CN103145593A - Preparation method of 4,4'-diaminobenzenesulphonamide - Google Patents
Preparation method of 4,4'-diaminobenzenesulphonamide Download PDFInfo
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Abstract
The invention discloses a preparation method of 4,4'-diaminobenzenesulphonamide. The method comprises the following steps of: based on acetanilide, chlorosulfonic acid, thionyl chloride, water, liquid caustic soda, p-phenylenediamine and the like as raw materials, implementing chlorosulfonation, ice separation, condensation, hydrolysis, neutralization, filter pressing and other processes to obtain the target product 4,4'-diaminobenzenesulphonamide. 4,4'-diaminobenzenesulphonamide prepared by the method disclosed by the invention is good in stability, quite stable, high in yield, and low in production cost.
Description
Technical field
The invention belongs to intermediate development technique field, be specifically related to a kind ofly relate to 4, the preparation method of 4 '-diaminobenzene sulfonanilide.
Background technology
4,4 '-diaminobenzene sulfonanilide is a kind of very important matching stain intermediate, the CAS Number:16803-97-7 of this compound, and its structural formula is:
This dyestuff intermediate is mainly as disabled dyestuff intermediate p-diaminodiphenyl and the substitute products of derivative thereof.Occupy very consequence by the ACID BLACK 210 of this dyestuff intermediate preparation, ACID BLACK 234 etc. in dye product.
Although 4,4 '-diaminobenzene sulfonanilide is a kind of very important dye material, the research report of pair its preparation method is arranged seldom.The present invention therefore.
Summary of the invention
It is a kind of 4 that the object of the invention is to provide, the preparation method of 4 '-diaminobenzene sulfonanilide, solved do not have in the prior art ripe 4, the problems such as synthesis technique of 4 '-diaminobenzene sulfonanilide.
In order to solve these problems of the prior art, technical scheme provided by the invention is:
A kind of 4, the preparation method of 4 '-diaminobenzene sulfonanilide is characterized in that said method comprising the steps of:
(1) make Acetanilide
First with halosulfonic acid generation sulfonation reaction after, then with the compound of sulfur oxychloride reaction production (I)
(I);
(2) make compound and the Ursol D of formula (I)
The compound that condensation reaction forms formula (II) occurs under alkaline condition
(3) make the compound generation hydrolysis reaction of formula (II) generate 4,4 '-diaminobenzene sulfonanilide
Wherein X is halogen atom, is selected from Cl, Br, F.
Preferably, in the middle sulfonation reaction of described method steps (1), halosulfonic acid is selected chlorsulfonic acid or bromine sulfonic acid.
Preferably, in described method steps (1), mole proportioning of Acetanilide and halosulfonic acid is 1:1~6, mole proportioning 1:0.5~2 of Acetanilide and sulfur oxychloride, and the temperature of sulfonation reaction is controlled at 30~65 ℃.
Preferably, when described method steps (1) Raw selected chlorsulfonic acid and sulfur oxychloride to participate in reaction, the compound of the formula that obtains (I) was separated out by frozen water, and Precipitation Temperature is controlled to be-10~20 ℃.
Preferably, in described method steps (2) neutral and alkali condition, alkali is that to be selected from mass concentration be 3%~30% sodium hydroxide solution.
Preferably, middle condensation temp 10-30 ℃ of described method steps (2), 3-5 hour condensation time.
Preferably, the hydrolyzed solution that in described method steps (3), hydrolysis reaction adopts is selected from sodium hydroxide, aqueous hydrochloric acid or aqueous sulfuric acid, and the compound of formula (II) and the mol ratio of hydrolyzed solution are 1:1~6, and hydrolysis temperature is 70~120 ℃.
Preferably, add reductive agent before neutralization after hydrolysis reaction in described method steps (3), described reductive agent is selected from one or more arbitrary combination of vat powder, sodium bisulfite, rongalite, Sodium Pyrosulfite.
In concrete technical scheme, take Acetanilide as start material, obtain the sulfonation material under chlorsulfonic acid and sulfur oxychloride serial action, the sulfonation material is added obtain p-acetaminobenzenesulfonyl chloride through press filtration again after separating out in frozen water, p-acetaminobenzenesulfonyl chloride have sodium hydroxide solution as under acid binding agent with the Ursol D condensation, after the press filtration of gained condensation material, filter cake adds sodium hydroxide solution by pyrohydrolysis again, the hydrolyzed solution slagging-off, add reductive agent, then with obtaining target product 4,4 ' diaminobenzene sulphonyl after acid neutralization, press filtration.
Concrete 4, the preparation process of 4 '-diaminobenzene sulfonanilide is carried out in accordance with the following steps:
(1) Acetanilide chlorosulphonation operation: when Acetanilide and chlorsulfonic acid and sulfur oxychloride chlorosulphonation, Acetanilide and chlorsulfonic acid mole proportioning is 1~6, and Acetanilide and sulfur oxychloride proportioning are 0,5~2, and the chlorosulphonation temperature is 30~65 ℃.
(2) the chlorosulphonation thing adopts frozen water to separate out, and Precipitation Temperature is controlled to be-10~20 ℃, and the chlorosulphonation thing obtains filter cake after ice is separated out just carries out (3) with the water mixture rear and go on foot condensation reaction.
(3) adopting mass concentration during condensation is 3%~30% the sodium hydroxide solution acid binding agent during as p-acetaminobenzenesulfonyl chloride and Ursol D condensation, condensation temp 10-30 ℃, and 3-5 hour condensation time.
(4) condenses that generates drops into after press filtration in sodium hydroxide or hydrochloric acid, aqueous sulfuric acid (wherein condenses and acid or alkali proportioning are 1~6), and hydrolysis temperature is 70~120 ℃.
(5), add reductive agent before neutralization, the indication reductive agent comprises vat powder, sodium bisulfite, rongalite, Sodium Pyrosulfite etc.Hydrolyzed solution neutralizes with acid, and neutral temperature is 30~70 ℃.
In the present invention 4, the chemical structural formula of 4 '-diaminobenzene sulfonanilide is:
(1) sulfonation process:
(2) ice is analysed: ClSO
2OH+H
2OH
2SO
4+ HCl
(3) condensation course (amidate action):
(4) hydrolysis:
(5) neutralization
H
2SO
4+2NaOHNa
2SO
4+2H
2O
HCl+NaOHNaCl+H
2O
Below above-mentioned reaction scheme made an explanation be described as follows:
(1) chlorosulphonation and ice are analysed process
A mole of Acetanilide joined in the chlorsulfonic acid of (1-6) A mole, joining day 1-5 hour, control 30~50 ℃ of temperature during adding and finish 45~50 ℃ of insulations of rear liter control temperature 3 hours, then add (0.5~2) A mole of sulfur oxychloride, be warmed up to 50~65 ℃ of insulations 1~5 hour after finishing, insulation finishes, and is cooled to 30 ℃, the sulfonation material is slowly added in 100~400 moles of frozen water, and adition process keeps temperature-10-20 ℃.Add after the sulfonation material after the sulfonation material press filtration with dilution, obtain the sulfonation filter cake.
(2) sulfonation material condensation course
The sulfonation material is dropped in 100~250A mole of water stirred 4 hours; With 0.9~1.2A mole of Ursol D, add in 400~800A mole of water, be warmed up to 50~80 ℃ of dissolvings, then cool to 10~25 ℃; The sulfonation material is slowly added in Ursol D solution, and the sodium hydroxide solution take mass concentration as 3~30% during adding is as between acid binding agent adjustment reaction PH=4~9, and adding the sulfonation material time is 1~5 hour, 10~30 ℃ of setting-up point.The condensation terminal point gets the condensation filter cake to rear press filtration.
(3) hydrolysis, N-process
The condensation material is added in the water of (400~600) A mole, adds sodium hydroxide or hydrochloric acid, (the condensation material is 1~6 with the acid that adds or mole proportioning of alkali), then heating up is 70~120 ℃, be incubated 1~3 hour, the survey terminal point to after hydrolyzed solution is removed the gred.The filtrate temperature is transferred to 30~70 ℃, add (1~20) A mole of reductive agent (reductive agent is one or more in vat powder, sodium bisulfite, rongalite, Sodium Pyrosulfite), then be neutralized to 6.5~7.5 with acid.In the material press filtration is namely obtained 4 after becoming reconciled, 4 '-diaminobenzene sulfonanilide, product purity 93~99%, color and luster is that pink is to canescence.Overall yield of reaction 90~93%.
Below to the term that adopts in the reaction explanation that makes an explanation:
Halosulfonic acid: be called halosulfonic acid, i.e. XSO when in sulfuric acid, a hydroxyl is replaced by halogen atom X
3H or XSO
2-OH.As chlorsulfonic acid ClSO
3H。Chlorsulfonic acid is a kind of colourless fuming liquid, meets the explosive hydrolysis of water.This acid can not generate salt.With dry hydrogen chloride gas treatment S O
3Can make chlorsulfonic acid.Halosulfonic acid can be chlorsulfonic acid, fluosulfonic acid, bromine sulfonic acid.
Sulfur oxychloride is for containing sulfinyl (〉 S=O) organic compound of functional group, can be obtained by sulfide oxidation.
Add sulfur oxychloride in technical solution of the present invention in sulfonation reaction, can effectively avoid Acetanilide hyperoxidation in sulfonation process, the compound of the formula that obtains (I)
Purity is higher, greatly reduces intermediate product
Content.
In addition, the contriver also passes through
Add reductive agent when being hydrolyzed reaction, described reductive agent is selected from one or more in vat powder, sodium bisulfite, rongalite, Sodium Pyrosulfite, has reduced the generation of side reaction, has avoided amino oxidation to form nitro.
In technical solution of the present invention in condensation reaction by adopt mass concentration be 3~30% sodium hydroxide solution as acid binding agent, avoided the generation of carbonic acid gas in the reaction process, reduce product and gather and cause reaction not exclusively.
Technical solution of the present invention is take Acetanilide, chlorsulfonic acid, sulfur oxychloride, water, liquid caustic soda, Ursol D etc. as raw material, through chlorosulphonation, ice analyse, the operations such as condensation, hydrolysis, neutralization, press filtration obtain target product 4,4 '-diaminobenzene sulfonanilide.Adopt the method products obtained therefrom quality good and very stable, yield is high, and production cost significantly reduces.
With respect to scheme of the prior art, advantage of the present invention is:
The invention provides 4,4 '-diaminobenzene sulfonanilide preparation method, it is take chlorsulfonic acid, Acetanilide, sulfur oxychloride, sodium hydroxide, Ursol D etc. as main raw material, obtain target product 4,4 '-diaminobenzene sulfonanilide by operations such as chlorosulphonation, condensation, hydrolysis, neutralizations.Adopt the inventive method, chlorosulfonation has reduced the chlorsulfonic acid usage quantity, and the chlorosulphonation yield can reach more than 95%, condensation transformation efficiency and hydrolysis conversion also improve greatly, in and the time, added reductive agent in hydrolyzed solution, effectively reduce the oxidation probability of material, products obtained therefrom is of light color, and quality is good, and yield is high.Part waste water recoverable in production process, environmentally friendly, product yield can reach 90~93%.
Embodiment
Below in conjunction with specific embodiment, such scheme is described further.Should be understood that these embodiment are not limited to limit the scope of the invention for explanation the present invention.The implementation condition that adopts in embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in normal experiment, and the raw material that embodiment is used is except being commercially available industrial goods; Equipment used in embodiment is existing equipment.
Embodiment 1
Add 2500 kilograms of chlorsulfonic acids in 5000 liters of enamel reaction stills, 900 kilograms of Acetanilides are slowly added, during control 35 ℃ of temperature, be warming up to 45 ℃ of reactions 3 hours after finishing, then slowly add 600 kilograms of sulfur oxychlorides, finish 40-45 ℃ of reaction 2 hours, after reaction end arrives, the sulfonation material is slowly added in 5000 kilograms of mixture of ice and water, control during this time temperature not higher than 20 ℃, finish, gained is iced the analysis of material press filtration, the gained filter cake is stand-by after adding 4000 kg of water evenly.
750 kilograms of Ursol D add and are warming up to 60 ℃ of dissolvings in 6000 premium on currency, dissolve to finish with ice cube and open chilled brine and be cooled to 15 ℃, to ice analysis of material slowly adds, transfer PH to 8.0-8.5 with 15% sodium hydroxide solution during this time, temperature keeps 15-20 ℃, finish the condensation material, after reaction 3 lab scales survey terminal points arrive, the condensation material is squeezed into the pressure filter press filtration.
Filter cake drops in the water that is placed with 5000 kilograms, adds 2500 kilograms of liquid caustic soda, is warming up to 99 ℃ and is hydrolyzed, the hydrolysis terminal point to after material is removed the gred, filtrate changes the neutralization reaction still over to, before neutralization, temperature regulating to 60 ℃ adds the reductive agent sodium bisulfite, then acid adding slowly, when PH=7.5-8.5, stop neutralization, with temperature to 35 ℃, material is squeezed into the pressure filter press filtration, washing, drying.Product yield 92.5 content 98.7% purity 97.5%, product color is shallow.
The chromatographic data of final product:
Embodiment 2:
Add 3000 kilograms of chlorsulfonic acids in 5000 liters of enamel reaction stills, then slowly add 900 kilograms of Acetanilides, adition process is opened chuck cooling water control temperature in the kettle and is no more than 40 ℃, finish chlorsulfonic acid, adjust temperature 50-55 ℃ of insulation 3 hours, then slowly drip 700 kilograms of sulfur oxychlorides, control 55~60 ℃ of temperature during adding, finished insulation reaction 3 hours, and cooled to 25 ℃ of preparation ice and analyse.
The dilution still discharges water 4000 kilograms, and opening quotation pipe chilled brine cools to 0 ℃, and then 1000 kilograms on the rocks, the sulfonation material is slowly added, control temperature in the kettle not higher than 10 ℃, add the sulfonation material, the sulfonation material is squeezed into the pressure filter press filtration.Filter cake goes to condensation.
Discharge water 8000 kilograms in condensation kettle, be warmed up to 65 ℃, then add 760 kilograms of Ursol D, stir survey CL half an hour after, opening quotation pipe chilled brine and on the rocksly be cooled to 15 ℃, then sulfonation ice analysis of material slowly adds, transfer PH=7.0 with 20% sodium hydroxide solution during adding, control 15~20 ℃ of temperature, finished afterreaction 4 hours, press filtration, filter cake is prepared hydrolysis.
Hydrolysis kettle discharges water 7000 kilograms, 30% 1500 kilograms of liquid caustic soda, add the condensation filter cake, be warmed up to 105 ℃ the hydrolysis 4 hours, endpoint detection to after hydrolyzation material is removed the gred, filtrate is adjusted temperature 50 C, add 20 kilograms of Sodium Pyrosulfites, the spent acid that then reclaims with the sulfonation dilution is transferred PH=7.0-8.5, then isolates 4 by press filtration, the washing of 4 '-diaminobenzene sulfonanilide, oven dry.Get product yield 91.8%, content 98%, product purity 97.95%, product color is shallow.
The chromatographic data of final product:
Embodiment 3
Become 3000 kilograms with the chlorsulfonic acid consumption by 2500 kilograms except sulfonation, sulfur oxychloride becomes 500 kilograms by 600 kilograms, in and reductive agent change vat powder into all the other be all identical with embodiment 1 outward.Product yield 92%, content, 98.2%, purity, 98.7%, product color is shallow.
Embodiment 4
Except when hydrolysis adopts the condensation material to drop in 3000 kilograms of waste acid recoveries to be warming up to 98 ℃ of hydrolysis, in and the time use in liquid caustic soda and outer, all the other are all identical with embodiment 2.Product yield 92%, content: 98%, purity 97.3%, color and luster is greyish white.
Embodiment 5
Put 4000 kilograms of chlorsulfonic acids at 5000 liters of reactors, slowly drop into 900 kilograms of Acetanilides, keep 25 ℃ of temperature of reaction, finish Acetanilide and be warming up to 66 ℃, then continue reaction 6 hours, material is added to the water elutriation, keep temperature less than 25 ℃, after elutriation is complete with the material press filtration
900 kilograms of Ursol D are added in 10000 kg of water dissolve, slowly add the condensation of sulfonation filter cake, during control 20-25 ℃ of temperature, and transfer PH=8-9.5 with 10% sodium carbonate solution, be incubated 8 lab scales after finishing the sulfonation filter cake, then with the material press filtration,
Filter cake adds in 8000 premium on currency, adds 2600 kilograms of liquid caustic soda to be warming up to 90 ℃ of reactions 6 hours, then adds hydrochloric acid to be neutralized to 7.0, and the material that will neutralize cools to 40 ℃ of press filtrations, washing, and drying makes product yield 85%, content 92%, purity: 90%, product color is very dark.
Embodiment 5 compares with embodiment 1-4, and obviously, yield and quality product be all not as embodiment 1-4, and comparative example during due to sulfonation the chlorsulfonic acid consumption large, produce a large amount of spent acid, and its spent acid in process of production the no waste utilization become waste water, produce pollution.
Above-mentioned example only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the person skilled in the art can understand content of the present invention and implement according to this, can not limit protection scope of the present invention with this.All equivalent transformations that spirit is done according to the present invention or modification are within all should being encompassed in protection scope of the present invention.
Claims (8)
1. one kind 4, the preparation method of 4 '-diaminobenzene sulfonanilide is characterized in that said method comprising the steps of:
(1) make Acetanilide
First with halosulfonic acid generation sulfonation reaction after, then with the compound of sulfur oxychloride reaction production (I)
(2) make compound and the Ursol D of formula (I)
The compound that condensation reaction forms formula (II) occurs under alkaline condition
(3) make the compound generation hydrolysis reaction of formula (II) generate 4,4 '-diaminobenzene sulfonanilide
Wherein X is halogen atom, is selected from Cl, Br, F.
2. method according to claim 1, is characterized in that in the middle sulfonation reaction of described method steps (1), halosulfonic acid is selected chlorsulfonic acid or bromine sulfonic acid.
3. method according to claim 2, is characterized in that mole proportioning of the middle Acetanilide of described method steps (1) and halosulfonic acid is 1:1~6, mole proportioning 1:0.5~2 of Acetanilide and sulfur oxychloride, and the temperature of sulfonation reaction is controlled at 30~65 ℃.
4. method according to claim 2, when it is characterized in that described method steps (1) Raw selects chlorsulfonic acid and sulfur oxychloride to participate in reaction, the compound of the formula that obtains (I) is separated out by frozen water, and Precipitation Temperature is controlled to be-10~20 ℃.
5. method according to claim 2 is characterized in that it is 3%~30% sodium hydroxide solution that described method steps (2) neutral and alkali condition is selected from mass concentration.
6. method according to claim 2, is characterized in that middle condensation temp 10-30 ℃ of described method steps (2), 3-5 hour condensation time.
7. method according to claim 2, is characterized in that the hydrolyzed solution that in described method steps (3), hydrolysis reaction adopts is selected from aqueous sodium hydroxide solution, and the compound of formula (II) and the mol ratio of hydrolyzed solution are 1:1~6, and hydrolysis temperature is 70~120 ℃.
8. method according to claim 2 adds reductive agent, described reductive agent to be selected from one or more arbitrary combination of vat powder, sodium bisulfite, rongalite, Sodium Pyrosulfite when it is characterized in that hydrolysis reaction in described method steps (3).
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110041216A (en) * | 2019-03-06 | 2019-07-23 | 内蒙古利元科技有限公司 | A kind of novel OAVS production system and technique |
CN113636961A (en) * | 2021-07-09 | 2021-11-12 | 重庆康乐制药有限公司 | Preparation method of p-acetamidobenzenesulfonyl chloride |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE857082A (en) * | 1976-08-03 | 1978-01-25 | Ugine Kuhlmann | NEW WATER-SOLUBLE TRISAZOIC DYES |
FR2357611A1 (en) * | 1976-07-09 | 1978-02-03 | Ugine Kuhlmann | Water soluble benzene sulphanilide diazo dyes - give fast tints to wool, leather, sheepskin etc. |
DE10053794A1 (en) * | 2000-10-30 | 2002-05-08 | Bayer Ag | Amino- or amido-benzene N-phenylsulfonamide derivatives, useful for treating central nervous system disorders e.g. Alzheimer's disease, dementia, depression, are 5-HT6 receptor antagonists |
CN1683331A (en) * | 2004-04-16 | 2005-10-19 | 黄升 | Process for producing sulfanilic amide medicine mother substance p-acetamido benzene sulfonyl chloride |
CN101475515A (en) * | 2009-01-24 | 2009-07-08 | 温州大学 | Method for preparing 5-amino-2-chloro-N-(2,4-xylyl)-benzene sulfonic amide in water phase |
-
2013
- 2013-03-26 CN CN2013100982284A patent/CN103145593A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2357611A1 (en) * | 1976-07-09 | 1978-02-03 | Ugine Kuhlmann | Water soluble benzene sulphanilide diazo dyes - give fast tints to wool, leather, sheepskin etc. |
BE857082A (en) * | 1976-08-03 | 1978-01-25 | Ugine Kuhlmann | NEW WATER-SOLUBLE TRISAZOIC DYES |
DE10053794A1 (en) * | 2000-10-30 | 2002-05-08 | Bayer Ag | Amino- or amido-benzene N-phenylsulfonamide derivatives, useful for treating central nervous system disorders e.g. Alzheimer's disease, dementia, depression, are 5-HT6 receptor antagonists |
CN1683331A (en) * | 2004-04-16 | 2005-10-19 | 黄升 | Process for producing sulfanilic amide medicine mother substance p-acetamido benzene sulfonyl chloride |
CN101475515A (en) * | 2009-01-24 | 2009-07-08 | 温州大学 | Method for preparing 5-amino-2-chloro-N-(2,4-xylyl)-benzene sulfonic amide in water phase |
Non-Patent Citations (6)
Title |
---|
《染料与染色》 20130228 周增勇等 4,4'-二氨基苯磺酰替苯胺的合成工艺路线探讨 第50卷, 第1期 * |
《染料工业》 20010228 崔林 4一氨基苯基一beta一羟乙基砜硫酸酯(对位酯)工艺研究改进 第38卷, 第1期 * |
《精细化工》 20060831 王健等 4,4'-二氨基本磺酰胺苯胺的合成 第23卷, 第8期 * |
周增勇等: "4,4’-二氨基苯磺酰替苯胺的合成工艺路线探讨", 《染料与染色》, vol. 50, no. 1, 28 February 2013 (2013-02-28) * |
崔林: "4一氨基苯基一β一羟乙基砜硫酸酯(对位酯)工艺研究改进", 《染料工业》, vol. 38, no. 1, 28 February 2001 (2001-02-28) * |
王健等: "4,4’-二氨基本磺酰胺苯胺的合成", 《精细化工》, vol. 23, no. 8, 31 August 2006 (2006-08-31) * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110041216A (en) * | 2019-03-06 | 2019-07-23 | 内蒙古利元科技有限公司 | A kind of novel OAVS production system and technique |
CN113636961A (en) * | 2021-07-09 | 2021-11-12 | 重庆康乐制药有限公司 | Preparation method of p-acetamidobenzenesulfonyl chloride |
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