CN101811998A - Preparation method of 1-amino-2-naphthol-4-sulfonic acid - Google Patents
Preparation method of 1-amino-2-naphthol-4-sulfonic acid Download PDFInfo
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- CN101811998A CN101811998A CN 201010172800 CN201010172800A CN101811998A CN 101811998 A CN101811998 A CN 101811998A CN 201010172800 CN201010172800 CN 201010172800 CN 201010172800 A CN201010172800 A CN 201010172800A CN 101811998 A CN101811998 A CN 101811998A
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Abstract
The invention provides a preparation method of 1-amino-2-naphthol-4-sulfonic acid. 2-naphthol is fully dissolved in NaOH aqueous solution which is added with dispersant and has the concentration of 5 to 10 percent into phenol sodium salt, and the weight of the added dispersant is 0.05 to 5 percent of that of 2- naphthol; 34 percent of concentrated hydrochloric acid is dripped into the solution, and the pH is controlled to be 6 to 7; 2-naphthol crystal particles are acid out; NaNO2 aqueous solution is added into 2-naphthol suspension, and the use amount of sodium nitrite is 50 to 55 percent of the weight of 2- naphthol; and then 34 percent of concentrated hydrochloric acid is added in, and the use amount of the concentrated hydrochloric acid is 65 to 75 percent of the weight of 2-naphthol; and nitrosation is carried out, the nitrosation temperature is 0 to 5DEG C, and the reaction time is 2 to 6h. By adding effective dispersant in a nitrosation stage, the preparation method of the 1-amino-2-naphthol-4-sulfonic acid can significantly improve the yield of the 1-amino-2-naphthol-4-sulfonic acid, has little addition of the dispersant, does not need to add extra equipment, reduces the cost of the 1-amino-2-naphthol-4-sulfonic acid, is easy for industrialization, and has very good economic benefit.
Description
Technical field
The invention belongs to the synthetic field of dyestuff intermediate, proposed a kind of 1-amino-2-naphthol-4-sulfonic acid preparation method especially.
Background technology
1-amino-2-naphthol-4-sulfonic acid is called for short 1,2 again, and 4-acid is important dyestuff intermediate, can be used for preparing acid mordant dye, acidic complex dye, neutral dye etc., also can be with performing an analysis phosphoric acid salt and calcium salt, and of many uses, the huge market demand.The technology that multiple preparation 1-amino-2-naphthol-4-sulfonic acid is arranged in the document, but processing condition and result are all inequality.Synthetic route is to carry out nitrosification, sulphite addition, acidic reduction transposition by beta naphthal and make 1-amino-2-naphthol-4-sulfonic acid preferably.Concrete report technology has: (1) obtains 1-Nitroso-2-naphthol with the beta naphthal nitrosification in alcoholic solvent (as ethanol), again with sodium bisulfite addition, sulfuric acid in reduction, sulfonation obtains 1-amino-2-naphthol-4-sulfonic acid, total recovery 74%, solvent recyclable 85%.This process solvent cost is higher, and the recovery solvent also relatively consumes energy, equipment complexity (Chinese patent CN101092380); (2) in Virahol, the beta naphthal nitrosification is obtained 1-Nitroso-2-naphthol, again with Sodium Pyrosulfite addition, sulfuric acid in reduction, sulfonation obtains 1-amino-2-naphthol-4-sulfonic acid, total recovery 72%.This technology exists solvent cost higher equally, and reclaims also relatively power consumption of solvent, equipment complexity, 1-amino-2-naphthol-4-sulfonic acid yield not too high (fine-chemical intermediate, 2003,33 (5): 25-27); (3) in Virahol, the nitrosification of 2-phenol is obtained 1-Nitroso-2-naphthol equally, does not filter nitrosifying intermediate, but directly with in sodium bisulfite addition, the sulfuric acid reduce, sulfonation obtains 1-amino-2-naphthol-4-sulfonic acid, total recovery 85.4%.Though this technology 1-amino-2-naphthol-4-sulfonic acid yield is higher, exists solvent cost higher equally, and the recovery solvent also relatively consumes energy, equipment complexity (German patent DE 3431695); (4) beta naphthal is ground to certain fineness in water-dispersant media after, nitrosification again, sodium bisulfite addition, acidic reduction obtain 1-amino-2-naphthol-4-sulfonic acid, yield 85% (U.S. Pat 4929752).Ball-grinding machine complexity, difficult amplification, big, the power consumption height of noise; (5) beta naphthal alkali is molten, acid out, nitrosification, with sodium bisulfite addition, sulfuric acid in reduction, sulfonation obtain 1-amino-2-naphthol-4-sulfonic acid, total recovery 68.4% (Institutes Of Technology Of Tianjin's journal, 2005,21 (3): 76-77).This process recovery ratio is not high.At present industrial also is the route that generally adopts similar this technology, and yield is also suitable therewith.
Summary of the invention
At using alcoholic solvent in the 1-amino-2-naphthol-4-sulfonic acid building-up process, being difficult for recovery, higher, the cost problem of higher of the inflammable and explosive danger of solvent, be difficult for industrialized problem at large-scale ball-grinding machine, and problem such as the 1-amino-2-naphthol-4-sulfonic acid yield is lower, the improved synthetic method of 1-amino-2-naphthol-4-sulfonic acid of the present invention does not adopt organic solvent, does not relate to the recovery of water-miscible organic solvent, does not adopt complicated ball-grinding machine, and the yield of 1-amino-2-naphthol-4-sulfonic acid is reached about 80%.Production technique is easy to industrializing implementation, and cost is lower.
By carrying out detailed analysis, can know that nitrosation reaction is very crucial reaction to carry out the technology that nitrosification, sulphite addition, acidic reduction transposition make 1-amino-2-naphthol-4-sulfonic acid by beta naphthal.When beta naphthal is carried out nitrosation reaction, if the beta naphthal solid particulate is bigger, be difficult for carrying out nitrosation reaction, nitrosation reaction is incomplete, can make the 1-amino-2-naphthol-4-sulfonic acid yield lower.In addition,, then be easy to be oxidized to the tar thing etc. of baroque by product such as black, can make the 1-amino-2-naphthol-4-sulfonic acid yield lower equally by nitrous acid if 2-phenol can not be very fast by nitrosification.
At above-mentioned analysis reason, the present invention mainly improves the nitrosation reaction process.It is as follows to take measures: when beta naphthal being carried out the buck dissolving, adding dispersion agent in reaction system, add acid then again in system, is that beta naphthal solid fine particle is separated out again with the acidifying of beta naphthal sodium.Owing to there is dispersion agent to exist, the beta naphthal particle of separating out is thin, even, is easy to carry out nitrosation reaction.Make the tar that nitrosation reaction speed is fast, side reaction generates less, when making 1-amino-2-naphthol-4-sulfonic acid through sulphite addition, acidic reduction transposition again, yield is higher.Reaction equation is as follows:
Technical scheme of the present invention is:
A kind of 1-amino-2-naphthol-4-sulfonic acid preparation method, improve the nitrosification technology that beta naphthal carries out in nitrosification, sulphite addition, the acidic reduction transposition technology:
1) be in the NaOH aqueous solution of 5-10% in the concentration that is added with dispersion agent, beta naphthal is dissolved as sodium phenolate fully, the interpolation weight of dispersion agent is the 0.05%-5% of beta naphthal weight;
2) in the solution of step 1), drip 34% concentrated hydrochloric acid, control pH=6-7; Acid out goes out the beta naphthal crystalline particle;
3) to step 2) beta naphthal suspension in add NaNO
2The aqueous solution, Sodium Nitrite consumption are the 50%-55% of beta naphthal weight; Add 34% concentrated hydrochloric acid again, the concentrated hydrochloric acid consumption is the 65%-75% of beta naphthal weight; Carry out nitrosation reaction, the nitrosation reaction temperature is at 0-5 ℃, 2-6 hour nitrosation reaction time.
Described dispersion agent is turkey red oil, sodium laurylsulfonate, tween 80 or Subwet 159.
Nitrosation reaction finishes, and directly adds Sodium Pyrosulfite and carry out addition in reaction system, filters, adds conventional process such as sulfuric acid, reduction transposition sulfonation again and obtain 1-amino-2-naphthol-4-sulfonic acid.
When the molten beta naphthal of alkali, buck concentration is at 5-10%; Added dispersion agent had turkey red oil, sodium laurylsulfonate, tween 80, Subwet 159 when alkali was molten.The interpolation weight of dispersion agent is the 0.05%-5% of beta naphthal weight.The concentrated hydrochloric acid interpolation is difficult for too much during acid out, and pH is that 6-7 is better with control.During nitrosation reaction, Sodium Nitrite is difficult for too much, and the Sodium Nitrite consumption is that the 50%-55% of beta naphthal weight is better.The concentrated hydrochloric acid that uses during nitrosation reaction (weight concentration 34%) consumption is the 65%-75% of beta naphthal weight.Better nitrosifying temperature of reaction is at 0-5 ℃, 2-6 hour nitrosation reaction time.
By the present invention, the mode of effective dispersion agent is added in employing in the nitrosification stage, the 1-amino-2-naphthol-4-sulfonic acid yield is obviously improved, the dispersion agent addition is less, do not need to add extra equipment, reduced the cost of 1-amino-2-naphthol-4-sulfonic acid, and be easy to industrialization, extraordinary economic benefit has been arranged.
Embodiment
Embodiment 1
Nitrosation reaction:
In the four-hole bottle of 1000mL, adding concentration is 7% NaOH aqueous solution 162g, adds dispersion agent turkey red oil 1.2g again, and stir about 20 minutes makes it to dissolve fully.Beta naphthal 36g (0.25mol) after adding folding hundred under the good stirring stirs 30min, makes beta naphthal be dissolved as sodium phenolate fully, cools to about 10 ℃ with ice-water bath.
Measure 34% the about 27g of concentrated hydrochloric acid, slowly be added dropwise to (about 20 minutes) in the four-hole bottle, make beta naphthal be fine particle and separate out, to obtain meticulous crystalline beta naphthal particle.Acid out terminal point pH=7, about 10 ℃ of temperature.
With the NaNO for preparing
2Solution (NaNO
218g and H
2The mixture of O 80mL) slowly adds in the above-mentioned solution, be cooled to 0-2 ℃ then.Measure 34% concentrated hydrochloric acid 24.5g, evenly be added dropwise to (about 1.5h adds) in the four-hole bottle lentamente under good the stirring, this process keeps 0-2 ℃ of temperature (ice-water bath).After dripping hydrochloric acid, keep 0-2 ℃ to continue to stir nitrosation reaction 4h, make remaining unreacted beta naphthal can finish nitrosification.
Addition reaction:
Under good the stirring, with NaOH solution above-mentioned nitrosification mixture is neutralized to pH=7, be warmed up to 25 ℃ then, add Na
2S
2O
563g and H
2The mixture of O 120mL, and stirring reaction 3h.Filter, get reddish-brown filtrate, keep and get single step reaction ready.Filter cake is a small amount of tar, discards.
Reduction reaction:
Above-mentioned filtrate is poured in the 1000mL four-hole bottle, add CuSO
45H
2O 0.3g, 35% sulfuric acid 105mL are warming up to 46 ℃ ± 1 ℃, reaction 12h.Be cooled to room temperature, filter 1-amino-2-naphthol-4-sulfonic acid product filter cake.Analyze 1-amino-2-naphthol-4-sulfonic acid yield 80.2% by diazotization titration.
Embodiment 2
Nitrosation reaction:
In the four-hole bottle of 1000mL, adding concentration is 5% NaOH aqueous solution 224g, adds dispersion agent turkey red oil 1.8g again, and stir about 20 minutes makes it to dissolve fully.Beta naphthal 36g (0.25mol) after adding folding hundred under the good stirring stirs 30min, makes beta naphthal be dissolved as sodium phenolate fully, cools to about 10 ℃ with ice-water bath.
Measure 34% the about 28g of concentrated hydrochloric acid, slowly be added dropwise to (about 20 minutes) in the four-hole bottle, make beta naphthal be fine particle and separate out, to obtain meticulous crystalline beta naphthal particle.Acid out terminal point pH=6, about 10 ℃ of temperature.
With the NaNO for preparing
2Solution (NaNO
219.8g and H
2The mixture of O 80mL) slowly adds in the above-mentioned solution, be cooled to 2-5 ℃ then.Measure 34% concentrated hydrochloric acid 27g, evenly be added dropwise to (about 1.5h adds) in the four-hole bottle lentamente under good the stirring, this process keeps 2-5 ℃ of temperature (ice-water bath).After dripping hydrochloric acid, keep 2-5 ℃ to continue to stir nitrosation reaction 2h, make remaining unreacted beta naphthal can finish nitrosification.
Addition reaction and reduction reaction are with embodiment 1, and the 1-amino-2-naphthol-4-sulfonic acid yield is 79.8%.
Embodiment 3
Nitrosation reaction:
In the four-hole bottle of 1000mL, adding concentration is 10% NaOH aqueous solution 112g, adds dispersion agent turkey red oil 0.018g again, and stir about 20 minutes makes it to dissolve fully.Beta naphthal 36g (0.25mol) after adding folding hundred under the good stirring stirs 30min, makes beta naphthal be dissolved as sodium phenolate fully, cools to about 10 ℃ with ice-water bath.
Measure 34% the about 28g of concentrated hydrochloric acid, slowly be added dropwise to (about 20 minutes) in the four-hole bottle, make beta naphthal be fine particle and separate out, to obtain meticulous crystalline beta naphthal particle.Acid out terminal point pH=6.5, about 10 ℃ of temperature.
With the NaNO for preparing
2Solution (NaNO
219.1g and H
2The mixture of O 80mL) slowly adds in the above-mentioned solution, be cooled to 0-2 ℃ then.Measure 34% concentrated hydrochloric acid 23.4g, evenly be added dropwise to (about 1.5h adds) in the four-hole bottle lentamente under good the stirring, this process keeps 0-2 ℃ of temperature (ice-water bath).After dripping hydrochloric acid, keep 0-2 ℃ to continue to stir nitrosation reaction 6h, make remaining unreacted beta naphthal can finish nitrosification.
Addition reaction and reduction reaction are with embodiment 1, and the 1-amino-2-naphthol-4-sulfonic acid yield is 81%.
Embodiment 4
Dispersion agent 1.2g turkey red oil among the embodiment 1 is replaced with the 0.6g tween 80, and other condition is constant, and the 1-amino-2-naphthol-4-sulfonic acid yield is 79.6%.
Embodiment 5
Dispersion agent 1.2g turkey red oil among the embodiment 1 is replaced with the 0.15g sodium laurylsulfonate, and other condition is constant, and the 1-amino-2-naphthol-4-sulfonic acid yield is 79.5%.
Embodiment 6
Dispersion agent 1.2g turkey red oil among the embodiment 1 is replaced with 0.3g Subwet 159, and other condition is constant, and the 1-amino-2-naphthol-4-sulfonic acid yield is 80.1%.
Claims (2)
1. an improved 1-amino-2-naphthol-4-sulfonic acid preparation method improves the nitrosification technology that beta naphthal carries out in nitrosification, sulphite addition, the acidic reduction transposition technology, it is characterized in that:
1) be in the NaOH aqueous solution of 5-10% in the concentration that is added with dispersion agent, beta naphthal is dissolved as sodium phenolate fully, the interpolation weight of dispersion agent is the 0.05%-5% of beta naphthal weight;
2) in the solution of step 1), drip 34% concentrated hydrochloric acid, control pH=6-7; Acid out goes out the beta naphthal crystalline particle;
3) to step 2) beta naphthal suspension in add NaNO
2The aqueous solution, Sodium Nitrite consumption are the 50%-55% of beta naphthal weight; Add 34% concentrated hydrochloric acid again, the concentrated hydrochloric acid consumption is the 65%-75% of beta naphthal weight; Carry out nitrosation reaction, the nitrosation reaction temperature is at 0-5 ℃, 2-6 hour nitrosation reaction time.
2. the method for claim 1 is characterized in that described dispersion agent is turkey red oil, sodium laurylsulfonate, tween 80 or Subwet 159.
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| CN 201010172800 CN101811998A (en) | 2010-05-17 | 2010-05-17 | Preparation method of 1-amino-2-naphthol-4-sulfonic acid |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102352007A (en) * | 2011-07-26 | 2012-02-15 | 浙江秦燕化工有限公司 | Method for preparing amino aryl sulfonic acid series high-molecular dispersant utilizing organic component in waste water from CLT acid production |
| CN104744320A (en) * | 2013-12-31 | 2015-07-01 | 天津市光复科技发展有限公司 | Preparation method of azomethine-H acid |
| CN104910052A (en) * | 2015-07-07 | 2015-09-16 | 金双蕾 | System for preparing 2-amidogen-1-naphthalene sulfonic acid |
| CN105017095A (en) * | 2015-07-07 | 2015-11-04 | 叶光明 | Method for preparing 2-amino-5-naphthol-7-sulfonic acid |
| CN105017094A (en) * | 2015-07-07 | 2015-11-04 | 金双蕾 | Method for preparing 2-amino-1-naphthalene sulfonic acid |
| CN105777588A (en) * | 2016-04-02 | 2016-07-20 | 田菱精细化工（大连）有限公司 | Method for preparing amino-naphthol-sulfonic acid through catalytic hydrogenation |
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|---|---|---|---|---|
| DE3431695A1 (en) * | 1984-08-29 | 1986-03-13 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING 1-AMINO-2-NAPHTOL-4-SULPHONIC ACID |
| US4929752A (en) * | 1986-09-23 | 1990-05-29 | Ciba-Geigy Corporation | Process for the preparation of 1-amine-2-naphthol-4-sulfonic acid |
| CN101092380A (en) * | 2007-07-11 | 2007-12-26 | 重庆大学 | Method for preparing 1,2,4 acid through synthesis in homogeneous phase between water and alcohol solvent |
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2010
- 2010-05-17 CN CN 201010172800 patent/CN101811998A/en active Pending
Patent Citations (3)
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|---|---|---|---|---|
| DE3431695A1 (en) * | 1984-08-29 | 1986-03-13 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING 1-AMINO-2-NAPHTOL-4-SULPHONIC ACID |
| US4929752A (en) * | 1986-09-23 | 1990-05-29 | Ciba-Geigy Corporation | Process for the preparation of 1-amine-2-naphthol-4-sulfonic acid |
| CN101092380A (en) * | 2007-07-11 | 2007-12-26 | 重庆大学 | Method for preparing 1,2,4 acid through synthesis in homogeneous phase between water and alcohol solvent |
Non-Patent Citations (2)
| Title |
|---|
| 《天津理工大学学报》 20050630 高素华等 染料中间体1-氨基-2-羟基-4-萘磺酸的催化合成研究 第21卷, 第3期 * |
| 《精细化工中间体》 20031031 苏琼等 1-氨基-2-萘酚-4-磺酸的合成工艺研究 第33卷, 第5期 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102352007A (en) * | 2011-07-26 | 2012-02-15 | 浙江秦燕化工有限公司 | Method for preparing amino aryl sulfonic acid series high-molecular dispersant utilizing organic component in waste water from CLT acid production |
| CN102352007B (en) * | 2011-07-26 | 2012-09-05 | 浙江秦燕化工有限公司 | Method for preparing amino aryl sulfonic acid series high-molecular dispersant utilizing organic component in waste water from CLT acid production |
| CN104744320A (en) * | 2013-12-31 | 2015-07-01 | 天津市光复科技发展有限公司 | Preparation method of azomethine-H acid |
| CN104910052A (en) * | 2015-07-07 | 2015-09-16 | 金双蕾 | System for preparing 2-amidogen-1-naphthalene sulfonic acid |
| CN105017095A (en) * | 2015-07-07 | 2015-11-04 | 叶光明 | Method for preparing 2-amino-5-naphthol-7-sulfonic acid |
| CN105017094A (en) * | 2015-07-07 | 2015-11-04 | 金双蕾 | Method for preparing 2-amino-1-naphthalene sulfonic acid |
| CN105017094B (en) * | 2015-07-07 | 2016-08-31 | 温州泓呈祥科技有限公司 | A kind of method preparing 2-amino-1-naphthalene sulfonic aicd |
| CN104910052B (en) * | 2015-07-07 | 2017-01-11 | 金华知产婺源信息技术有限公司 | System for preparing 2-amidogen-1-naphthalene sulfonic acid |
| CN105777588A (en) * | 2016-04-02 | 2016-07-20 | 田菱精细化工（大连）有限公司 | Method for preparing amino-naphthol-sulfonic acid through catalytic hydrogenation |
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Application publication date: 20100825 |