CN115636733A - Preparation method of high-selectivity 4-chloro-2-methylphenol - Google Patents
Preparation method of high-selectivity 4-chloro-2-methylphenol Download PDFInfo
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- CN115636733A CN115636733A CN202211197071.6A CN202211197071A CN115636733A CN 115636733 A CN115636733 A CN 115636733A CN 202211197071 A CN202211197071 A CN 202211197071A CN 115636733 A CN115636733 A CN 115636733A
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- methylphenol
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- hydrochloric acid
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- RHPUJHQBPORFGV-UHFFFAOYSA-N 4-chloro-2-methylphenol Chemical compound CC1=CC(Cl)=CC=C1O RHPUJHQBPORFGV-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 54
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims abstract description 43
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 23
- 239000004094 surface-active agent Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims description 34
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000012295 chemical reaction liquid Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000012044 organic layer Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 244000060011 Cocos nucifera Species 0.000 claims description 4
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 4
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical group CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000460 chlorine Substances 0.000 abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000002209 hydrophobic effect Effects 0.000 abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 238000003780 insertion Methods 0.000 abstract description 2
- 230000037431 insertion Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 8
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WJQZZLQMLJPKQH-UHFFFAOYSA-N 2,4-dichloro-6-methylphenol Chemical compound CC1=CC(Cl)=CC(Cl)=C1O WJQZZLQMLJPKQH-UHFFFAOYSA-N 0.000 description 1
- YPNZJHFXFVLXSE-UHFFFAOYSA-N 2-chloro-6-methylphenol Chemical compound CC1=CC=CC(Cl)=C1O YPNZJHFXFVLXSE-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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Classifications
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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
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a preparation method of high-selectivity 4-chloro-2-methylphenol, which relates to the technical field of organic synthesis, and is characterized in that 2-methylphenol is used as a raw material, copper chloride is used as a chlorine source, a surfactant is used as a catalyst to prepare 4-chloro-2-methylphenol, the hydrophobic end of the surfactant and the methyl of the 2-methylphenol are utilized to form an intermolecular C-H bond, the steric hindrance of the hydroxyl ortho position is increased, the para insertion of chlorine atoms is effectively improved, and the 4-chloro-2-methylphenol is efficiently prepared; the technology has high para-position selectivity, simple post-treatment, higher environmental protection and easier industrialization, and the solvent hydrochloric acid can be used mechanically after simple treatment.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of high-selectivity 4-chloro-2-methylphenol.
Background
4-chloro-2-methylphenol has wide application, is an important chemical raw material for organic synthesis and fine chemical intermediates, and is widely applied to various fields of medicines, pesticides, solvents, dyes, pigments, mildewproof agents, surfactants, spices and the like. The synthesis method comprises the steps of introducing chlorine gas under the action of Lewis acid (lithium chloride, copper chloride and aluminum chloride) to generate a mixture of 4-chloro-2-methylphenol, 6-chloro-2-methylphenol and 4, 6-dichloro-2-methylphenol, and has low reaction selectivity and high rectification cost due to small difference between boiling points of raw materials and products. The preparation of 4-chloro-2-methylphenol proposed in US patent 2494993 can be purified by secondary distillation, but the process gives low product yield and purity. US patent 4429168 reports that monochlorophenol can be isolated by complexation with compounds, but this process is too costly to be suitable for industrial production. It has been reported in the Japanese literature (Japanese society for chemical industries, 1987, (9): 1753-1755) that cuprous chloride produced by the reaction is converted into copper chloride again by the action of chlorine gas, which is introduced into an aqueous hydrochloric acid solution of phenol and copper chloride, and reacted at a high temperature, and hydrochloric acid is also produced as a by-product. The process has the main problems that the solubility of chlorine in water is low, a large amount of chlorine needs to be introduced, the chlorine has strong oxidizability and corrosivity and is easy to leak, the chlorine is one of the most dangerous chemicals in China, and meanwhile, the process needs to add large excess copper chloride, and the yield can only reach 81.8%.
Therefore, starting from the reaction, the method improves the para-selectivity of 2-methylphenol, reduces the complicated post-treatment process, and is the key point for the investigation of the people.
Disclosure of Invention
Aiming at the technical defects, the invention provides a preparation method of high-selectivity 4-chloro-2-methylphenol.
In order to realize the purpose, the technical scheme of the invention is as follows:
a preparation method of high-selectivity 4-chloro-2-methylphenol comprises the following steps:
the mass ratio of the 2-methylphenol, the hydrochloric acid, the copper chloride and the surfactant is 1: 50-100: 1-10 parts of;
the mass concentration of the hydrochloric acid is 25-36.5%;
the surfactant is nonylphenol polyoxyethylene ether, sodium dodecyl sulfate, coconut diethanolamide or sodium dodecyl benzene sulfonate;
the organic solvent is dichloromethane, ethyl acetate or toluene;
said step (c) is
The mass ratio of the obtained reaction liquid to the organic solvent is 1:10 to 30.
The synthetic route of the high-selectivity 4-chloro-2-methylphenol is as follows:
preferably, step (ii)
The mass ratio of the 2-methylphenol, the hydrochloric acid, the copper chloride and the surfactant is 1:65:1.2:0.03.
Preferably, step (ii)
Wherein the mass concentration of the hydrochloric acid is 30%.
Preferably, step (ii)
Wherein the reaction temperature is 90 ℃.
Preferably, step (ii)
The reaction time in (1) is 10h.
Preferably, step (ii)
Wherein the surfactant is sodium dodecyl benzene sulfonate.
Preferably, step (ii)
Wherein the organic solvent is dichloromethane.
The invention has the following beneficial effects:
the preparation method of the high-selectivity 4-chloro-2-methylphenol uses 2-methylphenol as a raw material, copper chloride as a chlorine source and a surfactant as a catalyst to prepare the 4-chloro-2-methylphenol. According to the method, the hydrophobic end of the surfactant and the 2-methylphenol methyl form an intermolecular C-H bond, so that a large steric hindrance is formed around the phenolic hydroxyl, the para-insertion of chlorine atoms is effectively controlled, and the 4-chloro-2-methylphenol is efficiently prepared. The technology has high para-selectivity, simple post-treatment, higher environmental protection and easier industrialization, and the solvent hydrochloric acid can be used mechanically after being simply treated.
Drawings
FIG. 1 is a diagram showing the methyl interaction between the hydrophobic end of the surfactant used in the present invention and 2-methylphenol.
Detailed Description
The technical solutions of the present invention will be described in further detail below by way of specific embodiments in the form of examples, but it should not be construed that the scope of the above-described subject matter of the present invention is limited to the examples below. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
A preparation method of high-selectivity 4-chloro-2-methylphenol comprises the following steps:
the mass ratio of the 2-methylphenol, the hydrochloric acid, the copper chloride and the surfactant is 1: 50-100: 1-10 parts of;
the mass concentration of the hydrochloric acid is 25-36.5%;
the surfactant is nonylphenol polyoxyethylene ether, sodium dodecyl sulfate, coconut diethanolamide or sodium dodecyl benzene sulfonate;
the organic solvent is dichloromethane, ethyl acetate or toluene;
said step (c) is
The mass ratio of the obtained reaction liquid to the organic solvent is 1:10 to 30.
According to the method, copper chloride is used as a chlorine source, hydrochloric acid is used as a solvent, a surfactant is added, so that a hydrophobic end of the copper chloride and a methyl form an intermolecular C-H bond, the steric hindrance of the ortho position of a phenolic hydroxyl group is increased, the interaction of the surfactant and the methyl is shown in figure 1, chloride ions are easy to attack the para position, the 2-methylphenol para-position chlorination reaction is further increased, and the selectivity is improved. Compared with the reported technology, the whole reaction process is carried out in a water phase under normal pressure, the yield of the 4-chloro-2-methylphenol is higher than 95%, the reaction solvent hydrochloric acid can be simply treated and then used, and the technical advantage is obvious.
Preferably, step (ii)
Wherein the mass ratio of the 2-methylphenol, the hydrochloric acid, the copper chloride and the surfactant is 1:65:1.2:0.03.
Preferably, step (ii)
Wherein the mass concentration of the hydrochloric acid is 30%.
Preferably, the step
Wherein the reaction temperature is 90 ℃.
Preferably, the step
The reaction time in (1) is 10h.
Preferably, step (ii)
Wherein the surfactant is sodium dodecyl benzene sulfonate.
Preferably, step (ii)
Wherein the organic solvent is dichloromethane.
Example 1
Adding 3.2kg of 2-methylphenol, 208kg of hydrochloric acid (with the mass concentration of 30%) and 3.84kg of copper chloride into a reaction kettle, then adding 0.096kg of sodium dodecyl benzene sulfonate, stirring and heating to 90 ℃, and reacting for 10 hours to obtain a reaction solution; after the reaction is finished, cooling the reaction liquid to 25 ℃, standing for 50min, extracting for 3 times by using dichloromethane, collecting an organic layer, and concentrating to obtain 4.1kg of light yellow solid, wherein the yield is 98.5%, and the purity of the product is 99.4%.
Example 2
Adding 3.2kg of 2-methylphenol, 160kg of hydrochloric acid (with the mass concentration of 25%) and 3.2kg of copper chloride into a reaction kettle, then adding 0.03kg of nonylphenol polyoxyethylene ether, stirring and heating to 60 ℃, and reacting for 6 hours to obtain a reaction solution; after the reaction is finished, cooling the reaction liquid to 25 ℃, standing for 30min, extracting for 3 times by using ethyl acetate, collecting an organic layer, and concentrating to obtain 4.0kg of light yellow solid, wherein the yield is 95.4%, and the purity of the product is 99.3%.
Example 3
Adding 3.2kg of 2-methylphenol, 320kg of hydrochloric acid (the mass concentration is 36.5%) and 32kg of copper chloride into a reaction kettle, then adding 112kg of coconut diethanolamide, stirring and heating to 95 ℃, and reacting for 14 hours to obtain a reaction solution; after the reaction is finished, the reaction liquid is cooled to 30 ℃, kept stand for 60min, extracted for 5 times by using toluene, an organic layer is collected and concentrated to obtain 3.9kg of light yellow solid, the yield is 93.2%, and the product purity is 99.0%.
Example 4
Adding 3.2kg of 2-methylphenol, 192kg of hydrochloric acid (with the mass concentration of 30%) and 16kg of copper chloride into a reaction kettle, then adding 32kg of sodium dodecyl sulfate, stirring and heating to 70 ℃, and reacting for 8 hours to obtain a reaction solution; after the reaction is finished, the reaction liquid is cooled to 27 ℃, kept stand for 60min, extracted for 4 times by using dichloromethane, an organic layer is collected and concentrated to obtain 4.04kg of light yellow solid, the yield is 96.2 percent, and the product purity is 99.3 percent.
Example 5
Adding 3.2kg of 2-methylphenol, 224kg of hydrochloric acid (the mass concentration is 33%) and 22.4kg of copper chloride into a reaction kettle, then adding 64kg of sodium dodecyl sulfate, stirring and heating to 85 ℃, and reacting for 9 hours to obtain a reaction solution; after the reaction is finished, cooling the reaction liquid to 26 ℃, standing for 45min, extracting for 3 times by using toluene, collecting an organic layer, and concentrating to obtain 4.03kg of light yellow solid, wherein the yield is 96.0 percent, and the purity of the product is 99.4 percent.
Example 6
Adding 3.2kg of 2-methylphenol, 288kg of hydrochloric acid (the mass concentration is 35%) and 28.8kg of copper chloride into a reaction kettle, then adding 96kg of sodium dodecyl sulfate, stirring and heating to 90 ℃, and reacting for 12 hours to obtain a reaction solution; after the reaction is finished, cooling the reaction liquid to 29 ℃, standing for 40min, extracting for 5 times by using ethyl acetate, collecting an organic layer, and concentrating to obtain 4.02kg of light yellow solid, wherein the yield is 95.8 percent, and the purity of the product is 99.3 percent.
Although the present invention has been described with reference to the specific embodiments, it is not intended to limit the scope of the present invention, and various modifications and variations can be made by those skilled in the art without inventive changes based on the technical solution of the present invention.
Claims (7)
1. A preparation method of high-selectivity 4-chloro-2-methylphenol is characterized by comprising the following steps: the method comprises the following steps:
the mass ratio of the 2-methylphenol, the hydrochloric acid, the copper chloride and the surfactant is 1: 1-10 parts of;
the mass concentration of the hydrochloric acid is 25-36.5%;
the surfactant is nonylphenol polyoxyethylene ether, sodium dodecyl sulfate, coconut diethanolamide or sodium dodecyl benzene sulfonate;
the organic solvent is dichloromethane, ethyl acetate or toluene;
said step (c) is
The mass ratio of the obtained reaction liquid to the organic solvent is 1:10 to 30.
2. The process for producing 4-chloro-2-methylphenol with high selectivity according to claim 1, wherein: step (ii) of
Wherein the mass ratio of the 2-methylphenol, the hydrochloric acid, the copper chloride and the surfactant is 1: 1.2:0.03.
3. The process for producing 4-chloro-2-methylphenol with high selectivity according to claim 1, wherein: step (ii) of
Wherein the mass concentration of the hydrochloric acid is 30%.
4. The process for producing 4-chloro-2-methylphenol with high selectivity according to claim 1, wherein: step (ii) of
Wherein the reaction temperature is 90 ℃.
5. The process for producing 4-chloro-2-methylphenol with high selectivity according to claim 1, wherein: step (ii) of
The reaction time in (1) is 10h.
6. The process for producing 4-chloro-2-methylphenol with high selectivity according to claim 1, wherein: step (ii) of
Wherein the surfactant is sodium dodecyl benzene sulfonate.
7. The process for producing 4-chloro-2-methylphenol with high selectivity according to claim 1, wherein: step (ii) of
Wherein the organic solvent is dichloromethane.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5436221A (en) * | 1977-08-23 | 1979-03-16 | Mitsui Toatsu Chem Inc | Preparation of parachlorophenol |
| CN1761651A (en) * | 2003-01-20 | 2006-04-19 | 拜尔农作物科学股份公司 | 2,4-dihalogen-6-(c2-c3-alkyl)-phenyl substituted tetramic acid derivatives |
| KR20130117316A (en) * | 2012-04-18 | 2013-10-25 | 주식회사 한남코퍼레이션 | A method for preparing 3-amino-6-chlorotoluene-4-sulfonic acid |
| CN105503626A (en) * | 2015-12-12 | 2016-04-20 | 常州大学 | Synthesis method of 2-amino-4-chloro-6-metoxyphenol |
| CN107963961A (en) * | 2017-12-13 | 2018-04-27 | 南京大学扬州化学化工研究院 | A kind of preparation method of parachlorophenol |
-
2022
- 2022-09-29 CN CN202211197071.6A patent/CN115636733A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5436221A (en) * | 1977-08-23 | 1979-03-16 | Mitsui Toatsu Chem Inc | Preparation of parachlorophenol |
| CN1761651A (en) * | 2003-01-20 | 2006-04-19 | 拜尔农作物科学股份公司 | 2,4-dihalogen-6-(c2-c3-alkyl)-phenyl substituted tetramic acid derivatives |
| KR20130117316A (en) * | 2012-04-18 | 2013-10-25 | 주식회사 한남코퍼레이션 | A method for preparing 3-amino-6-chlorotoluene-4-sulfonic acid |
| CN105503626A (en) * | 2015-12-12 | 2016-04-20 | 常州大学 | Synthesis method of 2-amino-4-chloro-6-metoxyphenol |
| CN107963961A (en) * | 2017-12-13 | 2018-04-27 | 南京大学扬州化学化工研究院 | A kind of preparation method of parachlorophenol |
Non-Patent Citations (2)
| Title |
|---|
| 刘江等: ""对氯苯酚合成新方法"", 陕西化工, no. 1, pages 11 - 13 * |
| 吴飞: ""3, 5-二甲基苯酚氧化氯化合成4-氯-3, 5-二甲苯酚的工艺研究"", 中国优秀硕士学位论文全文数据库工程科技I辑, no. 05, pages 016 - 43 * |
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