CN116655456A - Method for efficiently purifying and separating 2-chloro-4-trifluoromethyl phenol - Google Patents
Method for efficiently purifying and separating 2-chloro-4-trifluoromethyl phenol Download PDFInfo
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- CN116655456A CN116655456A CN202310569132.5A CN202310569132A CN116655456A CN 116655456 A CN116655456 A CN 116655456A CN 202310569132 A CN202310569132 A CN 202310569132A CN 116655456 A CN116655456 A CN 116655456A
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- trifluoromethylphenol
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- YNWKEXMSQQUMEL-UHFFFAOYSA-N 2-chloro-4-(trifluoromethyl)phenol Chemical compound OC1=CC=C(C(F)(F)F)C=C1Cl YNWKEXMSQQUMEL-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- -1 2-chloro-4-trifluoromethyl phenol hydrate Chemical compound 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- SUIZARUATMVYRT-UHFFFAOYSA-N 2-chloro-5-(trifluoromethyl)phenol Chemical compound OC1=CC(C(F)(F)F)=CC=C1Cl SUIZARUATMVYRT-UHFFFAOYSA-N 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 239000012454 non-polar solvent Substances 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- BGXZMBZFGAIBDH-UHFFFAOYSA-N 2-chloro-3-(trifluoromethyl)phenol Chemical compound OC1=CC=CC(C(F)(F)F)=C1Cl BGXZMBZFGAIBDH-UHFFFAOYSA-N 0.000 claims description 2
- GIBYEQRMTYSGII-UHFFFAOYSA-N 2-chloro-6-(trifluoromethyl)phenol Chemical compound OC1=C(Cl)C=CC=C1C(F)(F)F GIBYEQRMTYSGII-UHFFFAOYSA-N 0.000 claims description 2
- WIMFOMTYQPDJBK-UHFFFAOYSA-N 3-chloro-2-(trifluoromethyl)phenol Chemical compound OC1=CC=CC(Cl)=C1C(F)(F)F WIMFOMTYQPDJBK-UHFFFAOYSA-N 0.000 claims description 2
- KQFQPAJCFHNHKB-UHFFFAOYSA-N 3-chloro-4-(trifluoromethyl)phenol Chemical compound OC1=CC=C(C(F)(F)F)C(Cl)=C1 KQFQPAJCFHNHKB-UHFFFAOYSA-N 0.000 claims description 2
- BPJWMOPEHPOKFT-UHFFFAOYSA-N 3-chloro-5-(trifluoromethyl)phenol Chemical compound OC1=CC(Cl)=CC(C(F)(F)F)=C1 BPJWMOPEHPOKFT-UHFFFAOYSA-N 0.000 claims description 2
- LUYVFIYUQPJQOJ-UHFFFAOYSA-N 4-chloro-2-(trifluoromethyl)phenol Chemical compound OC1=CC=C(Cl)C=C1C(F)(F)F LUYVFIYUQPJQOJ-UHFFFAOYSA-N 0.000 claims description 2
- ZLFPIEUWXNRPNM-UHFFFAOYSA-N 4-chloro-3-(trifluoromethyl)phenol Chemical compound OC1=CC=C(Cl)C(C(F)(F)F)=C1 ZLFPIEUWXNRPNM-UHFFFAOYSA-N 0.000 claims description 2
- GUUHTCHBMKBRDT-UHFFFAOYSA-N 5-chloro-2-(trifluoromethyl)phenol Chemical compound OC1=CC(Cl)=CC=C1C(F)(F)F GUUHTCHBMKBRDT-UHFFFAOYSA-N 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 34
- 238000000746 purification Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OQMBBFQZGJFLBU-UHFFFAOYSA-N Oxyfluorfen Chemical compound C1=C([N+]([O-])=O)C(OCC)=CC(OC=2C(=CC(=CC=2)C(F)(F)F)Cl)=C1 OQMBBFQZGJFLBU-UHFFFAOYSA-N 0.000 description 2
- 239000005590 Oxyfluorfen Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- 239000012264 purified product Substances 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 1
- 239000012156 elution solvent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011877 solvent mixture Substances 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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/685—Processes comprising at least two steps in series
-
- 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
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/86—Purification; separation; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for purifying and separating 2-chloro-4-trifluoromethyl phenol, belonging to the field of chemical industry. It comprises the following steps: the mixture containing 2-chloro-4-trifluoromethyl phenol is mixed with water or an aqueous solvent to form 2-chloro-4-trifluoromethyl phenol hydrate in a separated solid form at a certain temperature, and a purified 2-chloro-4-trifluoromethyl phenol product is obtained. The method provided by the invention can simply and effectively separate and purify the 2-chloro-4-trifluoromethyl phenol from the mixture containing the 2-chloro-4-trifluoromethyl phenol or the mixture of the 2-chloro-4-trifluoromethyl phenol and the isomer thereof, avoids the use of a large amount of organic solvents and acid and alkali, saves energy consumption and is environment-friendly.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a method for purifying and separating 2-chloro-4-trifluoromethyl phenol.
Background
2-chloro-4-trifluoromethylphenol is an important byproduct (US 4046798) for producing oxyfluorfen by a double etherification route, and a plurality of patents report that the 2-chloro-4-trifluoromethylphenol can be used for preparing the oxyfluorfen in recent years (CN 101891623, CN109280008, CN109970567 and CN 102030655), and the effective recycling of the byproduct 2-chloro-4-trifluoromethylphenol has important significance and value. However, as described in the comprehensive literature, 2-chloro-4-trifluoromethylphenol often exists together with an isomer of 2-chloro-4-trifluoromethylphenol in the production process, and the isomer can participate in the preparation reaction in parallel to generate an isomer of the target compound, so that further purification is required, and further investment and waste generation are increased, which ultimately affects the yield of the reaction.
In view of the fact that 2-chloro-4-trifluoromethylphenol is liquid at normal temperature and has a very low freezing point, and is difficult to purify by conventional crystallization methods, separation by column separation and rectification is generally required, a large amount of solvents and equipment are required for the process, and the cost and the process are high.
U.S. patent No. W02018185559 discloses a separation method for converting 2-chloro-4-trifluoromethylphenol into salt form and filtering to remove isomers, which reduces purification cost, but still requires adding a large amount of alkali, and the step of salifying-re-acidifying is required to obtain pure 2-chloro-4-trifluoromethylphenol, and the process has the disadvantages of avoiding acid input and salt output.
Disclosure of Invention
1. Technical problem to be solved
Aiming at the problems in the prior art, the invention aims to provide a method for separating and purifying 2-chloro-4-trifluoromethyl phenol in a mode of not needing column separation, rectification or salifying by adding alkali.
2. Technical proposal
In order to solve the problems, the invention adopts the following technical scheme.
A method for efficiently purifying and separating 2-chloro-4-trifluoromethylphenol comprises the steps of mixing a mixture containing 2-chloro-4-trifluoromethylphenol (hereinafter referred to as a phenol mixture) with water or an aqueous solvent to form 2-chloro-4-trifluoromethylphenol hydrate in a solid form, and separating to obtain a purified 2-chloro-4-trifluoromethylphenol product;
wherein the mixture of the 2-chloro-4-trifluoromethyl phenol contains isomers of the 2-chloro-4-trifluoromethyl phenol and a solvent.
Further, the isomer of the 2-chloro-4-trifluoromethylphenol contained in the phenol mixture is 2-chloro-3-trifluoromethylphenol, 2-chloro-5-trifluoromethylphenol, 2-chloro-6-trifluoromethylphenol, 3-chloro-2-trifluoromethylphenol, 3-chloro-4-trifluoromethylphenol, 3-chloro-5-trifluoromethylphenol, 3-chloro-6-trifluoromethylphenol, 4-chloro-2-trifluoromethylphenol and 4-chloro-3-trifluoromethylphenol, and the isomer structures thereof are shown in the figure:
further, the ratio of the isomers of 2-chloro-4-trifluoromethylphenol contained in the phenol mixture to the isomers of 2-chloro-4-trifluoromethylphenol contained in the phenol mixture is 1000:1 to 1:1000.
Further, the content of 2-chloro-4-trifluoromethylphenol in the phenol mixture is preferably not less than 60%.
Further, the water or water as a reactant in the aqueous solvent is added in an amount of 0.5 to 30 times by weight of 2-chloro-4-trifluoromethylphenol in the mixture of 2-chloro-4-trifluoromethylphenol.
Further, the aqueous solvent is a mixture of water and a non-polar solvent, wherein the non-polar solvent comprises n-hexane, n-heptane, cyclohexane, methylcyclohexane, diethyl ether, petroleum ether, chloroform, dichloroethane, toluene, and any combination thereof.
Further, the mixing of the phenol mixture with water or an aqueous solvent requires a temperature of-16 to 16 ℃.
Further, the separation mode includes, but is not limited to, filtration and centrifugation, and in the separation mode, solvents used for the filter cake used in filtration may be water and nonpolar solvents, wherein the nonpolar solvents include, but are not limited to, n-hexane, cyclohexane, petroleum ether, chloroform, dichloroethane and toluene, the amount of the nonpolar solvents affects the yield, and the temperature of the nonpolar solvents is below the crystallization temperature of the hydrate.
Further, the temperature is-16 ℃ to 16 ℃, preferably-4 ℃ to 12 ℃.
3. Advantageous effects
Compared with the prior art, the invention has the advantages that:
(1) According to the invention, the hydrate solid is separated by utilizing the characteristic that 2-chloro-4-trifluoromethylphenol and water form a hydrate in a solid state at low temperature, so that a purified 2-chloro-4-trifluoromethylphenol product is obtained, and the complexity of a process for purifying and separating 2-chloro-4-trifluoromethylphenol is greatly reduced;
(2) The final product of the invention is purified white solid 2-chloro-4-trifluoromethyl phenol hydrate, because the solid needs to be stored at low temperature, the contact area is small, the packaging is easy, the volatility is low, the hydrate can not be decomposed to cause corrosion as long as the temperature is ensured after the hydrate is formed, the final product of the prior art is liquid, the liquid is easy to volatilize to generate smell, and the liquid can be slowly decomposed to generate acid and fluoride ions to cause equipment corrosion, so the proposal can greatly reduce the source of smell and the corrosion of phenol to the equipment;
(3) The solvents used in the separation and purification process are water and nonpolar solvents, so that the use of a large amount of organic solvents and acid and alkali is avoided, and the three wastes discharged in the industrial production process are reduced to a great extent;
(4) The device used in the separation and purification process is simple, does not need complex equipment such as high-temperature rectification and the like, and is simple, efficient, energy-saving and environment-friendly.
Drawings
FIG. 1 is a graph of a phenol mixture containing isomers prior to purification and gas phase comparison data in accordance with the present invention;
FIG. 2 is a graph of a phenol mixture containing only isomers prior to purification according to the present invention and comparison of gas phase returns;
FIG. 3 is a graph of the phenol product after purification and ratio data of the present invention;
FIG. 4 shows the product profile and ratio data of the present invention after purification with little isomer.
Detailed Description
The invention will be further illustrated with reference to specific examples, but the scope of the invention is not limited thereto.
In the phenol mixture of the isomers of 2-chloro-4-trifluoromethylphenol and 2-chloro-4-trifluoromethylphenol in the examples, the ratio of the isomers of 2-chloro-4-trifluoromethylphenol in the 2-chloro-4-trifluoromethylphenol and phenol mixture was 1000:1 to 1:1000; in the 2-chloro-4-trifluoromethylphenol hydrate obtained by purification in the examples, the ratio of 2-chloro-4-trifluoromethylphenol to the isomer of 2-chloro-4-trifluoromethylphenol in the hydrate is 93:2 to 99.99:0.01, and the purity of 2-chloro-4-trifluoromethylphenol in the purified hydrate is 97% or more, and can be up to 99.9%; the best mode of mixing the phenol mixture with water or an aqueous solvent is to dropwise add the phenol mixture into the water or the aqueous solvent, so that a better crystal form is obtained, and the mixing mode has no influence on the reaction; the 2-chloro-4-trifluoromethylphenol hydrate obtained in the examples was generally in the form of white flakes or blocks of crystals, and in some cases the hydrate was a white powdery solid.
Referring to FIGS. 1-4, comparing the ratio data of the phenol mixture containing isomers before purification of the present invention in FIG. 1 with the ratio data of the phenol product after purification according to the technical scheme of the present invention in FIG. 3, it is known from the change of the peak area that the concentration of 2-chloro-4-trifluoromethylphenol in the phenol mixture is from a ratio of 15.744% to a ratio of 95.389% of the concentration of 2-chloro-4-trifluoromethylphenol in the phenol product obtained by purification;
comparing the proportion data of the phenol mixture containing only isomers before purification of the invention in FIG. 2 with the proportion data of the phenol product after purification according to the technical scheme adopted in the invention in FIG. 3, the change of the peak area shows that the concentration of 2-chloro-4-trifluoromethyl phenol in the phenol mixture reaches 98.389 percent of the concentration of 2-chloro-4-trifluoromethyl phenol in the phenol product obtained by purification from the proportion of 80.678 percent.
Comparing the proportion data of the phenol mixture containing isomers before purification of the present invention in FIG. 1 with the proportion data of the purified product almost free of isomers obtained according to the present technical scheme in FIG. 4, it is known from the change of the peak area that the concentration of 2-chloro-4-trifluoromethylphenol in the phenol mixture is from a ratio of 15.744% to a ratio of 100.000% in the phenol product almost free of isomers;
comparing the proportion data of the phenol mixture containing only isomers before purification of the invention in FIG. 2 with the proportion data of the purified product almost without isomers obtained according to the technical scheme in FIG. 4, the change of the peak area shows that the concentration of the 2-chloro-4-trifluoromethylphenol in the phenol mixture reaches the proportion of 100.000% of the concentration of the 2-chloro-4-trifluoromethylphenol in the phenol product almost without isomers from the proportion of 80.678%, and the comparison of the data further shows that the purity of the final product obtained by adopting the technical scheme of the invention is excellent.
Example 1:
a method for purifying and separating 2-chloro-4-trifluoromethyl phenol, which comprises the following steps:
s1, adding 50g of water into a 250ml four-neck flask, and cooling to 6 ℃;
s2, dropwise adding 30g of a mixture (0.15 mol) of 2-chloro-4-trifluoromethylphenol and isomer 2-chloro-5-trifluoromethylphenol into cooled water, wherein white solid precipitation occurs in the water in the dropwise adding process;
s3, after the dripping is finished, carrying out heat preservation and stirring on the phenol mixture in the 250ml four-neck flask for 10min;
s4, filtering the stirred phenol mixture, and washing a filter cake by water to obtain 32g of 2-chloro-4-trifluoromethyl phenol hydrate, wherein the ratio of the 2-chloro-4-trifluoromethyl phenol to the isomer 2-chloro-5-trifluoromethyl phenol is 97.2:1.9.
Example 2:
a method for purifying and separating 2-chloro-4-trifluoromethyl phenol, which comprises the following steps:
s1, adding 50g of water into a 250ml four-neck flask, and cooling to 6 ℃;
s2, dropwise adding 30g of a mixture (0.15 mol) of 2-chloro-4-trifluoromethylphenol and isomer 2-chloro-5-trifluoromethylphenol into cooled water, wherein white solid precipitation occurs in the water in the dropwise adding process;
s3, after the dripping is finished, carrying out heat preservation and stirring on the phenol mixture in the 250ml four-neck flask for 10min;
s4, filtering the stirred phenol mixture, and washing a filter cake by adopting normal hexane with the temperature below the crystallization temperature of the hydrate, wherein 29.5g of 2-chloro-4-trifluoromethyl phenol hydrate is obtained after filtering, and the ratio of 2-chloro-4-trifluoromethyl phenol to isomer 2-chloro-5-trifluoromethyl phenol is 97.8:0.6.
Example 3:
a method for purifying and separating 2-chloro-4-trifluoromethyl phenol, which comprises the following steps:
s1, adding 30g of normal hexane and 20g of water into a 250ml four-neck flask, and cooling to 9 ℃;
s2, dropwise adding 30g of a mixture (0.15 mol) of 2-chloro-4-trifluoromethylphenol and isomer 2-chloro-5-trifluoromethylphenol into the cooled mixed solution, wherein white solid precipitation occurs in water in the dropwise adding process;
s3, after the dripping is finished, carrying out heat preservation and stirring on the phenol mixture in the 250ml four-neck flask for 10min;
s4, filtering the stirred phenol mixture, and washing a filter cake by adopting normal hexane with the temperature below the crystallization temperature of the hydrate, wherein 26.8g of 2-chloro-4-trifluoromethyl phenol hydrate is obtained after filtering, and the ratio of 2-chloro-4-trifluoromethyl phenol to isomer 2-chloro-5-trifluoromethyl phenol is 99.8:0.01.
Comparative example 1:
a method for purifying and separating 2-chloro-4-trifluoromethyl phenol by column chromatography comprises the following steps:
s1, taking 3g (0.015 mol) of a mixture of 2-chloro-4-trifluoromethylphenol and an isomer of 2-chloro-5-trifluoromethylphenol for column chromatography purification and separation;
s2, mixing 80g of petroleum ether and 130g of ethyl acetate to elution solvents with different proportions to elute the sample;
s3, respectively summarizing and desolventizing according to sample detection results received by a bottle, and finally obtaining 1.8g of pale yellow liquid mixed by 2-chloro-4-trifluoromethylphenol and isomer 2-chloro-5-trifluoromethylphenol, wherein the ratio of the 2-chloro-4-trifluoromethylphenol to the isomer 2-chloro-5-trifluoromethylphenol is 99.3:0.2, and 1.2g of eluting solvent mixture liquid. The method has complex process, needs to be summarized and desolventized respectively according to the detection results of the samples received by the split bottles, inputs a large amount of solvents to cause high cost, and produces excessive invalid waste, and the obtained product is liquid which is easy to volatilize and generates smell, which means that the product can be automatically decomposed to generate acid and fluoride ions to corrode equipment.
Comparative example 2:
a method for separating 2-chloro-4-trifluoromethylphenol by salifying, comprising the following steps:
s1, adding 400g of toluene, 25g of ethanol, 15g of water and 90g of flaky potassium hydroxide into a 1000ml four-necked flask, stirring for 1h, and cooling to 20 ℃;
s2, dropwise adding 300g (1.5 mol) of a mixture of 2-chloro-4-trifluoromethylphenol and an isomer of 2-chloro-5-trifluoromethylphenol at 15-22 ℃, and preserving heat and stirring for 3 hours after the dropwise adding is finished;
s3, filtering, and leaching a filter cake by using 50g of toluene to obtain 360g of off-white solid 2-chloro-4-trifluoromethylphenol potassium salt hydrate wet product, wherein the moisture content is 18.15%, and the ratio of 2-chloro-4-trifluoromethylphenol to isomer 2-chloro-5-trifluoromethylphenol is 93:0.6.
S4, adding the 2-chloro-4-trifluoromethyl phenol potassium salt hydrate wet product into a 1000ml four-neck flask, adding 400g of toluene, and uniformly stirring;
s5, dropwise adding 30% hydrochloric acid to a 1000ml four-neck flask at the temperature below 40 ℃ until the pH value is lower than 2, consuming 162g of hydrochloric acid, standing for layering, washing with 50g of water, and desolventizing an upper layer to obtain 246g of 2-chloro-4-trifluoromethylphenol, wherein the ratio of 2-chloro-4-trifluoromethylphenol to isomer 2-chloro-5-trifluoromethylphenol is 98:0.8. In the process of the method, a large amount of organic solvent, a strong alkaline compound and a strong acid mixture are added, so that excessive three wastes are discharged and industrial pollution is caused, and the development of subsequent environmental protection work is not facilitated.
Claims (8)
1. A method for efficiently purifying and separating 2-chloro-4-trifluoromethyl phenol is characterized in that: and mixing the mixture containing 2-chloro-4-trifluoromethyl phenol with water or an aqueous solvent to form 2-chloro-4-trifluoromethyl phenol hydrate in a solid form, and separating to obtain a purified 2-chloro-4-trifluoromethyl phenol product.
2. The method for efficiently purifying and separating 2-chloro-4-trifluoromethylphenol according to claim 1, which is characterized in that: the 2-chloro-4-trifluoromethylphenol mixture contains 2-chloro-3-trifluoromethylphenol, 2-chloro-5-trifluoromethylphenol, 2-chloro-6-trifluoromethylphenol, 3-chloro-2-trifluoromethylphenol, 3-chloro-4-trifluoromethylphenol, 3-chloro-5-trifluoromethylphenol, 3-chloro-6-trifluoromethylphenol, 4-chloro-2-trifluoromethylphenol and 4-chloro-3-trifluoromethylphenol as isomers.
3. The method for efficiently purifying and separating 2-chloro-4-trifluoromethylphenol according to claim 2, which is characterized in that: the ratio of the 2-chloro-4-trifluoromethylphenol contained in the 2-chloro-4-trifluoromethylphenol mixture to the isomer of 2-chloro-4-trifluoromethylphenol contained in the 2-chloro-4-trifluoromethylphenol mixture is 1000:1-1:1000.
4. a method for efficiently purifying and separating 2-chloro-4-trifluoromethylphenol according to claim 3, wherein: the content of the 2-chloro-4-trifluoromethyl phenol in the mixture of the 2-chloro-4-trifluoromethyl phenol is preferably more than or equal to 60 percent.
5. The method for efficiently purifying and separating 2-chloro-4-trifluoromethylphenol according to claim 1, which is characterized in that: the water or water-containing solvent is added as a reactant in an amount of 0.5 to 30 times by weight of the 2-chloro-4-trifluoromethylphenol in the mixture of 2-chloro-4-trifluoromethylphenols.
6. The method for efficiently purifying and separating 2-chloro-4-trifluoromethylphenol according to claim 1, which is characterized in that: the aqueous solvent is a mixture of water and a non-polar solvent, wherein the non-polar solvent comprises n-hexane, n-heptane, cyclohexane, methylcyclohexane, diethyl ether, petroleum ether, chloroform, dichloroethane, toluene, and any combination thereof.
7. The method for efficiently purifying and separating 2-chloro-4-trifluoromethylphenol according to claim 1, which is characterized in that: the mixture containing 2-chloro-4-trifluoromethylphenol is mixed with water or an aqueous solvent at a temperature of-16 to 16 ℃.
8. The method for efficiently purifying and separating 2-chloro-4-trifluoromethylphenol according to claim 1, which is characterized in that: such separation means include, but are not limited to, filtration and centrifugation.
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