CN108640862A - A kind of antifebrin of energy-saving and emission-reduction prepares the method and P-aminobenzene-sulfonamide of P-aminobenzene-sulfonamide - Google Patents
A kind of antifebrin of energy-saving and emission-reduction prepares the method and P-aminobenzene-sulfonamide of P-aminobenzene-sulfonamide Download PDFInfo
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- CN108640862A CN108640862A CN201810642751.1A CN201810642751A CN108640862A CN 108640862 A CN108640862 A CN 108640862A CN 201810642751 A CN201810642751 A CN 201810642751A CN 108640862 A CN108640862 A CN 108640862A
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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
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
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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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- 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
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/38—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
Abstract
A kind of antifebrin of energy-saving and emission-reduction prepares the method and P-aminobenzene-sulfonamide of P-aminobenzene-sulfonamide, belongs to P-aminobenzene-sulfonamide synthesis field.Method includes：Under the conditions of the agitating and heating of 60 70 DEG C of temperature, antifebrin and glacial acetic acid are mixed to get sulfonation stoste, sulfur trioxide gas is passed through into sulfonation stoste and carries out sulfonating reaction, glacial acetic acid is recovered under reduced pressure and obtains sulfonated products.Sulfonated products are mixed with thionyl chloride and carry out chlorination reaction, remaining thionyl chloride is recovered under reduced pressure and obtains N-acetylsulfanilyl chloride, tail gas is passed through in receiving liquid in chlorination reaction and obtains acid recovery liquid.It is reacted being hydrolyzed with the mixed liquor of concentrated hydrochloric acid using acid recovery liquid after N-acetylsulfanilyl chloride progress aminating reaction.To raw material availability height, avoids generating spent acid and waste gas circulation is utilized, energy conservation and environmental protection, green emission reduction.P-aminobenzene-sulfonamide is made according to above-mentioned method, environmental friendly, at low cost, purity is high.
Description
Technical field
The present invention relates to P-aminobenzene-sulfonamide to synthesize field, and prepared by the antifebrin of more particularly to a kind of energy-saving and emission-reduction
The method and P-aminobenzene-sulfonamide of P-aminobenzene-sulfonamide.
Background technology
P-aminobenzene-sulfonamide is for external application except for producing sulphanilamide crystal in addition to anti-inflammatory, can also synthesize other sulfa drugs
Such as sulphoamidine, kynix, sulfamethyldiazine are a kind of important medicine and intermediate.
Currently, antifebrin is a kind of common route as Material synthesis P-aminobenzene-sulfonamide.It adopts in the prior art
Chlorosulfonation is carried out to antifebrin with chlorosulfonic acid, since the reaction is balanced reaction, is needed using a large amount of and excessive chlorine
Sulfonic acid participates in reaction, leads to problems such as raw material expend spent acid that is big, generating more.
In view of this, special propose the application.
Invention content
It is right the purpose of the present invention is to provide a kind of method that the antifebrin of energy-saving and emission-reduction prepares P-aminobenzene-sulfonamide
Raw material availability is high, avoids generating spent acid and be utilized to waste gas circulation, energy conservation and environmental protection, green emission reduction.
It is environmental friendly, at low cost, purity is high another object of the present invention is to provide a kind of P-aminobenzene-sulfonamide.
The present invention solves its technical problem using following technical scheme to realize.
The present invention proposes a kind of method that the antifebrin of energy-saving and emission-reduction prepares P-aminobenzene-sulfonamide, including：In temperature
Under the conditions of 60-70 DEG C of agitating and heating, antifebrin and glacial acetic acid are mixed to get sulfonation stoste, three are passed through into sulfonation stoste
Sulfur oxide gas carries out sulfonating reaction, and glacial acetic acid is recovered under reduced pressure and obtains sulfonated products；Sulfonated products and thionyl chloride are mixed into
Row chlorination reaction is recovered under reduced pressure remaining thionyl chloride and obtains N-acetylsulfanilyl chloride, is passed through tail gas in chlorination reaction
Acid recovery liquid is obtained in receiving liquid；N-acetylsulfanilyl chloride is carried out after aminating reaction using acid recovery liquid and concentrated hydrochloric acid
Reaction is hydrolyzed in mixed liquor.
The present invention proposes a kind of P-aminobenzene-sulfonamide, is made according to above-mentioned method.
The advantageous effect of the embodiment of the present invention is：
The method that the antifebrin of energy-saving and emission-reduction provided by the invention prepares P-aminobenzene-sulfonamide, using sulfur trioxide as sulphur
Agent carries out sulfonation in glacial acetic acid solvent to antifebrin, then carries out chlorination by chlorinating agent of thionyl chloride, both can guarantee
The quality of N-acetylsulfanilyl chloride；Chlorosulfonic acid is not used during simultaneous reactions, by glacial acetic acid and extra thionyl chloride
Recycling, consumption of raw materials is few to be avoided generating waste water and spent acid again.Hydrogen chloride tail gas is will produce in chlorination process, by hydrogen chloride in reaction
Tail gas, which is passed through in receiving liquid, obtains acid recovery liquid, which is mixed with concentrated hydrochloric acid and is operated applied to acidification hydrolization, by chlorine
Change the progress of hydrogen tail gas and adequately recycle saving raw material, while avoiding exhaust emission again.
P-aminobenzene-sulfonamide provided by the invention is made according to above-mentioned method, correspondingly has environmental friendly, cost
Low, the advantages that purity is high.
Specific implementation mode
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, builds according to normal condition or manufacturer
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Prepared by the method for P-aminobenzene-sulfonamide to the antifebrin of the energy-saving and emission-reduction of the embodiment of the present invention below and to ammonia
Base benzsulfamide is specifically described.
The present invention provides a kind of method that the antifebrin of energy-saving and emission-reduction prepares P-aminobenzene-sulfonamide, including：Using second
Anilide, as chlorinating agent, carries out sulfonating reaction, chlorine successively as raw material, sulfur trioxide gas as sulfonating agent, thionyl chloride
Change reaction, aminating reaction and hydrolysis.
Specifically：
(1) sulfonating reaction includes：Under the conditions of the agitating and heating of 60-70 DEG C of temperature, antifebrin is mixed with glacial acetic acid
Sulfonation stoste is obtained, sulfur trioxide gas is passed through into sulfonation stoste and carries out sulfonating reaction, glacial acetic acid is recovered under reduced pressure and obtains sulfonation
Product.
In sulfonating reaction, using sulfur trioxide as sulfonating agent in glacial acetic acid solvent to antifebrin carry out sulfonation, Ji Nengbao
The quality of N-acetylsulfanilyl chloride is demonstrate,proved, is convenient for after the completion by depressurizing steaming without adding chlorosulfonic acid and reacting in simultaneous reactions
It evaporates and recycles glacial acetic acid, consumption of raw materials is few to be avoided generating waste water and spent acid again.
Optionally, before being passed through sulfur trioxide gas into sulfonation stoste, dry air is passed through into sulfonation stoste to anti-
Answer container inner pressure to reach 0.3-0.4Mpa, for example, make in reaction vessel pressure reach 0.3Mpa, 0.32Mpa, 0.34Mpa,
0.36Mpa, 0.38Mpa, 0.4Mpa etc..
The speed for being passed through dry air is that the volume ratio of the volume and sulfonation stoste of the dry air per minute being passed through is
0.8-1.2:1, such as 0.8:1、0.9:1、1:1、1.1:1、1.2:1 etc..
The operation of dry air is passed through into sulfonation stoste, gas is to the disturbance cooperative mechanical stirring action of liquid material to sulfonation
Stoste is sufficiently mixed, and so that antifebrin is fully dissolved and is homogeneously dispersed in glacial acetic acid.Sulfonation during ventilation
Stoste gradually completes mixing and heats up, without individually carrying out.Aeration forms a large amount of bubbles in liquid material and is conducive to subsequently instead
It answers coming into full contact with for raw material and fully reacts, while supercharging is carried out to conducive to reaction later stage material content to reaction vessel interior
Reaction can continue fully to carry out when the relatively low and extent of reaction is higher.
Further, after being passed through dry air into sulfonation stoste, sulfur trioxide gas is passed through into sulfonation stoste to anti-
Answer container inner pressure to reach 0.6-0.8Mpa, for example, make in reaction vessel pressure reach 0.6Mpa, 0.65Mpa, 0.7Mpa,
0.75Mpa, 0.8Mpa etc..Then stop external aeration and the inner air of reaction vessel be passed through sulfonation stoste to carry out internal sky
Gas recycles.
In some specific embodiments of the invention, it is passed through the speed of sulfur trioxide gas and is passed through three oxidations to be per minute
The volume of sulphur gas is 0.8-1.2 with the volume ratio of sulfonation stoste:1, it is passed through the speed of inner air and is passed through inside to be per minute
The volume of air is 0.8-1.2 with the volume ratio of sulfonation stoste:1.Such as 0.8:1、0.9:1、1:1、1.1:1、1.2:1 etc..
Since sulfur trioxide gas cannot be reacted with antifebrin completely in time during being passed through sulfonation stoste, three
The inner air of reaction vessel is passed through in stoste by sulfur oxide gas after the completion of being passed through continues sulfonating reaction, is conducive to accumulate
It is recycled in sulfonation stoste and is further carried out with antifebrin quickly, fully in a large amount of sulfur trioxide gas in reaction vessel
Reaction.The cycle of the inner air of reaction vessel can also coordinate stirring action to be sufficiently mixed liquid material, accelerate reaction
Carry out, improve the utilization rate of raw material.
(2) chlorination reaction includes：The agitating and heating condition for keeping 60-70 DEG C of temperature, sulfonated products and thionyl chloride are mixed
It closes and carries out chlorination reaction, remaining thionyl chloride is recovered under reduced pressure and obtains N-acetylsulfanilyl chloride, by tail gas in chlorination reaction
It is passed through in receiving liquid and obtains acid recovery liquid.
Optionally, the molar ratio of antifebrin and thionyl chloride is 1:1.0-1.1 such as 1:1.0、 1:1.02、1:
1.05、1:1.08、1:1.1 waiting.The time of chlorination reaction is optionally 2-3h, as 120min, 130min, 140min,
150min, 160min, 170min, 180min etc..The receiving liquid that tail gas is passed through is optionally water or hydrochloric acid solution.
Using thionyl chloride as chlorinating agent in chlorination reaction, thionyl chloride has higher chlorination performance, chlorination reaction velocity
Soon, reaction is thorough.Extra thionyl chloride is recycled convenient for passing through vacuum distillation after the completion of reaction.
In some preferable embodiments of the invention, the hybrid manipulation of sulfonated products and thionyl chloride includes：In chlorination
Thionyl chloride is gradually instilled into sulfonated products in reaction whole process.
Since thionyl chloride has extremely strong smoking property, thionyl chloride is added dropwise in entire reaction process step by step into
Row reaction, the thionyl chloride being gradually added dropwise can in time, promptly be reacted when contacting sulfonated products, make thionyl chloride
Utilization rate improves.
Further, the hybrid manipulation of the sulfonated products and thionyl chloride includes the first feeding stage, the second feeding stage
And third feeding stage.Charging rate in each feeding stage generally remains inconvenient easy to operation, while the first feeding stage
Charging rate, the charging rate of the charging rate of the second feeding stage and third feeding stage is sequentially reduced.
As the extent of reaction is higher and higher, the amount of the sulfonated products of non-chlorination is fewer and fewer, thionyl chloride and sulfonation
The reaction speed of product is gradually reduced, and the first feeding stage to the second feeding stage is correspondingly controlled during charging again to the
The charging rate of three feeding stages is gradually reduced, and is matched with the reaction speed of sulfonated products with thionyl chloride, thionyl chloride and sulphur
The reaction for changing product is more abundant.
In some specific embodiments of the invention, the first feeding stage, the second feeding stage and third feeding stage
Charging rate ratio be followed successively by 3-4:1.5-2.5:1, such as 3:1.5:1、 3:2:1、3:2.5:1、3.5:1.5:1、3.5:2:1、
3.5:2.5:1、4:1.5:1、4:2:1、4:2.5:1 etc..
The molar ratio that thionyl chloride is added in first feeding stage, the second feeding stage and third feeding stage is 3-4:3-4:
1, such as 3:3:1、3:3.5:1、3:4:1、3.5:3:1、3.5:3.5:1、3.5:4:1、 4:3:1、4:3.5:1、4:4:1 etc..
Further, between the first feeding stage and the second feeding stage and the second feeding stage and third feeding stage
Between include the exhaust phase of 10-20min.
Stop the operation that thionyl chloride is added dropwise in bleeding, only carry out the tail gas discharge to hydrogen chloride gas and absorbs behaviour
Make, reduce the content of hydrogen chloride in the inner air of reaction kettle, is conducive to the progress of reaction.
(3) aminating reaction includes：Mass concentration, which is added, in the N-acetylsulfanilyl chloride that chlorination reaction obtains is about
In 20% ammonium hydroxide, 3h is reacted under conditions of about 50 DEG C of temperature, after reacting fully heating remove extra ammonia, keep yield close
Maximum value and impurity content is low.
(4) hydrolysis operation includes：It is mixed the acid recovery liquid that hydrogen chloride tail gas obtains is recycled in chlorination reaction with concentrated hydrochloric acid,
Be configured to mass concentration be 28-35% hydrochloric acid, such as be configured to mass concentration be 28%, 29%, 30%, 31%, 32%,
33%, 34%, 35% etc. hydrochloric acid.
The hydrochloric acid moderate heat heating reflux reaction that the preparation obtains is added in aminate.Mass concentration is added after the completion of reaction
About 40% sodium hydroxide solution adjusts pH to 6.2-7, crystallisation by cooling.
Aminate is hydrolyzed using acid solution, hydrolysis operation is convenient and hydrolysis is thorough.In hydrolysis operation, by chlorine
Change the acid recovery liquid that tail gas recycle obtains in reaction adequately to recycle, saves raw material, while avoiding exhaust emission again.
The present invention also provides a kind of P-aminobenzene-sulfonamide, be made according to above-mentioned method, correspondingly have it is environmental friendly,
At low cost, the advantages that purity is high.
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of method that the antifebrin of energy-saving and emission-reduction prepares P-aminobenzene-sulfonamide, including：
Under conditions of 65 DEG C of temperature, mixing speed 500r/min：
S1, by mass ratio be 1:3.5 antifebrin mixes in a kettle with glacial acetic acid, obtains sulfonation stoste.
It is passed through dry air to reacting kettle inner pressure into sulfonation stoste and reaches 0.35Mpa.It is passed through three into sulfonation stoste
Sulfur oxide gas to reacting kettle inner pressure reaches 0.7Mpa.Stop external aeration, the inner air extraction of reaction kettle is passed into
Sulfonation stoste reacts 4h, and glacial acetic acid is recovered under reduced pressure and obtains sulfonated products.
S2, according to antifebrin：The molar ratio of thionyl chloride is 1:1.05 are on the waiting list thionyl chloride, by thionyl chloride according to
3.5:3.5:1 molar ratio is divided into first part, second part and third part.
First part of thionyl chloride is added dropwise to hydrogen chloride tail in 30min in sulfonated products while carrying out chlorination reaction
Gas, which is passed through in water, obtains acid recovery liquid, stops charging 15min and is only exhausted；Then by second part of thionyl chloride in 60min
It is added dropwise in sulfonated products and carries out chlorination reaction, stop charging 15min and be only exhausted；Then third part thionyl chloride is existed
It is added dropwise in 30min in sulfonated products and carries out chlorination reaction, stopped charging 15min and be only exhausted；Then by extra dichloro
Sulfoxide vacuum distillation recycling, obtains acetamidobenzenesulfonyl chloride.
In S3, the ammonium hydroxide for being about 20% by N-acetylsulfanilyl chloride addition mass concentration, 50 DEG C of reaction 3h are heated to,
Heating removes extra ammonia and obtains aminate.
S4, it the acid recovery liquid in S2 is mixed with concentrated hydrochloric acid is made into the hydrochloric acid that mass concentration is 30%.By the amination in S4
Small fire heating reflux reaction in the hydrochloric acid being made into is added in product, and the sodium hydroxide solution that mass concentration 40% is then added is adjusted
PH to 7, crystallisation by cooling obtains P-aminobenzene-sulfonamide.
The yield of P-aminobenzene-sulfonamide is 94.35%, product purity 95.16%.
Embodiment 2
A kind of method that the antifebrin of energy-saving and emission-reduction prepares P-aminobenzene-sulfonamide, including：
Under conditions of 65 DEG C of temperature, mixing speed 500r/min：
S1, by mass ratio be 1:3.5 antifebrin mixes in a kettle with glacial acetic acid, obtains sulfonation stoste.
It is passed through dry air to reacting kettle inner pressure into sulfonation stoste and reaches 0.3Mpa.Three oxygen are passed through into sulfonation stoste
Change sulphur gas to reacting kettle inner pressure and reaches 0.6Mpa.Stop external aeration, the inner air extraction of reaction kettle is passed into sulphur
Change stoste and react 5h, glacial acetic acid is recovered under reduced pressure and obtains sulfonated products.
S2, according to antifebrin：The molar ratio of thionyl chloride is 1:1 is on the waiting list thionyl chloride, by thionyl chloride according to 3:4:1
Molar ratio be divided into first part, second part and third part.
First part of thionyl chloride is added dropwise to hydrogen chloride tail in 30min in sulfonated products while carrying out chlorination reaction
Gas, which is passed through in water, obtains acid recovery liquid, stops charging 15min and is only exhausted；Then by second part of thionyl chloride in 80min
It is added dropwise in sulfonated products and carries out chlorination reaction, stop charging 15min and be only exhausted；Then third part thionyl chloride is existed
It is added dropwise in 30min in sulfonated products and carries out chlorination reaction, stopped charging 15min and be only exhausted；Then by extra dichloro
Sulfoxide vacuum distillation recycling, obtains acetamidobenzenesulfonyl chloride.
In S3, the ammonium hydroxide for being about 20% by N-acetylsulfanilyl chloride addition mass concentration, 50 DEG C of reaction 3h are heated to,
Heating removes extra ammonia and obtains aminate.
S4, it the acid recovery liquid in S2 is mixed with concentrated hydrochloric acid is made into the hydrochloric acid that mass concentration is 28%.By the amination in S4
Small fire heating reflux reaction in the hydrochloric acid being made into is added in product, and the sodium hydroxide solution that mass concentration 40% is then added is adjusted
PH to 7, crystallisation by cooling obtains P-aminobenzene-sulfonamide.
The yield of P-aminobenzene-sulfonamide is 94.54%, product purity 94.86%.
Embodiment 3
A kind of method that the antifebrin of energy-saving and emission-reduction prepares P-aminobenzene-sulfonamide, including：
Under conditions of 65 DEG C of temperature, mixing speed 500r/min：
S1, by mass ratio be 1:3.5 antifebrin mixes in a kettle with glacial acetic acid, obtains sulfonation stoste.
It is passed through dry air to reacting kettle inner pressure into sulfonation stoste and reaches 0.4Mpa.Three oxygen are passed through into sulfonation stoste
Change sulphur gas to reacting kettle inner pressure and reaches 0.8Mpa.Stop external aeration, the inner air extraction of reaction kettle is passed into sulphur
Change stoste and react 3h, glacial acetic acid is recovered under reduced pressure and obtains sulfonated products.
S2, according to antifebrin：The molar ratio of thionyl chloride is 1:1.05 are on the waiting list thionyl chloride, by thionyl chloride according to 4:
3:1 molar ratio is divided into first part, second part and third part.
First part of thionyl chloride is added dropwise to hydrogen chloride tail in 40min in sulfonated products while carrying out chlorination reaction
Gas, which is passed through in water, obtains acid recovery liquid, stops charging 15min and is only exhausted；Then by second part of thionyl chloride in 60min
It is added dropwise in sulfonated products and carries out chlorination reaction, stop charging 15min and be only exhausted；Then third part thionyl chloride is existed
It is added dropwise in 30min in sulfonated products and carries out chlorination reaction, stopped charging 15min and be only exhausted；Then by extra dichloro
Sulfoxide vacuum distillation recycling, obtains acetamidobenzenesulfonyl chloride.
In S3, the ammonium hydroxide for being about 20% by N-acetylsulfanilyl chloride addition mass concentration, 50 DEG C of reaction 3h are heated to,
Heating removes extra ammonia and obtains aminate.
S4, it the acid recovery liquid in S2 is mixed with concentrated hydrochloric acid is made into the hydrochloric acid that mass concentration is 33%.By the amination in S4
Small fire heating reflux reaction in the hydrochloric acid being made into is added in product, and the sodium hydroxide solution that mass concentration 40% is then added is adjusted
PH to 7, crystallisation by cooling obtains P-aminobenzene-sulfonamide.
The yield of P-aminobenzene-sulfonamide is 93.79%, product purity 95.23%.
Embodiment 4
A kind of method that the antifebrin of energy-saving and emission-reduction prepares P-aminobenzene-sulfonamide, the difference with embodiment 1
It is：
It is anti-it to be passed through sulfur trioxide gas in S1, in the entire reaction of sulfonating reaction, constantly and only into sulfonation stoste
4h is answered, dry air is not passed through before being passed through sulfur trioxide gas, is passed through without inner air after being passed through sulfur trioxide gas
The operation of sulfonation stoste.
The yield of P-aminobenzene-sulfonamide is 89.34%, product purity 94.21%.
Embodiment 5
A kind of method that the antifebrin of energy-saving and emission-reduction prepares P-aminobenzene-sulfonamide, the difference with embodiment 1
It is：
In S2, between the first feeding stage and the second feeding stage and between the second feeding stage and third feeding stage
Without bleeding.
The yield of P-aminobenzene-sulfonamide is 92.46%, product purity 94.09%.
Embodiment 5
A kind of method that the antifebrin of energy-saving and emission-reduction prepares P-aminobenzene-sulfonamide, the difference with embodiment 1
It is：
In S2, the charging rate of thionyl chloride remains unchanged and without bleeding.
The yield of P-aminobenzene-sulfonamide is 91.28%, product purity 93.17%.
To sum up, the method that the antifebrin of the energy-saving and emission-reduction of the embodiment of the present invention prepares P-aminobenzene-sulfonamide, with three oxygen
It is that sulfonating agent carries out sulfonation in glacial acetic acid solvent to antifebrin to change sulphur, then carries out chlorination by chlorinating agent of thionyl chloride,
Both the quality of N-acetylsulfanilyl chloride had been can guarantee；Chlorosulfonic acid is not used during simultaneous reactions, by glacial acetic acid and extra
Thionyl chloride recycles, and consumption of raw materials is few to be avoided generating waste water and spent acid again.Hydrogen chloride tail gas is will produce in chlorination process, in reaction
Hydrogen chloride tail gas is passed through in receiving liquid and obtains acid recovery liquid, which is mixed with concentrated hydrochloric acid and is grasped applied to acidification hydrolization
Make, hydrogen chloride tail gas progress is adequately recycled into saving raw material, while avoiding exhaust emission again.It is prepared by this method
The P-aminobenzene-sulfonamide arrived, correspondingly has the advantages that environmental friendly, at low cost, purity is high.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.The reality of the present invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of the selected implementation of the present invention
Example.Based on the embodiments of the present invention, those of ordinary skill in the art are obtained without creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (10)
1. a kind of method that the antifebrin of energy-saving and emission-reduction prepares P-aminobenzene-sulfonamide, which is characterized in that including：In temperature
Under the conditions of 60-70 DEG C of agitating and heating, antifebrin and glacial acetic acid are mixed to get sulfonation stoste, led into the sulfonation stoste
Enter sulfur trioxide gas and carry out sulfonating reaction, the glacial acetic acid is recovered under reduced pressure and obtains sulfonated products；By the sulfonated products and two
The mixing of chlorine sulfoxide carries out chlorination reaction, and the remaining thionyl chloride is recovered under reduced pressure and obtains N-acetylsulfanilyl chloride, chlorination
Tail gas is passed through in receiving liquid in reaction and obtains acid recovery liquid；It is adopted after the N-acetylsulfanilyl chloride is carried out aminating reaction
It is hydrolyzed and is reacted with the mixed liquor of concentrated hydrochloric acid with the acid recovery liquid.
2. according to the method described in claim 1, it is characterized in that, the hybrid manipulation of the sulfonated products and the thionyl chloride
Including：The thionyl chloride is gradually instilled into the sulfonated products in chlorination reaction whole process.
3. according to the method described in claim 2, it is characterized in that, the hybrid manipulation of the sulfonated products and the thionyl chloride
Including：First feeding stage, the second feeding stage and third feeding stage, the charging rate of the first feeding stage, the second charging
The charging rate in stage and the charging rate of third feeding stage are sequentially reduced.
4. according to the method described in claim 3, it is characterized in that, the first feeding stage, the second feeding stage and third charging
The charging rate ratio in stage is followed successively by 3-4:1.5-2.5:1.
5. according to the method described in claim 4, it is characterized in that, the first feeding stage, the second feeding stage and third charging
The molar ratio that the thionyl chloride is added in stage is 3-4:3-4:1.
6. according to the method described in claim 3, it is characterized in that, between the first feeding stage and the second feeding stage and
Include the exhaust phase of 10-20min between two feeding stages and third feeding stage.
7. according to the method described in claim 1, it is characterized in that, being passed through the sulfur trioxide gas into the sulfonation stoste
Before, it is passed through pressure in dry air to reaction vessel into the sulfonation stoste and reaches 0.3-0.4Mpa.
8. the method according to the description of claim 7 is characterized in that being passed through the sulfur trioxide gas into the sulfonation stoste
Pressure stops after reaching 0.6-0.8Mpa from external aeration in the reaction vessel, then by the inside of reaction vessel sky
Gas is passed through the sulfonation stoste.
9. according to the method described in claim 8, it is characterized in that, per minute be passed through three oxidation into the sulfonation stoste
The volume ratio of the volume of sulphur gas and the sulfonation stoste is 0.8-1.2:1；
And/or the volume of the inner air per minute that the reaction vessel is passed through into the sulfonation stoste and the sulfonation are former
The volume ratio of liquid is 0.8-1.2:1.
10. P-aminobenzene-sulfonamide made from claim 1-9 any one of them methods.
Priority Applications (1)
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| CN116199603A (en) * | 2022-12-27 | 2023-06-02 | 沈阳化工研究院有限公司 | Method for synthesizing N, N-diethyl-4-aminobenzenesulfonic acid by adopting continuous flow |
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| CN116199603A (en) * | 2022-12-27 | 2023-06-02 | 沈阳化工研究院有限公司 | Method for synthesizing N, N-diethyl-4-aminobenzenesulfonic acid by adopting continuous flow |
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