CN116730799A - OLED compound containing spirofluorene structure and preparation method thereof - Google Patents
OLED compound containing spirofluorene structure and preparation method thereof Download PDFInfo
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- CN116730799A CN116730799A CN202310611709.4A CN202310611709A CN116730799A CN 116730799 A CN116730799 A CN 116730799A CN 202310611709 A CN202310611709 A CN 202310611709A CN 116730799 A CN116730799 A CN 116730799A
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- spirofluorene
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- tertiary alcohol
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title abstract description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 57
- 150000003509 tertiary alcohols Chemical class 0.000 claims abstract description 51
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 claims abstract description 27
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005859 coupling reaction Methods 0.000 claims abstract description 16
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 14
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 38
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- IUYHWZFSGMZEOG-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].C[CH-]C IUYHWZFSGMZEOG-UHFFFAOYSA-M 0.000 claims description 26
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 21
- 239000012074 organic phase Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 18
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 15
- 239000002274 desiccant Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 238000004811 liquid chromatography Methods 0.000 claims description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 claims description 6
- 230000020477 pH reduction Effects 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000007363 ring formation reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 description 14
- 239000002253 acid Substances 0.000 description 7
- -1 adding THF100ml Chemical compound 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006798 ring closing metathesis reaction Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ICPSWZFVWAPUKF-UHFFFAOYSA-N 1,1'-spirobi[fluorene] Chemical compound C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 ICPSWZFVWAPUKF-UHFFFAOYSA-N 0.000 description 1
- QFUPJXCUNNWZJQ-UHFFFAOYSA-N 2-bromofluoren-1-one Chemical compound C1=CC=C2C3=CC=C(Br)C(=O)C3=CC2=C1 QFUPJXCUNNWZJQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
- C07C25/18—Polycyclic aromatic halogenated hydrocarbons
- C07C25/22—Polycyclic aromatic halogenated hydrocarbons with condensed rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
- C07C1/30—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms by splitting-off the elements of hydrogen halide from a single molecule
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
- C07C13/72—Spiro hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- 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
- C07C17/2637—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions between a compound containing only oxygen and possibly halogen as hetero-atoms and a halogenated hydrocarbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/14—Carrier transporting layers
- H10K50/15—Hole transporting layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/93—Spiro compounds
- C07C2603/94—Spiro compounds containing "free" spiro atoms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The application discloses an OLED compound containing a spirofluorene structure and a preparation method thereof, wherein during the preparation, o-bromoiodobenzene is firstly prepared into Grignard reagent to attack fluorenone and derivatives thereof, tertiary alcohol is prepared, then the tertiary alcohol and benzene are subjected to coupling reaction at low temperature to obtain an intermediate D, and the intermediate D is subjected to weak base ring-closure reaction to obtain the OLED compound containing the spirofluorene structure.
Description
Technical Field
The application belongs to the technical field of organic chemical synthesis, relates to a synthesis method of a material containing a spirofluorene structure, and in particular relates to an OLED compound containing a spirofluorene structure and a preparation method thereof.
Background
At present, spirofluorene is widely applied to electroluminescent materials, and has the following advantages:
1. the orthogonal three-dimensional structure of the spirofluorene can avoid the close packing of chromophores in molecules, thereby reducing the formation of aggregates or excimer and reducing the quenching of the luminescence of the material;
2. the molecules realize the control of effective conjugation length on the basis of keeping the electronic and optical properties of two orthogonal molecular chains at the SP3 hybridized C atom;
3. the thermal property of the material is improved, the Tg of the material is effectively improved, the tendency of molecular crystallization is reduced, and a stable amorphous material is obtained;
4. the 2,2', 7' position has good reactivity, which facilitates the extension of the structure to the three-dimensional space and is beneficial to improving the solubility of the electroluminescent material.
Therefore, the synthesis of materials containing a spirofluorene structure is of great significance, and the current synthesis methods of materials containing a spirofluorene structure comprise the following two methods.
Reported in patent 1, CN 111592464A
The general formula is reported in the synthesis of benzonaphthalene cyclospirofluorene, wherein raw material A is added with bromofluorenone under the action of n-butyllithium reagent to obtain intermediate alcohol B, and dihalogenated benzospirobifluorene C is generated by dehydration under acidic condition.
The disadvantages are as follows:
1. the first step uses ultralow temperature reaction, fluorenone is poorly dissolved at low temperature, so the consumed solvent and energy consumption are high, the requirements on equipment are severe, the reaction conditions are severe, and the amplification preparation is limited.
2. The second step of acid ring closure is affected by steric hindrance, and a great deal of waste acid is generated by the requirement of strong acid, concentrated sulfuric acid, polyphosphoric acid and the like at the height Wen Gehuan, so that the post-treatment and equipment selection are difficult, and the high-temperature strong acid ring closure is not friendly to equipment and environment, has large pollution and is unfavorable for the amplified production.
Reported in patent 2, CN 108779103B
The general formula is reported in the synthesis of spirobifluorene, and the preparation method and the defects are similar to those of patent 1CN 111592464A.
The disadvantages of the prior art are: the reaction steric hindrance is relatively large, the acid ring closure is affected by the steric hindrance, a great amount of waste acid is generated by strong acid, concentrated sulfuric acid, polyphosphoric acid and the like which are needed to be high Wen Gehuan, and the post-treatment is difficult, so that development of a novel preparation method of a material containing a spirofluorene structure is urgently needed.
Disclosure of Invention
The application aims to overcome the defects of the prior art and provides an OLED compound containing a spirofluorene structure and a preparation method thereof.
In order to solve the technical problems, the technical scheme of the application is as follows: a method for preparing an OLED compound containing a spirofluorene structure, comprising the steps of:
step 1: exchange O-bromoiodobenzene and Grignard reagent of isopropyl magnesium chloride, attack fluorenone and its derivative to prepare intermediate tertiary alcohol C with the molar ratio of O-bromoiodobenzene to isopropyl magnesium chloride of 1:1-1.3,the mol ratio of the o-bromoiodobenzene to fluorenone and the derivatives thereof is 1-1.3:1; the structural formula of the fluorenone and the derivative thereof isIntermediate tertiary alcohol C has the structural formula +.>R1 and R2 are each one of H, F, C1 or Br;
step 2: the intermediate tertiary alcohol C and benzene are subjected to coupling reaction under the catalysis of aluminum trichloride to prepare an intermediate D, wherein the dosage ratio of the intermediate tertiary alcohol C to the benzene is 0.01 mol:41-43 ml, and the molar ratio of the intermediate tertiary alcohol C to the aluminum trichloride is 1:1.4-1.6; the structural formula of the intermediate D isR1 and R2 are each one of H, F, cl or Br;
step 3: the intermediate D is subjected to coupling reaction under the catalysis of a palladium acetate catalyst to prepare the target OLED compound containing the spirofluorene structure, the molar ratio of the intermediate D to the palladium acetate catalyst is 1:0.02-0.05, and the structural formula of the OLED compound containing the spirofluorene structure isR1 and R2 are each one of H, F, cl or Br.
Preferably, the step 1 specifically includes: under the protection of nitrogen, adding THF and o-bromoiodobenzene into a reaction bottle, controlling the temperature to be 10-15 ℃, adding a Grignard reagent of isopropyl magnesium chloride, stirring for 30min, adding a THF solution of fluorenone and a derivative thereof, heating to 50 ℃ for reaction, and stopping the reaction after detecting the complete reaction of fluorenone and a derivative thereof by liquid chromatography to obtain an intermediate tertiary alcohol C solution, wherein the dosage ratio of o-bromoiodobenzene to THF is 0.01mol: 18-19 ml, the dosage ratio of fluorenone and its derivative to THF is 0.01 mol:7.5-12.5 ml.
Preferably, the post-treatment of the intermediate tertiary alcohol C solution is: adding water and ethyl acetate into the intermediate tertiary alcohol C solution for extraction, washing with water, drying the organic phase with anhydrous magnesium sulfate, filtering to remove the drying agent, concentrating, and recrystallizing with n-hexane to obtain the intermediate tertiary alcohol C.
Preferably, the step 2 specifically includes: adding intermediate tertiary alcohol C and benzene into a reaction bottle, adding aluminum trichloride in batches at the temperature of 0 ℃, continuously stirring for 5 hours, and stopping the reaction after detecting that the intermediate tertiary alcohol C is completely reacted by liquid chromatography to obtain an intermediate D solution, wherein the dosage ratio of the intermediate tertiary alcohol C to the benzene is 0.01 mol:41-43 ml, and the molar ratio of the intermediate tertiary alcohol C to the aluminum trichloride is 1:1.4-1.5.
Preferably, the post-treatment of the intermediate D solution is: adding dilute hydrochloric acid into the solution of the intermediate D for acidification, separating the solution, washing the organic phase with sodium chloride aqueous solution, filtering out the drying agent, concentrating, and passing through a silica gel column by using ethyl acetate/petroleum ether to obtain the intermediate D.
Preferably, the step 3 specifically includes: adding an intermediate D, palladium acetate, diazabicyclo and N-methylpyrrolidone into a reaction bottle, heating to 150 ℃ for reaction for 12 hours, and stopping the reaction after detecting that the intermediate D is completely reacted by liquid chromatography to obtain a solution of the OLED compound containing a spirofluorene structure, wherein the mol ratio of the intermediate D to the diazabicyclo is 1:3, and the dosage ratio of the intermediate D to the N-methylpyrrolidone is 0.01 mol:45 ml.
Preferably, the molar ratio of the intermediate D to the palladium acetate catalyst is 1:0.025.
Preferably, the post-treatment of the solution of the OLED compound containing a spirofluorene structure is: concentrating the solution containing the OLED compound with the spirofluorene structure under reduced pressure to remove the solvent, adding toluene water, stirring and washing, separating the liquid, drying the organic phase, concentrating, and recrystallizing the n-hexane to obtain the OLED compound containing the spirofluorene structure.
Preferably, the structural formula of the OLED compound containing the spirofluorene structure is as followsR1 and R2 are each one of H, F, cl or Br.
Preferably, the specific structure of the OLED compound containing a spirofluorene structure is:
compared with the prior art, the application has the advantages that:
(1) The application provides a preparation method of an OLED compound containing a spirofluorene structure, which comprises the steps of firstly preparing o-bromoiodobenzene into Grignard reagent to attack fluorenone and derivatives thereof, preparing tertiary alcohol, then carrying out coupling reaction on the tertiary alcohol and benzene at low temperature to obtain an intermediate D, and carrying out weak base ring closure reaction on the intermediate D to obtain the OLED compound containing the spirofluorene structure;
(2) The preparation method comprises the steps of firstly preparing a Grignard reagent by a format exchange method, preparing o-bromoiodobenzene into Grignard reagent, attacking fluorenone and derivatives thereof, and preparing tertiary alcohol, wherein the reaction temperature is about 50 ℃, and the reaction condition is mild; after the reaction is completed, adding water and EA for extraction, washing, drying an organic phase by anhydrous magnesium sulfate, filtering out a drying agent, concentrating, recrystallizing n-hexane to obtain tertiary alcohol, and carrying out aftertreatment easily and conveniently;
(3) The second step of the application adopts low-temperature coupling reaction, the third step adopts weak base ring closure, which is friendly to equipment and environment, has little pollution, reduces cost and is beneficial to amplified production;
(4) The synthetic route of the application can not generate isomer, has good structural selectivity, single product structure, no position isomerism, no coupling product and no polyhalogenate, has wide applicability, and is applicable to introducing other derivative structures such as halogen, aromatic ring, alkyl and the like into spirofluorene;
(5) The application discloses a synthetic method of a new material, which can improve the efficiency of a device, reduce the driving voltage and/or improve the service life characteristic when an OLED compound containing a spirofluorene structure is used for hole injection and/or hole transport materials, and the device has low driving voltage and long service life and shows high-stability device performance.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the product of example 1 of the present application;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of the product of example 2 of the present application;
FIG. 3 shows a nuclear magnetic resonance hydrogen spectrum of the product of example 3 of the present application.
Detailed Description
The application will now be described with reference to the following examples, which are given by way of illustration of the application, but are not intended to limit the scope of the application, using conventional commercial products as raw materials, solvents and catalysts.
The application discloses a preparation method of an OLED compound containing a spirofluorene structure, which comprises the following steps:
step 1: exchanging the Grignard reagent of the o-bromoiodobenzene and the isopropyl magnesium chloride, then attacking fluorenone and the derivative thereof to prepare intermediate tertiary alcohol C, wherein the mol ratio of the o-bromoiodobenzene to the isopropyl magnesium chloride is 1:1-1.3, and the mol ratio of the o-bromoiodobenzene to the fluorenone and the derivative thereof is 1-1.3:1; the structural formula of the fluorenone and the derivative thereof isIntermediate tertiary alcohol C has the structural formula +.>R1 and R2 are each one of H, F, cl or Br;
step 2: the intermediate tertiary alcohol C and benzene are subjected to coupling reaction under the catalysis of aluminum trichloride to prepare an intermediate D, wherein the dosage ratio of the intermediate tertiary alcohol C to the benzene is 0.01 mol:41-43 ml, and the molar ratio of the intermediate tertiary alcohol C to the aluminum trichloride is 1:1.4-1.6; the structural formula of the intermediate D isR1 and R2 are each one of H, F, cl or Br;
step 3: the intermediate D is subjected to coupling reaction under the catalysis of a palladium acetate catalyst to prepare the target OLED compound containing the spirofluorene structure, the mol ratio of the intermediate D to the palladium acetate catalyst is 1:0.02-0.05, and the OL containing the spirofluorene structure is preparedED compounds have the structural formulaR1 and R2 are each one of H, F, cl or Br.
Preferably, the step 1 specifically includes: under the protection of nitrogen, adding THF and o-bromoiodobenzene into a reaction bottle, controlling the temperature to be 10-15 ℃, adding a Grignard reagent of isopropyl magnesium chloride, stirring for 30min, adding a THF solution of fluorenone and a derivative thereof, heating to 50 ℃ for reaction, and stopping the reaction after detecting the complete reaction of fluorenone and a derivative thereof by liquid chromatography to obtain an intermediate tertiary alcohol C solution, wherein the dosage ratio of o-bromoiodobenzene to THF is 0.01mol: 18-19 ml, the dosage ratio of fluorenone and its derivative to THF is 0.01 mol:7.5-12.5 ml.
Preferably, the post-treatment of the intermediate tertiary alcohol C solution is: adding water and ethyl acetate into the intermediate tertiary alcohol C solution for extraction, washing with water, drying the organic phase with anhydrous magnesium sulfate, filtering to remove the drying agent, concentrating, and recrystallizing with n-hexane to obtain the intermediate tertiary alcohol C.
Preferably, the step 2 specifically includes: adding intermediate tertiary alcohol C and benzene into a reaction bottle, adding aluminum trichloride in batches at the temperature of 0 ℃, continuously stirring for 5 hours, and stopping the reaction after detecting that the intermediate tertiary alcohol C is completely reacted by liquid chromatography to obtain an intermediate D solution, wherein the dosage ratio of the intermediate tertiary alcohol C to the benzene is 0.01 mol:41-43 ml, and the molar ratio of the intermediate tertiary alcohol C to the aluminum trichloride is 1:1.4-1.5.
Preferably, the post-treatment of the intermediate D solution is: adding dilute hydrochloric acid into the solution of the intermediate D for acidification, separating the solution, washing the organic phase with sodium chloride aqueous solution, filtering out the drying agent, concentrating, and passing through a silica gel column by using ethyl acetate/petroleum ether to obtain the intermediate D.
Preferably, the step 3 specifically includes: adding an intermediate D, palladium acetate, diazabicyclo and N-methylpyrrolidone into a reaction bottle, heating to 150 ℃ for reaction for 12 hours, and stopping the reaction after detecting that the intermediate D is completely reacted by liquid chromatography to obtain a solution of the OLED compound containing a spirofluorene structure, wherein the mol ratio of the intermediate D to the diazabicyclo is 1:3, and the dosage ratio of the intermediate D to the N-methylpyrrolidone is 0.01 mol:45 ml.
Preferably, the molar ratio of the intermediate D to the palladium acetate catalyst is 1:0.025.
Preferably, the post-treatment of the solution of the OLED compound containing a spirofluorene structure is: concentrating the solution containing the OLED compound with the spirofluorene structure under reduced pressure to remove the solvent, adding toluene water, stirring and washing, separating the liquid, drying the organic phase, concentrating, and recrystallizing the n-hexane to obtain the OLED compound containing the spirofluorene structure.
Preferably, the structural formula of the OLED compound containing the spirofluorene structure is as followsR1 and R2 are each one of H, F, cl or Br.
Preferably, the specific structure of the OLED compound containing a spirofluorene structure is:
example 1
The embodiment provides a preparation method of an OLED compound containing a spirofluorene structure, which comprises the following steps:
the first step:
under the protection of nitrogen, adding THF100ml, o-bromoiodobenzene 15g (1-A) (0.053 Mol), controlling the temperature to be 10-15 ℃, adding isopropyl magnesium chloride 58ml (1 Mol/L,0.058 Mol), stirring for 30min, adding a THF solution (fluorenone 8.6g 0.048mol,THF50ml) of fluorenone (1-B), heating to 50 ℃ for reaction, detecting complete fluorenone reaction by TLC, stopping the reaction, adding water and EA for extraction, washing, drying an organic phase by anhydrous magnesium sulfate, filtering a drying agent, concentrating, recrystallizing n-hexane to obtain 13.7g 1-C, and obtaining the yield of 85%.
And a second step of:
to a reaction flask was added 1-C13.7 g (0.041 mol), benzene 137ml, aluminum trichloride 8.2 (0.061 mol) was added in portions at 0deg.C, stirring was continued for 5h, TLC was used to check that the 1-C reaction was completely stopped, diluted hydrochloric acid was added to acidify, the organic phase was separated, washed with aqueous sodium chloride, the drying agent was filtered off, concentrated, and silica gel column was run with ethyl acetate/petroleum ether to give 14.5g 1-D (yield 88.1%).
And a third step of:
to the reaction flask was added 1-D14.5 g (0.036 mol), palladium acetate 0.2g (0.0009 mol), DBU 16.4g (0.108 mol), NMP 150ml, heated to 150℃for 12h, and TLC monitored to stop the reaction completely; the solvent was removed by concentrating under reduced pressure, washing with toluene water under stirring, separating the liquid, drying the organic phase, concentrating, and recrystallizing with n-hexane to give 1-E10.1 g (0.032 mol) with a yield of 88.9%.
DBU (diazabicyclo) is a colorless or pale yellow liquid, is a sterically hindered amidine, and is alkaline. Used as catalysts, ligands and non-nucleophilic bases in organic synthesis. The catalytic activity of DBU increases significantly with increasing temperature. The DBU is mainly used as an excellent organic alkali deacidification agent for drug synthesis. DBU is used as a catalyst in the polyurethane industry and is a very active low odor gel catalyst, and DBU is mainly used in applications requiring strong gel catalysis, including formulations containing cycloaliphatic or aliphatic isocyanates, which require a very strong catalyst because they are less active than aromatic isocyanates. DBU hardly reacts with epoxy resin in the range of room temperature to 40 ℃, and the epoxy resin can be gelled in 15min when the temperature is increased to 100 ℃.
DBU is used in the present application to provide an alkaline environment for the reaction.
NMP is N-methyl pyrrolidone, chinese alias: NMP; 1-methyl-2 pyrrolidone; n-methyl-2-pyrrolidone; colorless transparent oily liquid, slightly having an amine smell; is miscible with water, alcohols, ethers, esters, ketones, halogenated hydrocarbons, aromatic hydrocarbons and castor oil; low volatility, good thermal stability and chemical stability, can volatilize along with water vapor, has hygroscopicity and is sensitive to light; n-methyl pyrrolidone is widely applied in industries such as lithium batteries, medicines, pesticides, pigments, cleaning agents, insulating materials and the like.
As shown in FIG. 1, the nuclear magnetic resonance spectrum of the product of this example was 1H NMR (500 MHz, chloroform) delta 7.89 (s, 4H), 7.53 (s, 4H), 7.29 (s, 4H), 7.23 (s, 4H).
Example 2
The embodiment provides a preparation method of an OLED compound containing a spirofluorene structure, which comprises the following steps:
the first step:
under the protection of nitrogen, adding 140ml of THF (2-A) (0.074 Mol) into a reaction bottle, controlling the temperature to be 10-15 ℃, adding 80ml of isopropyl magnesium chloride (1 Mol/L,0.080 Mol), stirring for 30min, adding a THF solution (17.3 g of 0.067Mol, THF50 ml) of 1-bromofluorenone (2-B) into the reaction bottle, heating to 50 ℃, detecting the complete reaction of 1-bromofluorenone by TLC, stopping the reaction, adding water and EA for extraction, washing, drying an organic phase by anhydrous magnesium sulfate, filtering a drying agent, concentrating, recrystallizing n-hexane to obtain 22.1g of 2-C, and obtaining the yield of 79.2%.
And a second step of:
2-C22.1 g (0.053 mol) of benzene 220ml, 10.6g (0.079 mol) of aluminum trichloride are added in batches at 0 ℃ and stirring is continued for 5h, TLC detects that the 2-C reaction is completely stopped, dilute hydrochloric acid is added for acidification, the organic phase is washed with aqueous sodium chloride solution, the drying agent is filtered off, concentrated, and the organic phase is filtered through a silica gel column by ethyl acetate/petroleum ether to obtain 21.4g of 2-D (yield 85.3%)
And a third step of:
2-D21.4 g (0.045 mol), palladium acetate 0.25g (0.00113 mol), DBU 20.5g (0.135 mol), NMP 200ml, heating to 150 ℃ for 12h, TLC monitoring, completely stopping the reaction, concentrating under reduced pressure to remove the solvent, adding toluene water, stirring and washing, separating the liquid, drying the organic phase, concentrating, recrystallizing n-hexane to obtain 2-E13.4 g (0.034 mol) with a yield of 75.8%.
As shown in FIG. 2, the nuclear magnetic resonance spectrum of the product of this example, 1H NMR (500 MHz, chloroform) delta 7.89 (d, J=5.0 Hz, 3H), 7.83 (s, 1H), 7.55-7.47 (m, 4H), 7.34 (s, 2H), 7.24 (d, J=5.0 Hz, 4H), 7.13 (s, 1H).
Example 3
The embodiment provides a preparation method of an OLED compound containing a spirofluorene structure, which comprises the following steps:
the first step:
under the protection of nitrogen, adding THF70ml, o-bromoiodobenzene 10g (3-A) (0.035 Mol), controlling the temperature to 10-15 ℃, adding isopropyl magnesium chloride 39ml (1 Mol/L,0.039 Mol), stirring for 30min, adding THF solution (2-bromo-6-chlorofluorenone 9.4g 0.032mol,THF40ml) of 2-bromo-6-chlorofluorenone (3-B), heating to 50 ℃ for reaction, detecting that the 2-bromo-6-chlorofluorenone is completely reacted by TLC, stopping the reaction, adding water and EA for extraction, washing, drying an organic phase by anhydrous magnesium sulfate, filtering a drying agent, concentrating, recrystallizing n-hexane to obtain 12.6g of 3-C, and obtaining the yield of 87.6%.
And a second step of:
to the reaction flask was added 3-C12.6 g (0.028 mol), benzene 120ml, aluminum trichloride 5.6g (0.042 mol) was added in portions at 0deg.C, stirring was continued for 5h, TLC was used to check that the 3-C reaction was completely stopped, diluted hydrochloric acid was added to acidify, the separated liquid, the organic phase was washed with aqueous sodium chloride solution, the drying agent was filtered off, concentrated, and the silica gel column was passed with ethyl acetate/petroleum ether to give 11.7g of 3-D (yield 81.5%).
And a third step of:
3-D11.7g (0.023 mol), palladium acetate 0.13g (0.000575 mol), DBU 10.5g (0.069 mol), NMP 120ml, heat to 150℃for 12h, and TLC monitor reaction completely stops; the solvent was removed by concentration under reduced pressure, washed with toluene water under stirring, separated, the organic phase was dried, concentrated, and recrystallized from n-hexane to give 3-E7.7g (0.018 mol) in 78.3% yield.
As shown in FIG. 3, the nuclear magnetic resonance hydrogen spectrum of the product of this example was 1H NMR (500 MHz, chloroform) delta 7.91 (d, J=9.6 Hz, 3H), 7.77 (d, J=6.4 Hz, 2H), 7.57 (s, 1H), 7.50 (s, 2H), 7.40 (s, 1H), 7.33 (d, J=12.1 Hz, 3H), 7.24 (s, 2H).
Experiments prove that various structures of the OLED compound containing the spirofluorene structure can be prepared by the method provided by the application, the preparation methods are the same, and the application is not repeated.
The reaction principle of the application is as follows:
according to the application, a raw material A and a Grignard reagent of isopropyl magnesium chloride are exchanged, then the raw material B is attacked, intermediate tertiary alcohol C is prepared, the intermediate tertiary alcohol C and benzene are subjected to coupling reaction under the catalysis of aluminum trichloride, intermediate D is prepared, and the intermediate D is subjected to coupling reaction under the catalysis of a catalyst, so that the target OLED compound containing the spirofluorene structure is prepared. The application adopts low-temperature coupling reaction and weak base ring closure reaction for preparation, has mild reaction condition, is friendly to equipment and is easy to carry out production amplification.
The application provides a preparation method of an OLED compound containing a spirofluorene structure, which comprises the steps of firstly preparing o-bromoiodobenzene into Grignard reagent to attack fluorenone and derivatives thereof, preparing tertiary alcohol, then carrying out coupling reaction on the tertiary alcohol and benzene at low temperature to obtain an intermediate D, and carrying out weak base cyclization reaction on the intermediate D to obtain the OLED compound containing the spirofluorene structure.
The preparation method comprises the steps of firstly preparing a Grignard reagent by a format exchange method, preparing o-bromoiodobenzene into Grignard reagent, attacking fluorenone and derivatives thereof, and preparing tertiary alcohol, wherein the reaction temperature is about 50 ℃, and the reaction condition is mild; after the reaction is completed, adding water and EA for extraction, washing, drying the organic phase by anhydrous magnesium sulfate, filtering out the drying agent, concentrating, recrystallizing n-hexane to obtain tertiary alcohol, and carrying out aftertreatment easily and conveniently.
The second step of the application adopts low-temperature coupling reaction, and the third step adopts weak base ring closure, which is friendly to equipment and environment, has little pollution, reduces cost and is beneficial to amplified production.
The synthetic route of the application can not generate isomer, has good structural selectivity, single structure of the product, no position isomerism, no coupling product and no polyhalogenation, has wide applicability, and is applicable to introducing other derivative structures such as halogen, aromatic ring, alkyl and the like into spirofluorene.
The application discloses a synthetic method of a new material, which can improve the efficiency of a device, reduce the driving voltage and/or improve the service life characteristic when an OLED compound containing a spirofluorene structure is used for hole injection and/or hole transport materials, and the device has low driving voltage and long service life and shows high-stability device performance.
While the preferred embodiments of the present application have been described in detail, the present application is not limited to the above embodiments, and various changes may be made without departing from the spirit of the present application within the knowledge of those skilled in the art.
Many other changes and modifications may be made without departing from the spirit and scope of the application. It is to be understood that the application is not to be limited to the specific embodiments, but only by the scope of the appended claims.
Claims (10)
1. A method for preparing an OLED compound containing a spirofluorene structure, comprising the steps of:
step 1: exchanging the Grignard reagent of the o-bromoiodobenzene and the isopropyl magnesium chloride, then attacking fluorenone and the derivative thereof to prepare intermediate tertiary alcohol C, wherein the mol ratio of the o-bromoiodobenzene to the isopropyl magnesium chloride is 1:1-1.3, and the mol ratio of the o-bromoiodobenzene to the fluorenone and the derivative thereof is 1-1.3:1; the structural formula of the fluorenone and the derivative thereof isIntermediate tertiary alcohol C has the structural formula +.>R 1 And R is 2 H, F, C1 or Br, respectively;
step 2: the intermediate tertiary alcohol C and benzene are subjected to coupling reaction under the catalysis of aluminum trichloride to prepare an intermediate D, wherein the dosage ratio of the intermediate tertiary alcohol C to the benzene is 0.01 mol:41-43 ml, and the molar ratio of the intermediate tertiary alcohol C to the aluminum trichloride is 1:1.4 to 1.6; the structural formula of the intermediate D isR 1 And R is 2 H, F, cl or Br, respectively;
step 3: the intermediate D is subjected to coupling reaction under the catalysis of a palladium acetate catalyst to prepare the target OLED compound containing the spirofluorene structure, the molar ratio of the intermediate D to the palladium acetate catalyst is 1:0.02-0.05, and the structural formula of the OLED compound containing the spirofluorene structure isR 1 And R is 2 H, F, cl or Br, respectively.
2. The method for preparing an OLED compound containing a spirofluorene structure according to claim 1, wherein step 1 specifically comprises: under the protection of nitrogen, adding THF and o-bromoiodobenzene into a reaction bottle, controlling the temperature to be 10-15 ℃, adding Grignard reagent of isopropyl magnesium chloride, stirring for 30min, adding THF solution of fluorenone and derivatives thereof, heating to 50 ℃ for reaction, and stopping the reaction after detecting that the fluorenone and derivatives thereof react completely through liquid chromatography to obtain intermediate tertiary alcohol C solution, wherein the dosage ratio of the o-bromoiodobenzene to the THF is 0.01 mol:18-19 ml, and the dosage ratio of the fluorenone and derivatives thereof to the THF is 0.01 mol:7.5-12.5 ml.
3. The method for preparing the spirofluorene-containing OLED compound according to claim 2, wherein the post-treatment of the intermediate tertiary alcohol C solution is: adding water and ethyl acetate into the intermediate tertiary alcohol C solution for extraction, washing with water, drying the organic phase with anhydrous magnesium sulfate, filtering to remove the drying agent, concentrating, and recrystallizing with n-hexane to obtain the intermediate tertiary alcohol C.
4. The method for preparing an OLED compound containing a spirofluorene structure according to claim 1, wherein step 2 specifically comprises: adding intermediate tertiary alcohol C and benzene into a reaction bottle, adding aluminum trichloride in batches at the temperature of 0 ℃, continuously stirring for 5 hours, and stopping the reaction after detecting that the intermediate tertiary alcohol C is completely reacted by liquid chromatography to obtain an intermediate D solution, wherein the dosage ratio of the intermediate tertiary alcohol C to the benzene is 0.01 mol:41-43 ml, and the molar ratio of the intermediate tertiary alcohol C to the aluminum trichloride is 1:1.4-1.5.
5. The method for preparing an OLED compound containing a spirofluorene structure according to claim 4, wherein the post-treatment of the intermediate D solution is: adding dilute hydrochloric acid into the solution of the intermediate D for acidification, separating the solution, washing the organic phase with sodium chloride aqueous solution, filtering out the drying agent, concentrating, and passing through a silica gel column by using ethyl acetate/petroleum ether to obtain the intermediate D.
6. The method for preparing an OLED compound containing a spirofluorene structure according to claim 1, wherein the step 3 specifically comprises: adding an intermediate D, palladium acetate, diazabicyclo and N-methylpyrrolidone into a reaction bottle, heating to 150 ℃ for reaction for 12 hours, and stopping the reaction after detecting that the intermediate D is completely reacted by liquid chromatography to obtain a solution of the OLED compound containing a spirofluorene structure, wherein the mol ratio of the intermediate D to the diazabicyclo is 1:3, and the dosage ratio of the intermediate D to the N-methylpyrrolidone is 0.01 mol:45 ml.
7. The method for preparing the spirofluorene-containing OLED compound according to claim 6, wherein: the molar ratio of the intermediate D to the palladium acetate catalyst is 1:0.025.
8. The method for preparing the spirofluorene-containing OLED compound according to claim 6, wherein the post-treatment of the solution of the spirofluorene-containing OLED compound is as follows: concentrating the solution containing the OLED compound with the spirofluorene structure under reduced pressure to remove the solvent, adding toluene water, stirring and washing, separating the liquid, drying the organic phase, concentrating, and recrystallizing the n-hexane to obtain the OLED compound containing the spirofluorene structure.
9. An OLED compound containing a spirofluorene structure is characterized in that the structural formula of the OLED compound containing the spirofluorene structure is as followsR 1 And R is 2 H, F, C1 or Br, respectively.
10. The OLED compound containing a spirofluorene structure according to claim 9, wherein the specific structure of the OLED compound containing a spirofluorene structure is:
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