CN107663169A - A kind of 6H naphtho-s [2,1,8,7 klmn] acridine derivatives and its application - Google Patents

A kind of 6H naphtho-s [2,1,8,7 klmn] acridine derivatives and its application Download PDF

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CN107663169A
CN107663169A CN201610602533.6A CN201610602533A CN107663169A CN 107663169 A CN107663169 A CN 107663169A CN 201610602533 A CN201610602533 A CN 201610602533A CN 107663169 A CN107663169 A CN 107663169A
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naphtho
klmn
amine
iodo
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CN107663169B (en
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范洪涛
邵爽
任雪艳
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Beijing Eternal Material Technology Co Ltd
Guan Eternal Material Technology Co Ltd
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Beijing Eternal Material Technology Co Ltd
Guan Eternal Material Technology Co Ltd
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Abstract

The present invention relates to a kind of new organic materials, more particularly to a kind of 6H naphtho-s [2,1,8,7 klmn] acridine derivatives for organic electroluminescence device and its application in ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field.6H naphtho-s [2,1,8,7 klmn] a word used for translation derivative of the present invention, torsion bent to a certain degree is formed on space multistory, increases its film forming；And because molecule has sufficiently large conjugated system so that the charge mobility of material is substantially improved.And device evaluation and test data also fully prove, compound-material of the present invention has higher hole transport or hole injection efficiency, for hole injection or hole mobile material, obtained organic electroluminescence device, bright voltage can be effectively reduced, improves current efficiency.

Description

A kind of 6H- naphtho-s [2,1,8,7-klmn] acridine derivatives and its application
Technical field
The present invention relates to a kind of new organic materials, more particularly to a kind of 6H- naphtho-s for organic electroluminescence device [2,1,8,7-klmn] acridine derivatives and its application in ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field.
Background technology
Electroluminescent (electroluminescence, EL) refers to luminescent material under electric field action, by electric current and electricity Exciting and luminous phenomenon, it is an a kind of luminescence process that electric energy is converted into luminous energy.It can produce electroluminescent Luminous solid material is a lot, studies more and can reach use level, mainly inorganic semiconductor material.But nothing The cost of manufacture height of machine El element, processing difficulties, efficiency are low, glow color is not easy condition, than total colouring relatively difficult to achieve, and And the FPD of large area difficult to realize, it further limit the development of inorganxc EL device.1963, Pope and his colleague Organic electroluminescent phenomenon is found that earliest, they have found the single layer crystal of anthracene under the driving of more than 100V voltages, Ke Yifa Go out faint blue light.1987, doctor Deng Qingyun of Eastman Kodak et al. was prepared for brightness height, work using ultra-thin membrane technology Voltage is low, the double-deck organic electroluminescence device of efficiency high, and OLED (OrganicLight Emitting have been opened from this Device research prelude).
The continuous propulsion in two big fields is being illuminated and is showing now with OLED technology, people grind for its core material Study carefully and focus more on, the organic electroluminescence device of an excellent in efficiency long lifespan is typically device architecture and various organic materials Optimize the result of collocation, this functionalization material that various structures are just designed and developed for chemists provides great opportunity and chosen War.
Relative to phosphor, electroluminescent organic material has lot of advantages, such as：Processing characteristics is good, can be with The film forming on any substrate by evaporation or the method for spin coating, it is possible to achieve Flexible Displays and large-area displays；It can pass through Change the structure of molecule, adjust optical property, electric property and stability of material etc., the selection of material has very big sky Between.Typical OLED structure, generally comprise substrate, first electrode, second electrode and be arranged on two and interelectrode have Machine light emitting functional layer.Material wherein for organic luminescence function layer can include according to its function：Hole-injecting material, hole Transmission material, hole barrier materials, electron injection material, electron transport material, electron-blocking materials, light emitting host material, hair Light guest materials etc..For the more preferable luminescent device of processability, industry is directed to developing new organic electroluminescence material always Expect further to improve the luminous efficiency of device and life-span.
Hole-injecting material (HIM) requires its HOMO energy level between anode and hole transmission layer, is advantageous to increase boundary Hole injection between face.Hole mobile material (HTM), it is desirable to there is high heat endurance (high Tg), with anode or sky Hole injection material has less potential barrier, and higher cavity transmission ability can vacuum evaporation formation pin-hole free films.Sent out in Organic Electricity The hole injection used always in optical device and transmission material are usually an aromatic amino-derivative, and its in general is structurally characterized in that work For injection material when, one arylamine construction unit is at least at more than one in a molecule, and with a phenyl ring between two N Separate；And when being used as transmission material, one arylamine construction unit is usually two in a molecule, and with connection between two N Benzene separates, and in this kind of material, typical example is NPB.
Chinese granted patent CN103183638B and CN103183664B protects one kind to carry diaryl-amine group and carbazole The naphthacridine mother nucleus structure compound of group substitution, it is utilized respectively the different holes of triaryl amine unit structure and carbazole group Transport property collocation naphthacridine parent specific to electronic effect, make such compound turn into have superior hole injection and The hole transport and material of main part of transport property.However, hole injection and transmission material also need in terms of organic electroluminescent There is bigger room for improvement, to meet the needs of OLED and screen body performance step up, therefore industry needs exploitation badly newly Hole mobile material and hole-injecting material, there is critically important application value.
The content of the invention
Therefore, the present invention provide firstly a kind of new 6H- naphtho-s [2,1,8,7- to solve above-mentioned technical problem Klmn] acridine derivatives, and further disclose its preparation method.
Secondly, the invention provides the application that said derivative is used for ORGANIC ELECTROLUMINESCENCE DISPLAYS field, specifically institute Derivative is stated in display of organic electroluminescence, as hole-injecting material, hole mobile material and material of main part.
In order to solve the above technical problems, 6H- naphtho-s [2,1,8,7-klmn] acridine derivatives of the present invention, have such as Structural formula shown in formula (M)：
Wherein, Ar1And Ar2It is independent of each other to be selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C4- C30 heteroaryls；Or the Ar1And Ar2It is interconnected to aromatic ring or aliphatic ring；
R1To R8It is independent of each other to be selected from H, substitution or unsubstituted alkyl or amido, substituted or unsubstituted aryl or ring Aryl, substituted or unsubstituted condensed-nuclei aromatics base or condensed hetero ring aryl；
The L is singly-bound, substituted or unsubstituted aromatic ring or heteroaromatic.
Hetero atom in the heteroaryl or condensed hetero ring aryl is at least one hetero atom in N, O, S.
Preferably, the aryl include phenyl, xenyl, naphthyl, anthryl, phenanthryl, fluorenyl and its derivative, fluoranthene base, Sanya phenyl, pyrenyl, base or base；
The heteroaryl includes dibenzofuran group, thienyl, benzothienyl, dibenzothiophenes base or carbazyl.
More excellent, the Ar1And Ar2It is independent of each other to be selected from following group：
More excellent, the Ar1And Ar2It is interconnected to the aromatic ring or aliphatic ring of following structure：
Preferably, the alkyl includes methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary fourth Base, amyl group, cyclohexyl etc.；
The amido includes diaryl-amine；
The aryl includes phenyl, tolyl, ethylbenzene, xylyl, tert-butyl-phenyl, xenyl；
The heterocyclic arene base include furans, benzofuran, dibenzofurans, thiophene, benzothiophene, dibenzothiophenes, Carbazole, pyridine, indoles, pyrazine, 2.4- methyl isophthalic acid .3.5 triazines, 4.6 diphenylpyrimidins；
The condensed-nuclei aromatics base includes naphthyl, phenanthryl, anthryl, pyrenyl, 9.9- dimethyl -2- fluorenyls.
Optimal, the derivative is selected from structure shown in following M1-M54：
It is used to prepare organic electroluminescence hair the invention also discloses described 6H- naphtho-s [2,1,8,7-klmn] acridine derivatives The application of optical device.
Specifically, 6H- naphtho-s [2,1,8, the 7-klmn] acridine derivatives are used as hole mobile material, hole injection material Material and/or light emitting host material.
The invention also discloses a kind of organic electroluminescence device, including substrate, and sequentially form on the substrate Anode layer, organic luminescence function layer and cathode layer；
The organic luminescence function layer includes hole injection layer, hole transmission layer, organic luminous layer and electron transfer layer；
The hole-injecting material and/or the sky of the material of main part of the organic luminous layer and/or the hole injection layer The hole mobile material of cave transport layer includes at least one described 6H- naphtho-s [2,1,8,7-klmn] acridine derivatives material.
The invention discloses a kind of 6H- naphtho-s [2,1,8,7-klmn] acridine derivatives, are formed on space multistory certain Degree is bent to be turned round, and increases its film forming.And because molecule has sufficiently large conjugated system so that the charge mobility of material is big Width is lifted.And device test and appraisal data also fully prove that compound-material of the present invention has higher hole transport or hole Injection efficiency, for hole injection or hole mobile material, obtained organic electroluminescence device, it can effectively reduce bright Voltage, improve current efficiency.
Brief description of the drawings
In order that present disclosure is more likely to be clearly understood, specific embodiment and combination below according to the present invention Accompanying drawing, the present invention is further detailed explanation, wherein,
Fig. 1 is 6H- naphtho-s [2,1,8,7-klmn] acridine derivatives M0 of the present invention mass-spectrogram；
Fig. 2 be compound M5 nuclear magnetic spectrogram carbon spectrum (13C)；
Fig. 3 be compound M10 nuclear magnetic spectrogram carbon spectrum (13C)；
Fig. 4 be compound M18 nuclear magnetic spectrogram carbon spectrum (13C)；
Fig. 5 be compound M33 nuclear magnetic spectrogram carbon spectrum (13C)；
Fig. 6 be compound M52 nuclear magnetic spectrogram carbon spectrum (13C)。
Embodiment
Dichloro pyrimidine used, trichloropyrimidine, dichloropyrazine, Cyanuric Chloride, aryl boric acid carbazole, aryl are secondary in the present invention Amine, four (triphenyl phosphorus) palladiums, lithium hydroxide, thionyl chloride, alchlor, bromine, potassium acetate, potassium carbonate, diphenylamines, toluene, It the basic chemical industry raw material such as tetrahydrofuran, chemical products can be commercially available at home, or prepare factory in relevant organic intermediate and determine Do；
Boric acid when preparing compound of the present invention used in coupling reaction is by purchase, or according to Patents Document prepares (CN2012105910269, D.J.Hall, Boronic Acids:Preparation and applications in Organic Synthesis andMedicine,Wiley-Vch,2005)。
Embodiment 1
The present embodiment is according to following circuit formula (M0) shown in structure intermediate：
The present embodiment method with reference to shown in Chinese patent CN103570620A, is synthesized in accordance with the following steps：
(1) P1 synthesis
In 500 milliliters of there-necked flasks, add the bromo- 2- methyl naphthalenes of 1-, the concentrated sulfuric acid, 1,2- dichloroethane feedstocks and mix, temperature control Less than 0 DEG C, nitric acid is slowly added dropwise under stirring, is kept for 0-5 DEG C stir 2 hours, is slowly poured into frozen water, liquid separation simultaneously uses organic layer Washing, separated after drying using silica gel column chromatography, and using volume ratio as 1：2 ethyl acetate-light petrol elution, is obtained shallow Yellow product P1；
(2) P2 synthesis
In 500 milliliters of there-necked flasks, add obtained P1 in step (1), carbon tetrachloride, N- bromo-succinimides and lack Benzoyl peroxide, backflow cooling and filtering reacting liquid are measured, is separated after mother liquor concentrations are dry using silica gel column chromatography, and with volume ratio For 1：5 ethyl acetate-light petrol elution, obtains yellow solid P2；
(3) P3 synthesis
In 500 milliliters of there-necked flasks, obtained P2, Trimethyl phosphite in step (2) are added, under nitrogen protection, oil The lower back flow reaction of bath 4 hours, slow cooling, and the bromo- 3- nitrobenzaldehydes of tetrahydrofuran, sodium hydride, 2- are added, it is to slowly warm up to 40 DEG C are reacted 2 hours, then are warming up to 55 DEG C and are reacted 2 hours；Absolute ethyl alcohol, which is slowly added to, after backflow cooling decomposes excessive hydrogenation Sodium, after stirring 30 minutes, reaction solution is poured into 500 milliliters of water, stirred 2 hours, reaction product, and water are extracted with dichloromethane Dichloromethane extract is washed to neutrality, is dried with sodium sulphate, is concentrated to dryness with organic layer, separated using silica gel column chromatography, and with Volume ratio is 1：2 ethyl acetate-light petrol elution, obtains yellow solid P3；
(4) P4 synthesis
In 250 milliliters of there-necked flasks, under argon gas protection, add obtained in 150 milliliters of dimethylbenzene, step (3) P38.0g, copper powder 1g are mixed, and back flow reaction 48 hours, are filtered after cooling, and wash filtrate with dichloromethane, and mother liquor divides after merging Liquid, water layer is extracted with dichloromethane, and dried with magnesium sulfate, then separated using silica gel column chromatography, and using volume ratio as 1：2 Ethyl acetate-light petrol elution, obtain yellow solid P4 4.16g, measure MS (m/e)：318, calculate product yield 78.1%；
(5)M0Synthesis
In 500 milliliters of there-necked flasks, add obtained P4 in step (4) and add ethanol, water, sodium hydroxide mixing, rise Temperature flows back 2 hours to flowing back after then adding zinc powder, filtering and liquid separation after cooling, washing organic layer to neutrality, is steamed after drying It is dry, separated using silica gel column chromatography, and using volume ratio as 1：6 ethyl acetate-light petrol elution, obtains pale yellow colored solid Body M0。
To the M of acquisition0Solid Mass Spectrometer Method, its mass-spectrogram is as described in Fig. 1, it is seen then that its product structure is correct.
Embodiment 2
Compound of the present embodiment shown according to following synthetic route formula M1：
Under nitrogen protection, DMPU (1,3- DMPU), the intermediate prepared in embodiment 1 are added in there-necked flask M0, 7- iodo- N, N- mix to toluene triphenylene -2- amine, potassium carbonate, cuprous iodide, and 18- crown-s 6, and oil bath heating backflow 2 is small When, cool and simultaneously reaction solution be poured into distilled water, extracted with dichloromethane, and dried with magnesium sulfate, after concentration is dry with ethanol and Toluene Mixed Solvent crystallizes, and obtains slightly yellow solid M1.
Embodiment 3
The present embodiment synthesis compound M2 preparation method is same as Example 2, and it is differed only in the iodo- N of raw material 7-, N- replaces with 6,6,9,12,12- pentamethyls-biphenyl -6,12- [1,2-b] N, N- to toluene triphenylene -2- amine to toluene Sanya Benzene -2- amine, other raw materials and preparation method are identical.
Embodiment 4
The present embodiment synthesis compound M3 preparation method is same as Example 2, and it is differed only in the iodo- N of raw material 7-, N- replaces with the iodo- N of 8-, N- dibenzo thiophenes [2,3-f] benzothiophene -8- amine, other raw materials and system to toluene triphenylene -2- amine Preparation Method is identical.
Embodiment 5
The present embodiment synthesis compound M4 preparation method is same as Example 2, and it is differed only in the iodo- N of raw material 7-, N- replaces the iodo- 11,11- dimethyl-N -s benzene -11H- benzos [b] of N- (4- (tert-butyl group) phenyl) -3- to toluene triphenylene -2- amine Fluorenes [2,3-d] thiophene -9- amine, other raw materials and preparation method are identical.
Embodiment 6
The present embodiment synthesis compound M5 preparation method is same as Example 2, and it is differed only in the iodo- N of raw material 7-, N- replaces 8- iodo- N, N, 5 to toluene triphenylene -2- amine, 11, -4 phenyl -5,11- indoles simultaneously [3,2-b] carbazole -2- amine, other Raw material and preparation method are identical.Nuclear-magnetism carbon spectrum detection is carried out to the compound of acquisition, its nuclear-magnetism carbon spectrogram is composed as shown in Figure 2, It can be seen that product structure is correct.
Embodiment 7
The present embodiment synthesis compound M6 preparation method is same as Example 2, and it is differed only in the iodo- N of raw material 7-, N- replaces the iodo- 11,11- dimethyl -11H- benzos of N- (3- hexamethylenes)-N- (4- hexamethylenes) -2- to toluene triphenylene -2- amine [b] fluorenes [2,3-d] thiophene -8- amine, other raw materials and preparation method are identical.
Embodiment 8
The present embodiment synthesis compound M7 preparation method is same as Example 2, and it is differed only in the iodo- N of raw material 7-, N- replaces iodo- 9- benzene-N, N-di-p- the tolyl -9H- carbazole -3- amine of 6-, other raw materials and system to toluene triphenylene -2- amine Preparation Method is identical.
Embodiment 9
Compound of the present embodiment shown according to following synthetic route formula M8：
Synthesis compound P5 preparation method is same as Example 2, and it is differed only in the iodo- N of raw material 7-, and N- is to toluene Triphenylene -2- amine replace N- (3- cyclohexyl phenyls) -7- iodo- N- (naphthalene -2-yl) -9- benzene -9H- carbazole -2- amine, other raw materials with And preparation method is identical.
20 milliliters of DMF of addition, compound P5 are stirred and evenly mixed in there-necked flask, control 30-35 DEG C of temperature, and bromine containing N- is added dropwise For the DMF solution of succimide, 30-35 DEG C of computer heating control is reacted 6 hours, and reaction solution is poured into distilled water, is filtered, adopted second Alcohol and chloroform mixed solvent recrystallization, obtain yellow solid M8.
Embodiment 10
The present embodiment synthesis compound M9 preparation method is same as Example 2, and it is differed only in the iodo- N of raw material 7-, N- replaces N, N- ([1,1- biphenyl -] 3) the iodo- dibenzo of -7- [b, d] furans -3- amine, other raw materials to toluene triphenylene -2- amine And preparation method is identical.
Embodiment 11
Compound of the present embodiment shown according to following synthetic route formula M10：
The present embodiment enters with reference to the building-up process of the presoma S4 disclosed in embodiment 4 in Chinese patent CN103664894A Row compound M10 preparation, it, which is differed only in, changes the raw material aniline in the first step into N2- 4- [1,1- phenylbenzenes] -9,9- Dimethyl-N2-2- naphthalene 9H- fluorenes -2,7- diamines, other raw materials and preparation method are identical.Nuclear-magnetism is carried out to the compound of acquisition Carbon spectrum detection, its nuclear-magnetism carbon spectrogram are composed as shown in Figure 3, it is seen then that product structure is correct.
Embodiment 12
The present embodiment synthesis compound M11 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace N- (4- (7- iodine dibenzo [b, d] thiophene -3) phenyl)-N- (naphthalene -1-yl) naphthalene -1- to toluene triphenylene -2- amine Amine, other raw materials and preparation method are identical.
Embodiment 13
The present embodiment synthesis compound M12 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace N- (4- (8- iodine dibenzo [b, d] thiophene -2) phenyl)-N- (naphthalene -2-yl) naphthalene -2- to toluene triphenylene -2- amine Amine, other raw materials and preparation method are identical.
Embodiment 14
The present embodiment synthesis compound M13 preparation method is same as Example 9, and it differs only in raw material 7- is iodo- N, N- replace N- (4- [1,1- biphenyl]) -7- iodo- 9,9- dimethyl-N -s (2- naphthalenes) -9H- fluorenes -2- to toluene triphenylene -2- amine Amine, other raw materials and preparation method are identical.
Embodiment 15
The present embodiment synthesis compound M14 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace N- (3- [1,1- biphenyl]) -6- iodo- 9,9- dimethyl-N -s (1- naphthalenes) -9H- fluorenes -3- to toluene triphenylene -2- amine Amine, other raw materials and preparation method are identical.
Embodiment 16
The present embodiment synthesis compound M15 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace N- (4- [1,1- biphenyl])-N- (the iodo- 4- of 4- [1,1- biphenyl]) phenanthrene -9- amine to toluene triphenylene -2- amine, and other are former Material and preparation method are identical.
Embodiment 17
The present embodiment enters with reference to the building-up process of the presoma S4 disclosed in embodiment 4 in Chinese patent CN103664894A Row compound M16 preparation, it, which is differed only in, changes the raw material aniline in the first step into N3-2-N3- 9- phenanthrene-[1,1- di-s Benzene] -3,4- diamines, other raw materials and preparation method are identical.
Embodiment 18
The present embodiment synthesis compound M17 preparation method is same as Example 9, and it is differed only in raw material N- (4- Iodo- 3- [1,1- biphenyl]-N- (9- is luxuriant and rich with fragrance) phenanthrene -9- amine is replaced, and other raw materials and preparation method are identical.
Embodiment 19
The present embodiment synthesis compound M18 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- to toluene triphenylene -2- amine replace N- (4- (8- iodine dibenzo [b, d] thiophene -2-yl) phenyl)-N- (naphthalene -2-yl) naphthalene - 2- amine, other raw materials and preparation method are identical.Nuclear-magnetism carbon spectrum detection is carried out to the compound of acquisition, its nuclear-magnetism carbon spectrogram spectrum is shown in Shown in Fig. 4, it is seen then that product structure is correct.
Embodiment 20
The present embodiment synthesis compound M19 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace N- (iodo- (4- [1,1- biphenyl]-N- (2- is luxuriant and rich with fragrance) phenanthrene -2- amine, other raw materials and systems of 3- to toluene triphenylene -2- amine Preparation Method is identical.
Embodiment 21
The present embodiment synthesis compound M20 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace N- (3- [1,1- biphenyl])-N- (benzene -9H- carbazoles -2- of the iodo- 4- of 3- [1,1- biphenyl] -9 to toluene triphenylene -2- amine Amine, other raw materials and preparation method are identical.
Embodiment 22
The present embodiment synthesis compound M21 preparation method is same as Example 2, and it is differed only in raw material N- (4- Iodobenzene) -9- benzene-N- (9- benzene -9H-3- carbazoles) -9H- carbazole -3- amine, other raw materials and preparation method are identical.
Embodiment 23
The present embodiment synthesis compound M22 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace N- (the iodo- 4- of 4- [1,1 ', 4 ', 1 "-terphenyl])-N- (2- naphthalenes) -9- benzene -9H- clicks to toluene triphenylene -2- amine Azoles -4- amine, other raw materials and preparation method are identical.
Embodiment 24
The present embodiment synthesis compound M23 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace N- (the iodo- 3- of 4- [1, Isosorbide-5-Nitrae, 1- terphenyls])-N- (2- naphthalenes) pyrene -2- amine, other raw materials to toluene triphenylene -2- amine And preparation method is identical.
Embodiment 25
The present embodiment synthesis compound M24 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- to toluene triphenylene -2- amine replace N- (4- [1,1- terphenyls])-N-3- (4- iodo- [1,1,3,1- terphenyls] -3) pyrene - 1- amine, other raw materials and preparation method are identical.
Embodiment 26
The present embodiment synthesis compound M25 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- to toluene triphenylene -2- amine replace N- (4- iodo- [1,1,3,1- terphenyl])-N- (1- naphthalenes) pyrene -4- amine, other raw materials with And preparation method is identical.
Embodiment 27
The present embodiment synthesis compound M26 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- to toluene triphenylene -2- amine replace N- (4- [1,1- terphenyls])-N- (the iodo- 4- of 3- [1,1,3,1- terphenyls]) fluoranthene - 3- amine, other raw materials and preparation method are identical.
Embodiment 28
The present embodiment synthesis compound M27 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- to toluene triphenylene -2- amine replace N- (the iodo- 3- of 4- [1,1- terphenyl])-N- (2- naphthalenes) fluoranthene -3- amine, other raw materials with And preparation method is identical.
Embodiment 29
The present embodiment synthesis compound M28 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- to toluene triphenylene -2- amine replace N- (8- fluoranthene)-N- (5- iodine naphthalene) -9- benzene -9H- carbazole -3- amine, other raw materials and Preparation method is identical.
Embodiment 30
The present embodiment synthesis compound M29 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- to toluene triphenylene -2- amine replace N- (5- iodine naphthalene)-N- (4- methyl -3- [1,1- biphenyl]) -3- amine, other raw materials and Preparation method is identical.
Embodiment 31
The present embodiment synthesis compound M30 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace N-2- (5- iodine naphthalene)-N- (2- naphthalenes) -3- amine to toluene triphenylene -2- amine, and other raw materials and preparation method are identical.
Embodiment 32
The present embodiment synthesis compound M31 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- to toluene triphenylene -2- amine replace N- (4- (tert-butyl group) benzene-N- (the iodo- 4- of 4- [1,1- biphenyl]) dibenzofurans [b, D] -2- amine, other raw materials and preparation method are identical.
Embodiment 33
The present embodiment synthesis compound M32 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- to toluene triphenylene -2- amine replace N- (4- [1,1- biphenyl]-N- (7-9,9- diformazan -9H- bases fluorenes) dibenzofurans [b, D] -2- amine, other raw materials and preparation method are identical.
Embodiment 34
The present embodiment synthesis compound M33 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace N- (7- iodine phenanthrene -2)-N- (1- naphthalenes) dibenzofurans [b, d] -1- amine to toluene triphenylene -2- amine, other raw materials with And preparation method is identical.Nuclear-magnetism carbon spectrum detection is carried out to the compound of acquisition, its nuclear-magnetism carbon spectrogram is composed as shown in Figure 5, it is seen then that production Thing structure is correct.
Embodiment 35
The present embodiment synthesis compound M34 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- to toluene triphenylene -2- amine replace N- (3- dibenzofurans [b, d]-N-4- (and iodo- [1,1- the biphenyl] -3- amine of 4-, other Raw material and preparation method are identical.
Embodiment 36
The present embodiment synthesis compound M35 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace N- (the iodo- 4- of 4- [1,1- biphenyl])-N- (1- naphthalenes) dibenzofurans [b, d] -3- amine to toluene triphenylene -2- amine, Other raw materials and preparation method are identical.
Embodiment 37
The present embodiment synthesis compound M36 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace N- (4- iodobenzenes)-N- triphenylene -2- amine to toluene triphenylene -2- amine, and other raw materials and preparation method are identical.
Embodiment 38
The present embodiment synthesis compound M37 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace N- (4- iodo- 4 [1,1- biphenyl])-N- (1- naphthalenes) dibenzothiophenes [b, d] -2- amine to toluene triphenylene -2- amine, its His raw material and preparation method are identical.
Embodiment 39
The present embodiment synthesis compound M38 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace N- (4 [1,1- biphenyl])-N- (7- phenanthrene -3) dibenzo [b, d] thiophene -1- amine to toluene triphenylene -2- amine, other Raw material and preparation method are identical.
Embodiment 40
The present embodiment synthesis compound M39 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace N- (the iodo- 4- of 4- [1,1- biphenyl])-N- (1- naphthalenes) dibenzo [b, d] thiophene -3- amine to toluene triphenylene -2- amine, Other raw materials and preparation method are identical.
Embodiment 41
The present embodiment synthesis compound M40 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- to toluene triphenylene -2- amine replace N- (3- [1,1- biphenyl])-N- (the iodo- 4- of 4- [1,1- biphenyl] benzo [b, d] naphthalene [2, 3-d] thiophene -2- amine, other raw materials and preparation method are identical.
Embodiment 42
The present embodiment synthesis compound M41 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace N- (4- iodo- [1,1,4,1- terphenyls])-N- (1- naphthalenes) benzo [b] naphthalene [2,1-d] thiophene to toluene triphenylene -2- amine Fen -8- amine, other raw materials and preparation method are identical.
Embodiment 43
The present embodiment synthesis compound M42 preparation method is same as Example 2, and it is differed only in raw material N- (7- Iodine terphenyl) (1- naphthalenes benzo [b] naphtho- [1,2-d] thiophene -10- amine, other raw materials and preparation method are identical by-N-.
Embodiment 44
The present embodiment synthesis compound M43 preparation method is same as Example 2, and it is differed only in raw material N- (4- Iodo- [1,1- biphenyl]) luxuriant and rich with fragrance [9, the 10-d] thiophene -12- amine of-N- (1- naphthalenes) benzos [b], other raw materials and preparation method are identical.
Embodiment 45
The present embodiment synthesis compound M44 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- to toluene triphenylene -2- amine replace N- (the iodo- 4- of 4- [1,1- biphenyl])-N, 5- tolylthiophene 2- amine, other raw materials and Preparation method is identical.
Embodiment 46
The present embodiment synthesis compound M45 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace 9- (the iodo- 4- of 4- [1, Isosorbide-5-Nitrae, 1- terphenyls]) -3,6- biphenyl -9H- carbazoles to toluene triphenylene -2- amine, and other are former Material and preparation method are identical.
Embodiment 47
The present embodiment synthesis compound M46 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace 7- (7- iodobenzenes simultaneously [b, d] furans) -7H- benzos [c] carbazole, other raw materials and system to toluene triphenylene -2- amine Preparation Method is identical.
Embodiment 48
The present embodiment synthesis compound M47 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace 5- (7- iodobenzenes simultaneously [b, d] thiophene) -5H- benzos [b] carbazole, other raw materials and system to toluene triphenylene -2- amine Preparation Method is identical.
Embodiment 49
The present embodiment synthesis compound M48 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- to toluene triphenylene -2- amine replace 11- (the iodo- 9- benzene -9H-2- carbazoles of 7-) -11H- benzos [a] carbazole, other raw materials with And preparation method is identical.
Embodiment 50
The present embodiment synthesis compound M49 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace 7- (iodo- 9,9- dimethyl -9H- fluorenes [b, the g] carbazoles of 7-, other raw materials and preparation side to toluene triphenylene -2- amine Method is identical.
Embodiment 51
The present embodiment synthesis compound M50 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace 10- (the iodo- 9- benzene -9H- carbazoles of 7-) -9,9- dimethyl -9,10- acridans to toluene triphenylene -2- amine, other Raw material and preparation method are identical.
Embodiment 52
The present embodiment synthesis compound M51 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace 5- (8- iodobenzenes simultaneously [b, d] furans) -5H- dibenzo [b, f] azatropylidene, other raw materials to toluene triphenylene -2- amine And preparation method is identical.
Embodiment 53
The present embodiment synthesis compound M52 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace 9- (iodo- 9, the 9- dimethyl -9H- of 6-) three benzos [b, d, f] azatropylidene, other raw materials to toluene triphenylene -2- amine And preparation method is identical.
Embodiment 54
The present embodiment synthesis compound M53 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace 7- (3- iodo- [1, Isosorbide-5-Nitrae, 1- terphenyls]) -7H- benzos [a, g] carbazole, other raw materials to toluene triphenylene -2- amine And preparation method is identical.Nuclear-magnetism carbon spectrum detection is carried out to the compound of acquisition, its nuclear-magnetism carbon spectrogram is composed as shown in Figure 6, it is seen then that Product structure is correct.
Embodiment 55
The present embodiment synthesis compound M54 preparation method is same as Example 2, and it differs only in raw material 7- is iodo- N, N- replace 7- (4- iodo- [1, Isosorbide-5-Nitrae, 1- terphenyls]) -7H- dibenzo [c, g] carbazole to toluene triphenylene -2- amine, and other are former Material and preparation method are identical.
Device application examples
The luminescent layer and organic electroluminescence device of organic electroluminescence device of the invention are illustrated below.
The structure of OLED is in the application example：Substrate/anode (ITO)/hole injection layer (HIL)/hole transmission layer (HTL) organic luminous layer (EL) of/dopant dye/electron transfer layer (ETL)/negative electrode (metal electrode).Above-mentioned "/" represents different It is laminated in order between functional layer.
Electroluminescent device of the present invention is conventional structure, and substrate can be sent out using conventional organic luminescence organic electroluminescence Substrate in optical device, such as：Glass or plastics.Anode material can use transparent high conductivity material, such as indium tin oxygen (ITO), indium zinc oxygen (IZO), tin ash (SnO2), zinc oxide (ZnO) etc.；Hole injection layer (HIL) material can be used various Easily provide more arylamine of electronics；Hole mobile material can use various suitable tri-arylamine group materials；Organic luminous layer by Light emitting host material and dopant material composition；Electron transport layer materials can select it is all kinds of common are many materials, including Alq3, BPhen etc.；Negative electrode can use metal and its mixture structure, such as Mg：Ag、Ca：Ag etc. or electron injection Layer/metal-layer structure, such as LiF/Al, Li2O/Al common cathode structure.
In the following organic electroluminescence devices being used for technique effect contrast of embodiment, from glass substrate, ITO makees Anode material, hole-injecting material select 2-TNATA, and hole mobile material selects NPB, the material of main part choosing of luminous organic material With ADN, luminescent dopant material is DSA-Ph, and electron transport material selects common Bphen, and cathode material selects LiF/Al.
Wherein 2-TNATA, NPB, ADN, DSA-Ph and Bphen structure is respectively：
The preparation process of each organic electroluminescence device (including comparative device) is as follows in the following application examples of the present invention：
The glass plate for being coated with transparent conductive layer is ultrasonically treated in commercial detergent, rinsed in deionized water, In acetone：Ultrasonic oil removing in alcohol mixed solvent, it is baked under clean environment and removes moisture content completely, it is clear with ultraviolet light and ozone Wash, and with low energy cation beam bombarded surface；
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 2 × 10-5-2×10-4Pa, above-mentioned Vacuum evaporation 2-TNATA or particular compound of the present invention are as hole injection layer, evaporation rate 0.1nm/ on anode tunic S, evaporation thickness are 50nm；
Particular compound in one layer of NPB or the present invention is deposited again on hole injection layer as hole transmission layer, Evaporation rate is 0.1nm/s, and evaporation thickness is 40nm；
On hole transmission layer by the way of codope vacuum evaporation light emitting host layer ADN and DSA-Ph (ratio 95%：5%), evaporation rate 0.1nm/s, evaporation total film thickness are 30nm；
One layer of BPhen of vacuum evaporation is distinguished on luminescent layer as electron transport material, its evaporation rate is 0.1nm/ S, evaporation total film thickness are 20nm；
Vacuum evaporation thickness is 0.5nm LiF as electron injecting layer, thickness 150nm on electron transfer layer (ETL) Negative electrode of the Al layers as device.
Device application examples 1
Compound is as the hole-injecting material in organic electroluminescence device in the application example, according to aforementioned preparation process Multiple organic electroluminescence devices are prepared for altogether, and its structure is：ITO/ hole-injecting materials (50nm)/NPB (40nm) ADN： DSA-Ph(30nm)/Bphen(20nm)/LiF(0.5nm)/Al(150nm)。
Contrast in organic electroluminescence device, hole-injecting material selects 2-TNATA, the choosing of remaining organic electroluminescence device The material described in following table, and the performance of each organic electroluminescence device is detected, record to table 1 below.
Results of property of 1 compound of the present invention of table as hole-injecting material
Above testing result shows that new organic materials of the invention are used for organic electroluminescence device, can be effective Bright voltage is reduced, current efficiency is improved, is hole-injecting material of good performance.
Device application examples 2
Compound is as the hole mobile material in organic electroluminescence device in the application example, according to aforementioned preparation process Multiple organic electroluminescence devices are prepared for altogether, and its structure is：ITO/2-TNATA (50nm)/hole mobile material (40nm)/ ADN：DSA-Ph(30nm)/Bphen(20nm)/LiF(0.5nm)/Al(150nm).
Contrast in organic electroluminescence device, hole mobile material selects NPB, under the selection of remaining organic electroluminescence device Material described in table, and the performance of each organic electroluminescence device is detected, record to table 2 below.
Results of property of 2 compound of the present invention of table as hole mobile material
Above test result shows that new organic materials of the invention are used for the hole transport material of organic electroluminescence device Material, bright voltage can be effectively reduced, improve current efficiency, be hole mobile material of good performance.
Obviously, above-described embodiment is only intended to clearly illustrate example, and is not the restriction to embodiment.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or Among changing still in the protection domain of the invention.

Claims (10)

1. a kind of 6H- naphtho-s [2,1,8,7-klmn] acridine derivatives, it is characterised in that there is the structural formula as shown in formula (M)：
Wherein, Ar1And Ar2It is independent of each other miscellaneous selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C4-C30 Aryl；Or the Ar1And Ar2It is interconnected to aromatic ring or aliphatic ring；
R1To R8It is independent of each other to be selected from H, substitution or unsubstituted alkyl or amido, substituted or unsubstituted aryl or PAH Base, substituted or unsubstituted condensed-nuclei aromatics base or condensed hetero ring aryl；
The L is singly-bound, substituted or unsubstituted aromatic ring or heteroaromatic.
2. 6H- naphtho-s [2,1,8,7-klmn] acridine derivatives according to claim 1, it is characterised in that the heteroaryl Hetero atom in base or condensed hetero ring aryl is at least one hetero atom in N, O, S.
3. 6H- naphtho-s [2,1,8,7-klmn] acridine derivatives according to claim 1 or 2, it is characterised in that：
The aryl includes phenyl, xenyl, naphthyl, anthryl, phenanthryl, fluorenyl and its derivative, fluoranthene base, Sanya phenyl, pyrene Base, base or base；
The heteroaryl includes dibenzofuran group, thienyl, benzothienyl, dibenzothiophenes base or carbazyl.
4. according to any described 6H- naphtho-s [2,1,8, the 7-klmn] acridine derivatives of claim 1-3, it is characterised in that institute State Ar1And Ar2It is independent of each other to be selected from following group：
5. according to any described 6H- naphtho-s [2,1,8, the 7-klmn] acridine derivatives of claim 1-3, it is characterised in that institute State Ar1And Ar2It is interconnected to the aromatic ring or aliphatic ring of following structure：
6. 6H- naphtho-s [2,1,8,7-klmn] acridine derivatives according to claim 1-5, it is characterised in that：
The alkyl includes methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, amyl group, hexamethylene Base etc.；
The amido includes diaryl-amine；
The aryl includes phenyl, tolyl, ethylbenzene, xylyl, tert-butyl-phenyl, xenyl；
The heterocyclic arene base include furans, benzofuran, dibenzofurans, thiophene, benzothiophene, dibenzothiophenes, carbazole, Pyridine, indoles, pyrazine, 2.4- methyl isophthalic acid .3.5 triazines, 4.6 diphenylpyrimidins；
The condensed-nuclei aromatics base includes naphthyl, phenanthryl, anthryl, pyrenyl, 9.9- dimethyl -2- fluorenyls.
7. 6H- naphtho-s [2,1,8,7-klmn] acridine derivatives according to claim 1-6, it is characterised in that described to spread out Biology is selected from structure shown in following M1-M54：
8. any described 6H- naphtho-s [2,1,8,7-klmn] acridine derivatives of claim 1-7 are used to prepare organic electroluminescence hair The application of optical device.
9. application according to claim 8, it is characterised in that 6H- naphtho-s [2,1,8, the 7-klmn] acridine derivatives As hole mobile material, hole-injecting material and/or light emitting host material.
10. a kind of organic electroluminescence device, including substrate, and sequentially form anode layer, You Jifa on the substrate Light functional layer and cathode layer；
The organic luminescence function layer includes hole injection layer, hole transmission layer, organic luminous layer and electron transfer layer；It is special Sign is：
The material of main part of the organic luminous layer and/or the hole-injecting material of the hole injection layer and/or the hole pass The hole mobile material of defeated layer includes any described 6H- naphtho-s [2,1,8,7-klmn] acridines of at least one claim 1-7 Derivant material.
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