CN115433060A - Preparation method of monochlorophenol compound - Google Patents
Preparation method of monochlorophenol compound Download PDFInfo
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- CN115433060A CN115433060A CN202211345826.2A CN202211345826A CN115433060A CN 115433060 A CN115433060 A CN 115433060A CN 202211345826 A CN202211345826 A CN 202211345826A CN 115433060 A CN115433060 A CN 115433060A
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- monochlorophenol
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- -1 monochlorophenol compound Chemical class 0.000 title claims description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 82
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims description 95
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 44
- 239000001301 oxygen Substances 0.000 claims description 44
- 229910052760 oxygen Inorganic materials 0.000 claims description 44
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 239000000919 ceramic Substances 0.000 claims description 25
- 239000012982 microporous membrane Substances 0.000 claims description 25
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- 150000002989 phenols Chemical class 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 9
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 7
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical class OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 abstract description 34
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229910001385 heavy metal Inorganic materials 0.000 abstract 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 17
- RHPUJHQBPORFGV-UHFFFAOYSA-N 4-chloro-2-methylphenol Chemical compound CC1=CC(Cl)=CC=C1O RHPUJHQBPORFGV-UHFFFAOYSA-N 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000012320 chlorinating reagent Substances 0.000 description 5
- 238000005660 chlorination reaction Methods 0.000 description 5
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical class OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- OWEGWHBOCFMBLP-UHFFFAOYSA-N 1-(4-chlorophenoxy)-1-(1H-imidazol-1-yl)-3,3-dimethylbutan-2-one Chemical compound C1=CN=CN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 OWEGWHBOCFMBLP-UHFFFAOYSA-N 0.000 description 1
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 1
- HOLHYSJJBXSLMV-UHFFFAOYSA-N 2,6-dichlorophenol Chemical compound OC1=C(Cl)C=CC=C1Cl HOLHYSJJBXSLMV-UHFFFAOYSA-N 0.000 description 1
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- SWFNPENEBHAHEB-UHFFFAOYSA-N 2-amino-4-chlorophenol Chemical compound NC1=CC(Cl)=CC=C1O SWFNPENEBHAHEB-UHFFFAOYSA-N 0.000 description 1
- MJHYMUJODIELHK-UHFFFAOYSA-N [Cl].S(Cl)Cl Chemical compound [Cl].S(Cl)Cl MJHYMUJODIELHK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229960003344 climbazole Drugs 0.000 description 1
- KNHUKKLJHYUCFP-UHFFFAOYSA-N clofibrate Chemical compound CCOC(=O)C(C)(C)OC1=CC=C(Cl)C=C1 KNHUKKLJHYUCFP-UHFFFAOYSA-N 0.000 description 1
- 229960001214 clofibrate Drugs 0.000 description 1
- 208000029078 coronary artery disease Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229940090668 parachlorophenol Drugs 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- GUEIZVNYDFNHJU-UHFFFAOYSA-N quinizarin Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2O GUEIZVNYDFNHJU-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of monochlorophenol compounds, which belongs to the technical field of compound synthesis. The invention consumes hydrochloric acid, can be repeatedly used and can solve the problem that a large amount of industrial byproduct hydrochloric acid is difficult to treat; copper chloride only needs catalytic amount, so that the use of heavy metal is remarkably reduced; the method has mild condition, controllable operation and easy realization of industrialization.
Description
Technical Field
The invention relates to the technical field of compound synthesis, in particular to a preparation method of a monochlorophenol compound.
Background
The chlorinated phenolic compounds are important organic chemical intermediates, and are intermediates of pesticides, medicines and dyes, such as pesticide triadimefon and climbazole; clofibrate, clofazid and cloxazole, which are medicines for treating coronary heart disease; dye intermediates 1, 4-dihydroxyanthraquinone and 5-chloro-2-hydroxyaniline, and the like. Particularly, in recent years, with the development of p-chlorophenol into various novel dyes and intermediates for pharmaceutical synthesis, market demand for chlorophenol compounds at home and abroad is rapidly increasing.
There are three main methods for preparing chlorophenols, depending on the chlorine substitution reagent: chlorine, chlorine-sulfur chloride and copper chloride; wherein the chlorination method is a method adopted by most domestic enterprises, and is characterized in that a phenol compound and chlorine are melted or directly subjected to chlorination reaction in an inert solvent to generate p-chlorophenol, and byproducts of 2-chlorophenol, 2, 4-dichlorophenol, 2,4, 6-dichlorophenol and a small amount of 2, 6-dichlorophenol are produced at the same time. The process of the route is simple, but the selectivity is low, and rectification and purification are required.
The sulfuryl chloride method is to react phenol compound with sulfuryl chloride in AlCl 3 、FeCl 3 、ZnCl 2 And the like under the action of a catalyst. The conversion rate of the p-chlorophenol in the route is improved compared with that in a chlorine method, but a large amount of hydrochloric acid and sulfur dioxide are produced as byproducts, and the metal salt is used as waste after reaction to seriously pollute the environment, so that the technology is gradually eliminated by the market at present along with environmental protection factors and cost reasons.
The copper chloride process, as reported in japanese patent No. JPS5436221, uses copper chloride as a chlorinating agent and hydrochloric acid as a solvent, and reacts at a high pressure of 130 ℃, and the para/ortho ratio in the monochlorinated product reaches 10:1, but has the disadvantages of large dosage of copper chloride, high reaction pressure, high recovery rate, high cost and environmental pollution.
The common technical disadvantage is that a large amount of waste hydrochloric acid is generated, the waste hydrochloric acid is used as hazardous waste to be managed in various countries, and the waste hydrochloric acid is also listed as 'national hazardous waste list (2021 edition)'. At present, the existing phenol chlorination technology cannot meet the national conditions of China, and people are always exploring the synthesis and production of p-chlorophenol compounds by using an efficient and green method. The Gusev-skaya group reported the synthesis of para-chlorophenol by copper chloride as catalyst, oxygen as oxidant and lithium chloride as chlorinating agent (Chem Commun, 2006, 209). The method adopts expensive lithium chloride as a chlorine source, and cannot generate economic benefit.
The Duan and Feng project group subsequently reported the preparation of monochlorophenol (j.chem. Vol. 2016, ID 2960414) using microwave technology with hydrochloric acid as solvent, oxygen as oxidant, and copper chloride as catalyst. The method is novel, can digest a large amount of hydrochloric acid, but needs microwave technology, cannot realize industrialization, and only stays at an experimental stage.
Therefore, research on a preparation method capable of consuming hydrochloric acid and synthesizing chlorophenol with high added value is urgently needed.
Disclosure of Invention
In order to solve the problems that the existing synthesis of chlorinated phenol compound has harsh reaction conditions, is not easy to industrialize and generates a large amount of hydrochloric acid, the invention aims to provide a preparation method of monochlorophenol compound.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of a monochlorophenol compound comprises the following steps: adding a hydrochloric acid solution into a reaction kettle, introducing oxygen into a ceramic microporous membrane tube for 30 minutes to remove the oxygen in the reaction kettle, then adding a phenol compound and copper chloride into the reaction kettle under stirring, heating to 70-100 ℃ after the addition is finished, reacting for 4-12 hours at the temperature, continuously introducing oxygen into the reaction kettle by using the ceramic microporous membrane tube in the whole reaction, and extracting by using an organic solvent after the reaction is finished to obtain a monochlorophenol compound; the phenol compound is phenol or methyl substituted phenol; oxygen enters a reaction system through a ceramic microporous membrane tube to form micro-bubble oxygen in the system, the content of the oxygen in the reaction system is maintained, so that harsh reaction conditions such as microwave are avoided, and a catalytic amount of CuCl is utilized 2 As a catalyst, hydrochloric acid solution is used as a solvent and a chlorinating agent to perform high-selectivity chlorination on the phenol compounds;
the mass concentration of the hydrochloric acid solution is 15 to 37 percent; the organic solvent is dichloromethane, dichloroethane, ethyl acetate or methyl acetate;
wherein the molar ratio of the copper chloride to the phenol compounds is 1:10 to 100; the mass ratio of the phenol compound to the hydrochloric acid solution is 1:5 to 20.
Preferably, the phenol compound is phenol or 2-methylphenol.
Preferably, the organic solvent is dichloromethane.
Preferably, the mass concentration of the hydrochloric acid solution is 30 to 37%.
Preferably, the molar ratio of the phenol compound to the copper chloride is 20:1.
preferably, the mass ratio of the phenol compound to the hydrochloric acid solution is 1:10.
preferably, the reaction temperature is 80 ℃.
Compared with the prior art, the invention has the following advantages:
the preparation method of the monochloro phenol compound takes phenol/substituted phenol as a raw material, hydrochloric acid as a chlorine source and a solvent, copper chloride as a catalyst and oxygen as an oxidant to obtain the monochloro phenol compound, wherein the substitution position of chlorine element is 4-position, and the selectivity is up to 98%;
the preparation method of the monochlorophenol compound can synthesize the monochlorophenol compound with high selectivity, has simple operation method and mild reaction condition, uses the microbubble oxygen to improve the oxygen content in a reaction system, avoids harsh reaction conditions such as microwave and the like, can realize large-scale industrial production, can consume a large amount of industrial byproduct hydrochloric acid on the other hand, and has good economic benefit and social benefit.
Detailed Description
The present invention is directed to a process for the preparation of monochlorophenol compounds, and the invention is further described with reference to the following specific examples.
A preparation method of a monochlorophenol compound comprises the following steps: adding a hydrochloric acid solution into a reaction kettle, introducing oxygen for 30 minutes by using a ceramic microporous membrane tube, removing the oxygen in the reaction kettle, then adding a phenol compound and copper chloride into the reaction kettle while stirring, heating to 70-100 ℃ after the addition is finished, reacting for 4-12 hours at the temperature, and continuously using the ceramic microporous membrane tube to reversely react in the whole reactionIntroducing oxygen into the reactor, and extracting with an organic solvent after the reaction is finished to obtain a monochlorophenol compound; the phenol compound is phenol or methyl substituted phenol; oxygen enters the reaction system through the ceramic microporous membrane tube to form micro-bubble oxygen in the system and maintain the oxygen content in the reaction system, thereby avoiding harsh reaction conditions such as microwave and the like and utilizing catalytic amount of CuCl 2 As a catalyst, hydrochloric acid solution is used as a solvent and a chlorinating agent to perform high-selectivity chlorination on the phenol compounds;
the mass concentration of the hydrochloric acid solution is 15 to 37 percent; the organic solvent is dichloromethane, dichloroethane, ethyl acetate or methyl acetate;
wherein the molar ratio of the copper chloride to the phenol compound is 1:10 to 100; the mass ratio of the phenol compound to the hydrochloric acid solution is 1:5 to 20;
the reaction equation is as follows:
wherein R is hydrogen or methyl.
Preferably, the phenol compound is phenol or 2-methylphenol.
Preferably, the organic solvent is dichloromethane.
Preferably, the mass concentration of the hydrochloric acid solution is 30 to 37%.
Preferably, the molar ratio of the phenol compound to the copper chloride is 20:1.
preferably, the mass ratio of the phenol compound to the hydrochloric acid solution is 1:10.
preferably, the reaction temperature is 80 ℃.
Example 1
A preparation method of a monochlorophenol compound 4-chlorophenol comprises the following steps: adding 4.7kg of hydrochloric acid solution with the mass concentration of 15% into a reaction kettle, firstly introducing oxygen by using a ceramic microporous membrane tube, removing air in the reaction kettle, then adding 0.94kg of phenol and 0.013kg of copper chloride into the reaction kettle under stirring, raising the temperature to 70 ℃ after the addition is finished, reacting for 12 hours at the temperature, continuously introducing oxygen into the reaction kettle by using the ceramic microporous membrane tube in the whole reaction, extracting for 2 times by using methyl acetate after the reaction is finished, wherein the volume of the methyl acetate is 5L each time, obtaining 1.16kg of 4-chlorophenol, the conversion rate is 91.0%, and the selectivity of the 4-chlorophenol is 98.3% by using HPLC (high performance liquid chromatography).
Phenol is chlorinated under the technical condition to generate 2-chlorophenol, 4-chlorophenol and 2, 4-dichlorophenol, and the three substances have different peak positions in HPLC due to different polarities and boiling points, so that the three substances can be well separated and quantified.
Example 2
A preparation method of a monochlorophenol compound 4-chlorophenol comprises the following steps: adding 18.8kg of hydrochloric acid solution with the mass concentration of 37.5% into a reaction kettle, introducing oxygen by using a ceramic microporous membrane tube at the oxygen flow rate of 40ml/min, removing air in the reaction kettle, then adding 0.94kg of phenol and 0.134kg of copper chloride into the reaction kettle under stirring, raising the temperature to 100 ℃ after the addition is finished, reacting for 4 hours at the temperature, continuously introducing oxygen into the reaction kettle by using the ceramic microporous membrane tube in the whole reaction, extracting for 2 times by using dichloroethane after the reaction is finished, wherein the volume of the dichloroethane is 15L each time, obtaining 1.22kg of 4-chlorophenol, the conversion rate is 95.3%, and the selectivity of the 4-chlorophenol is 98.5% by HPLC (high performance liquid chromatography).
Example 3
A preparation method of a monochlorophenol compound 4-chlorophenol comprises the following steps: adding 18.8kg of hydrochloric acid solution with the mass concentration of 30% into a reaction kettle, introducing oxygen by using a ceramic microporous membrane tube at the oxygen flow rate of 25ml/min, removing air in the reaction kettle, adding 0.94kg of phenol and 0.01kg of copper chloride into the reaction kettle under stirring, raising the temperature to 90 ℃ after the addition is finished, reacting for 5 hours at the temperature, continuously introducing oxygen into the reaction kettle by using the ceramic microporous membrane tube in the whole reaction, extracting for 2 times by using ethyl acetate after the reaction is finished, wherein the volume of ethyl acetate is 8L each time, obtaining 1.20kg of 4-chlorophenol, the conversion rate is 93.8%, and the selectivity of the 4-chlorophenol is 98.0% by using HPLC (high performance liquid chromatography).
Example 4
A preparation method of a monochlorophenol compound 4-chlorophenol comprises the following steps: adding 9.4kg of hydrochloric acid solution with the mass concentration of 35% into a reaction kettle, introducing oxygen by using a ceramic microporous membrane tube at the oxygen flow rate of 30ml/min, removing air in the reaction kettle, adding 0.94kg of phenol and 0.08kg of copper chloride into the reaction kettle under stirring, raising the temperature to 80 ℃ after the addition is finished, reacting for 8 hours at the temperature, continuously introducing oxygen into the reaction kettle by using the ceramic microporous membrane tube in the whole reaction, extracting for 2 times by using dichloromethane after the reaction is finished, wherein the volume of dichloromethane in each time is 6L to obtain 1.24kg of 4-chlorophenol, the conversion rate is 96.8%, and the selectivity of 4-chlorophenol is 98.6% by using HPLC (high performance liquid chromatography).
Example 5
A preparation method of a monochlorophenol compound 4-chloro-2-methylphenol, comprising the following steps: adding 5.4kg of hydrochloric acid solution with the mass concentration of 15% into a reaction kettle, firstly introducing oxygen by using a ceramic microporous membrane tube, wherein the oxygen flow rate is 20ml/min, removing air in the reaction kettle, then adding 1.08kg of 2-methylphenol and 0.013kg of copper chloride into the reaction kettle under stirring, raising the temperature to 70 ℃ after the addition is finished, reacting for 12 hours at the temperature, continuously introducing oxygen into the reaction kettle by using the ceramic microporous membrane tube in the whole reaction, extracting for 2 times by using methyl acetate after the reaction is finished, wherein the volume of the methyl acetate is 6L each time, obtaining 1.29kg of 4-chloro-2-methylphenol, the conversion rate is 90.8%, and the selectivity of the 4-chlorophenol is 98.0% by using HPLC (high performance liquid chromatography).
Example 6
A preparation method of a monochlorophenol compound 4-chloro-2-methylphenol, comprising the following steps: a preparation method of a monochlorophenol compound 4-chlorophenol comprises the following steps: adding 21.6kg of hydrochloric acid solution with the mass concentration of 37.5% into a reaction kettle, introducing oxygen by using a ceramic microporous membrane tube at the oxygen flow rate of 40ml/min, removing air in the reaction kettle, adding 1.08kg of 2-methylphenol and 0.130kg of copper chloride into the reaction kettle under stirring, raising the temperature to 100 ℃ after the addition is finished, reacting for 4 hours at the temperature, continuously introducing oxygen into the reaction kettle by using the ceramic microporous membrane tube in the whole reaction, extracting 2 times by using dichloroethane after the reaction is finished, wherein the volume of the dichloroethane is 18L each time, obtaining 1.31kg of 4-chloro-2-methylphenol, the conversion rate is 92.2%, and the selectivity of the 4-chlorophenol is 98.4% by HPLC (high performance liquid chromatography).
Example 7
A preparation method of a monochlorophenol compound 4-chloro-2-methylphenol, comprising the following steps:
adding 6.48kg of hydrochloric acid solution with the mass concentration of 30% into a reaction kettle, introducing oxygen by using a ceramic microporous membrane tube at the oxygen flow rate of 25ml/min, removing air in the reaction kettle, adding 1.08kg of 2-methylphenol and 0.06kg of copper chloride into the reaction kettle under stirring, raising the temperature to 75 ℃ after the addition is finished, reacting for 6 hours at the temperature, continuously introducing oxygen into the reaction kettle by using the ceramic microporous membrane tube in the whole reaction, extracting for 2 times by using ethyl acetate after the reaction is finished, wherein the volume of ethyl acetate is 10L each time, obtaining 1.35kg of 4-chloro-2-methylphenol, the conversion rate is 95.1%, and the selectivity of the 4-chloro-2-methylphenol is 98.2% by using HPLC (high performance liquid chromatography).
Example 8
A preparation method of a monochlorophenol compound 4-chloro-2-methylphenol, comprising the following steps:
adding 10.8kg of 35% hydrochloric acid solution with mass concentration into a reaction kettle, introducing oxygen by using a ceramic microporous membrane tube at an oxygen flow rate of 30ml/min, removing air in the reaction kettle, adding 1.08kg of 2-methylphenol and 0.065kg of copper chloride into the reaction kettle under stirring, heating to 80 ℃ after the addition is finished, reacting for 8 hours at the temperature, continuously introducing oxygen into the reaction kettle by using the ceramic microporous membrane tube in the whole reaction, extracting for 2 times by using dichloromethane after the reaction is finished, wherein the volume of the dichloromethane is 6L each time, obtaining 1.36kg of 4-chlorophenol, the conversion rate is 95.8%, and the selectivity of the 4-chloro-2-methylphenol is 98.5% by HPLC (high performance liquid chromatography).
The embodiment shows that the preparation method of the monochlorophenol compound adopts hydrochloric acid as the solvent and the chlorinating agent, oxygen uniformly enters the system through the ceramic microporous membrane tube, the oxygen is uniformly distributed in the solution, the reaction is promoted to be smoothly carried out, and the phenomenon of implosion is avoided. The monochlorophenol compound obtained by the method is high in conversion rate and selectivity, and the hydrochloric acid solution can be used as a solvent repeatedly, so that the pollution of hydrochloric acid to the environment is reduced, and better economic benefits and social benefits are realized.
Claims (7)
1. A preparation method of a monochlorophenol compound is characterized by comprising the following steps: the method comprises the following steps: adding a hydrochloric acid solution into a reaction kettle, introducing oxygen by using a ceramic microporous membrane tube, removing air in the reaction kettle, adding a phenol compound and copper chloride into the reaction kettle under stirring, heating to 70-100 ℃ after the addition is finished, reacting for 4-12 hours at the temperature, continuously introducing oxygen into the reaction kettle by using the ceramic microporous membrane tube in the whole reaction, and extracting by using an organic solvent after the reaction is finished to obtain a monochlorophenol compound; the phenol compound is phenol or methyl substituted phenol;
the mass concentration of the hydrochloric acid solution is 15 to 37 percent; the organic solvent is dichloromethane, dichloroethane, ethyl acetate or methyl acetate;
wherein the molar ratio of the copper chloride to the phenol compounds is 1:10 to 100; the mass ratio of the phenol compound to the hydrochloric acid solution is 1:5 to 20.
2. The method according to claim 1, wherein the reaction is carried out in the presence of a compound selected from the group consisting of: the phenol compound is phenol or 2-methylphenol.
3. The method according to claim 1, wherein the reaction is carried out in the presence of a compound selected from the group consisting of: the organic solvent is dichloromethane.
4. The method for producing a monochlorophenol compound according to claim 1, wherein: the mass concentration of the hydrochloric acid solution is 30 to 37 percent.
5. The method for producing a monochlorophenol compound according to claim 1, wherein: the molar ratio of the phenol compounds to the copper chloride is 20:1.
6. the method according to claim 1, wherein the reaction is carried out in the presence of a compound selected from the group consisting of: the mass ratio of the phenol compound to the hydrochloric acid solution is 1:10.
7. the method according to claim 1, wherein the reaction is carried out in the presence of a compound selected from the group consisting of: the reaction temperature was 80 ℃.
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Citations (9)
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