CN103588726A - Spirobifluorene olefine organic electroluminescent material and preparation method thereof - Google Patents
Spirobifluorene olefine organic electroluminescent material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a spirobifluorene olefine organic luminescent material which is characterized in that the material has the following structural general formula shown in the specification, wherein the A group represents phenyl, biphenyl, naphthyl, aromatic amino, carbazolyl, substituted carbazolyl, N-phenyl, quinolyl, thiazolyl, thienyl, aromatic amino, azole-containing structural group, aromatic heterocyclic group, substituted aromatic heterocyclic group or aniline series group composed of 6-50 atoms. According to the invention, due to the introduction of double bonds, the material has better planar structure and conjugation system in comparison with simple spirobifluorene; electron transition regulates luminescence peak positions, thus obtaining the required light blue organic electroluminescent material; and the material has high luminescence efficiency, the luminescence efficiency in a dilute solution is about 95%, and the luminescence efficiency in a film can be up to about 62%.
Description
Technical field
The invention belongs to organic photoelectrical material field, particularly a kind of spiral shell two fluorenes olefines luminous organic materials and preparation method thereof.
Background technology
Organic electroluminescence device is as a kind of flat panel display, have such as luminous, high brightness, wide visual angle, ultra-thin, less energy-consumption, fast response time, can be curling, can realize the many merits such as Full color, and enjoy people's concern.By adopting suitable device architecture, element manufacturing technology and organic materials, the performance of organic electroluminescence device is improved significantly.Such as, aspect panchromatic demonstration, high-level efficiency, stable Green organic light emitting diode have reached degree of being practical, compare with Green organic light emitting diode, blue organic electroluminescent device can't meet the requirement of panchromatic demonstration completely, and its efficiency and purity of color especially need to improve.Yet, make blue organic electroluminescent device and must use blue light organic luminescent material, still, due to blue light organic luminescent material luminous efficiency and brightness not high, the problems such as the life-span is very low, and blue organic electroluminescent device is subject to certain restrictions in the application aspect full colour developing.At present, blue light organic luminescent material mainly concentrates on some classical compound systems such as three arylamine systems, anthracene derivative, carbazole derivative, metal complexes, but, existing these blue light organic luminescent materials are a pure difficult problem in application also, such as the life-span, brightness, efficiency is lower, cannot meet the demand of industrialization; And the synthetic method of these materials is complicated, purification difficult, also can use more virose raw material in building-up process.Therefore blue light organic luminescent material, how to develop excellent property is exactly the task of top priority.
Summary of the invention
The present invention is the technical problem that the existing blue light organic luminescent material luminous efficiency of solution is low and the life-span is short, and provides a kind of luminous efficiency high, the spiral shell two fluorenes olefines luminous organic materials that the life-span is long; A kind of preparation method of spiral shell two fluorenes olefines luminous organic materials is also provided.
In order to solve the problems of the technologies described above, the invention provides a kind of spiral shell two fluorenes olefines luminous organic materials, the general structure of this material is as follows:
Wherein, the representative of A group is by phenyl, xenyl, naphthyl, fragrant amido, carbazole, substituted carbazole, N-phenyl, quinoline, thiazolyl, thienyl, fragrant amido, the aromatic heterocyclic radical that contains azoles building stone, aromatic heterocyclic radical, replacement or the aniline series group of 6-50 atomic building.
Described A group includes but not limited to 9-carbazyl, N-phenyl carbazole-3-base, N-(4-xenyl) carbazole-3-base, N-ethyl carbazole-3-base, 2-pyridyl, 3-pyridyl, N-phenylaniline base, N-phenyl-1-naphthylamine base, N-phenyl-2-naphthylamine base, 1,10-phenanthroline-3-base, thionaphthene-2-base, 2-quinolyl, 1-isoquinolyl, 3-isobenzofuran-base, diazosulfide-2-base, N-phenyl benzimidazolyl-2 radicals-Ji or 4-(4-phenyl-5-H-quinolyl) phenyl.
The spiral shell two fluorenes alkene luminous organic material specific exampless that structural formula of the present invention represents are as follows, but are not limited to these compounds that following instance provides:
It is more than the molecular structural formula of some particular compound, but spiral shell two fluorenes olefines luminous organic materials provided by the present invention are not limited to the compound shown in listed molecular structural formula, the series compound of the spiral shell two fluorenes alkene that every A base replaces is included in spiral shell two fluorenes olefines luminous organic materials provided by the present invention.
The preparation method that described spiral shell two fluorenes olefines luminous organic materials are also provided in the present invention, this preparation method's concrete steps and condition are as follows:
(1) take magnesium rod some, add iodine and cause, add the tetrahydrofuran solution of 2,7-dibromo spiral shell, two fluorenes, under ice-water bath condition, react 2 ~ 2.5 hours, continue to drip DMF, then rise at leisure room temperature, continue reaction 3 ~ 4 hours, through separatory, extraction, dry, concentrated, column chromatography, obtain containing spiral shell two fluorenes aldehydes derivatives;
(2) in molar ratio for 1:2 takes containing spiral shell two fluorenes aldehydes derivatives and 4-bromobenzyl diethyl phosphite; Under nitrogen protection condition, add 4-bromobenzyl diethyl phosphite and tetrahydrofuran (THF), be cooled to, after-70 ℃, add potassium tert.-butoxide, react 1.5 ~ 2.0 hours, to the solution that drips spiral shell two fluorenes aldehydes derivatives in reaction solution, continue reaction 1.5 ~ 2.0 hours, rise to room temperature, continue reaction after 2 ~ 2.5 hours, through separatory, extraction, dry, concentrated, recrystallization, obtain spiral shell two fluorenes bromo olefines derivatives;
(3) by above-mentioned spiral shell two fluorenes bromo olefines derivatives, the substituent boric acid of A or aminated compounds, put in proportion reaction system, add alkali and catalyzer, maintain the temperature at 80 ~ 120 ℃, isothermal reaction 15 ~ 25 hours.
All raw materials all will carry out strict deoxidation treatment, guarantee that described preparation process carries out under oxygen free condition.
The mol ratio of described spiral shell two fluorenes bromo alkene derivatives and the substituent boric acid of A is 1:2.5 ~ 4; Described alkali is salt of wormwood, and the mol ratio of described spiral shell two fluorenes bromo alkene derivatives and salt of wormwood is 1:1.5 ~ 3, and described solvent is water and toluene, and the volume ratio of toluene and water is 2:1; Described catalyzer is tetrakis triphenylphosphine palladium, and tetrakis triphenylphosphine palladium is 0.005 ~ 0.02:1 with spiral shell two fluorenes bromo alkene derivatives molar weight ratios;
The mol ratio of described spiral shell two fluorenes bromo alkene derivatives and A substitutional amine-group compound is 1:2.2 ~ 2.4; Described alkali is potassium tert.-butoxide, and the mol ratio of described spiral shell two fluorenes class bromo alkene derivatives and potassium tert.-butoxide is 2.2 ~ 2.4:1; Described solvent is toluene; Described catalyzer is acid chloride, tri-tert phosphorus, and the mol ratio of spiral shell two fluorenes class bromo alkene derivatives and acid chloride is 20 ~ 22:1, and the mol ratio of spiral shell two fluorenes class bromo alkene derivatives and tri-tert phosphorus is 20 ~ 22:1.
The spiral shell two fluorenes olefines luminous organic materials that the present invention prepares, can be as in organic electroluminescence device structure, the introducing of two keys, make this material compare simple spiral shell two fluorenes classes and have better two dimensional structure and conjugated system, transition of electron has regulated luminous peak position, obtains required light blue electroluminescent organic material, and such material has very high luminous efficiency, luminous efficiency in dilute solution is 95% left and right, and the luminous efficiency in film can reach 62% left and right.
The preparation method of spiral shell two fluorenes olefines luminous organic materials of the present invention, by optimizing reaction conditions, make reaction solvent change common solvent into, convenient operation, easily purifies, and increases substantially productive rate, and reduced cost, make the spiral shell two fluorenes olefines luminous organic materials that prepare become possibility for the making of OLED device, the spiral shell two fluorenes olefines luminous organic material luminous efficiencies that prepare due to the method are higher, in organic light-emitting device application, have reasonable using value.
Embodiment
Spiral shell two fluorenes olefines electroluminescent organic materials provided by the invention, with bromo spiral shell two compound of fluorene class, the reaction of 4-bromobenzyl diethyl phosphite, to obtain the spiral shell two fluorenes alkenes compounds of bromo, with the substituent boric acid of A or aminated compounds, reaction obtains containing the substituent spiral shell two fluorenes alkenes compounds of A
Embodiment 1: the concrete synthetic route of compound 001 is as follows:
(1), under nitrogen protection condition, in there-necked flask, add anhydrous tetrahydrofuran solution 10ml, magnesium rod 0.5g; 1 of iodine; Grignard reagent adds 4.74g 2, the anhydrous tetrahydrofuran solution 10ml of 7-dibromo spiral shell two fluorenes after causing; under ice-water bath condition; react 2 hours, in this reaction solution, drip after the anhydrous DMF of 2ml; then rise at leisure room temperature, continue reaction 3 hours.Add 1M hydrochloric acid, 30ml ethyl acetate is carried out after separatory and extraction, with distilled water, saturated aqueous common salt, clean organic layer, by dried over sodium sulfate, concentrated, by the crude product column chromatography (hexanaphthene/methylene dichloride=2/1) of gained, gained liquid is revolved to steaming, dry, result obtains 2.98g light yellow solid spiral shell two fluorenes aldehydes derivatives.
(2) under nitrogen protection condition; add 4-bromobenzyl diethyl phosphite 4.92g and tetrahydrofuran solution 50ml; be cooled to after-65 ℃; add potassium tert.-butoxide 3.59g; react after 1.5 hours, to the tetrahydrofuran solution 20ml that drips spiral shell two fluorenes aldehydes derivatives in reaction solution, continue reaction after 1.5 hours; warming while stirring, to room temperature, continues reaction 2 hours.In the reaction solution of gained, add separatory after distilled water, toluene, form water layer and organic layer.With toluene, extract after this water layer, this toluene and organic layer are merged, with distilled water, saturated aqueous common salt, clean, with anhydrous sodium sulfate drying, concentrated, use toluene recrystallization, the solid of gained is carried out to drying under reduced pressure, and result obtains 4.23g white-yellowish solid spiral shell two fluorenes bromo olefines luminous organic materials.
(3) by A substituted boracic acid 3.66g, above-mentioned intermediate, salt of wormwood 2.41g puts into there-necked flask, vacuumizes logical nitrogen, under nitrogen protection, adds deoxidation treatment toluene and water, adds tetrakis triphenylphosphine palladium 0.007g, and reaction is warmed up to 100 ℃, reacts 20 hours.Cooling, suction filtration, ethanol is washed, separatory, column chromatography, recrystallization, obtains product 4.23g white solid compound 001, and productive rate is greater than 80%.HPLC purity is greater than 98%.Mass spectrum calculated value is 849.07; Test value is 849.09.Ultimate analysis: calculated value is C:94.78%; H:5.22%; Test value is C:4.76%; H:5.24%;
Embodiment 2: the concrete synthetic route of compound 002 is as follows:
(1), under nitrogen protection condition, in there-necked flask, add anhydrous tetrahydrofuran solution 10ml, magnesium rod 0.5g; 1 of iodine; Grignard reagent adds 4.74g 2, the anhydrous tetrahydrofuran solution 10ml of 7-dibromo spiral shell two fluorenes after causing; under ice-water bath condition; react 2.1 hours, in this reaction solution, drip after the anhydrous DMF of 2ml; then rise at leisure room temperature, continue reaction 3.2 hours.Add 1M hydrochloric acid, 30ml ethyl acetate is carried out after separatory and extraction, with distilled water, saturated aqueous common salt, clean organic layer, by dried over sodium sulfate, concentrated, by the crude product column chromatography (hexanaphthene/methylene dichloride=2/1) of gained, gained liquid is revolved to steaming, dry, result obtains 2.98g light yellow solid spiral shell two fluorenes aldehydes derivatives.
(2) under nitrogen protection condition; add 4-bromobenzyl diethyl phosphite 4.92g and tetrahydrofuran solution 50ml; be cooled to after-65 ℃; add potassium tert.-butoxide 3.59g; react after 1.6 hours, to the tetrahydrofuran solution 20ml that drips spiral shell two fluorenes aldehydes derivatives in reaction solution, continue reaction after 1.6 hours; warming while stirring, to room temperature, continues reaction 2.1 hours.In the reaction solution of gained, add separatory after distilled water, toluene, form water layer and organic layer.With toluene, extract after this water layer, this toluene and organic layer are merged, with distilled water, saturated aqueous common salt, clean, with anhydrous sodium sulfate drying, concentrated, use toluene recrystallization, the solid of gained is carried out to drying under reduced pressure, and result obtains 4.23g white-yellowish solid spiral shell two fluorenes bromo olefines luminous organic materials.
(3) by benzothiazole-2-phenyl-boron dihydroxide 5.08g, above-mentioned intermediate, salt of wormwood 2.75g puts into there-necked flask; vacuumize logical nitrogen, under nitrogen protection, add deoxidation treatment toluene and water; add tetrakis triphenylphosphine palladium, reaction is warmed up to 90 ℃, reacts 22 hours.Cooling, suction filtration, ethanol is washed, separatory, column chromatography, recrystallization, obtains product 4.39g white-yellowish solid compound 002, and productive rate is greater than 75%.HPLC purity is greater than 99%.Mass spectrum calculated value is 939.19; Test value is 939.20.Ultimate analysis: calculated value is C:85.68%; H:4.51%; N:2.98%; S:6.83%; Test value is C:85.67%; H:4.53%; N:2.99%; S:6.81%;
Embodiment 3: the concrete synthetic route of compound 003 is as follows:
(1), under nitrogen protection condition, in there-necked flask, add anhydrous tetrahydrofuran solution 10ml, magnesium rod 0.5g; 1 of iodine; Grignard reagent adds 4.74g 2, the anhydrous tetrahydrofuran solution 10ml of 7-dibromo spiral shell two fluorenes after causing; under ice-water bath condition; react 2.2 hours, in this reaction solution, drip after the anhydrous DMF of 2ml; then rise at leisure room temperature, continue reaction 3.4 hours.Add 1M hydrochloric acid, 30ml ethyl acetate is carried out after separatory and extraction, with distilled water, saturated aqueous common salt, clean organic layer, by dried over sodium sulfate, concentrated, by the crude product column chromatography (hexanaphthene/methylene dichloride=2/1) of gained, gained liquid is revolved to steaming, dry, result obtains 2.98g light yellow solid spiral shell two fluorenes aldehydes derivatives.
(2) under nitrogen protection condition; add 4-bromobenzyl diethyl phosphite 4.92g and tetrahydrofuran solution 50ml; be cooled to after-65 ℃; add potassium tert.-butoxide 3.59g; react after 1.7 hours, to the tetrahydrofuran solution 20ml that drips spiral shell two fluorenes aldehydes derivatives in reaction solution, continue reaction after 1.7 hours; warming while stirring, to room temperature, continues reaction 2.2 hours.In the reaction solution of gained, add separatory after distilled water, toluene, form water layer and organic layer.With toluene, extract after this water layer, this toluene and organic layer are merged, with distilled water, saturated aqueous common salt, clean, with anhydrous sodium sulfate drying, concentrated, use toluene recrystallization, the solid of gained is carried out to drying under reduced pressure, and result obtains 4.23g white-yellowish solid spiral shell two fluorenes bromo olefines luminous organic materials.
(3) by 9,9-dimethyl-2-fluorenes boric acid 4.45g, above-mentioned intermediate, salt of wormwood 2.58g puts into there-necked flask; vacuumize logical nitrogen, under nitrogen protection, add deoxidation treatment toluene and water; add tetrakis triphenylphosphine palladium 0.007g, reaction is warmed up to 90 ℃, reacts 18 hours.Cooling, suction filtration, ethanol is washed, separatory, column chromatography, recrystallization, obtains product 4.96g white solid compound 003, and productive rate is greater than 88%.HPLC purity is greater than 98%.Mass spectrum calculated value is 905.17; Test value is 905.17.Ultimate analysis: calculated value is C:94.21%; H:5.79%; Test value is C:94.18%; H:5.82%;
Embodiment 4: the concrete synthetic route of compound 004 is as follows:
(1), under nitrogen protection condition, in there-necked flask, add anhydrous tetrahydrofuran solution 10ml, magnesium rod 0.5g; 1 of iodine; Grignard reagent adds 4.74g 2, the anhydrous tetrahydrofuran solution 10ml of 7-dibromo spiral shell two fluorenes after causing; under ice-water bath condition; react 2.3 hours, in this reaction solution, drip after the anhydrous DMF of 2ml; then rise at leisure room temperature, continue reaction 3.6 hours.Add 1M hydrochloric acid, 30ml ethyl acetate is carried out after separatory and extraction, with distilled water, saturated aqueous common salt, clean organic layer, by dried over sodium sulfate, concentrated, by the crude product column chromatography (hexanaphthene/methylene dichloride=2/1) of gained, gained liquid is revolved to steaming, dry, result obtains 2.98g light yellow solid spiral shell two fluorenes aldehydes derivatives.
(2) under nitrogen protection condition; add 4-bromobenzyl diethyl phosphite 4.92g and tetrahydrofuran solution 50ml; be cooled to after-65 ℃; add potassium tert.-butoxide 3.59g; react after 1.8 hours, to the tetrahydrofuran solution 20ml that drips spiral shell two fluorenes aldehydes derivatives in reaction solution, continue reaction after 1.8 hours; warming while stirring, to room temperature, continues reaction 2.3 hours.In the reaction solution of gained, add separatory after distilled water, toluene, form water layer and organic layer.With toluene, extract after this water layer, this toluene and organic layer are merged, with distilled water, saturated aqueous common salt, clean, with anhydrous sodium sulfate drying, concentrated, use toluene recrystallization, the solid of gained is carried out to drying under reduced pressure, and result obtains 4.23g white-yellowish solid spiral shell two fluorenes bromo olefines luminous organic materials.
(3) by pyrene boric acid 4.60g, above-mentioned intermediate, salt of wormwood 2.58g puts into there-necked flask, vacuumizes logical nitrogen, under nitrogen protection, adds deoxidation treatment toluene and water, adds tetrakis triphenylphosphine palladium 0.007g, and reaction is warmed up to 110 ℃, reacts 22 hours.Cooling, suction filtration, ethanol is washed, separatory, column chromatography, recrystallization, obtains product 4.7g white powder solid chemical compound 004, productive rate 82%.HPLC purity is greater than 98%.Mass spectrum calculated value is 921.13; Test value is 921.13.Ultimate analysis: calculated value is C:95.19%; H:4.81%; Test value is C:95.18%; H:4.82%;
Embodiment 5: the concrete synthetic route of compound 005 is as follows:
(1), under nitrogen protection condition, in there-necked flask, add anhydrous tetrahydrofuran solution 10ml, magnesium rod 0.5g; 1 of iodine; Grignard reagent adds 4.74g 2, the anhydrous tetrahydrofuran solution 10ml of 7-dibromo spiral shell two fluorenes after causing; under ice-water bath condition; react 2.4 hours, in this reaction solution, drip after the anhydrous DMF of 2ml; then rise at leisure room temperature, continue reaction 3.8 hours.Add 1M hydrochloric acid, 30ml ethyl acetate is carried out after separatory and extraction, with distilled water, saturated aqueous common salt, clean organic layer, by dried over sodium sulfate, concentrated, by the crude product column chromatography (hexanaphthene/methylene dichloride=2/1) of gained, gained liquid is revolved to steaming, dry, result obtains 2.98g light yellow solid spiral shell two fluorenes aldehydes derivatives.
(2) under nitrogen protection condition; add 4-bromobenzyl diethyl phosphite 4.92g and tetrahydrofuran solution 50ml; be cooled to after-65 ℃; add potassium tert.-butoxide 3.59g; react after 1.9 hours, to the tetrahydrofuran solution 20ml that drips spiral shell two fluorenes aldehydes derivatives in reaction solution, continue reaction after 1.9 hours; warming while stirring, to room temperature, continues reaction 2.4 hours.In the reaction solution of gained, add separatory after distilled water, toluene, form water layer and organic layer.With toluene, extract after this water layer, this toluene and organic layer are merged, with distilled water, saturated aqueous common salt, clean, with anhydrous sodium sulfate drying, concentrated, use toluene recrystallization, the solid of gained is carried out to drying under reduced pressure, and result obtains 4.23g white-yellowish solid spiral shell two fluorenes bromo olefines luminous organic materials.
(3) by N-phenyl carbazole-2-boric acid 6.26g, above-mentioned intermediate, salt of wormwood 3.01g puts into there-necked flask; vacuumize logical nitrogen, under nitrogen protection, add deoxidation treatment toluene and water; add tetrakis triphenylphosphine palladium 0.007g, reaction is warmed up to 105 ℃, reacts 22 hours.Cooling, suction filtration, ethanol is washed, separatory, column chromatography, recrystallization, obtains product 4.88g white powder solid chemical compound 005, and productive rate is greater than 78%.HPLC purity is greater than 98%.Mass spectrum calculated value is 1003.23; Test value is 1003.22.Ultimate analysis: calculated value is C:92.18%; H:5.02%N:2.79%; Test value is C:92.16%; H:5.03%; N:2.80%;
Embodiment 6: the concrete synthetic route of compound 006 is as follows:
(1), under nitrogen protection condition, in there-necked flask, add anhydrous tetrahydrofuran solution 10ml, magnesium rod 0.5g; 1 of iodine; Grignard reagent adds 4.74g 2, the anhydrous tetrahydrofuran solution 10ml of 7-dibromo spiral shell two fluorenes after causing; under ice-water bath condition; react 2.5 hours, in this reaction solution, drip after the anhydrous DMF of 2ml; then rise at leisure room temperature, continue reaction 4.0 hours.Add 1M hydrochloric acid, 30ml ethyl acetate is carried out after separatory and extraction, with distilled water, saturated aqueous common salt, clean organic layer, by dried over sodium sulfate, concentrated, by the crude product column chromatography (hexanaphthene/methylene dichloride=2/1) of gained, gained liquid is revolved to steaming, dry, result obtains 2.98g light yellow solid spiral shell two fluorenes aldehydes derivatives.
(2) under nitrogen protection condition; add 4-bromobenzyl diethyl phosphite 4.92g and tetrahydrofuran solution 50ml; be cooled to after-65 ℃; add potassium tert.-butoxide 3.59g; react after 2.0 hours, to the tetrahydrofuran solution 20ml that drips spiral shell two fluorenes aldehydes derivatives in reaction solution, continue reaction after 2.0 hours; warming while stirring, to room temperature, continues reaction 2.5 hours.In the reaction solution of gained, add separatory after distilled water, toluene, form water layer and organic layer.With toluene, extract after this water layer, this toluene and organic layer are merged, with distilled water, saturated aqueous common salt, clean, with anhydrous sodium sulfate drying, concentrated, use toluene recrystallization, the solid of gained is carried out to drying under reduced pressure, and result obtains 4.23g white-yellowish solid spiral shell two fluorenes bromo olefines luminous organic materials.
(3) by naphthalene boronic acids 2.68g, above-mentioned intermediate, salt of wormwood 2.15g puts into there-necked flask, vacuumizes logical nitrogen, under nitrogen protection, adds deoxidation treatment toluene and water, adds tetrakis triphenylphosphine palladium 0.007g, and reaction is warmed up to 80 ℃, reacts 15 hours.Cooling, suction filtration, ethanol is washed, separatory, column chromatography, recrystallization, obtains product 4.33g white-yellowish solid compound 006, and productive rate is greater than 90%.HPLC purity is greater than 99%.Mass spectrum calculated value is 772.97; Test value is 772.99.Ultimate analysis: calculated value is C:94.78%; H:5.22%; Test value is C:94.80%; H:5.20%;
Embodiment 7: the concrete synthetic route of compound 007 is as follows:
(1), under nitrogen protection condition, in there-necked flask, add anhydrous tetrahydrofuran solution 10ml, magnesium rod 0.5g; 1 of iodine; Grignard reagent adds 4.74g 2, the anhydrous tetrahydrofuran solution 10ml of 7-dibromo spiral shell two fluorenes after causing; under ice-water bath condition; react 2.2 hours, in this reaction solution, drip after the anhydrous DMF of 2ml; then rise at leisure room temperature, continue reaction 3.6 hours.Add 1M hydrochloric acid, 30ml ethyl acetate is carried out after separatory and extraction, with distilled water, saturated aqueous common salt, clean organic layer, by dried over sodium sulfate, concentrated, by the crude product column chromatography (hexanaphthene/methylene dichloride=2/1) of gained, gained liquid is revolved to steaming, dry, result obtains 2.98g light yellow solid spiral shell two fluorenes aldehydes derivatives.
(2) under nitrogen protection condition; add 4-bromobenzyl diethyl phosphite 4.92g and tetrahydrofuran solution 50ml; be cooled to after-65 ℃; add potassium tert.-butoxide 3.59g; react after 1.6 hours, to the tetrahydrofuran solution 20ml that drips spiral shell two fluorenes aldehydes derivatives in reaction solution, continue reaction after 1.5 hours; warming while stirring, to room temperature, continues reaction 2 hours.In the reaction solution of gained, add separatory after distilled water, toluene, form water layer and organic layer.With toluene, extract after this water layer, this toluene and organic layer are merged, with distilled water, saturated aqueous common salt, clean, with anhydrous sodium sulfate drying, concentrated, use toluene recrystallization, the solid of gained is carried out to drying under reduced pressure, and result obtains 4.23g white-yellowish solid spiral shell two fluorenes bromo olefines luminous organic materials.
(3) by above-mentioned intermediate and 2-naphthyl phenyl amine 3.28g, potassium tert.-butoxide 1.68g, acid chloride (II) 0.07g, tri-tert phosphorus 0.06g, dissolves with 50ml toluene, under nitrogen protection, in 120 ℃ of reactions 24 hours.Filtering reacting solution, with the refining crude product obtaining of silica gel chromatography, then carries out recrystallization with toluene to the solid obtaining, dry, obtains 5.06g lightpink solid chemical compound 007, and productive rate is more than 85%, and HPLC purity is greater than 99%.Mass spectrum: calculated value is 955.19; Test value is 955.18.Ultimate analysis: calculated value is C:91.79%; H:5.28%; N:2.93%; Test value is C:91.77%; H:5.27%; N:2.96%.
Embodiment 8: the concrete synthetic route of compound 008 is as follows:
(1), under nitrogen protection condition, in there-necked flask, add anhydrous tetrahydrofuran solution 10ml, magnesium rod 0.5g; 1 of iodine; Grignard reagent adds 4.74g 2, the anhydrous tetrahydrofuran solution 10ml of 7-dibromo spiral shell two fluorenes after causing; under ice-water bath condition; react 2.3 hours, in this reaction solution, drip after the anhydrous DMF of 2ml; then rise at leisure room temperature, continue reaction 3.8 hours.Add 1M hydrochloric acid, 30ml ethyl acetate is carried out after separatory and extraction, with distilled water, saturated aqueous common salt, clean organic layer, by dried over sodium sulfate, concentrated, by the crude product column chromatography (hexanaphthene/methylene dichloride=2/1) of gained, gained liquid is revolved to steaming, dry, result obtains 2.98g light yellow solid spiral shell two fluorenes aldehydes derivatives.
(2) under nitrogen protection condition; add 4-bromobenzyl diethyl phosphite 4.92g and tetrahydrofuran solution 50ml; be cooled to after-65 ℃; add potassium tert.-butoxide 3.59g; react after 1.7 hours, to the tetrahydrofuran solution 20ml that drips spiral shell two fluorenes aldehydes derivatives in reaction solution, continue reaction after 1.6 hours; warming while stirring, to room temperature, continues reaction 2.3 hours.In the reaction solution of gained, add separatory after distilled water, toluene, form water layer and organic layer.With toluene, extract after this water layer, this toluene and organic layer are merged, with distilled water, saturated aqueous common salt, clean, with anhydrous sodium sulfate drying, concentrated, use toluene recrystallization, the solid of gained is carried out to drying under reduced pressure, and result obtains 4.23g white-yellowish solid spiral shell two fluorenes bromo olefines luminous organic materials.
(3) by above-mentioned intermediate and carbazole 2.29g, potassium tert.-butoxide 1.54g, acid chloride (II) 0.063g, tri-tert phosphorus 0.057g, dissolves with 50ml toluene, under nitrogen protection, in 110 ℃ of reactions 20 hours.Filtering reacting solution, with the refining crude product obtaining of silica gel chromatography, then carries out recrystallization with toluene to the solid obtaining, dry, obtains 4.51g light yellow solid compound 008, and productive rate is more than 85%, and HPLC purity is greater than 99%.Mass spectrum: calculated value is 851.04; Test value is 851.04.Ultimate analysis: calculated value is C:91.73%; H:4.97%; N:3.29%; Test value is C:91.74%; H:4.98%; N:3.27%.
application example
Respectively sample preparation being become to concentration is 1 * 10
-6the dilute solution of mol/L, by Edinburdh-FLS920(stable state/transient state fluorescence spectrophotometer) equipment uses spin-coating method that solution is made into film, tests respectively the luminous efficiency of above-mentioned dilute solution and film, and concrete data are as table 1.
The luminosity factor of gained compound 001-008 in table 1 embodiment
| Sample | Luminous efficiency in dilute solution | Luminous efficiency in film | HLPC purity |
| Compound 001 | 92% | 60% | >98% |
| Compound 002 | 95% | 60% | >99% |
| Compound 003 | 98% | 59% | >98% |
| Compound 004 | 97% | 61% | >98% |
| Compound 005 | 97% | 63% | >98% |
| Compound 006 | 95% | 61% | >99% |
| Compound 007 | 94% | 62% | >99% |
| Compound 008 | 96% | 60% | >99% |
As can be seen from Table 1, compound prepared by the embodiment 1-8 luminous efficiency in dilute solution is 96%, luminous efficiency in film is 60%, show that these spiral shell two compound of fluorene class have high luminous efficiency, can be used as luminescent material or luminous material of main part and transport material, be applied in electroluminescent device.
Obviously, above-described embodiment is only for example is clearly described, and the not restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without also giving all embodiments.And the apparent variation of being extended out thus or change are still among the protection domain in the invention.
Claims (6)
1. spiral shell two fluorenes olefines luminous organic materials, is characterized in that: the general structure of this material is as follows:
Wherein, the representative of A group is by phenyl, xenyl, naphthyl, fragrant amido, carbazole, substituted carbazole, N-phenyl, quinoline, thiazolyl, thienyl, fragrant amido, the aromatic heterocyclic radical that contains azoles building stone, aromatic heterocyclic radical, replacement or the aniline series group of 6-50 atomic building.
2. a kind of spiral shell two fluorenes olefines luminous organic materials according to claim 1, it is characterized in that: described A group includes but not limited to 9-carbazyl, N-phenyl carbazole-3-base, N-(4-xenyl) carbazole-3-base, N-ethyl carbazole-3-base, 2-pyridyl, 3-pyridyl, N-phenylaniline base, N-phenyl-1-naphthylamine base, N-phenyl-2-naphthylamine base, 1, 10-phenanthroline-3-base, thionaphthene-2-base, 2-quinolyl, 1-isoquinolyl, 3-isobenzofuran-base, diazosulfide-2-base, N-phenyl benzimidazolyl-2 radicals-Ji or 4-(4-phenyl-5-H-quinolyl) phenyl.
3. a kind of spiral shell two fluorenes olefines luminous organic materials according to claim 2, is characterized in that: the spiral shell two fluorenes alkene luminous organic materials that comprise following structural
4. the preparation method of a kind of spiral shell two fluorenes olefines luminous organic materials according to claim 1, is characterized in that comprising the following steps:
(1) take magnesium rod some, add iodine and cause, add the tetrahydrofuran solution of 2,7-dibromo spiral shell, two fluorenes, under ice-water bath condition, react 2 ~ 2.5 hours, continue to drip DMF, then rise at leisure room temperature, continue reaction 3 ~ 4 hours, through separatory, extraction, dry, concentrated, column chromatography, obtain containing spiral shell two fluorenes aldehydes derivatives;
(2) in molar ratio for 1:2 takes containing spiral shell two fluorenes aldehydes derivatives and 4-bromobenzyl diethyl phosphite; Under nitrogen protection condition, add 4-bromobenzyl diethyl phosphite and tetrahydrofuran (THF), be cooled to, after-70 ℃, add potassium tert.-butoxide, react 1.5 ~ 2.0 hours, to the solution that drips spiral shell two fluorenes aldehydes derivatives in reaction solution, continue reaction 1.5 ~ 2.0 hours, rise to room temperature, continue reaction after 2 ~ 2.5 hours, through separatory, extraction, dry, concentrated, recrystallization, obtain spiral shell two fluorenes bromo olefines derivatives;
(3) by above-mentioned spiral shell two fluorenes bromo olefines derivatives, the substituent boric acid of A or aminated compounds, put in proportion reaction system, add alkali and catalyzer, maintain the temperature at 80 ~ 120 ℃, isothermal reaction 15 ~ 25 hours.
5. the preparation method of a kind of spiral shell two fluorenes olefines luminous organic materials according to claim 4, is characterized in that:
The mol ratio of described spiral shell two fluorenes bromo alkene derivatives and the substituent boric acid of A is 1:2.5 ~ 4; Described alkali is salt of wormwood, and the mol ratio of described spiral shell two fluorenes bromo alkene derivatives and salt of wormwood is 1:1.5 ~ 3, and described solvent is water and toluene, and the volume ratio of toluene and water is 2:1; Described catalyzer is tetrakis triphenylphosphine palladium, and tetrakis triphenylphosphine palladium is 0.005 ~ 0.02:1 with spiral shell two fluorenes bromo alkene derivatives molar weight ratios.
6. the preparation method of a kind of spiral shell two fluorenes olefines luminous organic materials according to claim 4, is characterized in that:
The mol ratio of described spiral shell two fluorenes bromo alkene derivatives and A substitutional amine-group compound is 1:2.2 ~ 2.4; Described alkali is potassium tert.-butoxide, and the mol ratio of described spiral shell two fluorenes class bromo alkene derivatives and potassium tert.-butoxide is 2.2 ~ 2.4:1; Described solvent is toluene; Described catalyzer is acid chloride, tri-tert phosphorus, and the mol ratio of spiral shell two fluorenes class bromo alkene derivatives and acid chloride is 20 ~ 22:1, and the mol ratio of spiral shell two fluorenes class bromo alkene derivatives and tri-tert phosphorus is 20 ~ 22:1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650066A (en) * | 2014-08-05 | 2015-05-27 | 吉林奥来德光电材料股份有限公司 | Preparation of green light material, as well as organic light emitting device of green light material |
| KR101802924B1 (en) * | 2015-12-10 | 2017-11-29 | 성균관대학교산학협력단 | Organic electroluminescent compound, producing method of the same and organic electroluminescent device including the same |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112951A (en) * | 1994-04-07 | 1995-12-06 | 赫彻斯特股份公司 | Spiro-compound and application as electric luminescent material |
| CN1289317A (en) * | 1998-02-04 | 2001-03-28 | 阿克西瓦有限公司 | spirans and the use thereof |
| JP2002316955A (en) * | 2001-04-20 | 2002-10-31 | Sony Corp | Polyarylene compound |
| TW200730025A (en) * | 2006-01-20 | 2007-08-01 | Gracel Display Inc | Organic light emitting diodes |
| JP2008106032A (en) * | 2006-09-25 | 2008-05-08 | Kyushu Univ | Carbazole derivative and organic solid laser material using the same |
| CN101671291A (en) * | 2008-06-25 | 2010-03-17 | 葛来西雅帝史派有限公司 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
| CN103204797A (en) * | 2012-11-09 | 2013-07-17 | 吉林奥来德光电材料股份有限公司 | Arylamine organic luminescence material of dihydropentacene, and preparation method thereof |
-
2013
- 2013-09-17 CN CN201310422738.2A patent/CN103588726A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112951A (en) * | 1994-04-07 | 1995-12-06 | 赫彻斯特股份公司 | Spiro-compound and application as electric luminescent material |
| CN1289317A (en) * | 1998-02-04 | 2001-03-28 | 阿克西瓦有限公司 | spirans and the use thereof |
| JP2002316955A (en) * | 2001-04-20 | 2002-10-31 | Sony Corp | Polyarylene compound |
| TW200730025A (en) * | 2006-01-20 | 2007-08-01 | Gracel Display Inc | Organic light emitting diodes |
| JP2008106032A (en) * | 2006-09-25 | 2008-05-08 | Kyushu Univ | Carbazole derivative and organic solid laser material using the same |
| CN101671291A (en) * | 2008-06-25 | 2010-03-17 | 葛来西雅帝史派有限公司 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
| CN103204797A (en) * | 2012-11-09 | 2013-07-17 | 吉林奥来德光电材料股份有限公司 | Arylamine organic luminescence material of dihydropentacene, and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| CHIH-CHIN CHI ET AL.: "Synthesis and Spectroscopic Characterization of Dual Absorption BODIPY Type Dyes and their Light Harvesting Application in Polymer-Based Bulk Hetrojunction Organic Photovoltaics", 《JOURNAL OF THE CHINESE CHEMICAL SOCIETY》, vol. 59, 17 January 2012 (2012-01-17), pages 305 - 316 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104650066A (en) * | 2014-08-05 | 2015-05-27 | 吉林奥来德光电材料股份有限公司 | Preparation of green light material, as well as organic light emitting device of green light material |
| CN104650066B (en) * | 2014-08-05 | 2017-10-24 | 吉林奥来德光电材料股份有限公司 | A kind of preparation of green light material and its organic luminescent device |
| KR101802924B1 (en) * | 2015-12-10 | 2017-11-29 | 성균관대학교산학협력단 | Organic electroluminescent compound, producing method of the same and organic electroluminescent device including the same |
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