CN100558703C - 2, the synthetic method of 4-diamino benzene sulfonic acid and salt thereof - Google Patents
2, the synthetic method of 4-diamino benzene sulfonic acid and salt thereof Download PDFInfo
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- CN100558703C CN100558703C CNB2006101169332A CN200610116933A CN100558703C CN 100558703 C CN100558703 C CN 100558703C CN B2006101169332 A CNB2006101169332 A CN B2006101169332A CN 200610116933 A CN200610116933 A CN 200610116933A CN 100558703 C CN100558703 C CN 100558703C
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- sulfuric acid
- benzene sulfonic
- oleum
- sulfonic acid
- diamino benzene
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Abstract
A kind of preparation 2 is disclosed, the method for 4-diamino benzene sulfonic acid, this method may further comprise the steps: mphenylenediamine and sulfuric acid or oleum are reacted in 160～250 ℃ temperature range, make 2, the 4-diamino benzene sulfonic acid.A kind of preparation 2 is also disclosed, the method for 4-diamino benzene sulfonic acid salt, this method may further comprise the steps: will as above make 2,4-diamino benzene sulfonic acid, and then be carried out to reactant salt, make required 2,4-diamino benzene sulfonic acid salt.Method of the present invention can solve the problem that is risen by the environmental pollution of using a large amount of sulfuric acid to cause and production cost in the prior art effectively, can obtain higher reaction yield and quality product simultaneously.
Description
Technical field
The present invention relates to 2, the synthetic method of 4-diamino benzene sulfonic acid and salt thereof.
Background technology
2, the 4-diamino benzene sulfonic acid, the m-phenylenediamine-4-sulfonic acid that is otherwise known as has following structural formula:
2,4-diamino benzene sulfonic acid and salt thereof (particularly sodium salt) is mainly as the important intermediate of synthetic dyestuff, their derived product we production and life in obtained using very widely.
Be feedstock production 2 with the mphenylenediamine in the prior art, the method of 4-diamino benzene sulfonic acid (for example day clear 57-48961 of disclosure special permission communique, day flat 4-13657 of disclosure special permission communique) all is a liquid phase method, promptly to make solvent, then with oleum or SO with a large amount of sulfuric acid (or oleum)
3Gas carries out sulfonation as sulphonating agent to mphenylenediamine to be handled, and obtains product 2 thus, the 4-diamino benzene sulfonic acid.This preparation method's shortcoming is to need to use a large amount of sulfuric acid (or oleum), the vitriolic consumption is that 5 times of mphenylenediamine are more than the weight at least, even it is more, because these sulfuric acid can't effectively reclaim, can only discharge by the form of waste liquid, therefore environment is caused very serious pollution, increased production cost simultaneously.Another shortcoming of aforesaid method is SO
3Gas is as the use of sulphonating agent, SO
3The source of the gas of gas is preserved, transports, uses and is recycled except meeting increases the complicacy of technology, and security also is a problem.
Summary of the invention
The object of the present invention is to provide a kind of preparation 2, the method for 4-diamino benzene sulfonic acid, this method can overcome in the prior art problem that rises owing to the environmental pollution that needs to use a large amount of sulfuric acid (or oleum) to cause and production cost.And the reaction scheme of this method is short, technology is simple, can obtain higher reaction yield, quality product and production efficiency.
The present inventor finds through the further investigation back, prepare 2 by in specified temp, carrying out solid state reaction with the sulfuric acid of specified quantitative or oleum and mphenylenediamine, the 4-diamino benzene sulfonic acid, the problem that rises by the environmental pollution of using a large amount of sulfuric acid to cause and production cost in the prior art can be solved effectively, higher reaction yield and quality product can be obtained simultaneously.
In one aspect of the invention, a kind of preparation 2 is provided, the method of 4-diamino benzene sulfonic acid, this method may further comprise the steps, mphenylenediamine and sulfuric acid or oleum are reacted in 160～250 ℃ temperature range, make 2, the 4-diamino benzene sulfonic acid, the weight ratio of wherein said mphenylenediamine and sulfuric acid or oleum is in 1: 0.9～1: 3 scope, with 100% sulphur acid meter.
In aforesaid method, preferably, the weight ratio of mphenylenediamine and sulfuric acid or oleum is in 1: 0.9～1: 3 scope, with 100% sulphur acid meter.Be more preferably in 1: 1.2～1: 2.8 scope, with 100% sulphur acid meter.Especially preferably in 1: 1.5～1: 2.6 scope, with 100% sulphur acid meter.
In another aspect of the present invention, provide a kind of preparation 2, the method for 4-diamino benzene sulfonic acid salt, this method may further comprise the steps: make 2 by the described method of claim 1, and the 4-diamino benzene sulfonic acid, and then be carried out to reactant salt, make required 2,4-diamino benzene sulfonic acid salt.
Preferably, described 2,4-diamino benzene sulfonic acid salt is sodium salt or sylvite.
In a preferred embodiment of the present invention, mphenylenediamine and sulfuric acid or oleum carry out solid state reaction in 160～250 ℃ temperature range.
In a preferred embodiment of the present invention, mphenylenediamine and sulfuric acid or oleum react in 165～220 ℃ temperature range.
In a preferred embodiment of the present invention, mphenylenediamine and sulfuric acid or oleum react in 170～220 ℃ temperature range.
In a preferred embodiment of the present invention, mphenylenediamine and sulfuric acid or oleum react in 181～210 ℃ temperature range.
In a preferred embodiment of the present invention, described weight ratio is in 1: 1.5～1: 2.6 scope, with 100% sulphur acid meter.
In a preferred embodiment of the present invention, described oleum is selected from SO
3Concentration is greater than 0% and smaller or equal to 70% oleum; And/or described sulfuric acid is selected from the sulfuric acid that concentration is 0.1-100% or is diluted to the oleum of any concentration of 0.1-100% vitriolic through water.
In aforesaid method, preferably, described oleum is selected from SO
3Concentration is greater than 0% and smaller or equal to 70% oleum.Be more preferably, oleum is selected from SO
3Concentration is greater than 0% and smaller or equal to 10% oleum.Again preferably, oleum is selected from SO
3Concentration is greater than 0% and smaller or equal to 5% oleum.Especially preferably, oleum is selected from SO
3Concentration is greater than 0% and smaller or equal to 1% oleum, for example concentration is the oleum of 0.1-1%.
In aforesaid method, preferably, described sulfuric acid is selected from the sulfuric acid that concentration is 0.1-100% or is diluted to the oleum of any concentration of 0.1-100% vitriolic through water.Be more preferably, described sulfuric acid is selected from the sulfuric acid that concentration is 60-100%.Again preferably, described sulfuric acid is selected from the sulfuric acid that concentration is 80-100%.Especially preferably, described sulfuric acid is selected from the sulfuric acid that concentration is 85-100%.
In a preferred embodiment of the present invention, described oleum is selected from SO
3Concentration is greater than 0% and smaller or equal to 5% oleum; And/or described sulfuric acid is selected from the sulfuric acid that concentration is 85-100wt%.
In a preferred embodiment of the present invention, the reaction times of mphenylenediamine and sulfuric acid or oleum was 1～34 hour scope.
Preferably, the reaction times is 2～24 hours, more preferably 2～12 hours, and most preferably 3～10 hours.
Embodiment
The invention provides a kind of with sulfuric acid or oleum sulfonation m-phenylenediamine preparation 2, the method of 4-diamino benzene sulfonic acid, this method may further comprise the steps: mphenylenediamine and sulfuric acid or oleum are reacted in 160～250 ℃ temperature range, make 2, the 4-diamino benzene sulfonic acid, this synthetic method can be represented with following reaction formula:
The present invention also provides 2, the synthetic method of 4-diamino benzene sulfonic acid salt, this method comprise with as above obtain 2, the 4-diamino benzene sulfonic acid is carried out to reactant salt, make required 2,4-diamino benzene sulfonic acid salt.
Described salt-forming reaction can be any reaction that can form required benzene sulfonate, as long as this instead would not have a negative impact to the present invention.Employed reagent of salt-forming reaction and reaction conditions are that those skilled in the art can rule of thumb determine.
At Japanese Patent (for example clear 57-48961 of day disclosure special permission communique, day flat 4-13657 of disclosure special permission communique) and application number is disclosed preparation 2 in 200510027110.8 the Chinese patent application, (with the mphenylenediamine is raw material in the method for 4-diamino benzene sulfonic acid, in 5 times of oleums more than the weight, carry out sulfonation reaction), the capital produces a large amount of two sulfonated products (being mphenylenediamine-4, the 6-disulfonic acid).In order to obtain product 2, it (is product 2 that the 4-diamino benzene sulfonic acid all needs through further pyrohydrolysis two sulfonated products that produce to be hydrolyzed into a sulfonated bodies in post-processing step, the 4-diamino benzene sulfonic acid), this step needs strict control, otherwise all sulfonated bodiess all may be hydrolyzed into the stock yard phenylenediamine, and can not obtain product 2, the 4-diamino benzene sulfonic acid.
In order to address the above problem, the inventor carries out extensive and deep research on the basis of Chinese application number 200510027110.8, improve preparation technology, and be surprised to find that, by under comparatively high temps,, can avoid two sulfonated generation in the reaction with a small amount of quantitatively sulfuric acid sulfonation mphenylenediamine, directly obtain product 2, the 4-diamino benzene sulfonic acid.With respect to a large amount of oleums that prior art adopts, the yield of reaction rises on the contrary.The contriver also finds, though also can adopt oleum in the technical scheme of the present invention, contains SO in the oleum
3Concentration improve reaction not have helps, the contriver adopts the less sulfuric acid of environmental pollution to make on the contrary to react more successfully to carry out the productive rate rising.
Solid state reaction of the present invention is meant that mphenylenediamine and sulfuric acid are mixed and made into arylamine vitriol, at high temperature bakes and banks up with earth dehydration then, and intramolecular rearrangement takes place simultaneously, obtains arylamine sulfonic acid.
Temperature of reaction
In preparation method of the present invention, sulfonation reaction is carried out in 160～250 ℃ temperature range, preferably in 165～220 ℃ temperature range, carry out, more preferably carry out in 170～220 ℃ the temperature range, particularly preferably in carrying out in 175～220 ℃ the temperature range.
The consumption of reactant
Used " sulfuric acid " of the present invention is meant the sulfuric acid of any concentration or is diluted to the oleum of any concentration of any concentration vitriolic through water.For example, the used sulfuric acid of the present invention can be that concentration is the sulfuric acid of 0.1-100% or the oleum that is diluted to any concentration of 0.1-100% vitriolic through water.Sulfuric acid is more preferably the sulfuric acid that content is 60-100%, and preferably content is the sulfuric acid of 85-100% again, and special preferably content is the sulfuric acid of 90-100%.
Used oleum SO preferably among the preparation method of the present invention
3Concentration is greater than 0% and smaller or equal to 70% oleum, for example concentration is the oleum of 0.1-70%.Be more preferably, oleum is selected from SO
3Concentration is greater than 0% and smaller or equal to 10% oleum, for example concentration is the oleum of 0.1-10%.Again preferably, oleum is selected from SO
3Concentration is greater than 0% and smaller or equal to 5% oleum, for example concentration is the oleum of 0.1-5%.Especially preferably, oleum is selected from SO
3Concentration is greater than 0% and smaller or equal to 1% oleum, for example concentration is the oleum of 0.1-1%.
The consumption of reactant is that the weight ratio of mphenylenediamine and sulfuric acid or oleum is in 1: 0.9～1: 3.0 scope, with 100% sulphur acid meter in the inventive method; Be more preferably, mphenylenediamine and vitriolic weight ratio are in 1: 1.2～1: 2.8 scope, with 100% sulphur acid meter.Especially preferably, mphenylenediamine and vitriolic weight ratio are in 1: 1.5～1: 2.6 scope, with 100% sulphur acid meter.If recently represent the consumption of reactant with mole, then the mol ratio of mphenylenediamine and sulfuric acid or oleum (with 100% sulphur acid meter) is in 1: 1～1: 3.3 scope, be more preferably in 1: 1.3～1: 3 scope, especially preferably in 1: 1.7～1: 2.9 scope.
Reaction times
Reaction times of the present invention has no particular limits, only otherwise influencing goal of the invention of the present invention gets final product.Preferably in 1～34 hour.Preferably, the reaction times is 2～24 hours, more preferably 2～12 hours, and most preferably 3～10 hours.
Major advantage of the present invention is as follows:
(1) synthetic method of the present invention is by preparing 2 in specific temperature with the sulfuric acid or the oleum sulfonation m-phenylenediamine of specified quantitative, the 4-diamino benzene sulfonic acid, this method can significantly reduce the consumption of sulfuric acid or oleum, avoids in the prior art problem that rises owing to the environmental pollution that needs to use a large amount of sulfuric acid to cause and production cost so effectively.
(2) synthetic method reaction scheme of the present invention is short, technology is simple, has simplified the equipment of industrial product and production technique widely, consider from ecological and economic angle, and be quite favourable.
(3) synthetic method of the present invention can obtain higher reaction yield and production efficiency, has good quality product simultaneously, and for example the purity of product is very high.
(4) in preferred implementation of the present invention, the present invention is by the combination of specified temp, specific proportioning, specific reaction times, specific concentrations, obtain one and significantly reduced the sulfuric acid consumption, and the reaction scheme that does not need solvent (inorganic and organic), the product purity height that this reaction scheme obtains, and, make post-processing step simplify greatly owing to do not need solvent.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, or carries out according to the condition that manufacturer advises.Unless otherwise indicated, otherwise all umbers are weight part, and all per-cents are weight percentage.
Embodiment 1
In reactor, add 100 milliliter of 98% sulfuric acid (184 gram) (100% sulfuric acid that is equivalent to 180 gram 100% sulfuric acid or 1.84 moles) and 100% mphenylenediamine 100 and restrain (being equivalent to 0.926 mole), after mixing, be warming up to 181 ℃, 181～185 ℃ the reaction 4 hours after, cooling adds 400 milliliters in water, through decolorization and purification, obtain 2,4-diamino benzene sulfonic acid 168.8 grams.The outward appearance of products obtained therefrom is a white crystal, and chromatogram content is 99% (HPLC mensuration), chemical content 98% (diazonium titration measuring), product yield 95% (in mphenylenediamine).
Embodiment 2
Add 260 gram 100% sulfuric acid and 100% mphenylenediamine, 100 grams in reactor, after mixing, be warming up to 210 ℃, after 4 hours, cooling adds 400 milliliters in water, through decolorization and purification, obtains 2 210-215 ℃ of reaction, 4-diamino benzene sulfonic acid 159.9 grams.The outward appearance of products obtained therefrom is a white crystal, and chromatogram content is 99% (HPLC mensuration), chemical content 98% (diazonium titration measuring), product yield 90% (in mphenylenediamine).
Embodiment 3
In reactor, add 1% oleum, 120 grams (being equivalent to 120 grams, 100% sulfuric acid) and 100% mphenylenediamine, 100 grams, after mixing, be warming up to 185 ℃, 185～190 ℃ the reaction 5 hours after, cooling adds 400 milliliters in water, through purifying and decolouring, obtain 2,4-diamino benzene sulfonic acid 163.4 grams.The outward appearance of products obtained therefrom is a white crystal, and chromatogram content is 99% (HPLC mensuration), chemical content 98% (diazonium titration measuring), product yield 92% (in mphenylenediamine).
Embodiment 4
In reactor, add 85% sulfuric acid, 194 grams (being equivalent to 165 grams, 100% sulfuric acid) and 100% mphenylenediamine, 100 grams, after mixing, be warming up to 160 ℃, after 6 hours, cooling adds 400 milliliters in water 160-165 ℃ of reaction, through purifying and decolouring, obtain 2,4-diamino benzene sulfonic acid 158.1 grams.The outward appearance of products obtained therefrom is a white crystal, and chromatogram content is 99% (HPLC mensuration), chemical content 98% (diazonium titration measuring), product yield 89% (in mphenylenediamine).
Embodiment 5
In reactor, add 50 milliliter of 98% sulfuric acid (92 gram) (100% sulfuric acid that is equivalent to 90 gram 100% sulfuric acid or 0.92 mole) and 100% mphenylenediamine 100 and restrain (being equivalent to 0.926 mole), after mixing, be warming up to 245 ℃, 245～250 ℃ the reaction 4 hours after, cooling adds 400 milliliters in water, through purifying and decolouring, obtain 2,4-diamino benzene sulfonic acid 155.4 grams.The outward appearance of products obtained therefrom is a white crystal, and chromatogram content is 99% (HPLC mensuration), chemical content 98% (diazonium titration measuring), product yield 87.5% (in mphenylenediamine).
Embodiment 6
In reactor, add 167 milliliter of 98% sulfuric acid (307 gram) (100% sulfuric acid that is equivalent to 300 gram 100% sulfuric acid or 3.07 moles) and 100% mphenylenediamine 100 and restrain (being equivalent to 0.926 mole), after mixing, be warming up to 170 ℃, 170～175 ℃ the reaction 4 hours after, cooling adds 400 milliliters in water, through purifying and decolouring, obtain 2,4-diamino benzene sulfonic acid 154.1 grams.The outward appearance of products obtained therefrom is a white crystal, and chromatogram content is 99% (HPLC mensuration), chemical content 98% (diazonium titration measuring), product yield 86% (in mphenylenediamine).
Embodiment 7
In reactor, add 83 milliliter of 98% sulfuric acid (153 gram) (100% sulfuric acid that is equivalent to 150 gram 100% sulfuric acid or 1.53 moles) and 100% mphenylenediamine 100 and restrain (being equivalent to 0.926 mole), after mixing, be warming up to 181 ℃, 181～185 ℃ the reaction 4 hours after, cooling adds 400 milliliters in water, through purifying and decolouring, obtain 2,4 diamino benzene sulfonic acids, 168.8 grams.The outward appearance of products obtained therefrom is a white crystal, and chromatogram content is 99% (HPLC mensuration), chemical content 98% (diazonium titration measuring), product yield 95% (in mphenylenediamine).
Embodiment 8
In reactor, add 133 milliliter of 98% sulfuric acid (245 gram) (100% sulfuric acid that is equivalent to 240 gram 100% sulfuric acid or 2.45 moles) and 100% mphenylenediamine 100 and restrain (being equivalent to 0.926 mole), after mixing, be warming up to 175 ℃, 175～180 ℃ the reaction 4 hours after, cooling adds 400 milliliters in water, through purifying and decolouring, obtain 2,4-diamino benzene sulfonic acid 170.5 grams.The outward appearance of products obtained therefrom is a white crystal, and chromatogram content is 99% (HPLC mensuration), chemical content 98% (diazonium titration measuring), product yield 96% (in mphenylenediamine).
Embodiment 9
With embodiment 1 make 2,4-diamino benzene sulfonic acid and 30% sodium hydroxide react in 35 ℃ for about 100 milliliters, through purifying, make product 2,4-diamino benzene sulfonic acid sodium 178.6 grams.The outward appearance of products obtained therefrom is a white crystal, and chromatogram content (HPLC mensuration) is 99%, and chemical content (diazonium titration measuring) is 98%, and product yield is 90% (in mphenylenediamine).
Comparative Examples 1
In reactor, add 20% oleum, 450 grams (being equivalent to 470 grams, 100% sulfuric acid) and 100% mphenylenediamine, 100 grams, be warming up to 181 ℃, 181～185 ℃ the reaction 4 hours after, add less water be hydrolyzed handle after, cooling adds 400 milliliters in water, through purifying and decolouring, obtain 2,4-diamino benzene sulfonic acid 128 grams.The outward appearance of products obtained therefrom is a white crystal, and chromatogram content is 99% (HPLC mensuration), chemical content 98% (diazonium titration measuring), product yield 72% (in mphenylenediamine).
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (5)
1. one kind prepares 2, the method of 4-diamino benzene sulfonic acid, this method may further comprise the steps, mphenylenediamine and sulfuric acid or oleum are reacted in 175～220 ℃ temperature range, make 2,4-diamino benzene sulfonic acid, the weight ratio of wherein said mphenylenediamine and sulfuric acid or oleum are in 1: 0.9～1: 3 scope, with 100% sulphur acid meter;
Described oleum is selected from SO
3Concentration is greater than 0% and smaller or equal to 5% oleum; Described sulfuric acid is selected from the sulfuric acid that concentration is 85-100wt%.
2. one kind prepares 2, the method for 4-diamino benzene sulfonic acid salt, this method may further comprise the steps: make 2 by the described method of claim 1,4-diamino benzene sulfonic acid, and then be carried out to reactant salt, make required 2,4-diamino benzene sulfonic acid salt.
3. method as claimed in claim 1 or 2 is characterized in that mphenylenediamine and sulfuric acid or oleum react in 181～210 ℃ temperature range.
4. method as claimed in claim 1 or 2 is characterized in that, described weight ratio is in 1: 1.5～1: 2.6 scope, with 100% sulphur acid meter.
5. method as claimed in claim 1 or 2 is characterized in that, the reaction times of mphenylenediamine and sulfuric acid or oleum was 1～34 hour scope.
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| CNB2006101169332A CN100558703C (en) | 2006-10-09 | 2006-10-09 | 2, the synthetic method of 4-diamino benzene sulfonic acid and salt thereof |
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| CN100558703C true CN100558703C (en) | 2009-11-11 |
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| CN108675946A (en) * | 2018-06-21 | 2018-10-19 | 中北大学 | A method of preparing 2,4- diamino benzene sulfonic acids |
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Effective date of registration: 20091204 Address after: Building 8, building 1199, 88 North Road, Shanghai, Qinzhou: 200233 Co-patentee after: Shanghai Shizhan Chemical Technology Co., Ltd. Patentee after: Shanghai Shi Jing International Trade Co., Ltd. Address before: Building 8, building 1199, 88 North Road, Shanghai, Qinzhou: 200233 Co-patentee before: Shanghai World-Prospect Industry Co., Ltd. Patentee before: Shanghai Shi Jing International Trade Co., Ltd. |
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