CN113563227A - Preparation method of bromoxynil octanoate byproduct regenerated raw medicine - Google Patents
Preparation method of bromoxynil octanoate byproduct regenerated raw medicine Download PDFInfo
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- CN113563227A CN113563227A CN202010857322.3A CN202010857322A CN113563227A CN 113563227 A CN113563227 A CN 113563227A CN 202010857322 A CN202010857322 A CN 202010857322A CN 113563227 A CN113563227 A CN 113563227A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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Abstract
The invention discloses a preparation method of a bromoxynil octanoate byproduct regenerated original drug, which comprises an ester exchange reaction step, 1) taking bromoxynil, methyl octanoate and a solvent as raw materials, heating and refluxing under the action of an alkaline catalyst, continuously distilling off methanol, and evaporating the solvent to obtain a crude bromoxynil octanoate product; 2) and (3) completely dissolving the bromoxynil octanoate crude product in a recrystallization solvent under the action of temperature rise, cooling to 0-10 ℃, recrystallizing, and centrifuging, drying and drying to obtain a high-content bromoxynil octanoate original drug. According to the invention, the byproduct methyl caprylate is regenerated into bromoxynil octanoate raw drug by an ester exchange method, the raw drug content is up to 98.5%, the yield of the applied recrystallization mother liquor can reach 92-94%, a special reaction solvent is selected to ensure smooth reaction, and the generated methanol is applied as the recrystallization solvent.
Description
Technical Field
The invention belongs to the technical field of pesticide raw drug synthesis, and particularly relates to a preparation method of bromoxynil octanoate by-product regenerated raw drug.
Background
At present, bromoxynil octanoate is generally synthesized by two steps, namely, bromoxynil is synthesized by bromination, and then, the bromoxynil octanoate is obtained by acylation reaction. Bromoxynil generated by bromination is solid and needs centrifugal separation, and the transportation requirement after centrifugal separation is extremely high, so that serious environmental pollution accidents can be caused once leakage occurs.
However, in the existing preparation method, the bromoxynil octanoate content is about 97%, if a bromoxynil octanoate raw drug with a content of more than 98.5% is required, 97% of bromoxynil octanoate needs to be recrystallized and refined, methanol which is cheap and easy to obtain and has a good refining effect is generally selected as a recrystallization solvent, a certain amount of by-product methyl octanoate is generated in a recrystallization mother liquor, the by-product methyl octanoate needs to be rectified and removed when the content of the methyl octanoate in the mother liquor is high, and the methyl octanoate is harmful to the environment and cannot enter the environment. For this reason, a new technical solution is needed to solve the above technical problems.
Disclosure of Invention
The invention aims to provide a method for preparing bromoxynil octanoate by-product regenerated raw pesticide, which aims to solve the problem that the existing recrystallization mother liquor in the background technology is harmful to the environment due to the generation of higher content of methyl octanoate.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of bromoxynil octanoate by-product regenerated raw medicine is characterized by comprising the step of ester exchange reaction, wherein the specific synthetic route is as follows:
the specific transesterification reaction steps are as follows:
1) preparation of bromoxynil octanoate crude product: bromoxynil and methyl caprylate are used as raw materials, a solvent is used as an auxiliary material, and under the action of a basic catalyst, heating and refluxing are carried out to prepare a bromoxynil octanoate crude product;
2) preparing bromoxynil octanoate bulk drug: adding a certain amount of methanol, completely dissolving the mixture under the action of temperature rise, then cooling to 0-10 ℃, recrystallizing, centrifuging and drying to obtain the bromoxynil octanoate technical product with high content.
In the step 1, the molar ratio of bromoxynil to methyl caprylate is 1: 1-1.05, the solvent amount is 2-3 times of the weight of bromoxynil, and the alkaline catalyst is 3% -5% of the weight of bromoxynil.
In the step 1, methyl caprylate and bromoxynil are subjected to ester exchange reaction in the presence of an alkaline catalyst, and methanol is continuously distilled out in the reaction process, so that the ester exchange reaction is balanced and shifted to the right.
In the step 1, the solvent is methyl cyclohexane and n-heptane, and the boiling points of the methyl cyclohexane and the n-heptane are 90-120 ℃ and the methyl cyclohexane and the n-heptane are not mutually soluble with methanol.
In the step 2, the amount of the methanol is 1.3 to 1.5 times of the weight of the bromoxynil.
In the step 2, methanol generated by the reaction is used as a recrystallization solvent.
In the step 2, the bromoxynil octanoate technical centrifugation mother liquor can be used as a recrystallization solvent.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the byproduct methyl caprylate is regenerated into bromoxynil octanoate raw drug by an ester exchange method, the raw drug content is up to 98.5%, the yield of the applied recrystallization mother liquor can reach 92-94%, a special reaction solvent is selected to ensure smooth reaction, and the generated methanol is applied as the recrystallization solvent.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
Example 1:
step one, preparing bromoxynil octanoate crude products:
277.00g of bromoxynil, 158.00g of methyl caprylate and 554.00g of solvent are put into a reaction kettle, the temperature is raised and the reflux is carried out under the action of 8.31g of basic catalyst, the reflux is carried out to a water separator to separate methanol, the bromoxynil is controlled within 5 hours to ensure that the content of the bromoxynil is less than 1%, and the solvent is evaporated after the reaction is finished.
Step two, preparing bromoxynil octanoate raw pesticide:
adding 360.1g of methanol as a recrystallization solvent, completely dissolving the methanol under the action of temperature rise, then cooling to 4 ℃, and carrying out heat preservation and recrystallization for 3 hours. After centrifugation, drying, 347.8g of bromoxynil octanoate with the content of 98.5 percent was obtained with the yield of 85 percent.
Example 2:
step one, preparing bromoxynil octanoate crude products:
277.00g of bromoxynil, 160.00g of methyl caprylate and 600.00g of solvent are put into a reaction kettle, the mixture is heated and refluxed under the action of 10.00g of basic catalyst, methanol is separated out from the mixture after the mixture is refluxed to a water separator, the bromoxynil is controlled within 5 hours until the content of the bromoxynil is less than 1%, and the solvent is evaporated after the reaction is finished.
Step two, preparing bromoxynil octanoate raw pesticide:
400.00g of the centrifugal mother liquor in the second step of the embodiment 1 is added and used as a recrystallization solvent, and the centrifugal mother liquor is completely dissolved under the action of temperature rise, then the temperature is reduced to 4 ℃, and the temperature is preserved for recrystallization for 3 hours. The mixture was centrifuged, dried and dried to obtain 388.5g of bromoxynil octanoate with a yield of 95% and a content of 98.5%. In this case, the average yield of example 1 and example 2 was 90%.
Example 3:
step one, preparing bromoxynil octanoate crude products:
277.00g of bromoxynil, 164.90g of methyl caprylate and 800.00g of solvent are put into a reaction kettle, the temperature is raised and the reflux is carried out under the action of 12.00g of basic catalyst, the methanol is separated out from the water separator after the reflux is carried out, the bromoxynil is controlled within 5 hours until the content of the bromoxynil is less than 1%, and the solvent is evaporated after the reaction is finished.
Step two, preparing bromoxynil octanoate raw pesticide:
410.00g of the centrifugal mother liquor in the second step of the embodiment 2 is added and used as a recrystallization solvent, the centrifugal mother liquor is completely dissolved under the action of temperature rise, then the temperature is reduced to 4 ℃, and the temperature is preserved for recrystallization for 3 hours. The mixture was centrifuged, dried and dried to obtain 400.4g of bromoxynil octanoate with a yield of 98.6%. In this case, the average yield in example 1, example 2 and example 3 was 92.7%.
Example 4:
step one, preparing bromoxynil octanoate crude products:
277.00g of bromoxynil, 165.90g of methyl caprylate and 831.00g of solvent are put into a reaction kettle, the temperature is raised and the reflux is carried out under the action of 13.85g of basic catalyst, the reflux is carried out to a water separator to separate methanol, the bromoxynil is controlled within 5 hours to ensure that the content of the bromoxynil is less than 1%, and the solvent is evaporated after the reaction is finished.
Step two, preparing bromoxynil octanoate raw pesticide:
415.50g of the centrifugal mother liquor in the second step of the embodiment 3 is added and used as a recrystallization solvent, the centrifugal mother liquor is completely dissolved under the action of temperature rise, then the temperature is reduced to 4 ℃, and the temperature is preserved for recrystallization for 3 hours. The mixture was centrifuged, dried and dried to obtain 400.9g of bromoxynil octanoate with a yield of 98.5%. In this case, the average yield of examples 1, 2, 3 and 4 was 94.0%.
The following table shows the conditions of the content and yield of bromoxynil octanoate used as a recrystallization solvent for the mother solutions in the following examples 1 to 4:
therefore, the yield of bromoxynil octanoate can be improved by using the centrifugal mother liquor.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A preparation method of bromoxynil octanoate by-product regenerated raw medicine is characterized by comprising an ester exchange reaction, wherein the specific synthetic route is as follows:
2. the method for preparing bromoxynil octanoate by-product regenerated technical material according to claim 1, which is characterized in that: the specific transesterification reaction steps are as follows:
1) preparation of bromoxynil octanoate crude product: bromoxynil and methyl caprylate are used as raw materials, a solvent is used as an auxiliary material, and under the action of a basic catalyst, heating and refluxing are carried out to prepare a bromoxynil octanoate crude product;
2) preparing bromoxynil octanoate bulk drug: adding a certain amount of methanol, heating to completely dissolve the bromoxynil, then cooling to 0-10 ℃, recrystallizing, centrifuging and drying to obtain the high-content bromoxynil octanoate technical product.
3. The method for preparing bromoxynil octanoate by-product regenerated technical material according to claim 2, which is characterized in that: in the step 1, the molar ratio of bromoxynil to methyl caprylate is 1: 1-1.05, the solvent amount is 2-3 times of the weight of bromoxynil, and the dosage of the alkaline catalyst is 3% -5% of the weight of bromoxynil.
4. The method for preparing bromoxynil octanoate by-product regenerated technical material according to claim 2, which is characterized in that: in the step 1, methyl caprylate and bromoxynil are subjected to ester exchange reaction in the presence of an alkaline catalyst, and methanol is continuously distilled out in the reaction process, so that the ester exchange reaction is balanced and shifted to the right.
5. The method for preparing bromoxynil octanoate by-product regenerated technical material according to claim 2, which is characterized in that: in the step 1, the solvent is methyl cyclohexane and n-heptane, and the boiling points of the methyl cyclohexane and the n-heptane are 90-120 ℃ and the methyl cyclohexane and the n-heptane are not mutually soluble with methanol.
6. The method for preparing bromoxynil octanoate by-product regenerated technical material according to claim 2, which is characterized in that: in the step 2, the amount of the methanol is 1.3 to 1.5 times of the weight of the bromoxynil.
7. The method for preparing bromoxynil octanoate by-product regenerated technical material according to claim 2, which is characterized in that: in the step 2, methanol generated by the reaction is used as a recrystallization solvent.
8. The method for preparing bromoxynil octanoate by-product regenerated technical material according to claim 2, which is characterized in that: in the step 2, the bromoxynil octanoate technical centrifugation mother liquor can be used as a recrystallization solvent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114573478A (en) * | 2022-03-11 | 2022-06-03 | 南京先进生物材料与过程装备研究院有限公司 | Method for preparing bromoxynil octanoate |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114573478A (en) * | 2022-03-11 | 2022-06-03 | 南京先进生物材料与过程装备研究院有限公司 | Method for preparing bromoxynil octanoate |
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