CN106831773A - Compound containing 9,9 ' spiral shell acridines and its preparation method and application - Google Patents
Compound containing 9,9 ' spiral shell acridines and its preparation method and application Download PDFInfo
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- CN106831773A CN106831773A CN201710006576.2A CN201710006576A CN106831773A CN 106831773 A CN106831773 A CN 106831773A CN 201710006576 A CN201710006576 A CN 201710006576A CN 106831773 A CN106831773 A CN 106831773A
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- 0 CCC(C1(C(C)=C(*2)C=CC=C)c3ccccc3Nc3ccccc13)=C2C=C=CC Chemical compound CCC(C1(C(C)=C(*2)C=CC=C)c3ccccc3Nc3ccccc13)=C2C=C=CC 0.000 description 2
- LIZPTLFFUJDYOL-UHFFFAOYSA-N CC/N=C(/C1C=CC=CC1)\NC Chemical compound CC/N=C(/C1C=CC=CC1)\NC LIZPTLFFUJDYOL-UHFFFAOYSA-N 0.000 description 1
- PXXJHWLDUBFPOL-UHFFFAOYSA-N NC(c1ccccc1)=N Chemical compound NC(c1ccccc1)=N PXXJHWLDUBFPOL-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N c1ccccc1 Chemical compound c1ccccc1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
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- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
Abstract
The invention discloses the compound containing 9,9 ' spiral shell acridines, with 9,9 ' spiral shell acridines for core, 9,9 ' spiral shell acridines are combined with peripheral electrophilic Ar with Ar ' units.Contain 9 the invention also discloses above-mentioned, the preparation method of the compound of 9 ' spiral shell acridines, by the Ar units and Ar ' units that select different halogens to replace, with 10H, the spiral shell acridines of 10 ' H 9,9 ' carry out Buchwald Hartwig coupling reactions, copper catalysis halogenated aryl hydrocarbon ammoxidation, or the nucleophilic substitution under basic conditions obtains the compound containing 9,9 ' spiral shell acridines.The present invention discloses the application of the above-mentioned compound for containing 9,9 ' spiral shell acridines.The compound for containing 9,9 ' spiral shell acridines of the invention, with strong fluorescence, with certain electric conductivity, can be applied to make the luminescent layer of organic electroluminescent LED as illuminator.
Description
Technical field
The present invention relates to electroluminescent material technical field, compound and its preparation more particularly to containing 9,9 '-spiral shell acridine
Methods and applications.
Background technology
Recent two decades come, and organic electroluminescent LED (OLED) is because with efficient, low voltage drive, it is easy to large area system
The advantages of standby and total colouring, has broad application prospects, and obtains the extensive concern of people.The research starts from eighties of last century 50
In the age, sandwich device architecture is used in patent US4356429 until doctor Deng Qingyun of Kodak in 1987 waits,
The OLED developed luminosity under 10V direct voltage drives reaches 1000cd/m2, obtain OLED epoch-making
Development.
Organic electroluminescent is broadly divided into fluorescence and phosphorescence, but according to spin quantum statistical theory, singlet excitons and three
The probability of weight state exciton is 1:3, i.e., the theoretical limit of the fluorescence from singlet excitons radiation transistion is 25%, triplet exciton
The theoretical limit of the phosphorescence of radiation transistion is 75%.And due to spin forbidden, it is triple in conventional pure organic molecular compound
State exciton cannot directly carry out radiation transistion and light, and can only be sent to ground state by de excitation in the form of heat radiation, cause most of exciton
Waste and energy loss.Cause the theoretical external quantum efficiency limiting value only 6-7% of traditional OLED.How to utilize
The energy of 75% triplet excitons turns into the task of top priority.Adachi in 2012 find the compound that a class contains sulfuryl possess compared with
Small singlet state-triplet energy level is poor so that the exciton in triplet is able to by being crossing to singlet state between anti-gap, then by spoke
Penetrate transition and send fluorescence so that the theoretical limit of all fluorescence substantially exceeds 25%.Using this kind of compound containing sulfuryl as
Luminescence unit is entrained in prepared device in material of main part two (2- (diphenyl phosphorus oxygen) phenyl) ether (DPEPO) and obtains up to
9.9% external quantum efficiency, greatly exceed traditional organic fluorescent compounds level to be reached.From this, people couple
The electroluminescent compounds for possessing less singlet state-triplet energy level difference generate keen interest.
And to realize that less singlet state-triplet energy level is poor, there are strict requirements to the design of material, including
The control interacted to conjugate length and electron unit and short of electricity subelement.So far, only a few materials can
The conversion of singlet excitons is crossing between the anti-gap of triplet exciton is realized in electroluminescent device.Traditional organic light emission point
Son, usual electron unit and short of electricity subelement interact too strong, and the conjugated degree of molecule is excessive, cause triplet energy level compared with
It is low, it is difficult to realize that less singlet state-triplet energy level is poor.Accordingly, it would be desirable to develop new construction unit to control intermolecular electricity
Lotus shifts and conjugated degree is within the scope of rational.
The content of the invention
In order to overcome the disadvantages mentioned above and deficiency of prior art, 9,9 '-spiral shell a word used for translation are contained it is an object of the invention to provide one kind
The compound of pyridine, it is poor with relatively low singlet state-triplet energy level, with fluorescence quantum yield higher.
Another object of the present invention is the preparation method for providing the above-mentioned compound for containing 9,9 '-spiral shell acridine.
Still a further object of the present invention is that offer is above-mentioned contains the compound of 9,9 '-spiral shell acridine answering in Organic Light Emitting Diode
With.
The purpose of the present invention is achieved through the following technical solutions：
Compound containing 9,9 '-spiral shell acridine, with following structure：
Conjugate unit Ar and Ar ' are identical group or different groups；
The aromatic rings that Ar is constituted for hydrocarbon atom, the aromatic heterocycle that carbon nitrogen hydrogen atom is constituted, what carbon nitrogen oxygen hydrogen atom was constituted
Aromatic heterocycle, the aromatic heterocycle that carbon sulphur hydrogen atom is constituted, the aromatic heterocycle that carbon silicon hydrogen atom is constituted, what carbon nitrogen sulphur hydrogen atom was constituted
Aromatic heterocycle, one or more of combination in the aromatic heterocycle that carbon silicon sulphur hydrogen atom is constituted；
The aromatic rings that Ar ' is constituted for hydrocarbon atom, the aromatic heterocycle that carbon nitrogen hydrogen atom is constituted, what carbon nitrogen oxygen hydrogen atom was constituted
Aromatic heterocycle, the aromatic heterocycle that carbon sulphur hydrogen atom is constituted, the aromatic heterocycle that carbon silicon hydrogen atom is constituted, what carbon nitrogen sulphur hydrogen atom was constituted
Aromatic heterocycle, one or more of combination in the aromatic heterocycle that carbon silicon sulphur hydrogen atom is constituted.
Ar is the one kind in following structure：
Ar ' is the one kind in following structure：
Compound containing 9,9 '-spiral shell acridine has following structure：
The preparation method of the described compound containing 9,9 '-spiral shell acridine, when conjugate unit Ar and Ar ' they are identical group,
Comprise the following steps：
(1) 10H, 10 ' H-9,9 '-spiral shell acridine presoma are synthesized；
(2) the halogen X substituted compounds of 10H, 10 ' H-9,9 '-spiral shell acridine presoma and Ar units are according to 1：2.2~2.6
Mol ratio, by under Buchwald-Hartwig coupling reactions, copper catalysis halogenated aryl hydrocarbon ammoxidation or basic conditions
Nucleophilic substitution, prepare the compound containing 9,9 '-spiral shell acridine.
The preparation method of the described compound containing 9,9 '-spiral shell acridine, when conjugate unit Ar and Ar ' they are different groups,
Comprise the following steps：
(1) 10H, 10 ' H-9,9 '-spiral shell acridine presoma are synthesized；
(2) the halogen X substituted compounds of 10H, 10 ' H-9,9 '-spiral shell acridine presoma and Ar units are according to 1：0.8~1.0
Mol ratio, by Buchwald-Hartwig coupling reactions, copper catalysis halogenated aryl hydrocarbon ammoxidation, or under basic conditions
Nucleophilic substitution, prepare monosubstituted compound；
(3) the monosubstituted compound that step (2) is obtained by the halogen X substituted compounds with Ar ' units according to 1：1.1~
1.3 mol ratio, by Buchwald-Hartwig coupling reactions, copper catalysis halogenated aryl hydrocarbon ammoxidation, or highly basic bar
Nucleophilic substitution under part, prepares the compound containing 9,9 '-spiral shell acridine.
The compound containing 9,9 '-spiral shell acridine of the described compound containing 9,9 '-spiral shell acridine is as illuminator in Organic Electricity
Application in photoluminescence diode.
Mechanism of the invention is：
Compound of the invention with 9,9 '-spiral shell acridine be core, it is electrophilic with periphery using the electron rich of its aromatic amine
Ar and Ar ' units are combined, and obtaining a class has the molecule of Intramolecular electron transfer, utilizes again and is opened greatly in 9,9 '-spiral shell acridine molecule
Steric hindrance produced by angle, very big dihedral angle is formed with the Ar and Ar ' units that are connected, is shown below：
9,9 '-spiral shell acridine forms the conformation of near vertical with two ends phenyl ring, controls effective conjugated degree of whole molecule, makes
Obtaining molecule has triplet energies high, so that it is poor to reduce singlet state-triplet energy level so that the exciton in triplet is led to
Singlet state is crossing between crossing reverse gap, then fluorescence is sent by radiation transistion, to improve the utilization ratio of exciton, be finally reached and carry
The purpose of device performance high.
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) of the invention to contain 9, the compound of 9 '-spiral shell acridine is poor with relatively low singlet state-triplet energy level, is conducive to
The exciton utilization rate in device is improved, the outer quantum theory Efficiency Limit for breaking through conventional fluorescent material 6-7% is obtained.
(2) of the invention to contain 9, the compound of 9 '-spiral shell acridine, with fluorescence quantum yield higher, is advantageously implemented height
Device efficiency.
(3) of the invention to contain 9, the compound of 9 '-spiral shell acridine can be realized by connecting different units come adjustment structure
The launching light of different wave length.
Brief description of the drawings
Fig. 1 is the compound containing 9,9 '-spiral shell acridine obtained using embodiment 1, embodiment 2, embodiment 5 and embodiment 12
S1, S2, S5 and S12 are bent as the voltage-current density-brightness relationship of Organic Light Emitting Diode (OLED) device of luminescent material
Line is as schemed.
Fig. 2 is the compound containing 9,9 '-spiral shell acridine obtained using embodiment 1, embodiment 2, embodiment 5 and embodiment 12
S1, S2, S5 and S12 as Organic Light Emitting Diode (OLED) device of luminescent material current density-external quantum efficiency relation
Curve map.
Fig. 3 is to be utilized as the chemical combination containing 9,9 '-spiral shell acridine that embodiment 1, embodiment 2, embodiment 5 and embodiment 12 are obtained
Thing S1, S2, S5 and S12 as Organic Light Emitting Diode (OLED) device of luminescent material electroluminescent light spectrogram.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1：
Step 1：
The preparation of (4- bromophenyls)-Phenyl-carbamic acid tertiary butyl ester, reaction equation is as follows：
In 1 liter of single-necked flask, di-tert-butyl dicarbonate (BOC) (0.2mol, 43.6g) is added to 400 at room temperature
In the tetrahydrofuran of milliliter, then add to N- (dibromobenzene) aniline (0.1mol, 24.8g), be heated to flowing back and stirring 24
Hour.Then mixed liquor is poured into 1L water, and uses dichloromethane extraction product.Anhydrous magnesium sulfate dries organic phase, after separation
Removal solvent, colourless oil liquid (32.0g, yield 92%) is obtained with silica gel chromatographic column separating-purifying.
Step 2：
The preparation of 10- ((2- methoxy ethoxies) methyl) -9 (10H) acridones, reaction equation is as follows：
In 500 milliliters of there-necked flasks, 9 (10H) acridones (90mmol, 17.55g) are added to 200 milliliters of DMF
In, add the sodium hydride (120mmol, about 5.8g) that mass concentration is 50%.Reaction unit is stirred one hour under ice-water bath
Afterwards, 2- Methoxy-ethoxymethyls chlorine (180mmol, about 19mL) are added, after 10 hours of stirring, is then poured into mixed liquor
In 500 milliliters of water, and use dichloromethane extraction product.Anhydrous magnesium sulfate dries organic phase, and solvent is removed after separation, uses silica gel color
Spectrum post separation purification obtains white solid (20.6g, 81%).
Step 3：
10H, 10 ' H-9, the preparation of 9 '-spiral shell acridine, reaction equation is as follows：
In 200 milliliters of there-necked flasks, in (4- the bromophenyls)-Phenyl-carbamic acid tert-butyl group that will be prepared in embodiment 1
Ester (8mmol, 2.8g) is added in 60 milliliters of anhydrous tetrahydro furan, is then cooled to subzero 80 DEG C, then be slowly dropped into 1.6M
N-BuLi (9mmol, 5.2mL).Continue to stir 2 hours under an argon atmosphere.Add the 10- ((2- prepared in embodiment 2
Methoxy ethoxy) methyl) in 25 milliliters of solution of tetrahydrofuran, continuation stirs 2 to -9 (10H) acridones (8.1mmol, 2.3g)
Then hour is to slowly warm up to room temperature.15 milliliters of watery hydrochloric acid (1M) are subsequently adding, after being further continued for stirring 12 hours, mixed liquor are fallen
In entering 500 milliliters of water, and use dichloromethane extraction product.Anhydrous magnesium sulfate dries organic phase, and solvent is removed after separation, uses silica gel
Chromatographic column separating-purifying obtains faint yellow solid (1.4g, 51%).
Step 4：
The preparation of compound S1, reaction equation is as follows：
Under an argon atmosphere to adding 10H, 10 ' H-9,9 '-spiral shell acridine (1.2mmol, 0.42g) and 2- (4- in reaction bulb
Bromophenyl) -4,6- diphenyl -1,3,5-triazines (2.8mmol, 1.09g), 50 milliliters of toluene as solvent, 60 milligrams of palladium,
Tri-tert phosphorus (0.5mmol, 0.11g), and 0.48 gram of sodium tert-butoxide.It is heated to reflux lower stirring reaction 24 hours, after cooling, will
Mixed liquor is poured into 200 milliliters of water, and uses dichloromethane extraction product.Anhydrous magnesium sulfate dries organic phase, is removed after separation molten
Agent, yellow solid is obtained with silica gel chromatographic column separating-purifying.By drying high-purity product is obtained after sublime under vacuum conditions
(0.72g, yield 63%).
Embodiment 2：
The preparation of compound S2, reaction equation is as follows：
Under an argon atmosphere to adding 10H, 10 ' H-9,9 '-spiral shell acridine (1.2mmol, 0.42g) and 4- (4- in reaction bulb
Bromophenyl) -2,6- diphenylpyrimidins (2.7mmol, 1.04g), 50 milliliters of toluene are used as solvent, 60 milligrams of palladium, three tertiary fourths
Base phosphorus (0.5mmol, 0.11g), and 0.48 gram of sodium tert-butoxide.Lower stirring reaction is heated to reflux 24 hours, after cooling, by mixed liquor
Pour into 200 milliliters of water, and use dichloromethane extraction product.Anhydrous magnesium sulfate dries organic phase, and solvent is removed after separation, uses silicon
Glue chromatographic column separating-purifying obtains faint yellow solid.By drying high-purity product is obtained after sublime under vacuum conditions
(0.82g, yield 71%).
Embodiment 3：
The preparation of compound S3, reaction equation is as follows：
Under an argon atmosphere to adding 10H, 10 ' H-9,9 '-spiral shell acridine (1.2mmol, 0.42g) and 4'- (4- in reaction bulb
Bromophenyl) -2,2'；6', 2 "-terpyridyl (2.8mmol, 1.08g), 50 milliliters of toluene are used as solvent, 60 milligrams of palladium, three
Tert-butyl group phosphorus (0.5mmol, 0.11g), and 0.48 gram of sodium tert-butoxide.It is heated to reflux lower stirring reaction 24 hours, after cooling, will be mixed
Close liquid to pour into 200 milliliters of water, and use dichloromethane extraction product.Anhydrous magnesium sulfate dries organic phase, and solvent is removed after separation,
Pale solid is obtained with silica gel chromatographic column separating-purifying.By drying high-purity product is obtained after sublime under vacuum conditions
(0.68g, yield 59%).
Embodiment 4：
The preparation of compound S4, reaction equation is as follows：
Under an argon atmosphere to adding 10H, 10 ' H-9,9 '-spiral shell acridine (1.2mmol, 0.42g) and 4- (4- in reaction bulb
Bromophenyl) double o-tolyl borines (2.8mmol, 0.98g), 50 milliliters of toluene are used as solvent, 60 milligrams of palladium, tri-tert
Phosphorus (0.5mmol, 0.11g), and 0.48 gram of sodium tert-butoxide.It is heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is fallen
In entering 200 milliliters of water, and use dichloromethane extraction product.Anhydrous magnesium sulfate dries organic phase, and solvent is removed after separation, uses silica gel
Chromatographic column separating-purifying obtains white solid.By drying high-purity product (0.64g, product are obtained after sublime under vacuum conditions
Rate 61%).
Embodiment 5：
The preparation of compound S5, reaction equation is as follows：
Under an argon atmosphere to adding 10H, 10 ' H-9,9 '-spiral shell acridine (1.2mmol, 0.42g) and 2- (4- in reaction bulb
Bromophenyl) m-dicyanobenzene (2.7mmol, 0.76g), 50 milliliters of toluene are used as solvent, 60 milligrams of palladium, tri-tert phosphorus
(0.5mmol, 0.11g), and 0.48 gram of sodium tert-butoxide.It is heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into
In 200 milliliters of water, and use dichloromethane extraction product.Anhydrous magnesium sulfate dries organic phase, and solvent is removed after separation, uses silica gel color
Spectrum post separation purification obtains white solid.By drying high-purity product (0.64g, yield are obtained after sublime under vacuum conditions
71%).
Embodiment 6：
The preparation of compound s 6, reaction equation is as follows：
Under an argon atmosphere to adding 10H, 10 ' H-9,9 '-spiral shell acridine (1.2mmol, 0.42g) and 2- (4- in reaction bulb
Bromophenyl) nitrile of 1,3,5- benzene three (2.8mmol, 0.86g), 50 milliliters of toluene are used as solvent, 60 milligrams of palladium, tri-tert phosphorus
(0.5mmol, 0.11g), and 0.48 gram of sodium tert-butoxide.It is heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into
In 200 milliliters of water, and use dichloromethane extraction product.Anhydrous magnesium sulfate dries organic phase, and solvent is removed after separation, uses silica gel color
Spectrum post separation purification obtains faint yellow solid.By drying high-purity product (0.62g, product are obtained after sublime under vacuum conditions
Rate 65%).
Embodiment 7：
The preparation of compound S7, reaction equation is as follows：
Under an argon atmosphere to 10H is added in reaction bulb, 10 ' H-9,9 '-spiral shell acridine (1.2mmol, 0.42g) and 4'- are bromo-
2,6- dimethyl-[1,1'- biphenyl] -4- formonitrile HCNs (2.6mmol, 0.74g), 50 milliliters of toluene as solvent, 60 milligrams of palladium,
Tri-tert phosphorus (0.5mmol, 0.11g), and 0.48 gram of sodium tert-butoxide.It is heated to reflux lower stirring reaction 24 hours, after cooling, will
Mixed liquor is poured into 200 milliliters of water, and uses dichloromethane extraction product.Anhydrous magnesium sulfate dries organic phase, is removed after separation molten
Agent, white solid is obtained with silica gel chromatographic column separating-purifying.By drying high-purity product is obtained after sublime under vacuum conditions
(0.55g, yield 61%).
Embodiment 8：
The preparation of compound S8, reaction equation is as follows：
Under an argon atmosphere to adding 10H, 10 ' H-9,9 '-spiral shell acridine (1.2mmol, 0.42g) and 5- (4- in reaction bulb
Bromophenyl) -2- cyanopyridines (2.7mmol, 0.70g), 50 milliliters of toluene are used as solvent, 60 milligrams of palladium, tri-tert phosphorus
(0.5mmol, 0.11g), and 0.48 gram of sodium tert-butoxide.It is heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into
In 200 milliliters of water, and use dichloromethane extraction product.Anhydrous magnesium sulfate dries organic phase, and solvent is removed after separation, uses silica gel color
Spectrum post separation purification obtains faint yellow solid.By drying high-purity product (0.48g, product are obtained after sublime under vacuum conditions
Rate 57%).
Embodiment 9：
The preparation of compound S9, reaction equation is as follows：
Under an argon atmosphere to adding 10H, 10 ' H-9,9 '-spiral shell acridine (1.2mmol, 0.42g) and 5- (4- in reaction bulb
Bromophenyl) -2- cyanopyrimidines (2.6mmol, 0.68g), 50 milliliters of toluene work (2.6mmol, 0.74g), 50 milliliters of toluene conducts
Solvent, 60 milligrams of palladium, tri-tert phosphorus (0.5mmol, 0.11g), and 0.48 gram of sodium tert-butoxide.It is heated to reflux lower stirring anti-
Answer 24 hours, after cooling, mixed liquor is poured into 200 milliliters of water, and use dichloromethane extraction product.Anhydrous magnesium sulfate is dried to be had
Machine phase, removes solvent after separation, yellow solid is obtained with silica gel chromatographic column separating-purifying.By drying after liter under vacuum condition
China obtains high-purity product (0.53g, yield 63%).
Embodiment 10：
The preparation of compound S10, reaction equation is as follows：
Under an argon atmosphere to 10H is added in reaction bulb, 10 ' H-9,9 '-spiral shell acridine (1.2mmol, 0.42g) and 1- are bromo-
4- (benzene sulfonyl) benzene (2.8mmol, 0.83g), 50 milliliters of toluene are used as solvent, 60 milligrams of palladium, tri-tert phosphorus
(0.5mmol, 0.11g), and 0.48 gram of sodium tert-butoxide.It is heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into
In 200 milliliters of water, and use dichloromethane extraction product.Anhydrous magnesium sulfate dries organic phase, and solvent is removed after separation, uses silica gel color
Spectrum post separation purification obtains faint yellow solid.By drying high-purity product (0.63g, product are obtained after sublime under vacuum conditions
Rate 67%).
Embodiment 11：
The preparation of compound S11, reaction equation is as follows：
Under an argon atmosphere to adding 10H, 10 ' H-9,9 '-spiral shell acridine (1.2mmol, 0.42g) and 2- bromines 5 in reaction bulb,
5,10,10- tetra- oxygen thianthrenes (2.6mmol, 0.93g), 50 milliliters of toluene are used as solvent, 60 milligrams of palladium, tri-tert phosphorus
(0.5mmol, 0.11g), and 0.48 gram of sodium tert-butoxide.It is heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into
In 200 milliliters of water, and use dichloromethane extraction product.Anhydrous magnesium sulfate dries organic phase, and solvent is removed after separation, uses silica gel color
Spectrum post separation purification obtains faint yellow solid, and drying obtains high-purity product (0.68g, yield after sublimed under vacuum
63%).
Embodiment 12：
The preparation of compound S12, reaction equation is as follows：
Under an argon atmosphere to adding 10H, 10 ' H-9,9 '-spiral shell acridine (1.2mmol, 0.42g) and 3- bromines in reaction bulb
Benzene -10,10- dioxy phenoxazines thiophene (2.7mmol, 0.84g), 50 milliliters of toluene are used as solvent, 60 milligrams of palladium, tri-tert phosphorus
(0.5mmol, 0.11g), and 0.48 gram of sodium tert-butoxide.It is heated to reflux lower stirring reaction 24 hours, after cooling, mixed liquor is poured into
In 200 milliliters of water, and use dichloromethane extraction product.Anhydrous magnesium sulfate dries organic phase, and solvent is removed after separation, uses silica gel color
Spectrum post separation purification obtains white solid.By drying high-purity product (0.65g, yield are obtained after sublime under vacuum conditions
0.67%).
Embodiment 13：
Step 1：The preparation of compound S7a, reaction equation is as follows：
Under an argon atmosphere to 10H is added in reaction bulb, 10 ' H-9,9 '-spiral shell acridine (5.0mmol, 1.73g) and 4'- are bromo-
2,6- dimethyl-[1,1'- biphenyl] -4- formonitrile HCNs (4.5mmol, 1.56g), 100 milliliters of toluene are used as solvent, the milli of palladium 100
Gram, tri-tert phosphorus (1mmol, 0.22g), and 0.77 gram of sodium tert-butoxide.It is heated to reflux lower stirring reaction 24 hours, after cooling,
Mixed liquor is poured into 300 milliliters of water, and uses dichloromethane extraction product.Anhydrous magnesium sulfate dries organic phase, is removed after separation
Solvent, white solid (1.37g, yield 55%) is obtained with silica gel chromatographic column separating-purifying.
Step 2：The preparation of compound S13, reaction equation is as follows：
Under an argon atmosphere to compound S7a (1.0mmol, 0.55g) prepared in addition embodiment 16 in reaction bulb
With 5- (4- bromophenyls) -2- cyanopyrimidines (1.2mmol, 0.31g), 50 milliliters of toluene are used as solvent, 40 milligrams of palladium, three uncles
Butyl phosphorus (0.5mmol, 0.11g), and 0.48 gram of sodium tert-butoxide.It is heated to reflux lower stirring reaction 24 hours, after cooling, will mixes
Liquid is poured into 200 milliliters of water, and uses dichloromethane extraction product.Anhydrous magnesium sulfate dries organic phase, and solvent is removed after separation, uses
Silica gel chromatographic column separating-purifying obtains yellow solid.By drying high-purity product is obtained after sublime under vacuum conditions
(0.47g, yield 65%).
Embodiment 14：
The preparation of compound S14, reaction equation is as follows：
Under an argon atmosphere to compound S7a (1.0mmol, 0.55g) prepared in addition embodiment 16 in reaction bulb
With 2- (4- bromophenyls) -4,6- diphenyl -1,3,5-triazines (1.2mmol, 0.47g), 50 milliliters of toluene are used as solvent, palladium
40 milligrams, tri-tert phosphorus (0.5mmol, 0.11g), and 0.48 gram of sodium tert-butoxide.It is heated to reflux lower stirring reaction 24 hours, it is cold
But after, mixed liquor is poured into 200 milliliters of water, and use dichloromethane extraction product.Anhydrous magnesium sulfate dries organic phase, after separation
Removal solvent, yellow solid is obtained with silica gel chromatographic column separating-purifying.Obtain high-purity after sublime under vacuum conditions by drying
Degree product (0.52g, yield 60%).
Compound S1, S2, S5 containing 9,9 '-spiral shell acridine that embodiment 1, embodiment 2, embodiment 5 and embodiment 12 are obtained
It is used to prepare the performance test of Organic Light Emitting Diode (OLED) device with S12, device architecture is：ITO(120nm)/TAPC
(20nm)/mCP(10nm)/EML(20nm)/DPEPO(10nm)/B3PyPB(40nm)/LiF(0.5nm)/Al(100nm).Wherein
EML be by containing 9,9 '-spiral shell acridine it is compound doped enter DPEPO main bodys.
Wherein, the structural formula of TAPC, mCP, DPEPO, B3PyPB is as follows respectively:
Indium tin oxide-coated glass (ITO) with oxygen-Plasma by after ultrasonic wave cleaning, being processed, and the square of ito glass is electric
It is 10 Ω/cm to hinder2.Hole transmission layer is TAPC, and electronic barrier layer is mCP, luminescent layer be respectively adopted embodiment 1, embodiment 2,
The acridine compounds containing 9,9 '-spiral shell obtained by embodiment 5 and embodiment 12 are doped in material of main part DPEPO, exciton barrier-layer
It is DPEPO, electron transfer layer uses B3PyPB, cathode electrode to use LiF/Al metals.Apply positively biased between ITO and metal electrode
Pressure, tests the characteristic of device, as a result as shown in table 1 under different electric currents.
Table 1
Wherein λ represents the peak wavelength of luminescent spectrum；Current efficiency, power efficiency and external quantum efficiency are followed successively by maximum
It is worth and in 100cd/m2And 1000cd/m2Numerical value under brightness.
Compound S1, S2, S5 containing 9,9 '-spiral shell acridine that embodiment 1, embodiment 2, embodiment 5 and embodiment 12 are obtained
With S12 as Organic Light Emitting Diode (OLED) device of luminescent material voltage-current density-brightness relationship curve such as Fig. 1
It is shown；Its current density-external quantum efficiency relation curve is as shown in Figure 2；Its electroluminescent spectrum is as shown in Figure 3.
By the result in table 1 and Fig. 1 and Fig. 2 can be seen that it is of the invention contain 9, the compound of 9 '-spiral shell acridine has higher
Fluorescence quantum yield, Organic Light Emitting Diode (OLED) device with it as luminescent layer has luminous efficiency very high.It is special
It is not the OLED based on compound S1, its quantum efficiency has reached 33.1%.And the internal quantum effect of all devices
Rate is considerably beyond the theoretical limit of conventional fluorescent device 6% or so.Illustrate by using the material energy designed by the present invention
Enough so that the exciton in triplet is able to by being crossing to singlet state between reverse gap, then fluorescence is sent by radiation transistion, so that
Obtain device efficiency high.
Compound S3, S4, S6~11, S12~14 as Organic Light Emitting Diode (OLED) device of luminescent material property
Can test result and S1, S2, S5 and S12 as Organic Light Emitting Diode (OLED) device of luminescent material the performance test results
It is similar, will not be repeated here.
The compound for containing 9,9 '-spiral shell acridine of the invention can be prepared by the following method：10H, 10 ' H-9,9 '-spiral shell a word used for translation
The halogen X substituted compounds of pyridine presoma and Ar units are according to 1：2.2~2.6 mol ratio, by Buchwald-Hartwig
Nucleophilic substitution under coupling reaction, copper catalysis halogenated aryl hydrocarbon ammoxidation or basic conditions, prepare containing 9,9 '-
The compound of spiral shell acridine；
Can also be prepared by the following method：10H, 10 ' H-9,9 '-spiral shell acridine presoma replace with the halogen X of Ar units
Compound is according to 1：0.8~1.0 mol ratio, by Buchwald-Hartwig coupling reactions, copper catalysis halogenated aryl hydrocarbon amino
Change reaction, or the nucleophilic substitution under basic conditions, prepare monosubstituted compound；Monosubstituted compound by with
The halogen X substituted compounds of Ar ' units are according to 1：1.1~1.3 mol ratio, by Buchwald-Hartwig coupling reactions,
Copper catalysis halogenated aryl hydrocarbon ammoxidation, or the nucleophilic substitution under basic conditions, prepare containing 9,9 '-spiral shell acridine
Compound.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by the embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (7)
1. 9, the compound of 9 '-spiral shell acridine, it is characterised in that with following structure are contained：
Conjugate unit Ar and Ar ' are identical group or different groups；
Ar is the aromatic rings that hydrocarbon atom is constituted, the aromatic heterocycle that carbon nitrogen hydrogen atom is constituted, the fragrance that carbon nitrogen oxygen hydrogen atom is constituted
Heterocycle, the aromatic heterocycle that carbon sulphur hydrogen atom is constituted, the aromatic heterocycle that carbon silicon hydrogen atom is constituted, the fragrance that carbon nitrogen sulphur hydrogen atom is constituted
Heterocycle, one or more of combination in the aromatic heterocycle that carbon silicon sulphur hydrogen atom is constituted；
Ar ' is the aromatic rings that hydrocarbon atom is constituted, the aromatic heterocycle that carbon nitrogen hydrogen atom is constituted, the fragrance that carbon nitrogen oxygen hydrogen atom is constituted
Heterocycle, the aromatic heterocycle that carbon sulphur hydrogen atom is constituted, the aromatic heterocycle that carbon silicon hydrogen atom is constituted, the fragrance that carbon nitrogen sulphur hydrogen atom is constituted
Heterocycle, one or more of combination in the aromatic heterocycle that carbon silicon sulphur hydrogen atom is constituted.
2. it is according to claim 1 to contain 9, the compound of 9 '-spiral shell acridine, it is characterised in that Ar is in following structure
Kind：
3. it is according to claim 1 and 2 to contain 9, the compound of 9 '-spiral shell acridine, it is characterised in that Ar ' is in following structure
One kind：
4. it is according to claim 1 to contain 9, the compound of 9 '-spiral shell acridine, it is characterised in that the chemical combination containing 9,9 '-spiral shell acridine
Thing has following structure：
5. the preparation method of the compound containing 9,9 '-spiral shell acridine described in claim 1, it is characterised in that as conjugate unit Ar
And Ar ' is identical group, is comprised the following steps：
(1) 10H, 10 ' H-9,9 '-spiral shell acridine presoma are synthesized；
(2) the halogen X substituted compounds of 10H, 10 ' H-9,9 '-spiral shell acridine presoma and Ar units are according to 1：2.2~2.6 rub
You compare, by the parent under Buchwald-Hartwig coupling reactions, copper catalysis halogenated aryl hydrocarbon ammoxidation or basic conditions
Core substitution reaction, prepares the compound containing 9,9 '-spiral shell acridine.
6. contain 9, the preparation method of the compound of 9 '-spiral shell acridine described in claim 1, it is characterised in that as conjugate unit Ar and
Ar ' is different groups, is comprised the following steps：
(1) 10H, 10 ' H-9,9 '-spiral shell acridine presoma are synthesized；
(2) the halogen X substituted compounds of 10H, 10 ' H-9,9 '-spiral shell acridine presoma and Ar units are according to 1：0.8~1.0 rubs
You compare, by Buchwald-Hartwig coupling reactions, the parent under copper catalysis halogenated aryl hydrocarbon ammoxidation, or basic conditions
Core substitution reaction, prepares monosubstituted compound；
(3) the monosubstituted compound that step (2) is obtained by the halogen X substituted compounds with Ar ' units according to 1：1.1~1.3
Mol ratio, by Buchwald-Hartwig coupling reactions, copper catalysis halogenated aryl hydrocarbon ammoxidation, or under basic conditions
Nucleophilic substitution, prepare the compound containing 9,9 '-spiral shell acridine.
7. the compound containing 9,9 '-spiral shell acridine of the compound containing 9,9 '-spiral shell acridine described in any one of Claims 1 to 4 is made
The application for being illuminator in organic electroluminescent LED.
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