CN101475433B - Anthryl derivative and preparation thereof - Google Patents
Anthryl derivative and preparation thereof Download PDFInfo
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- CN101475433B CN101475433B CN2009100737341A CN200910073734A CN101475433B CN 101475433 B CN101475433 B CN 101475433B CN 2009100737341 A CN2009100737341 A CN 2009100737341A CN 200910073734 A CN200910073734 A CN 200910073734A CN 101475433 B CN101475433 B CN 101475433B
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- naphthalene
- alpha
- methyl
- anthryl
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- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006069 Suzuki reaction reaction Methods 0.000 claims abstract description 7
- 230000018044 dehydration Effects 0.000 claims abstract description 4
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 4
- 238000005893 bromination reaction Methods 0.000 claims abstract description 3
- 239000012467 final product Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 29
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 15
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 12
- -1 2-naphthalene boronic acids Chemical class 0.000 claims description 11
- 239000004327 boric acid Substances 0.000 claims description 10
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- VCJZTATVUDMNLU-UHFFFAOYSA-N dibromomethylbenzene Chemical group BrC(Br)C1=CC=CC=C1 VCJZTATVUDMNLU-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- JSRLURSZEMLAFO-UHFFFAOYSA-N 1,3-dibromobenzene Chemical compound BrC1=CC=CC(Br)=C1 JSRLURSZEMLAFO-UHFFFAOYSA-N 0.000 claims description 3
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 3
- 229910015900 BF3 Inorganic materials 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 claims description 3
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical group CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 claims description 3
- QCKHVNQHBOGZER-UHFFFAOYSA-N 1,2,4,5-tetrabromobenzene Chemical compound BrC1=CC(Br)=C(Br)C=C1Br QCKHVNQHBOGZER-UHFFFAOYSA-N 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methyl alcohol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 4
- ZLWIMPFRPFWOGK-UHFFFAOYSA-N 2-methylisoindole Chemical compound C1=CC=CC2=CN(C)C=C21 ZLWIMPFRPFWOGK-UHFFFAOYSA-N 0.000 claims 2
- 230000035484 reaction time Effects 0.000 claims 2
- 238000006482 condensation reaction Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 39
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 238000005401 electroluminescence Methods 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 125000005842 heteroatom Chemical group 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 125000005577 anthracene group Chemical group 0.000 abstract 1
- CPDRCKWKDRDHPW-UHFFFAOYSA-N boric acid;naphthalene Chemical compound OB(O)O.C1=CC=CC2=CC=CC=C21 CPDRCKWKDRDHPW-UHFFFAOYSA-N 0.000 abstract 1
- 238000004020 luminiscence type Methods 0.000 abstract 1
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract 1
- 238000007363 ring formation reaction Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 238000011160 research Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- RUIAUVYVCXIZFV-UHFFFAOYSA-N 1-methyl-2h-isoindole Chemical compound C1=CC=CC2=C(C)NC=C21 RUIAUVYVCXIZFV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000003245 working effect Effects 0.000 description 4
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 3
- 241001597008 Nomeidae Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001454 anthracenes Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LEMABCWCFKCYQC-UHFFFAOYSA-N OBO.C1=CC=CC2=CC=CC=C21 Chemical class OBO.C1=CC=CC2=CC=CC=C21 LEMABCWCFKCYQC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000003810 ethyl acetate extraction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WQONPSCCEXUXTQ-UHFFFAOYSA-N 1,2-dibromobenzene Chemical compound BrC1=CC=CC=C1Br WQONPSCCEXUXTQ-UHFFFAOYSA-N 0.000 description 1
- BRSRUYVJULRMRQ-UHFFFAOYSA-N 1-phenylanthracene Chemical class C1=CC=CC=C1C1=CC=CC2=CC3=CC=CC=C3C=C12 BRSRUYVJULRMRQ-UHFFFAOYSA-N 0.000 description 1
- PERDPGIWGFLYPX-UHFFFAOYSA-N 2,3,5,6-tetrabromo-5-methylcyclohexa-1,3-diene Chemical compound BrC1(C)C(C=C(C(=C1)Br)Br)Br PERDPGIWGFLYPX-UHFFFAOYSA-N 0.000 description 1
- RICKKZXCGCSLIU-UHFFFAOYSA-N 2-[2-[carboxymethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]ethyl-[[3-hydroxy-5-(hydroxymethyl)-2-methylpyridin-4-yl]methyl]amino]acetic acid Chemical compound CC1=NC=C(CO)C(CN(CCN(CC(O)=O)CC=2C(=C(C)N=CC=2CO)O)CC(O)=O)=C1O RICKKZXCGCSLIU-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Abstract
The invention belongs to the technical field of organic electroluminescence and relates to a blue organic electroluminescent material and a method for preparing the same, in particular to anthryl derivatives and a method for preparing the same. In the method for synthesizing the anthryl derivatives, o-dimethyl benzene and naphthalene boric acid are used as initial materials and are subjected to bromination reaction, Suzuki reaction, dehydration, cyclization and the like to further synthesize a final product. A prepared compound can be used as a blue luminescent material used in an electroluminescent device; as a molecular structure of the compound contains an anthracene ring with stable performance, the problem of the stability of the luminescent material is well solved; as the molecule contains no nitrogen atom, no sulphur atom and no other heteroatom, the service life of the luminescent material is prolonged; therefore, the problem that the blue luminescent material in tricolor luminescence has short service life is readily solved.
Description
Technical field
The invention belongs to technical field of organic electroluminescence, relate to a kind of blue organic electroluminescent material and preparation method thereof, particularly a kind of anthryl derivative and preparation method thereof.
Background technology
Along with the fast development of information technology, people have proposed more and more higher requirement to information display technology.Since the Tang C W of U.S. Kodak company in 1987 and Vanslyke S A had made the organic electroluminescence device of first excellent property, ORGANIC ELECTROLUMINESCENCE DISPLAYS was because its plurality of advantages that has has caused people's very big interest.
Organic electroluminescent (OEL) is meant organic materials under electric field action, is subjected to electric current and exciting of electric field and luminous phenomenon.Organic electroluminescent LED (OLED) is to utilize this phenomenon to realize the technique of display of new generation that shows.Compare with existing liquid crystal, plasma flat-plate technique of display, that the ORGANIC ELECTROLUMINESCENCE DISPLAYS technology has is simple in structure, active illuminating, high brightness, high-level efficiency, plurality of advantages such as the visual angle is big, response speed is fast, low dc voltage driving.Along with going deep into of research work, OLED has great market potential and competitive power as flat panel display of new generation.In the research of OLED, the material decisive role.The material of using among the OLED mainly contains hole-injecting material, hole mobile material, luminescent material, electron transport material and electronics injecting material etc.And luminescent material is a main raw wherein.
In OLED, realize panchromatic demonstration, the material of rubescent green-blue light is absolutely necessary, the green luminescent material of excellent property obtains now, the luminous efficiency and the brightness of ruddiness also are improved, and blue light material aspect colorimetric purity and the stability of photoluminescence all the time the end be resolved, so seek the important topic that high efficiency blue light-emitting material becomes the OLED field.Because the method for OLED colorize realization at present mainly is the three-color light-emitting method, if the inconsistent bulk life time that can influence display screen of three smooth life-spans of RGB.Lot of domestic and international research institution, enterprise are that the over-all properties that improves constantly luminescent material has been carried out number of research projects, have obtained abundant achievement in research, but present material property still can not satisfy the requirement of OLED to work-ing life and stability.
OLED is broadly divided into two classes according to the difference of its employed luminescent material.One class is to be the small molecules base OLED (small molecular organic light-emitting diode, be called for short SMOLED) of luminescent material with organic dye and pigment etc., delivers relevant achievement in research in 1987 the earliest by Kodak company; Another kind of is to be polymer-based OLED (the polymer organic light-emitting diode of luminescent material with the conjugated polymers, be called for short PLED), study successfully first polymer organic EL device in nineteen ninety by the Burroughes and the co-worker thereof of Cambridge University.
In various electroluminescent organic materials, anthracene single crystal was used as electroluminescent organic material first in 1963.It is reported that anthracene has higher fluorescence quantum efficiency, replace modification, can obtain multiple luminescent material at 9,10 or other carbon atom.The anthracenes luminescent material has become a class important in the electroluminescent organic material.
At present, mainly be by anthracene is replaced modification both at home and abroad, or the anthracene derivant unit introduced approach such as macromolecular material to improve luminescent properties to the research work of anthracenes luminescent material.
Patent CN200410071698 discloses a kind of anthracene compound that contains two silica-based phenyl that can be used as electroluminescent material, and shortcoming is that product yield is on the low side in the preparation process.
Patent US6465115 discloses a kind of anthracene compound that can be used as hole transmission layer and luminescent layer, and shortcoming is that luminous efficiency remains further to be improved.
Te Kaiping 8-12600 discloses and has utilized the element of phenylanthracene derivative as blue emitting material, Te Kaiping 11-3782 discloses 9,10 blue emitting materials with naphthyl at anthracene, but the weak point of above-mentioned luminescent material is can not meet the demands in work-ing life of luminous element.
Patent WO2004-18587 discloses a kind of the element of asymmetric anthracene derivant as blue emitting material, its luminous efficiency height and long service life, though asymmetric anthracene derivant is good blue emitting material but shortcoming is these, its part derivative has the low slightly shortcoming of glass transition temp (Tg).
Summary of the invention
Research situation at present blue organic electroluminescent material, problem solved by the invention is that blue electroluminescent material is when mixing the realization blue emission with fluorescence dye, because of the sterically hindered or unsaturated problem that causes less stable of ligancy, provide blue organic electroluminescent material that a kind of high purity, high yield, synthetic method are simple and stability is high and preparation method thereof.
The present invention has adopted following technical scheme in order to achieve the above object:
A kind of anthryl derivative is provided, it is characterized in that having following structure:
A kind of preparation method of above-mentioned anthryl derivative is provided, it is characterized in that the synthetic route of described anthryl derivative comprises A, B, three steps of C:
Wherein A step reaction is to be starting raw material with the o-Xylol, carries out five reactions, and synthetic 3-bromo-2-anthracene Virahol: (1) o-Xylol and bromine bromination take place under illumination generate adjacent dibromomethylbenzene; (2) reaction of adjacent dibromomethylbenzene and methyl hydrazine generates 1-methyl isoindole; (3) in 1-methyl isoindole, add 1,2,4,5-tetrabromo-benzene Synthetic 2,3-two bromo-11-methyl-5,10-dihydroanthracene-5,10-imines; (4) to 2,3-two bromo-11-methyl-5,10-dihydroanthracene-5 adds metachloroperbenzoic acid in the 10-imines, and reduction makes 2, the 3-dibromoanthracene; (5), add acetone in the 3-dibromoanthracene and generate target product 3-bromo-2-anthracene Virahol by the butyllithium catalyzed reaction to 2.Concrete reaction scheme is as follows:
B step reaction is to be starting raw material with the naphthalene boronic acids, and naphthalene boronic acids and dibromobenzene generate the naphthyl bromobenzene by suzuki reaction; The naphthyl bromobenzene generates the naphthyl phenylo boric acid with boric acid ester exchange hydrolysis after using the butyllithium lithiumation again, and concrete reaction scheme is as follows:
C step reaction is to be raw material with the different pure and mild naphthyl phenylo boric acid of 3-bromo-2-anthracene, generates naphthyl-anthracene Virahol through suzuki reaction earlier, and dehydration condensation generation final product takes place in the presence of boron trifluoride then.Concrete reaction scheme is as follows:
Major advantage of the present invention is:
1 compound stability height involved in the present invention, synthetic and purifying is easy,
2 compounds involved in the present invention have reached the luminous efficiency height as blue light material, the requirement that the life-span is long.
Owing to contain the anthracene nucleus of stable performance in the structure of The compounds of this invention, and do not contain just like heteroatomss such as nitrogen, sulphur, prolonged the work-ing life of luminescent material, according to test, blue light efficient may reach more than the 30cd/a, can be at 1000cd/m
2Down work of original intensity, the life-span reached more than 100,000 hours, thereby had improved the colorimetric purity of entire display screen, and obtained work-ing life prolonging.
Embodiment
In order to understand content of the present invention better, further specify technical scheme of the present invention below by specific embodiment, but this embodiment does not limit the present invention.
Preparing 13,13-dimethyl-3-(2-naphthalene)-13 indenos (1,2-b) anthracene is an example:
A goes on foot reaction:
1. in o-Xylol, add catalyzer, be cooled to below 5 ℃, drip bromine, dropwise, illumination reaction 20 hours is used 5% sodium hydroxide solution and distilled water wash then successively, and washing finishes, distillation gets the adjacent dibromomethylbenzene of product, and the yield of this reaction is about 85%.
2. add methylene dichloride and concentrated hydrochloric acid in adjacent dibromomethylbenzene, add methyl hydrazine while stirring, be warming up to 50 ℃ rapidly after reactant dissolves fully, reacted 4 hours, drip Sodium Nitrite then, distillation gets exsiccant 1-methyl isoindole.
3. in 1-methyl isoindole, add 1,2,4,5-tetrabromo toluene, cool the temperature to then below-60 ℃, drip butyllithium-diethyl ether solution (butyllithium-ether volume ratio is 1: 3), dropwise, slowly heat up, stirring reaction 20 hours, reaction finishes, and adds the dilute hydrochloric acid hydrolysis, filter product.
4. under nitrogen protection, add ether 15ml in 3 imines that generate, drip metachloroperbenzoic acid 3.5g then while stirring, stirring reaction 4 hours adds hydrochloric acid hydrolysis, standing demix, and extracted organic phase, filtration drying gets 2, the 3-dibromoanthracene.
5. with 2, the 3-dibromoanthracene fully is dissolved in the ether, drips n-Butyl Lithium-diethyl ether solution (volume ratio 1: 5) under nitrogen protection in solution; rate of addition is controlled at 5 droplets/second, keeps system temperature below-60 ℃, dropwises; reacted 3 hours, and then system temperature was dropped to below-71 ℃, drip acetone; dropwise, add Glacial acetic acid 10g, regulate pH value to 5.7; termination reaction is risen again naturally, filters; washing, evaporative crystallization gets 3-bromo-2-anthracene Virahol, and its physical parameter is:
Fusing point: 212-215 ℃; Mass spectrum: M/e=303; Uv-absorbing: λ max=450nm.
B goes on foot reaction:
Under nitrogen protection; in four-hole boiling flask, add 2-naphthalene boronic acids 15g; add the 50ml ether dissolution, slowly add m-dibromobenzene then while stirring, be warming up to 80 ℃ after adding and begin to reflux; with TLC monitoring reaction process; system is reduced to room temperature behind the no raw material, uses ethyl acetate extraction, drying; filter, evaporate product 3-(2-naphthalene) bromobenzene.
Under nitrogen protection, in four-hole boiling flask, add the 30ml ether, be cooled to-60 ℃; add the 6ml n-Butyl Lithium, drip 3-(2-naphthalene) bromobenzene-diethyl ether solution then, dropwise; controlled temperature is below-60 ℃, reacts to be cooled to-75 ℃ after one hour, begins to drip boric acid ester; temperature is controlled between (60 ℃--70 ℃), after reacting completely, adds the dilute hydrochloric acid termination reaction; filter, with tetrahydrofuran (THF) washing, drying; get white solid 3-(2-naphthalene) phenylo boric acid, its physical parameter is:
Fusing point: 〉=300 ℃; Mass spectrum: M/e=248; Outward appearance: white or off-white powder; Uv-absorbing: λ max=254nm.
C goes on foot reaction:
In four-hole boiling flask, add 3-bromo-2-anthracene Virahol 30g, 3-(2-naphthalene) phenylo boric acid 40g, catalyzer 3g, anhydrous sodium carbonate 72g, distilled water 320ml, add the back warming while stirring, begin in the time of 100 ℃ to reflux, afterreaction was finished in six hours, stop heating, system is reduced to room temperature, use ethyl acetate extraction, drying, decolouring, filter, remove solvent, get 3-[benzene (2-naphthyl) with Rotary Evaporators]-2-anthracene Virahol crude product, crude product is dissolved in the dehydrated alcohol, cool to 0 ℃, filter, use washing with alcohol again.The finished product 3-[benzene (2-naphthyl)]-yield of 2-anthracene Virahol is about 64.7%, purity reaches more than 99.0%.
Under nitrogen protection, add 3-[benzene (2-naphthyl)]-2-anthracene Virahol 15g, boron trifluoride 2.3g slowly is heated to 60 ℃, drips vitriol oil 5g then, finishes, and is warming up to 135-140 ℃, is incubated 30 minutes.Be cooled to then below 60 ℃, dropping sodium solution to system pH is 9, cooling, filter, filtrate rectifying gets the finished product 13.13-dimethyl-3-(2-naphthalene)-13-indeno (1.2-b) anthracene, product purity can reach more than 99.2%, and yield is about 68.2%, and its physical parameter is:
Fusing point: 〉=300 ℃; Mass spectrum: M/e=420; Uv-absorbing: λ max=270nm.
Claims (4)
1. anthryl derivative is characterized in that having following structure:
2. method for preparing the described anthryl derivative of claim 1 is characterized in that its synthetic route comprises A, B, three steps of C:
Wherein A step reaction is to be starting raw material with the o-Xylol, carries out five reactions, synthetic α, and alpha-alpha-dimethyl-(3-bromine anthryl-2-yl)-methyl alcohol: bromination takes place and generates adjacent dibromomethylbenzene in (1) o-Xylol and bromine under illumination; (2) reaction of adjacent dibromomethylbenzene and methyl hydrazine generates N-methyl-isoindole; (3) in N-methyl-isoindole, add 1,2,4,5-tetrabromo-benzene Synthetic 2,3-two bromo-11-methyl-9,10-dihydroanthracene-9,10-imines; (4) to 2,3-two bromo-11-methyl-9,10-dihydroanthracene-9 adds metachloroperbenzoic acid in the 10-imines, and oxidation makes 2, the 3-dibromoanthracene; (5), add acetone in the 3-dibromoanthracene and generate target product α, alpha-alpha-dimethyl-(3-bromine anthryl-2-yl)-methyl alcohol by the butyllithium catalyzed reaction to 2;
B step reaction is to be starting raw material with the 2-naphthalene boronic acids, and 2-naphthalene boronic acids and m-dibromobenzene generate 3-(2-naphthalene) bromobenzene by suzuki reaction; 3-(2-naphthalene) bromobenzene generates 3-(2-naphthalene) phenylo boric acid with boric acid ester exchange hydrolysis after using the butyllithium lithiumation again;
C step reaction is with α, alpha-alpha-dimethyl-(3-bromine anthryl-2-yl)-methyl alcohol and 3-(2-naphthalene) phenylo boric acid generate α through suzuki reaction, alpha-alpha-dimethyl-[3-[3-(2-naphthyl) phenyl] anthracene-2-yl]-methyl alcohol, dehydration condensation takes place in the presence of boron trifluoride generate final product.
3. preparation method as claimed in claim 2, it is characterized in that the 2-naphthalene boronic acids is 70-100 ℃ with the temperature of reaction that m-dibromobenzene carries out suzuki reaction in the B step reaction, the temperature that 3-(2-naphthalene) bromobenzene exchanges hydrolysis with boric acid ester after with the butyllithium lithiumation again is-60 ℃--70 ℃.
4. preparation method as claimed in claim 2 is characterized in that the temperature of reaction of suzuki reaction in the C step reaction is 80-120 ℃, and the reaction times is 5-8 hour, and the temperature of reaction of dehydration condensation reaction is 120-150 ℃, and the reaction times is 1-2 hour.
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| CN106279055B (en) * | 2015-05-12 | 2019-03-12 | 上海和辉光电有限公司 | A kind of miscellaneous generation anthracene compound of indeno and its application |
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| CN106543432B (en) * | 2016-10-25 | 2018-08-24 | 三明学院 | A kind of water-soluble polymer and its preparation method and application |
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| US5635308A (en) * | 1994-04-26 | 1997-06-03 | Tdk Corporation | Phenylanthracene derivative and organic EL element |
| CN101125794A (en) * | 2007-09-14 | 2008-02-20 | 中国科学院上海有机化学研究所 | Polycyclic arene compound, synthetic method and use thereof |
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| US5635308A (en) * | 1994-04-26 | 1997-06-03 | Tdk Corporation | Phenylanthracene derivative and organic EL element |
| CN101125794A (en) * | 2007-09-14 | 2008-02-20 | 中国科学院上海有机化学研究所 | Polycyclic arene compound, synthetic method and use thereof |
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