CN108440343A - Antifebrin is the method and P-aminobenzene-sulfonamide of Material synthesis P-aminobenzene-sulfonamide - Google Patents
Antifebrin is the method and P-aminobenzene-sulfonamide of Material synthesis P-aminobenzene-sulfonamide Download PDFInfo
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- CN108440343A CN108440343A CN201810339138.2A CN201810339138A CN108440343A CN 108440343 A CN108440343 A CN 108440343A CN 201810339138 A CN201810339138 A CN 201810339138A CN 108440343 A CN108440343 A CN 108440343A
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- aminobenzene
- mixed liquor
- sulfonamide
- chlorosulfonic acid
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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
- C07C303/02—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
- C07C303/36—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
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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
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/30—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/37—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups having the sulfur atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring
- C07C311/38—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups having the sulfur atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring having sulfur atoms of sulfonamide groups and amino groups bound to carbon atoms of six-membered rings of the same carbon skeleton
- C07C311/39—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups having the sulfur atom of at least one of the sulfonamide groups bound to a carbon atom of a six-membered aromatic ring having sulfur atoms of sulfonamide groups and amino groups bound to carbon atoms of six-membered rings of the same carbon skeleton having the nitrogen atom of at least one of the sulfonamide groups bound to hydrogen atoms or to an acyclic carbon atom
Abstract
Antifebrin is the method and P-aminobenzene-sulfonamide of Material synthesis P-aminobenzene-sulfonamide, belongs to P-aminobenzene-sulfonamide synthesis field.Method contains chlorosulfonic acid and carbon tetrachloride with 1:1.0 1.2 volume ratios mix to obtain the first, second and third raw material.First raw material and molten state antifebrin contact sulfonation and product are obtained the first mixed liquor through being coated with the strainer of phosphorus pentoxide after being atomized respectively.Second raw material and the first mixed liquor contact sulfonation and product are obtained the second mixed liquor through being coated with the strainer of phosphorus pentoxide after being atomized respectively.Third raw material and the second mixed liquor contact sulfonation and product are obtained third mixed liquor through being coated with the strainer of phosphorus pentoxide after being atomized respectively.Third mixed liquor carries out chlorination, amination and hydrolysis successively.Chlorosulfonic acid dosage is few, antifebrin reaction is abundant, and production cost is low, spent acid is greatly reduced, waste water load is small, product yield is high.Product is made according to aforementioned production method.Purity is high, production is environmentally friendly, at low cost.
Description
Technical field
The present invention relates to P-aminobenzene-sulfonamide synthesize field, and more particularly to a kind of antifebrin be Material synthesis to ammonia
The method and P-aminobenzene-sulfonamide of base benzsulfamide.
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, but existing skill
Art, since chlorosulphonation step must be balanced reaction, must just be participated in synthesis to improve yield with large excess of chlorosulfonic acid
Reaction, will produce a large amount of sulfuric acid wastewater containings.Simultaneously because the concentration of the sulfuric acid wastewater containing generated is relatively low, it is difficult to recycle, cause to equipment
There is also serious corrosion.
In view of this, special propose the present invention.
Invention content
The purpose of the present invention is to provide a kind of methods that antifebrin is Material synthesis P-aminobenzene-sulfonamide, have chlorine
The advantages that sulfonic acid dosage is few, antifebrin reaction is abundant, production cost is low, spent acid is greatly reduced, waste water load is small, product yield
It is high.
Another object of the present invention is to provide a kind of P-aminobenzene-sulfonamide, purity is high, at low cost.
The present invention solves its technical problem using following technical scheme to realize.
The present invention proposes that a kind of antifebrin is the method for Material synthesis P-aminobenzene-sulfonamide, including：By chlorosulfonic acid with
Carbon tetrachloride is with 1:The volume ratio of 1.0-1.2 mixes to obtain the first raw material, the second raw material and third raw material；By the first raw material and melting
After the antifebrin of state is atomized respectively contact sulfonation and by product by least one layer of strainer for being coated with phosphorus pentoxide, obtain the
One mixed liquor；Sulfonation is contacted after second raw material and the first mixed liquor are atomized respectively and product is coated with five by least one layer of
The strainer for aoxidizing two phosphorus obtains the second mixed liquor；Sulfonation is contacted after third raw material and the second mixed liquor are atomized respectively and by product
By at least one layer of strainer for being coated with phosphorus pentoxide, third mixed liquor is obtained；Make third mixed liquor carry out successively chlorination reaction,
Aminating reaction and hydrolysis.
The total amount of chlorosulfonic acid and the molar ratio of antifebrin are 1.85- in first raw material, the second raw material and third raw material
2.85:1。
The present invention proposes a kind of P-aminobenzene-sulfonamide, is made according to the method for above-mentioned synthesis P-aminobenzene-sulfonamide.
The advantageous effect of the embodiment of the present invention is：
Antifebrin provided by the invention is the method for Material synthesis P-aminobenzene-sulfonamide, and inventor has found due to chlorine sulphur
The viscosity of acid is larger, insufficient contact with the antifebrin hybrid reaction system of solid state, leads to reaction time length, reaction
It is not thorough.It is mixed with chlorosulfonic acid using carbon tetrachloride, and carries out contact after raw material is atomized respectively and carry out sulfonating reaction, reactant
The contact of system is abundant, reaction speed is fast, product yield is high, chlorosulfonic acid dosage significantly reduces.By chlorosulfonic acid raw material several times with
Antifebrin reacts, and it is more abundant to be conducive to reaction.It contacts the product after sulfonation and is coated with phosphorus pentoxide by least one layer
Strainer absorbs the water of the generation in product, chlorosulfonic acid is avoided to hydrolyze, and the positive of reaction is promoted to carry out, and reduces chlorosulfonic acid and uses
Amount reduces sulfuric acid wastewater containing yield；The phosphoric acid primary attachment of generation avoids being mixed into product largely containing phospha in screen surface
Matter, the purity higher of product.
P-aminobenzene-sulfonamide provided by the invention is made according to the method for above-mentioned synthesis P-aminobenzene-sulfonamide, because
And correspondingly has the advantages that purity is high, production is environmentally friendly, at low cost.
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.
It is below the method and p-aminophenyl of Material synthesis P-aminobenzene-sulfonamide to the antifebrin of the embodiment of the present invention
Sulfonamide is specifically described.
The present invention proposes that a kind of antifebrin is the method for Material synthesis P-aminobenzene-sulfonamide, including：
By chlorosulfonic acid and carbon tetrachloride with 1:The volume ratio of 1.0-1.2 mixes to obtain the first raw material, the second raw material and third original
Material.It refers to that the chlorosulfonic acid for being used to react is divided into three parts and is mixed with carbon tetrachloride, first raw material, the second raw material and the
Three raw materials are by chlorosulfonic acid and carbon tetrachloride with 1:What the volume ratio of 1.0-1.2 was mixed to get.
Sulfonation is contacted after first raw material and the antifebrin of molten state are atomized respectively and applies product by least one layer of
It is covered with the strainer of phosphorus pentoxide, obtains the first mixed liquor.Sulfonation is contacted after second raw material and the first mixed liquor are atomized respectively simultaneously
By product by least one layer of strainer for being coated with phosphorus pentoxide, the second mixed liquor is obtained.By third raw material and the second mixed liquor
Sulfonation is contacted after being atomized respectively and by product by least one layer of strainer for being coated with phosphorus pentoxide, obtain third mixed liquor.
Inventor has found since the viscosity of chlorosulfonic acid is larger, with the contact of the antifebrin hybrid reaction system of solid state
It is insufficient, cause reaction time length, reaction to be not thorough.It is mixed with chlorosulfonic acid using carbon tetrachloride, and after raw material is atomized respectively
It carries out contact and carries out sulfonating reaction, the contact of reaction system is abundant, reaction speed is fast, product yield is high, chlorosulfonic acid dosage is aobvious
Writing reduces.
Chlorosulfonic acid is subjected to sulfonating reaction with antifebrin raw material several times, avoids chlorosulfonic acid excessive and decomposes, make chlorine sulphur
Acid fully can have antifebrin to be reacted.
The product after sulfonation is contacted by least one layer of strainer for being coated with phosphorus pentoxide, absorbs the generation in product
Water promotes the positive of reaction to carry out, chlorosulfonic acid is avoided to hydrolyze, reduce chlorosulfonic acid dosage, reduces sulfuric acid wastewater containing yield；It generates
Phosphoric acid primary attachment in screen surface, avoid being mixed into product and largely contain phosphorus impurities, the purity higher of product.
In some of the invention preferred embodiments, it should include skeleton coated with strainer of phosphorus pentoxide and be coated on bone
Phosphorus pentoxide adsorption layer outside frame.
The muscles and bones and several muscles and bones being longitudinally arranged side by side that skeleton is arranged laterally side by side by several surround, two neighboring
The muscles and bones and the two neighboring muscles and bones being longitudinally arranged side by side being arranged laterally side by side surround filter opening.
One side surface of the feed liquor of each muscles and bones is arranged side by side in an axial direction multiple protrusions, and the side of the feed liquor refers to elder generation
With the side of the product contact after contact sulfonation.
Each protrusion is further preferably provided as the structure with the multiple struts being arranged radially.Specifically,
The same place for being connected to muscles and bones is converged in the end of the close muscles and bones of multiple struts of same protrusion, the same protrusion it is more
The end of the separate muscles and bones of a strut is radial to extend outwardly.The multiple struts being arranged radially can be coplanar with to enclose
At rough circle, each strut extends along the busbar of circle；Can also be that non-co-planar setting surrounds rough conical structure, each
Strut is extended along circle element of a cone.
Make the phosphorus pentoxide adsorption layer on skeleton surface that there is three-dimensional structure, has with the product after contact sulfonation larger
Contact area, soaking effect is more preferably.
According to above-mentioned method, in some specific embodiments of the invention, the total amount of chlorosulfonic acid and antifebrin
Molar ratio is 1.85-2.85:1, such as can be 1.85 in some optional embodiments:1、2:1、2.25:1、2.5:1、2.85:
1 etc..It makes chlorosulfonic acid and antifebrin have higher utilization rate.
In some preferred embodiments of the invention, mole of chlorosulfonic acid in the first raw material, the second raw material and third raw material
Than being followed successively by 1.5-2:2.5-3:1.Further it is preferably 2:3:1.
Inventor through it is long-term the study found that in the addition three times of chlorosulfonic acid dosage control carried out according to above-mentioned requirements, first
The chlorosulfonic acid that about one third is added directly carries out initial reaction with antifebrin, adds the chlorosulfonic acid and second of about half
Anilide fully reacts, and is eventually adding a small amount of chlorosulfonic acid and promotes reaction thorough, and the speed of forward reaction is fast, degree is high, more has
Conducive to the abundant reaction of chlorosulfonic acid and antifebrin.
Meanwhile through inventor the study found that carrying out the first raw material, the second raw material and the according to the ratio of above-mentioned chlorosulfonic acid
The preparation of three raw materials, with keep three times the addition of chlorosulfonic acid it is identical and in the case that other conditions are completely the same, add every time
The output increased 8-15% of the method sulfonated products of different amounts of chlorosulfonic acid.
Preferably, the volume ratio of chlorosulfonic acid and carbon tetrachloride is 1 in the first raw material:1.1-1.2 chlorosulfonic acid in the second raw material
Volume ratio with carbon tetrachloride is 1:0.95-1.05, the volume ratio of chlorosulfonic acid and carbon tetrachloride is 1 in third raw material:0.8-
0.9。
It is highly preferred that the volume ratio of chlorosulfonic acid and carbon tetrachloride is 1 in the first raw material:1.2, in the second raw material chlorosulfonic acid with
The volume ratio of carbon tetrachloride is 1:1, the volume ratio of chlorosulfonic acid and carbon tetrachloride is 1 in third raw material:0.8.
Due to the antifebrin extent of reaction of the raw material reacted with the first raw material, the second raw material and third raw material, acetophenone
Amine concentration has a greater change at the tools such as being grouped as, and adjusts to inventor's reasonability the first raw material, the second raw material and third raw material
The volume ratio of middle chlorosulfonic acid and carbon tetrachloride makes it have better reactivity.
Meanwhile through inventor the study found that according to the volume ratio of above-mentioned chlorosulfonic acid and carbon tetrachloride prepare the first raw material,
Second raw material and third raw material, and keep the situation that the volume ratio of chlorosulfonic acid and carbon tetrachloride is constant and other conditions are completely the same
Under, the output increased 10-20% of sulfonated products in the case of different volumes ratio.
Further, the reaction temperature of contact sulfonation is 55-60 DEG C every time, reaction time 10-30min.Specifically, it obtains
To the first mixed liquor contact sulfonation reaction time be 15-25min, preferably 18-22min, as 18min, 19min,
20min, 21min, 22min etc.；The reaction time for obtaining the contact sulfonation of the second mixed liquor is 25-30min, preferably 28-
30min, such as 28min, 29min, 30min；The reaction time for obtaining the contact sulfonation of third mixed liquor is 10-15min, preferably
Ground is 10-12min, such as 10min, 11min, 12min.
First raw material is directly reacted with antifebrin, and antifebrin is in apparent excessive situation, chlorosulfonic acid and second
Anilide has faster reaction speed and the larger extent of reaction, can suitably shorten the reaction time.Second raw material and first mixes
When closing liquid mixing, containing remaining antifebrin, remaining chlorosulfonic acid, sulfonated products etc. in the first mixed liquor, and chlorosulfonic acid addition compared with
Greatly, the proper extension reaction time reacts fully.Third raw material is mixed for reacting a small amount of remaining acetyl with the second mixed liquor
Aniline, in time filtering water removal avoid the decomposition of chlorosulfonic acid.
After the completion of sulfonating reaction, third mixed liquor is made to carry out chlorination reaction, aminating reaction and hydrolysis successively.
Aminating reaction and hydrolysis are with reference to the conventional practices in P-aminobenzene-sulfonamide synthesis.
In aminating process, the ammonium hydroxide that mass concentration is about 20% is added and reacts 3h under conditions of 50 DEG C, reacts fully
And remove extra ammonia, make yield close to maximum value and impurity content it is low.
In hydrolytic process, concentrated hydrochloric acid small fire is added and is heated to reflux, the hydrogen that mass concentration is about 40% is added after the completion of reaction
Sodium hydroxide solution adjusts pH to 6.2-7, crystallisation by cooling.
In preferred embodiments of the present invention, the chlorination reaction of third mixed liquor and the mixing containing thionyl chloride and phosphorus pentachloride
Object carries out.
Thionyl chloride and phosphorus pentachloride substitute most chlorosulfonic acid attack sulfonic group and carry out chlorination, reduce chlorosulfonic acid
Dosage reduces spent acid amount and reduces subsequent processing expense.The S-O attacks of Cl- p-sulfonic acids base in thionyl chloride and phosphorus pentachloride
Effect is more advantageous to the progress for making chlorination reaction more than the attacking role of chlorosulfonic acid.
Inventor it has been investigated that, thionyl chloride and phosphorus pentachloride are mixed and participate in chlorination reaction, and individually uses dichloro
Sulfoxide is individually compared using phosphorus pentachloride, and other reaction conditions identical in the integral molar quantity containing chlorine are identical, adopt
11-14% is improved with the conversion ratio of chlorination under conditions of the mixture of thionyl chloride and phosphorus pentachloride.
In some preferred embodiments of the invention, the reaction temperature of chlorination reaction is 60-65 DEG C, reaction time 100-
120min。
Further, the molar ratio of mixture and antifebrin is 1.5-1.8:1, further preferably 1.8:1.Mixing
The molar ratio of thionyl chloride and phosphorus pentachloride is 2-3 in object:1-2, further preferably 2.5:1.5.
The present invention also proposes a kind of P-aminobenzene-sulfonamide, according to the method system of above-mentioned synthesis P-aminobenzene-sulfonamide
, thus correspondingly have the advantages that purity is high, production is environmentally friendly, at low cost.
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of antifebrin is the method for Material synthesis P-aminobenzene-sulfonamide, including：
Preparing the strainer coated with phosphorus pentoxide, the muscles and bones that should be coated with the strainer of phosphorus pentoxide is equipped with protrusion,
Each protrusion includes the multiple struts being arranged radially.
According to chlorosulfonic acid：Antifebrin：Thionyl chloride：The molar ratio of phosphorus pentachloride is 2.50:1：1:0.6 is on the waiting list raw material.
By chlorosulfonic acid according to molar ratio be 2:3:1 point for three parts and marked as 1,2,3.By chlorosulfonic acid and the carbon tetrachloride marked as 1 with
1:1.2 volume ratio mixes to obtain the first raw material.By the chlorosulfonic acid marked as 2 with carbon tetrachloride with 1:1 volume ratio mix
Two raw materials.By the chlorosulfonic acid marked as 3 with carbon tetrachloride with 1:0.8 volume ratio mixes to obtain third raw material.
Will warm up molten state antifebrin be atomized respectively with the first raw material after contact, controlling reaction temperature 55-60
DEG C, the reaction time be 20min carry out sulfonating reaction.The strainer that product is had to phosphorus pentoxide by three-layer coating, it is mixed to obtain first
Close liquid.
It is contacted after first mixed liquor is atomized respectively with the second raw material, controlling reaction temperature is 55-60 DEG C, the reaction time is
30min carries out sulfonating reaction.The strainer that product is had to phosphorus pentoxide by three-layer coating, obtains the second mixed liquor.
It is contacted after second mixed liquor is atomized respectively with third raw material, controlling reaction temperature is 55-60 DEG C, the reaction time is
10min carries out sulfonating reaction.The strainer that product is had to phosphorus pentoxide by three-layer coating, obtains third mixed liquor.
Third mixed liquor is mixed with thionyl chloride and phosphorus pentachloride, controlling reaction temperature is 60-65 DEG C, the reaction time is
110min carries out chlorination reaction.
The ammonium hydroxide that mass concentration is about 20% is added into chlorosulfonation product and reacts 3h under conditions of 50 DEG C, completes amination
Reaction.Concentrated hydrochloric acid is added into aminate and is heated to reflux 0.5h, completes hydrolysis.Mass concentration is added into hydrolysate
About 40% sodium hydroxide solution adjusts pH to 6.2-7, crystallisation by cooling.
The product yield of P-aminobenzene-sulfonamide is 88.35%, purity 98.16%.
Embodiment 2
A kind of antifebrin is the method for Material synthesis P-aminobenzene-sulfonamide, including：
According to chlorosulfonic acid：Antifebrin：Thionyl chloride：The molar ratio of phosphorus pentachloride is 2.50:1：1:0.6 is on the waiting list raw material.
By chlorosulfonic acid according to molar ratio be 2:3:1 point for three parts and marked as 1,2,3.By chlorosulfonic acid and the carbon tetrachloride marked as 1 with
1:1.2 volume ratio mixes to obtain the first raw material.By the chlorosulfonic acid marked as 2 with carbon tetrachloride with 1:1 volume ratio mix
Two raw materials.By the chlorosulfonic acid marked as 3 with carbon tetrachloride with 1:0.8 volume ratio mixes to obtain third raw material.
Will warm up molten state antifebrin be atomized respectively with the first raw material after contact, controlling reaction temperature 55-60
DEG C, the reaction time be 20min carry out sulfonating reaction.The strainer that product is had to phosphorus pentoxide by three-layer coating, it is mixed to obtain first
Close liquid.
It is contacted after first mixed liquor is atomized respectively with the second raw material, controlling reaction temperature is 55-60 DEG C, the reaction time is
30min carries out sulfonating reaction.The strainer that product is had to phosphorus pentoxide by three-layer coating, obtains the second mixed liquor.
It is contacted after second mixed liquor is atomized respectively with third raw material, controlling reaction temperature is 55-60 DEG C, the reaction time is
10min carries out sulfonating reaction.The strainer that product is had to phosphorus pentoxide by three-layer coating, obtains third mixed liquor.
Third mixed liquor is mixed with thionyl chloride and phosphorus pentachloride, controlling reaction temperature is 60-65 DEG C, the reaction time is
110min carries out chlorination reaction.
Aminating reaction, hydrolysis, neutralization and crystallization are carried out successively to chlorosulfonation product according to the method in embodiment 1.
The product yield of P-aminobenzene-sulfonamide is 86.68%, purity 97.79%.
Embodiment 3
A kind of antifebrin is the method for Material synthesis P-aminobenzene-sulfonamide, including：
According to chlorosulfonic acid：Antifebrin：Thionyl chloride：The molar ratio of phosphorus pentachloride is 1.85:1：0.8:0.8 is on the waiting list original
Material.By chlorosulfonic acid according to molar ratio be 1.5:3:1 point for three parts and marked as 1,2,3.By marked as 1 chlorosulfonic acid and four chlorinations
Carbon is with 1:1.1 volume ratio mixes to obtain the first raw material.By the chlorosulfonic acid marked as 2 with carbon tetrachloride with 1:1.05 volume ratio is mixed
Close to obtain the second raw material.By the chlorosulfonic acid marked as 3 with carbon tetrachloride with 1:0.8 volume ratio mixes to obtain third raw material.
Will warm up molten state antifebrin be atomized respectively with the first raw material after contact, controlling reaction temperature 55-60
DEG C, the reaction time be 22min carry out sulfonating reaction.The strainer that product is had to phosphorus pentoxide by three-layer coating, it is mixed to obtain first
Close liquid.
It is contacted after first mixed liquor is atomized respectively with the second raw material, controlling reaction temperature is 55-60 DEG C, the reaction time is
28min carries out sulfonating reaction.The strainer that product is had to phosphorus pentoxide by three-layer coating, obtains the second mixed liquor.
It is contacted after second mixed liquor is atomized respectively with third raw material, controlling reaction temperature is 55-60 DEG C, the reaction time is
10min carries out sulfonating reaction.The strainer that product is had to phosphorus pentoxide by three-layer coating, obtains third mixed liquor.
Third mixed liquor is mixed with thionyl chloride and phosphorus pentachloride, controlling reaction temperature is 60-65 DEG C, the reaction time is
110min carries out chlorination reaction.
Aminating reaction, hydrolysis, neutralization and crystallization are carried out successively to chlorosulfonation product according to the method in embodiment 1.
The product yield of P-aminobenzene-sulfonamide is 85.94%, purity 96.94%.
Embodiment 4
A kind of antifebrin is the method for Material synthesis P-aminobenzene-sulfonamide, including：
According to chlorosulfonic acid：Antifebrin：Thionyl chloride：The molar ratio of phosphorus pentachloride is 1.85:1：1.2:0.6 is on the waiting list original
Material.By chlorosulfonic acid according to molar ratio be 2:2.5:1 point for three parts and marked as 1,2,3.By marked as 1 chlorosulfonic acid and four chlorinations
Carbon is with 1:1.1 volume ratio mixes to obtain the first raw material.By the chlorosulfonic acid marked as 2 with carbon tetrachloride with 1:0.95 volume ratio is mixed
Close to obtain the second raw material.By the chlorosulfonic acid marked as 3 with carbon tetrachloride with 1:0.9 volume ratio mixes to obtain third raw material.
Will warm up molten state antifebrin be atomized respectively with the first raw material after contact, controlling reaction temperature 55-60
DEG C, the reaction time be 18min carry out sulfonating reaction.The strainer that product is had to phosphorus pentoxide by three-layer coating, it is mixed to obtain first
Close liquid.
It is contacted after first mixed liquor is atomized respectively with the second raw material, controlling reaction temperature is 55-60 DEG C, the reaction time is
30min carries out sulfonating reaction.The strainer that product is had to phosphorus pentoxide by three-layer coating, obtains the second mixed liquor.
It is contacted after second mixed liquor is atomized respectively with third raw material, controlling reaction temperature is 55-60 DEG C, the reaction time is
12min carries out sulfonating reaction.The strainer that product is had to phosphorus pentoxide by three-layer coating, obtains third mixed liquor.
Third mixed liquor is mixed with thionyl chloride and phosphorus pentachloride, controlling reaction temperature is 60-65 DEG C, the reaction time is
120min carries out chlorination reaction.
Aminating reaction, hydrolysis, neutralization and crystallization are carried out successively to chlorosulfonation product according to the method in embodiment 1.
The product yield of P-aminobenzene-sulfonamide is 86.47%, purity 97.41%.
Embodiment 5
A kind of antifebrin is the method for Material synthesis P-aminobenzene-sulfonamide, including：
According to chlorosulfonic acid：Antifebrin：Thionyl chloride：The molar ratio of phosphorus pentachloride is 2.85:1：1.2:0.4 is on the waiting list original
Material.By chlorosulfonic acid according to molar ratio be 1.8:3:1 point for three parts and marked as 1,2,3.By marked as 1 chlorosulfonic acid and four chlorinations
Carbon is with 1:1.2 volume ratio mixes to obtain the first raw material.By the chlorosulfonic acid marked as 2 with carbon tetrachloride with 1:0.95 volume ratio is mixed
Close to obtain the second raw material.By the chlorosulfonic acid marked as 3 with carbon tetrachloride with 1:0.8 volume ratio mixes to obtain third raw material.
Will warm up molten state antifebrin be atomized respectively with the first raw material after contact, controlling reaction temperature 55-60
DEG C, the reaction time be 20min carry out sulfonating reaction.The strainer that product is had to phosphorus pentoxide by three-layer coating, it is mixed to obtain first
Close liquid.
It is contacted after first mixed liquor is atomized respectively with the second raw material, controlling reaction temperature is 55-60 DEG C, the reaction time is
30min carries out sulfonating reaction.The strainer that product is had to phosphorus pentoxide by three-layer coating, obtains the second mixed liquor.
It is contacted after second mixed liquor is atomized respectively with third raw material, controlling reaction temperature is 55-60 DEG C, the reaction time is
10min carries out sulfonating reaction.The strainer that product is had to phosphorus pentoxide by three-layer coating, obtains third mixed liquor.
Third mixed liquor is mixed with thionyl chloride and phosphorus pentachloride, controlling reaction temperature is 60-65 DEG C, the reaction time is
110min carries out chlorination reaction.
Aminating reaction, hydrolysis, neutralization and crystallization are carried out successively to chlorosulfonation product according to the method in embodiment 1.
The product yield of P-aminobenzene-sulfonamide is 85.73%, purity 96.84%.
Embodiment 6
A kind of antifebrin is the method for Material synthesis P-aminobenzene-sulfonamide, including：
According to chlorosulfonic acid：Antifebrin：Thionyl chloride：The molar ratio of phosphorus pentachloride is 2.85:1：0.9:0.6 is on the waiting list original
Material.By chlorosulfonic acid according to molar ratio be 2:2.8:1 point for three parts and marked as 1,2,3.By marked as 1 chlorosulfonic acid and four chlorinations
Carbon is with 1:1.1 volume ratio mixes to obtain the first raw material.By the chlorosulfonic acid marked as 2 with carbon tetrachloride with 1:0.95 volume ratio is mixed
Close to obtain the second raw material.By the chlorosulfonic acid marked as 3 with carbon tetrachloride with 1:0.9 volume ratio mixes to obtain third raw material.
Will warm up molten state antifebrin be atomized respectively with the first raw material after contact, controlling reaction temperature 55-60
DEG C, the reaction time be 20min carry out sulfonating reaction.The strainer that product is had to phosphorus pentoxide by three-layer coating, it is mixed to obtain first
Close liquid.
It is contacted after first mixed liquor is atomized respectively with the second raw material, controlling reaction temperature is 55-60 DEG C, the reaction time is
30min carries out sulfonating reaction.The strainer that product is had to phosphorus pentoxide by three-layer coating, obtains the second mixed liquor.
It is contacted after second mixed liquor is atomized respectively with third raw material, controlling reaction temperature is 55-60 DEG C, the reaction time is
10min carries out sulfonating reaction.The strainer that product is had to phosphorus pentoxide by three-layer coating, obtains third mixed liquor.
Third mixed liquor is mixed with thionyl chloride and phosphorus pentachloride, controlling reaction temperature is 60-65 DEG C, the reaction time is
100min carries out chlorination reaction.
Aminating reaction, hydrolysis, neutralization and crystallization are carried out successively to chlorosulfonation product according to the method in embodiment 1.
The product yield of P-aminobenzene-sulfonamide is 85.94%, purity 95.68%.
Comparative example 1
A kind of antifebrin is the method for Material synthesis P-aminobenzene-sulfonamide, it is different from the method for embodiment 2 it
Be in：By the first raw material, the second raw material and third raw material merge after and be heated to molten state antifebrin be atomized respectively after
Contact, controlling reaction temperature is 55-60 DEG C, the reaction time is that 60min carries out sulfonating reaction.
The product yield of P-aminobenzene-sulfonamide is 75.82%, purity 90.23%.
Comparative example 2
A kind of antifebrin is the method for Material synthesis P-aminobenzene-sulfonamide, it is different from the method for comparative example 1 it
Be in：Thionyl chloride and phosphorus pentachloride is replaced to carry out chlorination reaction using chlorosulfonic acid, the chlorine of the chlorosulfonic acid for chlorination reaction
Moles total number it is generally identical as the moles total number of thionyl chloride, the chlorine of phosphorus pentachloride.
The product yield of P-aminobenzene-sulfonamide is 72.13%, purity 92.33%.
Comparative example 3
A kind of antifebrin is the method for Material synthesis P-aminobenzene-sulfonamide, it is different from the method for comparative example 1 it
Be in：It is not handled using the strainer coated with phosphorus pentoxide.
The product yield of P-aminobenzene-sulfonamide is 70.16%, purity 86.59%.
According to embodiment 1-6 and comparative example 1-2 it is found that antifebrin provided by the invention is Material synthesis p-aminophenyl sulphur
The method of amide, the dosage of chlorosulfonic acid is small, spent acid production quantity is small, product yield is high.
In conclusion antifebrin provided by the invention is the method for Material synthesis P-aminobenzene-sulfonamide, has chlorine sulphur
The advantages that sour dosage is few, antifebrin reaction is abundant, production cost is low, spent acid is greatly reduced, waste water load is small, product yield
It is high.
P-aminobenzene-sulfonamide provided by the invention is made according to the method for above-mentioned synthesis P-aminobenzene-sulfonamide, because
And correspondingly has the advantages that purity is high, production is environmentally friendly, at low cost.
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 antifebrin is the method for Material synthesis P-aminobenzene-sulfonamide, which is characterized in that it includes：By chlorosulfonic acid with
Carbon tetrachloride is with 1:The volume ratio of 1.0-1.2 mixes to obtain the first raw material, the second raw material and third raw material；By first raw material and
The antifebrin of molten state contacts sulfonation and product is coated with to the strainer of phosphorus pentoxide by least one layer after being atomized respectively,
Obtain the first mixed liquor；Sulfonation is contacted after second raw material and first mixed liquor are atomized respectively and by product by least
One layer of strainer for being coated with phosphorus pentoxide, obtains the second mixed liquor；The third raw material and second mixed liquor are distinguished into mist
Sulfonation is contacted after change and by product by least one layer of strainer for being coated with phosphorus pentoxide, obtain third mixed liquor；Make described
Three mixed liquors carry out chlorination reaction, aminating reaction and hydrolysis successively；
The total amount of chlorosulfonic acid described in first raw material, second raw material and the third raw material and the antifebrin
Molar ratio is 1.85-2.85:1.
2. the method for synthesis P-aminobenzene-sulfonamide according to claim 1, which is characterized in that described to be coated with five oxidations
The strainer of two phosphorus includes skeleton and coated on the phosphorus pentoxide adsorption layer outside the skeleton, and the skeleton includes several muscles and bones,
One side surface of the feed liquor of each muscles and bones is arranged side by side in an axial direction multiple protrusions.
3. the method for synthesis P-aminobenzene-sulfonamide according to claim 2, which is characterized in that each protrusion packet
Include the multiple struts being arranged radially.
4. the method for synthesizing P-aminobenzene-sulfonamide according to claim 1-3 any one of them, which is characterized in that described first
The molar ratio of chlorosulfonic acid described in raw material, second raw material and the third raw material is followed successively by 1.5-2:2.5-3:1.
5. the method for synthesis P-aminobenzene-sulfonamide according to claim 4, which is characterized in that institute in first raw material
The volume ratio for stating chlorosulfonic acid and the carbon tetrachloride is 1:1.1-1.2, chlorosulfonic acid described in second raw material and the tetrachloro
The volume ratio for changing carbon is 1:The volume ratio of 0.95-1.05, chlorosulfonic acid described in the third raw material and the carbon tetrachloride is 1:
0.8-0.9。
6. the method for synthesis P-aminobenzene-sulfonamide according to claim 4, which is characterized in that contact sulfonation is anti-every time
It is 55-60 DEG C to answer temperature, and the reaction time for obtaining the contact sulfonation of first mixed liquor is 15-25min, obtains described second
The reaction time of the contact sulfonation of mixed liquor is 25-30min, and the reaction time for obtaining the contact sulfonation of the third mixed liquor is
10-15min。
7. the method for synthesizing P-aminobenzene-sulfonamide according to claim 1-3 any one of them, which is characterized in that the third
The chlorination reaction of mixed liquor is carried out with containing the mixture of thionyl chloride and phosphorus pentachloride.
8. it is according to claim 7 synthesis P-aminobenzene-sulfonamide method, which is characterized in that the mixture with it is described
The molar ratio of antifebrin is 1.5-1.8:1.
9. the method for synthesis P-aminobenzene-sulfonamide according to claim 7, which is characterized in that described in the mixture
The molar ratio of thionyl chloride and the phosphorus pentachloride is 2-3:1-2.
10. synthesizing sulfanilyl made from the method for P-aminobenzene-sulfonamide according to claim 1-9 any one of them
Amine.
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| CN109879771A (en) * | 2019-04-10 | 2019-06-14 | 新乡市锦源化工有限公司 | A method of using antifebrin as Material synthesis P-aminobenzene-sulfonamide |
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| CN101613308A (en) * | 2009-07-24 | 2009-12-30 | 重庆大学 | The method of synthesizing right-acetylsulphanilyl chloride with phosphorus pentachloride |
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