CN108047233A - A kind of carbazole analog derivative and its organic luminescent device - Google Patents

A kind of carbazole analog derivative and its organic luminescent device Download PDF

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CN108047233A
CN108047233A CN201711427729.7A CN201711427729A CN108047233A CN 108047233 A CN108047233 A CN 108047233A CN 201711427729 A CN201711427729 A CN 201711427729A CN 108047233 A CN108047233 A CN 108047233A
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unsubstituted
substituted
carbazole
analog derivative
derivative
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刘喜庆
蔡辉
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Changchun Haipurunsi Technology Co Ltd
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Abstract

The invention discloses a kind of carbazole analog derivative and its organic luminescent devices, are related to organic optoelectronic materials technology.On the one hand, the derivative of the present invention by two carbazole structures and together, is then connected to two such structures by anthracene, this method increases the rigidity of carbazole structure in structure, so as to not only increase the thermal stability of derivative, the possibility of molecule reunion is also reduced；On the one hand, since the substituent group of rigid radical introduces, also further improve the stability of derivative and reduce the possibility of molecule reunion.On the other hand, the alkyl structures such as methyl, tertiary butyl are introduced into structure, add the dissolubility of derivative.Its diffraction is prepared into device, especially as emitting layer material, device shows the advantages of driving voltage is low, luminous efficiency is high, better than existing common OLED device.

Description

A kind of carbazole analog derivative and its organic luminescent device
Technical field
The present invention relates to organic photoelectrical material technical field more particularly to a kind of carbazole analog derivatives and its organic illuminator Part.
Background technology
Organic electroluminescent LED (Organic Light Emitting Diode, OLED) is to utilize electronics and hole The recombination luminescence in organic film and the luminescent device prepared, have the following advantages：(1) from main light emission, backlight is not required； (2) brightness is high, there is high contrast, pure in colour, the problem of almost without visible angle；(3) it is ultra-thin, by very thin organic Material coating and basis material are formed, small to be suitable for portable product；(4) power consumption is very small, environmental protection and energy saving；(5) ring It answers speed fast, is the one thousandth of LCD；(6) use temperature range is wide, remains to normally show at -40 DEG C.
General organic luminescent device (OLED) is the organic matter layer structure by being inserted between cathode, anode and cathode and anode Into, the composition of device is transparent ITO anode, hole injection layer (TIL), hole transmission layer (HTL), luminescent layer (EL), hole The cathodes such as barrier layer (HBL), electron transfer layer (ETL), electron injecting layer (EIL), LiAl are formed.
Emitting layer material is divided into fluorescent material and phosphor material, and the forming method of luminescent layer is adulterated in fluorescent host material The method of method and fluorescent host material doping fluorescent (organic matter for including nitrogen) dopant of phosphor material (organic metal).Often Material of main part can be divided into several, such as hole transport material of main part, electron-transport material of main part, bipolar material of main part, lazy Property material of main part, fluorescence complex material of main part and phosphorescent complexes material of main part.Wherein, carbazole and its derivative are because its is peculiar Electric property, chemical property and Photophysics and be widely used in luminescent layer.
At present, the research of electroluminescent organic material is carried out extensively in academia and industrial quarters, a large amount of function admirables Electroluminescent organic material be developed successively, but the technological industrialization process still faces many key issues how The luminescent material for designing the better carbazole class formation of new performance is adjusted, and is always that those skilled in the art are urgently to be resolved hurrily Problem.
The content of the invention
The object of the present invention is to provide a kind of carbazole analog derivative and its organic luminescent devices.Carbazoles provided by the invention Derivative thermal stability is high, glass transition temperature is high, which is used in luminescent layer use and manufactured organic illuminator Part shows the advantages of driving voltage is low, luminous efficiency is high, is the luminous organic material of function admirable.
The present invention provides a kind of carbazole analog derivatives, and general formula of molecular structure is as shown in I：
Wherein, Ar1、Ar2Independently selected from hydrogen, substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C1~ C10Alkoxy, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50Heteroaryl, substitution or do not take The C in generation2~C50Amino in one kind；R is selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C1~C10 Alkoxy, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50Heteroaryl in one kind；N is selected From 0~4 integer.
Preferably, a kind of carbazole analog derivative, n is 0,1 or 2 in general formula of molecular structure.
Preferably, a kind of carbazole analog derivative, general formula of molecular structure is as shown in II, III or IV：
Wherein, Ar1、Ar2Independently selected from hydrogen, substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C6~ C30Aryl, substituted or unsubstituted C3~C30Heteroaryl, substituted or unsubstituted C10~C30Fragrant amino in one kind；R Selected from hydrogen, substituted or unsubstituted C1~C10Alkyl in one kind.
Preferably, the Ar1、Ar2Independently selected from hydrogen or with one kind in lower structure：
Wherein, R1~R7Independently selected from hydrogen, substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C1~ C10Alkoxy, substituted or unsubstituted C6~C30Aryl, substituted or unsubstituted C3~C30Heteroaryl in one kind；R8 ~R11Independently selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C1~C10Alkoxy, substitution or Unsubstituted C6~C30Aryl in one kind；A is selected from 0~4 integer.
Further preferably, any one of a kind of carbazole analog derivative in chemical constitution as follows：
The present invention also provides a kind of organic luminescent devices, including first electrode, second electrode and are placed in two electrode Between one or more organic compound layers, the organic compound layer contains a kind of carbazoles of any one of them and derives Object.
Preferably, organic compound layer includes luminescent layer, derives in luminescent layer containing a kind of carbazoles of any one of them Object.
Beneficial effects of the present invention：
The present invention provides a kind of carbazole analog derivatives, have the following effects that：
On the one hand, carbazole ring be easily formed metastable cation, intramolecular with larger conjugated system and The advantages of strong cyclic voltammetry method, generally has higher thermal stability.But its carbazole small molecule is due to the limitation of structure, Reunion is easily formed during solid phase, so as to cause being quenched.The compound of the present invention in the structure modifies carbazole molecules, by two A carbazole structure and together, is then connected to two such structures by anthracene, this method increases the rigidity of carbazole structure, So as to not only increase the thermal stability of derivative, the possibility of molecule reunion is also reduced；
On the one hand, by introducing the substituent group of rigid radical, in structure rigidity and the characteristics of non-co-planar also improve simultaneously The stability of derivative and the possibility for reducing molecule reunion.Also, using anthra carbazole as the symmetrically or non-symmetrically knot of core The glass transition temperature of carbazole derivates is improved greatly in structure.
On the other hand, the alkyl structures such as methyl, tertiary butyl are introduced into structure, increase the dissolving of the derivative of carbazole structure Property.
Carbazole analog derivative diffraction is prepared into device, especially as emitting layer material, device shows driving voltage Low, the advantages of luminous efficiency is high, better than existing common OLED device.The good application effect shown in OLED luminescent devices Fruit, this point show it with good industrialization prospect.
The derivative of the present invention is prepared by raw material of carbazole, since carbazole itself is one of coai-tar product, is easy to get, so The manufacturing cost of the derivative of the present invention is small, is easy to industrialized production.
Specific embodiment：
It is clearly and completely described below in conjunction with the technical solution of the embodiment of the present invention, it is clear that described implementation Example is only part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, art technology Personnel's all other embodiments obtained without making creative work, belong to protection scope of the present invention.
Alkyl of the present invention refers to minus the alkyl that a hydrogen atom forms in alkane molecule, can be straight chain alkane Base, branched alkyl, cycloalkyl, example may include methyl, ethyl, propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary fourth Base, amyl, isopentyl, cyclopenta, cyclohexyl 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, can be monocyclic aryl or fused ring aryl, example may include phenyl, xenyl, naphthalene, anthryl, phenanthryl or pyrenyl etc., but It is without being limited thereto.
Heteroaryl of the present invention refers to the group that one or more of aryl aromatic core carbon is substituted by hetero atom General name, the hetero atom include but not limited to oxygen, sulphur or nitrogen-atoms, and the heteroaryl can be bicyclic heteroaryl or condensed ring heteroaryl Base, example may include pyridyl group, pyrrole radicals, pyridyl group, thienyl, furyl, indyl, quinolyl, isoquinolyl, benzo thiophene Fen base, benzofuranyl, dibenzofuran group, dibenzothiophene, carbazyl etc., but not limited to this.
Aryl amine of the present invention refers to the amine with armaticity substituent group, i.e.-NH2,-NH- or nitrogen-containing group be connected to On aromatic hydrocarbon, example may include such as lower structure, but not limited to this
The present invention provides a kind of carbazole analog derivatives, and general formula of molecular structure is as shown in I：
Wherein, Ar1、Ar2Independently selected from hydrogen, substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C1~ C10Alkoxy, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50Heteroaryl, substitution or do not take The C in generation2~C50Amino in one kind；R is selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C1~C10 Alkoxy, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50Heteroaryl in one kind；N is selected From 0~4 integer.
According to the present invention, the substituted alkyl, the aryl of substitution, the heterocycle of substitution, the choosing of the substituent group independence From methyl, ethyl, isopropyl, tertiary butyl, phenyl, naphthalene, anthryl, phenanthryl, benzo phenanthryl, base, pyrenyl, benzyl, methoxy Base, methyl mercapto, phenoxy group, thiophenyl, fluorenyl, 9,9- dimethyl fluorenyl, hexichol amido, dimethylamino, carbazyl, 9- phenyl clicks Oxazolyl, furyl, thienyl, cyano, fluorine-based, deuterium base, triphenyl silicon substrate, trimethyl silicon substrate, phenothiazinyl, phenoxazine group, a word used for translation Piperidinyl, piperidyl, pyridyl group, pyrimidine radicals, xenyl, terphenyl, nitro etc., but not limited to this.
Preferably, a kind of carbazole analog derivative, n is 0,1 or 2 in general formula of molecular structure.
Preferably, a kind of carbazole analog derivative, general formula of molecular structure is as shown in II, III or IV：
Wherein, Ar1、Ar2Independently selected from hydrogen, substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C6~ C30Aryl, substituted or unsubstituted C3~C30Heteroaryl, substituted or unsubstituted C10~C30Fragrant amino in one kind；R Selected from hydrogen, substituted or unsubstituted C1~C10Alkyl in one kind.
Preferably, the Ar1、Ar2Independently selected from hydrogen or with one kind in lower structure：
Wherein, R1~R7Independently selected from hydrogen, substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C1~ C10Alkoxy, substituted or unsubstituted C6~C30Aryl, substituted or unsubstituted C3~C30Heteroaryl in one kind；R8 ~R11Independently selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C1~C10Alkoxy, substitution or Unsubstituted C6~C30Aryl in one kind；A is selected from 0~4 integer.
Further preferably, a kind of carbazole analog derivative, any one in chemical constitution as follows：
A kind of carbazole analog derivative of the present invention, syntheti c route is by taking the synthesis of compound 1 and compound 2 as an example, specifically It is as follows：
According to the present invention, compound 1 is prepared according to method as follows：
Hypoboric acid compound is obtained by the reaction with triisopropyl borate ester in 1,5- dibromoanthracene, even by Suzuki with 2- fluorine nitre benzene Compound a is obtained by the reaction in connection.Then compound b is obtained by the reaction in the case where triphenyl phosphine catalyst o-dichlorohenzene is solvent, changes Closing object b, further reaction obtains compound c to modify the N on carbazole with 2- fluorine nitre benzene, and compound c is anti-via reduction afterwards Should, cyclization obtains compound 1.
According to the present invention, compound 2 is prepared according to method as follows：
The reaction was continued for compound 1, and dibromide e first is obtained by the reaction with bromine, then is obtained by the reaction two with triisopropyl borate ester Boride f.It is protected in nitrogen, tetra-triphenylphosphine palladium is catalyst, and under conditions of potassium carbonate is alkali, it is even to pass through Suzuki with iodobenzene Compound 2 is obtained by the reaction in connection.
The present invention special limitation no to above-mentioned reaction is using popular response well-known to those skilled in the art Can, the preparation method is easy to operate, is readily produced.
The present invention also provides a kind of organic luminescent devices, including first electrode, second electrode and are placed in two electrode Between one or more organic compound layers, organic compound layer include hole injection layer, hole transmission layer, electronic blocking Layer, luminescent layer, hole blocking layer, electron transfer layer, at least one layer of electron injecting layer；At least one in the organic compound layer Layer includes a kind of carbazole analog derivative of the present invention.
Preferably, a kind of carbazole analog derivative can be as the emitting layer material in organic luminescent device.It uses Device architecture is preferably specially：NPB is used as hole transmission layer substance, and the carbazole analog derivative is used as luminescent layer substance, TPBi is used as electron-transporting material, to manufacture the organic luminescent device of construction same as below：Carbazole described in ITO/NPB/ Analog derivative/TPBi/LiF/Al.The organic electroluminescence device can be used for flat-panel monitor, lighting source, direction board, letter The application fields such as signal lamp.
The synthesis of [embodiment 1] compound 1
The synthesis of intermediate a
Under the protection of nitrogen, 1,5- dibromoanthracenes (33.6g, 0.1mol) are taken, after adding in suitable anhydrous THF dissolvings, drop N-BuLi (150ml, 0.22mol, 1.6M), when insulation reaction 0.5 is small, three isopropyl of fast drop boric acid is added dropwise to -78 DEG C in temperature Fat (41.4g, 0.22mol) is slowly warming up to room temperature, reacts 30min.After completion of the reaction, reaction solution is to entering diluted hydrochloric acid aqueous solution In in, have solid matter that filtering is precipitated, crude product obtains hypoboric acid compound via column chromatography.
By above-mentioned product (26.6g, 0.1mol), 2- fluoronitrobenzenes (29.6g, 0.21mol), potassium carbonate (69g, 0.5mol), 300mL water, 1L toluene are in 2L there-necked flasks, nitrogen protection, stirring at normal temperature, and system is white opacity, is added after 20min Enter tetra-triphenylphosphine palladium (1.1g, 1%), be heated to reflux 12 it is small when, system generates a large amount of solids, and suction filtration is obtained among solid product Body a (35.7g, yield 85%).Mass spectrum m/z：420.39 (calculated values：420.42).Theoretical elemental content (%) C26H16N2O4： C,74.28；H,3.84；N,6.66；O, 15.22 actual measurement constituent contents (%)：C,74.26；H,3.84；N,6.66；O,15.24. The above results confirm that it is target product to obtain product.
The synthesis of intermediate b
Intermediate a (11.3g, 27mmol) and triphenylphosphine (35.4g, 135mmol) are added in 100mL o-dichlorohenzenes, It after when heating stirring 12 is small, is cooled to room temperature, filters, 100mL water is added in filtrate, extraction merges organic phase, anhydrous MgSO4 Column chromatography is concentrated after drying, obtains intermediate b (3.8g, yield 40%).Mass spectrum m/z：356.39 (calculated values：356.42).Reason Argument cellulose content (%) C26H16N2：C,87.62；H,4.52；N, 7.86 actual measurement constituent contents (%)：C,87.63；H,4.53；N, 7.84.The above results confirm that it is target product to obtain product.
The synthesis of intermediate c
Compound b (21.3g, 59.8mmol), 2- fluoronitrobenzenes (16.8g, 120mmol) and Cs2CO3(46.8g, 144mmol) it is added in 200mL DMSO, stirs 15 hours.It is filtered after adding in 500mL water into system at the end of reaction, The extraction of 300mL dichloromethane is added in into filtrate, merges organic phase, anhydrous MgSO4Column chromatography is concentrated after drying, obtains intermediate C (26.8g, yield 75%).Mass spectrum m/z：598.59 (calculated values：598.61).Theoretical elemental content (%) C38H22N4O4：C, 76.24；H,3.70；N,9.36；O, 10.69 actual measurement constituent contents (%)：C,76.24；H,3.72；N,9.36；O,10.68.On Stating result confirms that it is target product to obtain product.
The synthesis of intermediate d
By intermediate c (20.7g, 34.7mmol) and SnCl2·2H2O (25.16g, 111mmol) is added in ethanol solution, System is when heating stirring 8 is small at 70 DEG C.Reaction terminates, after system is cooled to room temperature, thereto add in 300mL dichloromethane and 300mL saturations NaHCO3Solution merges organic phase, anhydrous MgSO after extraction4Column chromatography is concentrated after drying, obtains intermediate d (14.0g, yield 75%).Mass spectrum m/z：538.59 (calculated values：538.64).Theoretical elemental content (%) C38H26N4：C, 84.73；H,4.87；N, 10.40 actual measurement constituent contents (%)：C,84.73；H,4.85；N,10.42.The above results confirm to obtain Product is target product.
The synthesis of compound 1
By intermediate d (12.5g, 23.23mmol), 60mL glacial acetic acid and the dense H of 5mL2SO4It is put into reaction bulb, is stirred under ice bath Mixing 10 minutes makes system cool down completely.Then, 150mL NaNO are added in2Solution (1.6g, 1eq) after continue to stir, stirring After ten minutes, the temperature of mixture is 130 DEG C, is stirred for 20 minutes.After reaction, it is cooled to room temperature.It is added in into system 300mL water and 300mL dichloromethane merge organic phase, anhydrous MgSO after extraction4Column chromatography is concentrated after drying, obtains target production Compounds 1 (8.8g, yield 75%).Mass spectrum m/z：504.59 (calculated values：504.58).Theoretical elemental content (%) C38H20N2：C,90.45；H,4.00；N, 5.55 actual measurement constituent contents (%)：C,90.44；H,4.01；N,5.55.The above results are demonstrate,proved The real product that obtains is target product.
The synthesis of [embodiment 2] compound 2
The synthesis of intermediate e
Compound 1 (40.3g, 80mmol) is added in reaction vessel, the dissolving of 0.5L dichloromethane is added in, delays at room temperature The slow solution that bromine (29.3g, 176mmol) is added dropwise in 0.1L dichloromethane.Temperature is controlled to be no more than 40 DEG C.After being added dropwise, 3h is reacted at room temperature.After the completion of reaction, reaction solution is washed successively with water, saturation sodium hydrogensulfite, 10%wt NaOH solutions, Liquid separation, organic phase are dried with anhydrous sodium sulfate.Concentration, obtained white crude, via column chromatography obtain intermediate e (37.0g, Yield 70%).Mass spectrum m/z：662.39 (calculated values：662.37).Theoretical elemental content (%) C38H18N2Br2：C,68.90；H, 2.74；N,4.23；Br, 24.13 actual measurement constituent contents (%)：C,68.92；H,2.71；N,4.24；Br,24.13.The above results Confirm that it is target product to obtain product.
The synthesis of intermediate f
Under the protection of nitrogen, intermediate e (66.2g, 0.1mol) is taken, after adding in suitable anhydrous THF dissolvings, cooling To -78 DEG C, n-BuLi (150ml, 0.22mol, 1.6M), when insulation reaction 0.5 is small, three isopropyl ester of fast drop boric acid is added dropwise (41.3g, 0.22mol) is slowly warming up to room temperature, reacts 30min.After completion of the reaction, reaction solution is to entering in diluted hydrochloric acid aqueous solution, There is solid matter that filtering is precipitated, crude product obtains intermediate f (44.4g, yield 75%) via column chromatography.
The synthesis of compound 2
Weigh successively intermediate f (59.2g, 0.1mol), iodobenzene (42.8g, 0.21mol), potassium carbonate (69g, 0.5mol), 300mL water, 1L toluene are in 2L there-necked flasks, and nitrogen protection, stirring at normal temperature, system is white opacity, and four triphens are added in after 20min Base phosphine palladium (1.1g, 1%), be heated to reflux 12 it is small when, system generates a large amount of solids, and suction filtration obtains solid product compound 2 (55.8g, yield 85%).Mass spectrum m/z：656.73 (calculated values：656.77).Theoretical elemental content (%) C50H28N2：C, 91.44；H,4.30；N, 4.27 actual measurement constituent contents (%)：C,91.44；H,4.32；N,4.23.The above results confirmation is produced Object is target product.
The synthesis of [embodiment 3] compound 6
Change the iodobenzene in the synthesis of 2 compound 2 of embodiment into equimolar 1- tertiary butyls -4- bromobenzenes, other steps are equal It is identical with the synthesis of embodiment 2, obtain target product compound 6.Mass spectrum m/z：768.90 (calculated values：768.98).Theoretical member Cellulose content (%) C58H44N2：C,90.59；H,5.77；N, 3.64 actual measurement constituent contents (%)：C,90.57；H,5.77；N,3.66. The above results confirm that it is target product to obtain product.
The synthesis of [embodiment 4] compound 12
By tri-tert-butylphosphine (toluene solution of the 1.0M of 3mL, 7.32mmol), palladium (0.4g, 1.83mmol) and uncle Sodium butoxide (22.8g, 238mmol) is added to equal intermediate e (121.1g, 183mmol) and diphenylamines (64.9g, 384mmol) exists Solution in degassed toluene (1L), and by the mixture heat under reflux 2 it is small when.The reaction mixture is cooled to room Temperature is filtered with dilution with toluene and via diatomite.The filtrate water is diluted, and is extracted with toluene, and merges organic phase, It is evaporated under vacuo.The residue is filtered via silica gel, being recrystallized to give compound 12, (108.2g is received 75%) rate is.Mass spectrum m/z：838.92 (calculated values：838.99).Theoretical elemental content (%) C62H38N4：C,88.76；H, 4.57；N, 6.68 actual measurement constituent contents (%)：C,88.76；H,4.56；N,6.67.The above results confirm that it is target to obtain product Product.
The synthesis of [embodiment 5] compound 20
Change the iodobenzene in the synthesis of 2 compound 2 of embodiment into bromo- 9, the 9- dimethyl fluorenes of equimolar 2-, other steps It is identical with the synthesis of embodiment 2, obtain target product compound 20.Mass spectrum m/z：889.07 (calculated values：889.09).It is theoretical Constituent content (%) C68H44N2：C,91.86；H,4.99；N, 3.15 actual measurement constituent contents (%)：C,91.85；H,4.97；N, 3.18.The above results confirm that it is target product to obtain product.
The synthesis of [embodiment 6] compound 32
The synthesis of intermediate a-2
By above-mentioned hypoboric acid compound (26.6g, 0.1mol), the fluoro- 4- bromo nitrobenzenes (46.2g, 0.21mol) of 2-, carbonic acid Potassium (69g, 0.5mol), 300mL water, 1L toluene are in 2L there-necked flasks, and nitrogen protection, stirring at normal temperature, system is white opacity, Tetra-triphenylphosphine palladium (1.1g, 1%) is added in after 20min, be heated to reflux 12 it is small when, system generates a large amount of solids, and suction filtration is consolidated Body product Intermediate a-2 (49.1g, yield 85%).Mass spectrum m/z：578.18 (calculated values：578.21).Theoretical elemental content (%) C26H14Br2N2O4：C,54.01；H,2.44；Br,27.64；N,4.84；O, 11.07 actual measurement constituent contents (%)：C, 54.03；H,2.44；Br,27.64；N,4.84；O,11.05.The above results confirm that it is target product to obtain product.
The synthesis of intermediate b-2
Intermediate a-2 (15.6g, 27mmol) and triphenylphosphine (35.41g, 135mmol) are added in into 100mL o-dichlorohenzenes In, when heating stirring 12 is small after, be cooled to room temperature, filter, 100mL water is added in filtrate, extraction merges organic phase, anhydrous MgSO4Column chromatography is concentrated after drying, obtains intermediate b-2 (6.0g, yield 43%).Mass spectrum m/z：514.19 (calculated values： 514.21).Theoretical elemental content (%) C26H14Br2N2：C,60.73；H,2.74；Br,31.08；N, 5.45 actual measurement constituent contents (%)：C,60.75；H,2.72；Br,31.08；N,5.45.The above results confirm that it is target product to obtain product.
The synthesis of intermediate c-2
Compound b-2 (30.7g, 59.8mmol), 2- fluoronitrobenzenes (16.9g, 120mmol) and Cs2CO3(46.8g, 144mmol) it is added in 200mL DMSO, stirs 15 hours.It is filtered after adding in 500mL water into system at the end of reaction, The extraction of 300mL dichloromethane is added in into filtrate, merges organic phase, anhydrous MgSO4Column chromatography is concentrated after drying, obtains intermediate C-2 (33.9g, yield 75%).Mass spectrum m/z：756.39 (calculated values：756.40).Theoretical elemental content (%) C38H20Br2N4O4：C,60.34；H,2.67；Br,21.13；N,7.41；O, 8.46 actual measurement constituent contents (%)：C,60.34；H, 2.68；Br,21.13；N,7.42；O,8.43.The above results confirm that it is target product to obtain product.
The synthesis of intermediate d-2
By intermediate c-2 (26.2g, 34.7mmol) and SnCl2·2H2O (25.16g, 111mmol) adds in ethanol solution In, system is when heating stirring 8 is small at 70 DEG C.Reaction terminates, and after system is cooled to room temperature, adds in 300mL dichloromethanes thereto Alkane and 300mL saturations NaHCO3Solution merges organic phase, anhydrous MgSO after extraction4Column chromatography is concentrated after drying, obtains intermediate D-2 (16.9g, yield 70%).Mass spectrum m/z：696.39 (calculated values：696.43).Theoretical elemental content (%) C38H24Br2N4： C,65.53；H,3.47；Br,22.95；N, 8.04 actual measurement constituent contents (%)：C,65.53；H,3.48；Br,22.95；N, 8.04.The above results confirm that it is target product to obtain product.
The synthesis of intermediate g
By intermediate d-2 (16.2g, 23.23mmol), 60mL glacial acetic acid and the dense H of 5mL2SO4It is put into reaction bulb, under ice bath Stirring makes system cool down completely in 10 minutes.Then, 150mL NaNO are added in2Solution (1.6g, 1eq) after continue to stir, stirring It mixes after ten minutes, the temperature of mixture is 130 DEG C, is stirred for 20 minutes.After reaction, it is cooled to room temperature.Add into system Enter 300mL water and 300mL dichloromethane, organic phase, anhydrous MgSO are merged after extraction4Column chromatography is concentrated after drying, obtains target Product Intermediate g (10.8g, yield 70%).Mass spectrum m/z：662.39 (calculated values：662.37).Theoretical elemental content (%) C38H18Br2N2：C,68.90；H,2.74；Br,24.13；N, 4.23 actual measurement constituent contents (%)：C,68.91；H,2.74；Br, 24.13；N,4.24.The above results confirm that it is target product to obtain product.
The synthesis of intermediate e-2
Intermediate g (48.9g, 80mmol) is added in reaction vessel, the dissolving of 0.5L dichloromethane is added in, delays at room temperature The slow solution that bromine (27.2g, 170mmol) is added dropwise in 0.1L dichloromethane.Temperature is controlled to be no more than 40 DEG C.After being added dropwise, 3h is reacted at room temperature.After the completion of reaction, reaction solution is washed successively with water, saturation sodium hydrogensulfite, 10%wt NaOH solutions, Liquid separation, organic phase are dried with anhydrous sodium sulfate.Concentration, obtained white crude obtain intermediate e-2 via column chromatography (36.7g, yield 70%).Mass spectrum m/z：820.19 (calculated values：820.16).Theoretical elemental content (%) C38H16N2Br4：C, 55.65；H,1.97；N,3.42；Br, 38.97 actual measurement constituent contents (%)：C,55.66；H,1.96；N,3.41；Br,38.97. The above results confirm that it is target product to obtain product.
The synthesis of intermediate f-2
Under the protection of nitrogen, intermediate e (82.0g, 0.1mol) is taken, after adding in suitable anhydrous THF dissolvings, cooling To -78 DEG C, n-BuLi (262ml, 0.42mol, 1.6M), when insulation reaction 0.5 is small, three isopropyl ester of fast drop boric acid is added dropwise (80.8g, 0.43mol) is slowly warming up to room temperature, reacts 30min.After completion of the reaction, reaction solution is to entering in diluted hydrochloric acid aqueous solution, There is solid matter that filtering is precipitated, crude product obtains intermediate f-2 (47.6g, yield 70%) via column chromatography.
The synthesis of compound 32
Weigh successively intermediate f-2 (68.0g, 0.1mol), tert-bromo butane (57.5g, 0.42mol), potassium carbonate (69g, 0.5mol), 300mL water, 1L toluene are in 2L there-necked flasks, nitrogen protection, stirring at normal temperature, and system is white opacity, is added after 20min Enter tetra-triphenylphosphine palladium (1.1g, 1%), be heated to reflux 12 it is small when, system generates a large amount of solids, and suction filtration obtains solid product chemical combination Object 32 (61.0g, yield 90%).Mass spectrum m/z：729.03 (calculated values：729.00).Theoretical elemental content (%) C54H52N2： C,88.97；H,7.19；N, 3.84 actual measurement constituent contents (%)：C,88.99；H,7.19；N,3.82.The above results confirm to obtain Product is target product.
The synthesis of [embodiment 7] compound 52
Change the compound b-2 in the synthesis of 6 compound 32 of embodiment into equimolar compound b, it will be with compound b-2 The 2- fluoronitrobenzenes of reaction change the fluoro- 4- bromines nitros of equimolar 2- into, other steps are identical with the synthesis of embodiment 6, obtain Target product compound 52.Mass spectrum m/z：729.05 (calculated values：729.00).Theoretical elemental content (%) C54H52N2：C, 88.97；H,7.19；N, 3.84 actual measurement constituent contents (%)：C,88.99；H,7.18；N,3.83.The above results confirmation is produced Object is target product.
The synthesis of [embodiment 8] compound 69
The synthesis of intermediate k
It is fluoro- by equimolar 2- is changed into the 2- fluoronitrobenzenes of compound b-2 reactions in the synthesis of 6 intermediate g of embodiment 4- bromine nitros, other steps are identical with the synthesis of embodiment 6, obtain intermediate k.Mass spectrum m/z：820.15 (calculated values： 820.16).Theoretical elemental content (%) C38H16Br4N2：C,55.65；H,1.97；Br,38.97；N, 3.42 actual measurement constituent contents (%)：C,55.63；H,1.97；Br,38.98；N,3.42.The above results confirm that it is target product to obtain product.
The synthesis of intermediate m
Under the protection of nitrogen, intermediate k (82.0g, 0.1mol) is taken, after adding in suitable anhydrous THF dissolvings, cooling To -78 DEG C, n-BuLi (300ml, 0.44mol, 1.6M), when insulation reaction 0.5 is small, three isopropyl ester of fast drop boric acid is added dropwise (82.6g, 0.44mol) is slowly warming up to room temperature, reacts 30min.After completion of the reaction, reaction solution is to entering in diluted hydrochloric acid aqueous solution, There is solid matter that filtering is precipitated, crude product obtains intermediate m (51.0g, yield 75%) via column chromatography.
The synthesis of intermediate n
Weigh successively intermediate m (68.0g, 0.1mol), iodomethane (58.2g, 0.41mol), potassium carbonate (69g, 0.5mol), 300mL water, 1L toluene are in 2L there-necked flasks, nitrogen protection, stirring at normal temperature, and system is white opacity, is added after 20min Enter tetra-triphenylphosphine palladium (1.1g, 1%), be heated to reflux 12 it is small when, system generates a large amount of solids, and suction filtration is obtained among solid product Body n (50.5g, yield 90%).Mass spectrum m/z：560.79 (calculated values：560.69).Theoretical elemental content (%) C42H28N2：C, 89.97；H,5.03；N, 5.00 actual measurement constituent contents (%)：C,89.95；H,5.03；N,5.02.The above results confirmation is produced Object is target product.
The synthesis of intermediate o
Intermediate n (44.8g, 80mmol) is added in reaction vessel, the dissolving of 0.5L dichloromethane is added in, delays at room temperature The slow solution that bromine (32g, 170mmol) is added dropwise in 0.1L dichloromethane.Temperature is controlled to be no more than 40 DEG C.After being added dropwise, 3h is reacted at room temperature.After the completion of reaction, reaction solution is washed successively with water, saturation sodium hydrogensulfite, 10%wt NaOH solutions, point Liquid, organic phase are dried with anhydrous sodium sulfate.Concentration, obtained white crude, obtaining intermediate o via column chromatography, (40.2g is received Rate 70%).Mass spectrum m/z：718.49 (calculated values：718.48).Theoretical elemental content (%) C42H26N2Br2：C,70.21；H, 3.65；N,3.90；Br, 22.24 actual measurement constituent contents (%)：C,70.21；H,3.65；N,3.91；Br,22.23.The above results Confirm that it is target product to obtain product.
The synthesis of intermediate p
By tri-tert-butylphosphine (toluene solution of the 1.0M of 3mL, 7.32mmol), palladium (0.4g, 1.83mmol) and uncle Sodium butoxide (22.8g, 238mmol) is added to equal intermediate o (131.4g, 183mmol) and diphenylamines (31.2g, 185mmol) exists Solution in degassed toluene (1L), and by the mixture heat under reflux 2 it is small when.The reaction mixture is cooled to room Temperature is filtered with dilution with toluene and via diatomite.The filtrate water is diluted, and is extracted with toluene, and merges organic phase, It is evaporated under vacuo.The residue via silica gel is filtered, is recrystallized to give intermediate p (103.3g, yield For 70%).Mass spectrum m/z：806.79 (calculated values：806.78).Theoretical elemental content (%) C54H42BrN3：C,80.39；H, 4.50；Br,9.90；N, 5.21 actual measurement constituent contents (%)：C,80.37；H,4.51；Br,9.91；N,5.21.The above results are demonstrate,proved The real product that obtains is target product.
The synthesis of intermediate q
Under the protection of nitrogen, intermediate p (80.6g, 0.1mol) is taken, after adding in suitable anhydrous THF dissolvings, cooling To -78 DEG C, n-BuLi (75ml, 0.12mol, 1.6M), when insulation reaction 0.5 is small, three isopropyl ester of fast drop boric acid is added dropwise (24.4g, 0.13mol) is slowly warming up to room temperature, reacts 30min.After completion of the reaction, reaction solution is to entering in diluted hydrochloric acid aqueous solution, There is solid matter that filtering is precipitated, crude product obtains intermediate q (54.0g, yield 70%) via column chromatography.
The synthesis of compound 69
Weigh successively intermediate q (77.1g, 0.1mol), iodobenzene (22.4g, 0.11mol), potassium carbonate (69g, 0.5mol), 300mL water, 1L toluene are in 2L there-necked flasks, and nitrogen protection, stirring at normal temperature, system is white opacity, and four triphens are added in after 20min Base phosphine palladium (1.1g, 1%), be heated to reflux 12 it is small when, system generates a large amount of solids, and suction filtration obtains solid product compound 69 (68.3g, yield 85%).Mass spectrum m/z：803.92 (calculated values：803.99).Theoretical elemental content (%) C60H41N3：C, 89.63；H,5.14；N, 5.23 actual measurement constituent contents (%)：C,89.63；H,5.14；N,5.24.The above results confirmation is produced Object is target product.
[comparison Application Example]
Transparent anode electrode ito substrate in isopropanol is cleaned by ultrasonic 15 minutes, and is exposed 30 minutes under ultraviolet light, Then handled 10 minutes with plasma.Then by treated, ito substrate is put into evaporated device.One layer of 70nm's of vapor deposition first NPB is as hole transmission layer, evaporation rate 0.1nm/s, followed by the vapor deposition of luminescent layer, mixing vapor deposition CBP/Ir (PPy)3, Doping concentration is 10wt%, evaporation rate 0.005nm/s, evaporation thickness 30nm, and the TPBi of 50nm is then deposited as electricity Sub- transport layer, evaporation rate 0.01nm/s, vacuum evaporation LiF and Al is as cathode, thickness successively on the electron transport layer 200nm。
[Application Example]
Transparent anode electrode ito substrate in isopropanol is cleaned by ultrasonic 15 minutes, and is exposed 30 minutes under ultraviolet light, Then handled 10 minutes with plasma.Then by treated, ito substrate is put into evaporated device.One layer of 70nm's of vapor deposition first Then the carbazole analog derivative of 30nm is deposited as luminous as hole transmission layer, evaporation rate 0.1nm/s in NPB The TPBi of 50nm is then deposited as electron transfer layer in layer, evaporation rate 0.005nm/s, evaporation rate 0.01nm/s, On electron transfer layer successively vacuum evaporation LiF and Al as cathode, thickness 200nm.
The electron luminescence characteristic of the organic luminescent device of above method manufacture represents in the following table：
The above result shows that a kind of carbazole analog derivative of the invention is applied in organic luminescent device, especially as Luminescent material shows the advantages of driving voltage is low, luminous efficiency is high, is luminous organic material of good performance.
Obviously, the explanation of above example is only intended to help to understand method and its core concept of the invention.It should refer to Go out, it, without departing from the principle of the present invention, can also be to this hair for the those of ordinary skill of the technical field Bright some improvement and modification can also be carried out, these improvement and modification are also fallen into the protection domain of the claims in the present invention.

Claims (7)

1. a kind of carbazole analog derivative, which is characterized in that its general formula of molecular structure is as shown in I：
Wherein, Ar1、Ar2Independently selected from hydrogen, substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C1~C10's Alkoxy, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50Heteroaryl, substituted or unsubstituted C2~C50Amino in one kind；R is selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C1~C10Alkane Oxygroup, substituted or unsubstituted C6~C50Aryl, substituted or unsubstituted C3~C50Heteroaryl in one kind；N be selected from 0~ 4 integer.
A kind of 2. carbazole analog derivative according to claim 1, which is characterized in that n 0,1 or 2.
3. a kind of carbazole analog derivative according to claim 1, which is characterized in that its general formula of molecular structure such as II, III or Shown in IV：
Wherein, Ar1、Ar2Independently selected from hydrogen, substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C6~C30's Aryl, substituted or unsubstituted C3~C30Heteroaryl, substituted or unsubstituted C10~C30Fragrant amino in one kind；R is selected from Hydrogen, substituted or unsubstituted C1~C10Alkyl in one kind.
A kind of 4. carbazole analog derivative according to claim 1, which is characterized in that Ar1、Ar2Independently selected from hydrogen or following One kind in structure：
Wherein, R1~R7Independently selected from hydrogen, substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C1~C10's Alkoxy, substituted or unsubstituted C6~C30Aryl, substituted or unsubstituted C3~C30Heteroaryl in one kind；R8~R11 Independently selected from substituted or unsubstituted C1~C10Alkyl, substituted or unsubstituted C1~C10Alkoxy, substitution or do not take The C in generation6~C30Aryl in one kind；A is selected from 0~4 integer.
5. a kind of carbazole analog derivative according to claim 1, which is characterized in that in chemical constitution as follows Any one：
6. a kind of organic luminescent device, which is characterized in that the organic luminescent device includes cathode, anode and is placed in two electricity One or more organic compound layers between pole, the organic compound layer contain claim 1-5 any one of them A kind of carbazole analog derivative.
7. according to a kind of organic luminescent device described in claim 6, which is characterized in that the organic compound layer includes hair Photosphere contains a kind of carbazole analog derivative of claim 1-5 any one of them in luminescent layer.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108299295A (en) * 2018-02-07 2018-07-20 瑞声科技（南京）有限公司 A kind of organic photoelectrical material and organic light emitting diode device
CN110590790A (en) * 2019-08-29 2019-12-20 武汉华星光电半导体显示技术有限公司 Hole transport material based on spiro triphenylamine, preparation method thereof and organic electroluminescent device
WO2021096273A1 (en) * 2019-11-15 2021-05-20 주식회사 엘지화학 Heterocyclic compound and organic light emitting device comprising same

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KR20170092129A (en) * 2016-02-02 2017-08-10 주식회사 엘지화학 Fused cyclic compound including nitrogen and organic light emitting device using the same

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Publication number Priority date Publication date Assignee Title
KR20170092129A (en) * 2016-02-02 2017-08-10 주식회사 엘지화학 Fused cyclic compound including nitrogen and organic light emitting device using the same

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108299295A (en) * 2018-02-07 2018-07-20 瑞声科技（南京）有限公司 A kind of organic photoelectrical material and organic light emitting diode device
CN110590790A (en) * 2019-08-29 2019-12-20 武汉华星光电半导体显示技术有限公司 Hole transport material based on spiro triphenylamine, preparation method thereof and organic electroluminescent device
WO2021096273A1 (en) * 2019-11-15 2021-05-20 주식회사 엘지화학 Heterocyclic compound and organic light emitting device comprising same

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Application publication date: 20180518