CN1911904A - 2-substituted rubrene compound and its synthesis method and application - Google Patents
2-substituted rubrene compound and its synthesis method and application Download PDFInfo
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Abstract
The present invention is one kind of 2-substituted rubrene compound as shown and its synthesis process. The synthesis process includes the first synthesis of 2-formoxyl rubrene, and the subsequent oxidation, reduction and condensation with 2-formoxyl rubrene to obtain other 2-substituted rubrene compound. The synthesis process of 2-formoxyl rubrene under protection of inert gas includes the first reaction of 2-formoxyl -6, 11-diphenyl-5, 12-tetracene quinine material with glycol and catalyst at 120-160 deg.c; the subsequent reflux reaction with phenyl magnesium bromide and anhydrous tetrafuran; and final reflux reaction with iron powder and glacial acetic acid under heliophobic condition to obtain 2-formoxyl rubrene. The 2-substituted rubrene compound of the present invention as new type of red fluorescent material has high fluorescence quantum efficiency and may be used as the luminous material in electroluminescent device.
Description
Technical field
The present invention relates to a kind of 2-substituted rubrene compound and synthetic method and application.
Background technology
Functional pigmentedly can under various energy such as light, heat, electricity stimulate, produce some special replying, utilize these performances to can be used as the information record and the display material of electronic product; The sensitive materials of duplicating machine, laser printer; The laser energy transition material; Solar energy converting and stored material etc. all are widely used in fields such as communication, control automatically, military project, chemical industry, pharmacy, agricultural chemicals.
Polycyclic aromatics rubrene, its chemical name is 5,6,11,12-tetraphenyl tetracene, be a kind of dyestuff of high fluorescence efficiency, its luminous efficiency in solution is up to 99% (Yildiz A, Kissinger P T, Reilley C N.J.Chem.Phys., 1968,49:1403.), it can be applicable to many fields such as organic electroluminescent, chemoluminescence, photoluminescence, antioxidant, liquid crystal, optical communication, matrix material as functional fluorescent material.Now, the object twinkler is done with rubrene by SANYO GS company, and rubrene is dispersed in respectively in 10-hydroxy benzo quinoline beryllium layer or the hole transporting layer, and these two kinds of adulterated results can both produce above 10000cd/m
2The blue light of brightness makes luminous intensity improve 100 times, and has prolonged the work-ing life of element, reach degree of being practical (the clear KURA in field, palace. the most preceding Line .NTS of organic EL sub-prime と そ industrialization, 1998.).In the Chemiluminescence Study field, utilize rubrene to add 2 to as sensitizing agent, 4, in the luminescence system of the superoxide of 5-triphenyl imidazoles, because its intermolecular sensibilization, chemiluminescence intensity can be improved 6 times (Kimura Wins, red wood smoke etc. photochemistry discussion lecture main idea collection, 1994,269.).At present, existing bibliographical information 2-methyl rubrene, 2-imidazolyl substituted rubrene, 2,8-dimercapto rubrene, 2,8-rubrene dioctyl phthalate, 8-sulfydryl-2-rubrene formic acid, 2,8-disubstituted aryl rubrene, 2,3-dimethyl rubrene, 2,3-dimethoxy rubrene, 2, and 3-two (4-aminomethyl phenyl) rubrene, 2-substituted-amino rubrene, 2-(2-furyl) rubrene (know it recklessly, the Kimura rises. and Japan's chemistry can Chi, 2000, No.7:475-484; And Tian Gongxiong, the molecular luminescence device. Japan, spy open flat 11-265786; Tianjin difficult to understand acute hearing, beautiful wild Mercer, terrible Kubo person of outstanding talent one. luminous organic material and the application in electroluminescent device thereof. Japan, spy open flat 10-289786).But being reported as the 2-substituted rubrene mostly uses in making organic electroluminescence device, though and above-claimed cpd has realized making rubrene to have substituent purpose, but its substituting group is to improving the πDian Zi conjugated degree, it is not very big making emission wavelength red shift role, and their character torpescence, need be translated into active group, for example bromomethyl, aldehyde radical etc.Thereby reach by series reaction, for example nucleophilic substitution, condensation reaction, oxidizing reaction, reduction reaction etc. import different systems with rubrene, widen the purpose of the use range of rubrene.
If therefore on the parent-tetracene ring of rubrene, introduce formyl radical, conjugated system is strengthened, make the emission wavelength of fluorescent chemicals produce red displacement, prepare new red fluorescence compound; But also can or convert multiple functional group to by active group-formyl radical introducing, and then make multiple novel fluorescent chemicals, make the luminescent material of excellent property.
Summary of the invention
The purpose of this invention is to provide a kind of 2-substituted rubrene compound.
Another object of the present invention provides a kind of synthetic method of 2-substituted rubrene compound.
A further object of the present invention provides the purposes of a kind of 2-substituted rubrene compound as electroluminescent organic material.
According to a kind of 2-substituted rubrene compound of the present invention shown in following formula (I):
R wherein
1Be expressed as formyl radical, methylol, carboxyl,
R wherein
2, R
3, R
4, R
5Or R
6Be H, C
1-C
3Alkyl, vinyl, ethynyl, halogen, halogenated methyl, halogenated ethyl, phenyl, formyl radical, ethanoyl, carboxyl, methoxycarbonyl, formamyl, hydroxyl, sulfydryl, methoxyl group, methylthio group, nitro, amino, aminomethyl or cyano group, condition is R
5, R
6Can not be expressed as H simultaneously.
According to a kind of 2-substituted rubrene compound of the present invention, R wherein
1Further be expressed as formyl radical, methylol,
R wherein
2, R
5Or R
6Be H, C
1-C
3Alkyl, vinyl, ethynyl, halogen, halogenated methyl, halogenated ethyl, phenyl, formyl radical, ethanoyl, carboxyl, methoxycarbonyl, formamyl, hydroxyl, sulfydryl, methoxyl group, methylthio group, nitro, amino, aminomethyl or cyano group, condition is R
5, R
6Can not be expressed as H simultaneously.
According to a kind of 2-substituted rubrene compound of the present invention, R wherein
2, R
3Or R
4Can be expressed as H, C
1-C
3Alkyl or halogen, condition are R
5, R
6Can not be expressed as H simultaneously.
According to a kind of 2-substituted rubrene compound of the present invention, R wherein
2Preferably be expressed as H, C
1-C
3Alkyl, R
5Or R
6Preferably be expressed as halogen, especially F, Cl or Br simultaneously.
According to the synthetic method of a kind of 2-substituted rubrene compound of the present invention, at first Synthetic 2-formyl radical rubrene is synthetic other 2-substituted rubrene compound of raw material with it then, and concrete steps are as follows:
The total overall reaction process is all under protection of inert gas, at first according to 1: the mol ratio of 0.60-0.88 adds 2-formyl radical-6,11-phenylbenzene-5; 12-tetracene quinone and ethylene glycol; add again and be equivalent to 2-formyl radical-6,11-phenylbenzene-5, the catalyzer of 12-tetracene quinone weight 1-5%; react at 120-160 ℃; after reaction finishes, obtain 2-(1 ', 3 '-dioxolane)-6 according to the ordinary method separation; 11-phenylbenzene-5; 12-tetracene quinone is 1 according to mol ratio: 6-10: 0.15-0.25 adds 2-(1 ', 3 '-dioxolane)-6 successively; 11-phenylbenzene-5; 12-tetracene quinone; phenyl-magnesium-bromide and anhydrous tetrahydro furan, back flow reaction is after reaction finishes; obtain 2-(2 '-(1 ' according to the ordinary method separation; 3 '-dioxolanyl))-5,6,11; 12-tetraphenyl tetracene-5, the 12-glycol.At last under the lucifuge condition; by weight 1: 0.8-1.2: 40-50 adds 2-(2 '-(1 ', 3 '-dioxolanyl))-5,6 successively; 11; 12-tetraphenyl tetracene-5,12-glycol, iron powder and Glacial acetic acid; reflux; reaction finishes the back under the lucifuge condition, separates obtaining 2-formyl radical rubrene according to ordinary method
Wherein said catalyzer is the vitriol oil, p-methyl benzenesulfonic acid, nanometer Fe
2O
3/ SO
4 2-Or nanometer ZrO
2/ SO
4 2-, rare gas element is nitrogen or argon gas,
(2) 2-methylol rubrene synthetic method is as follows:
According to 1: the mol ratio of 3-5 adds 2-formyl radical rubrene and sodium borohydride griding reaction under shading,
(3) R
1Be expressed as
2-substituted rubrene synthetic method as follows:
According to 1: the mol ratio of 1-1.3 adds 2-formyl radical rubrene and amino benzenes compounds, adds 0～5% the p-methyl benzenesulfonic acid that is equivalent to 2-formyl radical rubrene weight, 50～100 times anhydrous tetrahydro furan again, under shading and nitrogen protection, react,
Described amino benzenes compounds is expressed as
(4) R
1Be expressed as
2-substituted rubrene synthetic method as follows:
According to 1: the mol ratio of 1-1.5 adds 2-formyl radical rubrene and 1, and the 2-cyclohexadione compounds adds and is equivalent to the ammonium acetate of 1.5～2.0 times of 2-formyl radical rubrene weight, 80～120 times Glacial acetic acid, back flow reaction under nitrogen protection,
Wherein 1, the 2-cyclohexadione compounds is expressed as
Described catalyzer is the vitriol oil, p-methyl benzenesulfonic acid, nanometer Fe
2O
3/ SO
4 2-Or nanometer ZrO
2/ SO
4 2-, catalyzer is preferably p-methyl benzenesulfonic acid, and rare gas element is preferably nitrogen.
Described 2-substituted rubrene compound can be used as the material of luminescent layer in the electroluminescent device.
2-substituted rubrene compound of the present invention; owing on rubrene parent 2-position, introduce the substituting group that conjugated system is strengthened; the fluorescent emission wavelength produces red displacement; fluorescent emission intensity increases; as 2-formyl radical rubrene red shift degree maximum; with respect to rubrene (fluorescence maximum emission wavelength 561nm) red shift 19nm; with 2-(4 '; 5 '-two (4 " fluorophenyl imidazolyl)) rubrene is the strongest; its fluorescent emission intensity is 3 times of rubrene; therefore introduce the formyl activity group on 2 of rubrene; it can pass through series reaction, for example nucleophilic substitution; condensation reaction; oxidizing reaction; reduction reaction etc., synthetic a series of novel 2-substituted rubrene compounds; rubrene is imported different systems, widen the range of application of rubrene.
Description of drawings
Fig. 1 is the emission wavelength-intensity curve of rubrene under different driving voltage.
Fig. 2 is the emission wavelength-normal intensity curve of rubrene under different driving voltage.
Fig. 3 is the emission wavelength-Strength Changes curve of 2-formyl radical rubrene of the present invention under different driving voltage.
Fig. 4 is the emission wavelength-normal intensity change curve of 2-formyl radical rubrene of the present invention under different driving voltage.
Embodiment
Further specify the present invention below by embodiment, but do not limit the present invention in any way.
Synthesizing of embodiment 1:2-formyl radical rubrene (2-formyl radical-5,6,11,12-tetraphenyl tetracene)
(1) intermediate 2-(1 ', 3 '-dioxolane)-6,11-phenylbenzene-5,12-tetracene quinone synthetic
In 100 milliliters of two mouthfuls of flasks, add 0.964 gram (2.00 mmole) 2-formyl radical-6,11-phenylbenzene-5,12-tetracene quinone, 60 milliliters of ethylene glycol, 28.9 milligrams of p-methyl benzenesulfonic acids are heated to about 8 hours of 160 ℃ of reactions under nitrogen protection.Water=9: 1) and TLC (normal hexane: ethyl acetate=8: 3) follow the tracks of entire reaction course, stopped reaction when raw material exhausts substantially use HPLC (methyl alcohol: therebetween.Reaction solution poured in an amount of saturated sodium bicarbonate aqueous solution refilter, the product that leaches separates (silica gel 500～800 orders with the column chromatography chromatogram method, eluent is a normal hexane: ethyl acetate=30: 1), obtain yellow powder shape solid 2-(1 ', 3 '-dioxolane)-6,11-phenylbenzene-5,12-tetracene quinone.(0.864 gram, yield 81.6%), fusing point: 269-271 ℃.IR (KBr, cm
-1) :～3050 ,～1677,1196,1160,1040 ,～1100; Mass spectrum (MS
+) 483.1 (molecular weight of product is 482);
1H NMR (500MHz, CD
2Cl
2): 8.04-8.06 (d, J=7.48,1H), 8.14 (s, 1H), 7.79-7.81 (d, J=7.48,1H), 7.31-7.61 (m, 14H), 5.87 (s, 1H), 4.03-4.13 (m, 4H); The liquid ultraviolet maximum absorption wavelength of product is respectively 249.97,296.67, and (solvent is CH to 394.78nm
2Cl
2); Liquid fluorescence maximum emission wavelength is that (solvent is CH to 569.72nm
2Cl
2, excitation wavelength is 250nm).
(2) 2-formyl radical rubrene (2-formyl radical-5,6,11,12-tetraphenyl tetracene) is synthetic
In 50 milliliters of two mouthfuls of reactors that drying is crossed, add (1) method synthetic 0.4825 gram (1 mmole) compound 2-(1 ', 3 '-dioxolane)-6 set by step, 11-phenylbenzene-5,12-tetracene quinone, reaction system is with nitrogen replacement.Add 15 milliliters of anhydrous tetrahydro furans and 8 mmole phenyl-magnesium-bromides successively, heating reflux reaction 6 hours, water=9: 1) and TLC (normal hexane: ethyl acetate=8: 3) follow the tracks of entire reaction course, use HPLC (methyl alcohol: therebetween when relative by-product peak, target product peak reaches stopped reaction when the highest.Reaction solution fully vibrates after adding saturated aqueous ammonium chloride, and the separatory extraction merges organic phase, and the rotation evaporate to dryness obtains light yellow solid, does not separate and directly carries out next step reaction.In two mouthfuls of round-bottomed flasks of 50 milliliters with the tinfoil shading, step synthetic 0.6216 gram light yellow solid before adding, 0.700 gram (12.5 mmole) Fe powder; 20 milliliters of Glacial acetic acid; under nitrogen protection, heating reflux reaction 2 hours adds 0.5 ml water with syringe again and reacted 1 hour down in 90 ℃.Entire reaction course is followed the tracks of with HPLC (moving phase is pure methyl alcohol), judges reaction end.After reaction finished, under the condition of shading, filtering reacting liquid was removed the Fe powder.With saturated aqueous common salt washing reaction liquid, add in the sodium bicarbonate saturated solution of capacity and deacidification, use the ethyl acetate extraction water lotion again, separatory, organic layer was with anhydrous magnesium sulfate drying 2 hours.The shading rotary evaporation is removed solvent.With column chromatography chromatogram method (silica gel 500～800 orders, eluent are pure hexane) product separation, finally obtain sheet dark red solid compound 2-formyl radical rubrene (2-formyl radical-5; 6; 11,12-tetraphenyl tetracene) (0.1491 gram, two step yields are 30.6%).Fusing point is greater than 300 ℃.IR(KBr，cm
-1)：1603，1621，1695，2720，3090；HRMS(EI)：M
+，found?561.2213.C
43H
28O?requires?560.2140。
1H NMR (500MHz, CD
2Cl
2): δ (ppm): 9.76 (s, 1H), 7.89 (s, 1H), 7.47-7.49 (d, J=9.29,1H), 7.40-7.44 (m, 2H), 7.40-7.44 (t, 1H), 7.15-7.12 (m, 2H), 7.15-7.12 (m, 4H), 7.08-7.13 (m, 8H), 6.87-6.93 (m, 8H); The liquid ultraviolet maximum absorption wavelength of product is respectively 314.49,439.47,509.39, and (solvent is CH to 545.13nm
2Cl
2); Liquid fluorescence maximum emission wavelength is that (solvent is CH to 576.73nm
2Cl
2, excitation wavelength is 314nm).
Synthesizing of embodiment 2:2-methylol rubrene
In the darkroom, with 56.1 milligrams of (0.1 mmole) 2-formyl radical rubrenes and 11.4 milligrams of (0.3 mmole) NaBH
4Add in the mortar, grind behind the thorough mixing, grind about 30min, the excessive sodium borohydride of water dissolution that adds 10 milliliters with 20 milliliters of chloroform extraction products, steams solvent, handle with solvent method and obtain target product (51.6 milligrams, yield is 91.9%), fusing point is greater than 300 ℃.IR (KBr, cm
-1): 1020,2928,2956,3070,3620; Mass spectrum (MS
-) 562.0 (molecular weight of product is 562.7);
1H NMR (500MHz, CD
2Cl
2): δ (ppm): 7.32-7.34 (m, 2H), 7.25 (s, 1H), 7.04-7.11 (m, 16H), 6.85-6.86 (m, 8H), 4.51-4.53 (m, 2H); The liquid ultraviolet maximum absorption wavelength of product is respectively 303.35,462.16,492.16, and (solvent is CH to 526.35nm
2Cl
2); Liquid fluorescence maximum emission wavelength is that (solvent is CH to 561.68nm
2Cl
2, excitation wavelength is 319nm).
Synthesizing of embodiment 3:N-(the glimmering thiazolinyl of 2 '-methylene red) aniline
In wrap 20 milliliters of two mouthfuls of reactors that also drying is crossed with tinfoil, add 56.1 milligrams of (0.1 mmole) 2-formyl radical rubrenes; the reaction system that drying is airtight vacuumized 2 hours with oil pump; therebetween with nitrogen replacement four times; add 9.2 microlitres (0.1 mmole) aniline with microsyringe; 5 milliliters of tetrahydrofuran (THF)s that add the no water treatment of process just again with syringe; heating reflux reaction 4 hours; use HPLC (moving phase is pure methyl alcohol) and TLC (normal hexane: ethyl acetate=10: 1) follow the tracks of entire reaction course, therebetween when the target product peak reaches stopped reaction when the highest relatively.Reaction solution is rotated evaporate to dryness, handle obtaining target product (52.3 milligrams, yield is 82.2%) again with solvent method.Fusing point is greater than 300 ℃.IR (KBr, cm-1): 1380,1616; HRMS (EI): M
+, found 636.2609.C
49H
33N requires 635.2613.
1H NMR (500MHz, CD
2Cl
2): δ (ppm): 8.31 (s, 1H), 7.83-7.88 (d, J=9.46,1H), 7.65 (s, 1H), 7.42-7.45 (d, 1H), and 7.39-7.41 (m, 2H), 7.34-7.38 (t, 2H), and 7.19-7.20 (t, 1H), 7.15-7.18 (m, 8H), 7.09-7.13 (m, 8H), and 6.90-6.94 (m, 8H); The liquid ultraviolet maximum absorption wavelength of product is respectively 317.33,355.75,470.10,501.94, and (solvent is CH to 537.92nm
2Cl
2); Liquid fluorescence maximum emission wavelength is that (solvent is CH to 565.55nm
2Cl
2, excitation wavelength is 317nm).
Synthesizing of embodiment 4 N-(the glimmering thiazolinyl of 2 '-methylene red)-4-isopropyl aniline
In wrap 20 milliliters of two mouthfuls of reactors that also drying is crossed with tinfoil, add 84.1 milligrams of (0.15 mmole) 2-formyl radical rubrenes; 2.1 milligram p-methyl benzenesulfonic acid; the reaction system that drying is airtight vacuumized 2 hours with oil pump; therebetween with nitrogen replacement four times; add 22 microlitres (0.15 mmole) 4-isopropyl aniline with microsyringe; 8 milliliters of tetrahydrofuran (THF)s that add the no water treatment of process just again with syringe; heating reflux reaction 9 hours; use HPLC (moving phase is pure methyl alcohol) and TLC (normal hexane: ethyl acetate=10: 1) follow the tracks of entire reaction course, therebetween when relative by-product peak, target product peak reaches stopped reaction when the highest.Pour in the saturated sodium bicarbonate aqueous solution reaction solution into fully vibration, the separatory extraction merges organic phase, the rotation evaporate to dryness, again with solvent method handle obtain target product (75.8 milligrams, yield: 74.6%).Fusing point is greater than 300 ℃.IR (KBr, cm
-1) :～1177,1158,1380,1616 ,～1450 ,～2960 ,～2870 ,～3070; HRMS (EI): M
+, found 677.3070.C
52H
39N requires 677.3083.
1H NMR (500MHz, CD
2Cl
2): δ (ppm): 8.32 (s, 1H), 7.81-7.86 (d, J=9.46,1H), 7.63 (s, 1H), 7.39-7.44 (m, 3H), and 7.22-7.24 (d, J=8.33,2H), 7.15-7.19 (m, 8H), 7.09-7.13 (m, 8H), 6.90-6.92 (m, 8H), 2.89-2.95 (m, 1H), 1.24-1.27 (d, J=6.88,6H); The liquid ultraviolet maximum absorption wavelength of product is respectively 314.78,359.93,469.58,501.50, and (solvent is CH to 537.64nm
2Cl
2); Liquid fluorescence maximum emission wavelength is that (solvent is CH to 567.20nm
2Cl
2, excitation wavelength is 315nm).
Embodiment 5 2-(4 ', 5 '-the difuryl imidazolyl) rubrene synthetic
In two mouthfuls of round-bottomed flasks of 30 milliliters with the tinfoil shading; add 112.2 milligrams of (0.2 mmole) 2-formyl radical rubrenes, 41.8 milligrams of (0.22 mmoles) 1,2-two (2-furyl) diketone, 185.3 milligrams of (2.4 mmole) ammonium acetates, 10 milliliters of Glacial acetic acid.Under the nitrogen protection, back flow reaction 20 hours is used HPLC (moving phase is pure methyl alcohol) and TLC (normal hexane: ethyl acetate=10: 1) follow the tracks of entire reaction course, when relative by product peak, target product peak reaches stopped reaction when the highest therebetween.Reaction solution is washed acid with 30 milliliters saturated sodium-chloride water solution earlier, again with 20 milliliters of saturated sodium bicarbonate aqueous solution neutralizations, use 30 milliliters of ethyl acetate extraction water lotions then, the extraction liquid that obtains Rotary Evaporators evaporation concentration is behind the removal solvent, with column chromatography chromatogram method (silica gel 500～800 orders, eluent is pure hexane) product separation, (98.2 milligrams, yield: 67.2%), this material is the dark red solid powder finally to obtain target product.Fusing point is greater than 300 ℃.Mass spectrum (MS
+) 730.9.IR(KBr，cm
-1)：700，3000，3060，3110。
1H NMR (500MHz, CD
2Cl
2): δ (ppm): 7.79 (s, 1H), 7.50-7.73 (m, 1H), 7.46-7.51 (m, 3H), 7.37-7.41 (m, 2H), 7.19-7.22 (m, 4H), 7.13-7.17 (m, 4H), 7.09-7.12 (m, 5H), 6.95-6.97 (m, 4H), 6.90-6.92 (m, 5H), 6.82-6.85 (m, 2H), 6.53-6.54 (t, 2H) (wherein hydrogen does not go out the peak on the imidazoles nitrogen); The liquid ultraviolet maximum absorption wavelength of product is respectively 304.53,360.10,536.21,501.50, and (solvent is CH to 576.34nm
2Cl
2); Liquid fluorescence maximum emission wavelength is that (solvent is CH to 572.65nm
2Cl
2, excitation wavelength is 304nm).
Embodiment 6 2-(4 ', 5 '-two (4 " fluorophenyl imidazolyl)) rubrene synthetic
In two mouthfuls of round-bottomed flasks of 30 milliliters with the tinfoil shading; add 112.2 milligrams of (0.2 mmole) 2-formyl radical rubrenes, 54.2 milligrams of (0.22 mmoles) 1,2-two (4-fluorophenyl) diketone, 185.3 milligrams of (2.4 mmole) ammonium acetates, 10 milliliters of Glacial acetic acid.Under the nitrogen protection, back flow reaction 22 hours is used HPLC (moving phase is pure methyl alcohol) and TLC (normal hexane: ethyl acetate=10: 1) follow the tracks of entire reaction course, when relative by product peak, target product peak reaches stopped reaction when the highest therebetween.Reaction solution is washed acid with 30 milliliters of saturated sodium-chloride water solutions earlier, again with 20 milliliters of saturated sodium bicarbonate aqueous solution neutralizations, use 30 milliliters of ethyl acetate extraction water lotions then, the extraction liquid that obtains Rotary Evaporators evaporation concentration is behind the removal solvent, with column chromatography chromatogram method (silica gel 500～800 orders, eluent is pure hexane) product separation, (103.2 milligrams, yield: 65.2%), this material is the dark red solid powder finally to obtain target product.Fusing point is greater than 300 ℃.Mass spectrum (MS
+) 786.5 (molecular weight of product is 786.3); IR (KBr, cm
-1): 1250,3000,3060,3110;
1H NMR (500MHz, CD
2Cl
2):
1H NMR (500MHz, CD
2Cl
2):
1H NMR (500MHz, CD
2Cl
2): δ (ppm): 7.69 (s, 1H), 7.63-7.65 (d, J=9.36,1H), 7.38-7.40 (d, J=4.20,1H), 7.36-7.38 (m, 1H), 7.32 (s, 4H), 7.11-7.16 (m, 4H), 7.10-7.12 (m, 6H), and 7.08-7.10 (m, 2H), 7.01-7.04 (m, 2H), 6.99-7.02 (m, 2H), 6.96-6.99 (m, 2H), 6.89-6.91 (m, 8H), 6.82-6.85 (m, 2H); The liquid ultraviolet maximum absorption wavelength of product is respectively 305.34,367.71,387.93,472.72,505.66, and (solvent is CH to 542.50nm
2Cl
2); Liquid fluorescence maximum emission wavelength is that (solvent is CH to 571.56nm
2Cl
2, excitation wavelength is 305nm).
Embodiment 7 2-formyl radical rubrenes are as the application of the material of luminescent layer in the electroluminescent device
Utilize rubrene and 2-formyl radical rubrene after distilling, made following device respectively:
(1)ITO/CuPc/NPB/NPB：1wt％mbrene/TPBi/LiF/Al
(2)ITO/CuPc/NPB/NPB：2wt％2-formylrubrene/TPBi/LiF/Al。
The ITO film of the organic film device that is coated with is directly connected the positive electrode of direct supply, and the aluminium symphysis connects the negative pole of direct supply.Along with the continuous rising of voltage, luminosity also changes thereupon.Respectively voltage is fixed on a certain value, has measured wavelength-normal intensity curve under emission wavelength-intensity curve and the relevant voltage thereof shown in Fig. 1,2,3,4.
For device (1), when the doping content of rubrene was 1wt%, its maximum luminous efficiency was 3.5cd/A, and high-high brightness is 2771cd/m
2From Fig. 1,2 as can be seen: maximum electroluminescent emission wavelength is 561nm, and does not move along with the increase of bias voltage.Therefore, can conclude that the migration of energy from main body luminescent material NPB to object luminescent material Rubrene is effectively and completely.
And for device (2), when the doping content of 2-formyl radical rubrene was 2wt%, its maximum luminous efficiency was 3.13cd/A, and high-high brightness is 1333cd/m
2From Fig. 3,4 as can be seen, during doping 2-formyl radical rubrene, maximum emission wavelength is 598nm, and does not move along with the increase of bias voltage.Compare during with the doping rubrene, red shift about 37nm.
Claims (6)
1, a kind of 2-substituted rubrene compound shown in following formula (I):
R wherein
1Be expressed as formyl radical, methylol, carboxyl,
Or
R wherein
2, R
3, R
4, R
5Or R
6Be H, C
1-C
3Alkyl, vinyl, ethynyl, halogen, halogenated methyl, halogenated ethyl, phenyl, formyl radical, ethanoyl, carboxyl, methoxycarbonyl, formamyl, hydroxyl, sulfydryl, methoxyl group, methylthio group, nitro, amino, aminomethyl or cyano group, condition is R
5, R
6Can not be expressed as H simultaneously.
2,2-substituted rubrene compound as claimed in claim 1 is characterized in that described R
1
Be expressed as formyl radical, methylol,
Or
R wherein
2, R
5Or R
6Be H, C
1-C
3Alkyl, vinyl, ethynyl, halogen, halogenated methyl, halogenated ethyl, phenyl, formyl radical, ethanoyl, carboxyl, methoxycarbonyl, formamyl, hydroxyl, sulfydryl, methoxyl group, methylthio group, nitro, amino, aminomethyl or cyano group, condition is R
5, R
6Can not be expressed as H simultaneously.
3,2-substituted rubrene compound as claimed in claim 1 is characterized in that described R
2, R
3Or R
4Be expressed as H, C
1-C
3Alkyl or halogen, condition are R
5, R
6Can not be expressed as H simultaneously.
4, a kind of synthetic method of 2-substituted rubrene compound as claimed in claim 1 is characterized in that at first Synthetic 2-formyl radical rubrene, is synthetic other 2-substituted rubrene compound of raw material with it then, and concrete steps are as follows:
(1) synthetic method of 2-formyl radical rubrene is as follows:
The total overall reaction process is all under protection of inert gas, at first according to 1: the mol ratio of 0.60-0.88 adds 2-formyl radical-6,11-phenylbenzene-5; 12-tetracene quinone and ethylene glycol; add again and be equivalent to 2-formyl radical-6,11-phenylbenzene-5, the catalyzer of 12-tetracene quinone weight 1-5%; react at 120-160 ℃; after reaction finishes, obtain 2-(1 ', 3 '-dioxolane)-6 according to the ordinary method separation; 11-phenylbenzene-5; 12-tetracene quinone is 1 according to mol ratio: 6-10: 0.15-0.25 adds 2-(1 ', 3 '-dioxolane)-6 successively; 11-phenylbenzene-5; 12-tetracene quinone; phenyl-magnesium-bromide and anhydrous tetrahydro furan, back flow reaction is after reaction finishes; obtain 2-(2 '-(1 ' according to the ordinary method separation; 3 '-dioxolanyl))-5,6,11; 12-tetraphenyl tetracene-5, the 12-glycol.At last under the lucifuge condition; by weight 1: 0.8-1.2: 40-50 adds 2-(2 '-(1 ', 3 '-dioxolanyl))-5,6 successively; 11; 12-tetraphenyl tetracene-5,12-glycol, iron powder and Glacial acetic acid; reflux; reaction finishes the back under the lucifuge condition, separates obtaining 2-formyl radical rubrene according to ordinary method
Wherein said catalyzer is the vitriol oil, p-methyl benzenesulfonic acid, nanometer Fe
2O
3/ SO
4 2-Or nanometer ZrO
2/ SO
4 2-, rare gas element is nitrogen or argon gas,
(2) 2-methylol rubrene synthetic method is as follows:
According to 1: the mol ratio of 3-5 adds 2-formyl radical rubrene and sodium borohydride griding reaction under shading,
(3) R
1Be expressed as
2-substituted rubrene synthetic method as follows:
According to 1: the mol ratio of 1-1.3 adds 2-formyl radical rubrene and amino benzenes compounds, adds the p-methyl benzenesulfonic acid of the 0-5% that is equivalent to 2-formyl radical rubrene weight, 50～100 times anhydrous tetrahydro furan again, under shading and nitrogen protection, react,
Described amino benzenes compounds is expressed as
(4) R
1Be expressed as
Or
2-substituted rubrene synthetic method as follows:
According to 1: the mol ratio of 1-1.5 adds 2-formyl radical rubrene and 1, and the 2-cyclohexadione compounds adds and is equivalent to the ammonium acetate of 1.5～2.0 times of 2-formyl radical rubrene weight, 80～120 times Glacial acetic acid, back flow reaction under nitrogen protection,
Wherein 1, the 2-cyclohexadione compounds is expressed as
Or
5, the synthetic method of 2-substituted rubrene compound as claimed in claim 4 is characterized in that described catalyzer is the vitriol oil, p-methyl benzenesulfonic acid, nanometer Fe
2O
3/ SO
4 2-Or nanometer ZrO
2/ SO
4 2-, rare gas element is a nitrogen.
6,, it is characterized in that can be used as the material of luminescent layer in the electroluminescent device as claim 1,2 or 3 described 2-substituted rubrene compounds.
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|---|---|---|---|---|
| CN106336393A (en) * | 2016-08-03 | 2017-01-18 | 长春海谱润斯科技有限公司 | Aromatic compound and organic light-emitting device using same |
| CN106946677A (en) * | 2017-04-20 | 2017-07-14 | 深圳市华星光电技术有限公司 | Fused ring compound and its application, electroluminescent device and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336393A (en) * | 2016-08-03 | 2017-01-18 | 长春海谱润斯科技有限公司 | Aromatic compound and organic light-emitting device using same |
| CN106336393B (en) * | 2016-08-03 | 2018-12-25 | 长春海谱润斯科技有限公司 | A kind of aromatic compound and the organic luminescent device using the compound |
| CN106946677A (en) * | 2017-04-20 | 2017-07-14 | 深圳市华星光电技术有限公司 | Fused ring compound and its application, electroluminescent device and preparation method thereof |
| WO2018192028A1 (en) * | 2017-04-20 | 2018-10-25 | 深圳市华星光电半导体显示技术有限公司 | Fused ring compound, electroluminescent device and preparation method therefor |
| CN106946677B (en) * | 2017-04-20 | 2019-07-12 | 深圳市华星光电半导体显示技术有限公司 | Fused ring compound and its application, electroluminescent device and preparation method thereof |
| US10424738B2 (en) | 2017-04-20 | 2019-09-24 | Shenzhen China Star Optoelectronics Semiconductor Display Technology Co., Ltd | Condensed-cyclic compound, electroluminescent device and method for manufacturing thereof |
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