CN100386312C - Process for synthesizing 2,4-diamino benzene sulfonic acid and its salt - Google Patents
Process for synthesizing 2,4-diamino benzene sulfonic acid and its salt Download PDFInfo
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- CN100386312C CN100386312C CNB2006100290512A CN200610029051A CN100386312C CN 100386312 C CN100386312 C CN 100386312C CN B2006100290512 A CNB2006100290512 A CN B2006100290512A CN 200610029051 A CN200610029051 A CN 200610029051A CN 100386312 C CN100386312 C CN 100386312C
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- mphenylenediamine
- oleum
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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
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic 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
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
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Abstract
The process of synthesizing 2, 4-diamino benzene sulfonic acid includes the following steps: the reaction between m-phenylene diamine and sulfuric acid inside solvent at 140-250 deg.c, with the solvent being one or several selected from inorganic solvent phosphoric acid and polyphosphoric acid and organic solvent with normal pressure boiling point over 140deg.c. The present invention also discloses the preparation process of 2, 4-diamino benzene sulfonate, which is prepared through the first preparing 2, 4-diamino benzene sulfonic acid and the subsequent salt forming reaction to obtain 2, 4-diamino benzene sulfonate. The present invention has less sulfuric acid consumption, less environmental pollution, low cost, high yield and high product quality.
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.
A kind of preparation 2 of routine, the method for 4-diamino benzene sulfonic acid is as follows: with 2, the 4-dinitrochlorobenzene is a raw material, gets with reduction after reacting with sodium bisulfite again.The shortcoming of this method is that reaction yield is low, poor product quality and production efficiency are low.
Disclosed another kind of preparation 2 in the prior art, (for example day clear 57-48961 of disclosure special permission communique, day flat 4-13657 of disclosure special permission communique) is as follows for the method for 4-diamino benzene sulfonic acid: with the mphenylenediamine is raw material, be dissolved in the above sulfuric acid of 5 times of weight, then with oleum or SO
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 need to use a large amount of sulfuric acid, and the vitriolic consumption is 5 times of mphenylenediamine more than the weight at least, even 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 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, by in specific solvent, preparing 2 with sulfuric acid or oleum sulfonation m-phenylenediamine, 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 a first aspect of the present 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 140～250 ℃ temperature range, make 2, the 4-diamino benzene sulfonic acid, described solvent is one or more in the following solvent: be selected from the inorganic solvent of phosphoric acid or Tripyrophosphoric acid and atmospheric boiling point at the organic solvent more than 140 ℃.
In a second 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 first aspect present invention, and the 4-diamino benzene sulfonic acid, and then be carried out to reactant salt, make required 2,4-diamino benzene sulfonic acid salt.
In above-mentioned synthetic method, preferably, described organic solvent is the organic solvent of atmospheric boiling point between 140～300 ℃.Be more preferably, described organic solvent is to be selected from the following solvent one or more: the aromatic hydrocarbons with 6-20 carbon atom or alkane aromatic hydrocarbons or aralkyl hydrocarbon, the methyl phenyl ketone that has the aromatic hydrocarbons of 8-20 carbon atom or alkane aromatic hydrocarbons or aralkyl hydrocarbon, replaced by halogen and/or nitro, the saturated alkane with 9-30 carbon atom, the saturated alkane with 2-30 carbon atom, pimelinketone, tetramethylene sulfone, succinonitrile and the adiponitrile that are replaced by halogen.Especially preferably, described organic solvent is to be selected from the following solvent one or more: dimethylbenzene, trimethylbenzene, isopropyl benzene, isobutyl-benzene, tert.-butylbenzene, isopropyl biphenyl, naphthalene, methylnaphthalene, tetraline, ditan, di-p-tolyl methane, dimethylated chlorobenzene, the trimethylammonium chlorobenzene, dichlorobenzene, trichlorobenzene, bromobenzene, toluene(mono)chloride, toluene dichloride, toluene bromide, dimethyl bromobenzene, oil of mirbane, nitrotoluene, nitro ethylbenzene, nitro-xylene, trimethylammonium oil of mirbane, nitro-chlorobenzene, methyl phenyl ketone, nonane, undecane, paraffin, clorafin, high temperature kerosene, thermal oil, tetrabromoethane, trichloropropane, tetrabromobutane, pimelinketone, tetramethylene sulfone, succinonitrile and adiponitrile.
In aforesaid method, preferably, the weight ratio of described inorganic solvent and mphenylenediamine is more preferably in 0.2: 1～1: 1 scope in 0.1: 1～5: 1 scope, again preferably in 0.3: 1～0.8: 1 scope, especially preferably in 0.4: 1～0.5: 1 scope.
In aforesaid method, preferably, the weight ratio of described organic solvent and mphenylenediamine is more preferably in 1: 1～10: 1 scope in 0.1: 1～30: 1 scope, again preferably in 2: 1～6: 1 scope, especially preferably in 3: 1～5: 1 scope.
In aforesaid method, preferably, the weight ratio of mphenylenediamine and sulfuric acid or oleum is in 1: 0.9～1: 4.5 scope, with 100% sulphur acid meter.Be more preferably in 1: 1.2～1: 3 scope, with 100% sulphur acid meter.Especially preferably in 1: 1.5～1: 2.4 scope, with 100% sulphur acid meter.
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 90-100%.
In aforesaid method, mphenylenediamine and sulfuric acid or oleum react in 160～210 ℃ temperature range, and described organic solvent is that atmospheric boiling point is at the organic solvent more than 160 ℃.Especially preferably, mphenylenediamine and sulfuric acid or oleum react in 170～200 ℃ temperature range, and described organic solvent is that atmospheric boiling point is at the organic solvent more than 170 ℃.
In the method for second aspect present invention, preferably described 2,4-diamino benzene sulfonic acid salt is sodium salt or sylvite.
Embodiment
The invention provides a kind of in solvent 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 140～250 ℃ temperature range, make 2, the 4-diamino benzene sulfonic acid, described solvent is one or more in the following solvent: be selected from the inorganic solvent of phosphoric acid or Tripyrophosphoric acid and atmospheric boiling point at the organic solvent more than 140 ℃.
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.
In above-mentioned synthetic method, preferably, described organic solvent is the organic solvent of atmospheric boiling point between 140～300 ℃.Be more preferably, described organic solvent is to be selected from the following solvent one or more: the aromatic hydrocarbons with 6-20 carbon atom or alkane aromatic hydrocarbons or aralkyl hydrocarbon, the methyl phenyl ketone that has the aromatic hydrocarbons of 8-20 carbon atom or alkane aromatic hydrocarbons or aralkyl hydrocarbon, replaced by halogen and/or nitro, the saturated alkane with 9-30 carbon atom, the saturated alkane with 2-30 carbon atom, pimelinketone, tetramethylene sulfone, succinonitrile and the adiponitrile that are replaced by halogen.Especially preferably, described organic solvent is to be selected from the following solvent one or more: dimethylbenzene, trimethylbenzene, isopropyl benzene, isobutyl-benzene, tert.-butylbenzene, isopropyl biphenyl, naphthalene, methylnaphthalene, tetraline, ditan, di-p-tolyl methane, dimethylated chlorobenzene, the trimethylammonium chlorobenzene, dichlorobenzene, trichlorobenzene, bromobenzene, toluene(mono)chloride, toluene dichloride, toluene bromide, dimethyl bromobenzene, oil of mirbane, nitrotoluene, nitro ethylbenzene, nitro-xylene, trimethylammonium oil of mirbane, nitro-chlorobenzene, methyl phenyl ketone, nonane, undecane, paraffin, clorafin, high temperature kerosene, thermal oil, tetrabromoethane, trichloropropane, tetrabromobutane, pimelinketone, tetramethylene sulfone, succinonitrile and adiponitrile.
In aforesaid method, preferably, the weight ratio of described inorganic solvent and mphenylenediamine is more preferably in 0.2: 1～1: 1 scope in 0.1: 1～5: 1 scope, again preferably in 0.3: 1～0.8: 1 scope, especially preferably in 0.4: 1～0.5: 1 scope.
In aforesaid method, preferably, the weight ratio of described organic solvent and mphenylenediamine is more preferably in 1: 1～10: 1 scope in 0.1: 1～30: 1 scope, again preferably in 2: 1～6: 1 scope, especially preferably in 3: 1～5: 1 scope.
In preparation method of the present invention, inorganic solvent and organic solvent can be used alone, but also also mix together.When mixing use inorganic solvent and organic solvent, can come to determine respectively concrete consumption according to above description to inorganic solvent and consumption of organic solvent.Particularly, the weight ratio of described inorganic solvent and mphenylenediamine is in 0.1: 1～5: 1 scope, and the weight ratio of described organic solvent and mphenylenediamine is in 0.1: 1～30: 1 scope.Preferably, the weight ratio of described inorganic solvent and mphenylenediamine is in 0.2: 1～1: 1 scope, and the weight ratio of described organic solvent and mphenylenediamine is in 1: 1～10: 1 scope.In preparation method of the present invention, sulfonation reaction is carried out in 140-250 ℃ temperature range, preferably carries out in 160～210 ℃ temperature range, particularly preferably in carrying out in 170～200 ℃ the temperature range.
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 80-100% 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: 4.5 scope, with 100% sulphur acid meter in the inventive method; Be more preferably, mphenylenediamine and vitriolic weight ratio are in 1: 1.2～1: 3 scope, with 100% sulphur acid meter.Especially preferably, mphenylenediamine and vitriolic weight ratio are in 1: 1.5～1: 2.4 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: 5 scope, be more preferably in 1: 1.3～1: 3.3 scope, especially preferably in 1: 1.7～1: 2.6 scope.
Major advantage of the present invention is as follows:
(1) synthetic method of the present invention is by preparing 2 with sulfuric acid or oleum sulfonation m-phenylenediamine in specific solvent, the 4-diamino benzene sulfonic acid, this method can significantly reduce the consumption of sulfuric acid or oleum, employed solvent can be recycled in the reaction simultaneously, avoids so effectively in the prior art owing to need the environmental pollution that a large amount of sulfuric acid of use cause and the problem of production cost rising.
(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.
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 the reactor of the condenser of being furnished with the profit skimmer, add 300 gram orthodichlorobenzenes, 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), be warming up to 175 ℃, 175～180 ℃ the reaction 4 hours after, cooling, add 400 milliliters in water, separate organic phase and water, organic phase can be used as the solvent of following batch of reaction, water is through purifying and decolouring, 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 30 gram phosphoric acid in reactor, 98% sulfuric acid, 155 grams (being equivalent to 150 grams, 100% sulfuric acid) and 100% mphenylenediamine, 100 grams are warming up to 195 ℃, after 6 hours, cooling adds 400 milliliters in water 195～200 ℃ of reactions, water obtains 2 through purifying and decolouring, 4-diamino benzene sulfonic acid 168.0 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 3
React by embodiment 2 identical methods, the consumption of different is phosphoric acid changes 80 grams into, obtains 2,4-diamino benzene sulfonic acid 167 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 94% (in mphenylenediamine).
Embodiment 4
In the reactor of the condenser of being furnished with the profit skimmer, add 200 gram orthodichlorobenzenes, 50 gram phosphoric acid, 98% sulfuric acid, 245 grams (being equivalent to 240 grams, 100% sulfuric acid) and 100% mphenylenediamine, 100 grams, be warming up to 175 ℃, 175～180 ℃ the reaction 4 hours after, cooling adds 400 milliliters in water, separates organic phase and water, organic phase can be used as the solvent of following batch of reaction, water obtains 2 through purifying and decolouring, 4-diamino benzene sulfonic acid 170 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 95.7% (in mphenylenediamine).
Embodiment 5
In the reactor of the condenser of being furnished with the profit skimmer, add 700 gram oil of mirbane, 260 gram 100% sulfuric acid and 100% mphenylenediamine, 100 grams, be warming up to 210 ℃, 210-215 ℃ the reaction 4 hours after, cooling adds 400 milliliters in water, separates organic phase and water, organic phase can be used as the solvent of following batch of reaction, water obtains 2 through purifying and decolouring, 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 6
In the reactor of the condenser of being furnished with the profit skimmer, add 500 grams 1,3,5-trichlorobenzene, 1% oleum, 120 grams (being equivalent to 120 grams, 100% sulfuric acid) and 100% mphenylenediamine, 100 grams are warming up to 170 ℃, 170～175 ℃ the reaction 5 hours after, cooling adds 400 milliliters in water, separates organic phase and water, organic phase can be used as the solvent of following batch of reaction, water obtains 2 through purifying and decolouring, 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 7
In the reactor of the condenser of being furnished with the profit skimmer, add 150 grams 1,3,5-trimethylbenzene, 85% sulfuric acid, 194 grams (being equivalent to 165 grams, 100% sulfuric acid) and 100% mphenylenediamine, 100 grams are warming up to 160 ℃, 160-165 ℃ the reaction 6 hours after, cooling adds 400 milliliters in water, separates organic phase and water, organic phase can be used as the solvent of following batch of reaction, water obtains 2 through purifying and decolouring, 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 8
In the reactor of the condenser of being furnished with the profit skimmer, add 200 gram undecanes, 90% sulfuric acid, 211 grams (being equivalent to 190 grams, 100% sulfuric acid) and 100% mphenylenediamine, 100 grams, be warming up to 150 ℃, 150-155 ℃ the reaction 6 hours after, cooling adds 400 milliliters in water, separates organic phase and water, organic phase can be used as the solvent of following batch of reaction, water obtains 2 through purifying and decolouring, 4-diamino benzene sulfonic acid 161.7 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 91% (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).
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 (10)
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 140～250 ℃ temperature range, make 2, the 4-diamino benzene sulfonic acid, described solvent is one or more in the following solvent: the inorganic solvent and the organic solvent of atmospheric boiling point between 140～300 ℃ that are selected from phosphoric acid or Tripyrophosphoric acid.
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, it is characterized in that described organic solvent is to be selected from the following solvent one or more: the aromatic hydrocarbons with 6-20 carbon atom or alkane aromatic hydrocarbons or aralkyl hydrocarbon, the methyl phenyl ketone that has the aromatic hydrocarbons of 8-20 carbon atom or alkane aromatic hydrocarbons or aralkyl hydrocarbon, replaced by halogen and/or nitro, saturated alkane, the saturated alkane with 2-30 carbon atom, pimelinketone, tetramethylene sulfone, succinonitrile and the adiponitrile that are replaced by halogen with 9-30 carbon atom.
4. method as claimed in claim 3, it is characterized in that, described organic solvent is to be selected from the following solvent one or more: dimethylbenzene, trimethylbenzene, isopropyl benzene, isobutyl-benzene, tert.-butylbenzene, isopropyl biphenyl, naphthalene, methylnaphthalene, tetraline, ditan, di-p-tolyl methane, dimethylated chlorobenzene, the trimethylammonium chlorobenzene, dichlorobenzene, trichlorobenzene, bromobenzene, toluene(mono)chloride, toluene dichloride, toluene bromide, dimethyl bromobenzene, oil of mirbane, nitrotoluene, nitro ethylbenzene, nitro-xylene, trimethylammonium oil of mirbane, nitro-chlorobenzene, methyl phenyl ketone, nonane, undecane, paraffin, clorafin, high temperature kerosene, thermal oil, tetrabromoethane, trichloropropane, tetrabromobutane, pimelinketone, tetramethylene sulfone, succinonitrile and adiponitrile.
5. method as claimed in claim 1 or 2 is characterized in that, the weight ratio of described inorganic solvent and mphenylenediamine is in 0.1: 1～5: 1 scope, and the weight ratio of described organic solvent and mphenylenediamine is in 0.1: 1～30: 1 scope.
6. method as claimed in claim 5 is characterized in that, the weight ratio of described inorganic solvent and mphenylenediamine is in 0.2: 1～1: 1 scope, and the weight ratio of described organic solvent and mphenylenediamine is in 1: 1～10: 1 scope.
7. method as claimed in claim 1 or 2 is characterized in that, the weight ratio of mphenylenediamine and sulfuric acid or oleum is in 1: 0.9～1: 4.5 scope, with 100% sulphur acid meter.
8. method as claimed in claim 1 or 2 is characterized in that described oleum is selected from SO
3Concentration is greater than 0% and smaller or equal to 70% oleum.
9. method as claimed in claim 1 or 2 is characterized in that, 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.
10. method as claimed in claim 1 or 2 is characterized in that mphenylenediamine and sulfuric acid or oleum react in 160～210 ℃ temperature range, described organic solvent is that atmospheric boiling point is at the organic solvent more than 160 ℃.
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| CNB2006100290512A CN100386312C (en) | 2006-07-18 | 2006-07-18 | Process for synthesizing 2,4-diamino benzene sulfonic acid and its salt |
| PCT/CN2007/070308 WO2008011830A1 (en) | 2006-07-18 | 2007-07-17 | Process for synthesizing 2,4-diamino benzene sulfonic acid and salts thereof |
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| CN100386312C (en) * | 2006-07-18 | 2008-05-07 | 上海世景国际贸易有限公司 | Process for synthesizing 2,4-diamino benzene sulfonic acid and its salt |
| CN103932988A (en) | 2009-04-24 | 2014-07-23 | 伊休蒂卡有限公司 | Novel Formulation of Indomethacin |
| CN102516137A (en) * | 2011-12-08 | 2012-06-27 | 江苏远征化工有限公司 | Production method of 2, |
| CN103553982A (en) * | 2013-08-22 | 2014-02-05 | 上海鸿源鑫创材料科技有限公司 | Preparation technology of 2,4-diaminobenzenesulfonic acid |
| US9526734B2 (en) | 2014-06-09 | 2016-12-27 | Iceutica Pty Ltd. | Formulation of meloxicam |
| 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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| JPS632256B2 (en) * | 1980-09-05 | 1988-01-18 | Sumitomo Chemical Co | |
| JPH0413657A (en) * | 1990-05-08 | 1992-01-17 | Nissan Chem Ind Ltd | Production of 2,4-diaminobenzenesulfonic acid |
| CN1486977A (en) * | 2002-09-17 | 2004-04-07 | Method for producing segregative 3,4-diamino benzene sulfonic | |
| CN1721398A (en) * | 2005-06-24 | 2006-01-18 | 上海世景国际贸易有限公司 | Process for synthesis of 2,4-diamino benzene sulfonic acid and its sodium salts |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100386312C (en) * | 2006-07-18 | 2008-05-07 | 上海世景国际贸易有限公司 | Process for synthesizing 2,4-diamino benzene sulfonic acid and its salt |
-
2006
- 2006-07-18 CN CNB2006100290512A patent/CN100386312C/en not_active Expired - Fee Related
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2007
- 2007-07-17 WO PCT/CN2007/070308 patent/WO2008011830A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS632256B2 (en) * | 1980-09-05 | 1988-01-18 | Sumitomo Chemical Co | |
| JPH0413657A (en) * | 1990-05-08 | 1992-01-17 | Nissan Chem Ind Ltd | Production of 2,4-diaminobenzenesulfonic acid |
| CN1486977A (en) * | 2002-09-17 | 2004-04-07 | Method for producing segregative 3,4-diamino benzene sulfonic | |
| CN1721398A (en) * | 2005-06-24 | 2006-01-18 | 上海世景国际贸易有限公司 | Process for synthesis of 2,4-diamino benzene sulfonic acid and its sodium salts |
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| WO2008011830A1 (en) | 2008-01-31 |
| CN1900058A (en) | 2007-01-24 |
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