CN110156643A - A kind of N-acetylsulfanilyl chloride efficient catalytic preparation method - Google Patents
A kind of N-acetylsulfanilyl chloride efficient catalytic preparation method Download PDFInfo
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- CN110156643A CN110156643A CN201910547851.0A CN201910547851A CN110156643A CN 110156643 A CN110156643 A CN 110156643A CN 201910547851 A CN201910547851 A CN 201910547851A CN 110156643 A CN110156643 A CN 110156643A
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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
- C07C303/08—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 halogenosulfonic acids
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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
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
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Abstract
The present invention relates to chemical intermediate synthesis technical fields, and disclose a kind of N-acetylsulfanilyl chloride efficient catalytic preparation method, the following steps are included: reaction dissolvent chloroform is added in reaction kettle first, secondly antifebrin and chlorosulfonic acid are added in chlorosulfonation kettle from two different directions respectively in proportion, the two sides of chlorosulfonation kettle are provided with material inlet pipe.The N-acetylsulfanilyl chloride efficient catalytic preparation method, by carrying out pressurizing atomizing processing to antifebrin and chlorosulfonic acid in initial reaction stage, and it is stirred, sulfonation process is set to can speed up progress, to improve reaction efficiency, and subsequent reaction process is by being added phosphorus pentachloride, carry out chlorination reaction, the waste liquid reduced in chlorosulfonic acid reaction process generates, calcium chloride is added simultaneously, the content of chloride ion in reaction process is significantly increased, reaction is promoted and is carried out towards the direction for generating N-acetylsulfanilyl chloride.
Description
Technical field
The present invention relates to chemical intermediate synthesis technical field, specially a kind of N-acetylsulfanilyl chloride efficient catalytic
Preparation method.
Background technique
N-acetylsulfanilyl chloride is medicine intermediate, is to prepare the sulfamidos such as sulfalene benzisoxazole and sulphathiazole
The primary raw material of medicine, current country are all to prepare wet product based on using by oneself and feed intake at once use, otherwise will be occurred point
It is solution, rotten, reach and guarantee the quality the stable time limit at most also just just three days, be really used as commodity, on the market at present or blank.State
Outer production is mainly using cryodrying technical equipment and spray granulating and drying come finished product, but additive has an impact to reaction.
Development trend is the stability for being conducive to be made product using cryodrying, but is invested larger.In addition, current synthetic method is logical
Often using chlorosulfonic acid as sulfonating agent, antifebrin is added portionwise in chlorosulfonic acid at 40~60 DEG C, reacts 2~4h, it is dilute by ice water
It releases, product is obtained by filtration, chlorosulfonic acid dosage is big in the technique, and the spent acid of generation is more, and processing cost is high.
Summary of the invention
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides a kind of N-acetylsulfanilyl chloride efficient catalytic preparation sides
Method has the advantages that chlorosulfonic acid dosage is few, byproduct of reaction is few and can be recycled to waste, solves previous technique stream
Chlorosulfonic acid dosage is excessive in journey, the inconvenient processing of spent acid and the higher problem of production cost.
(2) technical solution
To realize that above-mentioned chlorosulfonic acid dosage is few, byproduct of reaction is few and can be to the purpose that waste is recycled, this hair
It is bright to provide the following technical solutions: a kind of N-acetylsulfanilyl chloride efficient catalytic preparation method, comprising the following steps:
1) reaction dissolvent uses chloroform, and the chloroform of the amount of certain substance is added in chlorosulfonation kettle first, is added
After, antifebrin and chlorosulfonic acid are added in chlorosulfonation kettle from two different directions respectively in proportion, and is being added
Pressurizing atomizing processing is carried out in the process；
2) mixed liquor in step 1 is stirred, mixing time is 1~2h；
3) reaction solution in step 2 is heated, heating temperature is 60~70 degree, and keeps 2~3h；
4) phosphorus pentachloride, 3~4h of insulation reaction are added into the reaction solution in step 3, and calcium chloride is added；
5) solution in step 4 is subjected to centrifugal treating, 1~2h is stood after centrifugation, then imports lower liquid
In crystallization kettle, ice water is added and cools the temperature to 20 degree or less；
6) crystallization of step 5 is cleaned, collection is sealed after cleaning.
Preferably, the mass ratio of the material of the chloroform, antifebrin, chlorosulfonic acid, phosphorus pentachloride and calcium chloride are as follows: 3:1:2:
1:0.2。
Preferably, the two sides of the chlorosulfonation kettle are provided with material inlet pipe, the side setting of the material inlet pipe
There are solvent pump, the inclined placement of two material inlet pipes, and its axis is intersected in the center of chlorosulfonation kettle, one of object
It is passed through antifebrin in material inlet pipe, is passed through chlorosulfonic acid in another material inlet pipe.
Preferably, the pressure limit of the adition process is 0.15~0.25MP.
Preferably, the speed of centrifugal treating is 800~1500r/min in the step 4.
(3) beneficial effect
Compared with prior art, the present invention provides a kind of N-acetylsulfanilyl chloride efficient catalytic preparation method, tools
It is standby following the utility model has the advantages that
The N-acetylsulfanilyl chloride efficient catalytic preparation method, by initial reaction stage to antifebrin and chlorosulfonic acid
Pressurizing atomizing processing is carried out, and is stirred, sulfonation process is made to can speed up progress, so that reaction efficiency is improved, and after
Continuous reaction process carries out chlorination reaction, the waste liquid reduced in chlorosulfonic acid reaction process generates, together by the way that phosphorus pentachloride is added
When calcium chloride is added, significantly increase the content of chloride ion in reaction process, promote reaction towards generate acetparaminosalol
The direction of benzene sulfonyl chloride carries out, and further improves the purity of reaction product N-acetylsulfanilyl chloride, and extra calcium from
Sulfate ion reaction in son and solution, generates calcium sulfate precipitation, calcium sulfate is gypsum, so as to complete liquid waste processing mistake
Journey reduces the acid degree of waste liquid after reaction, is further processed to be conducive to the later period to waste liquid, it is higher to have reached practicability
With the purpose of save the cost.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution in the embodiment of the present invention is clearly and completely retouched
It states, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the present invention
In embodiment, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, shall fall within the protection scope of the present invention.
A kind of N-acetylsulfanilyl chloride efficient catalytic preparation method, comprising the following steps: first by reaction dissolvent chlorine
It is imitative to be added in reaction kettle, chlorosulfonation secondly is added from two different directions respectively in proportion in antifebrin and chlorosulfonic acid
In kettle, the two sides of chlorosulfonation kettle are provided with material inlet pipe, and the side of the material inlet pipe is provided with solvent pump, two objects
Expect the inclined placement of inlet pipe, and its axis is intersected in the center of chlorosulfonation kettle, is passed through second in one of material inlet pipe
Anilide is passed through chlorosulfonic acid in another material inlet pipe, and carries out pressurizing atomizing processing during the addition process, and pressure limit is
0.15~0.25MP；Mixed liquor is stirred, mixing time is 1~2h；Then reaction solution is heated, heating temperature
Degree is 60~70 degree, and keeps the backward reaction solution of 2~3h is interior phosphorus pentachloride, 3~4h of insulation reaction is added, and chlorination is added
Calcium, the mass ratio of the material of chloroform, antifebrin, chlorosulfonic acid, phosphorus pentachloride and calcium chloride are as follows: 3:1:2:1:0.2；After completion of the reaction
Centrifugal treating is carried out to solution, the speed of centrifugal treating is 800~1500r/min, and 1~2h is stood after centrifugation, then will
Lower liquid imports in crystallization kettle, and ice water is added and cools the temperature to 20 degree or less；Crystallization is cleaned, is carried out after cleaning
Sealing is collected.
Embodiment one:
A kind of N-acetylsulfanilyl chloride efficient catalytic preparation method, comprising the following steps: first by reaction dissolvent chlorine
It is imitative to be added in reaction kettle, chlorosulfonation secondly is added from two different directions respectively in proportion in antifebrin and chlorosulfonic acid
In kettle, the two sides of chlorosulfonation kettle are provided with material inlet pipe, and the side of the material inlet pipe is provided with solvent pump, two objects
Expect the inclined placement of inlet pipe, and its axis is intersected in the center of chlorosulfonation kettle, is passed through second in one of material inlet pipe
Anilide is passed through chlorosulfonic acid in another material inlet pipe, and carries out pressurizing atomizing processing during the addition process, and pressure limit is
0.15；Mixed liquor is stirred, mixing time 1h；Then reaction solution being heated, heating temperature is 60 degree, and
Keep addition phosphorus pentachloride in 2 backward reaction solution, insulation reaction 3h, and calcium chloride is added, chloroform, antifebrin, chlorosulfonic acid,
The mass ratio of the material of phosphorus pentachloride and calcium chloride are as follows: 3:1:2:1:0.2；Centrifugal treating, centrifugation are carried out to solution after completion of the reaction
The speed of processing is 800/min, and 1h is stood after centrifugation, then imports lower liquid in crystallization kettle, and ice water is added will be warm
Degree is down to 20 degree or less；Crystallization is cleaned, collection is sealed after cleaning.
Through this embodiment, the N-acetylsulfanilyl chloride of every 500kg chlorosulfonic acid output is 400kg, yield 80%.
Embodiment two:
A kind of N-acetylsulfanilyl chloride efficient catalytic preparation method, comprising the following steps: first by reaction dissolvent chlorine
It is imitative to be added in reaction kettle, chlorosulfonation secondly is added from two different directions respectively in proportion in antifebrin and chlorosulfonic acid
In kettle, the two sides of chlorosulfonation kettle are provided with material inlet pipe, and the side of the material inlet pipe is provided with solvent pump, two objects
Expect the inclined placement of inlet pipe, and its axis is intersected in the center of chlorosulfonation kettle, is passed through second in one of material inlet pipe
Anilide is passed through chlorosulfonic acid in another material inlet pipe, and carries out pressurizing atomizing processing during the addition process, and pressure limit is
0.2MP；Mixed liquor is stirred, mixing time 1.5h；Then reaction solution is heated, heating temperature 65
Degree, and keep the backward reaction solution of 2.5h is interior phosphorus pentachloride, insulation reaction 3.5h is added, and calcium chloride is added, chloroform, acetophenone
The mass ratio of the material of amine, chlorosulfonic acid, phosphorus pentachloride and calcium chloride are as follows: 3:1:2:1:0.2；Solution is centrifuged after completion of the reaction
The speed of processing, centrifugal treating is 1000r/min, and 1.5h is stood after centrifugation, then imports lower liquid in crystallization kettle,
Ice water is added and cools the temperature to 20 degree or less；Crystallization is cleaned, collection is sealed after cleaning.
Through this embodiment, the N-acetylsulfanilyl chloride of every 500kg chlorosulfonic acid output is 420kg, yield 84%
Embodiment three:
A kind of N-acetylsulfanilyl chloride efficient catalytic preparation method, comprising the following steps: first by reaction dissolvent chlorine
It is imitative to be added in reaction kettle, chlorosulfonation secondly is added from two different directions respectively in proportion in antifebrin and chlorosulfonic acid
In kettle, the two sides of chlorosulfonation kettle are provided with material inlet pipe, and the side of the material inlet pipe is provided with solvent pump, two objects
Expect the inclined placement of inlet pipe, and its axis is intersected in the center of chlorosulfonation kettle, is passed through second in one of material inlet pipe
Anilide is passed through chlorosulfonic acid in another material inlet pipe, and carries out pressurizing atomizing processing during the addition process, and pressure limit is
0.25MP；Mixed liquor is stirred, mixing time 2h；Then reaction solution being heated, heating temperature is 70 degree,
And keep the backward reaction solution of 3h is interior phosphorus pentachloride, insulation reaction 4h is added, and calcium chloride is added, chloroform, antifebrin, chlorine sulphur
The mass ratio of the material of acid, phosphorus pentachloride and calcium chloride are as follows: 3:1:2:1:0.2；Centrifugal treating is carried out to solution after completion of the reaction, from
The speed of heart processing is 1500r/min, and 2h is stood after centrifugation, then imports lower liquid in crystallization kettle, and ice water is added
Cool the temperature to 20 degree or less；Crystallization is cleaned, collection is sealed after cleaning.
Through this embodiment, the N-acetylsulfanilyl chloride of every 500kg chlorosulfonic acid output is 450kg, yield 90%.
Experimental example four:
A kind of N-acetylsulfanilyl chloride efficient catalytic preparation method, comprising the following steps: first by reaction dissolvent chlorine
It is imitative to be added in reaction kettle, chlorosulfonation secondly is added from two different directions respectively in proportion in antifebrin and chlorosulfonic acid
In kettle, the two sides of chlorosulfonation kettle are provided with material inlet pipe, and the side of the material inlet pipe is provided with solvent pump, two objects
Expect the inclined placement of inlet pipe, and its axis is intersected in the center of chlorosulfonation kettle, is passed through second in one of material inlet pipe
Anilide is passed through chlorosulfonic acid in another material inlet pipe, and carries out pressurizing atomizing processing during the addition process, and pressure limit is
0.25MP；Mixed liquor is stirred, mixing time 2h；Then reaction solution being heated, heating temperature is 65 degree,
And keep the backward reaction solution of 3h is interior phosphorus pentachloride, insulation reaction 4h is added, and calcium chloride is added, chloroform, antifebrin, chlorine sulphur
The mass ratio of the material of acid, phosphorus pentachloride and calcium chloride are as follows: 3:1:2:1:0.2；Centrifugal treating is carried out to solution after completion of the reaction, from
The speed of heart processing is 1200r/min, and 1~2h is stood after centrifugation, then imports lower liquid in crystallization kettle, and ice is added
Water cools the temperature to 20 degree or less；Crystallization is cleaned, collection is sealed after cleaning.
Through this embodiment, the N-acetylsulfanilyl chloride of every 500kg chlorosulfonic acid output is 430kg, yield 86%.
The beneficial effects of the present invention are: the N-acetylsulfanilyl chloride efficient catalytic preparation method, by first in reaction
Phase carries out pressurizing atomizing processing to antifebrin and chlorosulfonic acid, and is stirred, and so that sulfonation process is can speed up progress, to mention
High reaction efficiency, and subsequent reaction process carries out chlorination reaction, reduces chlorosulfonic acid reaction by the way that phosphorus pentachloride is added
Waste liquid in the process generates, while calcium chloride is added, and significantly increases the content of chloride ion in reaction process, promotes reaction
It is carried out towards the direction for generating N-acetylsulfanilyl chloride, further improves reaction product N-acetylsulfanilyl chloride
Purity, and the sulfate ion reaction in extra calcium ion and solution, generate calcium sulfate precipitation, and calcium sulfate is gypsum, from
And waste treatment process is completed, the acid degree of waste liquid after reaction is reduced, to be conducive to the later period to the further place of waste liquid
Reason has achieved the purpose that practicability is higher and save the cost.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (5)
1. a kind of N-acetylsulfanilyl chloride efficient catalytic preparation method, which comprises the following steps:
1) reaction dissolvent uses chloroform, the chloroform of the amount of certain substance is added in chlorosulfonation kettle first, addition finishes
Afterwards, antifebrin and chlorosulfonic acid are added in chlorosulfonation kettle from two different directions respectively in proportion, and in adition process
Middle progress pressurizing atomizing processing；
2) mixed liquor in step 1 is stirred, mixing time is 1~2h；
3) reaction solution in step 2 is heated, heating temperature is 60~70 degree, and keeps 2~3h；
4) phosphorus pentachloride, 3~4h of insulation reaction are added into the reaction solution in step 3, and calcium chloride is added；
5) solution in step 4 is subjected to centrifugal treating, 1~2h is stood after centrifugation, then lower liquid is imported and is crystallized
In kettle, ice water is added and cools the temperature to 20 degree or less；
6) crystallization of step 5 is cleaned, collection is sealed after cleaning.
2. a kind of N-acetylsulfanilyl chloride efficient catalytic preparation method according to claim 1, which is characterized in that institute
State the mass ratio of the material of chloroform, antifebrin, chlorosulfonic acid, phosphorus pentachloride and calcium chloride are as follows: 3:1:2:1:0.2.
3. a kind of N-acetylsulfanilyl chloride efficient catalytic preparation method according to claim 1, which is characterized in that institute
The two sides for stating chlorosulfonation kettle are provided with material inlet pipe, and the side of the material inlet pipe is provided with solvent pump, two materials
The inclined placement of inlet pipe, and its axis is intersected in the center of chlorosulfonation kettle, is passed through acetyl in one of material inlet pipe
Aniline is passed through chlorosulfonic acid in another material inlet pipe.
4. a kind of N-acetylsulfanilyl chloride efficient catalytic preparation method according to claim 1, which is characterized in that institute
The pressure limit for stating adition process is 0.15~0.25MP.
5. a kind of N-acetylsulfanilyl chloride efficient catalytic preparation method according to claim 1, which is characterized in that institute
The speed for stating centrifugal treating in step 4 is 800~1500r/min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110590608A (en) * | 2019-09-08 | 2019-12-20 | 天津大学 | Method for synthesizing p-acetamidobenzenesulfonyl chloride in tetrachloroethylene solvent |
| CN110724073A (en) * | 2019-10-28 | 2020-01-24 | 新乡市锦源化工有限公司 | Production process of p-acetamido-benzenesulfonyl chloride |
| CN113952827A (en) * | 2021-11-24 | 2022-01-21 | 吴赣药业（苏州）有限公司 | Method for treating organic waste gas in synthesis of p-acetamido benzenesulfonyl chloride |
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| WO2005063701A1 (en) * | 2003-12-29 | 2005-07-14 | Lek Pharmaceuticals D.D. | Synthesis of optically pure (r)-5-(2-aminopropyl)-2-methoxybenzenesulphonamide |
| CN102633696A (en) * | 2012-04-05 | 2012-08-15 | 天津理工大学 | Method and technology for preparing p-substituted alkyl benzene sulfonyl chloride by two-step synthesis |
| CN108640859A (en) * | 2018-06-12 | 2018-10-12 | 新乡市锦源化工有限公司 | The high-efficiency synthesis method and N-acetylsulfanilyl chloride of N-acetylsulfanilyl chloride |
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2019
- 2019-06-24 CN CN201910547851.0A patent/CN110156643A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005063701A1 (en) * | 2003-12-29 | 2005-07-14 | Lek Pharmaceuticals D.D. | Synthesis of optically pure (r)-5-(2-aminopropyl)-2-methoxybenzenesulphonamide |
| CN102633696A (en) * | 2012-04-05 | 2012-08-15 | 天津理工大学 | Method and technology for preparing p-substituted alkyl benzene sulfonyl chloride by two-step synthesis |
| CN108640859A (en) * | 2018-06-12 | 2018-10-12 | 新乡市锦源化工有限公司 | The high-efficiency synthesis method and N-acetylsulfanilyl chloride of N-acetylsulfanilyl chloride |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110590608A (en) * | 2019-09-08 | 2019-12-20 | 天津大学 | Method for synthesizing p-acetamidobenzenesulfonyl chloride in tetrachloroethylene solvent |
| CN110724073A (en) * | 2019-10-28 | 2020-01-24 | 新乡市锦源化工有限公司 | Production process of p-acetamido-benzenesulfonyl chloride |
| CN113952827A (en) * | 2021-11-24 | 2022-01-21 | 吴赣药业（苏州）有限公司 | Method for treating organic waste gas in synthesis of p-acetamido benzenesulfonyl chloride |
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Application publication date: 20190823 |