CN110963876A - Preparation and purification method of 9, 10-substituted anthracene - Google Patents
Preparation and purification method of 9, 10-substituted anthracene Download PDFInfo
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- CN110963876A CN110963876A CN201911329198.7A CN201911329198A CN110963876A CN 110963876 A CN110963876 A CN 110963876A CN 201911329198 A CN201911329198 A CN 201911329198A CN 110963876 A CN110963876 A CN 110963876A
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000000746 purification Methods 0.000 title claims abstract description 11
- -1 10-substituted anthracene Chemical class 0.000 title claims description 51
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000004327 boric acid Substances 0.000 claims abstract description 26
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 12
- 238000005859 coupling reaction Methods 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 75
- 239000007787 solid Substances 0.000 claims description 42
- 238000010992 reflux Methods 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 27
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 26
- 238000001914 filtration Methods 0.000 claims description 25
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000012043 crude product Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 14
- 239000000741 silica gel Substances 0.000 claims description 14
- 229910002027 silica gel Inorganic materials 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- KPTRDYONBVUWPD-UHFFFAOYSA-N naphthalen-2-ylboronic acid Chemical compound C1=CC=CC2=CC(B(O)O)=CC=C21 KPTRDYONBVUWPD-UHFFFAOYSA-N 0.000 claims description 9
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 8
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- ZIRVQSRSPDUEOJ-UHFFFAOYSA-N 9-bromoanthracene Chemical compound C1=CC=C2C(Br)=C(C=CC=C3)C3=CC2=C1 ZIRVQSRSPDUEOJ-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- UCCUXODGPMAHRL-UHFFFAOYSA-N 1-bromo-4-iodobenzene Chemical compound BrC1=CC=C(I)C=C1 UCCUXODGPMAHRL-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 5
- 238000005893 bromination reaction Methods 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000010828 elution Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000003444 phase transfer catalyst Substances 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 2
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 8
- 238000004128 high performance liquid chromatography Methods 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 16
- 239000012535 impurity Substances 0.000 abstract description 10
- IFFZVKXEHGJBIA-UHFFFAOYSA-N 9-naphthalen-1-yl-10-(4-naphthalen-2-ylphenyl)anthracene Chemical compound C12=CC=CC=C2C(C2=CC=C(C=C2)C2=CC3=CC=CC=C3C=C2)=C(C=CC=C2)C2=C1C1=CC=CC2=CC=CC=C12 IFFZVKXEHGJBIA-UHFFFAOYSA-N 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000010168 coupling process Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 238000003756 stirring Methods 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 8
- 150000001454 anthracenes Chemical class 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 6
- 238000010907 mechanical stirring Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- SYACRXBYRNYMLN-UHFFFAOYSA-N 9-bromo-10-naphthalen-1-ylanthracene Chemical compound C12=CC=CC=C2C(Br)=C(C=CC=C2)C2=C1C1=CC=CC2=CC=CC=C12 SYACRXBYRNYMLN-UHFFFAOYSA-N 0.000 description 3
- YPNZWHZIYLWEDR-UHFFFAOYSA-N 9-naphthalen-1-ylanthracene Chemical compound C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=C(C=CC=C3)C3=CC2=C1 YPNZWHZIYLWEDR-UHFFFAOYSA-N 0.000 description 3
- SAODOTSIOILVSO-UHFFFAOYSA-N 2-(4-bromophenyl)naphthalene Chemical compound C1=CC(Br)=CC=C1C1=CC=C(C=CC=C2)C2=C1 SAODOTSIOILVSO-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000005577 anthracene group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007256 debromination reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- NJSUFZNXBBXAAC-UHFFFAOYSA-N ethanol;toluene Chemical compound CCO.CC1=CC=CC=C1 NJSUFZNXBBXAAC-UHFFFAOYSA-N 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
- C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/14—Purification; Separation; Use of additives by crystallisation; Purification or separation of the crystals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
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Abstract
The invention belongs to the technical field of organic synthesis and catalysis, and particularly relates to a preparation method and a purification method for synthesizing 9- (naphthalene-1-yl) -10- (4- (naphthalene-2-yl) phenyl) anthracene through 5-step reaction. The method provided by the invention has the advantages of less catalyst consumption, high synthesis yield, less reaction by-products (impurities) (the content of the removed boric acid product is less than 1 percent, no boric acid self-coupling product is generated), high product purity (the HPLC purity is more than or equal to 99.99 percent) and the like, and can be directly applied to OLED terminal materials of devices; in addition, the process flow is simple and easy to operate, and is more suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis and catalysis, and particularly relates to a preparation and purification method of 9, 10-substituted 9- (naphthalene-1-yl) -10- (4- (naphthalene-2-yl) phenyl) anthracene.
Background
Organic Light Emitting Diodes (OLEDs), which are the third generation flat panel displays following cathode ray tube flat panel displays and liquid crystal displays, have the advantages of active light emission, low driving voltage, high luminance, fast response speed, no X-ray pollution, etc., and are the mainstream display technology in the future of the display field. The light emitting properties of OLEDs are mainly dependent on OLED materials, and therefore, in the process of preparing OLED materials, high purity OLED materials and their intermediates are required. However, the blue fluorescent material has a low color purity, and it is difficult to obtain deep blue having a high color purity, and the shorter the wavelength, the shorter the lifetime. Therefore, there is a strong demand for development of a material having a long life and capable of deep blue light, and other organic materials having energy levels matched to the material.
For blue-light OLEDs, the host material is the key material for determining the service life thereof, and the high-performance blue-light host material is always the development focus of people. The anthracene is a blue fluorescent material, however, due to the planar structure of anthracene molecules, the anthracene molecules are easy to aggregate to generate crystals, if groups are introduced at 9, 10-positions of the anthracene molecules, the aggregation of the anthracene molecules is reduced, and meanwhile, the anthracene has better photoelectric property, so that the practical application value of the anthracene derivatives in the organic electroluminescent device is greatly improved. Research shows that some anthracene derivatives have good film forming property, stability and proper carrier transmission property, so that the anthracene derivatives are widely concerned by people.
9, 10-substituted anthracene compounds are important OLED terminal materials, and are widely used in OLED devices as blue light host materials, and are found in many patent applications (WO2019098766, WO2018017288 and the like), the synthesis process of the compounds is performed by adopting Suzuki coupling reaction, but the Suzuki coupling reaction can generate by-products (impurities) such as removal of boric acid, boric acid self-coupling, debromination, bromide coupling and the like, and the impurities generated by different catalytic systems have great differences. After the product is purified to reach higher chemical purity, the product is sublimated and then is used for preparing the device, otherwise, the color purity of the device is greatly influenced.
The OLED terminal material for the device has extremely high requirements on chemical purity (the content is not less than99.95% of single impurity<100ppm) and the synthetically prepared monomers were used for device preparation by sublimation. The synthesis of 9, 10-substituted anthracene compounds reported at present mainly uses Pd (PPh)3)4As catalysts (KR2018071850, WO2018017288, WO2018070840, WO2019098766), although the conversion rate is high, boric acid self-coupling and impurities such as boric acid removal are generated, which leads to the reduction of yield and quality of target products, and the synthesized products are not further refined and purified in the above patents, so that the catalysts cannot be directly applied to OLED terminal materials of devices.
Disclosure of Invention
In order to overcome the problems of large impurities and low product content in the existing method, the invention provides a method for synthesizing and purifying 9, 10-substituted anthracene compounds as blue light host materials, and the method has the advantages of high synthesis yield, suitability for industrial production in a process and the like.
In the preparation method of the 9, 10-substituted anthracene provided by the invention, the 9, 10-substituted anthracene compound is shown as a formula (1):
the synthetic route and the synthetic steps of the 9, 10-substituted anthracene compound are as follows:
s1: carrying out coupling reaction on 2-naphthalene boric acid and p-bromoiodobenzene as raw materials to prepare an intermediate 1;
s2: carrying out Suzuki coupling reaction on 9-bromoanthracene and 1-naphthalene boric acid serving as raw materials to prepare an intermediate 2;
s3: carrying out bromination reaction on the intermediate 2 prepared in S2 to prepare an intermediate 3;
s4: reacting the intermediate 3 prepared by the S3 with boric acid ester to obtain an intermediate 4;
s5: carrying out Suzuki coupling reaction on the intermediate 4 prepared by the step S4 and the intermediate 1 prepared by the step S1 to prepare a target product;
wherein, the catalysts adopted in the Suzuki coupling reaction of S2 and S5 are Pd-132 catalysts.
Preferably, the specific reaction process of step S1 is: under the protection of inert gas or nitrogen, taking 2-naphthalene boric acid and p-bromoiodobenzene as raw materials, and Pd (PPh)3)4Taking dioxane and water as a solvent as a catalyst, adding potassium carbonate, heating and refluxing, and carrying out post-treatment on a reflux liquid to obtain an intermediate 1;
wherein the 2-naphthalene boronic acid, the p-bromoiodobenzene, the potassium carbonate and the Pd (PPh)3)4The molar ratio of the 2-naphthalene boric acid to the dioxane and the water is 1g to 5ml to 2 ml.
Preferably, the specific reaction process of step S2 is: under the protection of inert gas or nitrogen, 1-naphthalene boric acid and 9-bromoanthracene are used as raw materials, Pd-132 is used as a catalyst, toluene, ethanol and water are used as solvents, tetrabutylammonium bromide is used as a phase transfer catalyst, potassium carbonate is added, heating reflux is carried out, and a reflux liquid is subjected to post-treatment to obtain an intermediate 2;
wherein the molar ratio of the 1-naphthalene boric acid, the 9-bromoanthracene, the potassium carbonate, the tetrabutylammonium bromide and the Pd-132 is 1:1.1:2:0.2:0.001, and the dosage ratio of the 1-naphthalene boric acid to the toluene, the ethanol and the water is 1g:7ml:4ml:3 ml.
Preferably, the specific reaction process of step S3 is: taking the intermediate 2 as a raw material and dichloroethane as a solvent, adding a bromination reagent in batches, carrying out bromination reaction at-20-80 ℃, washing reaction liquid, separating liquid, and carrying out aftertreatment on an obtained organic phase to obtain an intermediate 3;
wherein the molar ratio of the intermediate 2 to the brominating reagent is 1:1.1, and the dosage ratio of the intermediate 2 to the dichloroethane is 1g:6 ml.
Preferably, the specific reaction process of step S4 is: under the protection of inert gas or nitrogen, taking the intermediate 3 and borate as raw materials, taking tetrahydrofuran as a solvent, and adding n-butyllithium to react at the temperature of-75-85 ℃; adjusting the pH value of the reaction solution to 5-6, concentrating, and performing post-treatment on the concentrated solution to obtain an intermediate 4;
wherein the boric acid ester is one of trimethyl borate, triisopropyl borate and tributyl borate;
the molar ratio of the intermediate 3, the borate and the n-butyllithium is 1:2:2, and the dosage ratio of the intermediate 3 to the tetrahydrofuran is 1g:16 ml.
Preferably, the specific reaction process of step S5 is: under the protection of inert gas or nitrogen, taking the intermediate 1 and the intermediate 4 as raw materials, adding a catalyst Pd-132 catalyst, alkali and a solvent, heating and refluxing an obtained reaction system, and carrying out aftertreatment on a reflux liquid to obtain a 9, 10-substituted anthracene crude product;
wherein the alkali is one of potassium carbonate, potassium phosphate, cesium carbonate and potassium hydroxide;
the solvent is a mixed system of an organic solvent and water, and the organic solvent is one of ethanol, toluene, tetrahydrofuran and dioxane;
the molar ratio of the intermediate 1, the intermediate 4, the Pd-132 to the base is 1:1:0.001: 2; the dosage ratio of the intermediate 1 to the organic solvent and water is 1g to 30ml to 2 ml.
The preparation method of the 9, 10-substituted anthracene provided by the invention also comprises a purification process of the 9, 10-substituted anthracene crude product, and specifically comprises the following steps:
s1, adding toluene into the 9, 10-substituted anthracene crude product according to the proportion of 1g: 10-30 mL to dissolve the toluene, passing the dissolved solution through a heat-preservation silica gel chromatographic column at the temperature of 60-80 ℃, concentrating the obtained chromatographic solution to 1g: 4-10 mL, cooling the concentrated solution to 0-30 ℃, crystallizing for 2-16 h, and filtering to obtain a first recrystallized solid;
s2, adding DMF (dimethyl formamide) into the first recrystallized solid according to the proportion of 1g: 10-30 ml to dissolve the DMF, crystallizing the dissolved solution at the temperature of 0-30 ℃ for 1-16 h, and filtering to obtain a second recrystallized solid;
s3, mixing the secondary recrystallized solid with an organic solvent according to the proportion of 1g: 5-20 ml, heating, refluxing and eluting the mixed solution for 1-3 h, crystallizing for 1-16 h at the temperature of 0-30 ℃, and sequentially filtering and drying to obtain the high-purity 9, 10-substituted anthracene finished product;
wherein the organic solvent is one of methanol, ethanol, n-hexane or n-heptane.
Preferably, the mixing ratio of the crude anthracene to the toluene in S1 is 1g:20 ml; the heat-preservation silica gel chromatographic column is used for sampling according to the mass ratio of the anthracene crude product to the silica gel of 1: 0.2-1; the crystallization time is 4 h.
Preferably, the mixing ratio of the first recrystallized solid to the DMF in S2 is 1g:15 ml; the crystallization time is 2 h.
Preferably, the mixing ratio of the second recrystallized solid to the organic solvent in S3 is 1g:10 ml; the reflux elution time is 1 h; the crystallization time is 2 h.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the 9, 10-substituted anthracene, Pd-132 is used as a catalyst, so that the catalytic activity is high, the main reaction speed is high, the reaction time is short, and only 1-2 hours are needed; the reaction impurities are less (the removed boric acid impurity content is less than 1 percent, boric acid self-coupling impurities are not generated), and the conversion rate is up to more than 97 percent;
2. the preparation method of the 9, 10-substituted anthracene provided by the invention also comprises a purification process of the 9, 10-substituted anthracene crude product, wherein the crude product obtained by filtering after the reaction is finished is recrystallized by toluene, then is recrystallized by DMF, and finally is pulped by low-boiling-point organic solvents such as methanol, and the purity of the final product can reach more than 99.99 percent, and the maximum single impurity is less than 100 ppm.
Drawings
FIG. 1 is an HPLC chromatogram of 9- (1-naphthyl) -10- (4- (2-naphthyl) phenyl) anthracene obtained by the preparation and purification method provided by the invention.
Detailed Description
The present invention is further illustrated by the following examples, but it should be understood that the examples are presented only to facilitate the understanding of the core methods and applications of the present invention, and the scope of the present invention is not limited thereto.
Example 1
A preparation method of 9, 10-substituted anthracene specifically comprises the following steps:
Under the protection of argon, adding 2-naphthalene boric acid (30.0g), bromoiodobenzene (49.35g), Pd (PPh3) (4.60g), potassium carbonate (24.11g), dioxane (150mL) and water (60mL) into a 300mL three-neck flask connected with a mechanical stirring, condensing tube and thermometer, carrying out reflux reaction at 84-88 ℃ for 9h, cooling to room temperature, filtering, washing a filter cake to be neutral (pH is 7), adding 250mL of toluene into the filter cake, carrying out reflux water separation, passing through an insulating column, carrying out column liquid recrystallization and drying to obtain 45.0g of light yellow solid 2- (4-bromophenyl) naphthalene (namely intermediate 1), wherein the yield is 91.11%; LC-MS 283;
Under the protection of argon, sequentially adding 1-naphthalene boric acid (28.09g), 9-bromoanthracene (40.0g), Pd-132(0.11g), potassium carbonate (42.99g), tetrabutylammonium bromide (10.03g), toluene (197ml), ethanol (112ml) and water (85ml) into a 1L three-neck flask provided with a mechanical stirring, condensing tube and thermometer, carrying out reflux reaction at 70-75 ℃ for 2h, cooling to below 60 ℃, separating, washing an obtained organic phase with water to be neutral (pH is 7), passing through a column, recrystallizing the column-passing liquid with toluene ethanol, and drying at-0.08 MPa to-0.06 MPa and 55-60 ℃ for 3h to obtain a light yellow solid 9- (1-naphthyl-) anthracene (namely an intermediate 2)46.15g with the HPLC purity of 99.8361% and the yield of 97.46%; LC-MS 304;
Under the protection of argon, adding 9- (1-naphthyl-) anthracene (20.0g) and dichloroethane (120mL) into a 300mL three-neck flask with a mechanical stirrer and a thermometer in sequence under stirring, cooling to 0-10 ℃, and adding NBS (12.28g) in 10 batches, wherein the weight of the NBS is 1.228g each time, and the interval of the NBS is 10min each time; after the addition, the reaction is carried out for 2 hours under the condition of heat preservation, the reaction solution is washed for three times by water, the obtained organic phase is dried, concentrated and concentrated to 1g: stopping concentration when the volume is 1ml, naturally cooling to 68-75 ℃ under stirring, and mixing the components according to the weight ratio of 1g: adding ethanol into 4ml of the mixture, boiling and washing the mixture for 1 hour under reflux at the temperature of between 75 and 80 ℃, cooling and filtering the mixture, and recrystallizing the obtained solid twice by using DMF to obtain 21.4g of light yellow solid 9-bromo-10- (1-naphthyl) anthracene (namely an intermediate 3), wherein the GC purity is 99.9127 percent, and the yield is 84.97 percent; GC-MS 382;
Under the protection of argon, sequentially adding 9-bromo-10- (1-naphthyl) anthracene (10.0g), THF (160mL) and tributyl borate (12.01g) into a 500mL three-neck flask provided with a mechanical stirring pipe, a condenser pipe and a low-temperature thermometer, cooling to-75 to-85 ℃, dropwise adding 26.1mL of n-butyllithium solution (the concentration of the n-butyllithium solution is 2mol/L), and after dropwise adding, carrying out heat preservation reaction for 2 hours; naturally heating the reaction solution to 0-20 ℃, slowly adding the reaction solution into 50mL of dilute hydrochloric acid with the concentration of 3mol/L, stirring, concentrating THF under reduced pressure, adding 200mL of water, stirring and filtering, and washing a filter cake to be neutral (pH is 7) by water; eluting the filter cake with n-hexane once, and drying to obtain (10- (1-naphthyl) anthracene-9-) boric acid (intermediate 4) white solid 8.10g with HPLC purity of 99.4546% and yield of 89.09%; LC-MS-348;
Under the protection of argon, sequentially adding (10- (1-naphthyl) anthracene-9-) boric acid (10.0g), 2- (4-bromophenyl) naphthacene (18.31g), ethanol (300mL) and Pd-132(0.020g) into a 500mL three-neck flask provided with a mechanical stirring, a condenser and a thermometer, continuously heating to 70-76 ℃, and continuously dropwise adding K2CO3Aqueous solution (K)2CO3The aqueous solution is prepared from 37.94g K2CO3Mixing with 25ml of secondary ultrapure water) (continuously dropwise adding for 2h), performing reflux reaction at 70-76 ℃ for 2h after dropwise adding, cooling the reflux liquid to 5-20 ℃, filtering, washing a filter cake to be neutral (pH is 7), and drying at-0.08 MPa to-0.09 MPa and 70-80 ℃ until the weight is constant to obtain 13.83g of 9-10 substituted anthracene crude product, wherein the yield is 95.03% and the HPLC purity is 99.2028%.
Further purifying the obtained 9, 10-substituted anthracene crude product, wherein the specific operation steps are as follows:
A. adding 138ml of toluene into the 9, 10-substituted anthracene crude product, heating and refluxing for 20min, cooling to 60 ℃, passing through a heat-preservation silica gel column (3 g of silica gel, the column temperature is 60 ℃), concentrating the column passing liquid until the column passing liquid is 1g, namely 4ml of toluene, stopping concentrating, cooling to 0 ℃, stirring and crystallizing for 2h, filtering to obtain a first recrystallized solid, wherein the HPLC purity is 99.9782%;
B. adding 200ml of DMF into the first recrystallized solid, heating and refluxing to dissolve, cooling the dissolved solution to 0 ℃, stirring and crystallizing for 1 hour, and filtering to obtain a second recrystallized solid;
C. and adding 138ml of ethanol into the second recrystallized solid, heating, refluxing, eluting for 1h, cooling to 0 ℃, stirring, crystallizing for 1h, filtering, and drying the obtained solid under the conditions of-0.08 MPa to-0.09 MPa and 80-90 ℃ to obtain 12.94g of white solid of 9- (1-naphthyl) -10- (4- (2-naphthyl) phenyl) anthracene with the HPLC purity of 99.9901% (the HPLC spectrogram of 9- (1-naphthyl) -10- (4- (2-naphthyl) phenyl) anthracene is shown in figure 1), wherein the yield is 88.92%, and the LC-MS (liquid chromatography-mass spectrometry) is equal to 506.
Example 2
The difference from example 1 lies in step 5 and the purification method in the preparation process, specifically:
under the protection of argon, toA500 mL three-neck flask equipped with a mechanical stirring, a condenser tube and a thermometer is sequentially added with (10- (1-naphthyl) anthracene-9-) boric acid (10.0g), 2- (4-bromophenyl) naphthacene (18.31g), toluene (300mL) and Pd-132(0.020g), the temperature is continuously increased to 70-76 ℃, and K is continuously dripped3PO4Aqueous solution (K)3PO4The aqueous solution is prepared from 58.28g K3PO4Mixing with 25ml of second-level ultrapure water (continuously dropwise adding for 2h), after dropwise adding, carrying out reflux reaction at 70-76 ℃ for 2h, cooling the obtained reflux liquid to 5-20 ℃, filtering, washing a filter cake to be neutral (pH is 7), and drying at-0.08 MPa to-0.09 MPa and 70-80 ℃ to constant weight to obtain 12.95g of 9-10 substituted anthracene crude product, wherein the yield is 93.25%, and the HPLC purity is 99.1225%.
Further purifying the obtained 9, 10-substituted anthracene crude product, wherein the specific operation steps are as follows:
A. adding 400ml of toluene into the 9, 10-substituted anthracene crude product, heating and refluxing for 20min, cooling to 80 ℃, passing through a heat-preservation silica gel column (3 g of silica gel, the column temperature is 80 ℃), concentrating the column passing liquid until the column passing liquid is concentrated to 1g of toluene, stopping concentration when the column passing liquid is 5ml of toluene, cooling to 30 ℃, stirring and crystallizing for 16h, filtering to obtain a first recrystallized solid, wherein the HPLC purity is 99.8341%;
B. adding 585ml of DMF into the first recrystallized solid, heating, refluxing, dissolving, cooling to 30 ℃, stirring, crystallizing for 16h, and filtering to obtain a second recrystallized solid;
C. and adding 138ml of methanol into the second recrystallized solid, heating, refluxing, eluting for 3h, cooling to 30 ℃, stirring, crystallizing for 1h, filtering, and drying the obtained solid under the conditions of-0.08 MPa to-0.09 MPa and 80-90 ℃ to obtain 10.94g of white solid of 9- (1-naphthyl) -10- (4- (2-naphthyl) phenyl) anthracene, wherein the HPLC purity is 99.9786%, the yield is 75.19%, and the LC-MS is 506.
Example 3
The difference from the above examples is in step 5 and the purification method in the preparation process, specifically:
to a 500mL three-necked flask equipped with a mechanical stirrer, a condenser and a thermometer under argon protection were added (10- (1-naphthyl) anthracene-9-) boronic acid (10.0g), 2- (4-bromophenyl) naphthacene (18.31g), tetrahydrofuran (300mL), and P in this orderd-132(0.020g), continuously heating to 70-76 ℃, and continuously dropwise adding Cs2CO3Aqueous solution (Cs)2CO3The aqueous solution consisted of 89.37g Cs2CO3And 25ml of second-level ultrapure water) (continuously dropwise adding for 2h), performing reflux reaction at 70-76 ℃ for 2h after dropwise adding, cooling to 5-20 ℃, filtering, washing a filter cake to be neutral (pH is 7), and drying at-0.08 MPa to-0.09 MPa and 70-80 ℃ to constant weight to obtain 13.10g of 9-10 substituted anthracene crude product, wherein the yield is 93.85%, and the HPLC purity is 99.0268%.
Further purifying the obtained 9, 10-substituted anthracene crude product, wherein the specific operation steps are as follows:
A. adding 280ml of toluene into the 9, 10-substituted anthracene crude product, heating and refluxing for 20min, cooling to 70 ℃, passing through a heat-preservation silica gel column (3 g of silica gel, the column temperature is 70 ℃), concentrating the column passing liquid until the column passing liquid is concentrated to 1g of 6ml of toluene, stopping concentrating, cooling to 10 ℃, stirring and crystallizing for 2h, filtering to obtain a first recrystallized solid with the HPLC purity of 99.9782%;
B. adding 585ml of DMF into the first recrystallized solid, heating, refluxing, dissolving, cooling to 10 ℃, stirring, crystallizing for 1h, and filtering to obtain a second recrystallized solid;
C. and adding 138ml of n-hexane into the second recrystallized solid, heating, refluxing, eluting for 1h, cooling to 10 ℃, stirring, crystallizing for 16h, filtering, and drying the obtained solid under the conditions of-0.08 MPa to-0.09 MPa and 80-90 ℃ to obtain 11.86g of white solid of 9- (1-naphthyl) -10- (4- (2-naphthyl) phenyl) anthracene, wherein the HPLC purity is 99.9707%, the yield is 81.51%, and the LC-MS is 506.
Example 4
The difference from the above examples is in step 5 and the purification method in the preparation process, specifically:
under the protection of argon, adding (10- (1-naphthyl) anthracene-9-) boric acid (10.0g), 2- (4-bromophenyl) naphthalene anthracene (18.31g), dioxane (300mL) and Pd-132(0.020g) into a 500mL three-neck flask provided with a mechanical stirring pipe, a condenser pipe and a thermometer in sequence, continuously heating to 70-76 ℃, continuously dropwise adding a KOH aqueous solution (15.42 g of KOH and 25mL of second-level ultrapure water) (continuously dropwise adding for 2h), carrying out reflux reaction for 2h at 70-76 ℃, cooling to 5-20 ℃, filtering, washing a filter cake to be neutral (pH 7), and drying to constant weight under the conditions of-0.08 MPa to-0.09 MPa and 70-80 ℃ to obtain 13.30g of 9-10 substituted anthracene crude product, wherein the yield is 94.12%, and the HPLC purity is 98.4298%.
Further purifying the obtained 9, 10-substituted anthracene crude product, wherein the specific operation steps are as follows:
A. adding 410ml of toluene into the 9, 10-substituted anthracene crude product, heating and refluxing for 20min, cooling to 70 ℃, passing through a heat-preservation silica gel column (3 g of silica gel, the column temperature is 70 ℃), concentrating the column passing liquid until the column passing liquid is concentrated to 1g of 10ml of toluene, stopping concentrating, cooling to 20 ℃, stirring and crystallizing for 10h, filtering to obtain a first recrystallized solid with the HPLC purity of 99.9653%;
B. adding 280ml of DMF into the first recrystallized solid, heating, refluxing, dissolving, cooling to 20 ℃, stirring, crystallizing for 12 hours, and filtering to obtain a second recrystallized solid;
C. 138ml of n-heptane is added into the second recrystallized solid, the mixture is heated and refluxed to elute for 1h, the temperature is reduced to 20 ℃, the mixture is stirred to crystallize for 8h, the obtained solid is filtered, and the obtained solid is dried under the conditions of-0.08 MPa to-0.09 MPa and 80 ℃ to 90 ℃ to obtain 11.95g of white solid of 9- (1-naphthyl) -10- (4- (2-naphthyl) phenyl) anthracene, the HPLC purity is 99.9758%, the yield is 82.13%, and the LC-MS is 506.
While the present invention has been described with respect to preferred embodiments, additional variations and modifications will occur to those embodiments once the basic inventive concepts are known to those skilled in the art. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that such changes and modifications be included within the scope of the appended claims and their equivalents.
Claims (10)
1. A method for preparing 9, 10-substituted anthracene, characterized in that, the 9, 10-substituted anthracene compound is represented by formula (1):
the synthetic route and the synthetic steps of the 9, 10-substituted anthracene compound are as follows:
s1: carrying out coupling reaction on 2-naphthalene boric acid and p-bromoiodobenzene as raw materials to prepare an intermediate 1;
s2: carrying out Suzuki coupling reaction on 9-bromoanthracene and 1-naphthalene boric acid serving as raw materials to prepare an intermediate 2;
s3: carrying out bromination reaction on the intermediate 2 prepared in S2 to prepare an intermediate 3;
s4: reacting the intermediate 3 prepared by the S3 with boric acid ester to obtain an intermediate 4;
s5: carrying out Suzuki coupling reaction on the intermediate 4 prepared by the step S4 and the intermediate 1 prepared by the step S1 to prepare a target product;
wherein, the catalysts adopted in the Suzuki coupling reaction of S2 and S5 are Pd-132 catalysts.
2. The method for producing 9, 10-substituted anthracene according to claim 1, wherein the specific reaction process of step S1 is: under the protection of inert gas or nitrogen, taking 2-naphthalene boric acid and p-bromoiodobenzene as raw materials, and Pd (PPh)3)4Taking dioxane and water as a solvent as a catalyst, adding potassium carbonate, heating and refluxing, and carrying out post-treatment on a reflux liquid to obtain an intermediate 1;
wherein the 2-naphthalene boronic acid, the p-bromoiodobenzene, the potassium carbonate and the Pd (PPh)3)4The molar ratio of the 2-naphthalene boric acid to the dioxane and the water is 1g to 5ml to 2 ml.
3. The method for producing 9, 10-substituted anthracene according to claim 1, wherein the specific reaction process of step S2 is: under the protection of inert gas or nitrogen, 1-naphthalene boric acid and 9-bromoanthracene are used as raw materials, Pd-132 is used as a catalyst, toluene, ethanol and water are used as solvents, tetrabutylammonium bromide is used as a phase transfer catalyst, potassium carbonate is added, heating reflux is carried out, and a reflux liquid is subjected to post-treatment to obtain an intermediate 2;
wherein the molar ratio of the 1-naphthalene boric acid, the 9-bromoanthracene, the potassium carbonate, the tetrabutylammonium bromide and the Pd-132 is 1:1.1:2:0.2:0.001, and the dosage ratio of the 1-naphthalene boric acid to the toluene, the ethanol and the water is 1g:7ml:4ml:3 ml.
4. The method for producing 9, 10-substituted anthracene according to claim 1, wherein the specific reaction process of step S3 is: taking the intermediate 2 as a raw material and dichloroethane as a solvent, adding a bromization reagent in several times, carrying out bromination reaction at-20-80 ℃, washing reaction liquid, separating liquid, and carrying out aftertreatment on an obtained organic phase to obtain an intermediate 3;
wherein the molar ratio of the intermediate 2 to the brominating reagent is 1:1.1, and the dosage ratio of the intermediate 2 to the dichloroethane is 1g:6 ml.
5. The method for producing 9, 10-substituted anthracene according to claim 1, wherein the specific reaction process of step S4 is: under the protection of inert gas or nitrogen, taking the intermediate 3 and borate as raw materials, taking tetrahydrofuran as a solvent, and adding n-butyllithium to react at the temperature of-75-85 ℃; adjusting the pH value of the reaction solution to 5-6, concentrating, and performing post-treatment on the concentrated solution to obtain an intermediate 4;
wherein the boric acid ester is one of trimethyl borate, triisopropyl borate and tributyl borate;
the molar ratio of the intermediate 3, the borate and the n-butyllithium is 1:2:2, and the dosage ratio of the intermediate 3 to the tetrahydrofuran is 1g:16 ml.
6. The method for producing 9, 10-substituted anthracene according to claim 1, wherein the specific reaction process of step S5 is: under the protection of inert gas or nitrogen, taking the intermediate 1 and the intermediate 4 as raw materials, adding a catalyst Pd-132 catalyst, alkali and a solvent, heating and refluxing an obtained reaction system, and carrying out aftertreatment on a reflux liquid to obtain a 9, 10-substituted anthracene crude product;
wherein the alkali is one of potassium carbonate, potassium phosphate, cesium carbonate and potassium hydroxide;
the solvent is a mixed system of an organic solvent and water, and the organic solvent is one of ethanol, toluene, tetrahydrofuran and dioxane;
the molar ratio of the intermediate 1, the intermediate 4, the Pd-132 to the base is 1:1:0.001: 2; the dosage ratio of the intermediate 1 to the organic solvent and water is 1g to 30ml to 2 ml.
7. The method for preparing 9, 10-substituted anthracene according to claim 1, wherein the method further comprises a purification process of the crude 9, 10-substituted anthracene, and the method specifically comprises the following steps:
s1, adding toluene into the 9, 10-substituted anthracene crude product according to the proportion of 1g: 10-30 mL to dissolve the toluene, passing the dissolved solution through a heat-preservation silica gel chromatographic column at the temperature of 60-80 ℃, concentrating the obtained chromatographic solution to 1g: 4-10 mL, cooling the concentrated solution to 0-30 ℃, crystallizing for 2-16 h, and filtering to obtain a first recrystallized solid;
s2, adding DMF (dimethyl formamide) into the first recrystallized solid according to the proportion of 1g: 10-30 ml to dissolve, crystallizing the dissolved solution at the temperature of 0-30 ℃ for 1-16 h, and filtering to obtain a second recrystallized solid;
s3, mixing the secondary recrystallized solid with an organic solvent according to the proportion of 1g: 5-20 ml, heating, refluxing and eluting the mixed solution for 1-3 h, crystallizing for 1-16 h at the temperature of 0-30 ℃, and sequentially filtering and drying to obtain the high-purity 9, 10-substituted anthracene finished product;
wherein the organic solvent is one of methanol, ethanol, n-hexane or n-heptane.
8. The method for producing 9, 10-substituted anthracene according to claim 7, wherein a mixing ratio of the crude anthracene to the toluene in step S1 is 1g:20 ml; the heat-preservation silica gel chromatographic column is used for sampling according to the mass ratio of the anthracene crude product to the silica gel of 1: 0.2-1; the crystallization time is 4 h.
9. The method for producing 9, 10-substituted anthracene according to claim 7, wherein a mixing ratio of the first recrystallized solid to DMF in step S2 is 1g:15 ml; the crystallization time is 2 h.
10. The method for producing 9, 10-substituted anthracene according to claim 7, characterized in that a mixing ratio of the second recrystallized solid to the organic solvent in step S3 is 1g:10 ml; the reflux elution time is 1 h; the crystallization time is 2 h.
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