CN113105312B - Method for preparing 4-chloro-3, 5-dimethylphenol - Google Patents
Method for preparing 4-chloro-3, 5-dimethylphenol Download PDFInfo
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- CN113105312B CN113105312B CN202110371005.5A CN202110371005A CN113105312B CN 113105312 B CN113105312 B CN 113105312B CN 202110371005 A CN202110371005 A CN 202110371005A CN 113105312 B CN113105312 B CN 113105312B
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- dimethylphenol
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- OSDLLIBGSJNGJE-UHFFFAOYSA-N 4-chloro-3,5-dimethylphenol Chemical compound CC1=CC(O)=CC(C)=C1Cl OSDLLIBGSJNGJE-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title abstract description 38
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000003054 catalyst Substances 0.000 claims abstract description 76
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 62
- 239000000047 product Substances 0.000 claims abstract description 49
- 239000013082 iron-based metal-organic framework Substances 0.000 claims abstract description 33
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012467 final product Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims description 75
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- 210000003298 dental enamel Anatomy 0.000 claims description 16
- 238000004817 gas chromatography Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 11
- 238000004064 recycling Methods 0.000 claims description 11
- 238000004090 dissolution Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 17
- 238000000746 purification Methods 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 abstract 1
- 230000008569 process Effects 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000012320 chlorinating reagent Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 229950011008 tetrachloroethylene Drugs 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 125000003963 dichloro group Chemical group Cl* 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000003586 protic polar solvent Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- HTIRHQRTDBPHNZ-UHFFFAOYSA-N Dibutyl sulfide Chemical compound CCCCSCCCC HTIRHQRTDBPHNZ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 1
- IYOLBFFHPZOQGW-UHFFFAOYSA-N 2,4-dichloro-3,5-dimethylphenol Chemical compound CC1=CC(O)=C(Cl)C(C)=C1Cl IYOLBFFHPZOQGW-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical group [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 150000003568 thioethers Chemical class 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- 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 relates to a method for preparing 4-chloro-3, 5-dimethylphenol, which comprises the following specific steps: fully dissolving 3, 5-dimethylphenol by using a proton type solvent, and dropwise adding sulfuryl chloride for chlorination reaction under the action of a directional chlorination catalyst to obtain 4-chloro-3, 5-dimethylphenol; the directional chlorination catalyst is Fe-MOFs. The directional catalyst/proton solvent combination system adopted by the invention is applied to the directional chlorination of 3, 5-dimethyl phenol, so that the selectivity of the chlorination reaction is effectively improved, 4-chloro-3, 5-methyl phenol products are efficiently prepared, and the final product with the content of 94% and the purity of up to 99.7% is obtained through one-step synthesis without purification. The method has the characteristics of simple and convenient operation, high product selectivity and the like, and has high industrial application value.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of 4-chloro-3, 5-dimethylphenol compound with disinfection and sterilization effects.
Background
4-chloro-3, 5-dimethylphenol, named PCMX for short, is a high-efficiency low-toxicity mildew-proof bactericide and is widely applied to mildew-proof sterilization in daily life and industrial fields. With the improvement of the living standard and the enhancement of health consciousness of people, the market demand of 4-chloro-3, 5-dimethylphenol is increasing year by year. At present, PCMX mainly comprises the following three production processes: the first process is to react with 3, 5-dimethyl phenol (MX for short) by using water as medium and sulfuryl chloride as chlorinating agent to generate 4-chloro-3, 5-dimethyl phenol; the second process is to react tetrachloroethylene as solvent and sulfuryl chloride as chlorinating agent with MX to produce 4-chloro-3, 5-dimethylphenol; the third process is to prepare 4-chloro-3, 5-dimethylphenol by oxychlorination with hydrochloric acid as chlorinating agent under the action of copper catalyst. The former two processes need to react at high temperature, so that the chlorination reaction has poor selectivity and more byproducts in the production process, and the content of the target PCMX is about 85 percent, and also contains 11 percent of OCMX and about 2 percent of DCMX. Although the selectivity of the chlorinated product in the third process is improved to a certain extent, the process is limited by reaction conditions, rectification and purification are needed, and the problem of decomposition of the high-boiling-point thermosensitive material PCMX is effectively solved at present.
To further increase the yield of PCMX, the selectivity in the chlorination process is increased by adding a certain amount of a directional catalyst to the reaction system. In US4245127, the chlorination of m-xylenol using organic sulfides and metal chlorides as co-catalysts is described, wherein titanium tetrachloride and dodecyl mercaptan as co-catalysts can achieve the greatest product selectivity, i.e. PCMX can reach 91.5%, however titanium tetrachloride has major safety hazards and post-treatment problems in practical industrial applications. Patent CN101085722a also describes the use of metal chlorides and organic sulfur or ether co-catalysts in chlorinated alkane solvents to effect chlorination of the alkylphenols. However, the reaction system can generate a large amount of crystallization precipitation in the later stage under the low temperature condition, so that mass transfer in the reaction system is affected, and polychlorinated products are generated. On the other hand, there have been few reports on a method for improving the yield of PCMX by improving the production process. In patent CN102675055a, a new process for preparing PCMX by high temperature chlorination process, i.e. using continuous reaction at high temperature of 110-130 ℃ to realize parachlorometaxylenol, is reported. Although the production efficiency of the process is improved, the dichloro product is obviously increased due to the excessively high reaction temperature. In CN10659528A, another process for continuously producing PCMX using three reactors in series is described, and a continuous reaction process with high conversion is achieved at a low temperature, but the process has problems of using a large amount of organic solvent and low selectivity (selectivity is only 83%), and the post-treatment process is complicated.
In view of the above-mentioned problems, development of a method for producing 4-chloro-3, 5-dimethylphenol with high selectivity under mild conditions is particularly urgent.
Disclosure of Invention
The invention solves the technical problem of providing a method for preparing 4-chloro-3, 5-dimethylphenol with high selectivity under mild conditions.
The technical proposal of the invention is that,
a process for preparing 4-chloro-3, 5-dimethylphenol comprising the steps of:
fully dissolving 3, 5-dimethylphenol by using a proton type solvent, and dropwise adding sulfuryl chloride for chlorination reaction under the action of a directional chlorination catalyst to obtain 4-chloro-3, 5-dimethylphenol; the directional chlorination catalyst is Fe-MOFs.
Preferably, the preparation method of the directional chlorination catalyst comprises the steps of mixing ferric trichloride serving as an iron source with a ligand, adding a certain amount of deionized water, stirring and dissolving, transferring into a sealed container, reacting at 140-220 ℃ for 5-6 hours, centrifuging, washing the product, and drying to obtain the target catalyst.
Preferably, the mass ratio of the iron source to the ligand is 1:0.8-1.5.
Preferably, the ligand is terephthalic acid, phthalic acid, trimesic acid or naphthalene dicarboxylic acid.
Preferably, the sealed container is a reaction kettle with polytetrafluoroethylene as an inner container.
Fe-MOFs is a porous material with a periodic network structure, has a higher specific surface area, and is favorable for fully contacting reactants with a chlorinating agent in a cavity to carry out chlorination reaction.
Preferably, the addition amount of the directional chlorination catalyst is 0.5% -8% of that of 3, 5-dimethylphenol in terms of mass parts.
Preferably, the addition amount of the directional chlorination catalyst is 5% of that of 3, 5-dimethylphenol in parts by mass.
The catalyst has great influence on the chemical reaction rate, and some catalysts can accelerate the chemical reaction rate by more than millions of times.
The catalyst dosage is lower than 0.5%, and the reaction rate is slower; above 8%, the catalytic effect is not increased, the reaction time is not obviously reduced, and the extra catalyst removal work is increased.
Preferably, the charging mole ratio of the sulfuryl chloride to the 3, 5-dimethylphenol is 1:1-1.5.
Preferably, the charging mole ratio of the sulfuryl chloride to the 3, 5-dimethylphenol is 1:1.2.
The chlorination of the dimethylphenol (MX) is not complete and less than 1:1,3, 5-dimethylphenol (MX) is not complete, and after the feeding molar ratio is higher than 1.5, the impurities in the product are increased, so that the production cost and the subsequent tail gas treatment process are increased.
Preferably, the addition amount of the proton-type solvent is 0.2 to 1.0 times of that of 3, 5-dimethylphenol in terms of parts by mass.
Preferably, the addition amount of the proton-type solvent is 0.8 times of that of 3, 5-dimethylphenol in terms of parts by mass.
At 0.8 times the amount added, the reactants can be dissolved with the least amount of solvent and the reaction rate is faster.
Preferably, the protic solvent is an alcoholic solvent.
Further preferably, the alcohol solvent is ethanol.
The ethanol is used as a solvent, so that the solubility of 3, 5-dimethylphenol and 4-chloro-3, 5-dimethylphenol in the solvent is greatly increased, further chlorination to generate dichloro byproducts due to solid precipitation in the chlorination process is avoided, and the purity and yield of the product are increased.
Preferably, the chlorination reaction time is 4-8 hours.
Preferably, the chlorination reaction is carried out in an open enamel reactor, the bottom price time of sulfuryl chloride is controlled to be 1.5-2.5h, and the temperature is controlled to be 5-15 ℃ in the reaction process.
Preferably, the reaction temperature control in the open enamel reaction kettle is realized by introducing saline water into a jacket of the reaction kettle and adjusting the flow rate of sulfuryl chloride gas.
Preferably, the method for preparing 4-chloro-3, 5-dimethylphenol further comprises the separation and purification of 4-chloro-3, 5-dimethylphenol product.
Preferably, the separation and purification comprises the following steps:
and (3) stopping the reaction when the content of 3, 5-dimethylphenol in the reactant is lower than 0.3% by gas chromatography, filtering to remove the catalyst, evaporating ethanol from the filtrate under normal pressure, adding high temperature water, reducing the temperature to obtain crystalline 4-chloro-3, 5-dimethylphenol, washing with tetrachloroethylene, and drying to obtain a final product.
The filtered catalyst is reused, and multiple experiments prove that the catalyst provided by the invention is reused in the preparation process of 4-chloro-3, 5-dimethylphenol, and the catalytic effect is still higher and the attenuation is very small.
When the content of 3, 5-dimethylphenol is less than 0.3%, the reaction is complete.
4-chloro-3, 5-dimethylphenol is purified by means of recrystallization. 4-chloro-3, 5-dimethylphenol (PCMX) has small solubility in normal temperature water and better solubility in high temperature water, and solid products can be separated out after the temperature is reduced.
The invention also provides application of the Fe-MOFs directional chlorination catalyst in preparation of 4-chloro-3, 5-dimethylphenol, and the preparation method of the Fe-MOFs directional chlorination catalyst comprises the steps of mixing ferric trichloride serving as an iron source with a ligand, adding a certain amount of deionized water, stirring and dissolving, transferring into a sealed container, reacting at 140-220 ℃ for 4-5h, centrifuging, washing, and drying a product to obtain the target catalyst.
The invention is further explained below:
the relationship between the catalyst and the reaction system is highly selective (or specific) just like the relationship between lock and key. A catalyst does not catalyze all chemical reactions, for example manganese dioxide catalyzes the decomposition of potassium chlorate by heat, accelerating the rate of chemical reaction, but does not necessarily catalyze other chemical reactions. If H is used as a catalyst for starch oxidation 2 O 2 When used as an oxidant, fe 2+ 、Mn 2+ Good equivalent effect, ni 2+ 、Cu 2+ 、Co 2+ The equivalent effect is poor; when KMnO is used 4 When the catalyst is an oxidant, mn is generated by self-reaction 2+ As catalyst, but Fe 2+ 、Ni 2+ 、Cu 2+ And the like have no catalytic effect. Most catalysts can only accelerate a certain chemical reaction, or a certain class of chemical reactions, and cannot be used to accelerate all chemical reactions. Fe-MOFs are disclosed in the prior art as catalysts for other reactions, but no prior art discloses Fe-MOFs as catalysts for the preparation of 4-chloro-3, 5-dimethylphenol.
Fe-MOFs is a porous material with a periodic network structure, has a higher specific surface area, and is favorable for fully contacting reactants with a chlorinating agent in a cavity to carry out chlorination reaction. The invention utilizes Fe-MOFs directional chlorination catalyst to catalyze the chlorination of 3, 5-dimethylphenol, not only has high effect, but also can be reused, and multiple experiments prove that the catalyst disclosed by the invention can be used for multiple times in the preparation process of 4-chloro-3, 5-dimethylphenol, and the catalytic effect is still higher, and the attenuation is very small. 3, 5-dimethylphenol (MX) and 4-chloro-3, 5-dimethylphenol (PCMX) are organic compounds containing a hydroxyl structure that have higher solubility in protic solvent alcohols according to similar compatible principles. And unexpectedly, the conversion of 3, 5-dimethylphenol in protic solvent alcohols is higher than other solvents.
The invention has the advantages that,
according to the invention, the alcohol compound is used as a solvent, so that the solubility of MX and PCMX in the solvent is greatly increased, further chlorination to generate dichloro byproducts caused by precipitation of solids in the chlorination process is avoided, and the conversion rate of the reaction is improved; meanwhile, the synthesis method of the added directional chlorination catalyst is simple, the reaction time is short, the catalyst has high activity and selectivity, the catalyst has good stability and can be repeatedly used, the cost is reduced, and the continuous industrial production is facilitated.
Drawings
Fig. 1 is a process flow diagram of the present invention.
Detailed Description
Example 1
The following operations are performed according to the process flow diagram of fig. 1:
(1) Preparation of Fe-MOFs directional chlorination catalyst
Adding 50.0kg of ferric trichloride hexahydrate and 50.0kg of terephthalic acid ligand into a container, adding a certain amount of deionized water, stirring for dissolution, transferring into a reaction kettle taking polytetrafluoroethylene as an inner container, sealing, reacting for 5 hours at 140-220 ℃, centrifuging, washing the product, and drying.
(2) Directed chlorination of MX: 1000+ -10 kg of ethanol and then 1000+ -10 kg of 3, 5-dimethylphenol material are added into a 3000L open enamel reactor through a metering tank, and are stirred sufficiently and uniformly for dissolution. 50+ -0.5 kg of Fe-MOFs directional chlorination catalyst is further added, and fully and uniformly stirred, 1106kg of sulfuryl chloride is gradually added dropwise within 2h, and the reaction temperature is controlled to be 5+ -3 ℃. After the reaction is continued for 2 hours, detecting that the MX content in the reaction system is lower than 0.3 percent by gas chromatography, stopping the reaction, filtering to remove the catalyst for standby, evaporating methanol at normal pressure for recycling, then adding 2000kg of high-temperature water to fully dissolve the product, then reducing the temperature to 25 ℃ to obtain a crystalline PCMX product, washing and drying to obtain 1189kg of a final product, wherein the yield is 94 percent, and the purity of the product reaches 99.7 percent.
Example 2
Fe-MOFs directional chlorination catalyst was prepared by the same method as in example 1.
1000+ -10 kg of methanol and then 1000+ -10 kg of 3, 5-dimethylphenol material are added into a 3000L open enamel reactor via a metering tank, and are stirred sufficiently and dissolved uniformly. 50+ -0.5 kg of Fe-MOFs directional chlorination catalyst is further added, and fully and uniformly stirred, 1106kg of sulfuryl chloride is gradually added dropwise within 2h, and the reaction temperature is controlled to be 5+ -3 ℃. After the reaction is continued for 2 hours, detecting that the MX content in the reaction system is lower than 0.3 percent by gas chromatography, stopping the reaction, filtering to remove the catalyst for standby, evaporating ethanol at normal pressure for recycling, then adding 2000kg of high-temperature water to fully dissolve the product, then reducing the temperature to 25 ℃ to obtain a crystalline PCMX product, washing and drying to obtain 1081kg of a final product, wherein the yield is 90.4 percent, and the purity of the product reaches 94.6 percent.
Example 3
Fe-MOFs directional chlorination catalyst was prepared by the same method as in example 1.
1000+ -10 kg of propanol and then 1000+ -10 kg of 3, 5-dimethylphenol material are added into a 3000L open enamel reactor via a metering tank, and are stirred thoroughly and dissolved uniformly. 50+ -0.5 kg of Fe-MOFs directional chlorination catalyst is further added, and fully and uniformly stirred, 1106kg of sulfuryl chloride is gradually added dropwise within 2h, and the reaction temperature is controlled to be 5+ -3 ℃. After the reaction is continued for 2 hours, detecting that the MX content in the reaction system is lower than 0.3 percent by gas chromatography, stopping the reaction, filtering to remove the catalyst for standby, evaporating propanol at normal pressure for recycling, then adding 2000kg of high-temperature water to fully dissolve the product, then reducing the temperature to 25 ℃ to obtain a crystalline PCMX product, washing and drying to obtain 980kg of a final product, wherein the yield is 90.3 percent, and the purity of the product reaches 94.5 percent.
Example 4
Fe-MOFs directional chlorination catalyst was prepared by the same method as in example 1.
1000+ -10 kg of ethanol and then 1000+ -10 kg of 3, 5-dimethylphenol material are added into a 3000L open enamel reactor through a metering tank, and are stirred sufficiently and uniformly for dissolution. 50+ -0.5 kg of Fe-MOFs directional chlorination catalyst is further added, and fully and uniformly stirred, 1327kg of sulfuryl chloride is gradually added dropwise within 2h, and the reaction temperature is controlled to be 5+ -3 ℃. After the reaction is continued for 2 hours, detecting that the MX content in the reaction system is lower than 0.3 percent by gas chromatography, stopping the reaction, filtering to remove the catalyst for standby, evaporating ethanol at normal pressure for recycling, then adding 2000kg of high-temperature water to fully dissolve the product, then reducing the temperature to 25 ℃ to obtain a crystalline PCMX product, washing and drying to obtain 1187kg of a final product, wherein the yield is 93.4 percent, and the product purity is up to 99.8 percent.
Example 5
Fe-MOFs directional chlorination catalyst was prepared by the same method as in example 1.
1000+ -10 kg of ethanol and then 1000+ -10 kg of 3, 5-dimethylphenol material are added into a 3000L open enamel reactor through a metering tank, and are stirred sufficiently and uniformly for dissolution. 50+ -0.5 kg of Fe-MOFs directional chlorination catalyst is further added, and fully and uniformly stirred, 1327kg of sulfuryl chloride is gradually added dropwise within 2h, and the reaction temperature is controlled at 20+ -3 ℃. After the reaction is continued for 2 hours, detecting that the MX content in the reaction system is lower than 0.3 percent by gas chromatography, stopping the reaction, filtering to remove the catalyst for standby, evaporating ethanol at normal pressure for recycling, then adding 2000kg of high-temperature water to fully dissolve the product, then reducing the temperature to 25 ℃ to obtain a crystalline PCMX product, washing and drying to obtain 1170kg of a final product, wherein the yield is 78.7 percent, and the purity of the product reaches 89.5 percent.
Example 6
Fe-MOFs directional chlorination catalyst was prepared by the same method as in example 1.
1000+ -10 kg of ethanol and then 1000+ -10 kg of 3, 5-dimethylphenol material are added into a 3000L open enamel reactor through a metering tank, and are stirred sufficiently and uniformly for dissolution. Further adding 40+ -0.5 kg of Fe-MOFs directional chlorination catalyst, fully and uniformly stirring, gradually dropwise adding 1106kg of sulfuryl chloride within 2h, and controlling the reaction temperature at 5+ -3 ℃. After the reaction is continued for 2 hours, detecting that the MX content in the reaction system is lower than 0.3 percent by gas chromatography, stopping the reaction, filtering to remove the catalyst for standby, evaporating ethanol at normal pressure for recycling, then adding 2000kg of high-temperature water, reducing the temperature to 25 ℃ to obtain a crystalline PCMX product, washing and drying to obtain 1165kg of a final product, wherein the yield is 71.1 percent, and the product purity reaches 98.8 percent.
Example 7
Fe-MOFs directional chlorination catalyst was prepared by the same method as in example 1.
1000+ -10 kg of ethanol and then 1000+ -10 kg of 3, 5-dimethylphenol material are added into a 3000L open enamel reactor through a metering tank, and are stirred sufficiently and uniformly for dissolution. Further adding 100+ -0.5 kg of Fe-MOFs directional chlorination catalyst, fully and uniformly stirring, gradually dropwise adding 1106kg of sulfuryl chloride within 2h, and controlling the reaction temperature at 5+ -3 ℃. After the reaction is continued for 2 hours, detecting that the MX content in the reaction system is lower than 0.3 percent by gas chromatography, stopping the reaction, filtering to remove the catalyst for standby, evaporating ethanol at normal pressure for recycling, then adding 2000kg of high-temperature water, reducing the temperature to 25 ℃, obtaining a crystalline PCMX product, washing and drying to obtain 1187kg of a final product, wherein the yield is 91.1 percent, and the product purity reaches 99.2 percent.
Example 8
Fe-MOFs directional chlorination catalyst was prepared by the same method as in example 1.
1000+ -10 kg of water and then 1000+ -10 kg of 3, 5-dimethylphenol material are added into a 3000L open enamel reactor via a metering tank, and are stirred sufficiently and dissolved uniformly. 50+ -0.5 kg of Fe-MOFs directional chlorination catalyst is further added, and fully and uniformly stirred, 1106kg of sulfuryl chloride is gradually added dropwise within 2h, and the reaction temperature is controlled to be 5+ -3 ℃. Stopping the reaction when the content of MX is lower than 0.3% by gas chromatography, filtering to remove the catalyst for standby, evaporating propanol at normal pressure for recycling, then adding 2000kg of high temperature water, reducing the temperature to 25 ℃ to obtain a crystalline PCMX product, washing and drying to obtain 1080kg of a final product with the yield of 87.3%, and the purity of the product reaching 95.3%.
Example 9
Fe-MOFs directional chlorination catalyst was prepared by the same method as in example 1.
1000+ -10 kg of isopropanol is added into a 3000L open enamel reactor through a metering tank, and then 1000+ -10 kg of 3, 5-dimethylphenol material is added, and the materials are fully and uniformly stirred for dissolution. 50+ -0.5 kg of Fe-MOFs directional chlorination catalyst is further added, and fully and uniformly stirred, 1106kg of sulfuryl chloride is gradually added dropwise within 2h, and the reaction temperature is controlled to be 5+ -3 ℃. Stopping the reaction when the content of MX is lower than 0.3% by gas chromatography, filtering to remove the catalyst for standby, steaming to remove isopropanol under normal pressure for recycling, then adding 2000kg of high-temperature water, reducing the temperature to 25 ℃ to obtain a crystalline PCMX product, washing and drying to obtain 981kg of final product, wherein the yield is 91.4%, and the purity of the product reaches 89.1%.
Example 10
Fe-MOFs directional chlorination catalyst was prepared by the same method as in example 1.
1200+ -10 kg of ethanol is added into a 3000L open enamel reactor through a metering tank, and then 1000+ -10 kg of 3, 5-dimethylphenol material is added, and the materials are fully and uniformly stirred for dissolution. 50+ -0.5 kg of Fe-MOFs directional chlorination catalyst is further added, and fully and uniformly stirred, 1106kg of sulfuryl chloride is gradually added dropwise within 2h, and the reaction temperature is controlled to be 10+ -3 ℃. Stopping the reaction when the content of MX is lower than 0.3% by gas chromatography, filtering to remove the catalyst for standby, evaporating ethanol at normal pressure for recycling, then adding 2000kg of high temperature water, reducing the temperature to 25 ℃ to obtain a crystalline PCMX product, washing and drying to obtain 1157kg of a final product with the yield of 90.6%, and the purity of the product reaching 99.1%.
Example 11
1000+ -10 kg of tetrachloroethylene and then 1000+ -10 kg of 3, 5-dimethylphenol material were added into a 3000L open enamel reactor via a metering tank, and were thoroughly stirred and dissolved. 50+ -0.5 kg of Fe-MOFs directional chlorination catalyst is further added, and fully and uniformly stirred, 1106kg of sulfuryl chloride is gradually added dropwise within 2h, and the reaction temperature is controlled to be 5+ -3 ℃. When the content of MX is lower than 0.3 percent by gas chromatography detection, stopping the reaction, reducing the temperature to 0-5 ℃, obtaining a crystalline PCMX product, washing and drying to obtain 886kg of a final product, wherein the yield is 75.1 percent, and the purity of the product reaches 72.1 percent.
Example 12
1000+ -10 kg of tetrachloroethylene and then 1000+ -10 kg of 3, 5-dimethylphenol material were added into a 3000L open enamel reactor via a metering tank, and were thoroughly stirred and dissolved. Further adding 100+ -1 kg of ferric trichloride and 20+ -0.2 kg of butyl thioether, stirring thoroughly and uniformly, gradually dropwise adding 1125kg of sulfuryl chloride within 3h, and controlling the reaction temperature at 20+ -3 ℃. After the dripping is completed, the temperature is kept for 1h, the temperature is raised to 40 ℃, the water is taken for washing, the water is kept stand for layering, the crystalline PCMX product is obtained, 886kg of the final product is obtained after washing and drying, the yield is 85.1%, and the purity of the product reaches 72.1%.
Example 13
1000+ -10 kg of ethanol and then 1000+ -10 kg of 3, 5-dimethylphenol material are added into a 3000L open enamel reactor through a metering tank, and are stirred sufficiently and uniformly for dissolution. Further adding 100+ -1 kg of ferric trichloride and 20+ -0.2 kg of butyl thioether, stirring thoroughly and uniformly, gradually dropwise adding 1125kg of sulfuryl chloride within 3h, and controlling the reaction temperature at 20+ -3 ℃. After the dripping is finished, the temperature is kept for 1h, the temperature is raised to 40 ℃, the water is taken for washing, the water is kept stand for layering, the crystallized PCMX product is obtained, 905kg of final product is obtained after washing and drying, the yield is 88.1%, and the purity of the product reaches 77.2%.
Example 14
Fe-MOFs directional chlorination catalyst was prepared by the same method as in example 1. The chlorination reaction procedure of 3, 5-dimethylphenol is the same as that of example 2, and the catalyst and the product are separated and recycled for 2 nd, 3 rd and 4 th times, and 5 th times, so that the influence of the use times of the catalyst on the chlorination process of 3, 5-dimethylphenol can be obtained, as shown in table 1:
TABLE 1 influence of the number of catalyst cycles on MX chlorination process
| Number of times of cyclic use | Product yield | Purity of the product |
| First time | 94.0％ | 99.7％ |
| Second time | 93.7％ | 99.5％ |
| Third time | 92.8％ | 99.2％ |
| Fourth time | 92.5％ | 99.0％ |
| Fifth time | 92.0％ | 98.9％ |
It can be seen that the catalyst is reused many times without a significant decrease in performance.
In conclusion, the invention uses the alcohol compound as the solvent, greatly increases the solubility of MX and PCMX in the solvent, and avoids the generation of further chlorination by-products due to solid precipitation in the chlorination process. Meanwhile, the synthesis method of the added directional chlorination catalyst is simple, the catalyst has higher activity and selectivity, the catalyst has better stability and can be repeatedly used, the cost is reduced, the reaction time is shortened, and the continuous industrial production is facilitated.
Claims (1)
1. A process for preparing 4-chloro-3, 5-dimethylphenol comprising the steps of:
(1) Preparation of Fe-MOFs directional chlorination catalyst
Adding 50.0kg of ferric trichloride hexahydrate and 50.0kg of terephthalic acid ligand into a container, adding a certain amount of deionized water, stirring and dissolving, transferring into a reaction kettle with polytetrafluoroethylene as an inner container, sealing, reacting for 5 hours at 140-220 ℃, centrifuging, washing a product, and drying;
(2) Directional chlorination of MX
1000+/-10 kg of ethanol is added into a 3000L open enamel reactor through a metering tank, and then 1000+/-10 kg of 3, 5-dimethylphenol material is added, and the materials are fully and uniformly stirred for dissolution; further adding 50+/-0.5 kg of Fe-MOFs directional chlorination catalyst, fully and uniformly stirring, gradually dropwise adding 1106kg of sulfuryl chloride within 2 hours, and controlling the reaction temperature to be 5+/-3 ℃; after the reaction is continued for 2 hours, detecting that the MX content in the reaction system is lower than 0.3 percent through gas chromatography, stopping the reaction, filtering to remove the catalyst for standby, evaporating methanol at normal pressure for recycling, then adding 2000kg of high-temperature water to fully dissolve the product, then reducing the temperature to 25 ℃ to obtain a crystalline PCMX product, and washing and drying to obtain the final product.
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| US4245127A (en) * | 1975-10-31 | 1981-01-13 | Seitetsu Kagaku Co., Ltd. | Process for chlorinating xylenols |
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| US4245127A (en) * | 1975-10-31 | 1981-01-13 | Seitetsu Kagaku Co., Ltd. | Process for chlorinating xylenols |
| US4250122A (en) * | 1979-09-07 | 1981-02-10 | Hooker Chemicals & Plastics Corp. | Process and catalyst mixture for the para-directed chlorination of alkylbenzenes |
| CN101085722A (en) * | 2007-01-10 | 2007-12-12 | 胡汉忠 | Industrial preparation method for p-chloroalkylphenols |
| WO2008129024A1 (en) * | 2007-04-24 | 2008-10-30 | Basf Se | Porous organometallic framework materials loaded with catalyst metal components |
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