CN111302983A - Preparation method for catalytically synthesizing 4,4' -dichlorobenzenesulfone - Google Patents
Preparation method for catalytically synthesizing 4,4' -dichlorobenzenesulfone Download PDFInfo
- Publication number
- CN111302983A CN111302983A CN202010249481.5A CN202010249481A CN111302983A CN 111302983 A CN111302983 A CN 111302983A CN 202010249481 A CN202010249481 A CN 202010249481A CN 111302983 A CN111302983 A CN 111302983A
- Authority
- CN
- China
- Prior art keywords
- reaction
- catalyst
- liquid
- filtering
- finished
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims abstract description 54
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000001914 filtration Methods 0.000 claims abstract description 37
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 238000001816 cooling Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002608 ionic liquid Substances 0.000 claims abstract description 24
- 239000002105 nanoparticle Substances 0.000 claims abstract description 21
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- KJGYFISADIZFEL-UHFFFAOYSA-N 1-chloro-4-(4-chlorophenyl)sulfinylbenzene Chemical compound C1=CC(Cl)=CC=C1S(=O)C1=CC=C(Cl)C=C1 KJGYFISADIZFEL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 15
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229960000583 acetic acid Drugs 0.000 claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 12
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 12
- 230000007935 neutral effect Effects 0.000 claims abstract description 12
- 238000002425 crystallisation Methods 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000005727 Friedel-Crafts reaction Methods 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- 239000007787 solid Substances 0.000 claims description 29
- 238000001035 drying Methods 0.000 claims description 20
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 19
- 238000010992 reflux Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- -1 imidazole amine Chemical class 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- ZTGQZSKPSJUEBU-UHFFFAOYSA-N 3-bromopropan-1-amine Chemical compound NCCCBr ZTGQZSKPSJUEBU-UHFFFAOYSA-N 0.000 claims description 3
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 5
- 239000000047 product Substances 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000001514 detection method Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 8
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 7
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 206010024229 Leprosy Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
- B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
-
- 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
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
-
- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
-
- 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
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method for catalytically synthesizing 4,4 '-dichlorodiphenylsulfone, which comprises the steps of taking superparamagnetic nanoparticle loaded ionic liquid as a catalyst, carrying out Friedel-crafts reaction on chlorobenzene and thionyl chloride under the action of the catalyst, adding a catalyst recovered by a magnetic field after the reaction is finished, pouring out reaction liquid, dropwise adding saturated sodium bicarbonate solution into the reaction liquid to adjust the pH value to be neutral, stirring, filtering the feed liquid while the feed liquid is hot, cooling the filtrate to 0-5 ℃ for crystallization, filtering to obtain 4,4' -dichlorodiphenylsulfoxide, dissolving the 4,4 '-dichlorodiphenylsulfone into glacial acetic acid, adding hydrogen peroxide for oxidation reaction, cooling after the reaction is finished, and filtering to obtain the 4,4' -dichlorodiphenylsulfone. The chlorobenzene is used as a reaction raw material and a solvent, other solvent impurities are not mixed, the process is simple, the cost is low, the impurities are few, the purity of the obtained product is high, the content is more than 99.2 percent, the content of the 2, 4' isomer is less than 0.1 percent, the yield is more than 90 percent, the economic benefit is good, and the method is suitable for industrial production.
Description
Technical Field
The invention relates to a preparation method of a compound, in particular to a method for preparing 4,4' -dichlorodiphenyl sulfone by taking superparamagnetic nanoparticle loaded ionic liquid as a catalyst, which is green and efficient.
Background
4,4' -dichlorodiphenyl sulfone (DDS) is an important organic synthetic product, is a main raw material for preparing engineering plastics such as polysulfone, polyether sulfone and the like, and is also an intermediate of medicines, dyes, pesticides and the like. It can be used for preparing various polymer products, such as bisphenol A type polysulfone, polyphenylene ether sulfone, polyamide sulfone and other resins, and can also be used for preparing leprosy drug intermediate 4,4' -diamino diphenyl sulfone. With the wide application of polymer materials, the demand of DDS is also increasing.
There are many industrial methods for producing DDS, mainly including sulfuric acid, chlorosulfonic acid, sulfur trioxide, and sulfoxide oxidation. The sulfuric acid process has low cost, simple material, low conversion rate, long reaction period, low product smelting point and poor product quality. The chlorosulfonic acid method has mature process, good product quality, high production cost and serious three wastes. The DDS preparation by sulfur trioxide is an improved method, and the method is reported to be adopted by UCC company in the United states, and the DDS is sulfonated by sulfur trioxide, so that the process is relatively complex. Chinese patent CN104402780 adopts a sulfoxide oxidation method, and takes anhydrous aluminum trichloride as a catalyst to prepare DDS, and the process generates a large amount of waste water, waste gas and solid waste.
In recent years, a catalyst catalysis technology loaded by superparamagnetic nano particles is widely used in organic synthesis production as a green reaction technology, superparamagnetic nano particle loaded ionic liquid is designed as a catalyst, and chlorobenzene and thionyl chloride are subjected to Friedel-crafts reaction under the action of the catalyst to prepare 4,4' -dichlorodiphenyl sulfone. Compared with the traditional phase process, the process is simple, the cost is low, impurities are few, the purity of the obtained product is high, the content is more than 99.2%, the content of the 2, 4' isomer is less than 0.1%, the yield is more than 90%, the catalytic activity of the catalyst is good (high specific surface area), the recovery is simple and convenient (recovery by an external magnetic field), the catalyst can be reused, the economic benefit is good, and the method is suitable for industrial production.
Disclosure of Invention
The invention aims to provide a method for catalytically synthesizing 4,4' -dichlorodiphenyl sulfone by using a novel superparamagnetic nanoparticle supported ionic liquid catalyst.
The technical scheme of the invention is as follows: a preparation method for catalytically synthesizing 4,4 '-dichlorodiphenylsulfone comprises the steps of taking superparamagnetic nanoparticle loaded ionic liquid as a catalyst, carrying out Friedel-crafts reaction on chlorobenzene and thionyl chloride under the action of the catalyst, adding the catalyst recovered by a magnetic field after the reaction is finished, pouring out reaction liquid, dropwise adding saturated sodium bicarbonate solution into the reaction liquid to adjust the pH value to be neutral, stirring for 0.5h, filtering the liquid when the liquid is hot, cooling the filtrate to 0-5 ℃ for crystallization, filtering to obtain 4,4' -dichlorodiphenylsulfoxide, dissolving the 4,4 '-dichlorodiphenylsulfone into glacial acetic acid, adding hydrogen peroxide for oxidation reaction, cooling after the reaction is finished, and filtering to obtain the 4,4' -dichlorodiphenylsulfone. Chlorobenzene is used as a reaction raw material and a solvent, other solvent impurities are not mixed, the cost is saved, the post-treatment is easier, and the product purity is high. The method has the advantages of simple process, low cost, less impurities, high purity of the obtained product, high yield up to 90 percent, high yield of more than 99.2 percent and less than 0.1 percent of 2, 4' isomer, and suitability for industrial production. Wherein the catalyst is:
preparation of a superparamagnetic nanoparticle supported ionic liquid catalyst: 3-chloropropyltriethoxysilane, imidazole, dry toluene in N2Carrying out reflux reaction under protection, and separating by column chromatography to obtain an intermediate; the intermediate is reacted with Fe3O4/SiO2Stirring the solid particles in anhydrous toluene for reaction, and carrying out reflux reaction on the solid collected by a magnet and bromopropylamine in the anhydrous toluene after the reaction is finishedCollecting the loaded imidazole amine functional ionic liquid PA-IL @ MNP by using a magnet after the reaction is finished, and carrying out reflux reaction on the loaded imidazole amine functional ionic liquid PA-IL @ MNP and acetylpyridine in anhydrous toluene; and cooling the reaction liquid to room temperature, collecting the reaction liquid by using a magnet to obtain superparamagnetic nanoparticle supported ionic liquid, and finally, carrying out reflux reaction on the superparamagnetic nanoparticle supported ionic liquid and palladium acetate in 20ml of acetone to obtain brown solid, collecting the brown solid by using the magnet, washing and drying to obtain superparamagnetic nanoparticle supported ionic liquid catalyst 7. The effective loading amount of the catalyst is 0.60mmol/g by element analysis;
wherein: the molar ratio of chlorobenzene to thionyl chloride is 2: 1-10: 1.
wherein: the molar ratio of the catalyst is 0.001-0.01 times of that of thionyl chloride.
Wherein: the concentration of the hydrogen peroxide as the oxidant is 30-50%, and the molar ratio of the hydrogen peroxide to the thionyl chloride is 1-5: 1.
Wherein: the hydrogen peroxide is dropwise added, the oxidation reaction temperature is 60-80 ℃, and the oxidation time is 1-2 hours.
After the reaction is finished, the catalyst is recovered by an external magnetic field, washed by ethanol and dried for 5 hours in vacuum at 60 ℃, can be repeatedly used, and the activity is not obviously reduced.
The invention has the advantages that: compared with the traditional phase process, the chlorobenzene is used as a reaction raw material and a solvent, other solvent impurities are not mixed, the process is simple, the cost is low, the solubility of the 4,4 '-dichlorodiphenylsulfoxide in the chlorobenzene is low at low temperature, the product purity is high by low-temperature crystallization and filtration, the content is more than 99.2 percent, the content of the 2, 4' isomer is less than 0.1 percent, the yield is more than 90 percent, the catalyst has good catalytic activity (high specific surface area) and simple and convenient recovery (recovery of an external magnetic field), can be repeatedly used, has good economic benefit and is suitable for industrial production.
Detailed Description
A preparation method for catalytically synthesizing 4,4' -dichlorobenzenesulfone is characterized in that a preparation process of a superparamagnetic nanoparticle supported ionic liquid catalyst used in the invention comprises the following steps:
3-chloropropyltriethoxysilane 1(12ml,50mmol) and imidazole 2(3.4g,50mmol) were weighed out separately in a reaction vessel, 50ml of dry toluene, N2Refluxing and stirring for reaction for 24h under protection, and separating by column chromatography to obtain an intermediate 3 (an EA as a developing agent); 1g of Fe is taken3O4/SiO2Adding solid particles into a reaction container, adding 50ml of anhydrous toluene, carrying out ultrasonic treatment for 1h, taking 0.5g of intermediate 3 after the ultrasonic treatment, dissolving the intermediate 3 into 20ml of anhydrous toluene, and then dropwise adding the intermediate into the reaction system, wherein N is2Carrying out reflux stirring reaction for 48h under protection, collecting by using a magnet after the reaction is finished, washing by using ethanol for three times, and drying in vacuum to obtain solid particles 4; 2g of solid particles 4 are taken in a reaction vessel, 100ml of anhydrous toluene is added, ultrasonic treatment is carried out for 1h, 4mmol (0.55g) of bromopropylamine is taken after the ultrasonic treatment is finished, dissolved in 20ml of anhydrous toluene and then is dripped into the reaction system, and N2And (2) carrying out reflux stirring reaction for 48h under the protection, collecting by using a magnet after the reaction is finished, washing for three times by using ethanol, and drying in vacuum to obtain the loaded imidazole amine type functional ionic liquid PA-IL @ MNP 5, wherein the mass of the finally obtained gray nano-particles is 2.0g, adding 30ml of anhydrous toluene into 2g of PA-IL @ MNP 5 and 0.5g of 2-hydroxybenzaldehyde, carrying out ultrasonic treatment for 1h, and carrying out mechanical stirring reflux for 3h at 110 ℃ under the protection of nitrogen. And cooling the reaction liquid to room temperature, collecting the obtained brown solid by using a magnet, washing by using ethanol, and carrying out vacuum drying at 60 ℃ for 10h to obtain a superparamagnetic nanoparticle supported ionic liquid 6, finally, taking 1g of superparamagnetic nanoparticle supported ionic liquid 6 and 0.75g of palladium acetate, mechanically stirring and refluxing in 20ml of acetone at room temperature for 4h, collecting the obtained brown solid by using a magnet, washing by using ethanol, and carrying out vacuum drying at 60 ℃ for 10h to obtain a superparamagnetic nanoparticle supported ionic liquid catalyst 7. The effective loading of the catalyst is 0.60mmol/g by element analysis.
The reaction formula is as follows:
the preparation process of the 4,4' -dichlorodiphenyl sulfoxide comprises the following steps: taking superparamagnetic nano particle loaded ionic liquid as a catalyst Cat, enabling chlorobenzene 8 and thionyl chloride 9 to perform Friedel-crafts reaction under the action of the catalyst, adding the catalyst recovered by a magnetic field after the reaction is finished, pouring out the reaction liquid, dropwise adding saturated sodium bicarbonate solution into the reaction liquid to adjust the pH value to be neutral, stirring for 0.5h, filtering the liquid while the liquid is hot, cooling the filtrate to 0-5 ℃ for crystallization, filtering to obtain 4,4' -dichlorodiphenyl sulfoxide 10, dissolving the 4,4' -dichlorodiphenyl sulfoxide in glacial acetic acid, adding hydrogen peroxide for oxidation reaction, cooling after the reaction is finished, and filtering to obtain 4,4' -dichlorodiphenyl sulfone 11.
The reaction formula is as follows:
example 1
Chlorobenzene (1.0mol, 112.5g) was added into a four-necked flask, then a catalyst (0.34g, 0.2mmol) was added, after stirring, thionyl chloride (0.2mol, 23.8g) was added dropwise, the reaction was exothermic, and the temperature was controlled at 30 ℃. Dropwise adding thionyl chloride, keeping the temperature and stirring for 1h, after the reaction is finished, adding a catalyst recovered by a magnetic field, pouring out the reaction solution, dropwise adding a saturated sodium bicarbonate solution into the reaction solution to adjust the pH value to be neutral, stirring for 0.5h, filtering while the solution is hot, cooling the filtrate to 0-5 ℃, crystallizing, filtering and drying to obtain solid 4,4 '-dichlorodiphenyl sulfoxide (0.19mol and 51.2g), heating and dissolving the solid with glacial acetic acid (0.3mol and 18g), dropwise adding 35% hydrogen peroxide (0.3mol and 30g) at 60 ℃, keeping the temperature for 2h, cooling, filtering and drying to obtain 4,4' -dichlorodiphenyl sulfone (0.18mol and 51.8g) with the content of 99.5% (HPLC detection), wherein the yield is 90.5%.
Example 2
Chlorobenzene (1.2mol, 135g) was added into a four-necked flask, then a catalyst (0.34g, 0.2mmol) was added, after stirring, thionyl chloride (0.2mol, 23.8g) was added dropwise, the reaction was exothermic, and the temperature was controlled at 30 ℃. Dropwise adding thionyl chloride, keeping the temperature and stirring for 1h, after the reaction is finished, adding a catalyst recovered by a magnetic field, pouring out the reaction solution, dropwise adding a saturated sodium bicarbonate solution into the reaction solution to adjust the pH value to be neutral, stirring for 0.5h, filtering while the solution is hot, cooling the filtrate to 0-5 ℃ for crystallization, filtering and drying to obtain solid 4,4 '-dichlorodiphenyl sulfoxide (0.185mol and 50.0g), heating and dissolving the solid with glacial acetic acid (0.3mol and 18g), dropwise adding 35% hydrogen peroxide (0.3mol and 30g) for oxidation at 60 ℃, keeping the temperature for 2h, cooling, filtering and drying to obtain 4,4' -dichlorodiphenyl sulfone (0.17mol and 50.0g), wherein the content is 99.6% (HPLC detection), and the yield is 87.5%.
Example 3
Chlorobenzene (0.8mol, 90.0g) was added into a four-necked flask, then a catalyst (0.34g, 0.2mmol) was added, after stirring, thionyl chloride (0.2mol, 23.8g) was added dropwise, the reaction was exothermic, and the temperature was controlled at 30 ℃. Dropwise adding thionyl chloride, keeping the temperature and stirring for 1h, after the reaction is finished, adding a catalyst recovered by a magnetic field, pouring out the reaction solution, dropwise adding a saturated sodium bicarbonate solution into the reaction solution to adjust the pH value to be neutral, stirring for 0.5h, filtering while the solution is hot, cooling the filtrate to 0-5 ℃ for crystallization, filtering and drying to obtain solid 4,4 '-dichlorodiphenyl sulfoxide (0.18mol, 48.5g), heating and dissolving with glacial acetic acid (0.3mol, 18g), dropwise adding 35% hydrogen peroxide (0.3mol, 30g) for oxidation at 60 ℃, keeping the temperature for 2h, cooling, filtering and drying to obtain 4,4' -dichlorodiphenyl sulfone (0.17mol, 50.0g), wherein the content is 99.2% (HPLC detection), and the yield is 87.5%.
Example 4
Chlorobenzene (1.0mol, 112.5g) was added into a four-necked flask, then a catalyst (0.68g, 0.4mmol) was added, after stirring, thionyl chloride (0.2mol, 23.8g) was added dropwise, the reaction was exothermic, and the temperature was controlled at 30 ℃. Dropwise adding thionyl chloride, keeping the temperature and stirring for 1h, after the reaction is finished, adding a catalyst recovered by a magnetic field, pouring out the reaction solution, dropwise adding a saturated sodium bicarbonate solution into the reaction solution to adjust the pH value to be neutral, stirring for 0.5h, filtering while the solution is hot, cooling the filtrate to 0-5 ℃ for crystallization, filtering and drying to obtain solid 4,4 '-dichlorodiphenyl sulfoxide (0.195mol and 52.5g), heating and dissolving the solid with glacial acetic acid (0.3mol and 18g), dropwise adding 35% hydrogen peroxide (0.3mol and 30g) at 60 ℃ for oxidation, keeping the temperature for 2h, cooling, filtering and drying to obtain 4,4' -dichlorodiphenyl sulfone (0.185mol and 53.2g), wherein the content is 99.3% (HPLC detection), and the yield is 93.0%.
Example 5
Chlorobenzene (1.0mol, 112.5g) was added into a four-necked flask, then a catalyst (0.68g, 0.4mmol) was added, after stirring, thionyl chloride (0.24mol, 28.5g) was added dropwise, the reaction was exothermic, and the temperature was controlled at 30 ℃. Dropwise adding thionyl chloride, keeping the temperature and stirring for 1h, after the reaction is finished, adding a catalyst recovered by a magnetic field, pouring out the reaction solution, dropwise adding a saturated sodium bicarbonate solution into the reaction solution to adjust the pH value to be neutral, stirring for 0.5h, filtering while the solution is hot, cooling the filtrate to 0-5 ℃ for crystallization, filtering and drying to obtain solid 4,4 '-dichlorodiphenyl sulfoxide (0.19mol, 51.2g), heating and dissolving the solid with glacial acetic acid (0.3mol, 18g), dropwise adding 35% hydrogen peroxide (0.3mol, 30g) for oxidation at 60 ℃, keeping the temperature for 2h, cooling, filtering and drying to obtain 4,4' -dichlorodiphenyl sulfone (0.18mol, 51.8g), wherein the content is 99.3% (HPLC detection), and the yield is 90.5%.
Example 6
Chlorobenzene (1.0mol, 112.5g) was added into a four-necked flask, then a catalyst (0.68g, 0.4mmol) was added, after stirring, thionyl chloride (0.2mol, 23.8g) was added dropwise, the reaction was exothermic, and the temperature was controlled at 30 ℃. Dropwise adding thionyl chloride, keeping the temperature and stirring for 1h, after the reaction is finished, adding a catalyst recovered by a magnetic field, pouring out the reaction solution, dropwise adding a saturated sodium bicarbonate solution into the reaction solution to adjust the pH value to be neutral, stirring for 0.5h, filtering while the solution is hot, cooling the filtrate to 0-5 ℃ for crystallization, filtering and drying to obtain solid 4,4 '-dichlorodiphenyl sulfoxide (0.19mol, 51.2g), heating and dissolving the solid with glacial acetic acid (0.3mol, 18g), dropwise adding 40% hydrogen peroxide (0.35mol, 30g) for oxidation at 60 ℃, keeping the temperature for 2h, cooling, filtering and drying to obtain 4,4' -dichlorodiphenyl sulfone (0.18mol, 51.8g), wherein the content is 99.4% (HPLC detection), and the yield is 90.5%.
Example 7
Chlorobenzene (1.0mol, 112.5g) was added into a four-necked flask, then a catalyst (0.68g, 0.4mmol) was added, after stirring, thionyl chloride (0.2mol, 23.8g) was added dropwise, the reaction was exothermic, and the temperature was controlled at 30 ℃. Dropwise adding thionyl chloride, keeping the temperature and stirring for 1h, after the reaction is finished, adding a catalyst recovered by a magnetic field, pouring out the reaction solution, dropwise adding a saturated sodium bicarbonate solution into the reaction solution to adjust the pH value to be neutral, stirring for 0.5h, filtering while the solution is hot, cooling the filtrate to 0-5 ℃ for crystallization, filtering and drying to obtain solid 4,4 '-dichlorodiphenyl sulfoxide (0.19mol, 51.2g), heating and dissolving the solid with glacial acetic acid (0.3mol, 18g), dropwise adding 30% hydrogen peroxide (0.3mol, 35g) for oxidation at 60 ℃, keeping the temperature for 2h, cooling, filtering and drying to obtain 4,4' -dichlorodiphenyl sulfone (0.175mol, 50.3g), wherein the content is 99.0% (HPLC detection), and the yield is 88.0%.
Example 8
Chlorobenzene (1.0mol, 112.5g) was added into a four-necked flask, then a catalyst (0.68g, 0.4mmol) was added, after stirring, thionyl chloride (0.2mol, 23.8g) was added dropwise, the reaction was exothermic, and the temperature was controlled at 30 ℃. Dropwise adding thionyl chloride, keeping the temperature and stirring for 1h, after the reaction is finished, adding a catalyst recovered by a magnetic field, pouring out the reaction solution, dropwise adding a saturated sodium bicarbonate solution into the reaction solution to adjust the pH value to be neutral, stirring for 0.5h, filtering while the solution is hot, cooling the filtrate to 0-5 ℃, crystallizing, filtering and drying to obtain solid 4,4 '-dichlorodiphenyl sulfoxide (0.19mol and 51.2g), heating and dissolving the solid with glacial acetic acid (0.3mol and 18g), dropwise adding 35% hydrogen peroxide (0.3mol and 30g) at 60 ℃, keeping the temperature for 2h, cooling, filtering and drying to obtain 4,4' -dichlorodiphenyl sulfone (0.18mol and 51.8g) with the content of 99.5% (HPLC detection), wherein the yield is 90.5%. The catalyst is repeatedly used for 5 times, the yield is not obviously reduced, and the specific result is shown in table 1.
It should be noted that the above summary and the detailed description are intended to demonstrate the practical application of the technical solutions provided by the present invention, and should not be construed as limiting the scope of the present invention. Various modifications, equivalent substitutions, or improvements will now occur to those skilled in the art without departing from the spirit and principles of the invention. The scope of the invention is to be determined by the appended claims.
Claims (6)
1. A preparation method for catalytically synthesizing 4,4' -dichlorobenzenesulfone is characterized by comprising the following steps: the method comprises the steps of taking superparamagnetic nanoparticle loaded ionic liquid as a catalyst, carrying out Friedel-crafts reaction on chlorobenzene and thionyl chloride under the action of the catalyst, pouring out reaction liquid after the reaction is finished and adding the catalyst recovered by a magnetic field, dropwise adding saturated sodium bicarbonate solution into the reaction liquid to adjust the pH value to be neutral, stirring for 0.5h, filtering the liquid while the liquid is hot, cooling the filtrate to 0-5 ℃ for crystallization, filtering to obtain 4,4' -dichlorodiphenyl sulfoxide, dissolving the 4,4' -dichlorodiphenyl sulfoxide in glacial acetic acid, adding hydrogen peroxide for oxidation reaction, cooling after the reaction is finished, and filtering to obtain 4,4' -dichlorodiphenyl sulfone; wherein the catalyst is:
preparation of a superparamagnetic nanoparticle supported ionic liquid catalyst: 3-chloropropyltriethoxysilane, imidazole, dry toluene in N2Carrying out reflux reaction under protection, and separating by column chromatography to obtain an intermediate; the intermediate is reacted with Fe3O4/SiO2Stirring the solid particles in anhydrous toluene for reaction, carrying out reflux reaction on the solid collected by a magnet and bromopropylamine in the anhydrous toluene after the reaction is finished, collecting the solid by the magnet after the reaction is finished to obtain a load imidazole amine type functional ionic liquid PA-IL @ MNP, and carrying out reflux reaction on the load imidazole amine type functional ionic liquid PA-IL @ MNP and acetylpyridine in the anhydrous toluene; cooling the reaction liquid to room temperature, collecting the reaction liquid by using a magnet to obtain superparamagnetic nanoparticle supported ionic liquid, and finally, carrying out reflux reaction on the superparamagnetic nanoparticle supported ionic liquid and palladium acetate in 20ml of acetone to obtain brown solid, collecting the brown solid by using the magnet, washing and drying to obtain a superparamagnetic nanoparticle supported ionic liquid catalyst 7; the reaction formula is as follows:
2. the process according to claim 1, wherein the synthesis is carried out in the presence of a catalyst selected from the group consisting of: the molar ratio of chlorobenzene to thionyl chloride is 2: 1-10: 1.
3. the process according to claim 1, wherein the synthesis is carried out in the presence of a catalyst selected from the group consisting of: the molar ratio of the catalyst is 0.001-0.01 times of that of thionyl chloride.
4. The process according to claim 1, wherein the synthesis is carried out in the presence of a catalyst selected from the group consisting of: the concentration of the hydrogen peroxide as the oxidant is 30-50%, and the molar ratio of the hydrogen peroxide to the thionyl chloride is 1-5: 1.
5. The process according to claim 1, wherein the synthesis is carried out in the presence of a catalyst selected from the group consisting of: the hydrogen peroxide is dropwise added, the oxidation reaction temperature is 60-80 ℃, and the oxidation time is 1-2 hours.
6. The process according to claim 1, wherein the synthesis is carried out in the presence of a catalyst selected from the group consisting of: after the reaction is finished, the catalyst is recovered by an external magnetic field, washed by ethanol and dried for 5 hours in vacuum at 60 ℃, can be repeatedly used, and the activity is not obviously reduced.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010249481.5A CN111302983A (en) | 2020-04-01 | 2020-04-01 | Preparation method for catalytically synthesizing 4,4' -dichlorobenzenesulfone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010249481.5A CN111302983A (en) | 2020-04-01 | 2020-04-01 | Preparation method for catalytically synthesizing 4,4' -dichlorobenzenesulfone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111302983A true CN111302983A (en) | 2020-06-19 |
Family
ID=71157820
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010249481.5A Withdrawn CN111302983A (en) | 2020-04-01 | 2020-04-01 | Preparation method for catalytically synthesizing 4,4' -dichlorobenzenesulfone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111302983A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113072452A (en) * | 2021-04-01 | 2021-07-06 | 九江善水科技股份有限公司 | Method for catalytically synthesizing o-aminophenol |
| CN113651737A (en) * | 2021-08-21 | 2021-11-16 | 九江中星医药化工有限公司 | Method for preparing 2,4' -dihydroxydiphenyl sulfone by catalytic selectivity |
| CN113861084A (en) * | 2021-12-03 | 2021-12-31 | 富海(东营)新材料科技有限公司 | Process for preparing 4,4' -dichlorodiphenyl sulfone by one-pot method |
| CN115286543A (en) * | 2022-09-05 | 2022-11-04 | 富海(东营)新材料科技有限公司 | Process for preparing 4,4' -dichlorodiphenyl sulfone by utilizing perfluoroalkyl sulfonic acid ionic liquid |
| CN116715611A (en) * | 2023-05-19 | 2023-09-08 | 锦州三丰科技有限公司 | Green synthesis method of 4,4' -dichlorodiphenyl sulfone |
| CN116768766A (en) * | 2023-05-19 | 2023-09-19 | 锦州三丰科技有限公司 | Preparation method of 4,4' -dichlorodiphenyl sulfone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402780A (en) * | 2014-12-12 | 2015-03-11 | 山东凯盛新材料有限公司 | Synthesis process of 4, 4'-dichlorodiphenyl sulfone |
-
2020
- 2020-04-01 CN CN202010249481.5A patent/CN111302983A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104402780A (en) * | 2014-12-12 | 2015-03-11 | 山东凯盛新材料有限公司 | Synthesis process of 4, 4'-dichlorodiphenyl sulfone |
Non-Patent Citations (7)
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113072452A (en) * | 2021-04-01 | 2021-07-06 | 九江善水科技股份有限公司 | Method for catalytically synthesizing o-aminophenol |
| CN113072452B (en) * | 2021-04-01 | 2023-03-14 | 九江善水科技股份有限公司 | Method for catalytically synthesizing o-aminophenol |
| CN113651737A (en) * | 2021-08-21 | 2021-11-16 | 九江中星医药化工有限公司 | Method for preparing 2,4' -dihydroxydiphenyl sulfone by catalytic selectivity |
| CN113861084A (en) * | 2021-12-03 | 2021-12-31 | 富海(东营)新材料科技有限公司 | Process for preparing 4,4' -dichlorodiphenyl sulfone by one-pot method |
| CN115286543A (en) * | 2022-09-05 | 2022-11-04 | 富海(东营)新材料科技有限公司 | Process for preparing 4,4' -dichlorodiphenyl sulfone by utilizing perfluoroalkyl sulfonic acid ionic liquid |
| CN115286543B (en) * | 2022-09-05 | 2023-12-01 | 富海(东营)新材料科技有限公司 | Process for preparing 4,4' -dichloro diphenyl sulfone by utilizing perfluoroalkyl sulfonic acid ionic liquid |
| CN116715611A (en) * | 2023-05-19 | 2023-09-08 | 锦州三丰科技有限公司 | Green synthesis method of 4,4' -dichlorodiphenyl sulfone |
| CN116768766A (en) * | 2023-05-19 | 2023-09-19 | 锦州三丰科技有限公司 | Preparation method of 4,4' -dichlorodiphenyl sulfone |
| CN116768766B (en) * | 2023-05-19 | 2024-05-31 | 锦州三丰科技有限公司 | Preparation method of 4,4' -dichlorodiphenyl sulfone |
| CN116715611B (en) * | 2023-05-19 | 2024-05-31 | 锦州三丰科技有限公司 | Green synthesis method of 4,4' -dichlorodiphenyl sulfone |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111302983A (en) | Preparation method for catalytically synthesizing 4,4' -dichlorobenzenesulfone | |
| CN110452392B (en) | Preparation method of cobalt-based metal organic framework material and application of cobalt-based metal organic framework material in p-xylene oxidation reaction | |
| CN102584650A (en) | Preparation method of 2-nitro-4-methylsulphonylbenzoic acid | |
| CN102936297B (en) | Porous chitosan metal porphyrin composite and preparation method and application thereof | |
| CN111302981B (en) | Method for preparing taurine | |
| CN111170829B (en) | Preparation method of hexamethyl indanol | |
| CN110590671B (en) | Copper complex catalyst, preparation method thereof and application thereof in synthesis of 4,4' -diamino diphenyl sulfone | |
| CN107827742A (en) | A kind of CO2The method that direct carboxylation method prepares aromatic acid | |
| CN113045440B (en) | Preparation method of 1-aminoanthraquinone | |
| CN112574229B (en) | Method for preparing isosorbide by dehydrating sorbitol and preparation method of copolymer-based catalyst thereof | |
| CN108187744B (en) | Method for catalytic synthesis of furfural ethylene glycol acetal from ammonium aluminum phosphotungstate complex salt | |
| CN102391170B (en) | A kind of preparation method of N, N-diallyl-5-methoxytryptamine hydrochlorides | |
| CN102212155A (en) | High-temperature-resistant guanidine-based strong-basic anion exchange resin for strong base and synthesis method thereof | |
| CN112574043A (en) | Production process of alkaline red intermediate 3-ethylaminop-methylphenol | |
| CN113773222B (en) | Refining and purifying method of 2-amino-4-acetamido anisole | |
| CN111302985A (en) | Method for synthesizing 4-hydroxy-4' -isopropoxy-diphenyl sulfone compound by microchannel reactor | |
| CN100378052C (en) | Method for producing 2,3,6,7,10,11-hexahydroxytriphenylene | |
| CN110124744B (en) | Catalyst for catalytic synthesis of chalcone compounds and application thereof | |
| CN112479863B (en) | Method for preparing 2-methyl-4-chlorophenoxyacetic acid by catalyzing and chlorinating 2-methylphenoxy acetic acid | |
| CN112574007B (en) | Novel cyclohexylimine ionic liquid and method for catalyzing synthesis of butyl citrate and bisphenol F | |
| CN113956268B (en) | 6-bromo-1-chlorobenzothiophene [2,3-c ] pyridine and synthetic method | |
| CN115304541B (en) | Preparation method of 3-chloro-4- (2-pyridylmethoxy) aniline | |
| CN115608390B (en) | Simple preparation of nitrogen-doped transition metal carbon catalyst and application thereof in organic S-N bond synthesis | |
| CN117244593A (en) | Solid acid catalyst and preparation method and application thereof | |
| CN117285500A (en) | Preparation method of high-purity sodium fluorescein |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20200619 |
|
| WW01 | Invention patent application withdrawn after publication |