CN111087294A - Preparation method of high-purity prohexadione calcium - Google Patents
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- CN111087294A CN111087294A CN201911311025.2A CN201911311025A CN111087294A CN 111087294 A CN111087294 A CN 111087294A CN 201911311025 A CN201911311025 A CN 201911311025A CN 111087294 A CN111087294 A CN 111087294A
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- C07C67/00—Preparation of carboxylic acid esters
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Abstract
The invention discloses a preparation method of high-purity prohexadione calcium, which comprises the following steps: sodium hydride is dissolved in an organic solvent A to prepare a liquid B. Adding a crude product of the rearrangement product of the 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester into the organic solvent A, stirring and dissolving for 0.5-2h, standing and precipitating, filtering to remove insoluble impurities, dropwise and slowly dropping the prepared liquid B into the formed solution for reaction, carrying out suction filtration after dropping, and obtaining a solid which is a purified rearrangement product of the sodium salt by suction filtration; hydrolyzing the obtained rearrangement product sodium salt under an alkaline condition, and acidifying to obtain a prohexadione; finally, the prohexadione reacts with calcium salt to prepare the target product prohexadione-calcium. The method has the advantages of simple reaction condition, convenient operation, no need of column chromatography separation, stable yield, low requirement on equipment, environmental friendliness and good industrialization prospect.
Description
Technical Field
The invention relates to the technical field of organic pesticide synthesis, in particular to a preparation method of high-purity prohexadione calcium.
Background
A plant growth regulator is a kind of agricultural chemicals for regulating plant growth and development, including artificially synthesized compound with similar action of natural plant hormone and natural plant hormone extracted from living beings. Prohexadione Calcium is a novel cyclohexenone plant growth regulator firstly developed by Nippon combinatorial chemistry industry company in 1983, belongs to 2-acyl-1, 3-cyclohexanedione compounds, has a chemical name of 3, 5-dioxo-4-propionyl cyclohexene carboxylate Calcium, is called Calcium 3, 5-dioxo-4-propionocyclohexenone carboxylic acid in English, and has a structural formula shown as formula 1:
the prohexadione calcium is mainly used for controlling the growth of cereal crops, can shorten the length of crop stems, can enhance the disease resistance, cold resistance and stress resistance of plants, and has obvious lodging resistance. Compared with the triazole retardant which is widely applied at present, Prohexadione-Ca has no residual toxicity to crop plants and no pollution to the environment, and is degraded into carbon dioxide very quickly under the conditions of flooding soil and mountain land soil, so that the Prohexadione-Ca can replace the triazole growth retardant and has wide market prospect.
The degradation reaction process of the prohexadione calcium in the soil is as follows:
in recent years, a great deal of research is carried out on the synthetic route of prohexadione calcium at home and abroad, for example, CN 104140368A introduces a route with industrial prospect. In the document, diethyl maleate is used as a starting material, and the prohexadione calcium is prepared through six steps of reactions such as Michale addition, Claisen condensation, acylation reaction, rearrangement, hydrolysis, salification and the like. Therefore, how to obtain prohexadione calcium with higher purity and improve the purity thereof is a technical problem to be solved urgently.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method for purifying prohexadione calcium, which has the advantages of simple preparation method, convenient operation and low requirement on equipment.
The preparation method of the high-purity prohexadione calcium is characterized by comprising the following steps:
1) dissolving sodium hydride in an organic solvent A to prepare a liquid B with the mass percent concentration of the sodium hydride of 1.5-5%;
2) adding a crude product of the rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester into an organic solvent A, stirring and dissolving for 0.5-2h, standing and precipitating, filtering to remove insoluble impurities, dropwise and slowly dropping the filtered solution into the liquid B obtained in the step 1) for reaction, carrying out suction filtration after the dropping of the liquid B is finished, wherein the solid obtained by suction filtration is the purified rearrangement product sodium salt, and the molecular structure of the rearrangement product sodium salt is shown as the formula (I);
3) stirring and hydrolyzing the rearrangement product sodium salt obtained in the step 2) in an alkaline solution, hydrolyzing the rearrangement product sodium salt to generate a cycloregulated acid sodium salt shown in a formula (II), adding an acid to regulate the pH value of the reaction solution to 7.5-8.5, acidifying the cycloregulated acid sodium salt shown in the formula (II) to generate cycloregulated acid, then adding a calcium salt to react at the temperature of 50-70 ℃ for 1-3h, and after the reaction is finished, carrying out post-treatment on the reaction solution to obtain the cycloregulated calcium salt product;
the preparation method of the high-purity prohexadione calcium is characterized in that the crude product of the rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylate is prepared by taking maleic acid diester and acetone as starting raw materials and sequentially carrying out Michale addition, Claisen condensation, acylation reaction and rearrangement reaction.
The preparation method of the high-purity prohexadione calcium is characterized in that the organic solvent A is one or two mixed solvents of methanol and acetone.
The preparation method of the high-purity prohexadione-calcium is characterized in that in the step 2), the standing and precipitating time is 2-2.5 h.
The preparation method of the high-purity prohexadione calcium is characterized in that in the step 2), the feeding molar ratio of the rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester to the sodium hydride is 1.0: 1.0-1.2, preferably 1: 1.1; the temperature at which the liquid B was added dropwise to carry out the reaction was room temperature.
The preparation method of the high-purity prohexadione calcium is characterized in that in the step 3), the alkaline solution is a NaoH aqueous solution with the mass concentration of 10-20%, the stirring hydrolysis temperature is 50-70 ℃, and the stirring hydrolysis time is 1-3 h.
The preparation method of the high-purity prohexadione calcium is characterized in that in the step 3), the feeding molar ratio of the rearrangement product sodium salt to the calcium salt is 1: 1-1.5, and preferably 1: 1.2.
The preparation method of the high-purity prohexadione-calcium is characterized in that in the step 3), the step of post-treating the reaction liquid is as follows: and (4) carrying out suction filtration on the reaction solution, washing filter residues with deionized water, and drying.
Compared with the prior art, the invention has the beneficial effects that:
firstly, a crude product of rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester reacts with sodium hydride in organic solvents such as methanol, acetone and the like, and the reaction formula is as follows:
the rearrangement product sodium salt which is insoluble in organic solvents such as methanol, acetone and the like is generated through the reaction, then the suction filtration is carried out, and the solid obtained through the suction filtration is the rearrangement product sodium salt after purification, and the good purification effect can be achieved through the operation process. Then stirring and hydrolyzing the purified rearrangement product sodium salt in NaOH aqueous solution, wherein the reaction formula of stirring and hydrolyzing is as follows:
sodium salt of prohexadione is generated after stirring and hydrolysis reaction, and then prohexadione is generated after acidification, and then the prohexadione reacts with calcium salt to obtain the prohexadione calcium product. In the process of preparing the high-purity prohexadione calcium, the invention has the advantages of simple operation steps, simple reaction conditions, low requirement on equipment and environmental protection, does not need column chromatography separation in the whole operation process, has stable yield of the target prohexadione calcium and has good industrialization prospect.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1
According to the route provided in example 1 of Chinese patent CN 104140368A, the crude product of rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester is prepared by using maleic acid diester as starting material and is marked as rearrangement product crude product.
The high-purity prohexadione calcium is prepared by taking the rearrangement product crude product as an initial raw material, and the steps are as follows:
1) dissolving sodium hydride by using methanol, preparing a liquid B with the mass percent concentration of the sodium hydride of 2.53 percent, and transferring the liquid B into a dropping funnel;
2) weighing 20g of the rearrangement product crude product, adding the rearrangement product crude product into 400ml of methanol, stirring and dissolving for 1h, standing and precipitating for 2h, filtering to remove insoluble impurities, and obtaining a clear rearrangement product methanol solution marked as liquid C;
3) slowly dropwise adding the liquid B (the feeding molar ratio of the rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester to the sodium hydride is 1.0:1.1) into the liquid C obtained in the step 2) at room temperature, and performing suction filtration after the dropwise adding is finished to obtain 16.4g of beige precipitate, wherein the beige precipitate is the rearrangement product sodium salt;
4) stirring and hydrolyzing the rearrangement product sodium salt obtained in the step 3) in a NaOH aqueous solution with the mass concentration of 15 percent, and performing hydrolysis at the temperature of 60 DEG CHydrolyzing for 1.5h (hydrolyzing rearrangement product sodium salt to generate cycloregulated acid sodium salt), adding acid to adjust the pH of the reaction solution to about 8.0 (acidifying the cycloregulated acid sodium salt to generate cycloregulated acid), and adding CaCl with the mass concentration of 10%288.8g of aqueous solution is reacted for 2 hours at the temperature of 60 ℃, then is filtered, and filter residue is washed by deionized water and then is dried, finally obtaining a light yellow solid product prohexadione calcium with the purity of 95.1 percent and the yield of 42.5 percent (calculated by the initial raw material maleic diester).
Example 2
According to the route provided in example 1 of Chinese patent CN 104140368A, the crude product of rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester is prepared by using maleic acid diester as starting material and is marked as rearrangement product crude product.
The high-purity prohexadione calcium is prepared by taking the rearrangement product crude product as an initial raw material, and the steps are as follows:
1) dissolving sodium hydride by using acetone, preparing a liquid B with the mass percent concentration of the sodium hydride of 2.53 percent, and transferring the liquid B into a dropping funnel;
2) weighing 20g of the rearrangement product crude product, adding the rearrangement product crude product into 400ml of acetone, stirring and dissolving for 1h, standing and precipitating for 2.3h, filtering to remove insoluble impurities, and obtaining a clear acetone solution of the rearrangement product, wherein the acetone solution is marked as liquid C;
3) slowly dropwise adding the liquid B (the feeding molar ratio of the rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester to the sodium hydride is 1.0:1.1) into the liquid C obtained in the step 2) at room temperature, and performing suction filtration after the dropwise adding is finished to obtain 16.2g of beige precipitate, wherein the beige precipitate is the rearrangement product sodium salt;
4) stirring and hydrolyzing the rearrangement product sodium salt obtained in the step 3) in a NaOH aqueous solution with the mass concentration of 15%, hydrolyzing for 1.5h at the temperature of 60 ℃ (hydrolyzing the rearrangement product sodium salt to generate a cycloregulated acid sodium salt), then adding acid to adjust the pH of the reaction solution to about 8.0 (acidifying the cycloregulated acid sodium salt to generate cycloregulated acid), and then adding CaCl with the mass concentration of 10%288.8g of aqueous solution is reacted for 2 hours at the temperature of 60 ℃, then is filtered, filter residue is washed by deionized water and is dried, finally, a light yellow solid product prohexadione calcium is obtained,purity 95.0% and yield 42.1% (based on the starting material, maleic diester).
Example 3
According to the route provided in example 1 of Chinese patent CN 104140368A, the crude product of rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester is prepared by using maleic acid diester as starting material and is marked as rearrangement product crude product.
The high-purity prohexadione calcium is prepared by taking the rearrangement product crude product as an initial raw material, and the steps are as follows:
1) dissolving sodium hydride by using methanol, preparing a liquid B with the mass percent concentration of the sodium hydride of 2.53 percent, and transferring the liquid B into a dropping funnel;
2) weighing 20g of the rearrangement product crude product, adding the rearrangement product crude product into 200ml of methanol, stirring and dissolving for 1h, standing and precipitating for 2h, filtering to remove insoluble impurities, and obtaining a clear rearrangement product methanol solution marked as liquid C;
3) slowly dropwise adding the liquid B (the feeding molar ratio of the rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester to the sodium hydride is 1.0:1.1) into the liquid C obtained in the step 2) at room temperature, and performing suction filtration after the dropwise adding is finished to obtain 16.1g of beige precipitate, wherein the beige precipitate is the rearrangement product sodium salt;
4) stirring and hydrolyzing the rearrangement product sodium salt obtained in the step 3) in a NaOH aqueous solution with the mass concentration of 15%, hydrolyzing for 1.5h at the temperature of 60 ℃ (hydrolyzing the rearrangement product sodium salt to generate a cycloregulated acid sodium salt), then adding acid to adjust the pH of the reaction solution to about 8.0 (acidifying the cycloregulated acid sodium salt to generate cycloregulated acid), and then adding CaCl with the mass concentration of 10%288.8g of aqueous solution is reacted for 2 hours at the temperature of 60 ℃, then is filtered, and filter residue is washed by deionized water and then is dried, finally obtaining a light yellow solid product prohexadione calcium with the purity of 94.1 percent and the yield of 42.4 percent (calculated by the initial raw material maleic diester).
Example 4
According to the route provided in example 1 of Chinese patent CN 104140368A, the crude product of rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester is prepared by using maleic acid diester as starting material and is marked as rearrangement product crude product.
The high-purity prohexadione calcium is prepared by taking the rearrangement product crude product as an initial raw material, and the steps are as follows:
1) dissolving sodium hydride by using acetone, preparing a liquid B with the mass percent concentration of the sodium hydride of 2.53 percent, and transferring the liquid B into a dropping funnel;
2) weighing 20g of the rearrangement product crude product, adding the rearrangement product crude product into 200ml of acetone, stirring and dissolving for 1h, standing and precipitating for 2.3h, filtering to remove insoluble impurities, and obtaining a clear acetone solution of the rearrangement product, wherein the acetone solution is marked as liquid C;
3) slowly dropwise adding the liquid B (the feeding molar ratio of the rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester to the sodium hydride is 1.0:1.1) into the liquid C obtained in the step 2) at room temperature, and performing suction filtration after the dropwise adding is finished to obtain 16.0g of beige precipitate, wherein the beige precipitate is the rearrangement product sodium salt;
4) stirring and hydrolyzing the rearrangement product sodium salt obtained in the step 3) in a NaOH aqueous solution with the mass concentration of 15%, hydrolyzing for 1.5h at the temperature of 60 ℃ (hydrolyzing the rearrangement product sodium salt to generate a cycloregulated acid sodium salt), then adding acid to adjust the pH of the reaction solution to about 8.0 (acidifying the cycloregulated acid sodium salt to generate cycloregulated acid), and then adding CaCl with the mass concentration of 10%288.8g of aqueous solution is reacted for 2 hours at the temperature of 60 ℃, then is filtered, and filter residue is washed by deionized water and then is dried, finally obtaining a light yellow solid product prohexadione calcium with the purity of 93.7 percent and the yield of 42.2 percent (calculated by the initial raw material maleic diester).
Example 5
According to the route provided in example 1 of Chinese patent CN 104140368A, the crude product of rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester is prepared by using maleic acid diester as starting material and is marked as rearrangement product crude product.
The high-purity prohexadione calcium is prepared by taking the rearrangement product crude product as an initial raw material, and the steps are as follows:
1) dissolving sodium hydride by using a methanol-acetone mixed solution with the volume ratio of 1:1, preparing to obtain a liquid B with the mass percent concentration of the sodium hydride of 2.53%, and transferring the liquid B into a dropping funnel;
2) weighing 20g of the rearrangement product crude product, adding the rearrangement product crude product into 400ml of methanol-acetone mixed solution with the volume ratio of 1:1, stirring and dissolving for 1h, standing and precipitating for 2.3h, filtering to remove insoluble impurities, and obtaining a clear solution marked as liquid C;
3) slowly dropwise adding the liquid B (the feeding molar ratio of the rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester to the sodium hydride is 1.0:1.1) into the liquid C obtained in the step 2) at room temperature, and performing suction filtration after the dropwise adding is finished to obtain 16.1g of beige precipitate, wherein the beige precipitate is the rearrangement product sodium salt;
4) stirring and hydrolyzing the rearrangement product sodium salt obtained in the step 3) in a NaOH aqueous solution with the mass concentration of 15%, hydrolyzing for 1.5h at the temperature of 60 ℃ (hydrolyzing the rearrangement product sodium salt to generate a cycloregulated acid sodium salt), then adding acid to adjust the pH of the reaction solution to about 8.0 (acidifying the cycloregulated acid sodium salt to generate cycloregulated acid), and then adding CaCl with the mass concentration of 10%288.8g of aqueous solution is reacted for 2 hours at the temperature of 60 ℃, then is filtered, and filter residue is washed by deionized water and then is dried, finally obtaining a light yellow solid product prohexadione calcium with the purity of 94.1 percent and the yield of 42.0 percent (calculated by the initial raw material maleic diester).
Example 6
According to the route provided in example 1 of Chinese patent CN 104140368A, the crude product of rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester is prepared by using maleic acid diester as starting material and is marked as rearrangement product crude product.
The high-purity prohexadione calcium is prepared by taking the rearrangement product crude product as an initial raw material, and the steps are as follows:
1) dissolving sodium hydride by using a methanol-acetone mixed solution with the volume ratio of 1:1, preparing to obtain a liquid B with the mass percent concentration of the sodium hydride of 2.53%, and transferring the liquid B into a dropping funnel;
2) weighing 20g of the rearrangement product crude product, adding the rearrangement product crude product into 200ml of methanol-acetone mixed solution with the volume ratio of 1:1, stirring and dissolving for 1h, standing and precipitating for 2.3h, filtering to remove insoluble impurities, and obtaining a clear solution marked as liquid C;
3) slowly dropwise adding the liquid B (the feeding molar ratio of the rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester to the sodium hydride is 1.0:1.1) into the liquid C obtained in the step 2) at room temperature, and performing suction filtration after the dropwise adding is finished to obtain 16.1g of beige precipitate, wherein the beige precipitate is the rearrangement product sodium salt;
4) stirring and hydrolyzing the rearrangement product sodium salt obtained in the step 3) in a NaOH aqueous solution with the mass concentration of 15%, hydrolyzing for 1.5h at the temperature of 60 ℃ (hydrolyzing the rearrangement product sodium salt to generate a cycloregulated acid sodium salt), then adding acid to adjust the pH of the reaction solution to about 8.0 (acidifying the cycloregulated acid sodium salt to generate cycloregulated acid), and then adding CaCl with the mass concentration of 10%288.8g of aqueous solution is reacted for 2 hours at the temperature of 60 ℃, then is filtered, and filter residue is washed by deionized water and then is dried, finally obtaining a light yellow solid product prohexadione calcium with the purity of 93.5 percent and the yield of 42.1 percent (calculated by the initial raw material maleic diester).
The purity of the prepared prohexadione-calcium product is detected by adopting a high performance liquid chromatography, a mixed solution of acetonitrile, water and phosphoric acid with the volume ratio of 70:30:0.1 is used as a mobile phase, and a chromatographic column uses C18The stainless steel column as filler was quantified by external standard method.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (8)
1. The preparation method of the high-purity prohexadione calcium is characterized by comprising the following steps:
1) dissolving sodium hydride in an organic solvent A to prepare a liquid B with the mass percent concentration of the sodium hydride of 1.5-5%;
2) adding a crude product of the rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester into an organic solvent A, stirring and dissolving for 0.5-2h, standing and precipitating, filtering to remove insoluble impurities, dropwise and slowly dropping the filtered solution into the liquid B obtained in the step 1) for reaction, carrying out suction filtration after the dropping of the liquid B is finished, wherein the solid obtained by suction filtration is the purified rearrangement product sodium salt, and the molecular structure of the rearrangement product sodium salt is shown as the formula (I);
3) stirring and hydrolyzing the rearrangement product sodium salt obtained in the step 2) in an alkaline solution, hydrolyzing the rearrangement product sodium salt to generate a cycloregulated acid sodium salt shown in a formula (II), adding an acid to regulate the pH value of the reaction solution to 7.5-8.5, acidifying the cycloregulated acid sodium salt shown in the formula (II) to generate cycloregulated acid, then adding a calcium salt to react at the temperature of 50-70 ℃ for 1-3h, and after the reaction is finished, carrying out post-treatment on the reaction solution to obtain the cycloregulated calcium salt product;
2. the method for preparing highly pure prohexadione-calcium as claimed in claim 1, wherein the crude product of rearrangement product ethyl 3, 5-dioxo-4-propionyl cyclohexanecarboxylate is prepared by Michale addition, Claisen condensation, acylation reaction and rearrangement reaction sequentially using maleic acid diester and acetone as starting materials.
3. The method for preparing highly pure prohexadione-calcium as claimed in claim 1, wherein the organic solvent A is one or a mixture of methanol and acetone.
4. The method for preparing high-purity prohexadione-calcium as claimed in claim 1, wherein the time of standing and precipitating in step 2) is 2-2.5 h.
5. The method for preparing highly pure prohexadione-calcium as claimed in claim 1, wherein in the step 2), the feeding molar ratio of the rearrangement product of ethyl 3, 5-dioxo-4-propionylcyclohexanecarboxylate to sodium hydride is 1.0: 1.0-1.2, preferably 1: 1.1; the temperature at which the liquid B was added dropwise to carry out the reaction was room temperature.
6. The method for preparing high-purity prohexadione-calcium as claimed in claim 1, wherein in the step 3), the alkaline solution is a NaoH aqueous solution with a mass concentration of 10-20%, the stirring hydrolysis temperature is 50-70 ℃, and the stirring hydrolysis time is 1-3 h.
7. The method for preparing high-purity prohexadione-calcium according to claim 1, wherein in the step 3), the feeding molar ratio of the sodium salt to the calcium salt of the rearrangement product is 1: 1-1.5, preferably 1: 1.2.
8. The method for preparing high-purity prohexadione-calcium as claimed in claim 1, wherein in the step 3), the step of post-treating the reaction solution is as follows: and (4) carrying out suction filtration on the reaction solution, washing filter residues with deionized water, and drying.
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| CN111972411A (en) * | 2020-09-07 | 2020-11-24 | 安徽省四达农药化工有限公司 | Preparation and application of prohexadione calcium suspending agent |
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Application publication date: 20200501 |