CN109851537A - The technique for preparing 4,4 '-dichloro diphenyl sulfones - Google Patents
The technique for preparing 4,4 '-dichloro diphenyl sulfones Download PDFInfo
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- CN109851537A CN109851537A CN201711240606.2A CN201711240606A CN109851537A CN 109851537 A CN109851537 A CN 109851537A CN 201711240606 A CN201711240606 A CN 201711240606A CN 109851537 A CN109851537 A CN 109851537A
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Abstract
The invention belongs to organic synthesis fields, and in particular to a kind of technique for preparing 4,4 '-dichloro diphenyl sulfones.Thionyl chloride and chlorobenzene are subjected to Friedel-Crafts reaction under the action of catalyst, cooling hydrolysis, then rising temperature for dissolving after reaction, then it cools down, crystal is precipitated, and 4,4'- dichloro sulfoxide is obtained by filtration, it is then dissolved in glacial acetic acid, hydrogen peroxide is added to carry out oxidation reaction, after completion of the reaction cooling down, filtering, obtain 4,4'- dichloro diphenyl sulfone；Catalyst used is the mixture of aluminum trichloride (anhydrous) and benzyltriethylammoinium chloride.Present invention process is simple, at low cost, impurity is few, using composite catalyst, and does not add solvent additionally, and obtained product purity is high, and for content 99.4% or more, yield reaches 92% or more, good in economic efficiency, easy to industrialized production.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to a kind of technique for preparing 4,4 '-dichloro diphenyl sulfones.
Background technique
4,4'- dichloro diphenyl sulfones (DDS) are a kind of important organic synthesis products, are to prepare the engineering plastics such as polysulfones and polyether sulfone
The intermediate of the primary raw material of material, and medicine, dyestuff and pesticide etc..It can be used for preparing multiple polymers product, such as bisphenol-A
The resins such as type polysulfones, Poly-s 179 and polyamide sulfone, it can also be used to prepare leprosy pharmaceutical intermediate 4,4'- diamino hexichol
Sulfone.With the extensive use of high molecular material, the demand of DDS is also increasing.
There are many method of industrial production DDS, mainly there is sulfuric acid process, chlorosulfonic acid method, sulfur trioxide method and sulfoxide oxidation method
Deng.Sulfuric acid process is at low cost, and raw material is simple, but conversion ratio is low, and the reaction time is long, and product fusing point is low, quality defect.Chlorosulfonic acid method work
Skill comparative maturity, good product quality, but high production cost, serious three wastes.It is a kind of modification method that sulfur trioxide method, which prepares DDS,
UCC company in the U.S. uses this method according to reports, it is with SO 3 sulfonated and thionyl chloride chloride route, technics comparing complexity.
Summary of the invention
In view of the deficiencies of the prior art, the object of the present invention is to provide a kind of technique for preparing 4,4 '-dichloro diphenyl sulfones, sections
Cost-saving post-processing is simple, and product purity is high, high income.
The technique of 4,4 '-dichloro diphenyl sulfones of preparation of the present invention, comprising the following steps:
Thionyl chloride and chlorobenzene are subjected to Friedel-Crafts reaction, after reaction cooling hydrolysis under the action of catalyst, then heated up
Dissolution, then cools down, and crystal is precipitated, and 4,4'- dichloro sulfoxide is obtained by filtration, is then dissolved in glacial acetic acid, adds dioxygen
Water carries out oxidation reaction, after completion of the reaction cooling down, and filtering obtains 4,4'- dichloro diphenyl sulfone；Catalyst used is anhydrous
The mixture of alchlor and benzyltriethylammoinium chloride.
Wherein:
Catalyst is that aluminum trichloride (anhydrous) and benzyltriethylammoinium chloride are 3:1 mixing in mass ratio.
The molar ratio of thionyl chloride and chlorobenzene is 1:4.
Friedel-Crafts reaction temperature is 20~30 DEG C, and the time is 1~2h.
The temperature of rising temperature for dissolving is 100 DEG C, and the time of rising temperature for dissolving is 2h.
The temperature of cooling hydrolysis is 10 DEG C, time 1h.
The hydrogen peroxide uses dropwise addition mode, and oxidizing reaction temperature is 60~80 DEG C, and oxidization time is 1~2h.
In conclusion the invention has the following advantages that
Present invention process is simple, at low cost, impurity is few, using composite catalyst, and does not add solvent additionally, obtained production
Product purity is high, for content 99.4% or more, yield reaches 92% or more, good in economic efficiency, easy to industrialized production.
Specific embodiment
Below with reference to embodiment, the present invention will be further described.
Embodiment 1
(1) thionyl chloride and chlorobenzene are subjected to Friedel-Crafts reaction under the action of catalyst, Friedel-Crafts reaction temperature is 25 DEG C, the time
For 1.5h, the molar ratio of thionyl chloride and chlorobenzene is 1:4, and catalyst is that aluminum trichloride (anhydrous) and benzyltriethylammoinium chloride press matter
Amount is than being 3:1；
(2) it is cooled to 10 DEG C of hydrolysis 1h after hybrid reaction, then is warming up to 100 DEG C of dissolution 2h, then cools down, crystal analysis
Out, 4,4'- dichloro sulfoxide is obtained by filtration；
(3) it is then dissolved in glacial acetic acid, hydrogen peroxide is added dropwise and carries out oxidation reaction, oxidizing reaction temperature is 70 DEG C, oxygen
The change time is 2h, after completion of the reaction cooling down, and filtering obtains 4,4'- dichloro diphenyl sulfone；Catalyst used is anhydrous trichlorine
Change the mixture of aluminium and benzyltriethylammoinium chloride.
4, the 4'- dichloro diphenyl sulfone purity being prepared is 99.8%, and purification yield is 92.5%.
Embodiment 2
(1) thionyl chloride and chlorobenzene are subjected to Friedel-Crafts reaction under the action of catalyst, Friedel-Crafts reaction temperature is 30 DEG C, the time
For 1h, the molar ratio of thionyl chloride and chlorobenzene is 1:4, and catalyst is that aluminum trichloride (anhydrous) and benzyltriethylammoinium chloride press quality
Than for 3:1；
(2) it is cooled to 10 DEG C of hydrolysis 1h after hybrid reaction, then is warming up to 100 DEG C of dissolution 2h, then cools down, crystal analysis
Out, 4,4'- dichloro sulfoxide is obtained by filtration；
(3) it is then dissolved in glacial acetic acid, hydrogen peroxide is added dropwise and carries out oxidation reaction, oxidizing reaction temperature is 80 DEG C, oxygen
The change time is 1h, after completion of the reaction cooling down, and filtering obtains 4,4'- dichloro diphenyl sulfone；Catalyst used is anhydrous trichlorine
Change the mixture of aluminium and benzyltriethylammoinium chloride.
4, the 4'- dichloro diphenyl sulfone purity being prepared is 99.8%, and purification yield is 92.8%.
Claims (7)
1. a kind of technique for preparing 4,4 '-dichloro diphenyl sulfones, it is characterised in that: the following steps are included:
Thionyl chloride and chlorobenzene are subjected to Friedel-Crafts reaction under the action of catalyst, cooling hydrolysis, then rising temperature for dissolving after reaction,
Then it cools down, crystal is precipitated, and 4,4'- dichloro sulfoxide is obtained by filtration, is then dissolved in glacial acetic acid, hydrogen peroxide is added to carry out
Oxidation reaction, cooling down, filtering obtain 4,4'- dichloro diphenyl sulfone after completion of the reaction；Catalyst used is anhydrous tri-chlorination
The mixture of aluminium and benzyltriethylammoinium chloride.
2. the technique of 4,4 '-dichloro diphenyl sulfones of preparation according to claim 1, it is characterised in that: catalyst is anhydrous three
Aluminium chloride and benzyltriethylammoinium chloride are 3:1 mixing in mass ratio.
3. the technique of 4,4 '-dichloro diphenyl sulfones of preparation according to claim 1, it is characterised in that: thionyl chloride and chlorobenzene
Molar ratio be 1:4.
4. the technique of 4,4 '-dichloro diphenyl sulfones of preparation according to claim 1, it is characterised in that: Friedel-Crafts reaction temperature is
20~30 DEG C, the time is 1~2h.
5. the technique of 4,4 '-dichloro diphenyl sulfones of preparation according to claim 1, it is characterised in that: the temperature of rising temperature for dissolving
It is 100 DEG C, the time of rising temperature for dissolving is 2h.
6. the technique of 4,4 '-dichloro diphenyl sulfones of preparation according to claim 1, it is characterised in that: the temperature for the hydrolysis that cools down
It is 10 DEG C, time 1h.
7. the technique of 4,4 '-dichloro diphenyl sulfones of preparation according to claim 1, it is characterised in that: the dioxygen hydromining
With the mode of dropwise addition, oxidizing reaction temperature is 60~80 DEG C, and oxidization time is 1~2h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201711240606.2A CN109851537A (en) | 2017-11-30 | 2017-11-30 | The technique for preparing 4,4 '-dichloro diphenyl sulfones |
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| CN201711240606.2A CN109851537A (en) | 2017-11-30 | 2017-11-30 | The technique for preparing 4,4 '-dichloro diphenyl sulfones |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112608258A (en) * | 2020-12-29 | 2021-04-06 | 江苏傲伦达科技实业股份有限公司 | Method for synthesizing 4,4' -dichlorodiphenyl sulfone by sulfoxide oxidation method |
| 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 |
| CN114341106A (en) * | 2019-08-27 | 2022-04-12 | 巴斯夫欧洲公司 | Method for preparing 4, 4' -dichlorodiphenyl sulfone |
-
2017
- 2017-11-30 CN CN201711240606.2A patent/CN109851537A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114341106A (en) * | 2019-08-27 | 2022-04-12 | 巴斯夫欧洲公司 | Method for preparing 4, 4' -dichlorodiphenyl sulfone |
| CN112608258A (en) * | 2020-12-29 | 2021-04-06 | 江苏傲伦达科技实业股份有限公司 | Method for synthesizing 4,4' -dichlorodiphenyl sulfone by sulfoxide oxidation method |
| 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 |
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Application publication date: 20190607 |
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