CN117720425A - Method for synthesizing Spiro-OMe TAD at low cost - Google Patents
Method for synthesizing Spiro-OMe TAD at low cost Download PDFInfo
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- CN117720425A CN117720425A CN202311760574.4A CN202311760574A CN117720425A CN 117720425 A CN117720425 A CN 117720425A CN 202311760574 A CN202311760574 A CN 202311760574A CN 117720425 A CN117720425 A CN 117720425A
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- VCOONNWIINSFBA-UHFFFAOYSA-N 4-methoxy-n-(4-methoxyphenyl)aniline Chemical compound C1=CC(OC)=CC=C1NC1=CC=C(OC)C=C1 VCOONNWIINSFBA-UHFFFAOYSA-N 0.000 claims abstract description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 44
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 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 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 8
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000012074 organic phase Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- 238000001308 synthesis method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 239000000463 material Substances 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
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 2
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention discloses a low-cost method for synthesizing a Spiro-OMe TAD, which takes NaH as an alkaline dehydrogenation reagent and tetraphenylphosphine palladium as a catalyst, and directly synthesizes the Spiro-OMe TAD through the reaction of 4,4' -dimethoxy diphenylamine and 2,2', 7' -tetrabromospiro bifluorene. The alkaline dehydrogenation reagent and the catalyst used in the invention have low cost, reduce the reaction cost, effectively inhibit the occurrence of side reaction and improve the reaction safety, selectivity and yield. Compared with the prior art that the Spiro-OMe TAD is treated after being synthesized, the method of the invention uses the activated carbon powder to remove the catalyst for the first time, further reduces the synthesis cost, is safer and more environment-friendly, and is suitable for being used in large-scale industrial production.
Description
Technical Field
The invention belongs to the technical field of synthesis of a hole transport material Spiro-OMe TAD of a perovskite photovoltaic device, and particularly relates to a method for synthesizing Spiro-OMe TAD directly through reaction of two precursors of 4,4' -dimethoxy diphenylamine and 2,2', 7' -tetrabromo spirobifluorene.
Background
Perovskite solar cells are of great interest because of their high photoelectric conversion efficiency and low manufacturing cost. The Spiro-OMe TAD (chemical name is 2,2', 7' -tetra [ n, n-di (4-methoxyphenyl) amino ] -9,9 '-Spiro [1, 3-dioxolane-2, 2' -dione ]) is used as a hole transport material, plays a key role in a perovskite solar cell, can effectively transport holes, improves the overall performance of the cell, and has wide application in the fields of perovskite solar cells, organic solar cells and the like. However, the synthesis process is complex, and the reaction conditions need to be strictly controlled; toxic or explosive substances can be involved in the synthesis process, so that the safety risk is high; the choice of catalyst and alkaline dehydrogenation reagent in the synthesis process also has a great influence on the purity of the product. Optimizing the reaction conditions and post-treatment processes becomes critical to improving the reaction yield. In the existing method for synthesizing the Spiro-OMe TAD, normal butyl lithium, sodium tert-butoxide and the like are generally adopted as alkaline reagents, and tetraphenylphosphine palladium is adopted as a catalyst, so that the reaction yield can only reach 60 percent at most. Moreover, the n-butyllithium has harsh preservation conditions, needs to be used at ultralow temperature, has strict requirements on reaction temperature and conditions, and seriously affects industrial production. Therefore, the invention discloses a safe, green and low-cost method for synthesizing the Spiro-OMe TAD, which has important significance for industrialized mass production of the Spiro-OMe TAD.
Disclosure of Invention
In view of the above problems, the present invention provides a method for synthesizing high purity Spiro-OMe TAD at low cost and high yield.
In order to solve the problems, the invention adopts the following technical scheme: adding 4,4' -dimethoxy diphenylamine, 2', 7' -tetrabromo spirobifluorene and NaH into tetrahydrofuran, adding tetraphenylphosphine palladium, carrying out reflux reaction in a nitrogen atmosphere, and recrystallizing after the reaction is finished to obtain pale yellow solid Spiro-OMe TAD; the reaction equation is as follows:
further, in the above synthesis method, the molar ratio of 4,4' -dimethoxydiphenylamine to 2,2', 7' -tetrabromospirobifluorene is preferably 4 to 5:1.
In the above synthesis method, the molar ratio of the 4,4' -dimethoxydiphenylamine to NaH is preferably 1:1 to 1.2.
In the above synthesis method, the amount of the palladium tetrakis triphenylphosphine to be added is preferably 0.3 to 0.6% of the molar amount of 2,2', 7' -tetrabromospirobifluorene.
In the above synthesis method, the temperature of the reflux reaction is preferably 60 to 80℃and the reaction time is preferably 18 to 24 hours.
In the above synthesis method, it is preferable that activated carbon is added during the recrystallization, and the addition amount of the activated carbon is 0.1% to 0.5% of the molar amount of 2,2', 7' -tetrabromospirobifluorene.
In the above synthesis method, the solvent used for the recrystallization is preferably selected from one of tetrahydrofuran/ethanol mixed solvent and dichloromethane/ethanol mixed solvent.
The beneficial effects of the invention are as follows:
1. according to the invention, the alkaline dehydrogenation reagent NaH is adopted to replace the traditional alkaline dehydrogenation reagent n-butyllithium, naH is used as a solid reagent, so that the solid reagent is easy to store, and is more stable, safer and cheaper than n-butyllithium and sodium tert-butoxide, and the operation is simpler, so that dangerous situations are not easy to occur. Compared with n-butyllithium, naH is easier to obtain and use, the cost is relatively lower, the potential safety hazard in the synthesis process is reduced, the reaction condition is more controllable, the reaction rate and selectivity are easier to control in actual operation, and the occurrence of side reactions is reduced.
2. Compared with the traditional palladium catalysts such as palladium acetate, palladium dichloride and tri-tert-butylphosphine palladium, the catalyst provided by the invention has the advantages that the price is lower, the catalytic performance is better, the catalyst is more environment-friendly and economical, and during post-treatment, the catalyst is more easily removed by adding a small amount of activated carbon, the purity of the product is improved, and the product has more excellent performance. And compared with petroleum ether used in the recrystallization by the traditional method, the ethanol solvent used in the post-treatment recrystallization has the advantages of lower cost, more environmental friendliness and safer experiment.
3. The method for synthesizing the Spiro-OMe TAD has higher yield and purity, the yield can reach more than 80 percent, the purity is more than 99 percent, and the method is far superior to the existing method for synthesizing the Spiro-OMe TAD, and is suitable for industrialized large-scale, safe, green and low-cost production.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the Spiro-OMe TAD synthesized in example 1.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, but the scope of the present invention is not limited to these examples.
Example 1
917.2mg (4 mmol) of 4,4' -dimethoxydiphenylamine, 632mg (1 mmol) of 2,2', 7' -tetrabromospirobifluorene and 96mg (4 mmol) of NaH were weighed into a two-necked flask, mixed uniformly, then three-charge and three-discharge were performed, the air in the two-necked flask was removed, 20mL of a tetrahydrofuran solution in which oxygen was removed by introducing nitrogen for 30 minutes in advance was further added into the two-necked flask, the reaction solution was heated to 60℃under nitrogen atmosphere, and then tetrakis triphenylphosphine palladium (5.78 mg,0.005 mmol) dissolved in 2mL of tetrahydrofuran was added and the mixture was refluxed for 24 hours. Maldi-TOF detects that 2,2', 7' -tetrabromospirobifluorene is reacted completely, cooling to room temperature, adding saturated ammonium chloride aqueous solution into the reaction solution, stirring for 30 minutes, stopping the reaction, filtering the reaction solution, extracting with dichloromethane and water, combining organic phases, adding 5mg (0.005 mmol) of activated carbon powder into the organic phases, stirring for 30 minutes, filtering the organic phases and drying with anhydrous sodium sulfate, spinning the organic phases, and recrystallizing for multiple times with a tetrahydrofuran/ethanol system to obtain light yellow solid Spiro-OMe TAD 980.4mg with the yield of 80% and the purity of >99%. The structural characterization data of the resulting Spiro-OMe TAD are shown in fig. 1.
Example 2
1.147g (5 mmol) of 4,4' -dimethoxydiphenylamine, 632mg (1 mmol) of 2,2', 7' -tetrabromospirobifluorene and 120mg (5 mmol) of NaH were weighed into a two-necked flask, mixed uniformly, then three-charge and three-discharge were performed, the air in the two-necked flask was removed, 20mL of a tetrahydrofuran solution in which oxygen was removed by introducing nitrogen for 30 minutes in advance was further added into the two-necked flask, the reaction solution was heated to 60℃under nitrogen atmosphere, and then tetrakis triphenylphosphine palladium (5.78 mg,0.005 mmol) dissolved in 2mL of tetrahydrofuran was added and the mixture was refluxed for 24 hours. Maldi-TOF detects that 2,2', 7' -tetrabromospirobifluorene is reacted completely, cooling to room temperature, adding saturated ammonium chloride aqueous solution into the reaction solution, stirring for 30 minutes, stopping the reaction, filtering the reaction solution, extracting with dichloromethane and water, combining organic phases, adding 5mg (0.005 mmol) of activated carbon powder into the organic phases, stirring for 30 minutes, filtering the organic phases and drying the organic phases with anhydrous sodium sulfate, spinning the organic phases, and recrystallizing for multiple times with a tetrahydrofuran/ethanol system to obtain light yellow solid Spiro-OMe TAD 992.25mg with the yield of 81% and the purity of >99%.
Example 3
917.2mg (4 mmol) of 4,4' -dimethoxydiphenylamine, 632mg (1 mmol) of 2,2', 7' -tetrabromospirobifluorene and 120mg (5 mmol) of NaH were weighed into a two-necked flask, mixed uniformly, then three-charge and three-discharge were performed, the air in the two-necked flask was removed, 20mL of a tetrahydrofuran solution in which oxygen was removed by introducing nitrogen for 30 minutes in advance was further added into the two-necked flask, the reaction solution was heated to 60℃under nitrogen atmosphere, and then tetrakis triphenylphosphine palladium (5.78 mg,0.005 mmol) dissolved in 2mL of tetrahydrofuran was added and the mixture was refluxed for 24 hours. Maldi-TOF detects that 2,2', 7' -tetrabromospirobifluorene is reacted completely, cooling to room temperature, adding saturated ammonium chloride aqueous solution into the reaction solution, stirring for 30 minutes, stopping the reaction, filtering the reaction solution, extracting with dichloromethane and water, combining organic phases, adding 5mg (0.005 mmol) of activated carbon powder into the organic phases, stirring for 30 minutes, filtering the organic phases and drying the organic phases with anhydrous sodium sulfate, spinning the organic phases, and recrystallizing for multiple times with a tetrahydrofuran/ethanol system to obtain light yellow solid Spiro-OMe TAD 998.8mg with the yield of 81.5% and the purity of >99%.
Example 4
917.2mg (4 mmol) of 4,4' -dimethoxydiphenylamine, 632mg (1 mmol) of 2,2', 7' -tetrabromospirobifluorene and 96mg (4 mmol) of NaH were weighed into a two-necked flask, mixed uniformly, then three-charge and three-discharge were performed, the air in the two-necked flask was removed, 20mL of a tetrahydrofuran solution in which oxygen was removed by introducing nitrogen for 30 minutes in advance was further added into the two-necked flask, the reaction solution was heated to 70℃under nitrogen atmosphere, and then tetrakis triphenylphosphine palladium (5.78 mg,0.005 mmol) dissolved in 2mL of tetrahydrofuran was added and the mixture was refluxed for 24 hours. Maldi-TOF detects that 2,2', 7' -tetrabromospirobifluorene is reacted completely, cooling to room temperature, adding saturated ammonium chloride aqueous solution into the reaction solution, stirring for 30 minutes, stopping the reaction, filtering the reaction solution, extracting with dichloromethane and water, combining organic phases, adding 5mg (0.005 mmol) of activated carbon powder into the organic phases, stirring for 30 minutes, filtering the organic phases and drying the organic phases with anhydrous sodium sulfate, spinning the organic phases, and recrystallizing for multiple times with a tetrahydrofuran/ethanol system to obtain pale yellow solid Spiro-OMe TAD 1.005g, wherein the yield is 82%, and the purity is >99%.
Example 5
917.2mg (4 mmol) of 4,4' -dimethoxydiphenylamine, 632mg (1 mmol) of 2,2', 7' -tetrabromospirobifluorene and 120mg (5 mmol) of NaH were weighed into a two-necked flask, mixed uniformly, then three-charge and three-discharge were performed, the air in the two-necked flask was removed, 20mL of a tetrahydrofuran solution in which oxygen was removed by introducing nitrogen for 30 minutes in advance was further added into the two-necked flask, the reaction solution was heated to 70℃under nitrogen atmosphere, and then tetrakis triphenylphosphine palladium (5.78 mg,0.005 mmol) dissolved in 2mL of tetrahydrofuran was added and the mixture was refluxed for 24 hours. Maldi-TOF detects that 2,2', 7' -tetrabromospirobifluorene is reacted completely, cooling to room temperature, adding saturated ammonium chloride aqueous solution into the reaction solution, stirring for 30 minutes, stopping the reaction, filtering the reaction solution, extracting with dichloromethane and water, combining organic phases, adding 5mg (0.005 mmol) of activated carbon powder into the organic phases, stirring for 30 minutes, filtering the organic phases and drying the organic phases with anhydrous sodium sulfate, spinning the organic phases, and recrystallizing for multiple times with a tetrahydrofuran/ethanol system to obtain pale yellow solid Spiro-OMe TAD 1.012g, yield 82.6%, purity >99%.
Example 6
1.147g (5 mmol) of 4,4' -dimethoxydiphenylamine, 632mg (1 mmol) of 2,2', 7' -tetrabromospirobifluorene and 120mg (5 mmol) of NaH were weighed into a two-necked flask, mixed uniformly, then three-charge and three-discharge were performed, the air in the two-necked flask was removed, 20mL of a tetrahydrofuran solution in which oxygen was removed by introducing nitrogen for 30 minutes in advance was further added into the two-necked flask, the reaction solution was heated to 70℃under nitrogen atmosphere, and then tetrakis triphenylphosphine palladium (5.78 mg,0.005 mmol) dissolved in 2mL of tetrahydrofuran was added and the mixture was refluxed for 24 hours. Maldi-TOF detects that 2,2', 7' -tetrabromospirobifluorene is reacted completely, cooling to room temperature, adding saturated ammonium chloride aqueous solution into the reaction solution, stirring for 30 minutes, stopping the reaction, filtering the reaction solution, extracting with dichloromethane and water, combining organic phases, adding 5mg (0.005 mmol) of activated carbon powder into the organic phases, stirring for 30 minutes, filtering the organic phases and drying the organic phases with anhydrous sodium sulfate, spinning the organic phases, and recrystallizing for multiple times with a tetrahydrofuran/ethanol system to obtain pale yellow solid Spiro-OMe TAD 1.029g, yield 84%, purity >99%.
Claims (7)
1. A method for synthesizing Spiro-OMe TAD at low cost, which is characterized by comprising the following steps: adding 4,4' -dimethoxy diphenylamine, 2', 7' -tetrabromo spirobifluorene and NaH into tetrahydrofuran, adding tetraphenylphosphine palladium, carrying out reflux reaction in a nitrogen atmosphere, and recrystallizing after the reaction is finished to obtain pale yellow solid Spiro-OMe TAD.
2. The method of low cost synthesis of a Spiro-OMe TAD according to claim 1, wherein: the molar ratio of the 4,4' -dimethoxy diphenylamine to the 2,2', 7' -tetrabromo spirobifluorene is 4-5:1.
3. The method of low cost synthesis of a Spiro-OMe TAD according to claim 1, wherein: the molar ratio of the 4,4' -dimethoxy diphenylamine to the NaH is 1:1-1.2.
4. The method of low cost synthesis of a Spiro-OMe TAD according to claim 1, wherein: the addition amount of the tetraphenylphosphine palladium is 0.3-0.6% of the molar amount of the 2,2', 7' -tetrabromospiro bifluorene.
5. The method of low cost synthesis of a Spiro-OMe TAD according to claim 1, wherein: the temperature of the reflux reaction is 60-80 ℃ and the reaction time is 18-24 hours.
6. The method of low cost synthesis of a Spiro-OMe TAD according to claim 1, wherein: activated carbon is added in the recrystallization process, and the addition amount of the activated carbon is 0.1-0.5% of the molar amount of 2,2', 7' -tetrabromospirobifluorene.
7. The method of low cost synthesis of a Spiro-OMe TAD according to claim 1, wherein: the solvent used for the recrystallization is selected from any one of tetrahydrofuran/ethanol mixed solvent and dichloromethane/ethanol mixed solvent.
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