CN111269198A - Method for continuously preparing bentazon - Google Patents
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Abstract
The invention discloses a method for continuously preparing bentazon, which comprises the following steps: dissolving isopropylamine and an acid-binding agent in a solvent to obtain a material A, using a methanol solution of sodium methoxide as a material F, conveying the material A and chlorosulfonic acid to a tubular reactor R1 for sulfonylation reaction, mixing the obtained isopropylaminosulfonic acid with methyl anthranilate, conveying the mixture and BTC to a tubular reactor R2 for chlorination-sulfonylation reaction to obtain a reaction liquid of an intermediate methyl isopropylaminosulfonamide benzoate, conveying the reaction liquid and the material F to a tubular reactor R3 for cyclization reaction, and adding an inorganic acid at a low temperature for acidification to obtain a bentazone finished product. According to the invention, the BTC is adopted for chlorination-sulfonylation reaction, so that the problems of equipment corrosion and the like caused by the fact that phosphorus oxychloride is volatile and is easy to hydrolyze are solved, the continuous and controllable whole process can be ensured, the online amount of raw materials is small, the safety is high, the closed, continuous and automatic production is easy to realize, the post-treatment is simple, and the BTC is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to a method for continuously preparing bentazon.
Background
Bentazon was successfully developed by BASF company of germany in 1966, and is a herbicide with the characteristics of high efficiency, low toxicity, low residue, wide weed control spectrum, strong selectivity and the like. At present, bentazon is used in a large amount worldwide, and has good application prospect and research value.
The literature reports three main synthetic routes for bentazon: (1) methyl anthranilate route: it is produced by reacting isopropylaminosulfonyl chloride with methyl anthranilate, and then using sodium methoxide to close the ring to obtain bentazone (DE 3428837). (2) Route of the Lianghong acid anhydride: the method comprises the steps of reacting the L-hydroxy-benzoic anhydride with isopropylamine to obtain anthranilic acid isopropylamine, sulfonating with sulfur trioxide chlorosulfonic acid in the presence of 2-methylpyridine, and cyclizing under the action of phosphorus oxychloride to obtain bentazone (DE2710382, CN 1063668). (3) Isopropyl sulfamic acid-methyl anthranilate method: isopropylamine and chlorosulfonic acid are used to generate isopropylaminosulfonic acid, which reacts with methyl anthranilate and phosphorus oxychloride in the presence of an acid-binding agent to generate an intermediate, i.e., isopropyl amino sulfonamide methyl benzoate, and the intermediate reacts with sodium methoxide to obtain the product bentazone after acidification. (Niulizhong. synthetic process research of herbicide bentazon [ D ]. Heilongjiang university, 2009.)
In the first route, isopropylaminosulfonyl chloride is used, so that raw materials are not easy to obtain and the operation is complex; the intermediate N-isopropyl anthranilamide in the second route is not easy to be further refined, anthranilic acid as an impurity exists, the impurities are not easy to be removed in the subsequent refining process, and the catalytic sulfonating agent is not ideal. The yield of the two routes is not high, the product purity is too low, the molecular utilization rate of the first step of the reaction is low, the wastewater discharge is large, and the environmental protection pressure is large. And the third route can improve the yield to a greater extent, improve the atom utilization rate and simplify the operation procedure. However, the third route has the following problems that the raw material isopropylamine is used for reaction in the reaction process, the boiling point of the isopropylamine is low and is only 33-34 ℃, and the heat release in the sulfonylation reaction is severe, so that the flushing is easily caused; secondly, phosphorus oxychloride is used as a chlorination reagent in the chlorination-sulfonylation process, and the phosphorus oxychloride is volatile and easy to hydrolyze, so that the apparatus and equipment are seriously corroded; in the ring-closing reaction, the reaction speed is slow, and the economic benefit is low.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a method for continuously preparing bentazon, which adopts a continuous tubular reactor to continuously prepare bentazon.
The continuous preparation method of the bentazon is characterized by comprising the following steps:
1) dissolving isopropylamine and an acid-binding agent in a solvent to obtain a material A, dissolving chlorosulfonic acid in a solvent to obtain a material B, dissolving methyl anthranilate in a solvent to obtain a material C, dissolving BTC in a solvent to obtain a material D, and dissolving sodium methoxide in a solvent to obtain a material F;
2) conveying the material A and the material B to a tubular reactor R1 through an infusion pump P1 and an infusion pump P2 respectively for sulfonylation reaction to obtain isopropylaminosulfonic acid, and mixing the isopropylaminosulfonic acid with the material C conveyed by the infusion pump P3 to obtain a mixed solution;
3) conveying the mixed solution obtained in the step 2) and a material D conveyed by an infusion pump P4 to a tubular reactor R2 for chlorination-sulfonylation reaction to obtain an intermediate isopropyl sulfamide methyl benzoate reaction solution serving as a material E for later use;
4) conveying the material E and the material F obtained in the step 3) to a tubular reactor R3 through a liquid conveying pump P5 and a liquid conveying pump P6 respectively for cyclization reaction to obtain a bentazon salt solution, adding an inorganic acid at a low temperature for acidification, and performing suction filtration to obtain a bentazon finished product;
the BTC structure of the present invention is shown below:
the method for continuously preparing the bentazon is characterized in that a solvent in the step 1) is dichloroethane or toluene, and an acid-binding agent is triethylamine, tripropylamine, tri-N-butylamine, pyridine or N, N-diisopropylethylamine.
The method for continuously preparing the bentazone is characterized in that the feeding molar flow ratio of the methyl anthranilate, the chlorosulfonic acid, the isopropylamine and the BTC in the step 1) is 1: 1.05-1.65: 1.15-1.75: 0.6 to 1.5.
The method for continuously preparing the bentazon is characterized in that the temperature of the inner side of the tubular reactor R1 in the step 2) is-15-30 ℃, and the retention time of materials in the tubular reactor R1 is controlled to be 0.4-4.5 min by setting the flow rate of a pump.
The method for continuously preparing the bentazon is characterized in that the temperature of the inner side of the tubular reactor R2 in the step 3) is 25-80 ℃, and the retention time of materials in the tubular reactor R2 is controlled to be 3-35 min by setting the pump flow rate.
The continuous preparation method of the bentazone is characterized in that the molar flow ratio of the o-isopropylaminosulfonamide methyl benzoate to the sodium methoxide in the step 4) is 1: 1.1-1.6.
The method for continuously preparing the bentazon is characterized in that the temperature of the inner side of the tubular reactor R3 in the step 4) is 30-75 ℃, and the retention time of materials in the tubular reactor R3 is controlled to be 10-55 min by setting the pump flow rate.
The method for continuously preparing the bentazon is characterized in that the temperature of the low-temperature acidification bentazon salt solution in the step 4) is-5-25 ℃, and the inorganic acid is hydrochloric acid or sulfuric acid.
By adopting the method, compared with the prior art, the method has the following beneficial effects:
1) the invention adopts the infusion pump to continuously feed materials, and the materials enter the tubular reactor to react, thereby realizing continuous and controllable process, less online quantity, easy realization of closed, continuous and automatic production and high safety;
2) the solid phosgene BTC is used as a chlorine source for chlorination-sulfonylation reaction, is solid in form, has strong stability, is convenient to store and transport, avoids the problems of corrosion of equipment and the like caused by the fact that phosphorus oxychloride is volatile and is easy to hydrolyze, has simple post-treatment, and is suitable for large-scale industrial production;
3) the invention has good mass and heat transfer effects by reacting in the tubular reactor, and the reaction substances are quickly and fully contacted, so that the whole process period is shortened to 20-90min, the production efficiency is improved, the yield is improved by 15 percent, and the product purity is also improved.
Drawings
FIG. 1 is a first reaction scheme of the present invention;
FIG. 2 is a second reaction scheme of the present invention.
In the figure: p1, P2, P3, P4, P5 and P6 are all infusion pumps, and R1, R2 and R3 are all tubular reactors.
Detailed Description
In order to make the technical solution and advantages of the present invention more clear, the present invention will be described in further detail below.
Comparative examples
Weighing 5g of isopropylamine, 36.5g of triethylamine and 100g of dichloroethane, mixing and dissolving in a 500ml three-neck flask, putting the three-neck flask in low-temperature circulating liquid, installing a mechanical stirrer and a thermometer in the three-neck flask, weighing 8.75g of chlorosulfonic acid, putting in a constant-pressure dropping funnel, slowly dropping the chlorosulfonic acid when the temperature in the three-neck flask is lower than-5 ℃, ensuring that the internal temperature of the three-neck flask is lower than 0 ℃, and after dropping is finished, carrying out constant-temperature reaction at 0 ℃ for 120 min; weighing 9g of methyl anthranilate, dropwise adding the methyl anthranilate into a three-neck flask, stirring for 30min, then weighing 6.25g of BTC and 50g of dichloroethane to mix, adjusting the temperature in the three-neck flask to be 40 ℃, slowly dropwise adding the dichloroethane solution of BTC into the flask, keeping the temperature at 40 ℃ for 120min, then adding 50ml of distilled water, stirring for 20min, separating liquid to obtain a dichloroethane layer, and spin-drying the dichloroethane solvent to obtain 13.38g of the intermediate product methyl isopropylaminosulfonamide benzoate, wherein the yield is 83.3%, and the content is 91.8%. Dissolving 13.4g of weighed isopropyl amino sulfonamide methyl benzoate in 60g of methanol, pouring into a 250ml three-neck flask, heating to 55 ℃, weighing 15.95g of 20% sodium methoxide, pouring into the three-neck flask, magnetically stirring, keeping the temperature for 120min, drying the solvent to obtain white solid, dissolving the solid in water, acidifying with inorganic salt at low temperature, filtering, and drying to obtain 9.52g of a solid bentazon finished product, wherein the yield is 80.7%, and the content is 91.3%.
Example 1
As shown in fig. 1 and fig. 2, 22g of isopropylamine and 145g of triethylamine as an acid-binding agent are mixed and dissolved with 200g of dichloroethane as a material a, 38.2g of chlorosulfonic acid as a material B, 45g of methyl anthranilate as a material C, 53.06 g of BTC and 250g of dichloroethane as a material D, the material a and the material B are respectively conveyed into a tubular reactor R1 through a liquid conveying pump P1 and a liquid conveying pump P2, the temperature of the tubular reactor R1 is controlled to be 0 ℃ through a water bath, the retention time of the material in the tubular reactor R1 is controlled to be 0.4min through setting the pump flow rate, sulfonylation reaction is carried out in the tubular reactor R1 to generate isopropylaminosulfonic acid, then the isopropylaminosulfonic acid is mixed with the material C conveyed by the liquid conveying pump P3, the mixed material and the mixed material are conveyed into the tubular reactor R2 together with the material D conveyed by the liquid conveying pump P4, the temperature of the tubular reactor R2 is, and (3) carrying out chlorination-sulfonylation reaction for 3min, and controlling the flow by a pump so that the feeding molar flow ratio of methyl anthranilate, chlorosulfonic acid, isopropylamine and triphosgene is 1: 1.1: 1.25: 0.6, the reaction solution flows into a receiving kettle filled with 100ml of water, the mixed solution in the receiving kettle is subjected to liquid separation, a dichloroethane layer is taken, and the solvent dichloroethane is dried in a spinning mode, so that 73.85g of the intermediate product, namely the isopropyl sulfamide methyl benzoate, is obtained, the yield is 91%, and the content is 92%. 73.85g of intermediate product methyl isopropylaminosulfonamide benzoate is dissolved in 250g of methanol to serve as a material E, 80.22g of 20% sodium methoxide to serve as a material F, the material E and the material F are respectively conveyed into a tubular reactor R3 through a liquid pump P5 and a liquid conveying pump P6, the temperature of the tubular reactor R3 is controlled to be 50 ℃ through water bath, cyclization reaction is carried out after 10min of residence time, and the flow is controlled through a pump to ensure that the feeding molar flow ratio of the methyl isopropylaminosulfonamide benzoate to the sodium methoxide is 1: 1.1. Then, acidifying with inorganic salt under the condition of low temperature, filtering, and drying to obtain 57.4g of finished product of the solid bentazon, wherein the yield is 88.1 percent, and the content is 98 percent.
Example 2
As shown in fig. 1 and fig. 2, 24.66g of isopropylamine and 145g of triethylamine as an acid-binding agent are mixed and dissolved with 200g of dichloroethane as a material a, 45.14g of chlorosulfonic acid as a material B, 45g of methyl anthranilate as a material C, 88.43 g of BTC and 250g of dichloroethane as a material D, the material a and the material B are respectively conveyed into a tubular reactor R1 by a liquid conveying pump P1 and a liquid conveying pump P2, the temperature of the tubular reactor R1 is controlled to be 15 ℃ by a water bath, the retention time of the material in the tubular reactor R1 is controlled to be 1.0min by setting the pump flow rate, sulfonylation reaction is carried out in the tubular reactor R1 to generate isopropylaminosulfonic acid, then the isopropylaminosulfonic acid is mixed with the material C conveyed by the liquid conveying pump P3, the mixed material is then conveyed into the tubular reactor R2 together with the material D conveyed by the liquid conveying pump P4, the temperature of the tubular reactor R2 is controlled to be, and (3) carrying out chlorination-sulfonylation reaction for 10min, and controlling the flow by a pump so that the feeding molar flow ratio of methyl anthranilate, chlorosulfonic acid, isopropylamine and triphosgene is 1: 1.3: 1.4: 1, flowing the reaction solution into a receiving kettle filled with 100ml of water, separating the mixed solution in the receiving kettle, taking a dichloroethane layer, and spin-drying the solvent dichloroethane to obtain 77.9g of an intermediate product, namely, the isopropyl amino sulfonamide methyl benzoate, with the yield of 96 percent and the content of 97 percent. 74.6g of intermediate product methyl isopropylaminosulfonamide benzoate is dissolved in 250g of methanol to serve as a material E, 105.88g of sodium methoxide serves as a material F, the material E and the material F are respectively conveyed into a tubular reactor R3 through a liquid pump P5 and a liquid conveying pump P6, the temperature of the tubular reactor R3 is controlled to be 60 ℃ through water bath, cyclization reaction is carried out after 17min of residence time, and the flow is controlled through a pump to ensure that the feeding molar flow ratio of the methyl isopropylaminosulfonamide benzoate to the sodium methoxide is 1: 1.4. Then, acidifying with inorganic salt at low temperature, and performing suction filtration to obtain 65.78g of a finished product of the solid bentazon, wherein the yield is 95.7 percent and the content is 99 percent.
Example 3
As shown in fig. 1 and fig. 2, 29.95g of isopropylamine and 145g of triethylamine as an acid-binding agent are mixed and dissolved with 200g of dichloroethane as a material a, 55.56g of chlorosulfonic acid as a material B, 45g of methyl anthranilate as a material C, 123.8 g of BTC and 250g of dichloroethane as a material D, the material a and the material B are respectively conveyed into a tubular reactor R1 through a liquid conveying pump P1 and a liquid conveying pump P2, the temperature of the tubular reactor R1 is controlled to be 30 ℃ through a water bath, the retention time of the materials in the tubular reactor R1 is controlled to be 1.5min through setting the pump flow rate, sulfonylation reaction is carried out in a tubular reactor R1 to generate isopropylaminosulfonic acid, then the isopropylaminosulfonic acid is mixed with the material C conveyed by the liquid conveying pump P3, the mixed material is then conveyed into the tubular reactor R2 together with the material D conveyed by the liquid conveying pump P4, the temperature of the tubular reactor R2 is controlled to be, performing chlorination-sulfonylation reaction for 15min, controlling the flow by a pump to ensure that the feeding molar flow ratio of methyl anthranilate, chlorosulfonic acid, isopropylamine and triphosgene is 1: 1.6: 1.7: 1.4, the reaction solution flows into a receiving kettle filled with 100ml of water, the mixed solution in the receiving kettle is subjected to liquid separation, a dichloroethane layer is taken, and the solvent dichloroethane is dried in a spinning mode, so that 80.34g of the intermediate product, namely the isopropyl amino sulfonamide methyl benzoate, is obtained, the yield is 99%, and the content is 98%. 76.8g of intermediate product methyl isopropylaminosulfonamide benzoate is dissolved in 250g of methanol to serve as a material E, 127.49g of sodium methoxide serves as a material F, the material E and the material F are respectively conveyed into a tubular reactor R3 through a liquid pump P5 and a liquid conveying pump P6, the temperature of the tubular reactor R3 is controlled to be 75 ℃ through water bath, cyclization reaction is carried out after 25min of residence time, and the flow is controlled through a pump to ensure that the feeding molar flow ratio of the methyl isopropylaminosulfonamide benzoate to the sodium methoxide is 1: 1.6. Then, acidifying with inorganic salt at low temperature, and performing suction filtration to obtain 65.77g of a finished product of the solid bentazon, wherein the yield is 92.78% and the content is 99%.
The yield and the content of the product obtained by the method are greatly higher than those of the products obtained by the existing methods. The above is a preferred embodiment of the present invention, but the present invention is not limited to the above data, and those skilled in the art can make reasonable changes to the technical solution of the present invention without departing from the spirit and scope of the present invention, and also fall into the protection scope of the present invention.
Claims (8)
1. A method for continuously preparing bentazon is characterized by comprising the following steps:
1) dissolving isopropylamine and an acid-binding agent in a solvent to obtain a material A, dissolving chlorosulfonic acid in a solvent to obtain a material B, dissolving methyl anthranilate in a solvent to obtain a material C, dissolving BTC in a solvent to obtain a material D, and dissolving sodium methoxide in a solvent to obtain a material F;
2) conveying the material A and the material B to a tubular reactor R1 through an infusion pump P1 and an infusion pump P2 respectively for sulfonylation reaction to obtain isopropylaminosulfonic acid, and mixing the isopropylaminosulfonic acid with the material C conveyed by the infusion pump P3 to obtain a mixed solution;
3) conveying the mixed solution obtained in the step 2) and a material D conveyed by an infusion pump P4 to a tubular reactor R2 for chlorination-sulfonylation reaction to obtain an intermediate isopropyl sulfamide methyl benzoate reaction solution serving as a material E for later use;
4) conveying the material E and the material F obtained in the step 3) to a tubular reactor R3 through a liquid conveying pump P5 and a liquid conveying pump P6 respectively for cyclization reaction to obtain a bentazon salt solution, adding an inorganic acid at a low temperature for acidification, and performing suction filtration to obtain a bentazon finished product.
2. The method for continuously preparing bentazon according to claim 1, wherein the solvent in step 1) is dichloroethane or toluene, and the acid-binding agent is triethylamine, tripropylamine, tri-N-butylamine, pyridine or N, N-diisopropylethylamine.
3. The continuous process for preparing bentazone according to claim 1, wherein the molar flow ratio of the methyl anthranilate, chlorosulfonic acid, isopropylamine, and BTC fed in step 1) is 1: 1.05-1.65: 1.15-1.75: 0.6 to 1.5.
4. The continuous preparation method of bentazon according to claim 1, wherein the temperature inside the tubular reactor R1 in the step 2) is-15 to 30 ℃, and the residence time of the materials in the tubular reactor R1 is controlled to be 0.4 to 4.5min by setting the pump flow rate.
5. The continuous preparation method of bentazon according to claim 1, wherein the temperature of the inner side of the tubular reactor R2 in the step 3) is 25-80 ℃, and the residence time of the materials in the tubular reactor R2 is controlled to be 3-35 min by setting the pump flow rate.
6. The continuous preparation method of bentazone according to claim 1, wherein the molar flow ratio of the methyl o-isopropylaminosulfonamide benzoate to the sodium methoxide in the step 4) is 1: 1.1-1.6.
7. The continuous preparation method of bentazon according to claim 1, wherein the temperature inside the tubular reactor R3 in the step 4) is 30-75 ℃, and the residence time of the materials in the tubular reactor R3 is controlled to be 10-55 min by setting the pump flow rate.
8. The method for continuously preparing bentazon according to claim 1, wherein the temperature of the low-temperature acidified bentazon salt solution in the step 4) is-5-25 ℃, and the inorganic acid is hydrochloric acid or sulfuric acid.
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Cited By (1)
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| CN112250590A (en) * | 2020-09-30 | 2021-01-22 | 广东石油化工学院 | Method for continuously preparing methyl anthranilate |
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