CN107629011A - A kind of organic compound and its application based on pyridine and quinoline beautiful jade - Google Patents
A kind of organic compound and its application based on pyridine and quinoline beautiful jade Download PDFInfo
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- 0 CC=*C(*1)=C(C)*c2c1cccc2 Chemical compound CC=*C(*1)=C(C)*c2c1cccc2 0.000 description 11
- NBCBNBMQPHBNRD-UHFFFAOYSA-N Bc(cc1)ccc1-c1c(-c2ccccc2)nc(C=CCC2)c2n1 Chemical compound Bc(cc1)ccc1-c1c(-c2ccccc2)nc(C=CCC2)c2n1 NBCBNBMQPHBNRD-UHFFFAOYSA-N 0.000 description 1
- FOOJOMCGDGBFEQ-UHFFFAOYSA-N CC(C)(C(C)(C)OCBc(cc1)ccc1-c1c(-c2ccccc2)nc(C=CCC2)c2n1)O Chemical compound CC(C)(C(C)(C)OCBc(cc1)ccc1-c1c(-c2ccccc2)nc(C=CCC2)c2n1)O FOOJOMCGDGBFEQ-UHFFFAOYSA-N 0.000 description 1
- HHOPQQUPXASMKW-UHFFFAOYSA-N CC1(C)NB(B2OC(C)(C)C(C)(C)O2)OC1(C)C Chemical compound CC1(C)NB(B2OC(C)(C)C(C)(C)O2)OC1(C)C HHOPQQUPXASMKW-UHFFFAOYSA-N 0.000 description 1
- KHGPWDJPXCBEML-CZSCZIAVSA-N CC1(C)OB(c(cc2)ccc2/C(/C2=C/C2=C(\CCC=C2)/C2=N)=C\c2ccccc2)OC1(C)C Chemical compound CC1(C)OB(c(cc2)ccc2/C(/C2=C/C2=C(\CCC=C2)/C2=N)=C\c2ccccc2)OC1(C)C KHGPWDJPXCBEML-CZSCZIAVSA-N 0.000 description 1
- CMHFOGHPWRFRLP-CKYLTHKJSA-N CC1=CC1/C(/c(nc1Cl)c(-c2cnccc2)nc1Cl)=C\C=C/N Chemical compound CC1=CC1/C(/c(nc1Cl)c(-c2cnccc2)nc1Cl)=C\C=C/N CMHFOGHPWRFRLP-CKYLTHKJSA-N 0.000 description 1
- SPXKFAQYAGEESW-UHFFFAOYSA-N Cc1nc(-c2ccccc2)nc(Cl)c1C1=CCCC=C1 Chemical compound Cc1nc(-c2ccccc2)nc(Cl)c1C1=CCCC=C1 SPXKFAQYAGEESW-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to a kind of organic compound based on pyridine and quinoline beautiful jade and its application in OLED, the compounds of this invention has higher glass transition temperature and molecule heat endurance；Absorb that low, refractive index is high in visible regime, when the CPL layers applied to OLED, can effectively lift the light extraction efficiency of OLED；The compounds of this invention also has deep HOMO energy levels and high electron mobility, can be as hole barrier/electron transport layer materials of OLED, it can effectively stop that hole or energy are transferred to electronic shell side from luminescent layer, so as to lift the combined efficiency of hole and electronics in luminescent layer, and then lift the luminous efficiency and service life of OLED.
Description
Technical field
The present invention relates to technical field of semiconductors, more particularly, to a kind of organic compound based on pyridine and quinoline beautiful jade
And its application on OLED.
Background technology
Organic electroluminescent (OLED:Organic Light Emission Diodes) device technology both can be used for make
New display product is made, can be used for making novel illumination product, and is expected to substitute existing liquid crystal display and fluorescent lamp photograph
Bright, application prospect is quite varied.OLED luminescent devices use the sandwich structure of sandwich-type more, and organic layer exactly is clipped in into both sides
Electrode between.Hole and electronics are injected from anode and negative electrode respectively, and are transmitted in organic layer, and exciton is formed after meeting,
Exciton recombination luminescence.
Currently, OLED Display Techniques are applied in fields such as smart mobile phone, tablet personal computers, will also be further to electricity
Depending on etc. large scale application field extension.But there is huge difference between the external quantum efficiency and internal quantum efficiency due to OLED
Away from significantly limit OLED development.Therefore, how to improve OLED light extraction efficiency turns into a big heat of this area research
Point.The interface and glass substrate of ito thin film and glass substrate and the interface of air can be totally reflected, and be emitted to OLED devices
The 20% of organic material film EL total amounts is accounted for the light of exterior space before part, remaining about 80% light is mainly limited in the form of guided wave
Make in organic material film, ito thin film and glass substrate.It can be seen that the light extraction efficiency of conventional OLED device is relatively low (about
20%), this development and application for seriously constraining OLED.Therefore how to reduce the total reflection effect in OLED, improve light
It is coupled to the extensive concern for causing people before device to the ratio (light extraction efficiency) of exterior space.
At present, realize improve OLED external quantum efficiencys a kind of important method be substrate light output surface formed as fold,
The structures such as photonic crystal, lenticule display (MLA) and addition surface coating.First two structure can influence OLED radiation spectrum
Angular distribution, the third structure fabrication processes are complicated, and use surface coating technique simple, luminous efficiency improve 30% with
On, and by people's extensive concern.According to optical principle, when light transmission superrefraction rate is n1Material to refractive index be n2Material
When (n1＞ n2), only in arcsin (n2/n1) angle in just to incide refractive index be n2Material in, absorptivity B can be with
Calculated with following formula：
If n1=nGeneral OLED organic materials=1.70, n2=nGlass=1.46, then 2B=0.49.Assuming that the light whole quilt outwards propagated
Metal electrode reflects, then only 51% luminous energy again may be by this by the organic film of high index of refraction and the waveguide of ITO layer institute
Mode calculate light from substrate of glass inject to air when transmitance.Therefore the light sent from organic layer projects the outside of device
When, only about 17% luminous energy is seen by people.Therefore, for the low present situation of current OLED light extraction efficiency, it is necessary to
Increase by one layer of CPL layer, i.e. light extraction material in the device structure, according to optical absorption, refraction principle, this surface coating material
Refractive index within the specific limits should be the higher the better.
Currently in order to improving the research of OLED luminescent device performances includes：Reduce the driving voltage of device, improve device
Luminous efficiency, the service life for improving device etc..In order to realize the continuous lifting of the performance of OLED, not only need from OLED
Device architecture and manufacture craft are innovated, and more oled light sulfate ferroelectric functional material are constantly studied and innovated, to formulate
Go out the OLED functional materials of higher performance.
The content of the invention
In view of the above-mentioned problems existing in the prior art, the applicant provides a kind of organic based on pyridine and quinoline beautiful jade
Compound and its application on organic electroluminescence device.The compounds of this invention contains pyridine and quinoline beautiful jade structure, has
Higher glass transition temperature and molecule heat endurance, visible regime absorb it is low, refractive index is high, when applied to OLED
CPL layers, the light extraction efficiency of OLED can be effectively lifted, and because pyridine and quinoline beautiful jade have deep HOMO energy levels,
Wide forbidden band (Eg) energy level, as hole barrier/electron transport layer materials of OLED hole can be stopped from luminescent layer transmission
To electronic shell side, the multiplicity of hole and electronics in luminescent layer is improved, so as to lift the luminous efficiency of OLED and make
Use the life-span.
Technical scheme is as follows：
A kind of organic compound based on pyridine and quinoline beautiful jade, shown in the structure such as formula (1) of the organic compound：
In formula (1), X1~X6It is each independent to be expressed as N atoms or C atoms, and N atoms number is 2；
Z is numeral 0,1,2,3 or 4；M, n independently be expressed as numeral 0,1,2 or 3, and m+n+z=4；
In formula (1), Ar1For singly-bound, substituted or unsubstituted C6-60Arlydene, heteroatomic take containing one or more
Generation or unsubstituted 5~60 yuan of heteroarylidenes；The hetero atom is nitrogen, oxygen or sulphur；
Ar2、Ar3Independently be expressed as substituted or unsubstituted C6-60Aryl, heteroatomic take containing one or more
Generation or unsubstituted 5-60 unit's heteroaryls；The hetero atom is nitrogen, oxygen or sulphur；Ar2、Ar3It is identical or different；
In formula (1), Ar2、Ar3Can also be independently be expressed as formula (2), tie shown in formula (3) or formula (4)
Structure；
Ar in formula (3), formula (4)4It is expressed as substituted or unsubstituted C6-60Arlydene, containing one or more miscellaneous
Substituted or unsubstituted 5~60 unit's heteroaryl of atom；The hetero atom is nitrogen, oxygen or sulphur；
In formula (2), formula (3) or formula (4), R2、R3、R4Being expressed as independently is substituted or unsubstituted
C6-60Aryl, contain one or more heteroatomic substituted or unsubstituted 5~60 unit's heteroaryls；The hetero atom is nitrogen, oxygen
Or sulphur；R2、R3、R4It is identical or different respectively；
In formula (4), x is expressed as integer 1 or 2；
In formula (1), R1It is expressed as structure shown in formula (5) or formula (6)；
Wherein, Ar5、Ar6、Ar7Independently be expressed as substituted or unsubstituted C6-60Aryl, contain one or more
Heteroatomic substituted or unsubstituted 5~60 unit's heteroaryl；The hetero atom is nitrogen, oxygen or sulphur.
The structural formula of the compound is any of formula (I)~(III)：
The structure of the compound is any of formula (1-1)~(4-1)：
The Ar1、Ar4Independently be expressed as C1-10Straight or branched alkyl, halogen atom, protium, deuterium, tritium atom take
Generation or unsubstituted phenylene；C1-10The substituted or unsubstituted sub- naphthalene of straight or branched alkyl, halogen atom, protium, deuterium, tritium atom
Base；C1-10The substituted or unsubstituted sub- dibiphenylyl of straight or branched alkyl, halogen atom, protium, deuterium, tritium atom；Sub- terphenyl
Base；Anthrylene；C1-10The substituted or unsubstituted sub- pyridine radicals of straight or branched alkyl, halogen atom, protium, deuterium, tritium atom；Sub- click
Oxazolyl；Sub- pyrimidine radicals；Sub- pyrazinyl；Sub- pyridazinyl；Dibenzofurans；9,9- dimethyl fluorenes；N- phenyl carbazoles；Sub- quinolyl；
One kind in sub- isoquinolyl or sub- naphthyridines base；The Ar2、Ar3、Ar5、Ar6、Ar7Independently be expressed as C1-10Straight chain or
Branched alkyl, halogen atom, protium, deuterium, the substituted or unsubstituted phenyl of tritium atom；C1-10Straight or branched alkyl, halogen atom,
Protium, deuterium, the substituted or unsubstituted naphthyl of tritium atom；C1-10Straight or branched alkyl, halogen atom, protium, deuterium, tritium atom substitution or
Unsubstituted dibiphenylyl；Terphenyl；Anthryl；C1-10Straight or branched alkyl, halogen atom, protium, deuterium, tritium atom substitution or
Unsubstituted pyridine radicals；Carbazyl；Pyrimidine radicals；Pyrazinyl；Pyridazinyl；Dibenzofurans；9,9- dimethyl fluorenes；N- phenyl clicks
Azoles；Quinolyl；One kind in isoquinolyl or naphthyridines base；Ar5、Ar6、Ar7、R2、R3、R4Independently be expressed as C1-10Straight chain
Or the substituted or unsubstituted phenyl of branched alkyl, halogen atom；C1-10Straight or branched alkyl, halogen atom substitution or unsubstituted
Naphthyl；C1-10The substituted or unsubstituted dibiphenylyl of straight or branched alkyl, halogen atom；C1-10Straight or branched alkyl, halogen
The plain substituted or unsubstituted pyridine radicals of atom；Carbazyl；Furyl；One kind in quinolyl or naphthyridines base.
The concrete structure formula of the organic compound is：
In any one.
A kind of preparation method of the organic compound, the reaction equation involved by the preparation method are：
(1) Ar is worked as2、Ar3When being connected with pyridine with C-C keys, two-step reaction occurs：
The first step is reacted：
Under nitrogen atmosphere, weigh raw material A and be dissolved in tetrahydrofuran, add Ar2-B(OH)2And Pd (PPh3)4, stirring
Mixture, wet chemical is added, it is small that the mixed solution of above-mentioned reactant is heated to reflux into 5-15 under the conditions of 70-90 DEG C
When；After reaction terminates, cooling adds water, extracted with dichloromethane, extract anhydrous sodium sulfate drying, filtering, filtrate revolving, mistake
Silicagel column purifies, and obtains compound intermediate I；
The raw material A and Ar2-B(OH)2Mol ratio be 1:1.0~4.5, Pd (PPh3)4Mol ratio with raw material A is
0.001~0.04:1, the mol ratio of potassium carbonate and raw material A is 1.0~6.0:1, the amount ratio of raw material A and tetrahydrofuran is 1g：
10~30ml；
Second step reacts：
Under nitrogen atmosphere, weigh intermediate compound I and be dissolved in tetrahydrofuran, add Ar3-B(OH)2And Pd (PPh3)4, stir
Mixture is mixed, adds wet chemical, the mixed solution of above-mentioned reactant is heated to reflux 5-15 under the conditions of 70-90 DEG C
Hour；After reaction terminates, cooling adds water, extracted with dichloromethane, extract anhydrous sodium sulfate drying, filtering, filtrate revolving,
Silicagel column purifying is crossed, obtains compound intermediate II；
The intermediate compound I and Ar3-B(OH)2Mol ratio be 1:1.0~4.5, Pd (PPh3)4With the mol ratio of intermediate compound I
For 0.001~0.04:1, the mol ratio of potassium carbonate and intermediate compound I is 1.0~6.0:1, the amount ratio of intermediate compound I and tetrahydrofuran
For 1g:10~30ml；
(2) Ar is worked as2、Ar3When being connected with pyridine with C-N keys, two-step reaction occurs：
The first step is reacted：
Weigh raw material A and Ar2- H, dissolved with toluene, add Pd2(dba)3, tri-butyl phosphine, sodium tert-butoxide；In inertia
Under atmosphere, the mixed solution of above-mentioned reactant is reacted 10~24 hours under the conditions of 95~110 DEG C, cools down and filters and react molten
Liquid, filtrate revolving, crosses silicagel column, obtains intermediate compound I；
The raw material A and Ar2- H mol ratio is 1:1.0~3, Pd2(dba)3With the mol ratio of raw material A for 0.006~
0.04:1, the mol ratio of tri-butyl phosphine and raw material A is 0.006~0.04:1, the mol ratio of sodium tert-butoxide and raw material A is 2.0
~3.0:1；
Second step reacts：
Weigh intermediate compound I and Ar3- H, dissolved with toluene, add Pd2(dba)3, tri-butyl phosphine, sodium tert-butoxide；Lazy
Under property atmosphere, the mixed solution of above-mentioned reactant is reacted 10~24 hours under the conditions of 95~110 DEG C, cools down and filters reaction
Solution, filtrate revolving, crosses silicagel column, obtains intermediate II；
The intermediate compound I and Ar3- H mol ratio is 1:1.0~3, Pd2(dba)3Mol ratio with intermediate compound I is 0.006
~0.04:1, the mol ratio of tri-butyl phosphine and intermediate compound I is 0.006~0.04:1, the mol ratio of sodium tert-butoxide and intermediate compound I
For 2.0~3.0:1；
(3) Ar is worked as2、Ar3It is connected with pyridine with C-C keys or Ar2、Ar3When being connected with pyridine with C-N keys, occur
Following reactions：
Under nitrogen atmosphere, weigh intermediate II and be dissolved in DMF, addAnd palladium, stirring are mixed
Compound, aqueous potassium phosphate solution is added, the mixed solution of above-mentioned reactant is heated to reflux 10-24 under the conditions of 120-150 DEG C
Hour；After reaction terminates, cooling Jia Shui, mixture is filtered and dried in vacuum drying chamber, gained residue crosses silicagel column
Purifying, obtains target compound；
The intermediate II withMol ratio be 1:1.0~6.0, mole of palladium and intermediate II
Than for 0.001~0.08:1, the mol ratio of potassium phosphate and intermediate II is 1.0~8.0:1, intermediate II and DMF amount ratio
For 1g:15~50ml.
A kind of application of the organic compound, the organic compound based on pyridine and quinoline beautiful jade have for preparation
Organic electroluminescence devices.
A kind of organic electroluminescence device containing the organic compound, the organic electroluminescence device are included at least
One one functional layer contains the organic compound based on pyridine and quinoline beautiful jade.
A kind of organic electroluminescence device containing the organic compound, including hole blocking layer/electron transfer layer, institute
State hole blocking layer/electron transfer layer and contain the organic compound based on pyridine and quinoline beautiful jade.
A kind of organic electroluminescence device containing the organic compound, including CPL layers, the CPL layers contain described
Organic compound based on pyridine and quinoline beautiful jade.
One kind illumination or display element, the element contain described organic electroluminescence device.
The present invention is beneficial to be had technical effect that：
Organic compound of the present invention contains two kinds of rigid radicals of pyridine and quinoline beautiful jade, improves the stabilization of material structure
Property；Material of the present invention containing strong electro quinoline beautiful jade group, and intersects between group and separated on space structure,
Group is avoided to rotate freely so that material has higher density, obtains higher refractive index；Simultaneously so that material of the present invention
Material all has very high Tg temperature；The evaporation temperature of material of the present invention under vacuum conditions is generally less than 350 DEG C, both ensure that
Material long-time deposition material in volume production does not decompose, and reduces again due to deformation of the heat radiation that temperature is deposited to evaporation MASK
Influence.
Material of the present invention applies the electronics and hole transport in CPL layers, being not involved in device in OLED, but to material
Heat endurance, membrane crystallization and optical transport (high index of refraction) there is very high requirement.As above analyze, pyridine and quinoline beautiful jade
For rigid radical, the stability of material is improved；High Tg temperature, it ensure that material does not crystallize under filminess；Low steaming
Temperature is plated, is the premise that material can be applied to volume production；High refractive index is then that material of the present invention can apply to the main of CPL layers
Factor.
Material of the present invention high electron mobility, can effectively stop hole or energy from hair due to the HOMO energy levels with depth
Photosphere is transferred to electronic shell side, so as to improve the combined efficiency of hole and electronics in luminescent layer, so as to lift OLED
Luminous efficiency and service life.After the CPL layers applied to OLED, the light that can effectively lift OLED takes the present invention
Go out efficiency.To sum up, compound of the present invention has good application effect and industrialization prospect in OLED luminescent devices.
Brief description of the drawings
Fig. 1 is the materials application cited by the present invention in the structural representation of OLED；Wherein, 1, OLED base
Plate, 2, anode layer, 3, hole injection layer, 4, hole transmission layer, 5, luminescent layer, 6, hole blocking layer/electron transfer layer, 7, electronics
Implanted layer, 8, cathode layer, 9, CPL layers.
Fig. 2 is the refraction index test figure of compound 20；
Fig. 3 is compound 32 and well known materials CBP film Acceleration study comparison diagram；
Fig. 4 is the efficiency curve diagram that device measures at different temperatures.
Embodiment
Embodiment 1：The synthesis of intermediate compound I
By taking the synthesis of intermediate A 1 as an example
In 250mL there-necked flasks, nitrogen is passed through, add 0.04mol raw materials 2, bromo- 5, the 6- dichloropyrazines of 3- bis-, 100ml's
THF, 0.1mol phenyl boric acid, 0.0008mol tetrakis triphenylphosphine palladiums, the K of stirring, then addition 0.12mol2CO3The aqueous solution
(2M), 80 DEG C are heated to, back flow reaction 5 hours, sample point plate, reaction is completely.Natural cooling, extracted with 200ml dichloromethane,
Layering, extract anhydrous sodium sulfate drying, filtering, filtrate revolving, silicagel column purifying is crossed, obtains intermediate A 1, HPLC purity
99.7%, yield 87.2%.
Elementary analysis structure (molecular formula C16H10Cl2N2)：Theoretical value C, 63.81；H,3.35；Cl,23.54；N,9.30；Survey
Examination value：C,63.79；H,3.34；Cl,23.55；N,9.32.ESI-MS(m/z)(M+)：Theoretical value 300.02, measured value are
300.48。
By taking the synthesis of intermediate A 12 as an example
250ml there-necked flask, under the atmosphere for being passed through nitrogen, 2,4,6- tri- bromo- 5- chlorine pyrimidines of 0.01mol are added,
0.012mol diphenylamines, 0.03mol sodium tert-butoxides, 1 × 10-4mol Pd2(dba)3, 1 × 10-4Mol tri-butyl phosphines, 150ml
Toluene, it is heated to reflux 10 hours, sample point plate, reaction is complete；Natural cooling, filtering, filtrate revolving, silicagel column is crossed, is obtained middle
Body A12, HPLC purity 99.5%, yield 82.7%.
Elementary analysis structure (molecular formula C16H10Br2ClN3)：Theoretical value C, 43.72；H,2.29；Br,36.36；Cl,
8.07；N,9.56；Test value：C,43.74；H,2.28；Br,36.37；Cl,8.06；N,9.55.ESI-MS(m/z)(M+)：Reason
It is 436.89 by value, measured value 437.06.
Intermediate compound I is prepared with intermediate A 1, A12 synthetic method, concrete structure is as shown in table 1.
Table 1
Embodiment 2：The synthesis of intermediate II
By taking the synthesis of intermediate B 1 as an example
In 250mL there-necked flasks, nitrogen is passed through, adds 0.02mol intermediate As 6,100ml THF, 0.03mol (4- (9-
H- carbazole -9- bases) phenyl) boric acid, 0.0004mol tetrakis triphenylphosphine palladiums, the K of stirring, then addition 0.06mol2CO3It is water-soluble
Liquid (2M), 80 DEG C are heated to, back flow reaction 5 hours, sample point plate, reaction is completely.Natural cooling, extracted with 200ml dichloromethane
Take, be layered, extract anhydrous sodium sulfate drying, filtering, filtrate revolving, cross silicagel column purifying, obtain intermediate B 1, HPLC is pure
Degree 99.4%, yield 75.3%.
Elementary analysis structure (molecular formula C34H22ClN3)：Theoretical value C, 80.38；H,4.36；Cl,6.98；N,8.27；Test
Value：C,80.41；H,4.35；Cl,6.99；N,8.25.ESI-MS(m/z)(M+)：Theoretical value 507.15, measured value are
507.58。
Intermediate II is prepared with the synthetic method of intermediate B 1, concrete structure is as shown in table 2.
Table 2
Embodiment 3：IntermediateSynthesis
Work as R1When being expressed as formula (5) structure,
(1) under nitrogen atmosphere, 2,3- dibromo quinoxalines is weighed and are dissolved in tetrahydrofuran, then by Ar5-B(OH)2And four (three
Phenylphosphine) palladium addition, mixture is stirred, unsaturated carbonate aqueous solutions of potassium is added, by the mixed solution of above-mentioned reactant in reaction
10-20 hours are heated to reflux at 70-90 DEG C of temperature；After reaction terminates, cooling, mixed liquor are extracted with dichloromethane, and extract is used
Anhydrous sodium sulfate drying processing, and concentrate under reduced pressure, thickened solid is crossed into silicagel column purifying, obtains compound intermediate M；
(2) under nitrogen atmosphere, weigh intermediate M and be dissolved in DMF (DMF), then will double (pinacols
Foundation) two boron, (1,1 '-bis- (diphenylphosphine) ferrocene) dichloro palladium (II) and potassium acetate add, and stirs mixture, and will be above-mentioned
The mixed solution of reactant is heated to reflux 5-10 hours at 120-150 DEG C of reaction temperature；After reaction terminates, cool down and will mix
Compound is filtered and dried in vacuum drying oven.The residue obtained is crossed into silica gel column separating purification, obtains compound intermediate
II-1；
Work as R1When being expressed as formula (6) structure,
(1) under nitrogen atmosphere, the bromo- 6- chloro-quinoxalines of 2,3- bis- is weighed and are dissolved in tetrahydrofuran, then by Ar6-B(OH)2And
Tetrakis triphenylphosphine palladium add, stir mixture, add unsaturated carbonate aqueous solutions of potassium, by the mixed solution of above-mentioned reactant in
10-20 hours are heated to reflux at 70-90 DEG C of reaction temperature；After reaction terminates, cooling, mixed liquor are extracted with dichloromethane, are extracted
Thing is handled with anhydrous sodium sulfate drying, and is concentrated under reduced pressure, and thickened solid is crossed into silicagel column purifying, obtains compound intermediate
O；
(2) under nitrogen atmosphere, weigh intermediate O and be dissolved in tetrahydrofuran, then by Ar7-B(OH)2And four (triphenylphosphine)
Palladium adds, and stirs mixture, unsaturated carbonate aqueous solutions of potassium is added, by the mixed solution of above-mentioned reactant in reaction temperature 70-
10-20 hours are heated to reflux at 90 DEG C；After reaction terminates, cooling, mixed liquor are extracted with dichloromethane, extract anhydrous slufuric acid
Sodium drying process, and concentrate under reduced pressure, thickened solid is crossed into silicagel column purifying, obtains compound intermediate P；
(3) under nitrogen atmosphere, weigh intermediate P and be dissolved in DMF (DMF), then will double (pinacols
Foundation) two boron, (1,1 '-bis- (diphenylphosphine) ferrocene) dichloro palladium (II) and potassium acetate add, and stirs mixture, and will be above-mentioned
The mixed solution of reactant is heated to reflux 5-10 hours at 120-150 DEG C of reaction temperature；After reaction terminates, cool down and will mix
Compound is filtered and dried in vacuum drying oven.The residue obtained is crossed into silica gel column separating purification, obtains compound intermediate
II-2；
IntermediateSynthesis
(1) under nitrogen atmosphere, weigh intermediate M or intermediate P is dissolved in tetrahydrofuran, then by Br-Ar1-B(OH)2And
Tetrakis triphenylphosphine palladium add, stir mixture, add unsaturated carbonate aqueous solutions of potassium, by the mixed solution of above-mentioned reactant in
10-20 hours are heated to reflux at 70-90 DEG C of reaction temperature；After reaction terminates, cooling, mixed liquor are extracted with dichloromethane, are extracted
Thing is handled with anhydrous sodium sulfate drying, and is concentrated under reduced pressure, and thickened solid is crossed into silicagel column purifying, obtains compound intermediate
N or intermediate Q；
(2) under nitrogen atmosphere, weigh intermediate N or intermediate Q and be dissolved in DMF (DMF), then will
Double (pinacol foundation) two boron, (1,1 '-bis- (diphenylphosphine) ferrocene) dichloro palladium (II) and potassium acetate add, and are stirred
Thing, the mixed solution of above-mentioned reactant is heated to reflux 5-10 hours at 120-150 DEG C of reaction temperature；It is cold after reaction terminates
But and by mixture filter and dried in vacuum drying oven.The residue obtained is crossed into silica gel column separating purification, obtains chemical combination
Thing intermediate II -3 or intermediate II -4；
By taking intermediate C1 synthesis as an example
(1) under nitrogen atmosphere, 2,3- dibromo quinoxalines is weighed and are dissolved in tetrahydrofuran, then by phenyl boric acid and four (triphens
Base phosphine) palladium addition, mixture is stirred, adds unsaturated carbonate aqueous solutions of potassium, by the mixed solution of above-mentioned reactant in reaction temperature
10-20 hours are heated to reflux at 70-90 DEG C of degree；After reaction terminates, cooling, mixed liquor are extracted with dichloromethane, extract nothing
Aqueous sodium persulfate drying process, and concentrate under reduced pressure, thickened solid is crossed into silicagel column purifying, obtains compound intermediate M1；
Elementary analysis structure (molecular formula C14H9BrN2)：Theoretical value C, 58.97；H,3.18；Br,28.02；N,9.82；Survey
Examination value：C,58.95；H,3.23；Br,28.05；N,9.79.ESI-MS(m/z)(M+)：Theoretical value 283.99, measured value are
285.14。
(2) in 250mL there-necked flasks, nitrogen is passed through, adds 0.04mol intermediates M1,100mlTHF, 0.05mol benzene boron
Acid, 0.0004mol tetrakis triphenylphosphine palladiums, stirring, then add 0.06mol K2CO3The aqueous solution (2M), is heated to 80 DEG C, returns
Stream reaction 10 hours, sample point plate, reaction are complete.Natural cooling, extracted with 200ml dichloromethane, layering, extract is with anhydrous
Sodium sulphate is dried, filtering, filtrate revolving, is crossed silicagel column purifying, is obtained intermediate N1, HPLC purity 99.6%, yield 84.9%.
Elementary analysis structure (molecular formula C20H13BrN2)：Theoretical value C, 66.50；H,3.63；Br,22.12；N,7.75；Survey
Examination value：C,66.56；H,3.64；Br,22.19；N,7.73.ESI-MS(m/z)(M+)：Theoretical value 360.03, measured value are
361.24。
(3) in 500mL there-necked flasks, nitrogen is passed through, 0.05 intermediate N1 is added and is dissolved in 300mlN, N- dimethyl formyls
In amine (DMF), then by double (pinacol foundation) two boron of 0.06mol, 0.0005mol (1,1 '-bis- (diphenylphosphine) ferrocene) two
Chlorine palladium (II) and 0.125mol potassium acetates add, and mixture are stirred, by the mixed solution of above-mentioned reactant in reaction temperature
It is heated to reflux at 120-150 DEG C 10 hours；After reaction terminates, cool down and add 200ml water and filter mixture and in vacuum
Dried in baking oven.The residue obtained is crossed into silica gel column separating purification, obtains compound intermediate C1；HPLC purity
99.5%, yield 84.1%.
Elementary analysis structure (molecular formula C26H25BN2O2)：Theoretical value C, 76.48；H,6.17；B,2.65；N,6.86；O,
7.84；Test value：C,76.47；H,6.15；B,2.67；N,6.87；O,7.83.ESI-MS(m/z)(M+)：Theoretical value
408.20 measured value 408.31.Intermediate compound IV is prepared with intermediate C1 synthetic method, concrete structure is as shown in table 3.
Table 3
Embodiment 4：The synthesis of compound 1：
In 250mL there-necked flasks, nitrogen is passed through, adds 0.01mol intermediate As 1,150mlDMF, 0.03mol intermediates
C1,0.0002mol palladium, stirring, then add 0.02mol K3PO4The aqueous solution, 150 DEG C are heated to, back flow reaction 24 is small
When, sample point plate, reaction is completely.Natural cooling, extracted with 200ml dichloromethane, layering, extract is done with anhydrous sodium sulfate
It is dry, filtering, filtrate revolving, silicagel column purifying is crossed, obtains target product, HPLC purity 99.3%, yield 61.9%.
Elementary analysis structure (molecular formula C56H36N6)：Theoretical value C, 84.82；H,4.58；N,10.60；Test value：C,
84.85；H,4.53；N,10.62.ESI-MS(m/z)(M+)：Theoretical value 792.30, measured value 792.95.
Embodiment 5：The synthesis of compound 7：
In 250mL there-necked flasks, nitrogen is passed through, adds 0.01mol intermediate As 2,150mlDMF, 0.03mol intermediates
C1,0.0002mol palladium, stirring, then add 0.02mol K3PO4The aqueous solution, 150 DEG C are heated to, back flow reaction 24 is small
When, sample point plate, reaction is completely.Natural cooling, extracted with 200ml dichloromethane, layering, extract is done with anhydrous sodium sulfate
It is dry, filtering, filtrate revolving, silicagel column purifying is crossed, obtains target product, HPLC purity 99.1%, yield 64.5%.
Elementary analysis structure (molecular formula C56H36N6)：Theoretical value C, 84.82；H,4.58；N,10.60；Test value：C,
84.83；H,4.61；N,10.61.ESI-MS(m/z)(M+)：Theoretical value 792.30, measured value 792.87.
Embodiment 6：The synthesis of compound 13：
With embodiment 4, difference is to replace A1 with intermediate B 4 preparation method of compound 13.
Elementary analysis structure (molecular formula C54H34N8)：Theoretical value C, 81.59；H,4.31；N,14.10；Test value：C,
81.53；H,4.33；N,14.12.ESI-MS(m/z)(M+)：Theoretical value 794.29, measured value 794.92.
Embodiment 7：The synthesis of compound 20：
With embodiment 4, difference is to replace intermediate A 1 with intermediate A 3 preparation method of compound 20.
Elementary analysis structure (molecular formula C54H34N8)：Theoretical value C, 81.59；H,4.31；N,14.10；Test value：C,
81.62；H,4.34；N,14.15.ESI-MS(m/z)(M+)：Theoretical value 794.29, measured value 794.96.
Embodiment 8：The synthesis of compound 32：
With embodiment 4, difference is to replace intermediate A 1 with intermediate A 4 preparation method of compound 32.
Elementary analysis structure (molecular formula C56H36N6)：Theoretical value C, 84.82；H,4.58；N,10.60；Test value：C,
84.84；H,4.61；N,10.65.ESI-MS(m/z)(M+)：Theoretical value 792.30, measured value 792.95.
Embodiment 9：The synthesis of compound 35：
With embodiment 4, difference is to replace intermediate A 1 with intermediate A 5 preparation method of compound 35.
Elementary analysis structure (molecular formula C54H34N8)：Theoretical value C, 81.59；H,4.31；N,14.10；Test value：C,
81.61；H,4.36；N,14.13.ESI-MS(m/z)(M+)：Theoretical value 794.29, measured value 794.92.
Embodiment 10：The synthesis of compound 46：
In 250mL there-necked flasks, nitrogen is passed through, adds 0.01mol intermediate Bs 1,150mlDMF, 0.015mol intermediates
C1,0.0001mol palladium, stirring, then add 0.01mol K3PO4The aqueous solution, 150 DEG C are heated to, back flow reaction 24 is small
When, sample point plate, reaction is completely.Natural cooling, extracted with 200ml dichloromethane, layering, extract is done with anhydrous sodium sulfate
It is dry, filtering, filtrate revolving, silicagel column purifying is crossed, obtains target product, HPLC purity 99.4%, yield 65.7%.
Elementary analysis structure (molecular formula C54H35N5)：Theoretical value C, 86.03；H,4.68；N,9.29；Test value：C,
86.07；H,4.67；N,9.25.ESI-MS(m/z)(M+)：Theoretical value 753.29, measured value 753.91.
Embodiment 11：The synthesis of compound 52：
In 250mL there-necked flasks, nitrogen is passed through, adds 0.01mol intermediate As 7,150mlDMF, 0.045mol intermediates
C1,0.0003mol palladium, stirring, then add 0.03mol K3PO4The aqueous solution, 150 DEG C are heated to, back flow reaction 24 is small
When, sample point plate, reaction is completely.Natural cooling, extracted with 200ml dichloromethane, layering, extract is done with anhydrous sodium sulfate
It is dry, filtering, filtrate revolving, silicagel column purifying is crossed, obtains target product, HPLC purity 99.1%, yield 57.3%.
Elementary analysis structure (molecular formula C70H44N8)：Theoretical value C, 84.31；H,4.45；N,11.24；Test value：C,
84.34；H,4.42；N,11.24.ESI-MS(m/z)(M+)：Theoretical value 996.37, measured value 997.18.
Embodiment 12：The synthesis of compound 57：
With embodiment 4, difference is to replace intermediate A 1 with intermediate A 8 preparation method of compound 57.
Elementary analysis structure (molecular formula C56H36N6)：Theoretical value C, 84.82；H,4.58；N,10.60；Test value：C,
84.79；H,4.56；N,10.64.ESI-MS(m/z)(M+)：Theoretical value 792.30, measured value 792.95.
Embodiment 13：The synthesis of compound 65：
With embodiment 4, difference is to replace intermediate A 1 with intermediate B 2 preparation method of compound 65.
Elementary analysis structure (molecular formula C58H36N8)：Theoretical value C, 82.44；H,4.29；N,13.26；Test value：C,
82.43；H,4.24；N,13.23.ESI-MS(m/z)(M+)：Theoretical value 844.31, measured value 844.98.
Embodiment 14：The synthesis of compound 82：
With embodiment 4, difference is to replace intermediate A 1 with intermediate B 3 preparation method of compound 82.
Elementary analysis structure (molecular formula C54H32N4O2)：Theoretical value C, 84.36；H,4.20；N,7.29；O,4.16；Test
Value：C,84.32；H,4.25；N,7.31；O,4.22.ESI-MS(m/z)(M+)：Theoretical value 768.25, measured value are
768.88。
Embodiment 15：The synthesis of compound 84：
With embodiment 4, difference is to replace intermediate A 1 with intermediate B 4 preparation method of compound 84.
Elementary analysis structure (molecular formula C52H34N6)：Theoretical value C, 84.07；H,4.61；N,11.31；Test value：C,
84.11；H,4.64；N,11.33.ESI-MS(m/z)(M+)：Theoretical value 742.28, measured value 742.89.
Embodiment 16：The synthesis of compound 95：
The preparation method of compound 95 is with embodiment 4, and difference is to replace intermediate A 1 with intermediate A 2, with centre
Body C2 replaces intermediate C1.
Elementary analysis structure (molecular formula C56H36N6)：Theoretical value C, 84.82；H,4.58；N,10.60；Test value：C,
84.83；H,4.53；N,10.64.ESI-MS(m/z)(M+)：Theoretical value 792.30, measured value 792.95.
Embodiment 17：The synthesis of compound 105：
The preparation method of compound 105 is with embodiment 4, and difference is to replace intermediate A 1 with intermediate B 5, in
Mesosome C2 replaces intermediate C1.
Elementary analysis structure (molecular formula C62H41N5)：Theoretical value C, 86.99；H,4.83；N,8.18；Test value：C,
87.04；H,4.85；N,8.11.ESI-MS(m/z)(M+)：Theoretical value 855.34, measured value 855.65.
The organic compound of the present invention uses in luminescent device, as CPL layer materials, has high Tg (Glass Transitions
Temperature) temperature, high index of refraction.Hot property and refraction index test are carried out respectively to the compounds of this invention and current material, as a result such as
Shown in table 4.The refraction index test figure of wherein compound 20 is as shown in Figure 2.
Table 4
Note：Glass transition temperature Tg is by differential scanning calorimetry (DSC, German Nai Chi companies DSC204F1 differential scanning calorimetries
Instrument) measure, 10 DEG C/min of heating rate；Refractive index is by ellipsometer (U.S.'s J.A.Woollam Co. models：ALPHA-SE) survey
Amount, is tested as atmospheric environment.
From upper table data, the materials such as CBP, Alq3 and the TPBi applied at present, organic compound of the invention are contrasted
With high glass transition temperature, high index of refraction, simultaneously because containing pyridine and quinoline beautiful jade rigid radical, material ensure that
Heat endurance.Therefore, the present invention is the organic material of core in the CPL layers applied to OLED using pyridine and quinoline beautiful jade
Afterwards, the light extraction efficiency of device can be effectively improved, and ensure that the long-life of OLED.
The OLED material of the invention synthesized is described in detail in device below by way of device embodiments 1~17 and device comparative example 1
Application effect in part.Device embodiments 2~17 of the present invention, the device compared with device embodiments 1 of device comparative example 1
Manufacture craft it is identical, and employed identical baseplate material and electrode material, the thickness of electrode material are also kept
Unanimously, except that the CPL layer materials in 2~14 pairs of devices of device embodiments convert；15~17 pairs of device embodiments
Hole barrier/electron transport layer materials of device convert, the performance test results such as institute of table 5 of each embodiment obtained device
Show.
Device embodiments 1：As shown in figure 1, a kind of electroluminescent device, its preparation process includes：
A) the ito anode layer 2 cleaned on transparent OLED device substrate 1 is clear with deionized water, acetone, EtOH Sonicate respectively
Wash each 15 minutes, then handled 2 minutes in plasma cleaner；B) on ito anode layer 2, vacuum evaporation mode is passed through
Hole injection layer material HAT-CN is deposited, thickness 10nm, this layer is as hole injection layer 3；C) on hole injection layer 3, lead to
Cross vacuum evaporation mode and hole mobile material NPB, thickness 80nm is deposited, the layer is hole transmission layer 4；D) in hole transmission layer
Luminescent layer 5 is deposited on 4, CBP is used as material of main part, Ir (ppy)3As dopant material, Ir (ppy)3With CBP quality
Than for 1:9, thickness 30nm；E) on luminescent layer 5, electron transport material TPBI, thickness are deposited by vacuum evaporation mode
For 40nm, this layer of organic material uses as hole barrier/electron transfer layer 6；F) on hole barrier/electron transfer layer 6,
Vacuum evaporation electron injecting layer LiF, thickness 1nm, the layer is electron injecting layer 7；G) on electron injecting layer 7, vacuum is steamed
Plate negative electrode Mg：Ag/Ag layers, Mg:Ag doping ratios are 9:1, thickness 15nm, Ag thickness 3nm, the layer are cathode layer 8；H) in negative electrode
On layer 8, CPL material compounds 1 are deposited by vacuum evaporation mode, thickness 50nm, this layer of organic material is as CPL layers 9
Use.After the making that electroluminescent device is completed according to above-mentioned steps, the current efficiency of measurement device and life-span, it the results are shown in Table
Shown in 4.The molecular machinery formula of associated materials is as follows：
Device embodiments 2：The CPL layer materials of electroluminescent device are changed into the compounds of this invention 7.Device embodiments 3：It is electroluminescent
The CPL layer materials of luminescent device are changed into the compounds of this invention 13.Device embodiments 4：The CPL layer materials of electroluminescent device are changed into
The compounds of this invention 20.Device embodiments 5：The CPL layer materials of electroluminescent device are changed into the compounds of this invention 32.Device is implemented
Example 6：The CPL layer materials of electroluminescent device are changed into the compounds of this invention 35.Device embodiments 7：The CPL layers of electroluminescent device
Material is changed into the compounds of this invention 46.Device embodiments 8：The CPL layer materials of electroluminescent device are changed into the compounds of this invention 52.
Device embodiments 9：The CPL layer materials of electroluminescent device are changed into the compounds of this invention 57.Device embodiments 10：Electroluminescent cell
The CPL layer materials of part are changed into the compounds of this invention 65.Device embodiments 11：The CPL layer materials of electroluminescent device are changed into this hair
Bright compound 82.Device embodiments 12：The CPL layer materials of electroluminescent device are changed into the compounds of this invention 84.Device embodiments
13：The CPL layer materials of electroluminescent device are changed into the compounds of this invention 95.Device embodiments 14：The CPL layers of electroluminescent device
Material is changed into the compounds of this invention 105.Device embodiments 15：The hole barrier of electroluminescent device/electron transport layer materials become
For the compounds of this invention 20.Device embodiments 16：Hole barrier/electron transport layer materials of electroluminescent device are changed into the present invention
Compound 35.Device embodiments 17：Hole barrier/electron transport layer materials of electroluminescent device are changed into the compounds of this invention
65.Device comparative example 1：The CPL layer materials of electroluminescent device are changed into well known materials Alq3.The detection of gained electroluminescent device
Data are shown in Table 5.
Table 5
It can be seen that the organic compound of the present invention using pyridine and quinoline beautiful jade as core is applied to by the result of table 5
After OLED luminescent devices make, compared with device comparative example 1, light, which takes out, to be obviously improved, and under same current density, device is bright
Degree and device efficiency are obtained for lifting, and because brightness and efficiency get a promotion, power consumption of the OLED in the case where determining brightness is relative
Reduce, service life is also improved.
In order to illustrate material membrane phase crystallization-stable performance of the present invention, by material compound 32 of the present invention and well known materials
CBP has carried out film and has accelerated crystallization experiment：Using vacuum evaporation mode, it is deposited respectively and compound 32 and CBP is vaporized on alkali-free glass
On glass, and it is packaged in glove box (water oxygen content ＜ 0.1ppm), by sample after encapsulation in double 85 (85 DEG C of temperature, humidity
85%) placed under the conditions of, the crystalline state of material membrane periodically observed with microscope (LEICA, DM8000M, 5*10 multiplying power),
Experimental result is as shown in table 6, and material surface form is as shown in Figure 3：
Table 6
| Title material | Compound 32 | CBP |
| After material filming | Smooth surface morphology even uniform | Smooth surface morphology even uniform |
| After experiment 72 hours | Smooth surface morphology even uniform, nodeless mesh | Surface forms some scattered circular crystal planes |
| After experiment 600 hours | Smooth surface morphology even uniform, nodeless mesh | Surface checking |
Above description of test, the membrane crystallization stability of material of the present invention is significantly larger than well known materials, applied to OLED devices
Service life after part has beneficial effect.
Work limitation rate is also more stable at low temperature for OLED prepared by further material of the present invention, and device is real
Apply example 7,8,15 and device comparative example 1 and carry out efficiency test in -10~80 DEG C of sections, acquired results are as shown in table 7 and Fig. 4.
Table 7
It was found from table 7 and Fig. 4 data, device embodiments 7,8,15 are material of the present invention and the device of known materials collocation
Structure, compared with device comparative example 1, not only Efficiency at Low Temperature is high, and in temperature elevation process, efficiency steadily raises.
To sum up, presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, all essences in the present invention
God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.
Claims (11)
1. a kind of organic compound based on pyridine and quinoline beautiful jade, it is characterised in that the structure of the organic compound is as led to
Shown in formula (1)：
In formula (1), X1~X6It is each independent to be expressed as N atoms or C atoms, and N atoms number is 2；
Z is numeral 0,1,2,3 or 4；M, n independently be expressed as numeral 0,1,2 or 3, and m+n+z=4；
In formula (1), Ar1For singly-bound, substituted or unsubstituted C6-60Arlydene, containing one or more heteroatomic substitutions or
Unsubstituted 5~60 yuan of heteroarylidenes；The hetero atom is nitrogen, oxygen or sulphur；
Ar2、Ar3Independently be expressed as substituted or unsubstituted C6-60Aryl, containing one or more heteroatomic substitutions or
Unsubstituted 5-60 unit's heteroaryls；The hetero atom is nitrogen, oxygen or sulphur；Ar2、Ar3It is identical or different；
In formula (1), Ar2、Ar3Can also be independently be expressed as formula (2), formula (3) or structure shown in formula (4)；
Ar in formula (3), formula (4)4It is expressed as substituted or unsubstituted C6-60Arlydene, contain one or more hetero atoms
Substituted or unsubstituted 5~60 unit's heteroaryl；The hetero atom is nitrogen, oxygen or sulphur；
In formula (2), formula (3) or formula (4), R2、R3、R4Independently be expressed as substituted or unsubstituted C6-60Virtue
Base, contain one or more heteroatomic substituted or unsubstituted 5~60 unit's heteroaryls；The hetero atom is nitrogen, oxygen or sulphur；
R2、R3、R4It is identical or different respectively；
In formula (4), x is expressed as integer 1 or 2；
In formula (1), R1It is expressed as structure shown in formula (5) or formula (6)；
Wherein, Ar5、Ar6、Ar7Independently be expressed as substituted or unsubstituted C6-60Aryl, contain one or more hetero atoms
Substituted or unsubstituted 5~60 unit's heteroaryl；The hetero atom is nitrogen, oxygen or sulphur.
2. organic compound according to claim 1, it is characterised in that the structural formula of the compound be formula (I)~
Any of (III)：
3. organic compound according to claim 1, it is characterised in that the structure of the compound be formula (1-1)~
Any of (4-1)：
4. organic compound according to claim 1, it is characterised in that the Ar1、Ar4Independently be expressed as C1-10
Straight or branched alkyl, halogen atom, protium, deuterium, the substituted or unsubstituted phenylene of tritium atom；C1-10Straight or branched alkyl,
Halogen atom, protium, deuterium, the substituted or unsubstituted naphthylene of tritium atom；C1-10Straight or branched alkyl, halogen atom, protium, deuterium,
The substituted or unsubstituted sub- dibiphenylyl of tritium atom；Sub- terphenyl；Anthrylene；C1-10Straight or branched alkyl, halogen atom,
The substituted or unsubstituted sub- pyridine radicals of protium, deuterium, tritium atom；Sub- carbazyl；Sub- pyrimidine radicals；Sub- pyrazinyl；Sub- pyridazinyl；Dibenzo
Furans；9,9- dimethyl fluorenes；N- phenyl carbazoles；Sub- quinolyl；One kind in sub- isoquinolyl or sub- naphthyridines base；The Ar2、
Ar3、Ar5、Ar6、Ar7Independently be expressed as C1-10Straight or branched alkyl, halogen atom, protium, deuterium, tritium atom substitution or not
Substituted phenyl；C1-10Straight or branched alkyl, halogen atom, protium, deuterium, the substituted or unsubstituted naphthyl of tritium atom；C1-10Straight chain
Or branched alkyl, halogen atom, protium, deuterium, the substituted or unsubstituted dibiphenylyl of tritium atom；Terphenyl；Anthryl；C1-10Straight chain
Or branched alkyl, halogen atom, protium, deuterium, the substituted or unsubstituted pyridine radicals of tritium atom；Carbazyl；Pyrimidine radicals；Pyrazinyl；Rattle away
Piperazine base；Dibenzofurans；9,9- dimethyl fluorenes；N- phenyl carbazoles；Quinolyl；One kind in isoquinolyl or naphthyridines base；Ar5、
Ar6、Ar7、R2、R3、R4Independently be expressed as C1-10The substituted or unsubstituted phenyl of straight or branched alkyl, halogen atom；
C1-10The substituted or unsubstituted naphthyl of straight or branched alkyl, halogen atom；C1-10Straight or branched alkyl, halogen atom substitution
Or unsubstituted dibiphenylyl；C1-10The substituted or unsubstituted pyridine radicals of straight or branched alkyl, halogen atom；Carbazyl；Furan
Mutter base；One kind in quinolyl or naphthyridines base.
5. organic compound according to claim 1, it is characterised in that the concrete structure formula of the organic compound is：
In any one.
A kind of 6. preparation method of any one of claim 1~6 organic compound, it is characterised in that the preparation method
Involved reaction equation is：
(1) Ar is worked as2、Ar3When being connected with pyridine with C-C keys, two-step reaction occurs：
The first step is reacted：
Under nitrogen atmosphere, weigh raw material A and be dissolved in tetrahydrofuran, add Ar2-B(OH)2And Pd (PPh3)4, it is stirred
Thing, wet chemical is added, the mixed solution of above-mentioned reactant is heated to reflux 5-15 hours under the conditions of 70-90 DEG C；
After reaction terminates, cooling adds water, extracted with dichloromethane, extract anhydrous sodium sulfate drying, filtering, filtrate revolving, crosses silicon
Glue post purifies, and obtains compound intermediate I；
The raw material A and Ar2-B(OH)2Mol ratio be 1:1.0~4.5, Pd (PPh3)4With the mol ratio of raw material A for 0.001~
0.04:1, the mol ratio of potassium carbonate and raw material A is 1.0~6.0:1, the amount ratio of raw material A and tetrahydrofuran is 1g：10~
30ml；
Second step reacts：
Under nitrogen atmosphere, weigh intermediate compound I and be dissolved in tetrahydrofuran, add Ar3-B(OH)2And Pd (PPh3)4, it is stirred
Thing, wet chemical is added, the mixed solution of above-mentioned reactant is heated to reflux 5-15 hours under the conditions of 70-90 DEG C；
After reaction terminates, cooling adds water, extracted with dichloromethane, extract anhydrous sodium sulfate drying, filtering, filtrate revolving, crosses silicon
Glue post purifies, and obtains compound intermediate II；
The intermediate compound I and Ar3-B(OH)2Mol ratio be 1:1.0~4.5, Pd (PPh3)4Mol ratio with intermediate compound I is
0.001~0.04:1, the mol ratio of potassium carbonate and intermediate compound I is 1.0~6.0:1, the amount ratio of intermediate compound I and tetrahydrofuran is
1g:10~30ml；
(2) Ar is worked as2、Ar3When being connected with pyridine with C-N keys, two-step reaction occurs：
The first step is reacted：
Weigh raw material A and Ar2- H, dissolved with toluene, add Pd2(dba)3, tri-butyl phosphine, sodium tert-butoxide；In inert atmosphere
Under, the mixed solution of above-mentioned reactant is reacted 10~24 hours under the conditions of 95~110 DEG C, cools down simultaneously filtering reacting solution,
Filtrate rotates, and crosses silicagel column, obtains intermediate compound I；
The raw material A and Ar2- H mol ratio is 1:1.0~3, Pd2(dba)3Mol ratio with raw material A is 0.006~0.04:
1, the mol ratio of tri-butyl phosphine and raw material A is 0.006~0.04:1, the mol ratio of sodium tert-butoxide and raw material A is 2.0~3.0:
1；
Second step reacts：
Weigh intermediate compound I and Ar3- H, dissolved with toluene, add Pd2(dba)3, tri-butyl phosphine, sodium tert-butoxide；In indifferent gas
Under atmosphere, the mixed solution of above-mentioned reactant is reacted 10~24 hours under the conditions of 95~110 DEG C, cools down and filters and react molten
Liquid, filtrate revolving, crosses silicagel column, obtains intermediate II；
The intermediate compound I and Ar3- H mol ratio is 1:1.0~3, Pd2(dba)3With the mol ratio of intermediate compound I for 0.006~
0.04:1, the mol ratio of tri-butyl phosphine and intermediate compound I is 0.006~0.04:1, the mol ratio of sodium tert-butoxide and intermediate compound I is
2.0~3.0:1；
(3) Ar is worked as2、Ar3It is connected with pyridine with C-C keys or Ar2、Ar3When being connected with pyridine with C-N keys, occur following
Reaction：
Under nitrogen atmosphere, weigh intermediate II and be dissolved in DMF, addAnd palladium, mixture is stirred,
Aqueous potassium phosphate solution is added, the mixed solution of above-mentioned reactant is heated to reflux 10-24 hours under the conditions of 120-150 DEG C；
After reaction terminates, cooling Jia Shui, mixture being filtered and dried in vacuum drying chamber, gained residue crosses silicagel column purifying,
Obtain target compound；
The intermediate II withMol ratio be 1:1.0~6.0, the mol ratio of palladium and intermediate II is
0.001~0.08:1, the mol ratio of potassium phosphate and intermediate II is 1.0~8.0:1, intermediate II and DMF amount ratio are 1g:
15~50ml.
7. the application of any one of a kind of Claims 1 to 5 organic compound, it is characterised in that described with pyridine and quinoline
Beautiful jade is used to prepare organic electroluminescence device for the organic compound of core.
A kind of 8. organic electroluminescence device containing any one of Claims 1 to 5 organic compound, it is characterised in that
The organic electroluminescence device contains the organic compound based on pyridine and quinoline beautiful jade including at least one layer of functional layer.
9. a kind of organic electroluminescence device containing any one of Claims 1 to 5 organic compound, including hole barrier
Layer/electron transfer layer, it is characterised in that the hole blocking layer/electron transfer layer, which contains, described is based on pyridine and quinoline beautiful jade
Organic compound.
10. a kind of organic electroluminescence device containing any one of Claims 1 to 5 organic compound, including CPL layers,
Characterized in that, the CPL layers contain the organic compound based on pyridine and quinoline beautiful jade.
11. one kind illumination or display element, it is characterised in that the element contains having described in any one of claim 8~10
Organic electroluminescence devices.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111057014A (en) * | 2019-12-27 | 2020-04-24 | 吉林奥来德光电材料股份有限公司 | Organic electroluminescent compound, preparation method thereof and electroluminescent device |
| WO2021029463A1 (en) * | 2019-08-12 | 2021-02-18 | 단국대학교 천안캠퍼스 산학협력단 | Organic material and organic light emitting diode comprising same |
| WO2022092638A1 (en) * | 2020-10-30 | 2022-05-05 | 주식회사 랩토 | Pyrimidin derivative and organic electroluminescent device comprising same |
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| CN106220609A (en) * | 2016-04-25 | 2016-12-14 | 中节能万润股份有限公司 | A kind of compound with pyridine as core and the application on organic electroluminescence device thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021029463A1 (en) * | 2019-08-12 | 2021-02-18 | 단국대학교 천안캠퍼스 산학협력단 | Organic material and organic light emitting diode comprising same |
| CN111057014A (en) * | 2019-12-27 | 2020-04-24 | 吉林奥来德光电材料股份有限公司 | Organic electroluminescent compound, preparation method thereof and electroluminescent device |
| WO2022092638A1 (en) * | 2020-10-30 | 2022-05-05 | 주식회사 랩토 | Pyrimidin derivative and organic electroluminescent device comprising same |
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