CN103045232B - Dihydro-pentacene-olefin organic light-emitting material, preparation method and application of dihydro-pentacene-olefin organic light-emitting material - Google Patents

Dihydro-pentacene-olefin organic light-emitting material, preparation method and application of dihydro-pentacene-olefin organic light-emitting material Download PDF

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CN103045232B
CN103045232B CN201210397673.6A CN201210397673A CN103045232B CN 103045232 B CN103045232 B CN 103045232B CN 201210397673 A CN201210397673 A CN 201210397673A CN 103045232 B CN103045232 B CN 103045232B
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pentacene
dihydro
dihydro pentacene
phenyl
hours
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CN103045232A (en
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马晓宇
王辉
李文军
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Jilin Optical and Electronic Materials Co Ltd
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Abstract

The invention relates to a dihydro-pentacene-olefin organic light-emitting material, a preparation method and an application of the dihydro-pentacene-olefin organic light-emitting material, and solves technical problems of low luminous efficiency and short service life of the existing blue organic light-emitting material. The material is based on a dihydro-pentacene compound which has a larger plane structure and a larger conjugated system in comparison with anthracene derivatives; and methyl and aryl substituent groups of other condensed rings are adopted, so that the performance of the dihydro-pentacene-olefin organic light-emitting material is improved well and the dihydro-pentacene-olefin organic light-emitting material is a novel high-performance electroluminescent material. The invention also provides the preparation method of the dihydro-pentacene-olefin organic light-emitting material. According to the preparation method, reaction conditions are optimized, so that a reaction solvent is changed to be an ordinary solvent, so that the operation is convenient, the purification is easy, the yield is greatly increased and the cost is lowered. The dihydro-pentacene-olefin organic light-emitting material provided by the invention is applied to the organic electroluminescent material and has high luminous efficiency.

Description

Dihydro pentacene olefines luminous organic material and its preparation method and application
Technical field
The invention belongs to organic photoelectrical material field, particularly a kind of dihydro pentacene olefines luminous organic material and its preparation method and application.
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, compared 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.But, make blue organic electroluminescent device 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 three arylamine systems, anthracene derivative, carbazole derivative, some classical compound systems such as metal complexes, but, existing these blue light organic luminescent materials are a pure difficult problem in application also, such as the life-span, and brightness, efficiency is lower, cannot meet the demand of industrialization; And, the synthetic method complexity of these materials, 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 solves the technical problem that existing blue light organic luminescent material luminous efficiency is low and the life-span is short, and provides a kind of luminous efficiency high, the dihydro pentacene olefines luminous organic material that the life-span is long; A kind of preparation method and application thereof of dihydro pentacene olefines luminous organic material are also provided.
In order to solve the problems of the technologies described above, technical scheme of the present invention is specific as follows:
Dihydro pentacene olefines luminous organic material, the general structure of this material as the formula (1):
Formula (1)
Wherein, R 1for aryl amine, C 10-C 19fused ring aryl, C 11-C 31the fused ring aryl, the C that replace 4-C 12aromatic heterocyclic radical or C 5-C 18the aromatic heterocyclic radical replacing.Preferably R 1for: N-phenyl-3-carbazyl, 3-coffee sieve quinoline base, triarylamine, 10-phenyl-2-anthryl, 9,9-dimethyl-2-fluorenyl or 2-pyrenyl; R 2for phenyl, p-methylphenyl or p-methoxyphenyl.
Preferred dihydro pentacene olefines luminous organic material of the present invention is:
R 1for N-phenyl-3-carbazyl, R 2for phenyl;
R 1for 3-coffee sieve quinoline base, R 2for phenyl;
R 1for triarylamine, R 2for phenyl;
R 1for 10-phenyl-2-anthryl, R 2for phenyl;
R 1be 9,9-dimethyl-2-fluorenyl, R 2p-methoxyphenyl;
R 1for 2-pyrenyl, R 2for p-methylphenyl.
Dihydro pentacene olefines luminous organic material, it is any one in following chemical structural formula 001-018:
Be exactly concrete structure formation more above, but this series compound does not limit to and these listed chemical structures.Every taking formula (1) as basis, R 1and R 2the arbitrary structures of the concrete structure providing before group is respectively, the compound of the simple transformation of these groups of every these groups and replacement thereof all should be included.
The preparation method of dihydro pentacene olefines luminous organic material, this preparation method's concrete steps and condition are as follows:
(1) for 1:2.2 ~ 2.5, to take 9-bromo-5,5,14 in molar ratio, 14-tetramethyl--4a, 5,13a, 14-dihydro pentacene-6,13 (4aH, 13aH) diketone and containing R 1substituent halogenide, dissolves with tetrahydrofuran (THF) respectively; Under acetone bath condition, to containing R 1in substituent halid tetrahydrofuran solution, drip n-Butyl Lithium, n-Butyl Lithium with containing R 1substituent halogenide mol ratio is 1:1.05 ~ 1.1, reacts 2 ~ 6 hours, drips 9-bromo-5; 5,14,14-tetramethyl--4a; 5,13a, 14-dihydro pentacene-6; the tetrahydrofuran solution of 13 (4aH, 13aH) diketone, after dropwising; under nitrogen protection condition; room temperature reaction 8 ~ 10 hours, after extraction, separatory, concentrated, recrystallization, obtains containing R 1substituent dihydro pentacene alcohol derivatives;
(2) take containing R 1substituent dihydro pentacene alcohol derivatives, adds in the vitriol oil, and room temperature reaction 9 ~ 11 hours, through hydrolysis, recrystallization, suction filtration, washing, oven dry, obtains containing R 1substituent dihydro pentacene analog derivative;
(3) take magnesium rod some, add iodine and cause, add containing R 1the tetrahydrofuran solution of substituent dihydro pentacene analog derivative, under ice-water bath condition, reacts 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 R 1substituent dihydro pentacene aldehydes derivative;
(4) take containing R for 1:2.0 ~ 2.2 in molar ratio 1substituent dihydro pentacene aldehydes derivative and containing R 2substituent diethyl phosphoric acid; Under nitrogen protection condition, add benzyl diethyl phosphoric acid and tetrahydrofuran (THF), be cooled to, after-65 DEG C ~-70 DEG C, add potassium tert.-butoxide, react 2 ~ 2.5 hours, to the solution that drips dihydro pentacene aldehydes derivative in reaction solution, continue reaction 2 ~ 2.5 hours, rise to room temperature, continue reaction after 2 ~ 2.5 hours, through separatory, extraction, dry, concentrated, recrystallization, obtain dihydro pentacene olefines luminous organic material;
Wherein, described R 1for aryl amine, C 10-C 19fused ring aryl, C 11-C 31the fused ring aryl, the C that replace 4-C 12aromatic heterocyclic radical or C 5-C 18the aromatic heterocyclic radical replacing; R 2for phenyl, p-methylphenyl or p-methoxyphenyl.
The invention has the beneficial effects as follows:
The dihydro pentacene olefines luminous organic material that the present invention prepares, this series derivates is taking dihydro pentacene compound as basis, compare anthracene derivative and have larger two dimensional structure and conjugated system, relatively simple pentacene compound simultaneously, owing to having introduced the aryl substituent of methyl and other condensed ring classes, can change lowest unoccupied molecular orbital (LUMO) and the highest occupied molecular orbital (HOMO) of this series derivates, change transition of electron energy level, thereby change luminescent spectrum, make the performance of dihydro pentacene olefines luminous organic material have good improvement, it is the novel high performance electroluminescent material of a class.
The preparation method of dihydro pentacene olefines luminous organic material of the present invention, by optimizing reaction conditions, make reaction solvent change common solvent into, convenient operation, easily purify, increase substantially productive rate, and reduce cost, make the dihydro pentacene olefines luminous organic material preparing become possibility for the making of OLED device, the dihydro pentacene olefines luminous organic material luminous efficiency preparing due to the method is higher, in organic light-emitting device application, has reasonable using value.
The dihydro pentacene olefines luminous organic material that the present invention prepares can be as in organic electroluminescence device structure, owing to introducing methyl on dihydro pentacene, material dissolves is good, film forming properties is good, easily as OLED device, particularly pass through aryl amine, replace or without replace fused ring aryl, replace or without the introducing of the substituted radical such as aromatic heterocyclic radical replacing, can regulate transition of electron, meet the demand to luminescent material, particularly present needed light blue luminescent material, such material has very high luminous efficiency, luminous efficiency in dilute solution is 97% left and right, luminous efficiency in film can reach 60% left and right.
Embodiment
Dihydro pentacene olefines luminous organic material provided by the invention, is bromo-5,5,14 with 9-, 14-tetramethyl--4a, 5,13a, 14-dihydro pentacene-6,13 (4aH, 13aH) diketone, aryl halide R 1-Br and containing R 2substituent diethyl phosphoric acid is raw material, through polystep reaction, obtains containing R 1substituting group and R 2substituent dihydro pentacene olefines luminous organic material.
Synthetic route is as follows:
Embodiment 1: compound 001 synthetic
Shown in the concrete following structural formula of synthetic route:
(1) under nitrogen protection system, take 3-bromine-N-phenylcarbazole 110mmol(49.3g), add the new tetrahydrofuran solution 300ml steaming, under-78 DEG C of conditions, drip n-Butyl Lithium 7.19g, react 2 hours, then drip 200ml containing 9-bromo-5, 5, 14, 14-tetramethyl--4a, 5, 13a, 14-dihydro pentacene-6, 13 (4aH, 13aH) diketone 50mmol(22.4g) tetrahydrofuran solution, after dropwising, under nitrogen protection condition, after room temperature reaction 8 hours, add 1M dilute hydrochloric acid 100ml, with ether 100ml extraction 3 times, separatory, concentrated, with methylene dichloride: sherwood oil=1:3 recrystallization, obtain 41.2g off-white color intermediate N phenyl-3-carbazyl dihydro pentacene alcohol derivatives.
(2) get N-phenyl-3-carbazyl dihydro pentacene alcohol derivatives, add in the 300ml vitriol oil, room temperature reaction 9 hours, through hydrolysis, extraction, separatory, recrystallization, obtains 40.7g off-white color N-phenyl-3-carbazyl dihydro pentacene analog derivative.
(3), under nitrogen protection condition, in there-necked flask, add anhydrous tetrahydrofuran solution 10ml, magnesium rod 1.5g; 1 of iodine; Grignard reagent adds the anhydrous tetrahydrofuran solution 200ml that contains N-phenyl-3-carbazyl dihydro pentacene analog derivative, under ice-water bath condition after causing; reaction 2; hour, in this reaction solution, drip after the anhydrous DMF of 18ml; then rise at leisure room temperature, continue reaction 3 hours.Add several 1M hydrochloric acid, 150ml ethyl acetate is carried out after separatory and extraction, clean organic layer with saturated aqueous common salt, with anhydrous sodium sulfate drying, concentrated, by the crude product column chromatography (hexanaphthene/methylene dichloride=2/1) of gained, gained liquid is revolved to steaming, dry, result obtains 35.7g white solid N-phenyl-3-carbazyl dihydro pentacene aldehydes derivative.
(4) under nitrogen protection condition; add benzyl diethyl phosphoric acid 17.3g and tetrahydrofuran (THF) 100ml; be cooled to after-65 DEG C; add potassium tert.-butoxide 9.1g; react after 2 hours, to the tetrahydrofuran solution 180ml that drips N-phenyl-3-carbazyl dihydro pentacene aldehydes derivative in reaction solution, continue reaction after 2 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.Extract after this water layer with toluene, this toluene and organic layer are merged, clean with saturated aqueous common salt, with anhydrous sodium sulfate drying, concentrated, use toluene recrystallization, the solid of gained is carried out to drying under reduced pressure, result obtains white-yellowish solid N-phenyl-3-carbazyl dihydro pentacene olefines luminous organic material of 30.5g.HPLC purity is greater than 98%.Mass spectrum: calculated value is 922.43; Test value is 922.40.Ultimate analysis: calculated value C:91.07%; H:5.90%; N:3.03%; Test value is: C:91.05%; H:5.91%; N:3.04%.
Embodiment 2: compound 004 synthetic
Shown in the concrete following structural formula of synthetic route:
(1) under nitrogen protection system, take bromo-coffee sieve of 3-quinoline base 110mmol(28.5g), add the new tetrahydrofuran solution 300ml steaming, under-78 DEG C of conditions, drip n-Butyl Lithium 7.19g, react 6 hours, then drip 200ml containing 9-bromo-5, 5, 14, 14-tetramethyl--4a, 5, 13a, 14-dihydro pentacene-6, 13 (4aH, 13aH) diketone 50mmol(22.4g) tetrahydrofuran solution, after dropwising, under nitrogen protection condition, after room temperature reaction 9 hours, add 1M dilute hydrochloric acid 100ml, with ether 100ml extraction 3 times, separatory, concentrated, with methylene dichloride: sherwood oil=1:3 recrystallization, obtain 39.4g off-white color intermediate 3-coffee sieve quinoline base dihydro pentacene alcohol derivatives.
(2) get 3-coffee sieve quinoline base dihydro pentacene alcohol derivatives, add in the 300ml vitriol oil, room temperature reaction 10 hours, through hydrolysis, extraction, separatory, recrystallization, obtains 37.68g white 3-coffee sieve quinoline base dihydro pentacene analog derivative.
(3) under nitrogen protection condition; in there-necked flask, add anhydrous tetrahydrofuran solution 10ml, magnesium rod 1.5g, 1 of iodine; after Grignard reagent causes; the anhydrous tetrahydrofuran solution 200ml that adds 3-coffee sieve quinoline base dihydro pentacene analog derivative, under ice-water bath condition, reacts 2.5 hours; in reaction solution, drip the anhydrous N of 18 ml; after dinethylformamide, then rise at leisure room temperature, continue reaction 4 hours.Add several 1M hydrochloric acid, 150ml ethyl acetate is carried out after separatory and extraction, with water purification, saturated aqueous common salt cleaning 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 35.7g white solid 3-coffee sieve quinoline base dihydro pentacene aldehydes derivative.
(4) under nitrogen protection condition; add benzyl diethyl phosphoric acid 19.3g and tetrahydrofuran solution 100ml; be cooled to after-70 DEG C; add potassium tert.-butoxide 9.1g; react after 2.5 hours, to the tetrahydrofuran solution 180ml that drips 3-coffee sieve quinoline base dihydro pentacene aldehydes derivative in reaction solution, continue reaction after 2 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.Extract after this water layer with toluene, this toluene and organic layer are merged, with distilled water, saturated aqueous common salt cleaning, with anhydrous sodium sulfate drying, concentrated, use toluene recrystallization, the solid of gained is carried out to drying under reduced pressure, result obtains 33.9g white-yellowish solid 3-coffee sieve quinoline base dihydro pentacene olefines luminous organic material.HPLC purity is greater than 98%.Mass spectrum: calculated value is 797.00; Test value is 796.98.Ultimate analysis: calculated value C:87.41%; H:5.56%; N:7.03%; Test value is: C:87.42%; H:5.57%; N:7.031%.
Embodiment 3: compound 007 synthetic
Shown in the concrete following structural formula of synthetic route:
(1) under nitrogen protection condition, take the bromo-triarylamine 110mmol(35.5g of 4-), add the new tetrahydrofuran solution 300ml steaming, under-78 DEG C of conditions, drip n-Butyl Lithium 7.19g, react 4 hours, then drip 200ml containing 9-bromo-5, 5, 14, 14-tetramethyl--4a, 5, 13a, 14-dihydro pentacene-6, 13 (4aH, 13aH) diketone 50mmol(22.4g) tetrahydrofuran solution, after dropwising, under nitrogen protection condition, after room temperature reaction 9 hours, add 1M dilute hydrochloric acid 100ml, with ether 100ml extraction 3 times, separatory, concentrated, with methylene dichloride: sherwood oil=1:3 recrystallization, obtain 41.6g off-white color intermediate triarylamine dihydro pentacene alcohol derivatives.
(2) get triarylamine dihydro pentacene alcohol derivatives, add in the 300ml vitriol oil, room temperature reaction 11 hours, through hydrolysis, extraction, separatory, recrystallization, obtains 40.2g off-white color triarylamine dihydro pentacene analog derivative.
(3) under nitrogen protection condition; in there-necked flask, add anhydrous tetrahydrofuran solution 10ml, magnesium rod 1.5g, 1 of iodine; after Grignard reagent causes; add the anhydrous tetrahydrofuran solution 200ml that contains triarylamine dihydro pentacene analog derivative, under ice-water bath condition, react 2.3 hours; in this reaction solution, drip the anhydrous N of 18ml; after dinethylformamide, then rise at leisure room temperature, continue reaction 3.5 hours.Add several 1M hydrochloric acid, 150ml ethyl acetate is carried out after separatory and extraction, with distilled water, saturated aqueous common salt cleaning 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 35.9g white solid triarylamine dihydro pentacene aldehydes derivative.
(4) under nitrogen protection condition; add benzyl diethyl phosphoric acid 17.5g and tetrahydrofuran solution 100ml; be cooled to after-65 DEG C; add potassium tert.-butoxide 9.1g; react after 2.5 hours, to the tetrahydrofuran solution 180ml that drips triarylamine dihydro pentacene aldehydes derivative in reaction solution, react after 2.5 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.Extract after this water layer with toluene, this toluene and organic layer are merged, with distilled water, saturated aqueous common salt cleaning, with anhydrous sodium sulfate drying, concentrated, use toluene recrystallization, the solid of gained is carried out to drying under reduced pressure, result obtains 30.9g white-yellowish solid triarylamine dihydro pentacene olefines luminous organic material.HPLC purity is greater than 98%.Mass spectrum: calculated value is 926.46; Test value is 926.40.Ultimate analysis: calculated value C:90.67%; H:6.70%; N:3.02%; Test value is: C:90.65%; H:6.71%; N:3.03%.
Embodiment 4: compound 013 synthetic
Shown in the concrete following structural formula of synthetic route:
(1) under nitrogen protection condition, take the bromo-10-phenylanthracene of 2-110mmol(36.7g), add the new tetrahydrofuran solution 300ml steaming, under-78 DEG C of conditions, drip n-Butyl Lithium 7.19g, react 2 hours, then drip with 200ml containing 9-bromo-5, 5, 14, 14-tetramethyl--4a, 5, 13a, 14-dihydro pentacene-6, 13 (4aH, 13aH) diketone 50mmol(22.4g) tetrahydrofuran solution, after dropwising, under nitrogen protection condition, after room temperature reaction 10 hours, add 1M dilute hydrochloric acid 100ml, with ether 100ml extraction 3 times, separatory, concentrated, with methylene dichloride: sherwood oil=1:3 recrystallization, obtain 46.9g off-white color intermediate 10-phenyl-2-anthryl dihydro pentacene alcohol derivatives.
(2) get 10-phenyl-2-anthryl dihydro pentacene alcohol derivatives, add in the 300ml vitriol oil, room temperature reaction 9 hours, through hydrolysis, extraction, separatory, recrystallization, obtains 45.9g off-white color 10-phenyl-2-anthryl dihydro pentacene analog derivative.
(3) under nitrogen protection condition; in there-necked flask, add anhydrous tetrahydrofuran solution 10ml, magnesium rod 1.5g, 1 of iodine; after Grignard reagent causes; add the anhydrous tetrahydrofuran solution 200ml that contains 10-phenyl-2-anthryl dihydro pentacene analog derivative, under ice-water bath condition, react 2.1 hours; in this reaction solution, drip the anhydrous N of 18ml; after dinethylformamide, then rise at leisure room temperature, continue reaction 4 hours.Add 1M hydrochloric acid, 150ml ethyl acetate is carried out after separatory and extraction, with distilled water, saturated aqueous common salt cleaning 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 42.35g white solid 10-phenyl-2-anthryl dihydro pentacene aldehydes derivative.
(4) under nitrogen protection condition; add benzyl diethyl phosphoric acid 19.3g and tetrahydrofuran solution 100ml; be cooled to after-65 DEG C; add potassium tert.-butoxide 9.1g; react after 2.2 hours, to the tetrahydrofuran solution 180ml that drips 10-phenyl-3-anthryl dihydro pentacene class aldehydes derivative in reaction solution, react after 2.5 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.Extract after this water layer with toluene, this toluene and organic layer are merged, with distilled water, saturated aqueous common salt cleaning, with anhydrous sodium sulfate drying, concentrated, use toluene recrystallization, the solid of gained is carried out to drying under reduced pressure, result obtains 41.71g white-yellowish solid 10-phenyl-2-anthryl dihydro pentacene olefines luminous organic material.HPLC purity is greater than 98%.Mass spectrum: calculated value is 981.27; Test value is 981.25.Ultimate analysis: calculated value C:90.58%; H:6.16%; O:3.26%; Test value is: C:90.60%; H:6.15%; O:3.27%.
Embodiment 5: compound 012 synthetic
Shown in the concrete following structural formula of synthetic route:
(1) under nitrogen protection system, take 2-bromo-9, 9-dimethyl fluorene 110mmol(49.3g), add the new tetrahydrofuran solution 300ml steaming, under-78 DEG C of conditions, drip n-Butyl Lithium 7.19g, react 2 hours, then drip with 200ml containing 9-bromo-5, 5, 14, 14-tetramethyl--4a, 5, 13a, 14-dihydro pentacene-6, 13 (4aH, 13aH) diketone 50mmol(22.4g) tetrahydrofuran solution, after dropwising, under nitrogen protection condition, after room temperature reaction 10 hours, add 1M dilute hydrochloric acid 100ml, with ether 100ml extraction 3 times, separatory, concentrated, with methylene dichloride: sherwood oil=1:3 recrystallization, obtain off-white color 41.2g intermediate 9, 9-dimethyl-2-fluorenyl dihydro pentacene alcohol derivatives.
(2) get 9,9-dimethyl-2-fluorenyl dihydro pentacene alcohol derivatives, add in the 300ml vitriol oil, room temperature reaction 9 hours, through hydrolysis, extraction, separatory, recrystallization, obtains 40.7g off-white color 9,9-dimethyl-2-fluorenyl dihydro pentacene analog derivative.
(3), under nitrogen protection condition, in there-necked flask, add anhydrous tetrahydrofuran solution 10ml, magnesium rod 1.5g; 1 of iodine; Grignard reagent adds the anhydrous tetrahydrofuran solution 200ml that contains 9,9-dimethyl-2-fluorenyl dihydro pentacene analog derivative after causing; under ice-water bath condition; react 2.2 hours, in this reaction solution, drip after the anhydrous DMF of 18ml; then rise at leisure room temperature, continue reaction 4 hours.Add several 1M hydrochloric acid, 150ml ethyl acetate is carried out after separatory and extraction, with distilled water, saturated aqueous common salt cleaning 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 35.7g white solid 9,9-dimethyl-2-fluorenyl dihydro pentacene aldehydes derivative.
(4) under nitrogen protection condition; add methoxy-benzyl diethyl phosphoric acid 25.1g and tetrahydrofuran (THF) 100ml; be cooled to after-65 DEG C; add potassium tert.-butoxide 9.1g, react after 2 hours, in reaction solution, drip 9; the tetrahydrofuran solution 180ml of 9-dimethyl-2-fluorenyl dihydro pentacene aldehydes derivative; continue reaction after 2 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.Extract after this water layer with toluene, this toluene and organic layer are merged, with distilled water, saturated aqueous common salt cleaning, with anhydrous sodium sulfate drying, concentrated, use toluene recrystallization, the solid of gained is carried out to drying under reduced pressure, result obtains 31.7g white-yellowish solid 9,9-dimethyl-2-fluorenyl dihydro pentacene olefines luminous organic material.HPLC purity is greater than 98%.Mass spectrum: calculated value is 852.43.; Test value is 852.40.Ultimate analysis: calculated value C:91.51%; H:6.62%; O:1.18%; Test value is: C:91.50%; H:6.61; O:1.20%.
Embodiment 6: compound 016 synthetic
Shown in the concrete following structural formula of synthetic route:
(1) under nitrogen protection condition, take 2-bromine pyrene 110mmol(28.5g), add the new tetrahydrofuran solution 300ml steaming, under-78 DEG C of conditions, drip n-Butyl Lithium 7.19g, react 2 hours, then drip 200ml containing 9-bromo-5, 5, 14, 14-tetramethyl--4a, 5, 13a, 14-dihydro pentacene-6, 13 (4aH, 13aH) diketone 50mmol(22.4g) tetrahydrofuran solution, after dropwising, under nitrogen protection condition, after room temperature reaction 9 hours, add 1M dilute hydrochloric acid 100ml, with ether 100ml extraction 3 times, separatory, concentrated, with methylene dichloride: sherwood oil=1:3 recrystallization, obtain off-white color 41.2g intermediate 2-pyrenyl dihydro pentacene alcohol derivatives.
(2) get 2-pyrenyl dihydro pentacene alcohol derivatives, add in the 300ml vitriol oil, room temperature reaction 10 hours, through hydrolysis, extraction, separatory, recrystallization, obtains 40.7g off-white color 2-pyrenyl dihydro pentacene analog derivative.
(3) under nitrogen protection condition; in there-necked flask, add anhydrous tetrahydrofuran solution 10ml, magnesium rod 1.5g, 1 of iodine; after Grignard reagent causes; add the anhydrous tetrahydrofuran solution 200ml containing 2-pyrenyl dihydro pentacene analog derivative, under ice-water bath condition, react 2.2 hours; in this reaction solution, drip the anhydrous N of 18ml; after dinethylformamide, then rise at leisure room temperature, continue reaction 3.5 hours.Add 1M hydrochloric acid, 150ml ethyl acetate is carried out after separatory and extraction, with distilled water, saturated aqueous common salt cleaning 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 35.7g white solid 2-pyrenyl dihydro pentacene aldehydes derivative.
(4) under nitrogen protection condition; add benzyl diethyl phosphoric acid 19.3g and tetrahydrofuran solution 100ml; be cooled to after-65 DEG C; add potassium tert.-butoxide 9.1g; react after 2 hours, to the tetrahydrofuran solution 180ml that drips 2-pyrenyl dihydro pentacene aldehydes derivative in reaction solution, continue reaction after 2 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.Extract after this water layer with toluene, this toluene and organic layer are merged, with distilled water, saturated aqueous common salt cleaning, with anhydrous sodium sulfate drying, concentrated, use toluene recrystallization, the solid of gained is carried out to drying under reduced pressure, result obtains 30.5g white-yellowish solid 2-pyrenyl dihydro pentacene olefines luminous organic material.HPLC purity is greater than 98%.Mass spectrum: calculated value is 854.39; Test value is 854.30.Ultimate analysis: calculated value C:94.11%; H:5.89%; Test value is: C:94.09%; H:5.91%.
Application implementation case 1
The ito glass substrate that it is formed with to 1000 thickness in the above, is placed on the ultrasonic middle cleaning 30 minutes of washings, then uses distilled water ultrasonic cleaning 10 minutes twice.After distilled water wash, use respectively Virahol, toluene, acetone, ethanol difference ultrasonic cleaning 30 minutes, then dry.Finally put into plasma washing machine, use oxygen plasma cleaning base plate 5 minutes, send into vacuum evaporation equipment and process.
By NPB, dihydro pentacene olefines luminous organic material, AlQ, LiF, Al respectively evaporation, to device, goes into object construction device: [ITO/NPB (20nm)/001(30nm)/AlQ (20nm)/LiF (5nm)/Al (10nm)], velocity of evaporation is that organism is 1/s, the velocity of evaporation of LiF is 0.5/s, and the velocity of evaporation of Al is 2/s, and vacuum keep is 10 -5vacuum tightness below pa normal atmosphere.
The test result of device 001 is cut-in voltage 4v, and high-high brightness is 3600cd/m 2, under 10v voltage, observing efficiency is 27Lm/w, chromaticity coordinates (CIE) value is x:0.19; Y:0.14, obtains a blue device, and life-span transformation period of device is 19000h.
The luminous efficiency of gained compound in table 1 embodiment
Sample Luminous efficiency in dilute solution Luminous efficiency in film
001 97% 56%
007 98% 59%
012 97% 57%
016 96% 58%
Can find out from the data of table 1, the dihydro pentacene olefines luminous organic material that embodiment prepares has high luminous efficiency, shows that this analog derivative can be used as luminescent material or luminous material of main part and transport material, is applied in electroluminescent device.Simultaneously according to application example 1, we are applied to this analog derivative in organic electroluminescence device, by data test and comparison, we find that this compounds is the electroluminescent organic material of excellent property really, particularly, as the good luminous material of main part of Performance Ratio and transport material, it is a very promising class electroluminescent organic material.
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 without also giving exhaustive to all embodiments.And the apparent variation of being extended out thus or variation are still among the protection domain in the invention.

Claims (9)

1. dihydro pentacene olefines luminous organic material, is characterized in that, the general structure of this material is suc as formula shown in (1):
Wherein, R 1for N-phenyl-3-carbazyl, 3-coffee sieve quinoline base, triarylamine, 10-phenyl-2-anthryl, 9,9-dimethyl-2-fluorenyl or 2-pyrenyl; R 2for phenyl, p-methylphenyl or p-methoxyphenyl.
2. dihydro pentacene olefines luminous organic material as claimed in claim 1, is characterized in that R 1for N-phenyl-3-carbazyl, R 2for phenyl.
3. dihydro pentacene olefines luminous organic material as claimed in claim 1, is characterized in that R 1for 3-coffee sieve quinoline base, R 2for phenyl.
4. dihydro pentacene olefines luminous organic material as claimed in claim 1, is characterized in that R 1for triarylamine, R 2for phenyl.
5. dihydro pentacene olefines luminous organic material as claimed in claim 1, is characterized in that R 1for 10-phenyl-2-anthryl, R 2for phenyl.
6. dihydro pentacene olefines luminous organic material as claimed in claim 1, is characterized in that R 1be 9,9-dimethyl-2-fluorenyl, R 2p-methoxyphenyl.
7. dihydro pentacene olefines luminous organic material as claimed in claim 1, is characterized in that R 1for 2-pyrenyl, R 2for p-methylphenyl.
8. the preparation method of dihydro pentacene olefines luminous organic material as claimed in claim 1, is characterized in that, this preparation method's concrete steps and condition are as follows:
(1) for 1:2.2～2.5, to take 9-bromo-5,5,14 in molar ratio, 14-tetramethyl--4a, 5,13a, 14-dihydro pentacene-6,13 (4aH, 13aH) diketone and containing R 1substituent halogenide, dissolves with tetrahydrofuran (THF) respectively; Under acetone bath condition, to containing R 1in substituent halid tetrahydrofuran solution, drip n-Butyl Lithium, n-Butyl Lithium with containing R 1substituent halogenide mol ratio is 1:1.05～1.1, reacts 2～6 hours, drips 9-bromo-5; 5,14,14-tetramethyl--4a; 5,13a, 14-dihydro pentacene-6; the tetrahydrofuran solution of 13 (4aH, 13aH) diketone, after dropwising; under nitrogen protection condition; room temperature reaction 8～10 hours, after extraction, separatory, concentrated, recrystallization, obtains containing R 1substituent dihydro pentacene alcohol derivatives;
(2) take containing R 1substituent dihydro pentacene alcohol derivatives, adds in the vitriol oil, and room temperature reaction 9～11 hours, through hydrolysis, recrystallization, suction filtration, washing, oven dry, obtains containing R 1substituent dihydro pentacene analog derivative;
(3) take magnesium rod some, add iodine and cause, add containing R 1the tetrahydrofuran solution of substituent dihydro pentacene analog derivative, under ice-water bath condition, reacts 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 R 1substituent dihydro pentacene aldehydes derivative;
(4) take containing R for 1:2.0～2.2 in molar ratio 1substituent dihydro pentacene aldehydes derivative and containing R 2substituent diethyl phosphoric acid; Under nitrogen protection condition, add benzyl diethyl phosphoric acid and tetrahydrofuran (THF), be cooled to, after-65 DEG C～-70 DEG C, add potassium tert.-butoxide, react 2～2.5 hours, to the solution that drips dihydro pentacene aldehydes derivative in reaction solution, continue reaction 2～2.5 hours, rise to room temperature, continue reaction after 2～2.5 hours, through separatory, extraction, dry, concentrated, recrystallization, obtain dihydro pentacene olefines luminous organic material;
Wherein, described R 1for N-phenyl-3-carbazyl, 3-coffee sieve quinoline base, triarylamine, 10-phenyl-2-anthryl, 9,9-dimethyl-2-fluorenyl or 2-pyrenyl; R 2for phenyl, p-methylphenyl or p-methoxyphenyl.
9. the application of dihydro pentacene olefines luminous organic material as claimed in claim 1, is characterized in that, this material can be used as luminescent material, luminous material of main part or transport material, is applied on electroluminescent device.
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