CN106631925B - It is a kind of to sulfoamido hydrazinobenzene hydrochloride salt and its preparation process - Google Patents
It is a kind of to sulfoamido hydrazinobenzene hydrochloride salt and its preparation process Download PDFInfo
- Publication number
- CN106631925B CN106631925B CN201611204209.5A CN201611204209A CN106631925B CN 106631925 B CN106631925 B CN 106631925B CN 201611204209 A CN201611204209 A CN 201611204209A CN 106631925 B CN106631925 B CN 106631925B
- Authority
- CN
- China
- Prior art keywords
- parts
- hydrochloric acid
- hydrochloride salt
- weight
- hydrazinobenzene hydrochloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of to sulfoamido hydrazinobenzene hydrochloride salt and its preparation process, prepare the raw material to sulfoamido hydrazinobenzene hydrochloride salt and be made of 80 100 parts of P-aminobenzene-sulfonamide, 150 220 parts of hydrochloric acid, 70 90 parts of sodium nitrites, 60 80 parts of caustic soda, 80 100 parts of sodium sulfites, 15 portions of phase transfer catalysts and 0.1 0.5 parts of strong acid catalysts；The strong acid catalyst is made of according to mass fraction 60 70 parts of serpentines, 120 130 parts of ammonium hydroxide, 40 50 parts of sulfuric acid and 10 20 parts of polyacrylamides；It is of the present invention to sulfoamido hydrazinobenzene hydrochloride salt and its preparation process, the yield of diazo reaction is increased by adding in strong acid catalyst, quality of finished product good, purity is high, alleviates the pressure of liquid waste processing, saves entreprise cost.
Description
Technical field
The present invention relates to organic synthesis technical fields more particularly to a kind of to sulfoamido hydrazinobenzene hydrochloride salt and its preparation
Technique.
Background technology
It is the important intermediate for synthesizing non-steroidal anti-inflammatory drugs celecoxib to sulfoamido hydrazinobenzene hydrochloride salt, celecoxib is
A kind of novel Selective COX-2 inhibitor prevents the synthesis two of prostanoid drug from reaching by the inhibition COX-2 of selectivity
To effect that is anti-inflammatory, easing pain and bring down a fever, it is now widely used in the treatment of the diseases such as rheumatoid arthritis, rheumatic arthritis.Often
In the preparation process to sulfoamido hydrazinobenzene hydrochloride salt of rule, diazo-reaction is incomplete, easily generates to sulfoamido phenylhydrazine
The isomers of hydrochloride, but when it prepare drug as raw material, is higher to its quality requirement, impurity must not exceed 0.2%,
Therefore the efficiency of the diazo-reaction of sulfoamido hydrazinobenzene hydrochloride salt can just obtain more pure product there is an urgent need for improving.
Invention content
To solve the above-mentioned problems, the purpose of the present invention is to propose to it is a kind of to sulfoamido hydrazinobenzene hydrochloride salt and its prepare work
Skill increases the yield of diazo reaction by adding in strong acid catalyst, and quality of finished product good, purity is high, alleviates liquid waste processing
Pressure saves entreprise cost.
The technical solution taken to solve the above-mentioned problems of the present invention is：It is a kind of to sulfoamido hydrazinobenzene hydrochloride salt, press
According to weight ratio, the raw material to sulfoamido hydrazinobenzene hydrochloride salt is prepared by 80-100 parts of P-aminobenzene-sulfonamide, 150-220 portions of salt
Acid, 70-90 parts of sodium nitrites, 60-80 parts of caustic soda, 80-100 parts of sodium sulfites, 1-5 portions of phase transfer catalysts and 0.1-0.5 parts
Strong acid catalyst forms；The strong acid catalyst is according to mass fraction by 60-70 parts of serpentines, 120-130 parts of ammonium hydroxide, 40-
50 parts of sulfuric acid and 10-20 parts of polyacrylamide compositions, the strong acid catalyst are first prepared before use, and concrete operations are：It is first
Each raw material of aforementioned proportion is first weighed, by 150-200 DEG C of calcining 1-2h of serpentine and powder I is ground to obtain, then to powder I
Middle addition ammonium hydroxide and polyacrylamide stand 3-5h after stirring and evenly mixing, and precipitation are precipitated, then precipitation filtration washing is dry and finely ground
Powder II is obtained, powder II is impregnated into 5-7h in sulfuric acid later, refilters and dries to obtain residue, finally by residue at 380-450 DEG C
It is lower baking 12-14h and crush can be prepared by the strong acid catalyst；
The hydrochloric acid is the concentrated hydrochloric acid of mass fraction 36%；
The phase transfer catalyst is polyethylene glycol, dialkylethers, tertiary amine, one kind in tri-n-butylamine or several
The mixture of kind arbitrary proportion；
A kind of preparation process to sulfoamido hydrazinobenzene hydrochloride salt weighs each raw material first, in accordance with the ratio of claim 1,
Then P-aminobenzene-sulfonamide, hydrochloric acid, sodium nitrite is taken to carry out diazo-reaction, sodium sulfite is added and carries out reduction reaction,
Precipitation crystal is acidified with hydrochloric acid after reaction and filtration drying can be prepared by product, first by the hydrochloric acid by weight 4:2:1
It is divided into tri- parts of a, b, c, when diazo reaction takes the hydrochloric acid of a parts by weight and the water of 3 times of its weight is added in into hydrochloric acid, then adds in pair
Aminobenzene sulfonamide adjusts the temperature to 0-5 DEG C, and the sodium nitrite solution for adding 30% stirs evenly simultaneously insulation reaction 30-
50min obtains diazonium salt solution；
In the reduction reaction, first add in the water dissolution of 4 times of sodium sulfite and its weight and ice bath be cooled to 0-3 DEG C,
Then add in diazonium salt solution and formed and reduction reaction system and adjust pH to 6-7, then adjust the temperature of the reduction reaction system to
85-90 DEG C and keep this temperature 1-2h carry out reduction reaction；
The hydrochloric acid for adding in b parts by weight in the hydrochloric acid acidization first into reduction reaction system forms acidification reaction
System adjusts the temperature of the acidification reaction system to 85-90 DEG C and this temperature 1-2h is kept to be acidified, then add in c thereto
Crystal is precipitated in the hydrochloric acid of parts by weight, which is cooled to 10 DEG C can be prepared by hereinafter, crossing to be filtered dry to sulphonyl
Amido hydrazinobenzene hydrochloride salt；
The exhaust gas generated in the acidification reaction system is absorbed with caustic soda and condensing crystallizing, and Asia is made in then filtering drying
Sodium sulphate returns to above-mentioned reduction reaction stage progress recycled, and filtrated stock is then used for tail gas absorption.
Beneficial effects of the present invention：
1st, the present invention by add in strong acid catalyst and the strong acid catalyst before use through pretreatment, serpentine is forged
The compounds such as the silica, the aluminium oxide that are formed after burning increase its mobility after being mixed with polyacrylamide and surface is lived
Property, itself and ammonium hydroxide is made to carry out precipitation reaction, increases flocculating effect, polyacrylamide can also incite somebody to action when sediment is immersed in sulfuric acid
Sulfuric acid is loaded on the hydroxide that flocculation obtains, and increases the catalytic activity of strong acid catalyst, prevents sulfate radical anti-in catalysis
Seasonable slow dissolution, excellent catalytic effect repeat utilization rate height, improve acidity in solution, and catalysis hydrochloric acid is given birth to sodium nitrite
Into nitrous acid, low yield, unstable products caused by preventing in solution due to acid concentration deficiency, while increase diazo reaction body
The acidity of system, excessive acid can be effectively prevented diazol and be decomposed since acidity is insufficient, increase the yield of diazo reaction,
The quality of finished product good made, and hydrochloric acid dosage is reduced, and reduces the pressure of liquid waste processing, yield is good, saves entreprise cost；
2nd, it is not only generated to sulfoamido hydrazinobenzene hydrochloride salt during diazo reaction, is also also easy to produce the sulphur of ortho position and isomery
Amide groups hydrazinobenzene hydrochloride salt because these impurity solution degree in acid solution is little, it is difficult to make diazo-reaction complete, therefore adds in
Phase transfer catalyst changes the solubility between sulfoamido hydrazinobenzene hydrochloride salt and its impurity, can be removed in caustic soda with decoloration
It goes, the salt acid out for adding 20-25% obtains the product of high-purity, reduces unknown object impurity, increases the quality of product, save
The cost of enterprise；
3rd, the exhaust gas generated in the acidification reaction system is absorbed with caustic soda and condensing crystallizing, then filtering drying are made
Sodium sulfite returns to above-mentioned reduction reaction stage progress recycled, and filtrated stock then for tail gas absorption, efficiently solves
The problem of liquid waste processing, the two product can be increased product output rate, saved entreprise cost with recycled.
Specific embodiment
With reference to specific examples below, the present invention is described in further detail, and protection scope of the present invention is not limited to
In following embodiment.Implement process, condition, reagent, experimental method of the present invention etc., in addition to the following content specially referred to,
It is among the general principles and common general knowledge in the art, content is not particularly limited in the present invention.
Embodiment 1
It is a kind of to sulfoamido hydrazinobenzene hydrochloride salt, according to weight ratio, prepare the raw material to sulfoamido hydrazinobenzene hydrochloride salt
It is urged by 80 parts of P-aminobenzene-sulfonamide, 150 parts of hydrochloric acid, 70 parts of sodium nitrites, 60 parts of caustic soda, 80 parts of sodium sulfites, 1 part of phase transfer
Agent and 0.1 part of strong acid catalyst composition；The strong acid catalyst according to mass fraction by 60 parts of serpentines, 120 parts of ammonium hydroxide,
40 parts of sulfuric acid and 10 parts of polyacrylamide compositions, the strong acid catalyst are first prepared before use, and concrete operations are：Claim first
Each raw material of aforementioned proportion is taken, by 150-200 DEG C of calcining 1-2h of serpentine and powder I is ground to obtain, then adds into powder I
Enter ammonium hydroxide and polyacrylamide stir and evenly mix after stand 3-5h, be precipitated precipitation, then will precipitation filtration washing it is dry and finely ground powder
End II, is impregnated into 5-7h in sulfuric acid by powder II later, refilters and dry to obtain residue, finally dry residue at 380-450 DEG C
It roasts 12-14h and crushes and can be prepared by the strong acid catalyst.
The hydrochloric acid is the concentrated hydrochloric acid of mass fraction 36%.
The phase transfer catalyst is polyethylene glycol, dialkylethers, tertiary amine, one kind in tri-n-butylamine or several
The mixture of kind arbitrary proportion.
A kind of preparation process to sulfoamido hydrazinobenzene hydrochloride salt weighs each raw material first, in accordance with the ratio of claim 1,
Then P-aminobenzene-sulfonamide, hydrochloric acid, sodium nitrite is taken to carry out diazo-reaction, sodium sulfite is added and carries out reduction reaction,
Precipitation crystal is acidified with hydrochloric acid after reaction and filtration drying can be prepared by product, first by the hydrochloric acid by weight 4:2:1
It is divided into tri- parts of a, b, c, when diazo reaction takes the hydrochloric acid of a parts by weight and the water of 3 times of its weight is added in into hydrochloric acid, then adds in pair
Aminobenzene sulfonamide adjusts the temperature to 0-5 DEG C, and the sodium nitrite solution for adding 30% stirs evenly simultaneously insulation reaction 30-
50min obtains diazonium salt solution；
In the reduction reaction, first add in the water dissolution of 4 times of sodium sulfite and its weight and ice bath be cooled to 0-3 DEG C,
Then add in diazonium salt solution and formed and reduction reaction system and adjust pH to 6-7, then adjust the temperature of the reduction reaction system to
85-90 DEG C and keep this temperature 1-2h carry out reduction reaction.
The hydrochloric acid for adding in b parts by weight in the hydrochloric acid acidization first into reduction reaction system forms acidification reaction
System adjusts the temperature of the acidification reaction system to 85-90 DEG C and this temperature 1-2h is kept to be acidified, then add in c thereto
Crystal is precipitated in the hydrochloric acid of parts by weight, which is cooled to 10 DEG C can be prepared by hereinafter, crossing to be filtered dry to sulphonyl
Amido hydrazinobenzene hydrochloride salt.
The exhaust gas generated in the acidification reaction system is absorbed with caustic soda and condensing crystallizing, and Asia is made in then filtering drying
Sodium sulphate returns to above-mentioned reduction reaction stage progress recycled, and filtrated stock is then used for tail gas absorption.
Embodiment 2
It is a kind of to sulfoamido hydrazinobenzene hydrochloride salt, according to weight ratio, prepare the raw material to sulfoamido hydrazinobenzene hydrochloride salt
It is urged by 85 parts of P-aminobenzene-sulfonamide, 185 parts of hydrochloric acid, 75 parts of sodium nitrites, 70 parts of caustic soda, 85 parts of sodium sulfites, 3 parts of phase transfers
Agent and 0.2 part of strong acid catalyst composition；The strong acid catalyst according to mass fraction by 65 parts of serpentines, 123 parts of ammonium hydroxide,
45 parts of sulfuric acid and 13 parts of polyacrylamide compositions, the strong acid catalyst are first prepared before use, and concrete operations are：Claim first
Each raw material of aforementioned proportion is taken, by 150-200 DEG C of calcining 1-2h of serpentine and powder I is ground to obtain, then adds into powder I
Enter ammonium hydroxide and polyacrylamide stir and evenly mix after stand 3-5h, be precipitated precipitation, then will precipitation filtration washing it is dry and finely ground powder
End II, is impregnated into 5-7h in sulfuric acid by powder II later, refilters and dry to obtain residue, finally dry residue at 420-450 DEG C
It roasts 10-12h and crushes and can be prepared by the strong acid catalyst.
The hydrochloric acid is the concentrated hydrochloric acid of mass fraction 36%.
The phase transfer catalyst is polyethylene glycol, dialkylethers, tertiary amine, one kind in tri-n-butylamine or several
The mixture of kind arbitrary proportion.
A kind of preparation process to sulfoamido hydrazinobenzene hydrochloride salt weighs each raw material first, in accordance with the ratio of claim 1,
Then P-aminobenzene-sulfonamide, hydrochloric acid, sodium nitrite is taken to carry out diazo-reaction, sodium sulfite is added and carries out reduction reaction,
Precipitation crystal is acidified with hydrochloric acid after reaction and filtration drying can be prepared by product, first by the hydrochloric acid by weight 4:2:1
It is divided into tri- parts of a, b, c, when diazo reaction takes the hydrochloric acid of a parts by weight and the water of 3 times of its weight is added in into hydrochloric acid, then adds in pair
Aminobenzene sulfonamide adjusts the temperature to 0-5 DEG C, and the sodium nitrite solution for adding 30% stirs evenly simultaneously insulation reaction 30-
50min obtains diazonium salt solution.
In the reduction reaction, first add in the water dissolution of 4 times of sodium sulfite and its weight and ice bath be cooled to 0-3 DEG C,
Then add in diazonium salt solution and formed and reduction reaction system and adjust pH to 6-7, then adjust the temperature of the reduction reaction system to
85-90 DEG C and keep this temperature 1-2h carry out reduction reaction.
The hydrochloric acid for adding in b parts by weight in the hydrochloric acid acidization first into reduction reaction system forms acidification reaction
System adjusts the temperature of the acidification reaction system to 85-90 DEG C and this temperature 1-2h is kept to be acidified, then add in c thereto
Crystal is precipitated in the hydrochloric acid of parts by weight, which is cooled to 10 DEG C can be prepared by hereinafter, crossing to be filtered dry to sulphonyl
Amido hydrazinobenzene hydrochloride salt.
The exhaust gas generated in the acidification reaction system is absorbed with caustic soda and condensing crystallizing, and Asia is made in then filtering drying
Sodium sulphate returns to above-mentioned reduction reaction stage progress recycled, and filtrated stock is then used for tail gas absorption.
Embodiment 3
It is a kind of to sulfoamido hydrazinobenzene hydrochloride salt, according to weight ratio, prepare the raw material to sulfoamido hydrazinobenzene hydrochloride salt
It is urged by 90 parts of P-aminobenzene-sulfonamide, 170 parts of hydrochloric acid, 80 parts of sodium nitrites, 65 parts of caustic soda, 90 parts of sodium sulfites, 2 parts of phase transfers
Agent and 0.3 part of strong acid catalyst composition；The strong acid catalyst according to mass fraction by 63 parts of serpentines, 125 parts of ammonium hydroxide,
43 parts of sulfuric acid and 15 parts of polyacrylamide compositions, the strong acid catalyst are first prepared before use, and concrete operations are：Claim first
Each raw material of aforementioned proportion is taken, by 150-200 DEG C of calcining 1-2h of serpentine and powder I is ground to obtain, then adds into powder I
Enter ammonium hydroxide and polyacrylamide stir and evenly mix after stand 3-5h, be precipitated precipitation, then will precipitation filtration washing it is dry and finely ground powder
End II, is impregnated into 5-7h in sulfuric acid by powder II later, refilters and dry to obtain residue, finally dry residue at 380-450 DEG C
It roasts 12-14h and crushes and can be prepared by the strong acid catalyst.
The hydrochloric acid is the concentrated hydrochloric acid of mass fraction 36%.
The phase transfer catalyst is polyethylene glycol, dialkylethers, tertiary amine, one kind in tri-n-butylamine or several
The mixture of kind arbitrary proportion.
A kind of preparation process to sulfoamido hydrazinobenzene hydrochloride salt weighs each raw material first, in accordance with the ratio of claim 1,
Then P-aminobenzene-sulfonamide, hydrochloric acid, sodium nitrite is taken to carry out diazo-reaction, sodium sulfite is added and carries out reduction reaction,
Precipitation crystal is acidified with hydrochloric acid after reaction and filtration drying can be prepared by product, first by the hydrochloric acid by weight 4:2:1
It is divided into tri- parts of a, b, c, when diazo reaction takes the hydrochloric acid of a parts by weight and the water of 3 times of its weight is added in into hydrochloric acid, then adds in pair
Aminobenzene sulfonamide adjusts the temperature to 0-5 DEG C, and the sodium nitrite solution for adding 30% stirs evenly simultaneously insulation reaction 30-
50min obtains diazonium salt solution.
In the reduction reaction, first add in the water dissolution of 4 times of sodium sulfite and its weight and ice bath be cooled to 0-3 DEG C,
Then add in diazonium salt solution and formed and reduction reaction system and adjust pH to 6-7, then adjust the temperature of the reduction reaction system to
85-90 DEG C and keep this temperature 1-2h carry out reduction reaction.
The hydrochloric acid for adding in b parts by weight in the hydrochloric acid acidization first into reduction reaction system forms acidification reaction
System adjusts the temperature of the acidification reaction system to 85-90 DEG C and this temperature 1-2h is kept to be acidified, then add in c thereto
Crystal is precipitated in the hydrochloric acid of parts by weight, which is cooled to 10 DEG C can be prepared by hereinafter, crossing to be filtered dry to sulphonyl
Amido hydrazinobenzene hydrochloride salt.
The exhaust gas generated in the acidification reaction system is absorbed with caustic soda and condensing crystallizing, and Asia is made in then filtering drying
Sodium sulphate returns to above-mentioned reduction reaction stage progress recycled, and filtrated stock is then used for tail gas absorption.
Embodiment 4
It is a kind of to sulfoamido hydrazinobenzene hydrochloride salt, according to weight ratio, prepare the raw material to sulfoamido hydrazinobenzene hydrochloride salt
It is urged by 95 parts of P-aminobenzene-sulfonamide, 220 parts of hydrochloric acid, 85 parts of sodium nitrites, 80 parts of caustic soda, 95 parts of sodium sulfites, 5 parts of phase transfers
Agent and 0.4 part of strong acid catalyst composition；The strong acid catalyst according to mass fraction by 70 parts of serpentines, 128 parts of ammonium hydroxide,
50 parts of sulfuric acid and 18 parts of polyacrylamide compositions, the strong acid catalyst are first prepared before use, and concrete operations are：Claim first
Each raw material of aforementioned proportion is taken, by 150-200 DEG C of calcining 1-2h of serpentine and powder I is ground to obtain, then adds into powder I
Enter ammonium hydroxide and polyacrylamide stir and evenly mix after stand 3-5h, be precipitated precipitation, then will precipitation filtration washing it is dry and finely ground powder
End II, is impregnated into 5-7h in sulfuric acid by powder II later, refilters and dry to obtain residue, finally dry residue at 430-450 DEG C
It roasts 9-10h and crushes and can be prepared by the strong acid catalyst.
The hydrochloric acid is the concentrated hydrochloric acid of mass fraction 36%.
The phase transfer catalyst is polyethylene glycol, dialkylethers, tertiary amine, one kind in tri-n-butylamine or several
The mixture of kind arbitrary proportion.
A kind of preparation process to sulfoamido hydrazinobenzene hydrochloride salt weighs each raw material first, in accordance with the ratio of claim 1,
Then P-aminobenzene-sulfonamide, hydrochloric acid, sodium nitrite is taken to carry out diazo-reaction, sodium sulfite is added and carries out reduction reaction,
Precipitation crystal is acidified with hydrochloric acid after reaction and filtration drying can be prepared by product, first by the hydrochloric acid by weight 4:2:1
It is divided into tri- parts of a, b, c, when diazo reaction takes the hydrochloric acid of a parts by weight and the water of 3 times of its weight is added in into hydrochloric acid, then adds in pair
Aminobenzene sulfonamide adjusts the temperature to 0-5 DEG C, and the sodium nitrite solution for adding 30% stirs evenly simultaneously insulation reaction 30-
50min obtains diazonium salt solution.
In the reduction reaction, first add in the water dissolution of 4 times of sodium sulfite and its weight and ice bath be cooled to 0-3 DEG C,
Then add in diazonium salt solution and formed and reduction reaction system and adjust pH to 6-7, then adjust the temperature of the reduction reaction system to
85-90 DEG C and keep this temperature 1-2h carry out reduction reaction.
The hydrochloric acid for adding in b parts by weight in the hydrochloric acid acidization first into reduction reaction system forms acidification reaction
System adjusts the temperature of the acidification reaction system to 85-90 DEG C and this temperature 1-2h is kept to be acidified, then add in c thereto
Crystal is precipitated in the hydrochloric acid of parts by weight, which is cooled to 10 DEG C can be prepared by hereinafter, crossing to be filtered dry to sulphonyl
Amido hydrazinobenzene hydrochloride salt.
The exhaust gas generated in the acidification reaction system is absorbed with caustic soda and condensing crystallizing, and Asia is made in then filtering drying
Sodium sulphate returns to above-mentioned reduction reaction stage progress recycled, and filtrated stock is then used for tail gas absorption.
Embodiment 5
It is a kind of to sulfoamido hydrazinobenzene hydrochloride salt, according to weight ratio, prepare the raw material to sulfoamido hydrazinobenzene hydrochloride salt
By 100 parts of P-aminobenzene-sulfonamide, 200 parts of hydrochloric acid, 90 parts of sodium nitrites, 75 parts of caustic soda, 100 parts of sodium sulfites, 4 parts of phase transfers
Catalyst and 0.5 part of strong acid catalyst composition；The strong acid catalyst is according to mass fraction by 68 parts of serpentines, 130 parts of ammonia
Water, 46 parts of sulfuric acid and 20 parts of polyacrylamide compositions, the strong acid catalyst are first prepared before use, and concrete operations are：It is first
Each raw material of aforementioned proportion is first weighed, by 150-200 DEG C of calcining 1-2h of serpentine and powder I is ground to obtain, then to powder I
Middle addition ammonium hydroxide and polyacrylamide stand 3-5h after stirring and evenly mixing, and precipitation are precipitated, then precipitation filtration washing is dry and finely ground
Powder II is obtained, powder II is impregnated into 5-7h in sulfuric acid later, refilters and dries to obtain residue, finally by residue at 380-100 DEG C
It is lower baking 13-14h and crush can be prepared by the strong acid catalyst.
The hydrochloric acid is the concentrated hydrochloric acid of mass fraction 36%.
The phase transfer catalyst is polyethylene glycol, dialkylethers, tertiary amine, one kind in tri-n-butylamine or several
The mixture of kind arbitrary proportion.
A kind of preparation process to sulfoamido hydrazinobenzene hydrochloride salt weighs each raw material first, in accordance with the ratio of claim 1,
Then P-aminobenzene-sulfonamide, hydrochloric acid, sodium nitrite is taken to carry out diazo-reaction, sodium sulfite is added and carries out reduction reaction,
Precipitation crystal is acidified with hydrochloric acid after reaction and filtration drying can be prepared by product, first by the hydrochloric acid by weight 4:2:1
It is divided into tri- parts of a, b, c, when diazo reaction takes the hydrochloric acid of a parts by weight and the water of 3 times of its weight is added in into hydrochloric acid, then adds in pair
Aminobenzene sulfonamide adjusts the temperature to 0-5 DEG C, and the sodium nitrite solution for adding 30% stirs evenly simultaneously insulation reaction 30-
50min obtains diazonium salt solution.
In the reduction reaction, first add in the water dissolution of 4 times of sodium sulfite and its weight and ice bath be cooled to 0-3 DEG C,
Then add in diazonium salt solution and formed and reduction reaction system and adjust pH to 6-7, then adjust the temperature of the reduction reaction system to
85-90 DEG C and keep this temperature 1-2h carry out reduction reaction.
The hydrochloric acid for adding in b parts by weight in the hydrochloric acid acidization first into reduction reaction system forms acidification reaction
System adjusts the temperature of the acidification reaction system to 85-90 DEG C and this temperature 1-2h is kept to be acidified, then add in c thereto
Crystal is precipitated in the hydrochloric acid of parts by weight, which is cooled to 10 DEG C can be prepared by hereinafter, crossing to be filtered dry to sulphonyl
Amido hydrazinobenzene hydrochloride salt.
The exhaust gas generated in the acidification reaction system is absorbed with caustic soda and condensing crystallizing, and Asia is made in then filtering drying
Sodium sulphate returns to above-mentioned reduction reaction stage progress recycled, and filtrated stock is then used for tail gas absorption.
In order to verify strong acid catalyst and phase transfer catalyst to preparing what effect rose to sulfoamido hydrazinobenzene hydrochloride salt
Effect, spy make comparative testing below：
Basic mode according to embodiment 1 prepares the product for containing strong acid catalyst as sample 1, at this point, to sulphonyl
The raw material of amido hydrazinobenzene hydrochloride salt is：Aminobenzene sulfonamide, hydrochloric acid, sodium nitrite, strong acid catalyst, caustic soda and sodium sulfite group
Into；
Method according to embodiment 1 prepares the product for containing phase transfer catalyst as sample 2, at this point, to sulfonamide
The raw material of base hydrazinobenzene hydrochloride salt is：Aminobenzene sulfonamide, hydrochloric acid, sodium nitrite, caustic soda, sodium sulfite and phase transfer catalyst group
Into；
Method according to embodiment 1 prepares the product that contains phase transfer catalyst and strong acid catalyst as sample 3, this
When, the raw material to sulfoamido hydrazinobenzene hydrochloride salt is：Aminobenzene sulfonamide, hydrochloric acid, sodium nitrite, strong acid catalyst, caustic soda, Asia
Sodium sulphate and phase transfer catalyst composition；
Method according to embodiment 1, which is prepared, does not contain the product of strong acid catalyst and phase transfer catalyst as a comparison
Example, at this point, being to the raw material of sulfoamido hydrazinobenzene hydrochloride salt：Aminobenzene sulfonamide, hydrochloric acid, sodium nitrite, caustic soda and sulfurous acid
Sodium forms.
The diazo reaction yield and isomer ratio of the different samples of table 1
| Group | Diazo reaction yield | Isomer ratio |
| Comparative example | 45%-50% | 3%-5% |
| Sample 1 | 65%-68% | 4%-6% |
| Sample 2 | 55%-60% | 0.1%-0.15% |
| Sample 3 | 65%-70% | 0.1%-0.13% |
It can be obtained by the data in upper table, after adding strong acid catalyst for comparative example, the yield of diazo reaction
Apparent increase, and after adding phase transfer catalyst, the ratio of isomers is greatly reduced, obtain to sulfoamido phenyl hydrazine hydrochloride
The purity higher of salt, effect is more preferable, and after adding in both substances simultaneously, the yield highest of diazo reaction, the ratio of isomers
At least, effect is best.
Claims (4)
1. a kind of preparation process to sulfoamido hydrazinobenzene hydrochloride salt takes P-aminobenzene-sulfonamide, hydrochloric acid, Asia first, in accordance with ratio
Sodium nitrate carries out diazo-reaction, adds sodium sulfite and carries out reduction reaction, is acidified after reaction with hydrochloric acid and crystal and mistake is precipitated
It is filtered dry and dry can be prepared by product, it is characterised in that：First by the hydrochloric acid by weight 4:2:1 point be tri- parts of a, b, c, diazonium
The hydrochloric acid of a parts by weight is taken during reaction and the water of 3 times of its weight is added in into hydrochloric acid, then adds in P-aminobenzene-sulfonamide, is adjusted
Temperature adds 30% sodium nitrite solution, phase transfer catalyst and strong acid catalyst and insulation reaction 30- to 0-5 DEG C
50min obtains diazonium salt solution；Prepare the raw material to sulfoamido hydrazinobenzene hydrochloride salt according to weight ratio by 80-100 parts to amino
Benzsulfamide, 150-220 part hydrochloric acid, 70-90 parts of sodium nitrites, 60-80 parts of caustic soda, 80-100 parts of sodium sulfites, 1-5 parts of phases turn
Shifting catalyst and 0.1-0.5 parts of strong acid catalyst compositions；The strong acid catalyst is according to mass fraction by 60-70 parts of snakes
Stone, 120-130 part ammonium hydroxide, 40-50 parts of sulfuric acid and 10-20 parts of polyacrylamide compositions, the strong acid catalyst are advanced before use
Prepared by row, concrete operations are：Each raw material of aforementioned proportion is weighed first, by 150-200 DEG C of calcining 1-2h of serpentine and grounds travel
Broken to obtain powder I, then into powder I, addition ammonium hydroxide and polyacrylamide stand 3-5h after stirring and evenly mixing, and precipitation are precipitated, then will sink
Shallow lake filtration washing it is dry and finely ground powder II, powder II is impregnated into 5-7h in sulfuric acid later, refilters and dries to obtain residue, most
Residue at 380-450 DEG C is baked to 12-14h afterwards and is crushed and can be prepared by the strong acid catalyst；The hydrochloric acid is matter
Measure the concentrated hydrochloric acid of score 36%；The phase transfer catalyst is one in polyethylene glycol, dialkylethers, tri-n-butylamine
The mixture of kind or several arbitrary proportions.
2. a kind of preparation process to sulfoamido hydrazinobenzene hydrochloride salt as described in claim 1, it is characterised in that：Described goes back
In original reaction, first add in the water dissolution of 4 times of sodium sulfite and its weight and be cooled to 0-3 DEG C, then add in diazonium salt solution shape
Into reduction reaction system and pH is adjusted to 6-7, then is adjusted the temperature of the reduction reaction system to 85-90 DEG C and kept this temperature 1-
2h carries out reduction reaction.
3. a kind of preparation process to sulfoamido hydrazinobenzene hydrochloride salt as described in claim 1, it is characterised in that：The salt
The hydrochloric acid for adding in b parts by weight in sour acidization first into reduction reaction system forms acidification reaction system, adjusts the acidification
The temperature of reaction system is to 85-90 DEG C and this temperature 1-2h is kept to be acidified, then adds in the hydrochloric acid precipitation of c parts by weight thereto
The acidification reaction system is cooled to 10 DEG C hereinafter, filtration drying can be prepared by sulfoamido hydrazinobenzene hydrochloride salt by crystal.
4. a kind of preparation process to sulfoamido hydrazinobenzene hydrochloride salt as described in claim 1, it is characterised in that：The acid
Change the exhaust gas generated in reaction system and absorb simultaneously condensing crystallizing with caustic soda, then filtering drying is made sodium sulfite and returns to above-mentioned go back
The former stage of reaction carries out recycled, and filtrated stock is then used for tail gas absorption.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611204209.5A CN106631925B (en) | 2016-12-23 | 2016-12-23 | It is a kind of to sulfoamido hydrazinobenzene hydrochloride salt and its preparation process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611204209.5A CN106631925B (en) | 2016-12-23 | 2016-12-23 | It is a kind of to sulfoamido hydrazinobenzene hydrochloride salt and its preparation process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106631925A CN106631925A (en) | 2017-05-10 |
| CN106631925B true CN106631925B (en) | 2018-06-22 |
Family
ID=58826832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611204209.5A Active CN106631925B (en) | 2016-12-23 | 2016-12-23 | It is a kind of to sulfoamido hydrazinobenzene hydrochloride salt and its preparation process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106631925B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110218161B (en) * | 2019-07-03 | 2022-02-22 | 河北民族师范学院 | Preparation method of para-substituted phenylhydrazine hydrochloride |
| CN113956187A (en) * | 2021-11-08 | 2022-01-21 | 山东省药学科学院 | Synthetic method of p-sulfanilamide phenylhydrazine hydrochloride |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2657691A1 (en) * | 2006-06-19 | 2007-12-27 | Vanderbilt University | Methods and compositions for diagnostic and therapeutic targeting of cox-2 |
| CN105130901A (en) * | 2015-08-06 | 2015-12-09 | 苏州二叶制药有限公司 | Celecoxib preparation method |
-
2016
- 2016-12-23 CN CN201611204209.5A patent/CN106631925B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106631925A (en) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106631925B (en) | It is a kind of to sulfoamido hydrazinobenzene hydrochloride salt and its preparation process | |
| CN103706383A (en) | Catalyst for preparing guaiacol from catechol and preparation method thereof | |
| CN101948388B (en) | Method for removing nitrite ions | |
| CN110252395A (en) | A kind of catalyst being used to prepare high-purity taurine and its application | |
| CN107382111A (en) | A kind of method that normal pressure salt solustion mehtod produces α super strong gypsums | |
| CN106220524A (en) | A kind of industrial raising N, the method for 2,3 trimethyl 2 butanamide production efficiencys | |
| CN104628605A (en) | Continuous catalytic sulfonation method of naphthalene and device thereof | |
| RU2009133838A (en) | METHOD FOR PRODUCING A RESTORING AGENT COMPOSITION | |
| CN104628670A (en) | 6-nitro-1,2-diazoxynaphthalene-4-sulfonic acid and preparation method thereof | |
| CN106345387B (en) | A kind of continuous reaction apparatus and method of amino acid surfactant | |
| CN108912019A (en) | The method that one kind recycling mantoquita and ethyl alcohol from D, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester mother liquor | |
| CN102329243B (en) | Tubular reaction method of L-(-)-3-chloro-2-hydroxypropyl trimethyl ammonium chloride | |
| CN105837452B (en) | 2- methyl-5-nitro phenol production process | |
| CN112358404B (en) | Preparation method of 2-chloro-6-methylaniline | |
| CN103420409B (en) | Method for synthesizing high-purity silver sulfate | |
| CN105906523A (en) | Synthesis method of zoalene | |
| US10947124B2 (en) | Concentrated aqueous solutions of aluminum chlorohydrate monohydrate | |
| CN204973899U (en) | Synthetic reation kettle that uses of sulfamic acid | |
| CN104945223B (en) | A kind of method that load molecular sieve catalysis toluene synthesizes ortho-chlorotolu'ene | |
| CN103910439A (en) | High chlorine ion-resistant corrosion inhibitor and preparation method thereof | |
| CN207313480U (en) | A kind of production after-treatment device of orthanilic acid | |
| CN104557693B (en) | A kind of synthetic method of 3,5-Dimethyl-4-nitropyridine-N-oxide | |
| CN108423790A (en) | A kind of preparation formula and preparation method thereof except fluorite mineralizer | |
| CN109678188B (en) | Comprehensive utilization method of waste acid in sulfamic acid production | |
| CN107151796A (en) | A kind of Aluminum sheets flash removed solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20180319 Address after: Pingdingshan chemical industry of Henan province 467200 city parks (three Lu Yexian County Gong Dian Xiang north of Shahe Zhuyuan three Road East) Applicant after: Pingdingshan Aosida Technology Co., Ltd. Address before: 467200 No. 4, Chemical Road, Pingdingshan, Henan, Yexian County Applicant before: HENAN AOSIDA NEW MATERIAL CO., LTD. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |