CN102295589A - Improved chlorosulfonic acid method for preparing 4,4-dichlorodiphenyl sulfone - Google Patents
Improved chlorosulfonic acid method for preparing 4,4-dichlorodiphenyl sulfone Download PDFInfo
- Publication number
- CN102295589A CN102295589A CN2011102459579A CN201110245957A CN102295589A CN 102295589 A CN102295589 A CN 102295589A CN 2011102459579 A CN2011102459579 A CN 2011102459579A CN 201110245957 A CN201110245957 A CN 201110245957A CN 102295589 A CN102295589 A CN 102295589A
- Authority
- CN
- China
- Prior art keywords
- chlorobenzene
- reaction
- chlorosulfonic acid
- preparation
- improved
- 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.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an improved chlorosulfonic acid method for preparing 4,4-dichlorodiphenyl sulfone. The improved chlorosulfonic acid method comprises the following steps of 1), 4-chlorobenzenesulfonyl chloride preparation comprising dissolving chlorosulfonic acid in carbon tetrachloride, cooling the mixture to room temperature, adding dropwisely chlorobenzene into the cooled mixture for a reaction, after the dropwise addition of chlorobenzene is finished, stirring the reaction solution at a temperature of 30 to 35 DEG C to obtain homogeneous chlorosulfonic acid, carbon tetrachloride and chlorobenzene, heating to a temperature of 70 DEG C at a rate of 0.5 to 0.8 DEG C per minute, maintaining the temperature of 70 DEG C for 1.5 to 3 hours, adding sodium chloride into the heated reaction solution in two stages for a reaction, wherein a time interval between the two stages of the addition is less than or equal to 2 hours, and after the reaction is finished, carrying out separation and treatment of the reaction products to obtain 4-chlorobenzenesulfonyl chloride, and 2), 4,4-dichlorodiphenyl sulfone preparation comprising finishing a condensation reaction of 4-chlorobenzenesulfonyl chloride and chlorobenzene in the presence of bismuth tris(trifluoromethanesulfonate) as a catalyst and tetrachloroethylene as a solvent, and carrying out separation and treatment to obtain 4,4-dichlorodiphenyl sulfone. Therefore, the improved chlorosulfonic acid method for preparing 4,4-dichlorodiphenyl sulfone has the advantages of energy saving, no generation of by-product and simple later separation and treatment processes.
Description
Technical field
The present invention relates to a kind of preparation method of 4.4-dichloro diphenyl sulfone, after especially a kind of employing chlorsulfonic acid carries out the chlorobenzene sulfonation, prepare the method for 4.4-dichloro diphenyl sulfone.
Background technology
4.4 the – dichloro diphenyl sulfone is called for short DDS, is white crystal, can distil, and is soluble in organic solvents such as benzene, chlorobenzene, DMF; Be slightly soluble in ethanol, methyl alcohol; Water insoluble.Its flash-point is 233 ℃, and boiling point then is 397 ℃.
4.4 the – dichloro diphenyl sulfone has purposes widely at engineering plastics and field of fine chemical, is the main raw material of engineering plastics such as preparation polysulfones, polyethersulfone, also is the intermediate of medicine, dyestuff, agricultural chemicals.
It is a kind of technology of comparative maturity that the chlorsulfonic acid legal system is equipped with 4.4 – dichloro diphenyl sulfones.At present, the general raw material that adopts of this chlorsulfonic acid method is: the vitriol oil, chlorobenzene, chlorsulfonic acid and catalyzer CCl3CCl3, dichloro diphenyl sulfone, its technical process is: under 150-160 ℃ chlorobenzene is carried out sulfonation with the vitriol oil earlier, after generating p-chlorobenzenesulfonic acid, drip chlorsulfonic acid again, with CCl3CCl3 as catalyzer, generate parachloroben-zenesulfonyl chloride in reaction under 80 degrees centigrade after 1 hour, then in the presence of dichloro diphenyl sulfone, parachloroben-zenesulfonyl chloride and chlorobenzene generation substitution reaction generate 4.4 – dichloro diphenyl sulfones.Hence one can see that, this method complex process, and it is many to relate to production unit, causes the production cost height, simultaneously the serious three wastes that is produced in the preparation process.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of chlorsulfonic acid method of improved preparation 4.4 – dichloro diphenyl sulfones is provided, when it carries out sulfonation reaction at chlorsulfonic acid to chlorobenzene, with the tetracol phenixin is solvent, and in the reaction later stage, add the by product sulfuric acid in the sodium-chlor decomposition chlorobenzene sulfonation reaction process, promote the chlorobenzene sulfonation reaction to carry out, thereby improved the transformation efficiency of parachloroben-zenesulfonyl chloride towards positive dirction; The present invention is in the preparation of carrying out the 4.4-dichloro diphenyl sulfone, with three (trifluoromethane sulfonic acid) bismuth is catalyzer, with the zellon is solvent, thereby make the condensation reaction of parachloroben-zenesulfonyl chloride and chlorobenzene at room temperature to carry out, in the time of energy-conservation, avoid production of by-products, simplify later stage separating treatment technology.
For realizing above technical purpose, the present invention will take following technical scheme:
A kind of chlorsulfonic acid method of improved preparation 4.4 – dichloro diphenyl sulfones may further comprise the steps: the preparation of (1) parachloroben-zenesulfonyl chloride---chlorsulfonic acid is dissolved in tetracol phenixin after, be cooled under the room temperature and drip chlorobenzene; After chlorobenzene is added dropwise to complete, under 30-35 ℃, reaction solution is stirred, so that chlorsulfonic acid, tetracol phenixin, chlorobenzene homogeneous phase, speed with the 0.5-0.8 degrees celsius/minute is warming up to 70 degrees centigrade afterwards, and under 70 degrees centigrade, be incubated 1.5-3 hour, and then in reaction solution, add sodium-chlor in two steps, the timed interval of twice interpolation is not higher than 2 hours, after finishing reaction, can make parachloroben-zenesulfonyl chloride through separating treatment; The preparation of (2) 4.4 – dichloro diphenyl sulfones---with three (trifluoromethane sulfonic acid) bismuth is catalyzer, is solvent with the zellon, at room temperature finishes the condensation reaction of parachloroben-zenesulfonyl chloride and chlorobenzene, makes the 4.4-dichloro diphenyl sulfone after separating treatment.
According to above technical scheme, can realize following beneficial effect:
When chlorsulfonic acid carries out sulfonation reaction to chlorobenzene, with the tetracol phenixin is solvent, and in the reaction later stage, adds the by product sulfuric acid in the sodium-chlor decomposition chlorobenzene sulfonation reaction process, promote the chlorobenzene sulfonation reaction to carry out, thereby improved the transformation efficiency of parachloroben-zenesulfonyl chloride towards positive dirction; The present invention is in the preparation of carrying out the 4.4-dichloro diphenyl sulfone, with three (trifluoromethane sulfonic acid) bismuth is catalyzer, with the zellon is solvent, thereby make the condensation reaction of parachloroben-zenesulfonyl chloride and chlorobenzene at room temperature to carry out, in the time of energy-conservation, avoid production of by-products, simplify later stage separating treatment technology.
Embodiment
Explain technical scheme of the present invention below with reference to embodiment.
The chlorsulfonic acid method of improved preparation 4.4 – dichloro diphenyl sulfones of the present invention may further comprise the steps:
The preparation of parachloroben-zenesulfonyl chloride: agitator is being housed, dropping funnel, in the reaction vessel of thermometer and device for recovering tail gas, add 0.3 mole of chlorsulfonic acid, tetracol phenixin 40ml is water-cooled to 25 ℃, slowly drips 0.1 mole of chlorobenzene, after adding, 30 degrees centigrade were stirred 1 hour down, slowly were warming up to 70 degrees centigrade then, and kept 2 hours under this temperature, add sodium-chlor afterwards, add 1 gram sodium-chlor after 1 hour again, finish reaction after 1 hour, reaction finishes the back and reclaims solvent, after the solvent reaction material is cooled to room temperature, pour in the frozen water, filter the flush away free acid, air-dry, get product 18.5 grams;
4.4-the preparation of dichloro diphenyl sulfone: generating by friedel-crafts reaction, is catalyzer with three (trifluoromethane sulfonic acid) bismuth, is solvent with the zellon, at room temperature can finish the condensation reaction of parachloroben-zenesulfonyl chloride and chlorobenzene; Be specially: prepared parachloroben-zenesulfonyl chloride is dissolved in the zellon, heating makes and after the cooling, adds three (trifluoromethane sulfonic acid) bismuth by both azeotropic, add chlorobenzene then, reaction is 2-3 hour under the room temperature, after the end, adds entry and distills, use acid treatment at last, cooling, suction filtration, water washing, the 4.4-dichloro diphenyl sulfone that the product that can obtain are of fine quality.
Claims (1)
1. the chlorsulfonic acid method of improved preparation 4.4 – dichloro diphenyl sulfones is characterized in that, may further comprise the steps: the preparation of (1) parachloroben-zenesulfonyl chloride---chlorsulfonic acid is dissolved in tetracol phenixin after, be cooled under the room temperature and drip chlorobenzene; After chlorobenzene is added dropwise to complete, under 30-35 ℃, reaction solution is stirred, so that chlorsulfonic acid, tetracol phenixin, chlorobenzene homogeneous phase, speed with the 0.5-0.8 degrees celsius/minute is warming up to 70 degrees centigrade afterwards, and under 70 degrees centigrade, be incubated 1.5-3 hour, and then in reaction solution, add sodium-chlor in two steps, the timed interval of twice interpolation is not higher than 2 hours, after finishing reaction, can make parachloroben-zenesulfonyl chloride through separating treatment; The preparation of (2) 4.4 – dichloro diphenyl sulfones---with three (trifluoromethane sulfonic acid) bismuth is catalyzer, is solvent with the zellon, at room temperature finishes the condensation reaction of parachloroben-zenesulfonyl chloride and chlorobenzene, makes the 4.4-dichloro diphenyl sulfone after separating treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102459579A CN102295589A (en) | 2011-08-25 | 2011-08-25 | Improved chlorosulfonic acid method for preparing 4,4-dichlorodiphenyl sulfone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102459579A CN102295589A (en) | 2011-08-25 | 2011-08-25 | Improved chlorosulfonic acid method for preparing 4,4-dichlorodiphenyl sulfone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102295589A true CN102295589A (en) | 2011-12-28 |
Family
ID=45356295
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102459579A Pending CN102295589A (en) | 2011-08-25 | 2011-08-25 | Improved chlorosulfonic acid method for preparing 4,4-dichlorodiphenyl sulfone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102295589A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58206551A (en) * | 1982-05-25 | 1983-12-01 | Konishi Kagaku Kogyo Kk | Production of diaryl sulfones |
| GB2135666A (en) * | 1981-08-31 | 1984-09-05 | Mitsui Toatsu Chemicals | Preparation of 4-chlorobenzenesulfonyl chloride and 4,4'-dichlorodiphenyl sulfone |
| US4871876A (en) * | 1987-02-17 | 1989-10-03 | Dresser Industries, Inc. | Preparation of 4,4' dichlorodiphenyl sulfone |
-
2011
- 2011-08-25 CN CN2011102459579A patent/CN102295589A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2135666A (en) * | 1981-08-31 | 1984-09-05 | Mitsui Toatsu Chemicals | Preparation of 4-chlorobenzenesulfonyl chloride and 4,4'-dichlorodiphenyl sulfone |
| JPS58206551A (en) * | 1982-05-25 | 1983-12-01 | Konishi Kagaku Kogyo Kk | Production of diaryl sulfones |
| US4871876A (en) * | 1987-02-17 | 1989-10-03 | Dresser Industries, Inc. | Preparation of 4,4' dichlorodiphenyl sulfone |
Non-Patent Citations (4)
| Title |
|---|
| 《太原科技》 20030426 黄月君 4,4'-二氯二苯砜的合成研究 , 第2期 * |
| 李丽娟，叶昌伦: "《药物合成反应与方法》", 1 July 2005 * |
| 苏砚溪，杨纪清: "对氯苯磺酰氯的合成研究", 《化学世界》 * |
| 黄月君: "4,4’-二氯二苯砜的合成研究", 《太原科技》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107827742B (en) | CO (carbon monoxide)2Method for preparing aromatic acid by direct carboxylation method | |
| CN103058899A (en) | Synthetic method for methyl-sulfuryl benzaldehyde | |
| CN102924346B (en) | Method for synthesizing methyl sulfone base dibromo toluene | |
| CN102295589A (en) | Improved chlorosulfonic acid method for preparing 4,4-dichlorodiphenyl sulfone | |
| CN112778094B (en) | Preparation process of high-purity tetrabromobisphenol A | |
| CN111187240B (en) | Preparation method of 4, 4-diphenyl ether dianhydride | |
| CN111320547B (en) | Synthesis method of lumefantrine-D9 | |
| CN111574416B (en) | Method for preparing tiamulin from isothiourea salt and pleuromutilin p-toluenesulfonate | |
| CN102295591A (en) | Novel preparation method of 4, 4-dichlorodiphenyl sulfone | |
| CN112707807A (en) | Preparation method of 4, 5-difluorophthalic acid | |
| CN111393254A (en) | Synthesis method of tetrabromo-neopentane | |
| CN107935913B (en) | Carbazole compound and synthesis method and application thereof | |
| CN102304072A (en) | Method for preparing 4.4-dichlorodiphenyl sulfone by using sulfur trioxide | |
| CN117946013B (en) | Method for synthesizing 5, 6-dihalogen-3-aminopyrazine-2-methyl formate by one-pot method | |
| CN102924369A (en) | Method for synthesizing 3,5-dibromo-4-iodopyridine by one step | |
| CN102304071A (en) | Method for synthesizing 4.4-dichlorodiphenyl sulfone by two-step process | |
| CN107973753A (en) | A kind of method of phase-transfer Wittig reaction 4-Hydroxyphenyl hydantoin | |
| CN103709210A (en) | Isopropyl-beta-D-thiogalactoside preparation technology | |
| CN117756625B (en) | Preparation method of o-ethoxybenzoyl chloride | |
| CN102351752A (en) | Chlorosulfonic acid optimization method for preparing 4,4-dichlorodiphenyl sulfone | |
| CN103224438B (en) | Method for synthesizing N, N-dimethyl amine compound by nucleophilic substitution of DMF | |
| CN111533699B (en) | Synthesis method of 2- (trifluoromethyl) pyrimidine-5-alcohol | |
| CN103694284B (en) | A kind of preparation technology of isopropyl-β-D-thiogalactoside(IPTG) | |
| CN105175320A (en) | Preparation method of 3-hydroxypyridine | |
| CN112745205B (en) | Preparation method of simod intermediate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20111228 |