CN109336825B - Method for improving quality of 5-aminobenzimidazole ketone - Google Patents
Method for improving quality of 5-aminobenzimidazole ketone Download PDFInfo
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- CN109336825B CN109336825B CN201811405311.0A CN201811405311A CN109336825B CN 109336825 B CN109336825 B CN 109336825B CN 201811405311 A CN201811405311 A CN 201811405311A CN 109336825 B CN109336825 B CN 109336825B
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- mother liquor
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- ketone
- sulfurous acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D235/26—Oxygen atoms
Abstract
The invention relates to a method for improving the quality of 5-aminobenzimidazole ketone, which comprises the steps of after the reduction of 5-nitro-benzimidazole ketone and iron powder in a reduction kettle is finished, adding alkali, adding a catalyst, filtering iron mud, cooling, adding the sulfurous acid amount required by the next batch into a mother liquor tank, then starting material pressing, leaving the required product 5-aminobenzimidazole ketone in a plate frame, and mixing the mother liquor with sulfurous acid added in advance in the mother liquor tank. The material becomes more stable and easier to store, the stability of the 5-aminobenzimidazole ketone in the mother liquor is improved, the possibility of oxidation of the 5-aminobenzimidazole ketone is further reduced, the mother liquor application batch is further improved, and the production cost is reduced; the catalyst is added, so that the purity of the 5-ABI is further improved, the purity of the 5-ABI reaches more than 99.05 percent, the yield reaches more than 91.20 percent, the mother liquor is prolonged from the original application of 50 batches to 80 batches, and the purity of the 5-ABI is kept at more than 99.00 percent after the application of 80 batches.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for improving the quality of 5-aminobenzimidazole ketone.
Background
5-aminobenzimidazole ketone (5-ABI) is an important intermediate for synthesizing benzimidazolone pigment, and the benzimidazolone pigment is an azo high-grade organic pigment with wide application. The molecular chemical structure of the high-grade organic pigment is mostly heterocyclic derivatives, the main structure of the benzimidazolone is azo, the main structure of the benzimidazolone has better molecular planarity and molecular symmetry, and intramolecular and intermolecular hydrogen bonds can be formed, or a metal complex is formed, or the relative molecular mass is increased, so that the performance of the pigment is improved. The existing 5-ABI production technology has the problems of high production cost, high danger, low product purity and yield and the like.
Disclosure of Invention
The invention aims to provide a method for improving the quality of 5-aminobenzimidazole ketone.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for improving the quality of 5-aminobenzimidazole ketone comprises the following steps:
1) putting 5-nitro-benzimidazolone, iron powder and inorganic acid into a reaction kettle according to the mass ratio of 1:0.9-1.1:0.3-0.35 for reaction;
2) preheating a plate frame after the reaction is finished, adjusting the pH value of a reaction solution to 7.5-9.5, adding a catalyst into a crystallization kettle, and filtering iron mud by using a membrane plate-and-frame filter press after the reaction is finished;
3) when the iron mud is filtered, cooling and crystallizing the feed liquid in a crystallization kettle, adding acid required by next reduction into a mother liquid tank, and when the temperature is reduced to 35-55 ℃, pressing and separating the material and the mother liquid;
4) the separated mother liquor enters a mother liquor tank to be mixed with the sulfurous acid added before for the reduction of the next batch.
Specifically, the inorganic acid in the step 1) is sulfurous acid.
Specifically, the adding mode of the sulfurous acid in the step 1) is to introduce sulfur dioxide gas.
Specifically, the reaction temperature in the step 1) is 95-100 ℃, and the reaction time is 2-4 h.
Specifically, the substance used for adjusting the pH value in the step 2) is sodium hydroxide or sodium carbonate.
Specifically, the catalyst in the step 2) is hydrazine or sodium hydrosulfite, and the mass ratio of the catalyst to the 5-nitro-benzimidazolone is 0.0041-0.0050: 1.
the invention has the following beneficial effects: according to the invention, by utilizing the principle that sulfurous acid and 5-aminobenzimidazole ketone react to form ammonium salt, the residual materials in the mother liquor are not easy to be oxidized and deteriorated, the application frequency of production is increased, and the discharge amount of sewage is reduced; sulfur dioxide gas is introduced to react with water to generate sulfurous acid, sodium bisulfite generated by the reaction of sulfurous acid and liquid alkali plays a role of an antioxidant, and the antioxidant does not need to be added independently, so that the production cost is further reduced, and the salt and organic matters in the mother liquor are reduced, so that the process is more environment-friendly; the mother liquor enters a mother liquor tank to be mixed with the sulfurous acid added in advance; under the medium acidic condition, materials in the mother liquor and sulfurous acid form ammonium salt, the materials become more stable and easier to store, the stability of 5-aminobenzimidazole ketone in the mother liquor is improved, the possibility of oxidation of the 5-aminobenzimidazole ketone is further reduced, the mother liquor recycling batch is further improved, and the production cost is reduced; the catalyst is added, so that the purity of the 5-ABI is further improved, the purity of the 5-ABI reaches more than 99.05 percent, the yield reaches more than 91.20 percent, the mother liquor is prolonged from the original application of 50 batches to 80 batches, and the purity of the 5-ABI is kept at more than 99.00 percent after the application of 80 batches.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the scope of the present invention is not limited to these examples. All changes, modifications and equivalents that do not depart from the spirit of the invention are intended to be included within the scope thereof.
Example 1
A method for improving the quality of 5-aminobenzimidazole ketone comprises the following steps:
1) adding 5-nitro-benzimidazolone, iron powder and sulfurous acid into a reaction kettle according to the mass ratio of 1:1:0.32 to react at the temperature of 98 ℃ for 4 hours, wherein sulfur dioxide gas is introduced into the reaction kettle.
2) Preheating a plate frame after the reaction is finished, adjusting the pH value of a reaction solution to 8 by using sodium hydroxide, adding a hydrazine catalyst into a crystallization kettle, wherein the mass ratio of the catalyst to 5-nitro-benzimidazolone is 0.0043: and 1, filtering the iron mud by a membrane plate-and-frame filter press after finishing.
3) And when the iron mud is filtered, cooling and crystallizing the feed liquid in a crystallization kettle, adding acid required by the next reduction into the mother liquid tank, and when the temperature is reduced to 45 ℃, pressing and separating the material and the mother liquid.
4) The separated mother liquor enters a mother liquor tank to be mixed with the sulfurous acid added before for the reduction of the next batch.
The purity of the obtained 5-ABI is 99.05 percent, the yield is 91.20 percent, the mother liquor is prolonged from the original application of 50 batches to 80 batches, and the purity of the material 5-ABI can be kept above 99.00 percent.
Example 2
A method for improving the quality of 5-aminobenzimidazole ketone comprises the following steps:
1) adding 5-nitro-benzimidazolone, iron powder and sulfurous acid into a reaction kettle according to the mass ratio of 1:0.9:0.33 for reaction, wherein the reaction temperature is 100 ℃, the reaction time is 3 hours, and the adding mode of the sulfurous acid is that sulfur dioxide gas is introduced.
2) Preheating a plate frame after the reaction is finished, adjusting the pH of a reaction solution to 9.5 by using sodium carbonate, adding a catalyst sodium hydrosulfite into a crystallization kettle, wherein the mass ratio of the catalyst to the 5-nitro-benzimidazolone is 0.0047: and 1, filtering the iron mud by a membrane plate-and-frame filter press after finishing.
3) And when the iron mud is filtered, cooling and crystallizing the feed liquid in a crystallization kettle, adding acid required by the next reduction into the mother liquid tank, and when the temperature is reduced to 50 ℃, pressing and separating the material and the mother liquid.
4) The separated mother liquor enters a mother liquor tank to be mixed with the sulfurous acid added before for the reduction of the next batch.
The purity of the obtained 5-ABI is 99.13 percent, the yield is 91.35 percent, the mother liquor is prolonged from the original application of 50 batches to 80 batches, and the purity of the material 5-ABI can be kept above 99.10 percent.
Example 3
A method for improving the quality of 5-aminobenzimidazole ketone comprises the following steps:
1) adding 5-nitro-benzimidazolone, iron powder and sulfurous acid into a reaction kettle according to the mass ratio of 1:1.1:0.3 for reaction, wherein the reaction temperature is 95 ℃, the reaction time is 2 hours, and the adding mode of the sulfurous acid is that sulfur dioxide gas is introduced.
2) Preheating a plate frame after the reaction is finished, adjusting the pH of a reaction solution to 7.5 by using sodium carbonate, adding a hydrazine catalyst into a crystallization kettle, wherein the mass ratio of the catalyst to 5-nitro-benzimidazolone is 0.0041: and 1, filtering the iron mud by a membrane plate-and-frame filter press after finishing.
3) And (3) cooling and crystallizing the feed liquid in a crystallization kettle after the iron mud is filtered, adding acid required by the next reduction into the mother liquid tank, and pressing and separating the material and the mother liquid when the temperature is reduced to 55 ℃.
4) The separated mother liquor enters a mother liquor tank to be mixed with the sulfurous acid added before for the reduction of the next batch.
The purity of the obtained 5-ABI is 99.15 percent, the yield is 91.30 percent, the mother liquor is prolonged from the original application of 50 batches to 80 batches, and the purity of the material 5-ABI can be kept above 99.10 percent.
Example 4
A method for improving the quality of 5-aminobenzimidazole ketone comprises the following steps:
1) adding 5-nitro-benzimidazolone, iron powder and sulfurous acid into a reaction kettle according to the mass ratio of 1:1.05:0.35 to react at the reaction temperature of 97 ℃ for 3 hours, wherein sulfur dioxide gas is introduced into the reaction kettle.
2) Preheating a plate frame after the reaction is finished, adjusting the pH of a reaction solution to 9 by using sodium hydroxide, adding a catalyst sodium hydrosulfite into a crystallization kettle, wherein the mass ratio of the catalyst to the 5-nitro-benzimidazolone is 0.0050: and 1, filtering the iron mud by a membrane plate-and-frame filter press after finishing.
3) And when the iron mud is filtered, cooling and crystallizing the feed liquid in a crystallization kettle, adding acid required by the next reduction into the mother liquid tank, and when the temperature is reduced to 35 ℃, pressing and separating the material and the mother liquid.
4) The separated mother liquor enters a mother liquor tank to be mixed with the sulfurous acid added before for the reduction of the next batch.
The purity of the obtained 5-ABI is 99.08 percent, the yield is 91.28 percent, the mother liquor is prolonged from the original application of 50 batches to 80 batches, and the purity of the material 5-ABI can be kept above 99.05 percent.
Claims (3)
1. A method for improving the quality of 5-aminobenzimidazole ketone is characterized by comprising the following steps:
1) putting 5-nitro-benzimidazolone, iron powder and inorganic acid into a reaction kettle according to the mass ratio of 1:0.9-1.1:0.3-0.35 for reaction; the reaction temperature is 95-100 ℃, and the reaction time is 2-4 h; the inorganic acid is sulfurous acid, and the sulfurous acid is added in a mode of introducing sulfur dioxide gas;
2) preheating a plate frame after the reaction is finished, adjusting the pH value of a reaction solution to 7.5-9.5, adding a catalyst into a crystallization kettle, and filtering iron mud by using a membrane plate-and-frame filter press after the reaction is finished, wherein the catalyst is hydrazine or sodium hydrosulfite;
3) when the iron mud is filtered, cooling and crystallizing the feed liquid in a crystallization kettle, adding acid required by next reduction into a mother liquid tank, and when the temperature is reduced to 35-55 ℃, pressing and separating the material and the mother liquid;
4) the separated mother liquor enters a mother liquor tank to be mixed with the sulfurous acid added before for the reduction of the next batch.
2. The method for improving the quality of 5-aminobenzimidazole ketone according to claim 1, wherein the substance used for adjusting the pH in step 2) is sodium hydroxide or sodium carbonate.
3. The method for improving the quality of 5-aminobenzimidazole ketone according to claim 1, wherein the mass ratio of the catalyst to the 5-nitro-benzimidazole ketone in the step 2) is 0.0041 to 0.0050: 1.
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| CN109748877A (en) * | 2019-03-21 | 2019-05-14 | 济南大学 | A kind of preparation method of 5-acetoacetamido benzimidazolone |
| CN111057012A (en) * | 2019-12-11 | 2020-04-24 | 山东汇海医药化工有限公司 | Method for removing residual iron ions in AABI (anaerobic-anoxic-oxic) by using chelating agent |
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| CN101307023B (en) * | 2008-05-23 | 2010-09-22 | 东营市天正化工有限公司 | Production process of 5-acetyl acetamino benzimidazolone |
| CN104130194B (en) * | 2014-08-12 | 2016-08-31 | 南通醋酸化工股份有限公司 | A kind of synthetic method of 5-Amino-2-benzimidazolinone |
| CN106397331B (en) * | 2016-08-30 | 2019-03-19 | 山东汇海医药化工有限公司 | A kind of preparation method of 5-Amino-2-benzimidazolinone |
| CN106397332A (en) * | 2016-08-30 | 2017-02-15 | 山东汇海医药化工有限公司 | Method for treating 5-nitrobenzimidazolone mother liquor by reduction with iron powder |
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Denomination of invention: A method for improving the quality of 5-aminobenzimidazolone Effective date of registration: 20211130 Granted publication date: 20201215 Pledgee: Dongying Hekou District sub branch of China Post Savings Bank Co.,Ltd. Pledgor: SHANDONG HUIHAI PHARMACEUTICAL& CHEMICAL Co.,Ltd. Registration number: Y2021980013568 |