CN107628984A - A kind of preparation of aromatic amine derivatives and its organic electroluminescence device containing dibenzo-carbazole class formation - Google Patents
A kind of preparation of aromatic amine derivatives and its organic electroluminescence device containing dibenzo-carbazole class formation Download PDFInfo
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- 0 CC(C)[n](c1c2)c3cc(N(C4C=CC=CC4)c4cc([n](C(C)C(CC5)=C6)c7cc(C8=C*=CCC8)c(cccc8)c8c77)c7c7c4cccc7)c6c5c3c1c(cccc1)c1c2-c1ccccc1 Chemical compound CC(C)[n](c1c2)c3cc(N(C4C=CC=CC4)c4cc([n](C(C)C(CC5)=C6)c7cc(C8=C*=CCC8)c(cccc8)c8c77)c7c7c4cccc7)c6c5c3c1c(cccc1)c1c2-c1ccccc1 0.000 description 18
- MHSFPLOMYHYNMF-UHFFFAOYSA-N Brc1cc([n](c2c3c(cccc4)c4cc2)-c2ccccc2)c3c2c1cccc2 Chemical compound Brc1cc([n](c2c3c(cccc4)c4cc2)-c2ccccc2)c3c2c1cccc2 MHSFPLOMYHYNMF-UHFFFAOYSA-N 0.000 description 1
- DXNAIAQDOISYFV-UHFFFAOYSA-N C(C1N(c2cc3ccccc3cc2)c2cc([n](c3ccc(cccc4)c4c33)-c4ccccc4)c3c3c2cccc3)c([n](c2c3c(cccc4)c4cc2)-c2ccccc2)c3-c2c1cccc2 Chemical compound C(C1N(c2cc3ccccc3cc2)c2cc([n](c3ccc(cccc4)c4c33)-c4ccccc4)c3c3c2cccc3)c([n](c2c3c(cccc4)c4cc2)-c2ccccc2)c3-c2c1cccc2 DXNAIAQDOISYFV-UHFFFAOYSA-N 0.000 description 1
- IBSGYBGKYGGFTB-UHFFFAOYSA-N CC1(C2)N(C)c3cc(-c4ccccc4)c(cccc4)c4c3C1=C(C=CC=C1)C1=C2N(c1ccccc1)c1cc([n](C)c2c3c(cccc4)c4c(C4=CC=CCC4)c2)c3c2c1cccc2 Chemical compound CC1(C2)N(C)c3cc(-c4ccccc4)c(cccc4)c4c3C1=C(C=CC=C1)C1=C2N(c1ccccc1)c1cc([n](C)c2c3c(cccc4)c4c(C4=CC=CCC4)c2)c3c2c1cccc2 IBSGYBGKYGGFTB-UHFFFAOYSA-N 0.000 description 1
- MQFYUZCANYLWEI-UHFFFAOYSA-N Cc(cc1)c(cccc2)c2c1N Chemical compound Cc(cc1)c(cccc2)c2c1N MQFYUZCANYLWEI-UHFFFAOYSA-N 0.000 description 1
- ZZLCFHIKESPLTH-UHFFFAOYSA-N Cc(cc1)ccc1-c1ccccc1 Chemical compound Cc(cc1)ccc1-c1ccccc1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 1
- KIBYTAROWZDJQF-UHFFFAOYSA-N Cc1cc(N(C)C(C2)C3c4ccccc4C2N(c2ccccc2)c2c(C)c([n](C)c4cc(C)c(cccc5)c5c44)c4c4c2cccc4)c3c2c1cccc2 Chemical compound Cc1cc(N(C)C(C2)C3c4ccccc4C2N(c2ccccc2)c2c(C)c([n](C)c4cc(C)c(cccc5)c5c44)c4c4c2cccc4)c3c2c1cccc2 KIBYTAROWZDJQF-UHFFFAOYSA-N 0.000 description 1
- ZLTBAVNWQOCMIB-UHFFFAOYSA-N Cc1ccc(C(F)(F)F)c2c1cccc2 Chemical compound Cc1ccc(C(F)(F)F)c2c1cccc2 ZLTBAVNWQOCMIB-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N Nc1cccc2ccccc12 Chemical compound Nc1cccc2ccccc12 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention provides a kind of preparation of aromatic amine derivatives and its organic electroluminescence device containing dibenzo-carbazole class formation, is related to organic optoelectronic materials technology.Dibenzo-carbazole structure has cavity transmission ability, plus introducing condensed ring class rigidity, asymmetric, close packed structure, make that the preparation of aromatic amine derivatives thermal stability obtained by the present invention is high, good film-forming property, available for preparing organic electroluminescence device, especially as the hole mobile material or material of main part in organic electroluminescence device, the advantages of showing high efficiency, low driving voltage and being not easy to crystallize, better than existing conventional OLED.
Description
Technical field
The present invention relates to organic photoelectrical material technical field, and in particular to a kind of fragrance containing dibenzo-carbazole class formation
Amine derivant and its organic electroluminescence device.
Background technology
Organic Light Emitting Diode (Organic Light-Emitting Diodes, electroluminescent) has become in recent years
Very popular emerging FPD industry both at home and abroad, there is self-luminous, visual angle wide (up to more than 170 °), fast response time
(~1 μ s), color is true to nature, definition is high, high-luminous-efficiency, operating voltage low (3~10V), plate thickness thin (being less than 2mm),
Large scale and flexible panel and the Making programme outstanding advantage such as simply can be made, just because of with very strong application background
The characteristics of being better than inorganic thin film device with many, electroluminescent organic material causes attracting attention for common people, has attracted more and more
Academic institution and company one of concern, ten big achievements being chosen as by the U.S. in 1992 annual chemical fields.
The synthetic method of electroluminescent organic material is varied, and reactive mode, reaction mechanism are also not quite similar, and easily produce
Raw side reaction, so the material that high-purity is made is relatively difficult.Electroluminescent organic material does not require nothing more than material purity
Height, but also require that material composition is single, therefore, the raising side of method and purity of each state all to luminous organic material synthesis
Face gives the attention of height.Electroluminescent organic material is the material base of organic electroluminescence device, and the property of material will
The performance of device is directly affected, the organic material for organic electroluminescence device should possess following properties：(1) 400~
There is higher fluorescence quantum efficiency in 700nm visible-ranges；(2) good characteristic of semiconductor, i.e., with high conductance,
Can effectively transporting holes or electronics；(3) material easily forms the amorphous film of densification and is not easy to change with the time；(4) have
There are good heat endurance and chemical stability.
At present, organic electroluminescence device develops towards practical, commercialization, but the brightness in device, efficiency and
Still need further to improve on life-span, this it is also proposed organic material higher requirement.It is more preferable how new performance is designed
Material be adjusted, be always those skilled in the art's urgent problem to be solved.
The content of the invention
It is an object of the invention to provide a kind of preparation of aromatic amine derivatives containing dibenzo-carbazole class formation and its have
Organic electroluminescence devices, organic compound thermal stability provided by the invention is high, good film-forming property, and preparation method is simple, by this
Organic electroluminescence device made of compound, it is property the advantages of showing high efficiency, low driving voltage life-span and be not easy to crystallize
The excellent luminous organic material of energy.
Present invention firstly provides a kind of preparation of aromatic amine derivatives containing dibenzo-carbazole class formation, structural formula is：
Wherein, Ar is selected from C6~C50 substituted or unsubstituted aryl, C6~C50 substituted or unsubstituted heteroaryl
In one kind；R1The alkoxy of alkyl, C1~C10 selected from C1~C10, C6~C50 substituted or unsubstituted aryl, C6~
One kind in C50 substituted or unsubstituted heteroaryl；R2Selected from hydrogen atom, C1~C10 alkyl, C1~C10 alkoxy,
One kind in C6~C50 substituted or unsubstituted aryl, C6~C50 substituted or unsubstituted heteroaryl.
Preferably, the Ar be selected from C6~C25 substituted or unsubstituted aryl, C6~C18 it is substituted or unsubstituted
One kind in heteroaryl；R1The alkoxy of alkyl, C1~C10 selected from C1~C10, C6~C25 substituted or unsubstituted virtue
Base, C6~C18 substituted or unsubstituted heteroaryl in one kind；R2Selected from hydrogen atom, C1~C10 alkyl, C1~C10
Alkoxy, C6~C25 substituted or unsubstituted aryl, C6~C18 substituted or unsubstituted heteroaryl in one kind.
Preferably, the Ar is selected from substituted or unsubstituted phenyl, naphthyl, anthryl, pyrenyl, xenyl, terphenyl, indenes
Base, indyl, pyridine radicals, furyl, thienyl, dibenzothiophenes base, dibenzofuran group, quinolyl, isoquinolyl, carbazole
Base, fluorenyl or the fluorenyl of spiral shell two.
Preferably, a kind of preparation of aromatic amine derivatives containing dibenzo-carbazole class formation is in structure as shown below
Any one：
The present invention also provides a kind of above-mentioned preparation of aromatic amine derivatives containing dibenzo-carbazole class formation and sent out in organic electroluminescence
Application in optical device.
Preferably, the organic electroluminescence device include negative electrode, anode and one be placed between two electrode or
Multiple organic compound layers, described organic compound layer contain a kind of described aromatic amine containing dibenzo-carbazole class formation
Analog derivative.
Preferably, described a kind of organic electroluminescence device, it is characterised in that the organic compound layer includes hole
Implanted layer, hole transmission layer, in electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer at least
One layer；It is at least one layer of in the organic compound layer to spread out containing a kind of described aromatic amine containing dibenzo-carbazole class formation
Biology.
Preferably, described a kind of organic electroluminescence device, it is characterised in that contain in hole transmission layer or luminescent layer
A kind of described preparation of aromatic amine derivatives containing dibenzo-carbazole class formation.
Beneficial effects of the present invention:
Present invention firstly provides a kind of preparation of aromatic amine derivatives containing dibenzo-carbazole class formation, the aromatic amine derives
Thing has structure shown in formula I, and dibenzo-carbazole structure has cavity transmission ability, and plus introducing, condensed ring class is rigid, asymmetric, close
Structure set, makes that the preparation of aromatic amine derivatives thermal stability obtained by the present invention is high, good film-forming property, available for preparing organic electroluminescence
Luminescent device, especially as the hole mobile material or material of main part in organic electroluminescence device, show high efficiency, low
Driving voltage and the advantages of being not easy to crystallize, better than existing conventional OLED.
Embodiment
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are simply further explanation the features and advantages of the present invention, rather than to the claims in the present invention
Limitation.
Alkyl of the present invention refers to minus the alkyl that a hydrogen atom forms in alkane molecule, and it can be straight chain alkane
Base, branched alkyl, cycloalkyl, example may include methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary fourth
Base, amyl group, isopentyl, cyclopenta, cyclohexyl etc., but not limited to this.
Alkoxy of the present invention refer to alkyl and oxygen atom link after group, example may include methoxyl group, ethyoxyl,
2- propoxyl group, 2- cyclohexyloxies etc., but not limited to this.
Aryl of the present invention refers to after removing a hydrogen atom on the aromatic core carbon of aromatic hydrocarbon molecule, is left the total of univalent perssad
Claiming, it can be monocyclic aryl or fused ring aryl, and example may include phenyl, xenyl, naphthyl, anthryl, phenanthryl or pyrenyl etc., but
Not limited to this.
Heteroaryl of the present invention refers to the group that one or more of aryl aromatic core carbon substitutes to obtain by hetero atom
General name, the hetero atom include but is not limited to oxygen, sulphur or nitrogen-atoms, and the heteroaryl can be bicyclic heteroaryl or condensed ring heteroaryl
Base, example may include pyridine radicals, pyrrole radicals, pyridine radicals, thienyl, furyl, indyl, quinolyl, isoquinolyl, benzo thiophene
Fen base, benzofuranyl, dibenzofuran group, dibenzothiophenes base, carbazyl etc., but not limited to this.
Present invention firstly provides a kind of preparation of aromatic amine derivatives containing dibenzo-carbazole class formation, structural formula is：
Wherein, Ar is selected from C6~C50 substituted or unsubstituted aryl, C6~C50 substituted or unsubstituted heteroaryl
In one kind；R1The alkoxy of alkyl, C1~C10 selected from C1~C10, C6~C50 substituted or unsubstituted aryl, C6~
One kind in C50 substituted or unsubstituted heteroaryl；R2Selected from hydrogen atom, C1~C10 alkyl, C1~C10 alkoxy,
One kind in C6~C50 substituted or unsubstituted aryl, C6~C50 substituted or unsubstituted heteroaryl.
Preferably Ar is selected from C6~C25 substituted or unsubstituted aryl, C6~C18 substituted or unsubstituted heteroaryl
In one kind；R1The alkoxy of alkyl, C1~C10 selected from C1~C10, C6~C25 substituted or unsubstituted aryl, C6~
One kind in C18 substituted or unsubstituted heteroaryl；R2Selected from hydrogen atom, C1~C10 alkyl, C1~C10 alkoxy,
One kind in C6~C25 substituted or unsubstituted aryl, C6~C18 substituted or unsubstituted heteroaryl.
According to the present invention, described substituted aryl, substitution five-ring heterocycles, substitution hexa-member heterocycle, substitution it is thick miscellaneous
In ring, substituent independence is selected from alkyl, alkoxy, amino, halogen, cyano group, nitro, hydroxyl or sulfydryl.
Most preferably Ar is selected from substituted or unsubstituted phenyl, naphthyl, anthryl, pyrenyl, xenyl, terphenyl, indenyl, Yin
Diindyl base, pyridine radicals, furyl, thienyl, dibenzothiophenes base, dibenzofuran group, quinolyl, isoquinolyl, carbazyl, fluorenes
Base or the fluorenyl of spiral shell two.
Specifically, a kind of preparation of aromatic amine derivatives containing dibenzo-carbazole class formation is preferably selected from knot as follows
Any one in structure：
A kind of preparation of aromatic amine derivatives containing dibenzo-carbazole class formation of the present invention, its preparation method are as follows：
Wherein, Ar is selected from C6~C50 substituted or unsubstituted aryl, C6~C50 substituted or unsubstituted heteroaryl
In one kind；R1The alkoxy of alkyl, C1~C10 selected from C1~C10, C6~C50 substituted or unsubstituted aryl, C6~
One kind in C50 substituted or unsubstituted heteroaryl；R2Selected from hydrogen atom, C1~C10 alkyl, C1~C10 alkoxy,
One kind in C6~C50 substituted or unsubstituted aryl, C6~C50 substituted or unsubstituted heteroaryl.
According to the present invention, the compound shown in intermediate A is prepared according to method as follows：
Under nitrogen protection, palladium and tri-butyl phosphine are catalyst, in the case that sodium tert-butoxide is alkali, by 7H- bis-
Benzo [c, g] carbazole reacts with the dibromo substituent that bromine reacts to obtain and shown halides, obtains intermediate A.
According to the present invention, the compound shown in intermediate B is prepared according to method as follows：
Under nitrogen protection, four triphenyl phosphorus palladiums are catalyst, in the case that potassium carbonate is alkali, by intermediate A and boric acid
Compound is reacted, and obtains intermediate B.
According to the present invention, the compound shown in structural formula I is prepared according to method as follows：
Under nitrogen protection, palladium and tri-butyl phosphine are catalyst, in the case that sodium tert-butoxide is alkali, by intermediate
B and primary amine reaction, obtain target product I.
The present invention does not have special limitation to the coupling reaction, using coupling reaction well-known to those skilled in the art
, the preparation method is simple, and raw material is easy to get.
The present invention also provides the above-mentioned preparation of aromatic amine derivatives containing dibenzo-carbazole class formation in organic electroluminescence
Application in part, a kind of preparation of aromatic amine derivatives containing dibenzo-carbazole class formation of the invention can be used as hole transport material
Material or emitting layer material are applied in terms of organic electroluminescence device, and the organic electroluminescence device includes anode, the moon
Pole and organic matter layer, organic matter layer include hole injection layer, hole transmission layer, electronic barrier layer, luminescent layer, hole blocking layer,
At least one layer in electron transfer layer, electron injecting layer；At least one layer in the organic matter layer contains described above contain
The preparation of aromatic amine derivatives of dibenzo-carbazole class formation.The present invention organic electroluminescence device be flat panel show, plane
Illuminator, illuminate with face illuminating OLED illuminator, flexible illuminator, duplicator, printer, LCD backlight lamp or dosing machine class
The suitable use such as light source, display board, mark.
The present invention has no particular limits to the raw material employed in following examples, can be for commercially available prod or using this
Preparation method known to art personnel is prepared.
Embodiment 1:
The preparation of intermediate A -1
The bromo- 1- iodine naphthalenes of 4- and nitration mixture (concentrated nitric acid and mixed sulfuric acid mixture) the effect generation iodo- 2- nitronaphthalenes of the bromo- 1- of 4-, take
37.8g, the 100mmol iodo- 2- nitronaphthalenes of the bromo- 1- of 4-, which add, is equipped with toluene, ethanol, in the three-necked flask of the mixed solvent of water,
Nitrogen protection is lower to add naphthalene boronic acids (17.2g, 100mmol), potassium carbonate (41.4g, 300mmol)), four triphenyl phosphorus palladiums
(1.154g, 1mmol), 5h is reacted under reflux temperature.After reaction terminates, deionized water is added, extracts and organic phase is washed with water, closed
And organic phase is dried, concentration, obtained crude product crosses silicagel column, obtains product intermediate A -1 (27.6g, yield 80%).Matter
Compose m/z：346.23 (calculated values：346.22).Theoretical elemental content (%) C20H12BrN：C,69.38；H,3.49；Br,23.08；
N, 4.05 actual measurement constituent contents (%)：C,69.39；H,3.49；Br,23.07；N,4.06.The above results confirm that obtaining product is
Target product.
The preparation of intermediate B -1
By tri-butyl phosphine (4.4mL 1.0M toluene solution, 1.48g, 0.05mmol), palladium (0.4g,
1.83mmol) and sodium tert-butoxide (22.8g, 238mmol) is added to intermediate A -1 (63.3g, 183mmol) and iodomethane
The solution of (26.3g, 185mmol) in degassed toluene (1L), and the mixture is heated 2 hours under reflux.This is anti-
Answer mixture to be cooled to room temperature, filtered with dilution with toluene and via diatomite.The filtrate water is diluted, and carried with toluene
Take, and merge organic phase, it is evaporated under vacuo.The residue is filtered via silica gel, and recrystallized.
To intermediate B -1 (46.1g, theoretical value 70%).Mass spectrum m/z：360.23 (calculated values：360.25).Theoretical elemental content (%)
C21H14BrN：C,70.01；H,3.92；Br,22.18；N, 3.89 actual measurement constituent contents (%)：C,70.02；H,3.92；Br,
22.18；N,3.88.The above results confirm that it is target product to obtain product.
Compound TM1 preparation
By tri-butyl phosphine (4.4mL 1.0M toluene solution, 1.48g, 0.05mmol), palladium (0.4g,
1.83mmol) and sodium tert-butoxide (22.8g, 238mmol) is added to intermediate B -1 (132.5g, 368mmol) and aniline
The solution of (17.0g, 183mmol) in degassed toluene (1L), and the mixture is heated 2 hours under reflux.This is anti-
Answer mixture to be cooled to room temperature, filtered with dilution with toluene and via diatomite.The filtrate water is diluted, and carried with toluene
Take, and merge organic phase, it is evaporated under vacuo.The residue is filtered via silica gel, and recrystallized.
To target product compound TM1 (77.4g, theoretical value 65%).Mass spectrum m/z：651.87 (calculated values：651.80).Theoretical elemental
Content (%) C48H33N3：C,88.45；H,5.10；N, 6.45 actual measurement constituent contents (%)：C,88.44；H,5.11；N,6.45.On
Stating result confirms that it is target product to obtain product.
Embodiment 2:
Change iodomethane in embodiment 1 into equimolar bromobenzene, other steps are identical, obtain compound TM5.Mass spectrum m/z：
775.97 (calculated values：775.93).Theoretical elemental content (%) C58H37N3：C,89.78；H,4.81；N, 5.42 actual measurement elements contain
Measure (%)：C,89.78；H,4.81；N,5.41.The above results confirm that it is target product to obtain product.
Embodiment 3：
Change iodomethane in embodiment 1 into equimolar 3- bromopyridines, other steps are identical, obtain compound TM7.Mass spectrum
m/z：777.99 (calculated values：777.91).Theoretical elemental content (%) C56H35N5：C,86.46；H,4.53；N, 9.00 actual measurement members
Cellulose content (%)：C,86.47；H,4.52；N,9.01.The above results confirm that it is target product to obtain product.
Embodiment 4：
Change iodomethane in embodiment 1 into equimolar 2- bromo- 9,9- dimethyl fluorenes, other steps are identical, obtain chemical combination
Thing TM8.Mass spectrum m/z：1008.29 (calculated value：1008.25).Theoretical elemental content (%) C76H53N3：C,90.53；H,5.30；
N, 4.17 actual measurement constituent contents (%)：C,90.51；H,5.33；N,4.16.The above results confirm that it is target product to obtain product.
Embodiment 5：
Changing iodomethane in embodiment 1 into equimolar 1- brominations naphthalene, aniline changes equimolar p-tert-butyl-aniline into, its
His step is identical, obtains compound TM14.Mass spectrum m/z：932.19 (calculated values：932.16).Theoretical elemental content (%)
C70H49N3：C,90.19；H,5.30；N, 4.51 actual measurement constituent contents (%)：C,90.18；H,5.31；N,4.51.The above results are demonstrate,proved
The real product that obtains is target product.
Embodiment 6：
Change iodomethane in embodiment 1 into equimolar bromobenzene, aniline changes equimolar 4- aminobphenyls, other steps into
It is identical, obtain compound TM20.Mass spectrum m/z：852.09 (calculated values：852.03).Theoretical elemental content (%) C64H41N3：C,
90.22；H,4.85；N, 4.93 actual measurement constituent contents (%)：C,90.23；H,4.86；N,4.92.The above results confirm to be produced
Thing is target product.
Embodiment 7:
The preparation of intermediate A -2
500mL dichloromethane is added into 7H- dibenzo [c, g] carbazole (26.7g, 100mmol), is slowly added dropwise at room temperature
The dichloromethane solution (bromine 40g, dichloromethane 250mL) of bromine, temperature is controlled to be no more than 40 DEG C during dropwise addition.Drip
Bi Hou, 3h is reacted at room temperature.After reaction terminates, reaction solution is washed with water, saturation sodium hydrogensulfite, the 10%NaOH aqueous solution successively
Wash, extract liquid separation, merge organic phase and drying, concentration, bromo- 7H- dibenzo [c, the g] carbazoles of 5,9- bis- are obtained via column chromatography.
By tri-butyl phosphine (4.4mL 1.0M toluene solution, 1.48g, 0.05mmol), palladium (0.4g,
1.83mmol) and sodium tert-butoxide (22.8g, 238mmol) added to bromo- 7H- dibenzo [c, the g] carbazoles of 5,9- bis- (77.7g,
183mmol) and solution of the iodomethane (26.3g, 185mmol) in degassed toluene (500mL), and the mixture is being flowed back
Lower heating 2 hours.The reactant mixture is cooled to room temperature, filtered with dilution with toluene and via diatomite.The filtrate is used
Water is diluted, and is extracted with toluene, and merges organic phase, and it is evaporated under vacuo.The residue is entered via silica gel
Row filtering, and recrystallize.Obtain intermediate A -2 (56.2g, theoretical value 70%).Mass spectrum m/z：439.13 (calculated values：
439.14).Theoretical elemental content (%) C21H13Br2N：C,57.44；H,2.98；Br,36.39；N, 3.19 actual measurement constituent contents
(%)：C,57.45；H,2.98；Br,36.38；N,3.19.The above results confirm that it is target product to obtain product.
The preparation of intermediate B -7
43.9g is taken, 100mmol intermediate A -2, which adds, is equipped with toluene, ethanol, in the three-necked flask of the mixed solvent of water,
Nitrogen protection is lower to add phenyl boric acid (12.1g, 100mmol), potassium carbonate (41.4g, 300mmol)), four triphenyl phosphorus palladiums
(1.154g, 1mmol), 5h is reacted under reflux temperature.After reaction terminates, deionized water is added, extracts and organic phase is washed with water, closed
And organic phase is dried, concentration, obtained crude product crosses silicagel column, obtains product intermediate B -7 (30.5g, yield 70%).Matter
Compose m/z：436.33 (calculated values：436.34).Theoretical elemental content (%) C27H18BrN：C,74.32；H,4.16；Br,18.31；
N, 3.21 actual measurement constituent contents (%)：C,74.32；H,4.15；Br,18.32；N,3.21.The above results confirm that obtaining product is
Target product.
Compound TM43 preparation
By tri-butyl phosphine (4.4mL 1.0M toluene solution, 1.48g, 0.05mmol), palladium (0.4g,
1.83mmol) and sodium tert-butoxide (22.8g, 238mmol) is added to intermediate B -7 (160.4g, 368mmol) and aniline
The solution of (17.0g, 183mmol) in degassed toluene (1L), and the mixture is heated 2 hours under reflux.This is anti-
Answer mixture to be cooled to room temperature, filtered with dilution with toluene and via diatomite.The filtrate water is diluted, and carried with toluene
Take, and merge organic phase, it is evaporated under vacuo.The residue is filtered via silica gel, and recrystallized.
To target product compound TM43 (95.5g, theoretical value 65%).Mass spectrum m/z：803.97 (calculated values：803.99).Theoretical elemental
Content (%) C60H41N3：C,89.63；H,5.14；N, 5.23 actual measurement constituent contents (%)：C,89.62；H,5.15；N,5.23.On
Stating result confirms that it is target product to obtain product.
Embodiment 8:
Change iodomethane in embodiment 7 into equimolar 2- N-Propyl Bromides, other steps are identical, obtain compound TM45.Matter
Compose m/z：874.39 (calculated values：874.42).Theoretical elemental content (%) C65H52N3：C,89.21；H,5.99；N, 4.80 actual measurements
Constituent content (%)：C,89.21；H,5.98；N,4.81.The above results confirm that it is target product to obtain product.
Embodiment 9：
Changing iodomethane in embodiment 7 into equimolar 3- bromopyridines, phenyl boric acid changes equimolar methoxy ylboronic acid into, its
His step is identical, obtains compound TM60.Mass spectrum m/z：837.92 (calculated values：837.96).Theoretical elemental content (%)
C58H39N5O2：C,83.13；H,4.69；N,8.36；O, 3.82 actual measurement constituent contents (%)：C,83.14；H,4.67；N,8.36；
O,3.83.The above results confirm that it is target product to obtain product.
Contrast Application Example
It is by Fisher Co., Ltd's coating layer thicknessIto glass substrate be placed in distilled water and clean 2 times, ultrasonic wave is washed
Wash 30 minutes, cleaned repeatedly with distilled water 2 times, ultrasonic washing 10 minutes, after distilled water cleaning terminates, isopropanol, acetone, first
Alcohol equal solvent in order dry later by ultrasonic washing, is transferred in plasma washing machine, aforesaid substrate is washed 5 minutes,
It is sent in evaporator.
Hole injection layer will be deposited on the ito transparent electrode being already prepared toHole transport is deposited
LayerLuminescent layer AND and dopant is depositedThen electronics is deposited to pass
Defeated layerNegative electrodeSaid process organic matter vaporization plating speed is to maintainLiF
It isAl is
Application Example：
A kind of described preparation of aromatic amine derivatives for containing dibenzo-carbazole class formation is replaced into α-NPD as hole transport
Layer in compound or replace AND be used as the material of main part in luminescent layer, with above-mentioned contrast Application Example equally
Method has manufactured the organic electroluminescence device for possessing following structure：
Device 1：ITO/2-TNATA/TM1/AND:DPAP-DPPA (5%)/TPBi/LiF/Al；
Device 2：ITO/2-TNATA/TM5/AND:DPAP-DPPA (5%)/TPBi/LiF/Al；
Device 3：ITO/2-TNATA/TM7/AND:DPAP-DPPA (5%)/TPBi/LiF/Al；
Device 4：ITO/2-TNATA/α-NPD/TM8:DPAP-DPPA (5%)/TPBi/LiF/Al；
Device 5：ITO/2-TNATA/α-NPD/TM14:DPAP-DPPA (5%)/TPBi/LiF/Al；
Device 6：ITO/2-TNATA/α-NPD/TM20:DPAP-DPPA (5%)/TPBi/LiF/Al；
Device 7：ITO/2-TNATA/α-NPD/TM43:DPAP-DPPA (5%)/TPBi/LiF/Al；
Device 8：ITO/2-TNATA/α-NPD/TM45:DPAP-DPPA (5%)/TPBi/LiF/Al；
Device 9：ITO/2-TNATA/α-NPD/TM60:DPAP-DPPA (5%)/TPBi/LiF/Al.
Evaluate example 1：Compare contrast Application Example and the evaluation of the Application Example characteristics of luminescence
It is set to light by direct current driven the organic electroluminescence device made as above, measurement result exists
The form of table 1 below shows.
Table 1
Result above shows that a kind of preparation of aromatic amine derivatives containing dibenzo-carbazole class formation of the invention is applied to have
In organic electroluminescence devices, especially as hole mobile material or material of main part, low driving voltage, high-luminous-efficiency are shown
The advantages of, it is luminous organic material of good performance.
Obviously, the explanation of above example is only intended to help the method and its core concept for understanding the present invention.It should refer to
Go out, under the premise without departing from the principles of the invention, can also be to this hair for the those of ordinary skill of the technical field
Bright to carry out some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (7)
1. a kind of preparation of aromatic amine derivatives containing dibenzo-carbazole class formation, it is characterised in that structural formula is as shown in formula I：
Wherein, in substituted or unsubstituted aryl of the Ar selected from C6~C50, C6~C50 substituted or unsubstituted heteroaryl
It is a kind of；R1The alkoxy of alkyl, C1~C10 selected from C1~C10, C6~C50 substituted or unsubstituted aryl, C6~C50
Substituted or unsubstituted heteroaryl in one kind；R2Selected from hydrogen atom, C1~C10 alkyl, C1~C10 alkoxy, C6
One kind in~C50 substituted or unsubstituted aryl, C6~C50 substituted or unsubstituted heteroaryl.
A kind of 2. preparation of aromatic amine derivatives containing dibenzo-carbazole class formation according to claim 1, it is characterised in that
Substituted or unsubstituted aryl of the Ar selected from C6~C25, C6~C18 substituted or unsubstituted heteroaryl in one kind；R1Choosing
The alkoxy of alkyl, C1~C10 from C1~C10, C6~C25 substituted or unsubstituted aryl, C6~C18 substitution or not
One kind in substituted heteroaryl；R2Substitution selected from hydrogen atom, C1~C10 alkyl, C1~C10 alkoxy, C6~C25
Or one kind in unsubstituted aryl, C6~C18 substituted or unsubstituted heteroaryl.
A kind of 3. preparation of aromatic amine derivatives containing dibenzo-carbazole class formation according to claim 1, it is characterised in that
Ar is selected from substituted or unsubstituted phenyl, naphthyl, anthryl, pyrenyl, xenyl, terphenyl, indenyl, indyl, pyridine radicals, furan
Mutter base, thienyl, dibenzothiophenes base, dibenzofuran group, quinolyl, isoquinolyl, carbazyl, fluorenyl or the fluorenyl of spiral shell two.
A kind of 4. preparation of aromatic amine derivatives containing dibenzo-carbazole class formation according to claim 1, it is characterised in that
Any one of the aromatic amine analog derivative in structure as shown below：
5. a kind of organic electroluminescence device, it is characterised in that the organic electroluminescence device includes negative electrode, anode and is placed in
One or more organic compound layers between two electrode, it is any that described organic compound layer contains claim 1-4
A kind of preparation of aromatic amine derivatives containing dibenzo-carbazole class formation described in.
6. according to a kind of organic electroluminescence device described in claim 5, it is characterised in that the organic compound layer bag
Hole injection layer, hole transmission layer are included, in electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer
At least one layer；At least one layer contains hexichol containing one kind described in claim any one of 1-4 in the organic compound layer
And the preparation of aromatic amine derivatives of carbazole class formation.
7. according to a kind of organic electroluminescence device described in claim 6, it is characterised in that hole transmission layer or luminescent layer
In contain a kind of preparation of aromatic amine derivatives containing dibenzo-carbazole class formation described in claims 1-5.
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| CN108218860A (en) * | 2018-01-18 | 2018-06-29 | 长春海谱润斯科技有限公司 | A kind of miscellaneous anthracene derivant and preparation method thereof and organic luminescent device |
| CN110343093A (en) * | 2018-04-02 | 2019-10-18 | 北京鼎材科技有限公司 | Dibenzo-carbazole compound and organic electroluminescence device |
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| CN106414428A (en) * | 2014-05-23 | 2017-02-15 | 罗门哈斯电子材料韩国有限公司 | An organic electroluminescent compound and an organic electroluminescent device comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106414428A (en) * | 2014-05-23 | 2017-02-15 | 罗门哈斯电子材料韩国有限公司 | An organic electroluminescent compound and an organic electroluminescent device comprising the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108218860A (en) * | 2018-01-18 | 2018-06-29 | 长春海谱润斯科技有限公司 | A kind of miscellaneous anthracene derivant and preparation method thereof and organic luminescent device |
| CN110343093A (en) * | 2018-04-02 | 2019-10-18 | 北京鼎材科技有限公司 | Dibenzo-carbazole compound and organic electroluminescence device |
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