substituted or unsubstituted carbonatoms 5 ~ 50 or substituted or unsubstituted carbonatoms 7 ~ 30;
Described L 1with L 2be asynchronously 0.
7. a preparation method for heteroaromatic compounds, comprising:
Compound shown in compound shown in formula (V) and formula (VI) and the compound shown in formula (VII) are reacted, obtains the heteroaromatic compounds shown in formula (I);
Wherein,
X ' is halogen atom, Y ' and Y 1' independently selected from B (OH) 2or H;
L 1, L 2, L 3, L 4independently selected from 0 or 1;
Q 1and Q 2independently selected from nitrogen, oxygen, sulphur, carbonatoms be 6 ~ 30 aryl or carbonatoms be 1 ~ 30 heterocyclic radical;
R 1and R 2independently selected from hydrogen atom, cyano group, the substituted or unsubstituted carbonatoms aryl that is 6 ~ 50, the substituted or unsubstituted carbonatoms heterocyclic radical that is 5 ~ 50, the substituted or unsubstituted carbonatoms aromatic series amido that is 7 ~ 30, the substituted or unsubstituted carbonatoms aralkoxy that is 7 ~ 30, substituted or unsubstituted carbonatoms be 7 ~ 30 aralkyl sulfydryl or carbonatoms be 1 ~ 30 alkyl;
Ar 1, Ar 2, Ar 3and Ar 4independently selected from hydrogen atom, the substituted or unsubstituted carbonatoms aralkyl that is 7 ~ 50, the substituted or unsubstituted carbonatoms aralkoxy that is 7 ~ 50, the substituted or unsubstituted carbonatoms aralkyl sulfydryl that is 7 ~ 50, the carbonatoms aryl that is 6 ~ 50, substituted or unsubstituted carbonatoms be 5 ~ 50 heterocyclic radical or substituted or unsubstituted carbonatoms be 7 ~ 30 aromatic series amido.
8. an organic electroluminescence device, comprises heteroaromatic compounds prepared by heteroaromatic compounds described in claim 1 ~ 6 any one or preparation method according to claim 7.
9. organic electroluminescence device according to claim 8, is characterized in that, the organic matter layer comprising the first electrode, the second electrode and be arranged between described first electrode and the second electrode;
Described organic matter layer comprises heteroaromatic compounds prepared by heteroaromatic compounds described in claim 1 ~ 6 any one or preparation method according to claim 7.
10. an organic photoelectrical material, is characterized in that, comprises heteroaromatic compounds prepared by heteroaromatic compounds described in claim 1 ~ 6 any one or preparation method according to claim 7;
Described organic photoelectrical material comprises organic photovoltaic cell, Electronic Paper, Organophotoreceptor or organic transistor.
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