CN1903830A - Preparation method of 2-bromo-2-nitro-1,3-propylene glycol - Google Patents
Preparation method of 2-bromo-2-nitro-1,3-propylene glycol Download PDFInfo
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- CN1903830A CN1903830A CN 200610041200 CN200610041200A CN1903830A CN 1903830 A CN1903830 A CN 1903830A CN 200610041200 CN200610041200 CN 200610041200 CN 200610041200 A CN200610041200 A CN 200610041200A CN 1903830 A CN1903830 A CN 1903830A
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Abstract
The present invention relates to a preparation method of 2-bromo-2-nitro-1,3-propanediol. Said method includes the following steps: adding nitromethane, bromine and water into a reactor, slowly adding sodium hydroxide aqueous solution, stirring for 0.5-2hr, introducing chlorine gas, stirring to make reaction at 0-70deg.C to obtain nitrobromoform, then stirring the obtained nitrobromoform, formaldehyde and nitromethane for 0.5-2hr, slowly adding aqueous solution of inorganic alkali catalyst at 60deg.C, making reaction for 0.5-2hr at 0-60deg.C, cooling, crystallizing, filtering and drying so as to obtain 2-bromo-3-nitro-1,3-propanediol.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and relates to a preparation method of 2-bromo-2-nitro-1, 3-propanediol (bronopol).
Background
The molecular formula of the 2-bromo-2-nitro-1, 3-propanediol (bronopol) is C3H6BrNO4And the molecular weight is 200.0. The cotton seed treating agent is developed by Boot Co.Ltd (AgEvo GmbH) in 1964 to be used as a cosmetic preservative and a medicine, then is used as an agricultural bactericide, is developed by China in 1990 to be used as a rice seed treating agent for preventing and treating rice bakanae disease, can be used as a cotton seed treating agent for preventing and treating cotton black-arm disease or bacterial wilt disease caused by cabbage black-rot yellow-stalk disease, has special effect, and has no chemical injury to cotton. Can also be used as industrial sterilizationAgents, such as bactericides for cooling towers. The structural formula of the bronopol is as follows:
german patent DE1954173 and japanese patents JP2424.1982, JP70911.1974, JP72108.1973, etc. have related preparation methods, and the prior synthesis method for preparing bronopol refers to the preparation methods in the former patents, generally, nitromethane, formaldehyde and alkali are firstly condensed under ethanol as solvent, then brominated to obtain crude product, and the crude product is obtained through exsolution concentration, filtration, crystallization and drying. The method has the following defects:
1. if the raw material uses bromine as the brominating agent, the bromine utilization rate is low, and is only 45%.
2. If bromosuccinimide is used as the brominating agent in the raw material, the yield can be improved, but the cost is increased.
3. If bromine chloride is used as brominating agent, the utilization rate of bromine can be increased, but the impurity content of the product is increased and reduced.
4. The introduction of the solvent ethanol not only increases the actual production cost, but also increases the equipment investment of a solvent recovery processing device and the like.
The invention content is as follows:
the invention aims to solve the technical problems and provides a method for preparing 2-bromo-2-nitro-1, 3-propanediol, which has low production cost, is suitable for industrial production, has a clean production process and improves the utilization rate of bromine to more than 90 percent.
The aim of the invention is achieved by the following technical measures:
a process for preparing 2-bromo-2-nitro-1, 3-propanediol comprising the steps of:
a. putting nitromethane, bromine and water into a reaction bottle, slowly adding an aqueous solution of sodium hydroxide, stirring for 0.5-2 hours, introducing chlorine, and stirring for reaction at 0-70 ℃ to obtain tribromonitromethane;
b. and c, stirring the tribromonitromethane obtained in the step a, formaldehyde and nitromethane for 0.5-2 hours, slowly adding an aqueous solution of an inorganic base catalyst at the temperature of below 60 ℃, reacting for 0.5-2 hours at the temperature of 0-60 ℃, cooling, crystallizing, filtering and drying to obtain the 2-bromo-2-nitro-1, 3-propanediol.
The preparation method comprises the step a, wherein the feeding ratio of nitromethane to bromine in the step a is 1: 1.5-1: 2.5 in a molar ratio, and the optimal feeding ratio is 1: 1.5-1: 1.8 in a molar ratio.
The preparation method comprises the step a, wherein the feeding ratio of bromine to chlorine in the step a is 1: 1-1: 1.2 by mol ratio.
The preparation method comprises the step a, wherein the feeding ratio of bromine to chlorine in the step a is 1: 1-1: 1.15 by mol ratio.
The preparation method comprises the step a, wherein the feeding ratio of nitromethane to sodium hydroxide is 1: 3-1: 4 by mol. Here, an aqueous sodium hydroxide solution was used as a reactant.
The preparation method comprises the step of controlling the temperature of the reaction liquid below 60 ℃ when the aqueous solution of the sodium hydroxide is added in the step a.
The preparation method comprises the step a and the step b, wherein the molar ratio of nitromethane added in the step a to the step b is 1: 1.5-1: 2.5.
The preparation method comprises the step of adding nitromethane in the step a and the step of adding formaldehyde in the step b according to the molar ratio of 1: 5.5-1: 7
The preparation method is characterized in that the inorganic base is one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate and potassium carbonate.
Sampling analysis (such as gas chromatography) can be timed and tracked in the middle of the preparation process until the raw materials are completely converted.
As chlorine and bromine are used in the invention, the chlorine and bromine have high toxicity, and ventilation needs to be paid attention during the experiment.
The reaction equation of the preparation method is as follows:
the invention has the beneficial effects that:
the preparation method starts from industrial production, replaces general organic solvent with water, is simple and easy to obtain, improves the utilization rate of bromine to more than 90percent, realizes the cleanness of the production process and greatly reduces the production cost.
Detailed description of the invention
The present invention will be described in detail with reference to examples.
Example 1: preparation method of 2-bromo-2-nitro-1, 3-propanediol
1 mol of nitromethane, 50 ml of water and 1.5 mol of bromine are put into a 1L reactor, 3 mol of 30% sodium hydroxide solution is slowly added, the mixture is stirred and reacted for 1 hour, 110 g of chlorine gas is introduced, the mixture is stirred and reacted for 1 hour at the temperature of 30-40 ℃, the mixture is kept stand and layered, 310.8 g of tribromonitromethane is separated, the purity is 99%, and the yield is 98%. 310.8 g of tribromonitromethane reaction liquid obtained by the reaction, 180 g of formaldehyde and 131 g of nitromethane are stirred and reacted for 1 hour, 10% sodium hydroxide solution is slowly dripped below 40 ℃, the reaction is carried out for 1 hour at 30-40 ℃, cooling, crystallization, filtration and drying are carried out, 564.2 g of finished product of bronopol is obtained, the purity is 99%, and the yield is 95%.
Example 2: preparation method of 2-bromo-2-nitro-1, 3-propanediol
1 mol of nitromethane, 50 ml of water and 1.5 mol of bromine are put into a 1L reactor, 3 mol of 30% sodium hydroxide solution is slowly added, the mixture is stirred and reacted for 1 hour, 106.5 g of chlorine gas is introduced, the mixture is stirred and reacted for 1 hour at the temperature of 30-40 ℃, the mixture is kept stand and layered, 306.7 g of tribromonitromethane is separated, the purity is 99%, and the yield is 96.7%. And (3) stirring 306.7 g of tribromonitromethane reaction liquid obtained by the reaction, 180 g of formaldehyde and 131g of nitromethane for reacting for 1 hour, slowly dropwise adding 10% sodium hydroxide solution below 40 ℃, reacting for 1 hour at 30-40 ℃, cooling, crystallizing, filtering and drying to obtain 562.6 g of finished product of bronopol, wherein the purity is 99%, and the yield is 96%.
Example 3: preparation method of 2-bromo-2-nitro-1, 3-propanediol
1 mol of nitromethane, 50 ml of water and 1.5 mol of bromine are put into a 1L reactor, 3 mol of 30% sodium hydroxide solution is slowly added, the mixture is stirred and reacted for 1 hour, 110 g of chlorine gas is introduced, the mixture is stirred and reacted for 1 hour at the temperature of 30-40 ℃, the mixture is kept stand and layered, 310.8 g of tribromonitromethane is separated, the purity is 99%, and the yield is 98%. And (3) stirring 310.8 g of tribromonitromethane reaction liquid obtained by the reaction, 180 g of formaldehyde and 131 g of nitromethane for reacting for 1 hour, slowly dropwise adding 10% potassium hydroxide solution below 40 ℃, reacting for 1 hour at 30-40 ℃, cooling, crystallizing, filtering and drying to obtain 569.7 g of finished product of bronopol, wherein the purity is 99%, and the yield is 94%.
Claims (10)
1. A process for the preparation of 2-bromo-2-nitro-1, 3-propanediol, characterized in that the process comprises the steps of:
a. putting nitromethane, bromine and water into a reaction bottle, slowly adding an aqueous solution of sodium hydroxide, stirring for 0.5-2 hours, introducing chlorine, and stirring for reaction at 0-70 ℃ to obtain tribromonitromethane;
b. and c, stirring the tribromonitromethane obtained in the step a, formaldehyde and nitromethane for 0.5-2 hours, slowly adding an aqueous solution of an inorganic base catalyst at the temperature of below 60 ℃, reacting for 0.5-2 hours at the temperature of 0-60 ℃, cooling, crystallizing, filtering and drying to obtain the 2-bromo-2-nitro-1, 3-propanediol.
2. The preparation method according to claim 1, wherein the feed ratio of nitromethane to bromine in step a is 1: 1.5-1: 2.5 by mol.
3. The preparation method according to claim 2, wherein the feed ratio of nitromethane to bromine in step a is 1: 1.5-1: 1.8 by mol
4. The preparation method according to claim 1, wherein the feeding ratio of bromine to chlorine in step a is 1: 1 to 1: 1.2 by mol.
5. The preparation method according to claim 4, wherein the molar ratio of bromine to chlorine in step a is 1: 1-1: 1.15.
6. The preparation method according to claim 1, wherein the feed ratio of nitromethane to sodium hydroxide in step a is 1: 3 to 1: 4 by mol.
7. The method according to claim 1, wherein the temperature of the reaction solution is controlled to be 60 ℃ or lower when the aqueous solution of sodium hydroxide is added in the step a.
8. The method according to claim 1, wherein the molar ratio of nitromethane added in step a to step b is 1: 1.5 to 1: 2.5.
9. The method according to claim 1, wherein the molar ratio of the nitromethane added in step a to the formaldehyde added in step b is 1: 5.5-1: 7.
10. The method of claim 1, wherein the inorganic base is one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, and potassium carbonate.
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| CNB2006100412007A CN100522923C (en) | 2006-08-11 | 2006-08-11 | Preparation method of 2-bromo-2-nitro-1,3-propylene glycol |
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| CNB2006100412007A CN100522923C (en) | 2006-08-11 | 2006-08-11 | Preparation method of 2-bromo-2-nitro-1,3-propylene glycol |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009107133A1 (en) | 2008-02-28 | 2009-09-03 | Bromine Compounds Ltd. | A process for the preparation of bronopol |
| JP2010528102A (en) * | 2007-05-27 | 2010-08-19 | ブローミン コンパウンズ リミテッド | Continuous process to prepare bromopicrin |
| CN102627566A (en) * | 2012-03-21 | 2012-08-08 | 山东润鑫精细化工有限公司 | Method for preparing bronopol through catalyzing by solid base |
| CN102850226A (en) * | 2012-10-15 | 2013-01-02 | 潍坊裕凯化工有限公司 | Method for synthesizing and preparing bronopol by one step |
| CN106631813A (en) * | 2016-12-22 | 2017-05-10 | 河北美邦工程科技股份有限公司 | Bronopol refining process |
-
2006
- 2006-08-11 CN CNB2006100412007A patent/CN100522923C/en active Active
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101765580B (en) * | 2007-05-27 | 2013-03-27 | 溴化合物有限公司 | Continuous process of preparing bromopicrin |
| JP2010528102A (en) * | 2007-05-27 | 2010-08-19 | ブローミン コンパウンズ リミテッド | Continuous process to prepare bromopicrin |
| US8415513B2 (en) | 2007-05-27 | 2013-04-09 | Bromine Compounds Ltd. | Continuous process of preparing bromopicrin |
| US8546619B2 (en) * | 2008-02-28 | 2013-10-01 | Bromine Compounds Ltd. | Process for the preparation of bronopol |
| JP2011513297A (en) * | 2008-02-28 | 2011-04-28 | ブロミン・コンパウンズ・リミテツド | Production method of bronopol |
| US20110065964A1 (en) * | 2008-02-28 | 2011-03-17 | Jacob Oren | Process For The Preparation Of Bronopol |
| CN101959842A (en) * | 2008-02-28 | 2011-01-26 | 溴化合物有限公司 | A process for the preparation of bronopol |
| WO2009107133A1 (en) | 2008-02-28 | 2009-09-03 | Bromine Compounds Ltd. | A process for the preparation of bronopol |
| US8729314B2 (en) | 2008-02-28 | 2014-05-20 | Bromine Compounds Ltd. | Process for the preparation of bronopol |
| CN101959842B (en) * | 2008-02-28 | 2014-09-10 | 溴化合物有限公司 | A process for the preparation of bronopol |
| CN103396317B (en) * | 2008-02-28 | 2016-04-27 | 溴化合物有限公司 | Prepare the method for bronopol |
| CN102627566A (en) * | 2012-03-21 | 2012-08-08 | 山东润鑫精细化工有限公司 | Method for preparing bronopol through catalyzing by solid base |
| CN102850226A (en) * | 2012-10-15 | 2013-01-02 | 潍坊裕凯化工有限公司 | Method for synthesizing and preparing bronopol by one step |
| CN106631813A (en) * | 2016-12-22 | 2017-05-10 | 河北美邦工程科技股份有限公司 | Bronopol refining process |
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| Publication number | Publication date |
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| CN100522923C (en) | 2009-08-05 |
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