CN102408362A - Method for producing 2-amino-4-methyl-5-chlorobenzenesulfonic acid (CLT acid) by reducing 6-chloro-3-aminotoluene-4-sulfonic acid - Google Patents
Method for producing 2-amino-4-methyl-5-chlorobenzenesulfonic acid (CLT acid) by reducing 6-chloro-3-aminotoluene-4-sulfonic acid Download PDFInfo
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- CN102408362A CN102408362A CN2011104390614A CN201110439061A CN102408362A CN 102408362 A CN102408362 A CN 102408362A CN 2011104390614 A CN2011104390614 A CN 2011104390614A CN 201110439061 A CN201110439061 A CN 201110439061A CN 102408362 A CN102408362 A CN 102408362A
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Abstract
The invention provides a method for producing 2-amino-4-methyl-5-chlorobenzenesulfonic acid (CLT acid) by reducing 6-chloro-3-aminotoluene-4-sulfonic acid, relates to a chemical synthesis method and in particular relates to the technical field of synthesis of pigment intermediates. A Pd/C catalyst is selected for a reaction and can be recycled, the demand of the Pd/C catalyst on the purity of 6-chloro-3-aminotoluene-4-sulfonic acid is low; and the reaction process of the method is mild, the reaction pressure is low, the reaction temperature is low, no solvent is used in the reaction process of the materials, the hydrogenation reduction process can be easily controlled and the yield is up to 96.3%.
Description
Technical field
The present invention relates to chemical synthesis process, particularly the synthesis technical field of Pigment Intermediates.
Background technology
CLT acid has another name called 6-chloro-3-phenylmethylamine-4-sulfonic acid, is mainly used in to make bright red color lake C, Lithol Red 2G, is widely used in preparation printing ink etc.This Pigment Intermediates is mainly used in the manufacturing bronze red C, the bright red isochrome variable pigments of bright red LG of rubber and plastics.
Existing from raw material 6-chloro-3-nitrotoluene-4-sulfonic acid reduction preparation 6-chloro-3-phenylmethylamine-4-sulfonic acid (CLT acid), three kinds of methods are arranged:
Method one: make catalyzer in order to platinum/carbon, the liquid-phase hydrogenatin reduction exists reaction process too fast, is difficult for grasping, and causes industrial accident easily.And the difficult collection fully of reaction back platinum/carbon, price comparison is high, has increased production cost, and this method generally is used for the laboratory.
Method two: with nickel as catalyzer; The process of hydrogenating reduction to the requirement of material purity than higher; Because nickel catalyzator is very easily destroyed by raw material impurity wherein, and reaction process need accomplish under the highly compressed situation, and reaction pressure reaches 4.0～4.3Mpa; Also high to equipment requirements, be not suitable for the industriallization continuous production.
Method three: as catalyzer, the production process of China CLT acid at present mainly is to take this method with iron powder.Though iron powder reducing is less demanding to material purity, product yield and purity are not high yet, in reaction process, need a large amount of iron powders to participate in reaction, and the reaction back produces a large amount of mud and sewage, are difficult for handling, and have problem of environmental pollution.
Summary of the invention
Goal of the invention is to propose a kind of method that is beneficial to industriallization continuous production, oligosaprobic reduction 6-chloro-3-phenylmethylamine-4-sulfonic acid production CLT acid.
Technical scheme of the present invention is: under oxygen free condition; Pa/C catalyzer, amine promotor, 6-chloro-3-nitrotoluene-4-sulfonic acid are dropped into reaction kettle; Under the 0.8Mpa pressure condition, stir, and slowly be warmed up to 70～75 ℃, feed hydrogen; Be to react 3.5～4 hours under the condition of 1.8～2.0Mpa at reacting kettle inner pressure, temperature of reaction is controlled at 85～90 ℃; After reaction finishes, treat that material is cooled to 30～40 ℃ naturally after, blowing; Again through after the press filtration, acid out, drying, dry product.
In addition, the Pa content of Pa/C catalyzer according to the invention is 5%, and when feeding intake, the mass ratio of said Pa/C catalyzer, amine promotor and 6-chloro-3-nitrotoluene-4-sulfonic acid is 1 ︰, 8 ︰ 1500.
The present invention chooses palladium-carbon catalyst (Pa/C) and participates in reaction, can recycle.The Pa/C catalyzer is not high to the purity requirement of raw material 6-chloro-3-nitrotoluene-4-sulfonic acid; Reaction process of the present invention is gentle, and reaction pressure is low, and temperature of reaction is low, and the material reaction process is easy to the control in the hydrogenating reduction process without solvent, and yield is up to 96.3%.
Embodiment
One, CLT acid industriallization reaction process:
5%Pa/C catalyzer, amine promotor, 6-chloro-3-nitrotoluene-4-sulfonic acid are dropped into reaction kettle according to mass ratio 1:8:1500.
Closed reactor goes out air with 0.3MPa nitrogen is twice replaced, go out nitrogen with the 0.5MPa hydrogen exchange again after, with the hydrogen pressurize of 0.8Mpa, confirm that reactor drum do not reveal.
After definite reactor drum is not revealed, open stirring, slowly be warmed up to 70～75 ℃; Open the hydrogen feed valve, adjust hydrogen pressure at 1.8～2.0Mpa, sustained reaction 3.5～4 hours; Temperature of reaction is controlled at 85～90 ℃, reacts not heat release and lowers the temperature naturally and be reaction end.
After reaction finishes, material is cooled to 30～40 ℃, through after the press filtration, through acid out, dry after, dry product, yield is up to 96.3%.
Two, product performance:
Outward appearance: white or blush pressed powder
Content: (total amino value): >=98.0
Moisture :≤1.0%
Ash content :≤1.0%
Dissolving situation in ammoniacal liquor: limpid be clear to almost limpid transparent.
Claims (2)
1. one kind is reduced 6-chloro-3-phenylmethylamine-4-sulfonic acid and produces the method for CLT acid; It is characterized in that: under oxygen free condition, Pa/C catalyzer, amine promotor, 6-chloro-3-nitrotoluene-4-sulfonic acid are dropped into reaction kettle, under the 0.8Mpa pressure condition, stir; And slowly be warmed up to 70～75 ℃; Feeding hydrogen, is to react 3.5～4 hours under the condition of 1.8～2.0Mpa at reacting kettle inner pressure, and temperature of reaction is controlled at 85～90 ℃; After reaction finishes, treat that material is cooled to 30～40 ℃ naturally after, blowing; Again through after the press filtration, acid out, drying, dry product.
2. ask reduction 6-chloro-3-phenylmethylamine-4-sulfonic acid to produce the method for CLT acid according to claim 1; The Pa content that it is characterized in that said Pa/C catalyzer is 5%; When feeding intake, the mass ratio of said Pa/C catalyzer, amine promotor and 6-chloro-3-nitrotoluene-4-sulfonic acid is 1 ︰, 8 ︰ 1500.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011104390614A CN102408362A (en) | 2011-12-26 | 2011-12-26 | Method for producing 2-amino-4-methyl-5-chlorobenzenesulfonic acid (CLT acid) by reducing 6-chloro-3-aminotoluene-4-sulfonic acid |
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| CN2011104390614A CN102408362A (en) | 2011-12-26 | 2011-12-26 | Method for producing 2-amino-4-methyl-5-chlorobenzenesulfonic acid (CLT acid) by reducing 6-chloro-3-aminotoluene-4-sulfonic acid |
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| CN102408362A true CN102408362A (en) | 2012-04-11 |
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| CN2011104390614A Pending CN102408362A (en) | 2011-12-26 | 2011-12-26 | Method for producing 2-amino-4-methyl-5-chlorobenzenesulfonic acid (CLT acid) by reducing 6-chloro-3-aminotoluene-4-sulfonic acid |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675162A (en) * | 2012-05-09 | 2012-09-19 | 辽宁大学 | Method for synthesizing CLT acid |
| CN102702042A (en) * | 2012-05-18 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Method for preparing CLT acid by using liquid-phase 6-chloro-3-nitrotoluene-4-sulfonic acid (CLT) in continuous hydrogenation reduction process |
| CN102702043A (en) * | 2012-05-18 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Method for preparing CLT acid (6-chloro-3-nitrotoluene-4-sulfonic acid) by continuous hydrogenation reduction of 6-chloro-3-nitrotoluene-4-sulfonicacid liquid phase |
| CN104402774A (en) * | 2014-11-21 | 2015-03-11 | 浙江秦燕化工有限公司 | Method for preparing CLT acid through continuous catalytic hydrogenation reduction |
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| JPS54151945A (en) * | 1978-05-18 | 1979-11-29 | Hodogaya Chem Co Ltd | Preparation of 6-chloro-3-toluidine-4-sulfonic acid |
| CN101811973A (en) * | 2010-04-23 | 2010-08-25 | 浙江工业大学 | Method for synthesizing halogen aromatic amines by high-selectivity liquid phase hydrogenation under the condition of no solvent |
| CN101906057A (en) * | 2010-08-06 | 2010-12-08 | 延边大学 | Method for preparing CLT acid (6-chloro-3-aminotoluene-4-sulfoacid) by utilizing o-chlorotoluene direct nitrification method |
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2011
- 2011-12-26 CN CN2011104390614A patent/CN102408362A/en active Pending
Patent Citations (3)
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| JPS54151945A (en) * | 1978-05-18 | 1979-11-29 | Hodogaya Chem Co Ltd | Preparation of 6-chloro-3-toluidine-4-sulfonic acid |
| CN101811973A (en) * | 2010-04-23 | 2010-08-25 | 浙江工业大学 | Method for synthesizing halogen aromatic amines by high-selectivity liquid phase hydrogenation under the condition of no solvent |
| CN101906057A (en) * | 2010-08-06 | 2010-12-08 | 延边大学 | Method for preparing CLT acid (6-chloro-3-aminotoluene-4-sulfoacid) by utilizing o-chlorotoluene direct nitrification method |
Non-Patent Citations (4)
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| 《化工时刊》 20040131 贾志刚等 "液相催化加氢法制取芳胺的研究进展" 第2页, 1.1 1-2 第18卷, 第1期 * |
| 《化工科技》 19980331 白彦兵 "6-氯-3-硝基甲苯-4-磺酸液相加氢制备CLT酸的研究" 第35-39页 1-2 第6卷, 第3期 * |
| 白彦兵: ""6-氯-3-硝基甲苯-4-磺酸液相加氢制备CLT酸的研究"", 《化工科技》, vol. 6, no. 3, 31 March 1998 (1998-03-31), pages 35 - 39 * |
| 贾志刚等: ""液相催化加氢法制取芳胺的研究进展"", 《化工时刊》, vol. 18, no. 1, 31 January 2004 (2004-01-31) * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675162A (en) * | 2012-05-09 | 2012-09-19 | 辽宁大学 | Method for synthesizing CLT acid |
| CN102675162B (en) * | 2012-05-09 | 2014-03-26 | 辽宁大学 | Method for synthesizing CLT acid |
| CN102702042A (en) * | 2012-05-18 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Method for preparing CLT acid by using liquid-phase 6-chloro-3-nitrotoluene-4-sulfonic acid (CLT) in continuous hydrogenation reduction process |
| CN102702043A (en) * | 2012-05-18 | 2012-10-03 | 中国科学院宁波材料技术与工程研究所 | Method for preparing CLT acid (6-chloro-3-nitrotoluene-4-sulfonic acid) by continuous hydrogenation reduction of 6-chloro-3-nitrotoluene-4-sulfonicacid liquid phase |
| CN102702043B (en) * | 2012-05-18 | 2015-04-29 | 中国科学院宁波材料技术与工程研究所 | Method for preparing CLT acid (6-chloro-3-nitrotoluene-4-sulfonic acid) by continuous hydrogenation reduction of 6-chloro-3-nitrotoluene-4-sulfonicacid liquid phase |
| CN102702042B (en) * | 2012-05-18 | 2015-04-29 | 中国科学院宁波材料技术与工程研究所 | Method for preparing CLT acid by using liquid-phase 6-chloro-3-nitrotoluene-4-sulfonic acid (CLT) in continuous hydrogenation reduction process |
| CN104402774A (en) * | 2014-11-21 | 2015-03-11 | 浙江秦燕化工有限公司 | Method for preparing CLT acid through continuous catalytic hydrogenation reduction |
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Application publication date: 20120411 |