CN102675128A - Dihydroanthracene derivative, preparation method and application thereof and luminescent device comprising dihydroanthracene derivative - Google Patents
Dihydroanthracene derivative, preparation method and application thereof and luminescent device comprising dihydroanthracene derivative Download PDFInfo
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- CN102675128A CN102675128A CN2011101512554A CN201110151255A CN102675128A CN 102675128 A CN102675128 A CN 102675128A CN 2011101512554 A CN2011101512554 A CN 2011101512554A CN 201110151255 A CN201110151255 A CN 201110151255A CN 102675128 A CN102675128 A CN 102675128A
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Abstract
The invention relates to a 9,9,10,10-tetra-aryl substitute dihydroanthracene derivative (definitions of all groups are shown in the specification) shown in a formula (1), a preparation method for the dihydroanthracene derivative, an organic electroluminescent material comprising the dihydroanthracene derivative and application of the dihydroanthracene derivative in the technical field of organic electroluminesence display.
Description
Technical field
The present invention relates to one type new 9,9,10,10-four aryl substituted-dihydro anthracene derivants, its preparation method comprise the electroluminescent organic material of this type of material and the application of this type of material in the ORGANIC ELECTROLUMINESCENCE DISPLAYS technical field.
Background technology
The electroluminescent technology of organic materials can be applied to aspects such as demonstration of ultra-thin plane and organic solid laser apparatus, is obtaining development at full speed over nearly 20 years, has realized the red, green, blue three-color light-emitting basically.Wherein, green material is with fastest developing speed, has reached the commercialization practical stage basically, and the problem of red and blue material is more, and particularly stable, high efficiency blue light has more challenge.
The organic electroluminescence device of having invented doping system since Kodak rises; Along with phosphorescence doping system host-guest transmission ofenergy theoretical development and small molecules doping continuous success therebetween; Doping system small molecules material of main part, especially dark blue smooth material of main part has become the business-like key of phosphorescence device.Phosphorescent coloring need be entrained in it in suitable material of main part usually not separately as luminescent layer, forms the Subjective and Objective luminescent layer.In order to realize effective transmission ofenergy, require the triplet E of material of main part usually
TThe triplet E that is higher than dye molecule
TFor redness or green phosphorescent dye, material of main part CBP (structural formula is as follows) performance commonly used at present is original.But for the blue phosphorescent dyestuff, the triplet energy state of itself is higher, and the material of main part of seeking the higher triplet energy state that is complementary with it is just comparatively difficult.
Blue phosphorescent dyestuff FIrpic with commonly used at present is an example, and its triplet is 2.65eV, and the triplet of material of main part CBP commonly used is 2.56eV, thereby the energy transfer process between from CBP to FIrpic is an endothermic process.Discover, for the phosphorescence Subjective and Objective system of heat absorption transmission ofenergy, device prepare in the process as introduced micro-water, oxygen contamination will cause device efficiency to reduce greatly; And when temperature reduces, the heat absorption energy transfer process will be restrained.Simultaneously, because a large amount of triplet excitons are present in the main body and can not energy be in time passed to phosphorescent coloring, this also is to cause one of of short duration reason blue phosphorescent device lifetime.Therefore, the material of main part of seeking high triplet energy state becomes one of main path that solves blue phosphorescent device lifetime and efficiency.
Since 2003, people synthesized the material of main part (as follows) that mCP, UGH, CDBP, SimCP etc. have high triplet energy state (2.7-3.2eV) through designing, and for the CBP material of main part, have improved the efficient of blue phosphorescent device greatly.In addition, discover that the glass transition temperature Tg of material of main part is not high enough (like mCP), perhaps do not have Tg (like CBP) at all, under filminess, be easy to crystallization, can influence the stability and the life-span of corresponding device greatly.Have been found that the TBCPF series blue phosphorescent material of main part TBCPF based on carbazole/fluorenyl has high triplet and the high stability of 2.84ev; (Tetrahedron 2007 particularly also to have realized wet method preparing the high efficiency blue phosphorescent device of small molecules individual layer; 63,10161-10168).The aforementioned body material is the material of main part that contains the inclined to one side hole transport ability of carbazole main body group mostly.
In recent years; For electronics and the hole in the balance OLED device; Electrophilic phosphorus oxygen base and benzoglyoxaline group are introduced in the molecular designing of phosphorescent light body material; Obtain some and had the material of main part of electronics or bipolar transmission ability, improved the efficient of blue phosphorescent even mazarine phosphorescence device to some extent.Following structural is represented some typical blue phosphorescent material of main parts,
Wherein, phosphorescent light body material PPO2 has the high triplet of 3.0ev, uses FCNIr to make phosphorescent dopants, obtain up to 18.4% external quantum efficiency (Advanced Functional Materials 2009,19,3644-3649); BM2CB makes main body, Ir (ppy)
3Make doping agent, (J.Phys.Chem.C 2010,114,5193-5198) to obtain the device of luminous efficiency 73.4lm/W, external quantum efficiency 18.7%.The variation of other materials and device architecture of following preparation OLED device is (like the hybrid agent material; Two hole transmission layers; Hole blocking layer etc.); Being that the luminous external quantum efficiency of blue phosphorescent device of dyestuff is the highest based on FIrpic has broken through 25%, and efficient has also obtained improvement to a certain degree with the problem that the increase of current density descends.But being noted that of value, most material of main parts are still realized the blue phosphorescent device with FIrpic as dyestuff, the luminous efficiency height difference of the FIrpic blue phosphorescent device of collocation different subjects material is very big.
Summary of the invention
The invention provides and a kind ofly contain 9,9,10; The novel phosphorescent light body material of 10-four aryl substituted-dihydro anthracene derivants; Have triarylamine group or carbazole group in the molecule, these compounds have bigger space structure, the stacking extinguishing of object in the energy transmission of can avoiding mixing; Bigger space structure makes the glass transition temperature Tg of material improve greatly simultaneously, and these materials have very high heat and chemicalstability equally.Find that unexpectedly these materials not only can be used as the electroluminescent phosphorescence main body in electroluminescence device, but also can in electroluminescence device, be used as hole mobile material.
An object of the present invention is to provide a kind of new 9,9,10,10-four aryl substituted-dihydro anthracene derivants, its structural formula is suc as formula shown in (1):
formula (1)
Wherein:
R
1And R
2Independently be selected from Wasserstoffatoms respectively or as shown in the formula the diaryl amido of (2) or the substituted azole base of formula (3),
Prerequisite is R
1And R
2Be not hydrogen simultaneously,
Ar
1And Ar
2Be independently selected from respectively and comprise that substituting group has the unsubstituted of 6～50 carbon atoms or is selected from C by at least one
1-C
6-alkyl or C
3-C
10The substituted phenyl of the group of-naphthenic base, naphthyl or anthryl;
A and B (comprising two carbon atoms on the pyrrole ring in its ring structure respectively, down together) are independently selected from respectively and comprise that substituting group has the unsubstituted of 6～50 carbon atoms or is selected from C by at least one
1-C
6-alkyl or C
3-C
10The substituted phenyl of the group of-naphthenic base, naphthyl or anthryl.
The invention still further relates to 9,9,10, the preparation method of 10-four aryl substituted-dihydro anthracene derivants, it may further comprise the steps:
(a) make the reaction of anthraquinone and phenyl grignard reagent,, generate formula (7) intermediate product of cis-trans isomerism form of mixtures product that obtains and acyl halide reaction,
X wherein
1Be selected from hydrogen or halogen, X ' is selected from halogen;
(b) with formula (7) intermediate product and the substituted phenyl lithium reaction of halogen, acquisition formula (4) compound
X wherein
1, X
2Be independently selected from hydrogen or halogen respectively, prerequisite is X
1, X
2Be not hydrogen simultaneously;
(c) with the diarylamine compound of the compound of formula (4) and formula (5) under protection of inert gas, react if be suitably under the existence of catalyzer,
Perhaps
The substituted azole compounds of the compound of formula (4) and formula (6) under protection of inert gas, is reacted if be suitably under the existence of catalyzer,
With production (1) compound,
Wherein
Ar
1And Ar
2Be independently selected from respectively and comprise that substituting group has the unsubstituted of 6～50 carbon atoms or is selected from C by at least one
1-C
6-alkyl or C
3-C
10The substituted phenyl of the group of-naphthenic base, naphthyl or anthryl;
A and B are independently selected from respectively and comprise that substituting group has the unsubstituted of 6～50 carbon atoms or is selected from C by at least one
1-C
6-alkyl or C
3-C
10The group of-naphthenic base substituted phenyl, naphthyl or anthryl.
It is of the present invention 9,9,10 that another aspect of the present invention relates to, and 10-four aryl substituted-dihydro anthracene derivants are as the purposes of phosphorescent light body material or hole mobile material.
Of the present inventionly relate in one aspect to a kind of organic electroluminescence device again, comprise negative electrode, anode and organic function layer, comprise at least one luminescent layer in this organic function layer; Comprise 9 of at least a formula (1) in this organic function layer; 9,10,10-four aryl substituted-dihydro anthracene derivants.
Organic materials of the present invention can be used as phosphorescent light body material in organic electroluminescence device, have higher current efficiency, effectively reduces simultaneously to open bright voltage.
Embodiment
One aspect of the present invention relates to 9,9,10, the substituted dihydroanthracene verivate of 10-four aryl, and its structural formula is suc as formula shown in (1):
formula (1)
Wherein:
R
1And R
2Be independently selected from Wasserstoffatoms respectively or as shown in the formula the diaryl amido of (2) or the substituted azole base of formula (3),
Prerequisite is R
1And R
2Be not hydrogen simultaneously,
Ar
1And Ar
2Be independently selected from respectively and comprise that substituting group has the unsubstituted of 6～50 carbon atoms or is selected from C by at least one
1-C
6-alkyl or C
3-C
10The substituted phenyl of the group of-naphthenic base, naphthyl or anthryl;
A and B are independently selected from respectively and comprise that substituting group has the unsubstituted of 6～50 carbon atoms or is selected from C by at least one
1-C
6-alkyl or C
3-C
10The substituted phenyl of the group of-naphthenic base, naphthyl or anthryl.
A kind of embodiment of the present invention comprises the compound of following formula (1), wherein
Preferably, R
1And R
2One of be hydrogen, another be between position or the diaryl amido of the formula that is selected from (2) of para-orientation or the substituted azole base of formula (3), perhaps, R
1And R
2The diaryl amido of the formula (2) of position or para-orientation or the substituted azole base of formula (3) between being independently selected from respectively.
Another embodiment of the present invention comprises the compound of following formula (1), wherein
Ar
1And Ar
2Preferred being independently selected from respectively comprises that substituting group has the unsubstituted of 6～30 carbon atoms or is selected from C by at least one
1-C
6-alkyl or C
3-C
10The substituted phenyl of the group of-naphthenic base, naphthyl or anthryl;
Ar
1And Ar
2More preferably be independently selected from respectively and comprise that substituting group has the unsubstituted of 6～16 carbon atoms or by the substituted phenyl or naphthyl of at least one substituting group, said substituting group is selected from C
1-C
6-alkyl or C
3-C
10-naphthenic base;
Ar
1And Ar
2Especially preferably be independently selected from unsubstituted respectively or by the substituted phenyl or naphthyl of one or two substituting group, said substituting group is selected from C
1-C
4-alkyl or C
3-C
6-naphthenic base.
Another embodiment of the present invention comprises following formula (1) compound, wherein
A and B are independently selected from respectively and comprise that substituting group has the unsubstituted of 6～30 carbon atoms or is selected from C by at least one
1-C
6-alkyl or C
3-C
10The substituted phenyl of the group of-naphthenic base, naphthyl or anthryl;
A and B more preferably are independently selected from respectively and comprise that substituting group has the unsubstituted of 6～16 carbon atoms or by the substituted phenyl or naphthyl of at least one substituting group, said substituting group is selected from C
1-C
6-alkyl or C
3-C
10-naphthenic base;
A and B especially preferably are independently selected from unsubstituted respectively or by the substituted phenyl or naphthyl of one or two substituting group, said substituting group is selected from C
1-C
4-alkyl or C
3-C
6-naphthenic base.
Preferably, formula (1) 9,9,10 of the present invention, in the substituted dihydroanthracene of 10-four aryl:
R
1And R
2One of be hydrogen, another be between the position or the diaryl amido that is selected from general formula (2) of para-orientation or the substituted azole base of general formula (3), perhaps, R
1And R
2The diaryl amido of the general formula (2) of position or para-orientation or the substituted azole base of general formula (3) between being independently selected from respectively;
Ar
1And Ar
2Be independently selected from respectively and comprise that substituting group has the unsubstituted of 6～30 carbon atoms or is selected from C by at least one
1-C
6-alkyl or C
3-C
10The substituted phenyl of the group of-naphthenic base, naphthyl or anthryl; And
A and B are independently selected from respectively and comprise that substituting group has the unsubstituted of 6～30 carbon atoms or is selected from C by at least one
1-C
6-alkyl or C
3-C
10The substituted phenyl of the group of-naphthenic base, naphthyl or anthryl.
More preferably, formula (1) 9,9,10 of the present invention, in the substituted dihydroanthracene of 10-four aryl:
R
1And R
2One of be hydrogen, another be between the position or the diaryl amido that is selected from general formula (2) of para-orientation or the substituted azole base of general formula (3), perhaps, R
1And R
2The diaryl amido of the general formula (2) of position or para-orientation or the substituted azole base of general formula (3) between all being selected from independently respectively;
Ar
1And Ar
2Be independently selected from respectively and comprise that substituting group has the unsubstituted of 6～16 carbon atoms or by the substituted phenyl or naphthyl of at least one substituting group, said substituting group is selected from C
1-C
6-alkyl or C
3-C
10-naphthenic base; And
A and B are independently selected from respectively and comprise that substituting group has the unsubstituted of 6～16 carbon atoms or by the substituted phenyl or naphthyl of at least one substituting group, said substituting group is selected from C
1-C
6-alkyl or C
3-C
10-naphthenic base.
Especially preferably, formula (1) 9,9,10 of the present invention, in the substituted dihydroanthracene of 10-four aryl:
R
1And R
2One of be hydrogen, another be between the position or the diaryl amido that is selected from general formula (2) of para-orientation or the substituted azole base of general formula (3), perhaps, R
1And R
2The diaryl amido of the formula (2) of position or para-orientation or the substituted azole base of formula (3) between all being selected from independently respectively;
Ar
1And Ar
2Be independently selected from unsubstituted respectively or by the substituted phenyl or naphthyl of one or two substituting group, said substituting group is selected from C
1-C
4-alkyl or C
3-C
6-naphthenic base; And
A and B are independently selected from unsubstituted respectively or by the substituted phenyl or naphthyl of one or two substituting group, said substituting group is selected from C
1-C
4-alkyl or C
3-C
6-naphthenic base.
More specifically preferably, formula of the present invention (1) examples for compounds comprises that (cis represents cis-isomeride to following P1-P26 compound; Trans represents trans-isomer(ide)):
In formula of the present invention (1) and every other formula, that alkyl can be straight chain or branching.Only if point out in addition, preferred rudimentary carbon skeleton in said group for example contains 1 to 6 carbon atom, particularly those groups of 1 to 4 carbon atom.Alkyl for example has: methyl, ethyl, propyl group (like n-propyl or sec.-propyl), butyl (like normal-butyl, isobutyl-or the tertiary butyl), amyl group (like n-pentyl, isopentyl or neo-pentyl) or hexyl are (like n-hexyl, isohexyl, 3-methyl amyl, 2; 2-dimethylbutyl or 2, the 3-dimethylbutyl).
The instance of naphthenic base has cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, suberyl and ring octyl group.Naphthenic base can be substituted, also can dicyclo or the existence of three loop types.
Halogen is fluorine, chlorine, bromine or iodine, preferred chlorine or bromine.
Aryl is monocycle, dicyclo or many cyclophanes fragrant system, for example phenyl, naphthyl or anthryl.
Unless in addition definition, " being replaced " by at least one group be meant by one or more identical or different groups and replace.
The substituting group of mentioning by way of example (" the first substituting group level "); If it comprises the hydrocarbonaceous part; Can be randomly in the hydrocarbonaceous part, be further replaced (" the second substituting group level "), for example replaced to one of substituting group of first substituting group level definition.Corresponding further substituting group level also is possible.Preferably, term " substituted group " only comprises one or two substituting group level.
When aryl was substituted, it can be preferably and is selected from C
1-C
4Alkyl or C
3-C
6The identical or different group list replacement of-naphthenic base or phenyl, naphthyl or the anthryl of polysubstituted (preferably being up to three replacements).
In said embodiment scope of the present invention, can combine substituent R as required
1, R
2, Ar
1, Ar
2, A and B various generally, preferably, more preferably, especially preferably and more specifically preferred meaning.This means that the present invention comprises such formula (1) compound, wherein substituent A r for example
1Have preferred meaning and all the other substituting groups have general sense, or for example substituent A have preferred meaning, substituent A r
1Have especially preferred meaning and all the other substituting groups and have general sense.For clarity sake clearly do not mention said various combination, but should think that it is contained by the present invention.
The present invention is to R
1Or R
2Definition in, " position or contraposition " is with respect to existing for key that dihydroanthracene links to each other on each phenyl ring in the formula (1), for example, represents para-orientation in the Compound P 1, between Compound P 2 representatives the position replaces.
Among the present invention to Ar
1Or Ar
2Definition in, in position or the contraposition, for example Compound P 23 be a para-orientation between substituting group preferably was present in, Compound P 20 is a contraposition and a position replacement.
In the present invention; The all possible steric isomer that is limited its concrete spatial form is contained in the definition of formula (1) fully; Like enantiomer, diastereomer and cis-trans isomer, i.e. the present invention had both comprised pure steric isomer, comprised its isomer mixture again.
For the various substituent possible combination of formula (1), must follow the rule of compound structure, promptly formula (1) does not comprise chemically infeasible any compound well known by persons skilled in the art.
The above-mentioned qualification that compound group is done also correspondingly is applicable to other theme of the present invention, comprises preparation method, compsn, application and organic luminescent device etc.
The invention still further relates to 9,9,10, the preparation method of 10-four aryl substituted-dihydro anthracene derivants, it may further comprise the steps:
(a) make the reaction of anthraquinone and phenyl grignard reagent,, generate formula (7) intermediate product of cis-trans isomerism form of mixtures product that obtains and acyl halide reaction,
X wherein
1Be selected from hydrogen or halogen, X ' is selected from halogen;
(b) with formula (7) intermediate product and the substituted phenyl lithium reaction of halogen, acquisition formula (4) compound
X wherein
1, X
2Be independently selected from hydrogen or halogen respectively, prerequisite is X
1, X
2Be not hydrogen simultaneously;
(c) with the diarylamine compound of the compound of formula (4) and formula (5) under protection of inert gas, react if be suitably under the existence of catalyzer,
Perhaps
The substituted azole compounds of the compound of formula (4) and formula (6) under protection of inert gas, is reacted if be suitably under the existence of catalyzer,
With production (1) compound,
Wherein
Ar
1And Ar
2Be independently selected from respectively and comprise that substituting group has the unsubstituted of 6～50 carbon atoms or is selected from C by at least one
1-C
6-alkyl or C
3-C
10The substituted phenyl of the group of-naphthenic base, naphthyl or anthryl;
A and B are independently selected from respectively and comprise that substituting group has the unsubstituted of 6～50 carbon atoms or is selected from C by at least one
1-C
6-alkyl or C
3-C
10The group of-naphthenic base substituted phenyl, naphthyl or anthryl.
Randomly, method of the present invention also comprises step (d): the product of step (c) gained is separated, obtain cis and trans-isomer(ide).Separation can use separation method known in the art to carry out, and especially preferably uses column chromatography.
The temperature of reaction of above-mentioned reaction is generally-100 ℃-150 ℃, preferred-78 ℃-110 ℃.Reaction pressure is generally normal pressure.Reaction times is 2-48 hour, preferred 4-36 hour, and more preferably 5-12 hour.
In the above-mentioned steps (a), reactant anthraquinone and Grignard reagent and acyl halide can be at mol ratio 1-15: 1-15: change preferred 1-10: 1-10: 1-8, more preferably 1-8: 1-8: 1-5 in the 1-12 scope.
In the above-mentioned steps (b), position or the mono-substituted phenyl lithium of contraposition between the substituted phenyl lithium of halogen is preferably, they can be through known method preparation, for example by bromo-iodobenzene and tert-butyl lithium preparation.Wherein, formula (7) intermediate product and the substituted phenyl lithium of halogen can be at mol ratio 1-15: change preferred 1-8: 1-8 in the 1-15 scope.
In the above-mentioned steps (c), the diarylamine of the compound of formula (4) and formula (5) or the substituted azole compounds of formula (6) can be at mol ratio 1-12: change preferred 1-8: change in the 1-8 scope in the 1-12 scope.
Can be used in the step (c) and the diarylamine compound catalyst for reaction of formula (5) transition-metal catalyst for linked reaction that can the catalysis halogenated aromatic compound; The catalyst system that forms of Pd compound and organophosphor ligand for example; Palladium acetylacetonate etc., preferred Pd (dba)
2(two (dibenzalacetone) palladium) and tri-butyl phosphine combination.
The substituted azole compounds catalyst for reaction that can be used in the step (c) with formula (6) is combining of crown ether-like catalyzer and metal-powder, preferred 18-hat-6 or 15-hat-5, and more preferably 18-hat-6 and for example copper powder combines.
It is of the present invention 9,9,10 that another aspect of the present invention relates to, and 10-four aryl substituted-dihydro anthracene derivants are as the purposes of phosphorescent light body material or hole mobile material.
Of the present inventionly relate in one aspect to a kind of organic electroluminescence device again, it comprises negative electrode, anode and organic function layer, comprises at least one luminescent layer in this organic function layer; Comprise 9 of at least a formula (1) in this organic function layer; 9,10,10-four aryl substituted-dihydro anthracene derivants.Formula (1) compound is preferably as the material of main part of luminescent layer.More preferably, also be doped with phosphorescent coloring in the luminescent layer, the doping of this phosphorescent coloring is about 2-20%, preferred 2-15%, and more preferably 3-12%, 5-10% most preferably is all based on the weight meter of material of main part and phosphorescent coloring.Said phosphorescent coloring is a phosphorescent coloring as known in the art, more preferably is used for the blue phosphorescent dyestuff, those that the beginning part for example of the present invention is listed.Most preferably, the phosphorescent coloring that is used for the present invention is blue phosphorescent dyestuff FIrpic or green glow dyestuff Ir (ppy)
3, or its binding substances.
Generally speaking, organic electroluminescence device comprises the multilayer organic function layer between negative electrode and anode, and it comprises hole transmission layer, luminescent layer, electron transfer layer and electron injecting layer etc., and wherein luminescent layer generally includes material of main part and dyestuff.Beyond content cited among following general explanation and the embodiment, other technology contents that includes organic electroluminescence devices well known by persons skilled in the art, for example making method and general one-tenth grade, and also are applicable among the present invention.
Substrate can use the substrate in traditional organic luminescent device, for example: glass or plastics.
Hole transmission layer can adopt various tri-arylamine group materials.
Negative electrode can adopt metal and composition thereof structure, like Mg:Ag, Ca:Ag etc., also can be electron injecting layer/metal-layer structure, like LiF/Al, Li
2Common cathode construction such as O.
If no special instructions; Various pharmaceutical chemicalss used among the present invention are as 9; The 10-DIANTHRAQUINONE, all are the raw materials that to buy to raw materials such as bromo-iodobenzene, a bromo-iodobenzene, m-dibromobenzene, paradibromobenzene, tert-butyl lithium, carbazole, diphenylamine, two (3, the 4-dimethyl-) aniline, two (the 4-tertiary butyl) aniline, Alpha-Naphthyl phenyl amine, betanaphthyl phenyl amine, Acetyl Chloride 98Min.s.
I. intermediate preparation instance
I) 9,9,10,10-four (to bromophenyl) dihydroanthracene synthetic
(1) intermediate A is synthetic
At N
2Protection down; Add 20.8g 9 in the 500ml there-necked flask, the anhydrous THF (THF) that 10-DIANTHRAQUINONE (0.1mol) and 200ml handled through the Na/ UVNUL MS-40, reaction system is cooled to-40 ℃; Slowly drip prepared fresh to bromophenyl grignard reagent THF solution (bromo-iodobenzene and 7.2g magnesium (0.3mol) being prepared) by 71g (0.25mol); After being added dropwise to complete, reaction system slowly is raised to room temperature, and at room temperature continues to stir 2 hours.Lentamente in the impouring saturated ammonium chloride solution, product is used the 200ml extracted with diethyl ether respectively three times, merges organic phase, anhydrous MgSO with reaction solution
4Drying is drained solvent, and thick product is used the column chromatography method purifying, obtains white solid intermediate A 42.8g (82%), is the mixture of cis-trans isomerism.
(2) intermediate B is synthetic
N
2Protection in the 250ml there-necked flask, adds A (26.2g down; 0.05mol), 100ml benzene, reflux slowly adds Acetyl Chloride 98Min. 25ml through constant pressure funnel; After being added dropwise to complete, continue under refluxad to stir, change into product fully up to all raw materials and midbody.The reaction system cool to room temperature; Slowly add the 400ml sherwood oil product separated out, leave standstill several hours after, the product that filter to collect generates; Thick product gets white solid B 22.4g (yield 80%) with sherwood oil/toluene (volume ratio 2: 1) system recrystallization, is the mixture of cis-trans isomerism.
(3) 9,9,10,10-four (to bromophenyl) dihydroanthracene synthetic
Under nitrogen protection, add 14g B (25mmol) and the anhydrous ether of 100ml in the 250ml there-necked flask, through constant pressure funnel add prepared beforehand good to bromophenyl lithium (bromo-iodobenzene (30mmol) and twice equivalent tert-butyl lithium being descended to react the diethyl ether solutions that make at-78 ℃) by 8.5g; After being added dropwise to complete, reaction mixture at room temperature stirs 2 hours, and then refluxes 2 hours; Collect the solid that produces; Isolating through purified to white 9,9,10; 10-four (to bromophenyl) dihydroanthracene solid 14g (molecular weight 800, productive rate 70%).
Ii) 9,10-phenylbenzene-9,10-two (to bromophenyl) dihydroanthracene synthetic
(1) at N
2Protection down; Add 20.8g 9 in the 500ml there-necked flask, the anhydrous THF that 10-DIANTHRAQUINONE (0.1mol) and 200ml handled through the Na/ UVNUL MS-40, reaction system is cooled to-40 ℃; Slowly drip the phenyl grignard reagent THF solution (by 39.3g (0.25mol) bromobenzene and 7.2g magnesium (0.3mol) preparation) of prepared fresh; After being added dropwise to complete, reaction system slowly is raised to room temperature, and at room temperature continues to stir 2 hours.Lentamente in the impouring saturated ammonium chloride solution, product is used the 200ml extracted with diethyl ether respectively three times, merges organic phase, anhydrous MgSO with reaction solution
4Drying is drained solvent, and thick product is used the column chromatography method purifying, obtains white solid midbody C 31g (85%) and is the mixture of cis-trans isomerism.
(2) N
2Under the protection, in the 250ml there-necked flask, adding C (18.2g, 0.05mol); 100ml benzene, reflux slowly adds Acetyl Chloride 98Min. 25ml through constant pressure funnel; After being added dropwise to complete, continue under refluxad to stir, change into product fully up to all raw materials and midbody.The reaction system cool to room temperature; Slowly add the 400ml sherwood oil product separated out, leave standstill several hours after, the product that filter to collect generates; Thick product gets white solid D17g (yield 84%) with sherwood oil/toluene (volume ratio 1: 1) system recrystallization, is the mixture of cis-trans isomerism.
(3) under nitrogen protection; Add 9.1g D (25mmol) and 100ml anhydrous diethyl ether in the 250ml there-necked flask, through constant pressure funnel add prepared beforehand good to bromophenyl lithium (by bromo-iodobenzene and two equivalent tert-butyl lithium are reacted the diethyl ether solutions that make down at-78 ℃), after being added dropwise to complete; Reaction mixture at room temperature stirred 2 hours; And then refluxed 2 hours, collect the solid that produces, isolating through purified to white solid 10g (67%).
Iii) 9,10-phenylbenzene-9,10-two (bromophenyl) dihydroanthracene synthetic
(1) at N
2Protection down; Add 20.8g 9 in the 500ml there-necked flask, the anhydrous THF that 10-DIANTHRAQUINONE (0.1mol) and 200ml handled through the Na/ UVNUL MS-40, reaction system is cooled to-40 ℃; Slowly drip the phenyl grignard reagent THF solution (by 39.3g (0.25mol) bromobenzene and 7.2g magnesium (0.3mol) preparation) of prepared fresh; After being added dropwise to complete, reaction system slowly is raised to room temperature, and at room temperature continues to stir 2 hours.Lentamente in the impouring saturated ammonium chloride solution, product is used the 200ml extracted with diethyl ether respectively three times, merges organic phase, anhydrous MgSO with reaction solution
4Drying is drained solvent, and thick product is used the column chromatography method purifying, obtains white solid midbody C 31g (85%), is the mixture of cis-trans isomerism.
(2) N
2Under the protection, in the 250ml there-necked flask, adding C (18.2g, 0.05mol); 100ml benzene, reflux slowly adds Acetyl Chloride 98Min. 25ml through constant pressure funnel; After being added dropwise to complete, continue under refluxad to stir, change into product fully up to all raw materials and midbody.The reaction system cool to room temperature; Slowly add the 400ml sherwood oil product separated out, leave standstill several hours after, the product that filter to collect generates; Thick product gets white solid D17g (yield 84%) with sherwood oil/toluene system (volume ratio 2: 1) recrystallization, is the mixture of cis-trans isomerism.
(3) under nitrogen protection; Add 9.1g D (25mmol) and 100ml anhydrous diethyl ether in the 250ml there-necked flask, through constant pressure funnel add prepared beforehand good between bromophenyl lithium (reacting the diethyl ether solutions that make down at-78 ℃) by a bromo-iodobenzene and two equivalent tert-butyl lithium, after being added dropwise to complete; Reaction mixture at room temperature stirred 2 hours; And then refluxed 2 hours, collect the solid that produces, isolating through purified to white solid 12g (75%).
Iv) 9,9,10,10-four (bromophenyl) dihydroanthracene synthetic
(1) at N
2Protection down; Add 20.8g 9 in the 500ml there-necked flask, the anhydrous THF that 10-DIANTHRAQUINONE (0.1mol) and 200ml handled through the Na/ UVNUL MS-40, reaction system is cooled to-40 ℃; Bromophenyl grignard reagent THF solution between slow dropping prepared fresh (by 59g (0.25mol) m-dibromobenzene and 7.2g magnesium (0.3mol) preparation); After being added dropwise to complete, reaction system slowly is raised to room temperature, and at room temperature continues to stir 2 hours.Lentamente in the impouring saturated ammonium chloride solution, product is used the 200ml extracted with diethyl ether respectively three times, merges organic phase, anhydrous MgSO with reaction solution
4Drying is drained solvent, and thick product is used the column chromatography method purifying, obtains white solid intermediate E 28.8g (79%), is the mixture of cis-trans isomerism.
(2) N
2Under the protection, in the 250ml there-necked flask, adding E (26.1g, 0.05mol); 100ml benzene, reflux slowly adds Acetyl Chloride 98Min. 25ml through constant pressure funnel; After being added dropwise to complete, continue under refluxad to stir, change into product fully up to all raw materials and midbody.The reaction system cool to room temperature; Slowly adding the 400ml sherwood oil separates out product; After leaving standstill several hours, filter and collect the product that generates, thick product gets white solid F 24.3g (yield 87%) with sherwood oil/toluene system (volume ratio 1: 1) recrystallization and is the mixture of cis-trans isomerism.
(3) under nitrogen protection; Add 14g F (25mmol) and 100ml anhydrous diethyl ether in the 250ml there-necked flask, through constant pressure funnel add prepared beforehand good between bromophenyl lithium (reacting the diethyl ether solutions that make down at-78 ℃) by a bromo-iodobenzene and two equivalent tert-butyl lithium, after being added dropwise to complete; Reaction mixture at room temperature stirred 2 hours; And then refluxed 2 hours, collect the solid that produces, isolating through purified to white solid 14.5g (72%).
II. the preparation embodiment of material of the present invention
The synthetic method of compound is in the present invention divided two types in work: four all substituted symmetrical compounds of phenyl ring (P1 and P2) and two substituted compounds of phenyl ring (all the other compounds).Specifically after each method, narrate.
Synthesizing of embodiment 1 Compound P 1
At N
2Protection adds 150ml toluene down successively in the 250ml there-necked flask that magnetic agitation is housed, 8g 9,9, and 10; 10-four (to bromophenyl) dihydroanthracene (10mmol), 8.46g diphenylamine (50mmol) under agitation, adds 5.76g sodium tert-butoxide (60mmol); Can not dissolve fully, (two dibenzylideneacetonepalladium palladium 0.3mmol), darken to add 173mgPd (dba) 2 again; Add 1.2g 10% tri-butyl phosphine hexane solution (0.6mmol) again, reflux, reaction solution becomes green, refluxes and puts plate after 8 hours; Basically do not have raw material, when being cooled to below 45 ℃, add the mixing solutions of 5ml concentrated hydrochloric acid and 100ml water, separatory; Water is used the 100ml extracted in toluene, merges to revolve the dried thick product that obtains, and thick product gets white solid 6.3g, yield with methylene dichloride/ethanol (volume ratio 1: 1) system recrystallization: 55%.
Synthesizing of embodiment 2 Compound P 2
At N
2Protection adds 150ml toluene, 8g 9,9,10 down successively in the 250ml there-necked flask that magnetic agitation is housed; 10-four (bromophenyl) dihydroanthracene (10mmol), 8.46g diphenylamine (50mmol) under agitation, add 5.76g sodium tert-butoxide (60mmol), can not dissolve fully; Add 173mgPd (dba) 2 (0.3mmol) again, darken, add 1.2g 10% tri-butyl phosphine hexane solution (0.6mmol) again, reflux; Reaction solution becomes green, refluxes and puts plate after 10 hours, does not have raw material basically, when being cooled to below 45 ℃; Add the mixing solutions of 5ml concentrated hydrochloric acid and 100ml water, separatory, water are used the 150ml extracted in toluene; Merge and revolve the dried thick product that obtains, thick product gets white solid 5.7g, yield with methylene dichloride/ethanol system (volume ratio 2: 1) recrystallization: 50%.
Embodiment 3 Compound P 3 and P4's is synthetic
At N
2Protection adds 150ml toluene down successively in the 250ml there-necked flask that magnetic agitation is housed, 6.4g 9,10-phenylbenzene-9; 10-two (to bromophenyl) dihydroanthracene (10mmol), 4.3g diphenylamine (25mmol) under agitation, add 2.9g sodium tert-butoxide (30mmol); Can not dissolve fully, add 86mg Pd (dba) 2 (0.15mmol) again, darken; Add 0.6g 10% tri-butyl phosphine hexane solution (0.3mmol) again, reflux, reaction solution becomes green; Reflux and put plate after 5 hours, do not have raw material basically, when being cooled to below 45 ℃; Add the mixing solutions of 5ml concentrated hydrochloric acid and 100ml water, separatory, water are used the 150ml extracted in toluene; Merge and revolve the dried thick product that obtains, thick product obtains two product 1.9g P3 and 3.1g P4 respectively through petrol ether/ethyl acetate (volume ratio 2: 1) system column chromatography, and yield is respectively: 23% and 37.8%.
Embodiment 4 Compound P 5 and P6's is synthetic
Under the nitrogen protection, with 6.4g 9,10-phenylbenzene-9,10-two (to bromophenyl) dihydroanthracene (10mmol); 4.18g carbazole (25mmol), 5.12g copper powder (80mmol), 1.34g 18-is preced with-6 (5mmol), 13.8g Anhydrous potassium carbonate (100mmol); The 100ml orthodichlorobenzene joins in three mouthfuls of reaction flasks of 250ML, stirs, and is warming up to back flow reaction 24 hours; Stopped reaction, filtered while hot is washed with methylene dichloride 50ml again; Remove solvent under reduced pressure, the thick product that obtains gets 1.8g P5 and 3.2g P6 with sherwood oil/methylene dichloride (volume ratio 1: 2) system column chromatography, and productive rate is respectively 21% and 39%.
Embodiment 5 Compound P 7 and P8's is synthetic
Diphenylamine among the embodiment 3 is changed to the phenyl Alpha-Naphthyl amine of equivalent, and other raw material and step all are same as embodiment 3, obtain white solid 1.84g P7 (20%) and 3.68g P8 (40%).
Embodiment 6 Compound P 9 and P10's is synthetic
Diphenylamine among the embodiment 3 is changed to the phenyl betanaphthyl amine of equivalent, and other raw material and step all are same as embodiment 3, obtain white solid 2g P9 (22%) and 3.9g P10 (42%).
Embodiment 7 Compound P 11 and P12's is synthetic
With 9 among the embodiment 4,10-phenylbenzene-9,10-two (to bromophenyl) dihydroanthracene changes 9 of equivalent into; 10-phenylbenzene-9; 10-two (bromophenyl) dihydroanthracene, other raw material and step all are same as embodiment 4, obtain white solid 1.7g P11 (20%) and 3.0g P12 (36.6%).
Preparation in accordance with the present invention, and, also prepare Compound P 13-P26 with reference to aforementioned specific embodiment.The P1-P26 compound is summarized in following table:
III. the application implementation of material of the present invention is routine
BPhen, Ir (ppy)
3, TAZ and FIrpic structural formula be:
In element manufacturing of the present invention, select glass substrate for use, ITO (tin indium oxide) makes anode material.
The hole mobile material of in element manufacturing of the present invention, being selected for use be NPB (N, N '-two (naphthalene-2-yl)-N, N '-two (phenyl) biphenyl-4,4 '-diamines).
The electronics injecting material of in element manufacturing of the present invention, being selected for use is LiF, and cathode material is Al.
Device of the present invention is made as follows:
With the sheet glass that has been coated with ITO transparency conducting layer supersound process in commercial clean-out system; In deionized water, wash; At acetone: ultrasonic oil removing in the alcohol mixed solvent (volume ratio 1: 1); Under clean environment, be baked to and remove moisture content fully, with UV-light and ozone clean, and with low energy positively charged ion bundle bombarded surface;
Place the above-mentioned anodic glass substrate that has in the vacuum chamber, be evacuated to 1 * 10
-5To 9 * 10
-3Pa, vacuum evaporation NPB is as hole transmission layer on above-mentioned anode tunic, and vapor deposition speed is 0.1nm/s, and the vapor deposition thickness is 40nm;
Vacuum evaporation compound of the present invention and contrast vapor deposition material C BP of the prior art or mCP are as the material of main part in the luminescent layer of device on hole transmission layer, and the while is vapor deposition luminescent dye Ir (ppy) jointly
3(shown in following each device architecture of its per-cent that adds separately), vapor deposition speed is 0.1nm/s, the vapor deposition total film thickness is 30nm;
Vacuum evaporation one deck Bphen or TAZ are as the electron transfer layer of device on luminescent layer, and its vapor deposition speed is 0.1nm/s, and the vapor deposition total film thickness is 20nm;
The LiF of vacuum evaporation 0.5nm is the negative electrode of the Al layer of 150nm as device as electron injecting layer and thickness on electron transfer layer.
Prepare following each device according to method mentioned above: make it have following structure:
First group
Comparative Examples 1:
ITO/NPB (40nm)/CBP:6%Ir (ppy)
3(30nm)/(wherein 6% expression is with respect to CBP+Ir (ppy) for Bphen (20nm)/LiF (0.5nm)/Al (150nm)
3, Ir (ppy)
3Weight ratio be 6%; Following examples are also expressed in this way)
Embodiment 1-1:
ITO/NPB(40nm)/P1：6％Ir(ppy)
3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al(150nm)
Embodiment 1-2:
ITO/NPB(40nm)/P2：6％Ir(ppy)
3(30nm)/Bphen(20nm)/LiF(0.5nm)/Al(150nm)
Table 1 device performance
Visible by 2 embodiment of the present invention, adopt the device of compound of the present invention all to obtain the higher current efficiency of relative prior art, effectively reduce simultaneously and open bright voltage.
Second group
Comparative Examples 2:
ITO/NPB(40nm)/mCP：10％FIrpic(30nm)/TAZ(20nm)/LiF(0.5nm)/Al(150nm)
Embodiment 2-1:
ITO/NPB(40nm)/P1：10％FIrpic(30nm)/TAZ(20nm)/LiF(0.5nm)/Al(150nm)
Embodiment 2-2:
ITO/NPB(40nm)/P2：10％FIrpic(30nm)/TAZ(20nm)/LiF(0.5nm)/Al(150nm)
Table 2 device performance
The 3rd group
Repeat first group experimental procedure, difference is to use respectively P3 and P4 to replace P1 and P2, and the result is as shown in table 3 below, uses P11 and P12 to replace P1 and P2 respectively, and the result is as shown in table 4 below:
Table 3
Table 4
The 4th group
Repeat second group experimental procedure, difference is to use respectively P5 and P6 to replace P1 and P2, and the result is as shown in table 5 below, uses P7 and P8 to replace P1 and P2 respectively, and the result is as shown in table 6 below:
Table 5
Table 6
Although describe the present invention in conjunction with embodiment; But the present invention is not limited to the foregoing description, should be appreciated that under the guiding of the present invention's design; Those skilled in the art can carry out various changes and modifications, and these variations and improvement also belong to content of the present invention.
Claims (12)
1. one kind 9,9,10,10-four aryl substituted-dihydro anthracene compounds, its structural formula is suc as formula shown in (1):
Wherein:
R
1And R
2Be independently selected from Wasserstoffatoms respectively or as shown in the formula the diaryl amido of (2) or the substituted azole base of formula (3),
Prerequisite is R
1And R
2Be not hydrogen simultaneously,
Ar
1And Ar
2Be independently selected from respectively and comprise that substituting group has the unsubstituted of 6～50 carbon atoms or is selected from C by at least one
1-C
6-alkyl or C
3-C
10The substituted phenyl of the group of-naphthenic base, naphthyl or anthryl;
A and B are independently selected from respectively and comprise that substituting group has the unsubstituted of 6～50 carbon atoms or is selected from C by at least one
1-C
6-alkyl or C
3-C
10The substituted phenyl of the group of-naphthenic base, naphthyl or anthryl.
2. the compound of claim 1, wherein
R
1And R
2One of be hydrogen, another be between position or the diaryl amido of the formula that is selected from (2) of para-orientation or the substituted azole base of formula (3), perhaps, R
1And R
2The diaryl amido of the formula (2) of position or para-orientation or the substituted azole base of formula (3) between being independently selected from respectively;
Ar
1And Ar
2Be independently selected from respectively and comprise that substituting group has the unsubstituted of 6～30 carbon atoms or is selected from C by at least one
1-C
6-alkyl or C
3-C
10The substituted phenyl of the group of-naphthenic base, naphthyl or anthryl; And
A and B are independently selected from respectively and comprise that substituting group has the unsubstituted of 6～30 carbon atoms or is selected from C by at least one
1-C
6-alkyl or C
3-C
10The substituted phenyl of the group of-naphthenic base, naphthyl or anthryl.
3. the compound of claim 1, wherein
R
1And R
2One of be hydrogen, another be between position or the diaryl amido of the formula that is selected from (2) of para-orientation or the substituted azole base of formula (3), perhaps, R
1And R
2The diaryl amido of the formula (2) of position or para-orientation or the substituted azole base of formula (3) between being independently selected from respectively;
Ar
1And Ar
2Be independently selected from respectively and comprise that substituting group has the unsubstituted of 6～16 carbon atoms or by the substituted phenyl or naphthyl of at least one substituting group, said substituting group is selected from C
1-C
6-alkyl or C
3-C
10-naphthenic base; And
A and B are independently selected from respectively and comprise that substituting group has the unsubstituted of 6～16 carbon atoms or by the substituted phenyl or naphthyl of at least one substituting group, said substituting group is selected from C
1-C
6-alkyl or C
3-C
10-naphthenic base.
4. the compound of claim 1, wherein
R
1And R
2One of be hydrogen, another be between position or the diaryl amido of the formula that is selected from (2) of para-orientation or the substituted azole base of formula (3), perhaps, R
1And R
2The diaryl amido of the formula (2) of position or para-orientation or the substituted azole base of formula (3) between being independently selected from respectively;
Ar
1And Ar
2Be independently selected from unsubstituted respectively or by the substituted phenyl or naphthyl of one or two substituting group, said substituting group is selected from C
1-C
4-alkyl or C
3-C
6-naphthenic base; And
A and B are independently selected from unsubstituted respectively or by the substituted phenyl or naphthyl of one or two substituting group, said substituting group is selected from C
1-C
4-alkyl or C
3-C
6-naphthenic base.
5. the compound of claim 1, for being selected from following a kind of compound, wherein cis represents cis, and the trans representative is trans:
6. one kind 9,9,10, the preparation method of 10-four aryl substituted-dihydro anthracene derivants may further comprise the steps:
(a) make the reaction of anthraquinone and phenyl grignard reagent,, generate formula (7) intermediate product of cis-trans isomerism form of mixtures product that obtains and acyl halide reaction,
X wherein
1Be selected from hydrogen or halogen, X ' is selected from halogen;
(b) with formula (7) intermediate product and the substituted phenyl lithium reaction of halogen, acquisition formula (4) compound
X wherein
1, X
2Be independently selected from hydrogen or halogen respectively, prerequisite is X
1, X
2Be not hydrogen simultaneously;
(c) with the diarylamine compound of the compound of formula (4) and formula (5) under protection of inert gas; React if be suitably under the existence of catalyzer; Perhaps with the substituted azole compounds of the compound of formula (4) and formula (6) under protection of inert gas; React if be suitably under the existence of catalyzer, with production (1) compound
Wherein
Ar
1And Ar
2Be independently selected from respectively and comprise that substituting group has the unsubstituted of 6～50 carbon atoms or is selected from C by at least one
1-C
6-alkyl or C
3-C
10The substituted phenyl of the group of-naphthenic base, naphthyl or anthryl;
A and B are independently selected from respectively and comprise that substituting group has the unsubstituted of 6～50 carbon atoms or is selected from C by at least one
1-C
6-alkyl or C
3-C
10The substituted phenyl of the group of-naphthenic base, naphthyl or anthryl.
7. the method for claim 6 further comprises step (d): the product of step (c) gained is separated, obtain cis and trans-isomer(ide).
8. compound has following formula:
X wherein
1, X
2Be independently selected from hydrogen or halogen respectively, prerequisite is X
1, X
2Be not hydrogen simultaneously.
9. 9,9,10 of claim 1,10-four aryl substituted-dihydro anthracene derivants are as the purposes of phosphorescent light body material or hole mobile material.
10. organic electroluminescence device, it comprises negative electrode, anode and organic function layer, comprises at least one luminescent layer in this organic function layer; The formula (1) 9 that comprises at least a claim 1 in the said organic function layer; 9,10,10-four aryl substituted-dihydro anthracene derivants.
The 2-20% that has an appointment 11. the electroluminescent device of claim 10, its Chinese style (1) compound as the material of main part of luminescent layer, wherein mix; Preferred 2-15%; More preferably 3-12%, 5-10% phosphorescent coloring most preferably is all based on the weight meter of material of main part and phosphorescent coloring.
12. the electroluminescent device of claim 11, wherein phosphorescent coloring is FIrpic or Ir (ppy)
3, or its binding substances.
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| CN115160272B (en) * | 2021-09-15 | 2023-10-31 | 陕西莱特光电材料股份有限公司 | Nitrogen-containing compound, and electronic element and electronic device using same |
| CN114539013A (en) * | 2022-02-23 | 2022-05-27 | 西安欧得光电材料有限公司 | Method for synthesizing OLED intermediate material 9, 10-dihydroanthracene |
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