CN115947705B - Method for preparing 1-nitrodibenzofuran by using ligand and o-bromophenol as raw materials - Google Patents
Method for preparing 1-nitrodibenzofuran by using ligand and o-bromophenol as raw materials Download PDFInfo
- Publication number
- CN115947705B CN115947705B CN202211718120.6A CN202211718120A CN115947705B CN 115947705 B CN115947705 B CN 115947705B CN 202211718120 A CN202211718120 A CN 202211718120A CN 115947705 B CN115947705 B CN 115947705B
- Authority
- CN
- China
- Prior art keywords
- bromophenol
- ligand
- butoxide
- nitrodibenzofuran
- potassium tert
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000003446 ligand Substances 0.000 title claims abstract description 38
- AMKYSWHDHALJOT-UHFFFAOYSA-N 1-nitrodibenzofuran Chemical compound O1C2=CC=CC=C2C2=C1C=CC=C2[N+](=O)[O-] AMKYSWHDHALJOT-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000002994 raw material Substances 0.000 title claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 32
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 27
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 238000010992 reflux Methods 0.000 claims description 19
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000012266 salt solution Substances 0.000 claims description 18
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 16
- JBGJVMVWYWUVOW-UHFFFAOYSA-N 1-(1-hydroxynaphthalen-2-yl)ethanone Chemical compound C1=CC=CC2=C(O)C(C(=O)C)=CC=C21 JBGJVMVWYWUVOW-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 9
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 7
- 229940045803 cuprous chloride Drugs 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical group [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000001514 detection method Methods 0.000 description 10
- KQDJTBPASNJQFQ-UHFFFAOYSA-N 2-iodophenol Chemical compound OC1=CC=CC=C1I KQDJTBPASNJQFQ-UHFFFAOYSA-N 0.000 description 9
- 238000005070 sampling Methods 0.000 description 7
- 239000000543 intermediate Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 4
- FFDGPVCHZBVARC-UHFFFAOYSA-N N,N-dimethylglycine Chemical compound CN(C)CC(O)=O FFDGPVCHZBVARC-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- 108700003601 dimethylglycine Proteins 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229940078490 n,n-dimethylglycine Drugs 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical group C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDNUEBSJWINEMI-UHFFFAOYSA-N ethyl nitrate Chemical compound CCO[N+]([O-])=O IDNUEBSJWINEMI-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000009789 rate limiting process Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for preparing 1-nitrodibenzofuran by using o-bromophenol as a raw material by using a ligand. The method has the advantages of convenient operation, low cost, high yield, no need of nitrogen protection, high safety coefficient, stable batch and suitability for industrial production.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for preparing 1-nitrodibenzofuran by using a ligand and o-bromophenol as raw materials.
Background
At present, organic photoelectric materials are widely applied to the fields of organic light emitting diodes, organic transistors, organic solar cells and the like, and are usually organic molecules rich in carbon atoms and having a large pi conjugated system. 1-nitrodibenzofurans are important intermediates in these processes and have high values in research and development. The cost for synthesizing 1-nitrodibenzofuran in the prior art is too high, and the main reasons are that the raw material o-iodophenol is expensive, the batch-to-batch difference is large, and the quality is unstable.
The current method for preparing 1-nitrodibenzofuran mainly comprises the following synthetic routes:
(1) Taking m-dinitrobenzene and o-iodophenol as raw materials, adding potassium tert-butoxide, cuprous chloride and pyridine, and refluxing in ethylene glycol dimethyl ether for 1.5 hours to obtain the product 1-nitrodibenzofuran. The synthesis method has the following problems: 1. the price of the o-iodophenol is 3000 yuan/500 g (Aba Ding Shiji), which is a heavy cost pressure for preparing the 1-nitrodibenzofuran and is not beneficial to the industrial production thereof; 2. the whole reaction process needs nitrogen protection, the air humidity has great influence on the yield, and the batch-to-batch difference is large; 3. the yield is poor and can only reach 73%; 4. the method is based on the attempt, o-bromophenol is used for replacing o-iodophenol, and the conversion rate is only 5-10%.
The synthetic route is as follows:
(2) The dibenzofuran is used as raw material, aluminum trichloride is used for catalysis, and ethyl nitrate is used for nitration to obtain the product 1-nitrodibenzofuran [ Bulletin of the Chemical Society of Japan,1982, vol.55, #2, p.629-630]. The synthesis method has the following problems: the conversion rate is only 5%, and the method is not suitable for large-scale production.
The synthetic route is as follows:
disclosure of Invention
Based on the problems existing in the prior art, the invention provides a method for efficiently preparing 1-nitrodibenzofuran by using special ligand and o-bromophenol instead of o-iodophenol; the method has the advantages of convenient operation, low cost, high yield, no need of nitrogen protection, high safety coefficient, stable batch and suitability for industrial production.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for preparing 1-nitrodibenzofuran by using o-bromophenol as a raw material by using a ligand, wherein the method uses o-bromophenol and m-dinitrobenzene as raw materials, 2-acetyl-1-naphthol as the ligand, and the 1-nitrodibenzofuran is obtained after heating and refluxing in an organic solvent under the conditions of potassium tert-butoxide, pyridine and a catalyst, and the o-bromophenol, m-dinitrobenzene, 2-acetyl-1-naphthol, potassium tert-butoxide, pyridine, the organic solvent and the catalyst are all put into use in an anhydrous state.
Preferably, the method comprises the steps of:
(1) Adding a part of the total amount of the potassium tert-butoxide, an organic solvent A and a catalyst into a reactor 1, uniformly mixing, cooling to 5-15 ℃, adding pyridine, m-dinitrobenzene and ligand 2-acetyl-1-naphthol into the mixture, and uniformly mixing to obtain a mixed solution;
(2) Adding o-bromophenol, an organic solvent A and the rest potassium tert-butoxide into a reactor 2 to obtain potassium salt solution of the o-bromophenol;
(3) Adding potassium salt solution of o-bromophenol into the mixed solution of the reactor 1, heating and refluxing for 1-3 hours, cooling to room temperature, filtering, concentrating the obtained filtrate, adding an organic solvent B (preferably anhydrous methanol) for crystallization, and filtering to obtain a product 1-nitrodibenzofuran;
further, the molar ratio of the o-bromophenol to the ligand 2-acetyl-1-naphthol is 1: (0.05-1), more preferably 1:0.087;
further, the molar ratio of the o-bromophenol to the m-dinitrobenzene is 1: (0.5 to 3), preferably 1:1, a step of;
further, the molar ratio of the o-bromophenol to the catalyst is 1: (0.1 to 0.5), more preferably 1:0.3;
further, the mole ratio of the o-bromophenol to the total amount of potassium tert-butoxide is 1: (2-5), preferably 1 (2-3);
still further, the molar ratio of potassium tert-butoxide in step (1) and step (2) is 1:1, a step of;
further, the mass ratio of the o-bromophenol to the pyridine is (10-30): 15, preferably 16:15.
The synthetic route of the 1-nitrodibenzofuran is as follows:
further, the organic solvent A is toluene or ethylene glycol dimethyl ether.
Further, the catalyst is one or more of copper acetate, copper chloride and cuprous chloride.
Compared with the prior art, the invention has the advantages that:
1) The invention uses o-bromophenol to replace o-iodophenol to realize the synthesis of 1-nitrodibenzofuran: the price of the o-iodophenol is 3000 yuan/500 g, the price of the o-bromophenol is 899 yuan/500 g (Aba Ding Shiji), and after replacement, the cost of the raw material is reduced to within one third of the previous cost.
2) The invention uses 2-acetyl-1-naphthol as ligand to be added into the reaction system, and nitrogen protection is not needed, so that the reaction can be smoothly carried out even if the environmental humidity is 90%.
3) The yield and purity of the synthesized 1-nitrodibenzofuran are high: the yield is above 90%, the HPLC purity is above 99%, and the requirements of industrial production and market of the product can be fully met.
Drawings
FIG. 1 shows the nuclear magnetic resonance spectrum of 1-nitrodibenzofuran obtained in example 1.
FIG. 2 shows an HPLC chromatogram of 1-nitrodibenzofuran obtained in example 1.
Detailed Description
The present invention will be described in detail with reference to specific embodiments by the applicant.
The raw materials, organic solvents, catalysts, ligands and the like used in the following examples were all analytically pure and in an anhydrous state unless otherwise specified, and the air humidity of the operating environment in each of the following examples was 40% to 60% unless otherwise specified.
The main control parameters for HPLC detection in the following examples are shown in table 1 below:
TABLE 1
Example 1 a process for the preparation of 1-nitrodibenzofurans starting from o-bromophenol using ligands comprising the steps of:
(1) 300ml of ethylene glycol dimethyl ether, 20.8g (185.0 mmol) of potassium tert-butoxide and 5.5g (55.5 mmol) of cuprous chloride are added into a 1000ml three-neck flask with a condensing reflux device, the mixture is cooled to 10 ℃ after being uniformly mixed, and then 30g of pyridine, 31.2g (185.6 mmol) of m-dinitrobenzene and 3g (16.1 mmol) of ligand 2-acetyl-1-naphthol are added into the mixture and uniformly stirred to obtain a mixed solution;
(2) At another 500A three-necked flask of 200ml of ethylene glycol dimethyl ether, 20.8g (185.0 mmol) of potassium tert-butoxide and 32g (185.0 mmol) of o-bromophenol were placed therein to prepare a potassium salt solution of o-bromophenol; adding the prepared potassium salt solution of the o-bromophenol into the mixed solution in the step (1), heating and refluxing for 1 hour (sampling for HPLC central control detection, calculating the conversion rate of the o-bromophenol to be 97%, wherein the calculation method comprises the following steps of (1-nitrodibenzofuran/(1-nitrodibenzofuran+o-bromophenol) and the like) according to the HPLC (peak area) ratio, cooling to room temperature, filtering, concentrating the obtained filtrate to 1/4 of the original volume, adding 500ml of methanol, stirring for 1 hour for crystallization, and filtering to obtain yellow solid, namely 1-nitrodibenzofuran, wherein the yellow solid is 1 The H nuclear magnetic pattern is shown in figure 1, and the HPLC pattern is shown in figure 2.
Yield: 91%; HPLC purity: 99.3%; 1 HNMR(400MHz，DMSO-d6)：δ8.47-8.52(bs，1H)，8.20-8.26(m，2H)，7.75-7.86(m，2H)，7.68-7.73(m，1H)，7.47-7.53(m，1H)。
example 2 a process for the preparation of 1-nitrodibenzofurans starting from o-bromophenol using ligands comprising the steps of:
(1) 300ml of toluene, 20.8g of potassium tert-butoxide and 10.1g (55.5 mmol) of copper acetate are added into a 1000ml three-neck flask with a condensing reflux device, the mixture is cooled to 10 ℃ after being uniformly mixed, and then 30g of pyridine, 31.2g of m-dinitrobenzene and 3g of ligand 2-acetyl-1-naphthol are added into the mixture and uniformly stirred to obtain a mixed solution;
(2) In another 500ml three-necked flask, 200ml toluene, 20.8g potassium tert-butoxide and 32g o-bromophenol were added to prepare a potassium salt solution of o-bromophenol; adding the prepared potassium salt solution of the o-bromophenol into the mixed solution in the step (1), heating and refluxing for 1 hour (sampling for HPLC (high performance liquid chromatography) central control detection, calculating the conversion rate of the o-bromophenol to be 98%), cooling to room temperature, filtering, concentrating the obtained filtrate to 1/4 of the original volume, adding 500ml of methanol into the filtrate, stirring for 1 hour, filtering to obtain yellow solid, namely 1-nitrodibenzofuran, the structure of which is that of 1 The detection result of the H nuclear magnetic resonance spectrum is confirmed, and the yield is: 92%; HPLC purity: 99.6%.
Example 3 a process for the preparation of 1-nitrodibenzofurans starting from o-bromophenol using ligands comprising the steps of: (this example is performed in an atmosphere with 90% air humidity.)
(1) 300ml of toluene, 20.8g of potassium tert-butoxide and 10.1g of copper acetate are added into a 1000ml three-neck flask with a condensing reflux device, the mixture is cooled to 10 ℃ after being uniformly mixed, and then 30g of pyridine, 31.2g of m-dinitrobenzene and 3g of ligand 2-acetyl-1-naphthol are added into the mixture and uniformly stirred to obtain a mixed solution;
(2) In another 500ml three-necked flask, 200ml toluene, 20.8 t-butyl alcohol potassium and 32g o-bromophenol were added to prepare a potassium salt solution of o-bromophenol; adding the prepared potassium salt solution of the o-bromophenol into the mixed solution in the step (1), heating and refluxing for 1 hour (sampling for HPLC (high performance liquid chromatography) central control detection, calculating the conversion rate of the o-bromophenol to be 97%), cooling to room temperature, filtering, concentrating the obtained filtrate to 1/4 of the original volume, adding 500ml of methanol into the filtrate, stirring for 1 hour, filtering to obtain yellow solid, namely 1-nitrodibenzofuran, the structure of which is that of 1 The detection result of the H nuclear magnetic resonance spectrum is confirmed, and the yield is: 91%; HPLC purity: 99.6%.
Comparative example 1 (without ligand)
(1) 300ml of ethylene glycol dimethyl ether, 20.8g of potassium tert-butoxide and 5.5g of cuprous chloride are added into a 1000ml three-neck flask with a condensing reflux device, the mixture is cooled to 10 ℃ after being uniformly mixed, and 30g of pyridine and 31.2g of m-dinitrobenzene are added into the mixture and then uniformly stirred to obtain a mixed solution;
(2) 200ml of ethylene glycol dimethyl ether, 20.8g of potassium tert-butoxide and 32g of o-bromophenol are added into another 500ml three-necked flask to prepare a potassium salt solution of o-bromophenol; and (3) adding the prepared potassium salt solution of the o-bromophenol into the mixed solution in the step (1), heating and refluxing for 1 hour, sampling, performing HPLC (high performance liquid chromatography) central control detection, and calculating that the conversion rate of the o-bromophenol is 7%.
Comparative example 2 (addition of ligand 2-aminopyridine)
(1) 300ml of toluene, 20.8g of potassium tert-butoxide and 10.1g of copper acetate are added into a 1000ml three-neck flask with a condensing reflux device, the mixture is cooled to 10 ℃ after being uniformly mixed, 30g of pyridine, 31.2g of m-dinitrobenzene and 1.6g (17.0 mmol) of ligand 2-aminopyridine are added into the mixture, and the mixture is uniformly stirred to obtain a mixed solution;
(2) In another 500ml three-necked flask, 200ml toluene, 20.8g potassium tert-butoxide and 32g o-bromophenol were added to prepare a potassium salt solution of o-bromophenol; and (3) adding the prepared potassium salt solution of the o-bromophenol into the mixed solution in the step (1), heating and refluxing for 1 hour, sampling, performing HPLC (high performance liquid chromatography) central control detection, and calculating that the conversion rate of the o-bromophenol is 42%.
Comparative example 3 (addition of ligand N, N-tetramethyl ethylenediamine)
(1) 300ml of toluene, 20.8g of potassium tert-butoxide and 5.5g of cuprous chloride are added into a 1000ml three-neck flask with a condensing reflux device, the mixture is cooled to 10 ℃ after being uniformly mixed, 30g of pyridine, 31.2g of m-dinitrobenzene and 2g (17.2 mmol) of ligand N, N-tetramethyl ethylenediamine are added into the mixture, and the mixture is uniformly stirred to obtain a mixed solution;
(2) In another 500ml three-necked flask, 200ml toluene, 20.8g potassium tert-butoxide and 32g o-bromophenol were added to prepare a potassium salt solution of o-bromophenol; and (3) adding the prepared potassium salt solution of the o-bromophenol into the mixed solution in the step (1), heating and refluxing for 1 hour, sampling, performing HPLC (high performance liquid chromatography) central control detection, and calculating that the conversion rate of the o-bromophenol is 27%.
Comparative example 4 (addition of ligand N, N-dimethylglycine)
(1) 300ml of toluene, 20.8g of potassium tert-butoxide and 10.1g of copper acetate are added into a 1000ml three-neck flask with a condensing reflux device, the mixture is cooled to 10 ℃ after being uniformly mixed, 30g of pyridine, 31.2g of m-dinitrobenzene and 1.7g (16.5 mmol) of ligand N, N-dimethylglycine are added into the mixture, and the mixture is uniformly stirred to obtain a mixed solution;
(2) In another 500ml three-necked flask, 200ml toluene, 20.8g potassium tert-butoxide and 32g o-bromophenol were added to prepare a potassium salt solution of o-bromophenol; and (3) adding the prepared potassium salt solution of the o-bromophenol into the mixed solution in the step (1), heating and refluxing for 1 hour, sampling, performing HPLC (high performance liquid chromatography) central control detection, and calculating that the conversion rate of the o-bromophenol is 35%.
It can be seen that the conversion of the o-bromophenol is significantly lower when no ligand is added or other materials are used as ligands than when 2-acetyl-1-naphthol is used as ligand, and the reaction mechanism after participation of the ligand 2-acetyl-1-naphthol is presumed to be as follows (example 1):
wherein, arBr is o-bromophenol; nuH is m-dinitrobenzene; base is potassium tert-butoxide (cuprous); compound 6 is 1-nitrodibenzofuran;
the specific process is as follows:
the preparation method comprises the steps of forming a complex 1 by cuprous chloride and ligand, carrying out oxidation addition with potassium salt of o-iodophenol to obtain an intermediate 2, carrying out substitution with potassium salt of m-dinitrobenzene, carrying out reduction elimination to obtain an intermediate 5, and closing a ring to obtain 1-nitrodibenzofuran.
From the results of the above examples, the technical scheme of the invention realizes the preparation of 1-nitrodibenzofuran by using o-bromophenol instead of o-iodophenol, the conversion rate of o-bromophenol in the preparation process is higher, the conversion rate can not be influenced by air humidity, and the analysis is performed on the mechanism, probably due to the stability (ligand effect) of intermediate 2. According to the Lewis acid-base theory, the soft ligand is easy to coordinate with the soft acid, the hard ligand is easy to coordinate with the hard acid, the corresponding metal complex is more stable, and Cu in the scheme of the invention + With Cu 2+ As stearic acid, the 2-acetyl-1-naphthol is a bidentate ligand which is easier to coordinate with a hard alkali coordination atom O, forms a coordination bond and is more stable; meanwhile, the strong electron donating effect of the ligand naphthol ring can promote the oxidation addition. The formation of intermediate state 2 (oxidation addition process) is generally considered in the art to be the rate limiting process; then according to the transition state theory, the more stable the intermediate state 2 (lower the energy), the lower the energy barrier required, the more easily formed, the faster the reaction speed, and the higher the conversion, so the conversion of inventive examples 1-3 is also much higher than comparative examples 1-4.
Claims (7)
1. A method for preparing 1-nitrodibenzofuran by using o-bromophenol as a raw material by using a ligand, wherein the method uses o-bromophenol and m-dinitrobenzene as raw materials, 2-acetyl-1-naphthol as the ligand, and the 1-nitrodibenzofuran is obtained after heating and refluxing in an organic solvent under the conditions of potassium tert-butoxide, pyridine and a catalyst, and the o-bromophenol, m-dinitrobenzene, 2-acetyl-1-naphthol, potassium tert-butoxide, pyridine, the organic solvent and the catalyst are all put into use in an anhydrous state;
the catalyst is copper acetate or cuprous chloride.
2. The method according to claim 1, characterized in that it comprises the steps of:
(1) Adding a part of the total amount of the potassium tert-butoxide, an organic solvent A and a catalyst into a reactor 1, uniformly mixing, cooling to 5-15 ℃, adding pyridine, m-dinitrobenzene and ligand 2-acetyl-1-naphthol into the mixture, and uniformly mixing to obtain a mixed solution;
(2) Adding o-bromophenol, an organic solvent A and the rest potassium tert-butoxide into a reactor 2 to obtain potassium salt solution of the o-bromophenol;
(3) Adding the potassium salt solution of the o-bromophenol in the reactor 2 into the mixed solution in the reactor 1, heating and refluxing for 1-3 hours, cooling to room temperature, filtering, concentrating the obtained filtrate, adding an organic solvent B, and crystallizing to obtain the product 1-nitrodibenzofuran.
3. The method according to claim 2, wherein the molar ratio of o-bromophenol to ligand 2-acetyl-1-naphthol, m-dinitrobenzene is 1: (0.05-1): (0.5-3).
4. The method according to claim 2, characterized in that the molar ratio of o-bromophenol to catalyst is 1: (0.1 to 0.5).
5. The method according to claim 2, characterized in that the molar ratio of o-bromophenol to total potassium tert-butoxide is 1: (2-5), the molar ratio of potassium tert-butoxide in step (1) and step (2) (1-3): 1.
6. the method according to claim 2, wherein the organic solvent a is toluene or ethylene glycol dimethyl ether and the organic solvent B is anhydrous methanol.
7. The method according to claim 2, wherein the mass ratio of o-bromophenol to pyridine is (10-30): 15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211718120.6A CN115947705B (en) | 2022-12-29 | 2022-12-29 | Method for preparing 1-nitrodibenzofuran by using ligand and o-bromophenol as raw materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211718120.6A CN115947705B (en) | 2022-12-29 | 2022-12-29 | Method for preparing 1-nitrodibenzofuran by using ligand and o-bromophenol as raw materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115947705A CN115947705A (en) | 2023-04-11 |
| CN115947705B true CN115947705B (en) | 2024-03-19 |
Family
ID=87287272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211718120.6A Active CN115947705B (en) | 2022-12-29 | 2022-12-29 | Method for preparing 1-nitrodibenzofuran by using ligand and o-bromophenol as raw materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115947705B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102770935A (en) * | 2010-02-25 | 2012-11-07 | 通用显示公司 | Phosphorescent emitters |
| CN108047235A (en) * | 2017-12-29 | 2018-05-18 | 西安瑞联新材料股份有限公司 | A kind of aromatic heterocyclic compounds and its application |
| CN110041295A (en) * | 2019-05-08 | 2019-07-23 | 苏州杉洋新材料有限公司 | The preparation method of 1- iodine dibenzofurans |
| CN115197182A (en) * | 2022-07-01 | 2022-10-18 | 安徽秀朗新材料科技有限公司 | Synthesis process of halogenated dibenzofuran derivative |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5849867B2 (en) * | 2012-06-21 | 2016-02-03 | コニカミノルタ株式会社 | Organic electroluminescence element, display device and lighting device |
-
2022
- 2022-12-29 CN CN202211718120.6A patent/CN115947705B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102770935A (en) * | 2010-02-25 | 2012-11-07 | 通用显示公司 | Phosphorescent emitters |
| CN108047235A (en) * | 2017-12-29 | 2018-05-18 | 西安瑞联新材料股份有限公司 | A kind of aromatic heterocyclic compounds and its application |
| CN110041295A (en) * | 2019-05-08 | 2019-07-23 | 苏州杉洋新材料有限公司 | The preparation method of 1- iodine dibenzofurans |
| CN115197182A (en) * | 2022-07-01 | 2022-10-18 | 安徽秀朗新材料科技有限公司 | Synthesis process of halogenated dibenzofuran derivative |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis, characterization and antimicrobial activity of some novel 1-amino dibenzofuran derivatives;S Syed Shafi et al.;Indian Journal of Chemistry;第60B卷;1022-1026 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115947705A (en) | 2023-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113583045B (en) | Catalyst composition containing bidentate phosphine ligand and application thereof | |
| CN114380675A (en) | Method for synthesizing aryl phenol by reaction of halogenated aromatic hydrocarbon and phenol compound induced by visible light | |
| CN114716371B (en) | N-containing active center metal organic catalyst for synthesizing cyclic carbonate, and preparation method and application thereof | |
| CN113957461B (en) | Electrochemical synthesis method of 1,1' -binaphthyl compound | |
| CN115947705B (en) | Method for preparing 1-nitrodibenzofuran by using ligand and o-bromophenol as raw materials | |
| CN116003360B (en) | Preparation method for synthesizing orange compounds from carbon dioxide and alkyne | |
| CN108276261B (en) | Method for preparing 2-bromofluorenone by catalyzing molecular oxygen oxidation in aqueous phase | |
| CN103319296B (en) | A kind of preparation method of tetramethyl biphenyl | |
| CN113583046B (en) | Bidentate phosphine ligand, preparation method and application thereof | |
| CN113105301B (en) | Method for preparing conjugated diyne compound by using copper complex | |
| CN109134538B (en) | Iodophosphine oxide ligands, method for the production thereof, complexes, catalyst systems comprising the complexes and use thereof | |
| CN112778378A (en) | Iridium structure coordination compound with half-sandwich and solid-phase synthesis method | |
| CN114213469B (en) | Metal organic complex containing benzimidazole skeleton and preparation method and application thereof | |
| CN112851521A (en) | Method for preparing primary amine by catalytic reduction of nitrile compound with nano porous palladium catalyst | |
| CN114736239B (en) | Bidentate phosphine ligand, and preparation method and application thereof | |
| JP5407332B2 (en) | Method for producing quarterpyridine derivative and its intermediate | |
| CN113563270B (en) | Synthesis method of 2-bromopyrimidine | |
| CN113264820B (en) | Method for preparing ketone compound from olefin | |
| EP4036189A1 (en) | Process for synthesis of polyhydrocarbons as heat transfer agents | |
| CN112876497B (en) | Preparation method of Narst reagent | |
| CN109053541B (en) | Nitrogen-oxygen-containing radical-containing oxygen-free radical sym-terphenyl (triazine) tricarboxylic acid copper complex and application thereof in preparation of menadione | |
| CN108774137B (en) | Method for catalytically synthesizing secondary amine compound by dinuclear manganese complex | |
| CN114832862A (en) | Catalytic composition for coupling reaction and application thereof in preparation of isoquinoline-1, 3-diketone compounds | |
| CN115286573A (en) | Green synthesis method of 1-alkoxy isoquinoline compound | |
| CN116410126A (en) | Ligand, ruthenium complex, preparation method thereof and application of ligand and ruthenium complex in catalyzing alkyne semi-hydrogenation reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |