CN115772105B - Synthesis method of 4-nitroanisole - Google Patents
Synthesis method of 4-nitroanisole Download PDFInfo
- Publication number
- CN115772105B CN115772105B CN202211391614.8A CN202211391614A CN115772105B CN 115772105 B CN115772105 B CN 115772105B CN 202211391614 A CN202211391614 A CN 202211391614A CN 115772105 B CN115772105 B CN 115772105B
- Authority
- CN
- China
- Prior art keywords
- nitroanisole
- reaction
- dimethyl sulfoxide
- parts
- ethyl acetate
- 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
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000001308 synthesis method Methods 0.000 title description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- 235000003270 potassium fluoride Nutrition 0.000 claims abstract description 21
- 239000011698 potassium fluoride Substances 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 120
- -1 4-nitroanisole sulfide Chemical compound 0.000 claims description 28
- 239000012295 chemical reaction liquid Substances 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000605 extraction Methods 0.000 claims description 13
- 239000012074 organic phase Substances 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 9
- 238000010025 steaming Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical group [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000010189 synthetic method Methods 0.000 claims description 4
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 238000009776 industrial production Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 description 4
- SCCCFNJTCDSLCY-UHFFFAOYSA-N 1-iodo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(I)C=C1 SCCCFNJTCDSLCY-UHFFFAOYSA-N 0.000 description 4
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- FYFDQJRXFWGIBS-UHFFFAOYSA-N 1,4-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=C([N+]([O-])=O)C=C1 FYFDQJRXFWGIBS-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- KFIMOMYDCZFXKC-UHFFFAOYSA-N (4-methylphenyl)-oxido-sulfanylideneazanium Chemical compound CC1=CC=C([N+]([O-])=S)C=C1 KFIMOMYDCZFXKC-UHFFFAOYSA-N 0.000 description 1
- XONGBDXIFQIQBN-UHFFFAOYSA-N 1-methylsulfonyl-4-nitrobenzene Chemical compound CS(=O)(=O)C1=CC=C([N+]([O-])=O)C=C1 XONGBDXIFQIQBN-UHFFFAOYSA-N 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000005181 nitrobenzenes Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003637 steroidlike 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for synthesizing 4-nitroanisole. The p-nitrochlorobenzene, potassium fluoride and dimethyl sulfoxide are used as raw materials, and 4-nitroanisole is generated by reaction under the action of a catalyst. The 4-nitroanisole synthesis process has the advantages of wide sources and low cost, mild reaction conditions, relatively simple process, conventional operation of each step of reaction and higher product yield. The method meets the basic requirement of industrial production of 4-nitroanisole.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a method for synthesizing 4-nitroanisole sulfide by taking p-nitrochlorobenzene and potassium fluoride as raw materials and reacting in dimethyl sulfoxide.
Background
4-Nitroanisole, also known as p-methylthionitrobenzene and p-nitrotoluene thioether, is a pale yellow to brown yellow solid at normal temperature, is easily dissolved in organic solvents such as ethyl acetate and the like, and has a structural formula shown as a formula S-1. 4-nitroanisole has wide application and is a common intermediate for fine chemical engineering such as medicines, pesticides, veterinary medicines and the like. For example, 4-nitroanisole is reduced by hydrogenation to obtain 4-amino anisole, which is one of the important raw materials of non-steroidal drug Ai Shali ketone (patent CN 114456098).
Literature (Journal of Fluorine Chemistry,245,109778; 2021) reports the preparation of 4-nitroanisole by reacting p-nitrofluorobenzene with dimethyldisulfide; literature (Tetrahedron Letters,56 (37), 5199-5202; 2015) reports the preparation of 4-nitroanisole by reaction of p-nitroiodobenzene or p-nitrobromobenzene with dimethylsulfoxide under the catalysis of cuprous iodide/triethylenediamine; literature (Tetrahedron Letters,56 (38)), 5323-5326;2014 reports the preparation of 4-nitroanisole by reacting p-nitrofluorobenzene or p-nitrochlorobenzene or p-dinitrobenzene with dimethyl sulfoxide under the catalysis of N, N-diisopropylethylamine, wherein the yield of the target product of the reaction using p-nitrochlorobenzene as a substrate is only 49%. In the synthetic route, the nitrobenzene derivatives (p-fluoronitrobenzene, p-bromonitrobenzene, p-iodonitrobenzene and p-dinitrobenzene) and the catalyst used as raw materials are expensive, have high cost or have low product yield (for example, p-chloronitrobenzene is used as a substrate). The literature (Phosphorus, sulfur and Silicon AND THE RELATED ELEMENTS,190 (7), 1169-1176; 2015) uses 1-methanesulfonyl 4-nitrobenzene to synthesize 4-nitroanisole sulfide, which is expensive and unsuitable for industrial production. Other methods for preparing 4-nitroanisole by reacting p-nitroiodobenzene or p-nitrobromobenzene or p-nitrochlorobenzene with dimethyl sulfoxide have been reported. In the synthetic route, the price of the p-nitroiodobenzene or the p-nitrobromobenzene is high, and the synthetic route is not suitable for industrial production; the p-nitrochlorobenzene is used as raw material, and has low yield and long reaction time, which is also unfavorable for industrial production.
In summary, the existing synthetic schemes of 4-nitroanisole have certain defects and shortages, so that the development of a synthetic process with high yield, low cost and simple process is significant for the industrial production of 4-nitroanisole.
Disclosure of Invention
The invention aims to provide a novel synthesis method of 4-nitroanisole,
The technical scheme of the invention is as follows:
a synthetic method of 4-nitroanisole comprises the following steps: the p-nitrochlorobenzene, potassium fluoride and dimethyl sulfoxide are used as raw materials, and 4-nitroanisole is generated by reaction under the action of a catalyst.
Preferably, the proportion of nitrochlorobenzene, potassium fluoride and dimethyl sulfoxide is 10-15 parts of potassium fluoride in mass ratio: 10-20 parts of p-nitrochlorobenzene: 30-100 parts of dimethyl sulfoxide.
Preferably, the reaction temperature is 185-220 ℃ and the reaction time is 12-15 h.
Preferably, the catalyst is tetramethyl ammonium chloride or polyethylene glycol 2000.
Preferably, the catalyst is used in an amount of 1 to 30 parts.
The other technical scheme of the invention is as follows:
a synthetic method of 4-nitroanisole comprises the following steps:
10-15 parts of potassium fluoride, 10-20 parts of paranitrochlorobenzene, 1-30 parts of catalyst and 30-100 parts of dimethyl sulfoxide are added into a reactor for reaction, the reaction temperature is 185-220 ℃, and the reaction time is 12-15 hours, so that the target product 4-nitroanisole is produced.
Preferably, after the target product 4-nitroanisole is produced, a product extraction step and a purification step are further included.
Preferably, the product extraction step includes:
After the reaction is finished, decompressing and steaming to remove the residual dimethyl sulfoxide in the reaction liquid, adding a proper amount of water and ethyl acetate into the reaction liquid for washing and extraction, and removing the ethyl acetate in the obtained organic phase to obtain a crude product of the 4-nitroanisole sulfide;
Preferably, the purification step is to purify the obtained 4-nitroanisole crude product to obtain the product 4-nitroanisole.
Preferably, the purification method employs recrystallization or rectification.
In the invention, in dimethyl sulfoxide solvent, p-nitrochlorobenzene and potassium fluoride react under the catalysis of a catalyst to generate a fluorine-containing intermediate (the obtained intermediate does not need to be separated), and the obtained intermediate further reacts with dimethyl sulfoxide to obtain the target product 4-nitroanisole sulfide. The reaction equation is shown as S-2.
The synthetic products of the invention can be analyzed by NMR.
Compared with the prior art, the invention has the beneficial effects that:
The 4-nitroanisole prepared by the method of the invention takes paranitrochlorobenzene and potassium fluoride as main raw materials, dimethyl sulfoxide as a sulfur methylation reagent and a solvent, and can be obtained with higher yield under milder reaction conditions. The process has low cost of raw materials, simple reaction and post-treatment process, and the yield of the target product is close to 90% under the condition of better process. Compared with the prior art, the method has the advantages of low raw material cost, convenient operation, high yield, simple post-treatment process and the like, and is a method for preparing the 4-nitroanisole sulfide with high efficiency and low cost.
Drawings
The following is a further detailed description of specific embodiments of the invention with reference to the accompanying drawings
FIG. 1 is a nuclear magnetic resonance spectrum of 4-nitroanisole of example 3 of the present invention.
FIG. 2 is a nuclear magnetic resonance spectrum of 4-nitroanisole of example 3 of the present invention.
Detailed Description
The invention discloses a method for synthesizing 4-nitroanisole, which comprises the following steps: the p-nitrochlorobenzene, potassium fluoride and dimethyl sulfoxide are used as raw materials, and 4-nitroanisole is generated by reaction under the action of a catalyst.
Preferably, the proportion of nitrochlorobenzene, potassium fluoride and dimethyl sulfoxide is 10-15 parts of potassium fluoride in mass ratio: 10-20 parts of p-nitrochlorobenzene: 30-100 parts of dimethyl sulfoxide.
Example 1
(1) 1.0G of potassium fluoride, 1.2g of paranitrochlorobenzene, 0.18g of tetramethyl ammonium chloride and 5.5g of dimethyl sulfoxide are weighed in a heatable pressure-resistant reactor, and are heated to 220 ℃ in an oil bath to be stirred and reacted for 15 hours;
(2) After the reaction is finished, reducing the temperature, decompressing and steaming to remove the residual dimethyl sulfoxide in the reaction liquid, then adding 50ml of water and 15ml of ethyl acetate into the reaction liquid for washing and extraction, extracting the obtained water phase with ethyl acetate for 2 times (15 ml of ethyl acetate is used each time), removing the solvent ethyl acetate in the obtained organic phase to obtain 1.3g of crude 4-nitroanisole sulfide, and further purifying the crude 4-nitroanisole sulfide to obtain 1.15g of 4-nitroanisole sulfide with the yield of 89.2%;
The reaction is extracted, distilled, removed from ethyl acetate, cooled to room temperature and then a gelatinous mixture, which can be further purified by rectification or recrystallization.
Example 2
(1) 1.0G of potassium fluoride, 1.2g of paranitrochlorobenzene, 0.18g of tetramethyl ammonium chloride and 5.5g of dimethyl sulfoxide are weighed in a heatable pressure-resistant reactor, and are heated to 220 ℃ in an oil bath to be stirred and reacted for 12 hours;
(2) After the reaction is finished, reducing the temperature, decompressing and steaming to remove the rest dimethyl sulfoxide in the reaction liquid, then adding 50ml of water and 15ml of ethyl acetate into the reaction liquid for washing and extraction, extracting the obtained water phase with ethyl acetate for 2 times (15 ml of ethyl acetate is used each time), removing the ethyl acetate solvent in the obtained organic phase to obtain 1.3g of crude 4-nitroanisole sulfide, and further purifying the crude 4-nitroanisole sulfide to obtain 1.06g of 4-nitroanisole sulfide with the yield of 82.2%;
The reaction is extracted, distilled, removed from ethyl acetate, cooled to room temperature and then a gelatinous mixture, which can be further purified by rectification or recrystallization.
Example 3
(1) Weighing 0.9g of potassium fluoride, 1.2g of paranitrochlorobenzene, 0.17g of tetramethyl ammonium chloride and 5.5g of dimethyl sulfoxide in a heatable pressure-resistant reactor, heating to 220 ℃ in an oil bath, and stirring for reaction for 12 hours;
(2) After the reaction is finished, reducing the temperature, decompressing and steaming to remove the residual dimethyl sulfoxide in the reaction liquid, then adding 50ml of water and 15ml of ethyl acetate into the reaction liquid for washing and extraction, extracting the obtained water phase with ethyl acetate for 2 times (15 ml of ethyl acetate is used each time), removing the ethyl acetate solvent in the obtained organic phase to obtain 1.3g of crude 4-nitroanisole sulfide, and further purifying the crude 4-nitroanisole sulfide to obtain 1.07g of 4-nitroanisole sulfide with the yield of 83.0%;
The reaction is extracted, distilled, removed from ethyl acetate, cooled to room temperature and then a gelatinous mixture, which can be further purified by rectification or recrystallization.
Example 4
(1) 1.0G of potassium fluoride, 1.2g of paranitrochlorobenzene, 0.18g of tetramethyl ammonium chloride and 5.5g of dimethyl sulfoxide are weighed in a heatable pressure-resistant reactor, and are heated to 185 ℃ in an oil bath to be stirred and reacted for 12 hours;
(2) After the reaction is finished, reducing the temperature, decompressing and steaming to remove the residual dimethyl sulfoxide in the reaction liquid, then adding 50ml of water and 15ml of ethyl acetate into the reaction liquid for washing and extraction, extracting the obtained water phase with ethyl acetate for 2 times (15 ml of ethyl acetate is used each time), removing the ethyl acetate solvent in the obtained organic phase to obtain 1.0g of crude 4-nitroanisole sulfide, and further purifying the crude 4-nitroanisole sulfide to obtain 0.62g of 4-nitroanisole sulfide with the yield of 48.0%;
The reaction is extracted, distilled, removed from ethyl acetate, cooled to room temperature and then a gelatinous mixture, which can be further purified by rectification or recrystallization.
Example 5
(1) 1.0G of potassium fluoride, 1.2g of p-nitrochlorobenzene, 3.2g of polyethylene glycol 2000 and 5.5g of dimethyl sulfoxide are weighed in a heatable pressure-resistant reactor, heated to 220 ℃ in an oil bath, stirred and reacted for 15 hours;
(2) After the reaction is finished, reducing the temperature, decompressing and steaming to remove the rest dimethyl sulfoxide in the reaction liquid, then adding 50ml of water and 15ml of ethyl acetate into the reaction liquid for washing and extraction, extracting the obtained water phase with ethyl acetate for 2 times (15 ml of ethyl acetate is used each time), removing the ethyl acetate solvent in the obtained organic phase to obtain 1.2g of crude 4-nitroanisole sulfide, and further purifying the crude 4-nitroanisole sulfide to obtain 0.96g of 4-nitroanisole sulfide with the yield of 74.5%;
The reaction is extracted, distilled, removed from ethyl acetate, cooled to room temperature and then a gelatinous mixture, which can be further purified by rectification or recrystallization.
Example 6
(1) 1.0G of potassium fluoride, 1.2g of p-nitrochlorobenzene, 3.2g of polyethylene glycol 2000 and 5.5g of dimethyl sulfoxide are weighed in a heatable pressure-resistant reactor, heated to 220 ℃ in an oil bath, stirred and reacted for 12 hours;
(2) After the reaction is finished, reducing the temperature, decompressing and steaming to remove the rest dimethyl sulfoxide in the reaction liquid, then adding 50ml of water and 15ml of ethyl acetate into the reaction liquid for washing and extraction, extracting the obtained water phase with ethyl acetate for 2 times (15 ml of ethyl acetate is used each time), removing the ethyl acetate solvent in the obtained organic phase to obtain 1.2g of crude 4-nitroanisole sulfide, and further purifying the crude 4-nitroanisole sulfide to obtain 0.87g of 4-nitroanisole sulfide with the yield of 67.5%;
The reaction is extracted, distilled, removed from ethyl acetate, cooled to room temperature and then a gelatinous mixture, which can be further purified by rectification or recrystallization.
Example 7
(1) Weighing 0.8g of potassium fluoride, 1.2g of paranitrochlorobenzene, 0.6g of polyethylene glycol 2000 and 5.5g of dimethyl sulfoxide in a heatable pressure-resistant reactor, heating to 220 ℃ in an oil bath, and stirring for reaction for 12 hours;
(2) After the reaction is finished, reducing the temperature, decompressing and steaming to remove the residual dimethyl sulfoxide in the reaction liquid, then adding 50ml of water and 15ml of ethyl acetate into the reaction liquid for washing and extraction, extracting the obtained water phase with ethyl acetate for 2 times (15 ml of ethyl acetate is used each time), removing the ethyl acetate solvent in the obtained organic phase to obtain 1.2g of crude 4-nitroanisole sulfide, and further purifying the crude 4-nitroanisole sulfide to obtain 0.89g of 4-nitroanisole sulfide with the yield of 69.0%;
The reaction is extracted, distilled, removed from ethyl acetate, cooled to room temperature and then a gelatinous mixture, which can be further purified by rectification or recrystallization.
The foregoing is only a few specific examples of the invention. Obviously, the invention is not limited to the above embodiments, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.
Claims (8)
1. A synthetic method of 4-nitroanisole comprises the following steps: using paranitrochlorobenzene, potassium fluoride and dimethyl sulfoxide as raw materials, and reacting under the action of a catalyst to generate 4-nitroanisole; the catalyst is tetramethyl ammonium chloride or polyethylene glycol 2000.
2. The method for synthesizing 4-nitroanisole as claimed in claim 1, wherein the proportion of nitrochlorobenzene, potassium fluoride and dimethyl sulfoxide is 10-15 parts by mass: 10-20 parts of p-nitrochlorobenzene: 30-100 parts of dimethyl sulfoxide.
3. The method for synthesizing 4-nitroanisole as claimed in claim 1, wherein the reaction temperature is 185-220 ℃ and the reaction time is 12-15 h.
4. A synthetic method of 4-nitroanisole comprises the following steps:
10-15 parts of potassium fluoride, 10-20 parts of paranitrochlorobenzene, 1-30 parts of catalyst and 30-100 parts of dimethyl sulfoxide are added into a reactor for reaction, the reaction temperature is 185-220 ℃, and the reaction time is 12-15 h to generate the target product 4-nitroanisole; the catalyst is tetramethyl ammonium chloride or polyethylene glycol 2000.
5. The method for synthesizing 4-nitroanisole as defined in claim 4, wherein: after the target product 4-nitroanisole is generated, the method also comprises a product extraction step and a purification step.
6. The method for synthesizing 4-nitroanisole as defined in claim 5, wherein: the product extraction step comprises the following steps:
And after the reaction is finished, decompressing and steaming to remove the residual dimethyl sulfoxide in the reaction liquid, adding a proper amount of water and ethyl acetate into the reaction liquid for washing and extraction, and removing the ethyl acetate in the obtained organic phase to obtain a crude product of the 4-nitroanisole sulfide.
7. The method for synthesizing 4-nitroanisole as defined in claim 6, wherein: the purification step is to purify the obtained crude 4-nitroanisole product to obtain the product 4-nitroanisole.
8. The method for synthesizing 4-nitroanisole as defined in claim 5, wherein: the purification step is carried out by adopting recrystallization or rectification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211391614.8A CN115772105B (en) | 2022-11-08 | 2022-11-08 | Synthesis method of 4-nitroanisole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211391614.8A CN115772105B (en) | 2022-11-08 | 2022-11-08 | Synthesis method of 4-nitroanisole |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115772105A CN115772105A (en) | 2023-03-10 |
| CN115772105B true CN115772105B (en) | 2024-06-11 |
Family
ID=85388874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211391614.8A Active CN115772105B (en) | 2022-11-08 | 2022-11-08 | Synthesis method of 4-nitroanisole |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115772105B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731352A (en) * | 2012-06-09 | 2012-10-17 | 浙江大学 | Preparation method of 4-methylthio benzaldehyde |
-
2022
- 2022-11-08 CN CN202211391614.8A patent/CN115772105B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731352A (en) * | 2012-06-09 | 2012-10-17 | 浙江大学 | Preparation method of 4-methylthio benzaldehyde |
Non-Patent Citations (2)
| Title |
|---|
| A Facile Route to Unsymmetrical Sulfide;Ying Hong ZHU 等;Chinese Chemical Letters;第14卷(第3期);第236-237页 Experiments and Results * |
| Copper-mediated methylthiolation of aryl halides with DMSO;Fang Luo 等;ChemComm;第47卷;5304-5306 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115772105A (en) | 2023-03-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114349674B (en) | Thiourea compound and preparation method thereof | |
| KR20110011917A (en) | Process for preparing of n-methyl pyrrolidone | |
| CN113444039B (en) | Method for preparing 2,2, 4-trimethyl-1, 2-dihydroquinoline by using ionic liquid | |
| CN115772105B (en) | Synthesis method of 4-nitroanisole | |
| US10414710B1 (en) | Method for manufacturing adipic acid using biomass | |
| CN113443950B (en) | Method for reducing carbonyl into methylene under illumination | |
| CN111704591B (en) | Synthesis method of copper-catalyzed thionaphthothiazolone compound | |
| CN107573263B (en) | Synthetic method of omega-substituted biuret compound | |
| CN110734354B (en) | Method for preparing biaryl compound from alcohol compound | |
| CN109232359B (en) | Synthesis method of nitramide | |
| AU2018241298B2 (en) | Method for the synthesis of 9,10-bis(chloromethyl)anthracene | |
| CN107513078B (en) | Preparation method of 2, 6-diaminopyridine condensed 3-carboxybenzaldehyde bis-Schiff base cobalt complex | |
| EP1468983B1 (en) | Process for producing 2,5-bis(trifluoromethyl)nitrobenzene | |
| CN117050010B (en) | Synthesis method of 2,2' -biquinoline and derivatives thereof | |
| CN115925554B (en) | Synthesis method of N-trifluoromethyl amine | |
| CN112625015B (en) | Preparation method of 2- (1, 3-dihydro-2-isobenzofuran) -1-acetophenone compound | |
| CN110452138B (en) | Method for preparing N-phenyl-3-methylsulfonyl propionamide | |
| CN115322070B (en) | Preparation method of p-alkylphenyl o-fluorobenzene | |
| CN115417799B (en) | Thiourea compound and preparation method thereof | |
| CN109970701B (en) | By using I2O5/NaNO2Process for nitrating electron-rich aromatic compounds | |
| CN115784895B (en) | Method for preparing arylamine compound by nonmetal reduction of aryl nitro compound | |
| JPS60237039A (en) | Benzalacetophenone, its derivative and their production | |
| CN115073285A (en) | Synthetic method of 3, 5-diiodo salicyloyl chloride | |
| CN116396180A (en) | Preparation method of formamide compound | |
| CN118652198A (en) | Synthesis method and application of renewable energy source induced urea |
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 |