CN106866466A - A kind of method for synthesizing N-acetylsulfanilyl chloride as sulfonating agent with sulfur trioxide - Google Patents
A kind of method for synthesizing N-acetylsulfanilyl chloride as sulfonating agent with sulfur trioxide Download PDFInfo
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- CN106866466A CN106866466A CN201710082815.2A CN201710082815A CN106866466A CN 106866466 A CN106866466 A CN 106866466A CN 201710082815 A CN201710082815 A CN 201710082815A CN 106866466 A CN106866466 A CN 106866466A
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- sulfur trioxide
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- antifebrin
- chloride
- sulfonating agent
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of method for synthesizing N-acetylsulfanilyl chloride as sulfonating agent with sulfur trioxide, it is comprised the following steps：（a）To antifebrin and glacial acetic acid is sequentially added in reactor, stirring is warming up to 40 ~ 70 DEG C；（b）To sulfur trioxide gas are passed through in reactor, reacted 3 ~ 15 hours at 40 ~ 70 DEG C, make the antifebrin conversion complete, stop being passed through sulfur trioxide gas；（c）Reactor temperature is risen to 65 ~ 80 DEG C, the glacial acetic acid is recovered under reduced pressure；（d）The temperature in the reactor is controlled for 60 ~ 90 DEG C, thionyl chloride is added dropwise and is reacted 2 ~ 4 hours, unreacted thionyl chloride is recovered under reduced pressure, cooled down.The quality of N-acetylsulfanilyl chloride was so both can guarantee that, has avoided producing waste water and spent acid again, saved processing cost, be conducive to environmental protection.
Description
Technical field
Chemical intermediate of the present invention synthesizes field, and in particular to a kind of to synthesize acetparaminosalol by sulfonating agent of sulfur trioxide
The method of benzene sulfonyl chloride.
Background technology
N-acetylsulfanilyl chloride is medicine intermediate, is to prepare the sulfamidos such as sulfalene Ben isoxazoles and sulphathiazole
The primary raw material of medicine, current country is all based on using by oneself, to prepare wet product and feed intake at once and use, and will otherwise be occurred point
It is solution, rotten, reach time limit of stabilization of guaranteeing the quality at most also just just three days, really as commodity, commercially at present or blank.State
Outer production is main to be had an impact come finished product, but additive using cryodrying technical equipment and spray granulating and drying to reaction.
Development trend is the stability for being conducive to being obtained product using cryodrying, but is invested larger.In addition, current synthetic method is led to
Often with chlorosulfonic acid as sulfonating agent, antifebrin is dividedly in some parts in chlorosulfonic acid at 40~60 DEG C, reacts 2~4h, it is dilute by frozen water
Release, be filtrated to get product, chlorosulfonic acid consumption is big in the technique, and the spent acid of generation is more, and processing cost is high.
The content of the invention
There is provided a kind of right as sulfonating agent synthesis with sulfur trioxide the invention aims to overcome the deficiencies in the prior art
The method of ASC.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：It is a kind of to synthesize to second by sulfonating agent of sulfur trioxide
The method of acylamino- benzene sulfonyl chloride, it is comprised the following steps：
A () is warming up to 40~70 DEG C to antifebrin and glacial acetic acid, stirring is sequentially added in reactor；
B () is reacted 3~15 hours to sulfur trioxide gas are passed through in reactor at 40~70 DEG C, make the antifebrin
Conversion is complete, and stopping is passed through sulfur trioxide gas；
C () makes reactor temperature rise to 65~80 DEG C, the glacial acetic acid is recovered under reduced pressure；
D it is 60~90 DEG C that () controls the temperature in the reactor, thionyl chloride is added dropwise and reacts 2~4 hours, is recovered under reduced pressure
Unreacted thionyl chloride, cooling.
Optimally, in the step (b), react when close to terminal, every 5~15min sampling analyses to antifebrin turn
Change complete.
Optimally, in step (a), the mass ratio of the antifebrin and glacial acetic acid is 13.5：30~60；In step (b),
The speed that is passed through of the sulfur trioxide gas is 2.5~13.0L/min.
Optimally, in step (d), reaction end gas are with the mass ratio of thionyl chloride with alkali liquor absorption, the antifebrin
13.5：12~15.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：The present invention is with three oxidations
Sulphur is the method that sulfonating agent synthesizes N-acetylsulfanilyl chloride, first causes antifebrin and sulfur trioxide by solvent of glacial acetic acid
Reacted, itself and thionyl chloride are then being carried out into reaction so that N-acetylsulfanilic acid is converted into acetylaminobenzene sulphur
Acyl chlorides, so both can guarantee that the quality of N-acetylsulfanilyl chloride, avoid producing waste water and spent acid again, has saved and has been processed into
This, is conducive to environmental protection.
Specific embodiment
The preferred embodiment of the invention will be described in detail below：
Embodiment 1
The present embodiment provides a kind of method for synthesizing N-acetylsulfanilyl chloride as sulfonating agent with sulfur trioxide, and it includes
Following steps：
A () is warming up to 40 DEG C to 13.5kg antifebrins and 30kg glacial acetic acid, stirring is sequentially added in reactor；
B () is reacted 15 hours to sulfur trioxide gas (flow of ventilation is 2.5L/min) are passed through in reactor at 40 DEG C；
During close to reaction end, per 15min sampling analyses (being analyzed using liquid chromatograph HPLC), converted to antifebrin
Entirely, stop being passed through sulfur trioxide gas；
C () makes reactor temperature rise to 65 DEG C, glacial acetic acid is recovered under reduced pressure；
D () controls temperature in reactor for 60 DEG C, be added dropwise thionyl chloride 12kg react 4 hours (tail gas with recycle of alkali liquor,
Such as the sodium carbonate liquor of 1mol/L), unreacted thionyl chloride is recovered under reduced pressure, cooling obtains final product N-acetylsulfanilyl chloride crude product
(purity is 95%, and 98%) yield is.
Embodiment 2
The present embodiment provides a kind of method for synthesizing N-acetylsulfanilyl chloride as sulfonating agent with sulfur trioxide, and it includes
Following steps：
A () is warming up to 70 DEG C to 13.5kg antifebrins and 60kg glacial acetic acid, stirring is sequentially added in reactor；
B () is reacted 3 hours to sulfur trioxide gas (flow of ventilation is 13.0L/min) are passed through in reactor at 70 DEG C；
It is complete to antifebrin conversion per 5min sampling analyses (being analyzed using liquid chromatograph HPLC) during close to reaction end,
Stopping is passed through sulfur trioxide gas；
C () makes reactor temperature rise to 80 DEG C, glacial acetic acid is recovered under reduced pressure；
D () controls temperature in reactor for 90 DEG C, be added dropwise thionyl chloride 15kg react 2 hours (tail gas with recycle of alkali liquor,
Such as the sodium carbonate liquor of 1mol/L), unreacted thionyl chloride is recovered under reduced pressure, cooling obtains final product N-acetylsulfanilyl chloride crude product
(purity is 96%, and 98%) yield is.
Embodiment 3
The present embodiment provides a kind of method for synthesizing N-acetylsulfanilyl chloride as sulfonating agent with sulfur trioxide, and it includes
Following steps：
A () is warming up to 50 DEG C to 13.5kg antifebrins and 45kg glacial acetic acid, stirring is sequentially added in reactor；
B () is reacted 5 hours to sulfur trioxide gas (flow of ventilation is 8.0L/min) are passed through in reactor at 50 DEG C；
During close to reaction end, per 10min sampling analyses (being analyzed using liquid chromatograph HPLC), converted to antifebrin
Entirely, stop being passed through sulfur trioxide gas；
C () makes reactor temperature rise to 70 DEG C, glacial acetic acid is recovered under reduced pressure；
D () controls temperature in reactor for 80 DEG C, be added dropwise thionyl chloride 13kg react 3 hours (tail gas with recycle of alkali liquor,
Such as the sodium carbonate liquor of 1mol/L), unreacted thionyl chloride is recovered under reduced pressure, cooling obtains final product N-acetylsulfanilyl chloride crude product
(purity is 96%, and 98%) yield is.
Comparative example 1
This example provides a kind of with the method that sulfur trioxide is sulfonating agent synthesis N-acetylsulfanilyl chloride, it and embodiment
Method in 1 is basically identical, the difference is that do not include step (d), specially：
A () is warming up to 40 DEG C to 13.5kg antifebrins and 30kg glacial acetic acid, stirring is sequentially added in reactor；
B () is reacted 15 hours to sulfur trioxide gas (flow of ventilation is 2.5L/min) are passed through in reactor at 40 DEG C；
During close to reaction end, per 15min sampling analyses (being analyzed using liquid chromatograph HPLC), converted to antifebrin
Entirely, stop being passed through sulfur trioxide gas；
C () makes reactor temperature rise to 65 DEG C, glacial acetic acid is recovered under reduced pressure, and what cooling was obtained is acetylaminobenzene sulphur
Acid.
The above embodiments merely illustrate the technical concept and features of the present invention, its object is to allow person skilled in the art
Scholar will appreciate that present disclosure and implement according to this that it is not intended to limit the scope of the present invention, all according to the present invention
The equivalent change or modification that Spirit Essence is made, should all be included within the scope of the present invention.
Claims (4)
1. it is a kind of with sulfur trioxide as sulfonating agent synthesize N-acetylsulfanilyl chloride method, it is characterised in that it include with
Lower step：
（a）To antifebrin and glacial acetic acid is sequentially added in reactor, stirring is warming up to 40 ~ 70 DEG C；
（b）To sulfur trioxide gas are passed through in reactor, reacted 3 ~ 15 hours at 40 ~ 70 DEG C, converted the antifebrin
Entirely, stop being passed through sulfur trioxide gas；
（c）Reactor temperature is risen to 65 ~ 80 DEG C, the glacial acetic acid is recovered under reduced pressure；
（d）The temperature in the reactor is controlled for 60 ~ 90 DEG C, thionyl chloride is added dropwise and is reacted 2 ~ 4 hours, unreacted is recovered under reduced pressure
Thionyl chloride, cooling.
2. the method for synthesizing N-acetylsulfanilyl chloride as sulfonating agent with sulfur trioxide according to claim 1, its feature
It is：The step（b）In, reacting when close to terminal, every 5 ~ 15min sampling analyses are complete to antifebrin conversion.
3. the method for synthesizing N-acetylsulfanilyl chloride as sulfonating agent with sulfur trioxide according to claim 1, its feature
It is：Step（a）In, the mass ratio of the antifebrin and glacial acetic acid is 13.5：30~60；Step（b）In, three oxidation
The speed that is passed through of sulphur gas is 2.5 ~ 13.0L/min.
4. the method for synthesizing N-acetylsulfanilyl chloride as sulfonating agent with sulfur trioxide according to claim 1, its feature
It is：Step（d）In, reaction end gas are 13.5 with the mass ratio of thionyl chloride with alkali liquor absorption, the antifebrin：12~15.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108558712A (en) * | 2018-06-20 | 2018-09-21 | 新乡市锦源化工有限公司 | It is a kind of using antifebrin as the method and P-aminobenzene-sulfonamide of Material synthesis high-purity P-aminobenzene-sulfonamide |
| CN108640860A (en) * | 2018-06-12 | 2018-10-12 | 新乡市锦源化工有限公司 | The preparation method and N-acetylsulfanilyl chloride of the N-acetylsulfanilyl chloride of green energy conservation |
| CN108640862A (en) * | 2018-06-20 | 2018-10-12 | 新乡市锦源化工有限公司 | A kind of antifebrin of energy-saving and emission-reduction prepares the method and P-aminobenzene-sulfonamide of P-aminobenzene-sulfonamide |
| CN111377837A (en) * | 2020-03-18 | 2020-07-07 | 湖南吴赣药业有限公司 | Green synthesis method of p-acetamido-benzenesulfonyl chloride |
| CN111718286A (en) * | 2020-07-23 | 2020-09-29 | 邓博天 | Industrial production method of aromatic hydrocarbon sulfonyl chloride with power supply group |
| CN114605295A (en) * | 2022-03-12 | 2022-06-10 | 青岛科技大学 | Method for preparing sulfamate derivative from sulfur trioxide |
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| CN102304070A (en) * | 2011-04-29 | 2012-01-04 | 苏州市吴赣药业有限公司 | Process for producing p-acetamidobenzene sulfonyl chloride |
| CN102786446A (en) * | 2012-08-23 | 2012-11-21 | 楚源高新科技集团股份有限公司 | New production process for chlorosulfonation of para-ester by using thionyl chloride |
| CN105237446A (en) * | 2015-08-28 | 2016-01-13 | 苏州市吴赣药业有限公司 | Synthetic method of p-aminobenzenesulfonamide |
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| CN102304070A (en) * | 2011-04-29 | 2012-01-04 | 苏州市吴赣药业有限公司 | Process for producing p-acetamidobenzene sulfonyl chloride |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108640860A (en) * | 2018-06-12 | 2018-10-12 | 新乡市锦源化工有限公司 | The preparation method and N-acetylsulfanilyl chloride of the N-acetylsulfanilyl chloride of green energy conservation |
| CN108558712A (en) * | 2018-06-20 | 2018-09-21 | 新乡市锦源化工有限公司 | It is a kind of using antifebrin as the method and P-aminobenzene-sulfonamide of Material synthesis high-purity P-aminobenzene-sulfonamide |
| CN108640862A (en) * | 2018-06-20 | 2018-10-12 | 新乡市锦源化工有限公司 | A kind of antifebrin of energy-saving and emission-reduction prepares the method and P-aminobenzene-sulfonamide of P-aminobenzene-sulfonamide |
| CN111377837A (en) * | 2020-03-18 | 2020-07-07 | 湖南吴赣药业有限公司 | Green synthesis method of p-acetamido-benzenesulfonyl chloride |
| CN111718286A (en) * | 2020-07-23 | 2020-09-29 | 邓博天 | Industrial production method of aromatic hydrocarbon sulfonyl chloride with power supply group |
| CN114605295A (en) * | 2022-03-12 | 2022-06-10 | 青岛科技大学 | Method for preparing sulfamate derivative from sulfur trioxide |
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