CN1253946A - Method for clean producing substituted arylamine sulfonic acid - Google Patents
Method for clean producing substituted arylamine sulfonic acid Download PDFInfo
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- CN1253946A CN1253946A CN 99116896 CN99116896A CN1253946A CN 1253946 A CN1253946 A CN 1253946A CN 99116896 CN99116896 CN 99116896 CN 99116896 A CN99116896 A CN 99116896A CN 1253946 A CN1253946 A CN 1253946A
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Abstract
The present invention discloses a cleansing production method of substituted arylamine sulfoacid, and is characterized by that it adds an inert organic solvent, for example chlorobenzene, dichlorobenzene, trichlorobenzene and nitrobenzene, etc. in the reaction of substituted arylamine and sulfuric acid, and utilizes the feature of that said inert organic solvent is easy to form azeotrope with water to continuously deliver the water produced in the couse of reaction from the reactor. It not only can prepare substituted arylamine sulfoacid with high-quality and high-yield, but also can easily control reaction temp., and reduce reaction temp.. At the same time it adopts lower mixing ratio of solfonating agent, and can effectively control sulfonation reaction, so that it can further raise the yield.
Description
The invention belongs to dyestuff and medicine intermediate-arylamine sulfonic acid preparing technical field, relate to a kind of preparation method of substituted arylamine sulfonic acid, relate in particular to and adopt sulfuric acid to carry out the method that sulfonation prepares substituted arylamine sulfonic acid.
The said substituted arylamine sulfonic acid of the present invention is a kind of important dyestuff and medicine intermediate, has a wide range of applications at industrial circles such as dyestuff, food dye, medicine.Shown under its general structure:
Wherein, R is methyl, methoxyl group or nitro etc., m=1～3; Said substituted arylamine sulfonic acid such as para-totuidine-2-sulfonic acid, 2-amino-3,5-acid dimethyl, 2-methyl-4-amino-5-methoxy benzenesulfonic acid and 3-nitro-4-amino-Phenylsulfonic acid etc.Present industrial production substituted arylamine sulfonic acid generally adopts the vitriol oil (or oleum) that arylamine is carried out sulfonation and makes.As document " intermediated chemistry and technology ", the technology that the .1984.P.79 of Chemical Industry Press is reported is a very typical example.In this reaction process, after reaction finishes, in order to obtain product, often adopt the method for thin up, so just produced a large amount of spent acid.Not only increased production cost, and environment has been caused serious pollution.According to parties concerned's measuring and calculating as can be known, 1 ton of arylamine sulfonic acid of every production will produce 50 tons of spent acid (acid concentration 4-10%) at least.At present, only producing the spent acid amount that this series products caused on dyestuffs industries is sizable source of pollution;
Above-mentioned works is discussed simultaneously and introduce the also available high temperature solid-state baking process of sulfonic group in arylamine.In the reaction, arylamine and equimolar effect of sulfuric acid generate sulfonic acid and water.The existence of water makes that reaction can not be complete.React completely for making, just must improve temperature of reaction and anhydrate to remove.So it is generally higher that solid phase is cured the sulfonated temperature of reaction, between 180-230 ℃.Under so high temperature, the more volatile and oxidation of most of arylamine.The amine steam that evaporates is healthy unfavorable to operator's, and the formed tarry materials of oxidation has reduced the quality of product.
Therefore, how to hang down to pollute or contamination-freely " clean " and produce substituted arylamine sulfonic acid and become the important topic that presses for solution.
The objective of the invention is to disclose the method that a kind of " liquid phase baking process " prepares substituted arylamine sulfonic acid, produce substituted arylamine sulfonic acid in the mode of " cleaning ", to overcome the existing in prior technology defective.
Design of the present invention is such: the contriver has added a kind of organic solvent inert in substituted aromatic amines and vitriolic reaction, as: chlorobenzene, dichlorobenzene, trichlorobenzene, oil of mirbane etc.Utilize its characteristics easy and water formation azeotrope, the water that reaction generates is constantly derived reactor.Recyclable the recycling of solvent of deriving, said method can not only high quality, high productivity prepares substituted arylamine sulfonic acid, and owing to react in organic solvent, control reaction temperature easily, and can reduce temperature of reaction.Owing to adopt lower sulphonating agent proportioning, so can suppress degree of depth sulfonation effectively again, therefore product yield also is further enhanced simultaneously.
Method of the present invention mainly may further comprise the steps successively:
(1) salt-forming reaction:
Substituted aromatic amines and sulfuric acid react in solvent, generate arylamine vitriol, and its reaction formula is:
Wherein, R is methyl, methoxyl group, hydroxyl or nitro etc.; M=1～3;
The mol ratio of substituted aromatic amines, sulfuric acid and solvent is:
Substituted aromatic amines: sulfuric acid: solvent=1: (1.01～1.10): (5～10);
Said solvent is that polyalkylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, oil of mirbane and dimethylbenzene etc. can generate azeotrope with water and does not participate in the organic solvent that reacts; In this reaction, temperature of reaction there is no strict demand, generally at room temperature can carry out.
(2) dehydration translocation reaction:
The arylamine vitriol that generates is further transposition and dehydration in solvent again, and water steam steams whole solvents,
Reaction times is 5～30 hours, when substituted aromatic amines has a plurality of substituting group, because of it has bigger solubleness in solvent, should get the long reaction times; Its reaction formula is:
(3) collection of product:
Adopt conventional method from reactant, to collect target product, as can be by the following method: add alkali, make product soluble in water, filter, discard filter cake and unreacted reactant or by product, filtrate is cooled to room temperature, under agitation adds sulfuric acid or hydrochloric acid, make PH≤3, so that the sulfonic acid that generates is separated out from water, leave standstill, filter, for several times with the cold water washing filter cake.Filter cake is the product of purifying after 60-80 ℃ of drying, purity can reach more than 98%, and yield can reach about 95%.
Said product can carry out assay with liquid chromatography: instrument: Model 510 Liquid chromatograph (Japanese Waters) Infrared spectroscopy: instrument: 7650 infrared spectrophotometers (Shanghai analytical instrument factory).
There is not environmental pollution basically in the said method of the present invention, is a kind of method of clean producing substituted arylamine sulfonic acid, and efficiency of pcr product and purity are all higher, and are convenient to suitability for industrialized production.
Embodiment 1
Synthesizing of para-totuidine-2-sulfonic acid:
In 250 milliliters of there-necked flasks, add 10.7 gram para-totuidine (0.1 mole) and 150 milliliters of dichlorobenzene, under agitation splash into 10.9 gram 98% sulfuric acid (0.11 mole), be warming up to backflow, so reacted 5 hours.Be cooled to 80 ℃, add 10 ml waters and 16 gram 33%NaOH solution.Material is transferred in 1000 milliliters of distilling flasks, and water steam steams whole solvents.Solvent recovering yield is more than 90%, and reusable.Filter, discard filter cake, filtrate is chilled to room temperature, under agitation add sulfuric acid, make PH=3, leave standstill, filter, for several times with the cold water washing filter cake.Filter cake is product after 70 ℃ of dryings, product tape 1/2 crystal water, and purity is more than 98%, and yield is about 95%.Its reaction formula is:
The ultimate analysis of product:
C H N theoretical value (%) 44.92 4.81 7.49 experimental values (%) 44.07 5.10 7.59
Embodiment 2
2-amino-3,5-acid dimethyl synthetic:
In the 250ml there-necked flask, add the 200ml dichlorobenzene, 24.2ml 2, and 4-xylidine (01.mol) under agitation splashes into 22 and restrains 98% sulfuric acid (0.22mol).Be heated to backflow, reaction adds water 50ml, 30%NaOH 26ml more than 15 hours then, and the steam distilled mode of water all steams solvent.Solvent recovering yield is more than 90%.Add the PH=10-11 that 30%NaOH makes vinasse, and add water and make its volume reach 400ml, after the heated and boiled, solution carries out heat filtering, removes insoluble impurities.Filtrate is acidified to PH＜3 with hydrochloric acid (industrial goods).Have a large amount of white solids to separate out this moment, and standing over night is filtered, a small amount of cold water washing of filter cake, and drying, the white solid that obtains is 2-amino-3, the 5-acid dimethyl, purity is more than 98%, yield 90%.Its reaction formula is:
The ultimate analysis of product:
C H N theoretical value (%) 47.76 5.32 6.97 experimental values (%) 47.16 5.36 7.01
Embodiment 3
Synthesizing of 2-methyl-4-amino-5-methoxy benzenesulfonic acid:
In the 250ml there-necked flask, add the 150ml chlorobenzene, 21g 2-methoxyl group-5-monomethylaniline (0.15mol) under agitation splashes into 15 and restrains 98% sulfuric acid.Be heated to backflow, reacted 30 hours, carry out steam distillation (add water 50ml, add 30%NaOH 26ml) then.Solvent recovering yield is more than 90%;
Add the PH=10-11 that 30%NaOH makes vinasse, and add water and make its volume reach 400ml, after the heated and boiled, solution carries out heat filtering, removes insoluble impurities.Filtrate is acidified to PH＜3 with hydrochloric acid (industrial goods).Have a large amount of white solids to separate out this moment, and standing over night is filtered, a small amount of cold water washing of filter cake, and drying must white 2-methyl-4-amino-5-methoxy benzenesulfonic acid, and purity is more than 98%, yield 90%.Its reaction formula is:
The ultimate analysis of product:
C H N theoretical value (%) 44.24 5.07 6.45 experimental values (%) 44.20 5.11 6.50
Embodiment 4
4,3-nitro-4-amino-Phenylsulfonic acid synthetic:
In the 250ml there-necked flask, add the 150ml dichlorobenzene, 21g o-Nitraniline (0.15mol) under agitation splashes into 15 and restrains 98% sulfuric acid.Be heated to backflow, reacted 20 hours, carry out steam distillation (add water 50ml, add 30%NaOH 26ml) then.Solvent recovering yield is more than 90%;
Add the PH=10-11 that 30%NaOH makes vinasse, and add water and make its volume reach 400ml, after the heated and boiled, solution carries out heat filtering, removes insoluble impurities.Filtrate is acidified to PH＜3 with hydrochloric acid (industrial goods).Have a large amount of white solids to separate out this moment, and standing over night is filtered, a small amount of cold water washing of filter cake, and drying must white 3-nitro-4-amino-Phenylsulfonic acid, and purity is more than 98%, yield 90%.Its reaction formula is:
The ultimate analysis of product:
C H N theoretical value (%) 33.03 2.75 15.60 experimental values (%) 33.09 2.80 15.56
Claims (7)
1. the method for a clean producing substituted arylamine sulfonic acid is characterized in that mainly may further comprise the steps successively: (1) salt-forming reaction:
Substituted aromatic amines and sulfuric acid react in solvent, generate arylamine vitriol, and its reaction formula is:
Wherein, R is methyl, methoxyl group, hydroxyl or nitro; M=1～3;
The mol ratio of substituted aromatic amines, sulfuric acid and solvent is:
Substituted aromatic amines: sulfuric acid: solvent=1: (1.01～1.10): (5～10);
Said solvent is in polyalkylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, oil of mirbane or the dimethylbenzene
A kind of; (2) dehydration translocation reaction:
The arylamine vitriol that generates is further transposition and dehydration under the reflux temperature in solvent again, and water steams
Decatize goes out whole solvents;
Reaction times is 5～30 hours; Its reaction formula is:
(3) collection of product:
Adopt conventional method from reactant, to collect target product.
2. the method for claim 1, it is characterized in that: said substituted aromatic amines is a para-totuidine.
3. the method for claim 1, it is characterized in that: said substituted aromatic amines is 2, the 4-xylidine.
4. the method for claim 1, it is characterized in that: said substituted aromatic amines is 2-methoxyl group-5-monomethylaniline.
5. the method for claim 1, it is characterized in that: said substituted aromatic amines is an o-Nitraniline.
6. method as claimed in claim 3 is characterized in that: the reaction times is 15 hours.
7. method as claimed in claim 4 is characterized in that: the reaction times is 30 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99116896 CN1253946A (en) | 1999-09-23 | 1999-09-23 | Method for clean producing substituted arylamine sulfonic acid |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 99116896 CN1253946A (en) | 1999-09-23 | 1999-09-23 | Method for clean producing substituted arylamine sulfonic acid |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613520A (en) * | 2013-10-23 | 2014-03-05 | 徐花 | Preparation method for 4-aminobenzenesulfonic acid |
| CN104016890A (en) * | 2014-06-13 | 2014-09-03 | 江苏华达化工集团有限公司 | Method for preparing 1-amino-4-sodium naphthalene sulfonate through solid-phase continuous reaction |
| CN109180537A (en) * | 2018-08-24 | 2019-01-11 | 浙江友联化学工业有限公司 | A kind of method that liquid phase baking process prepares 3- chlorine para-totuidine -6- sulfonic acid |
| CN110483339A (en) * | 2019-07-30 | 2019-11-22 | 浙江工业大学 | A method of CLT acid is prepared by raw material of meta-aminotoluene |
-
1999
- 1999-09-23 CN CN 99116896 patent/CN1253946A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613520A (en) * | 2013-10-23 | 2014-03-05 | 徐花 | Preparation method for 4-aminobenzenesulfonic acid |
| CN103613520B (en) * | 2013-10-23 | 2016-04-20 | 青岛文创科技有限公司 | A kind of preparation method of Sulphanilic Acid |
| CN104016890A (en) * | 2014-06-13 | 2014-09-03 | 江苏华达化工集团有限公司 | Method for preparing 1-amino-4-sodium naphthalene sulfonate through solid-phase continuous reaction |
| CN109180537A (en) * | 2018-08-24 | 2019-01-11 | 浙江友联化学工业有限公司 | A kind of method that liquid phase baking process prepares 3- chlorine para-totuidine -6- sulfonic acid |
| CN109180537B (en) * | 2018-08-24 | 2021-07-20 | 浙江友联化学工业有限公司 | Method for preparing 3-chloro-p-toluidine-6-sulfonic acid by liquid phase baking method |
| CN110483339A (en) * | 2019-07-30 | 2019-11-22 | 浙江工业大学 | A method of CLT acid is prepared by raw material of meta-aminotoluene |
| CN110483339B (en) * | 2019-07-30 | 2022-01-25 | 浙江工业大学 | Method for preparing CLT acid by using m-toluidine as raw material |
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