CN104003892A - Catalytic hydrogenation preparation method of 3,5-diaminobenzoic acid - Google Patents
Catalytic hydrogenation preparation method of 3,5-diaminobenzoic acid Download PDFInfo
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- CN104003892A CN104003892A CN201410262664.5A CN201410262664A CN104003892A CN 104003892 A CN104003892 A CN 104003892A CN 201410262664 A CN201410262664 A CN 201410262664A CN 104003892 A CN104003892 A CN 104003892A
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Abstract
The invention relates to the technical field of organic synthetic chemistry, in particular to a catalytic hydrogenation preparation method of 3,5-diaminobenzoic acid. According to the catalytic hydrogenation preparation method of the 3,5-diaminobenzoic acid, the 3,5-diaminobenzoic acid is prepared through an environment protecting process catalytic hydrogenation technology, the process can reduce three wastes, using of toxic hydrazine hydrate is avoided, energy consumption is reduced, the most important is that the automatic production can be adopted, the yield of the product can reach more than 95%, the product is a white to off-white solid body, the purity reaches more than 99%, and the application prospect of the product is improved to the maximum extent.
Description
Technical field
The present invention relates to the technical field of Synthetic Organic Chemistry, be specifically related to a kind of shortening preparation method of 3,5-diaminobenzoic acid.
Background technology
3; 5-diaminobenzoic acid is the important monomer of type material Kapton; Kapton is the high temperature resistant novel high polymer material of a class excellent combination property; be widely used in the fields such as high-temperaure coating, insulated wire, semiconductor protection layer, flexible printed circuit board, solar components; with 3; 5-diaminobenzoic acid be the synthetic tough and tensile transparent Kapton of monomer in keeping original polyimide excellent properties, can effectively improve film and other materials and carry out a high-intensity difficult problem of firmly cohering.
In addition 3,5-diaminobenzoic acid or important dyestuff, medicine intermediate, can derive a series of Yellow active dyes by it, both having can be used as deep yellow dyestuff uses, also can be used as the yellow color component of black dyes, wherein reactive orange 6R is one of three primary colors of many reactive black, is the important kind of the high-grade reactive dyestuffs of current national encourage growth.At field of medicaments, 3,5-diaminobenzoic acid is mainly used in synthesizing for cardiovascular and cerebrovascular diseases and diagnosis of urinary diseases contrast medium---Urogranoic acid; Can also wide, the inexpensive efficient sulfa drugs of synthetic antimicrobial spectrum.
In recent years along with novel material and the high-end fine chemicals market requirement constantly increase, 3,5-diaminobenzoic acid shows good market outlook, and current domestic 3,5-diaminobenzoic acid is produced synthetic the obtaining of main employing iron powder reducing, this route one is that environmental pollution is serious, and a large amount of iron mud that building-up process produces and " waste water " are difficult to administer; The 2nd, product color and second-rate, is difficult to meet type material, medicine and high-grade production requirement of dying pigment.
At present domestic and international 3,5-diaminobenzoic acid industrialized route mainly contains following three according to reductive agent difference, and the one, iron powder reducing method; The 2nd, hydrazine hydrate reduction method; The 3rd, shortening method.Because hydrazine hydrate reduction exists certain potential safety hazard, shortening synthesis technique difficulty is larger, and domestic industryization is produced and mainly adopted iron powder reducing route at present.
Iron powder reducing production process produces the waste residues such as a large amount of iron mud, produce a considerable amount of waste water simultaneously, in waste water, contain a large amount of amino substances, not only cause environmental pollution, and need to expend a large amount of labor forces, production environment is severe, level of automation is poor, and main is in product, easily to contain the impurity such as iron ion, cannot meet electronics material and medical Production requirement, and yield is not high, only in 90% left and right.
Hydrazine hydrate reduction is compared with iron powder reducing, although avoided iron mud to produce, wastewater flow rate also reduces, and its reduction is usually accompanied by other side chain reduction, and quality product is difficult to control; Higher and the hydrazine hydrate of the hydrazine hydrate concentration that simultaneously needs must be excessive, catalyzer is selected and preparation exists certain difficulty, all there is certain potential safety hazard in the accumulating of high density hydration hydrazine, generating the risk that also has blast in application, there is the not bad shortcoming of high product color and luster of yield simultaneously in hydrazine hydrate simultaneously equally.
Summary of the invention
In order to address the above problem, the present invention proposes the shortening preparation method of 3,5-diaminobenzoic acid, that a kind of environmental protection technique shortening technology prepares 3,5-diaminobenzoic acid, this technique had both reduced the three wastes, avoided using the hydrazine hydrate of hypertoxicity, reduce energy consumption, topmostly can adopt automatic production, and the yield of product can reach more than 95%, product is that white is to off-white color solid, purity more than 99%, has improved the application prospect of product to a great extent.
In order to reach foregoing invention object, the present invention proposes following scheme:
3,5-dinitrobenzoic acid is mixed with its aqueous solution with the sodium hydroxide of molar equivalent such as grade, the water of 5 times of quality, make under Pd/C catalysis again control hydrogen pressure 3-4MPa when hydrogenation, hydrogenation temperature 50-60 degree by oneself in 1% quality, react to pressure not step-down substantially, after membrane filtration recovery catalyzer (directly applying mechanically), then be acidified to pH value to 4-4.5, after suction filtration is dry, obtain white to off-white color solid, yield reaches more than 95%, and purity (HPLC) is more than 99%; Chemical equation is as follows:
In the present invention, catalyzer can be the one in Pd/C, Pd/Al2O3, Ru/C, Pt/C, active nano nickel, and it is good that the present invention requires Pd/C.
In the present invention, the consumption quality of aqueous solvent can be between 2 times-20 times of 3,5-dinitrobenzoic acid, and the present invention requires 5 times for good
Hydrogen pressure in the present invention when hydrogenation can be between 0.5-8MPa, and it is good that the present invention requires 3-4MPa.
In the present invention, the temperature of hydrogenation can be between 20-120, and it is good that the present invention requires 50-60.
Advantage of the present invention is that a kind of environmental protection technique shortening technology prepares 3,5-diaminobenzoic acid, this technique had both reduced the three wastes, the hydrazine hydrate of avoiding using hypertoxicity, has reduced energy consumption, topmostly can adopt automatic production, and the yield of product can reach more than 95%, product is white to off-white color solid, and purity more than 99%, has improved the application prospect of product to a great extent.3,5-dinitrobenzoic acid and sodium hydroxide are mixed with the aqueous solution of its sodium salt, then under Pd/C catalysis, Hydrogenation, for 3,5-diaminobenzoic acid, wherein utilizes membrane filtration recovery catalyzer.
Embodiment
Example one:
In 1L autoclave, add 50 grams of 3,5-dinitrobenzoic acids, 9.4 grams, 200 grams water of sodium hydroxide, after stirring, add again 0.5 gram of self-control Pd/C, after nitrogen replacement 3 times, control hydrogen pressure 3-4MPa, 50-60 degree, react to pressure not step-down substantially, membrane filtration reclaims after catalyzer, then with hcl acidifying to pH value to 4-4.5, after suction filtration is dry, obtain 34 grams of off-white color solids, yield reaches more than 95.1%, purity (HPLC) 99.3%.
Example two:
In 1L autoclave, add 100 grams of 3,5-dinitrobenzoic acids, 18.8 grams, 500 grams water of sodium hydroxide, after stirring, add again 1 gram of self-control Pd/C, after nitrogen replacement 3 times, control hydrogen pressure 3-4MPa, 50-60 degree, react to pressure not step-down substantially, membrane filtration reclaims after catalyzer, then with hcl acidifying to pH value to 4-4.5, after suction filtration is dry, obtain 68.5 grams of off-white color solids, yield reaches more than 95.5%, purity (HPLC) 99.3%.
Example three:
In 1L autoclave, add 120 grams of 3,5-dinitrobenzoic acids, 22.5 grams, 600 grams water of sodium hydroxide, after stirring, add again 1.2 grams of self-control Pd/C, after nitrogen replacement 3 times, control hydrogen pressure 3-4MPa, 50-60 degree, react to pressure not step-down substantially, membrane filtration reclaims after catalyzer, then with hcl acidifying to pH value to 4-4.5, after suction filtration is dry, obtain 82.4 grams of off-white color solids, yield reaches more than 95.8%, purity (HPLC) 99.4%.
Example four:
In 1L autoclave, add 3,150 grams of 5-dinitrobenzoic acids, 28.3 grams, 750 grams water of sodium hydroxide, after stirring, add again 1.5 grams of self-control Pd/C, after nitrogen replacement 3 times, control hydrogen pressure 3-4MPa, 50-60 degree, react to pressure not step-down substantially, membrane filtration reclaims after catalyzer and (reclaims catalyzer cover for example five), then with hcl acidifying to pH value to 4-4.5, after suction filtration is dry, obtain 103.4 grams of off-white color solids, yield reaches more than 96.2%, purity (HPLC) 99.2%.
Example five:
In 1L autoclave, add 3,150 grams of 5-dinitrobenzoic acids, 28.3 grams, 750 grams water of sodium hydroxide, after stirring, add again example four to reclaim catalyzer, after nitrogen replacement 3 times, control hydrogen pressure 3-4MPa, 50-60 degree, react to pressure not step-down substantially, membrane filtration reclaims after catalyzer and (reclaims catalyzer cover for example five), then with hcl acidifying to pH value to 4-4.5, after suction filtration is dry, obtain 103.1 grams of off-white color solids, yield reaches more than 96.1%, purity (HPLC) 99.5%.
Claims (6)
- The shortening preparation method of 1.3,5-diaminobenzoic acid, is characterized in that 3,5-dinitrobenzoic acid and sodium hydroxide, water are mixed with its aqueous solution, then under catalyst, control hydrogen pressure and hydrogenation temperature when hydrogenation, react to pressure not step-down substantially, membrane filtration reclaims after catalyzer, then is acidified to pH value to 4-4.5, after suction filtration is dry, obtains white to off-white color solid, just obtain 3,5-diaminobenzoic acid, yield reaches more than 95%, and purity HPLC is more than 99%; Its chemical equation: .
- 2. according to claim 13, the shortening preparation method of 5-diaminobenzoic acid, is characterized in that the amount of sodium hydroxide in described obtained aqueous solution is the molar equivalents such as 3,5-dinitrobenzoic acid.
- 3. according to claim 13, the shortening preparation method of 5-diaminobenzoic acid, the consumption quality that it is characterized in that described aqueous solvent can be that between 2 times-20 times of 3,5-dinitrobenzoic acid, the present invention requires 5 times for good.
- 4. according to claim 13, the shortening preparation method of 5-diaminobenzoic acid, is characterized in that described catalyzer can be the one in Pd/C, Pd/Al2O3, Ru/C, Pt/C, active nano nickel, and it is good that the present invention requires Pd/C.
- 5. according to claim 13, the shortening preparation method of 5-diaminobenzoic acid, is characterized in that described hydrogen pressure can be between 0.5-8MPa, and it is good that the present invention requires 3-4MPa.
- 6. according to claim 13, the shortening preparation method of 5-diaminobenzoic acid, is characterized in that the temperature of described hydrogenation can be between 20-120, and it is good that the present invention requires 50-60.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104326928A (en) * | 2014-11-18 | 2015-02-04 | 江苏恒祥化工有限责任公司 | Method for preparing 4-aminobenzoic acid by catalytic hydrogenation |
| CN105949076A (en) * | 2016-05-10 | 2016-09-21 | 上虞盛晖化工股份有限公司 | Preparation method of 3,5-diaminobenzoic acid |
| CN106995382A (en) * | 2016-01-25 | 2017-08-01 | 济南和润化工科技有限公司 | A kind of method of catalytic hydrogenation production 3- methyl-PABA |
| CN113563213A (en) * | 2021-08-30 | 2021-10-29 | 淄博晟亿弘新材料科技有限公司 | Preparation method of 3, 5-diaminobenzoic acid |
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| CN101362705A (en) * | 2008-09-27 | 2009-02-11 | 丽源（内蒙古）科技有限公司 | 3,5-diaminobenzoic acid preparation method |
| CN102249942A (en) * | 2011-05-20 | 2011-11-23 | 山东富原化工有限公司 | Method for synthesizing 3,5-diamido benzoic acid by industrial continuous hydrogenation |
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2014
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Patent Citations (3)
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| CN101092367A (en) * | 2007-07-20 | 2007-12-26 | 王研 | Method for preparing 4,6 diamino resorcin, and its hydrochlorate |
| CN101362705A (en) * | 2008-09-27 | 2009-02-11 | 丽源（内蒙古）科技有限公司 | 3,5-diaminobenzoic acid preparation method |
| CN102249942A (en) * | 2011-05-20 | 2011-11-23 | 山东富原化工有限公司 | Method for synthesizing 3,5-diamido benzoic acid by industrial continuous hydrogenation |
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| 张志达: "3,5-二氨基苯甲酸的合成及其在染料中的应用", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》, no. 2, 15 December 2011 (2011-12-15), pages 18 - 6 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104326928A (en) * | 2014-11-18 | 2015-02-04 | 江苏恒祥化工有限责任公司 | Method for preparing 4-aminobenzoic acid by catalytic hydrogenation |
| CN106995382A (en) * | 2016-01-25 | 2017-08-01 | 济南和润化工科技有限公司 | A kind of method of catalytic hydrogenation production 3- methyl-PABA |
| CN105949076A (en) * | 2016-05-10 | 2016-09-21 | 上虞盛晖化工股份有限公司 | Preparation method of 3,5-diaminobenzoic acid |
| CN105949076B (en) * | 2016-05-10 | 2018-01-23 | 浙江今晖新材料股份有限公司 | A kind of preparation method of 3,5 diaminobenzoic acid |
| CN113563213A (en) * | 2021-08-30 | 2021-10-29 | 淄博晟亿弘新材料科技有限公司 | Preparation method of 3, 5-diaminobenzoic acid |
| CN113563213B (en) * | 2021-08-30 | 2024-03-22 | 淄博晟亿弘新材料科技有限公司 | Preparation method of 3, 5-diaminobenzoic acid |
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Application publication date: 20140827 |