CN108047101A - A kind of synthesis technology of high-efficiency and continuous production 4,4- dichloro diphenyl sulfones - Google Patents

A kind of synthesis technology of high-efficiency and continuous production 4,4- dichloro diphenyl sulfones Download PDF

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Publication number
CN108047101A
CN108047101A CN201711281905.0A CN201711281905A CN108047101A CN 108047101 A CN108047101 A CN 108047101A CN 201711281905 A CN201711281905 A CN 201711281905A CN 108047101 A CN108047101 A CN 108047101A
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efficiency
continuous production
synthesis technology
dichlorodiphenyl sulfone
reaction
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周以鸿
程龙进
骆建轻
张银生
赖立冬
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Jiujiang Zhongxing Pharmaceutical Chemical Co Ltd
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Jiujiang Zhongxing Pharmaceutical Chemical Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00Preparation of sulfones; Preparation of sulfoxides
    • C07C315/02Preparation 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00Preparation of sulfones; Preparation of sulfoxides

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention discloses a kind of high-efficiency and continuous production 4; the synthesis technology of 4 dichloro diphenyl sulfones; thionyl chloride and excessive chlorobenzene are subjected to friedel-crafts acylation under lewis acid catalyst effect; pyrohydrolysis chlorination benzene is layered after reaction; sulfoxide organic layer oxidizer aoxidizes; add activated carbon decolorizing, filter;Filtrate cooling rejection filter obtains 4,4 dichloro diphenyl sulfones.The advantage of the invention is that:Chlorobenzene is that raw material is reaction dissolvent again, avoids multi-solvents cross-reference.A large amount of uses using acetic acid as oxidation solvent are particularly avoided, avoid the corrosion and environmental pollution of equipment.Entire technological process avoids the separation and Extraction of 4,4 dichloro sulfoxide of intermediate, substantially reduces the production time, has saved production cost.The oxidability of hydrogen peroxide is substantially increased by the use of hydrogen peroxide, acetic acid and the concentrated sulfuric acid as hybrid oxidant, greatly improves product yield and purity, for yield up to more than 90%, purity is more than 99.8%.

Description

A kind of synthesis technology of high-efficiency and continuous production 4,4- dichloro diphenyl sulfones
Technical field
The present invention relates to organic synthesis technique, especially a kind of synthesis work of high-efficiency and continuous production 4,4-dichlorodiphenyl sulfone Skill.
Background technology
4th, 4 '-dichloro diphenyl sulfone(DDS)It is to manufacture the main intermediate of polysulfones engineering plastics and synthesis treatment leprosy The raw material of medicine 4,4 '-diaminodiphenylsulfone.With the fast development of polysulfones resinoid, the demand of DDS, which is also suddenly gathered, to be increased. Therefore, the Study of synthesis method to compound and process modification, which seem, becomes more and more important.
The industrial preparative method of DDS has very much, can be divided into following several method by sulfonating agent classification:
1)Chlorosulfonic acid method:For this method due to chlorosulfonic acid to be used, which has the problems such as storage, transport and use, and raw A large amount of spent acid are generated during production and release a large amount of HCl gases, equipment corrosion and environmental pollution are caused to seriously affect.2)Three oxygen Change sulphur method:Due to raw material SO3Equally in storage, transport and the problems such as use, and to be used using a large amount of in production process SOCl2.A large amount of spent acid are generated simultaneously and release a large amount of HCl gases, and equipment corrosion and environmental pollution are caused to seriously affect.3)Sulphur Acid system:This method has the advantages that very big compared with chlorosulfonic acid method and sulfur trioxide method.The concentrated sulfuric acid is simple and easy to get, storage, transport It is convenient.Reaction process does not have the releasing of the sour gas such as HCl, SO2.But this method needs to carry out at high temperature, and reaction time Long products quality defect.4) sulfoxide oxidation method:The route is by SOCl2With chlorobenzene Fu Ke is carried out under lewis acid catalyst effect Acylation reaction obtains 4,4 '-dichloro sulfoxide intermediate.Sulfoxide is dissolved in acetum, hydrogen peroxide oxidant is added to aoxidize Obtain DDS.
Sulfoxide oxidation method reaction condition is mild, raw material is simple and easy to get, good product quality and high income, is a kind of to have very much industry The amplification production technology of prospect.But mostly need to be further improved with product quality there is currently technological process length, reaction dissolvent.Its Middle SOCl2With chlorobenzene effect generation 4,4 '-dichloro sulfoxide intermediate to crystallize filtering, drying carry out next step oxygen again Change, do not meet continuous production processes requirement, very big pressure is brought to production cost.Sulfoxide oxidation is molten using acetic acid as aoxidizing simultaneously Agent has a significant impact to equipment corrosion and product quality.Therefore DDS process routes are prepared to sulfoxide oxidation method rationally to be changed Into entire technological process continuous production is enable to have a very important significance.
The content of the invention
The deficiency of DDS technologies is prepared for existing sulfoxide oxidation method, the object of the present invention is to provide one kind efficiently to connect The improvement in synthesis of continuous production 4,4-dichlorodiphenyl sulfone, production cost is greatly saved in technique after improvement, and product purity is high.
The technical scheme is that:A kind of synthesis technology of high-efficiency and continuous production 4,4-dichlorodiphenyl sulfone, by protochloride Sulfone and excessive chlorobenzene carry out friedel-crafts acylation under lewis acid catalyst effect, after reaction pyrohydrolysis chlorination benzene Layering, sulfoxide organic layer oxidizer oxidation, adds activated carbon decolorizing, filters;Filtrate cooling rejection filter obtains 4,4- dichloro diphenyl sulfones.
Wherein:
The molar ratio of thionyl chloride and chlorobenzene is 1:3~1:5, chlorobenzene is that raw material is reaction dissolvent again.
Lewis acid catalyst be aluminum trichloride (anhydrous), anhydrous ferric trichloride and anhydrous zinc chloride, preferably anhydrous tri-chlorination Aluminium, catalyst are 1 with thionyl chloride molar ratio:1~1:1.1.
Friedel-crafts acylation temperature is 30 ~ 50 DEG C, and the reaction time is 0.5 ~ 2h.
Pyrohydrolysis temperature is 80 ~ 110 DEG C, and the pyrohydrolysis time is 1 ~ 4h.
It is 2 that layering, which adds chlorobenzene with thionyl chloride molar ratio,:1~5:1.
Oxidant hydrogen peroxide concentration used is 30 ~ 50%, and hydrogen peroxide and acetic acid and concentrated sulfuric acid molar ratio are 6 ~ 4:5~3:1.
Oxidizing reaction temperature is 70 ~ 90 DEG C, and oxidization time is 2 ~ 5h.
Oxidant uses hydrogen peroxide, acetic acid or the concentrated sulfuric acid.
The advantage of the invention is that:Chlorobenzene is that raw material is reaction dissolvent again, avoids multi-solvents cross-reference.Particularly A large amount of uses using acetic acid as oxidation solvent are avoided, avoid the corrosion and environmental pollution of equipment.Entire technological process is kept away Intermediate 4 is exempted from, the separation and Extraction of 4- dichloro sulfoxides substantially reduces the production time, saved production cost.With Hydrogen peroxide, acetic acid and the concentrated sulfuric acid substantially increase the oxidability of hydrogen peroxide as hybrid oxidant, make product yield and purity It greatly improves, for yield up to more than 90%, purity is more than 99.8%.
Specific embodiment
Embodiment 1:
60.0g aluminum trichloride (anhydrous)s, 160.0g chlorobenzenes are added in 500mL three-necked flasks, opens stirring.It is slowly added dropwise to system 52.5g thionyl chlorides, control temperature are not higher than 50 DEG C.It finishes, continues insulation reaction 1h.Reaction terminates, and reaction solution is slowly added It in the hot water for entering 90 DEG C of 120mL, finishes, 90 DEG C are continued to be stirred to react 2h.Reaction terminates, and continues to add 100 chlorobenzenes to system, It is layered after system dissolved clarification.Water layer is removed, organic layer is cooled to 80 DEG C of insulated and stirreds.The dense sulphur of 7.5g is slowly added dropwise into organic layer Acid, 25.0g acetic acid.After system stirs evenly, the hydrogen peroxide of 55.0g35% is slowly added dropwise to system.It finishes, system is anti-in 80 DEG C Answer 3h.After reaction, to system plus 5g activated carbons, 80 DEG C of stirring 0.5h.Filtering, filtrate slow cooling is to 15 DEG C, heat preservation analysis Brilliant 1h.Filtering, filter cake are dried in vacuo to obtain 4,4-dichlorodiphenyl sulfone 118.5g in 60 DEG C, and yield 93.8%, HPLC detection purity is big In 99.8%.
Embodiment 2:
65.0g aluminum trichloride (anhydrous)s, 200.0g chlorobenzenes are added in 500mL three-necked flasks, opens stirring.It is slowly added dropwise to system 52.5g thionyl chlorides, control temperature are not higher than 50 DEG C.It finishes, continues insulation reaction 2h.Reaction terminates, and reaction solution is slowly added It in the hot water for entering 90 DEG C of 130mL, finishes, 90 DEG C are continued to be stirred to react 3h.Reaction terminates, and continues to add 100 chlorobenzenes to system, It is layered after system dissolved clarification.Water layer is removed, organic layer is cooled to 80 DEG C of insulated and stirreds.The dense sulphur of 7.5g is slowly added dropwise into organic layer Acid, 30.0g acetic acid.After system stirs evenly, the hydrogen peroxide of 60.0g35% is slowly added dropwise to system.It finishes, system is anti-in 80 DEG C Answer 2h.After reaction, to system plus 5g activated carbons, 80 DEG C of stirring 0.5h.Filtering, filtrate slow cooling is to 15 DEG C, heat preservation analysis Brilliant 2h.Filtering, filter cake are dried in vacuo to obtain 4,4-dichlorodiphenyl sulfone 115.5g in 60 DEG C, and yield 91.0%, HPLC detection purity is big In 99.8%.

Claims (9)

1. a kind of synthesis technology of high-efficiency and continuous production 4,4-dichlorodiphenyl sulfone, it is characterised in that:By thionyl chloride and excess chlorine Benzene carries out friedel-crafts acylation under lewis acid catalyst effect, and pyrohydrolysis chlorination benzene is layered after reaction, sulfoxide Organic layer oxidizer aoxidizes, and adds activated carbon decolorizing, filters;Filtrate cooling rejection filter obtains 4,4- dichloro diphenyl sulfones.
2. the synthesis technology of high-efficiency and continuous production 4,4-dichlorodiphenyl sulfone according to claim 1, it is characterised in that:Oxidant Using hydrogen peroxide, acetic acid or the concentrated sulfuric acid.
3. the synthesis technology of high-efficiency and continuous production 4,4-dichlorodiphenyl sulfone according to claim 1, it is characterised in that:Protochloride The molar ratio of sulfone and chlorobenzene is 1:3~1:5, chlorobenzene is that raw material is reaction dissolvent again.
4. the synthesis technology of high-efficiency and continuous production 4,4-dichlorodiphenyl sulfone according to claim 1, it is characterised in that:Louis Acid catalyst is aluminum trichloride (anhydrous), anhydrous ferric trichloride and anhydrous zinc chloride, preferred aluminum trichloride (anhydrous), catalyst and chlorination Sulfoxide molar ratio is 1:1~1:1.1.
5. the synthesis technology of high-efficiency and continuous production 4,4-dichlorodiphenyl sulfone according to claim 1, it is characterised in that:Fu Ke acyls Glycosylation reaction temperature is 30 ~ 50 DEG C, and the reaction time is 0.5 ~ 2h.
6. the synthesis technology of high-efficiency and continuous production 4,4-dichlorodiphenyl sulfone according to claim 1, it is characterised in that:Oxygen used Agent hydrogen peroxide concentration is 30 ~ 50%, and hydrogen peroxide and acetic acid and concentrated sulfuric acid molar ratio are 6 ~ 4:5~3:1.
7. the synthesis technology of high-efficiency and continuous production 4,4-dichlorodiphenyl sulfone according to claim 1, it is characterised in that:High-temperature water It is 80 ~ 110 DEG C to solve temperature, and the pyrohydrolysis time is 1 ~ 4h.
8. the synthesis technology of high-efficiency and continuous production 4,4-dichlorodiphenyl sulfone according to claim 1, it is characterised in that:Layering is mended Chlorination benzene is 2 with thionyl chloride molar ratio:1~5:1.
9. the synthesis technology of high-efficiency and continuous production 4,4-dichlorodiphenyl sulfone according to claim 1, it is characterised in that:Oxidation is anti- Answering temperature, oxidization time is 2 ~ 5h for 70 ~ 90 DEG C.
CN201711281905.0A 2017-12-07 2017-12-07 A kind of synthesis technology of high-efficiency and continuous production 4,4- dichloro diphenyl sulfones Withdrawn CN108047101A (en)

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020161228A1 (en) 2019-02-08 2020-08-13 Basf Se Process for producing 4,4`-dichlorodiphenyl sulfoxide
WO2020161225A1 (en) 2019-02-08 2020-08-13 Basf Se Process for purifying 4,4'-dichlorodiphenyl sulfoxide
WO2020161232A1 (en) 2019-02-08 2020-08-13 Basf Se Process for producing 4,4'-dichlorodiphenyl sulfoxide
WO2020161226A1 (en) 2019-02-08 2020-08-13 Basf Se A process for obtaining 4,4'-dichlorodiphenyl sulfoxide
WO2020207929A1 (en) 2019-04-09 2020-10-15 Basf Se Process for working up a composition comprising solid 4,4'-dichlorodiphenyl sulfoxide and a solvent
WO2021037675A1 (en) 2019-08-27 2021-03-04 Basf Se Process for producing 4,4'-dichlorodiphenyl sulfone
WO2021037672A1 (en) 2019-08-27 2021-03-04 Basf Se A process for producing 4,4'-dichlorodiphenyl sulfone
WO2021037682A1 (en) 2019-08-27 2021-03-04 Basf Se A process for purifying crude 4,4'-dichlorodiphenyl sulfone
WO2021037680A1 (en) 2019-08-27 2021-03-04 Basf Se A process for obtaining 4,4'-dichlorodiphenyl sulfone
WO2021037683A1 (en) 2019-08-27 2021-03-04 Basf Se A process for purifying 4,4'-dichlorodiphenyl sulfone
DE102020113957A1 (en) 2020-05-25 2021-11-25 Basf Se Process for working up carboxylic acid-moist 4,4-dichlorodiphenyl sulfone
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
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

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CN102351758A (en) * 2011-08-25 2012-02-15 吴江市北厍盛源纺织品助剂厂 New preparation method of 4,4-dichlorodiphenyl sulfone
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
CN106349126A (en) * 2016-08-25 2017-01-25 江西金海新能源科技有限公司 Method for preparing 4,4'-dichloro sulfobenzide
CN107540581A (en) * 2016-06-27 2018-01-05 成都惠恩精细化工有限责任公司 The preparation method of 4,4 ' dichloro diphenyl sulfones

Patent Citations (4)

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CN102351758A (en) * 2011-08-25 2012-02-15 吴江市北厍盛源纺织品助剂厂 New preparation method of 4,4-dichlorodiphenyl sulfone
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
CN107540581A (en) * 2016-06-27 2018-01-05 成都惠恩精细化工有限责任公司 The preparation method of 4,4 ' dichloro diphenyl sulfones
CN106349126A (en) * 2016-08-25 2017-01-25 江西金海新能源科技有限公司 Method for preparing 4,4'-dichloro sulfobenzide

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020161228A1 (en) 2019-02-08 2020-08-13 Basf Se Process for producing 4,4`-dichlorodiphenyl sulfoxide
WO2020161225A1 (en) 2019-02-08 2020-08-13 Basf Se Process for purifying 4,4'-dichlorodiphenyl sulfoxide
WO2020161232A1 (en) 2019-02-08 2020-08-13 Basf Se Process for producing 4,4'-dichlorodiphenyl sulfoxide
WO2020161226A1 (en) 2019-02-08 2020-08-13 Basf Se A process for obtaining 4,4'-dichlorodiphenyl sulfoxide
WO2020207929A1 (en) 2019-04-09 2020-10-15 Basf Se Process for working up a composition comprising solid 4,4'-dichlorodiphenyl sulfoxide and a solvent
WO2021037680A1 (en) 2019-08-27 2021-03-04 Basf Se A process for obtaining 4,4'-dichlorodiphenyl sulfone
WO2021037672A1 (en) 2019-08-27 2021-03-04 Basf Se A process for producing 4,4'-dichlorodiphenyl sulfone
WO2021037682A1 (en) 2019-08-27 2021-03-04 Basf Se A process for purifying crude 4,4'-dichlorodiphenyl sulfone
WO2021037675A1 (en) 2019-08-27 2021-03-04 Basf Se Process for producing 4,4'-dichlorodiphenyl sulfone
WO2021037683A1 (en) 2019-08-27 2021-03-04 Basf Se A process for purifying 4,4'-dichlorodiphenyl sulfone
CN114286815A (en) * 2019-08-27 2022-04-05 巴斯夫欧洲公司 Method for obtaining 4, 4' -dichlorodiphenyl sulfone
CN114341105A (en) * 2019-08-27 2022-04-12 巴斯夫欧洲公司 Method for preparing 4, 4' -dichlorodiphenyl sulfone
DE102020113957A1 (en) 2020-05-25 2021-11-25 Basf Se Process for working up carboxylic acid-moist 4,4-dichlorodiphenyl sulfone
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
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
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

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Application publication date: 20180518