CN112939858B - Process for separating quinmerac and its isomer - Google Patents
Process for separating quinmerac and its isomer Download PDFInfo
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- CN112939858B CN112939858B CN201911259796.1A CN201911259796A CN112939858B CN 112939858 B CN112939858 B CN 112939858B CN 201911259796 A CN201911259796 A CN 201911259796A CN 112939858 B CN112939858 B CN 112939858B
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- quinmerac
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom 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 to ring carbon atoms
- C07D215/48—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of pesticides, and discloses a method for separating quinmerac and isomers thereof, which comprises the following steps: the method comprises the following steps of carrying out heat treatment on a crude product containing quinmerac and isomers thereof in a solvent, and then carrying out cooling and solid-liquid separation, wherein the solvent is a mixed solvent of alcohol with 1-4 carbon atoms or alcohol with 1-4 carbon atoms and water. The method for separating the quinmerac and the isomers thereof has the advantages of high yield and environmental friendliness.
Description
Technical Field
The invention relates to the field of pesticides, and particularly relates to a method for separating quinmerac and isomers thereof.
Background
Quinmerac can be used as a selective herbicide pesticide, and has the following structural formula:
however, its isomer (7-chloro-8-methylquinoline-3-carboxylic acid), whose formula is shown below, is not formed during the classical synthesis reaction:
the content of the isomer in the reaction acid-regulating filter cake in the refining section is up to 10 weight percent, the refining of the quinmerac at present is to use 2 times of 50 weight percent DMF aqueous solution to carry out pulping refining at 95-100 ℃, and the filter cake is further used 3 times of 50 weight percent DMF aqueous solution to carry out pulping refining at 95-100 ℃, so that the isomer can be effectively removed, and a qualified product is obtained. The method has the advantages that the waste DMF liquid contains a large amount of quinmerac, so that the refining yield is lower than 70 percent, and the production cost is high. Therefore, the method for separating the herbicide in the green environment is high in efficiency and simple and convenient to operate, and has important significance for industrial production of the herbicide.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a method for separating quinmerac and isomers thereof, and the separation method has the advantages of high yield and environmental friendliness.
In order to achieve the above object, the present invention provides a method for separating quinmerac and its isomers, the method comprising: the method comprises the following steps of carrying out heat treatment on a crude product containing quinmerac and isomers thereof in a solvent, and then carrying out cooling and solid-liquid separation, wherein the solvent is a mixed solvent of alcohol with 1-4 carbon atoms or alcohol with 1-4 carbon atoms and water.
Preferably, the alcohol having 1 to 4 carbon atoms is methanol, ethanol, propanol or butanol.
Preferably, the solvent is ethanol or a mixed solvent of ethanol and water.
Preferably, the solvent is used in an amount of 5-10ml relative to 1g of the crude product.
Preferably, the solvent is used in an amount of 5-7ml relative to 1g of the crude product.
Preferably, when the solvent is a mixed solvent of an alcohol having 1 to 4 carbon atoms and water, the content of the alcohol having 1 to 4 carbon atoms is 50% by weight or more.
Preferably, the conditions of the heat treatment include: the treatment temperature is 65-120 ℃, and the treatment time is 1-3 hours.
Preferably, the temperature of the heat treatment is a temperature at which the solvent is refluxed.
Preferably, cooling to 5-35 ℃.
Preferably, the content of the isomers of quinmerac in the crude product is 15 wt% or less.
Preferably, the content of the isomers of quinmerac in the crude product is 10 wt% or less.
The invention adopts the method of refining the quinmerac by using the primary alcohol and water mixed solvent or the alcohol to replace the secondary DMF and water mixed solvent, and the solubility of the quinmerac in the alcohol is far less than that of the quinmerac in the DMF, so the loss of the quinmerac along with the waste DMF liquid is reduced, and the yield is further improved; in addition, compared with the device for recovering DMF, the device for recovering the alcohol solution does not need negative pressure and high temperature, thereby improving the productivity and yield and reducing the energy consumption and environmental protection pressure of industrial production.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for separating quinmerac and isomers thereof, which comprises the following steps: the crude product containing the quinmerac and the isomers thereof is subjected to heat treatment in a solvent, and then cooling and solid-liquid separation are carried out, wherein the solvent is alcohol with 1-4 carbon atoms or a mixed solvent of the alcohol with 1-4 carbon atoms and water.
According to the present invention, the content of the isomers of quinmerac in the crude product may be 15 wt% or less, preferably 10 wt% or less, more preferably 8 wt% or less, and further preferably 1 wt% or more, more preferably 3 wt% or more, and further preferably 5 wt% or more.
The content of quinmerac in the crude product may be 80 wt% or more, preferably 85 wt% or more, more preferably 90 wt% or more, and preferably 99 wt% or less, more preferably 97 wt% or less, and still more preferably 95 wt% or less.
According to the present invention, preferably, the alcohol having 1 to 4 carbon atoms is methanol, ethanol, propanol or butanol.
In a particularly preferred embodiment of the present invention, the solvent is ethanol or a mixed solvent of ethanol and water. By using these solvents, the yield can be further significantly improved.
According to the invention, the amount of the solvent may be determined according to the amount of the crude product, preferably, the amount of the solvent is 5 to 10ml relative to 1g of the crude product; preferably, the solvent is used in an amount of 5-7ml relative to 1g of the crude product.
According to the present invention, when the solvent is a mixed solvent of an alcohol having 1 to 4 carbon atoms and water, the content of the alcohol having 1 to 4 carbon atoms is 50% by weight or more, and more preferably 85 to 95% by weight.
According to the present invention, preferably, the conditions of the heat treatment include: the treatment temperature is 65-120 ℃, and the treatment time is 1-3 hours; more preferably, the temperature of the heat treatment is a temperature at which the solvent is refluxed.
According to the invention, preferably, after said heat treatment, the heat-treated material is cooled to 5-35 ℃, more preferably to 10-30 ℃.
According to the present invention, the cooling treatment is followed by solid-liquid separation, and the method of solid-liquid separation is not particularly limited, and various methods generally used in the art may be used, and for example, solid-liquid separation may be performed by a method such as filtration or centrifugation.
The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.
Example 1
Weighing 40g of quinmerac crude product (quinmerac/isomer =90 wt%/10 wt%) in a 500ml four-necked bottle, adding 200g of ethanol water solution (ethanol content is 95 wt%), heating to 85-90 ℃, refluxing and stirring for 1h, then naturally cooling to room temperature (25 ℃), filtering, and drying a filter cake to obtain 32.5g of quinmerac, wherein the purity is 99 wt%, and the yield is 89.4%.
Example 2
40g of quinmerac crude product (quinmerac/isomer =90 wt%/10 wt%) is weighed into a 500ml four-necked bottle, 280g of ethanol water solution (ethanol content is 95 wt%) is added, the temperature is raised to 85-90 ℃, reflux stirring is carried out for 1h, then the temperature is naturally cooled to room temperature (25 ℃), filtration is carried out, and a filter cake is dried to obtain 32.2g of quinmerac, wherein the purity is 99.5 wt%, and the yield is 89.0%.
Example 3
Weighing 40g of crude acid adjusting filter cake (quinmerac/isomer =90 wt%/10 wt%) in a 500ml four-necked bottle, adding 200g of ethanol water solution (ethanol content is 85 wt%), heating to 85-90 ℃, refluxing and stirring for 1h, then naturally cooling to room temperature (25 ℃), filtering, and drying the filter cake to obtain 32.6g of quinmerac, wherein the purity is 98.0 wt%, and the yield is 88.7%.
Example 4
The procedure was followed as in example 1, except that 200g of an aqueous methanol solution (methanol content: 95% by weight) was used in place of the aqueous ethanol solution, and the heating temperature was set to the reflux temperature, to give 30.5g of quinmerac acid in a purity of 99.4% by weight in a yield of 84.2%.
Example 5
The procedure was followed as in example 1, except that 200g of an aqueous propanol solution (propanol content: 95% by weight) was used in place of the aqueous ethanol solution, and the heating temperature was set to the reflux temperature, to give 32.5g of quinmerac acid in which the purity was 98% by weight and the yield was 88.5%.
Example 6
The procedure was carried out as in example 1, except that 200g of methanol was used instead of the aqueous ethanol solution and the heating temperature was set to the reflux temperature, to give 30.0g of quinmerac acid in a purity of 99.3% by weight in a yield of 82.8%.
Example 7
The procedure was carried out as in example 1, except that 200g of ethanol was used instead of the aqueous ethanol solution, and the heating temperature was set to the reflux temperature, to give 32.6g of quinmerac acid in which the purity was 98.4% by weight and the yield was 89.1%.
Example 8
The procedure was carried out as in example 1, except that 200g of propanol was used instead of the aqueous ethanol solution and the heating temperature was set to the reflux temperature, to give 32.7g of quinmerac acid in which the purity was 98.0% by weight and the yield was 89.0%.
Comparative example 1
Following the procedure of example 1, except for using 200g of an aqueous DMF solution (DMF content: 95% by weight) in place of the aqueous ethanol solution and heating at the reflux temperature, 23g of quinmerac acid, of which the purity was 99.9% by weight and the yield was 63.8%, was obtained.
Comparative example 2
According to the procedure of example 1, except for using 200g of pentanol instead of the aqueous ethanol solution and heating at the reflux temperature, 34.0g of quinmerac acid, of which the purity was 92% by weight and the yield was 86.9%, was obtained.
Comparative example 3
Weighing 40g of crude acid adjusting filter cake (quinmerac/isomer =90 wt%/10 wt%) in a 250ml four-necked bottle, adding 80g of DMF aqueous solution (DMF content is 50 wt%), heating to 95-100 ℃, stirring for 1h, then cooling to room temperature (25 ℃), and filtering; and putting the filter cake into a four-mouth bottle again, adding 120g of DMF aqueous solution (the DMF content is 50 wt%), heating to 95-100 ℃, stirring for 1h, then cooling to room temperature, filtering, and drying the filter cake to obtain 25.2g of quinmerac acid, wherein the purity of the quinmerac is 99 wt%, and the yield is 69.3%.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (5)
1. A method for separating quinmerac and its isomers, the method comprising: carrying out heat treatment on a crude product containing quinmerac and isomers thereof in a solvent, and then carrying out cooling and solid-liquid separation, wherein the solvent is a mixed solvent of ethanol and water, the content of the ethanol in the mixed solvent is 95 wt%, the dosage of the solvent is 5-7ml relative to 1g of the crude product, and the heat treatment conditions comprise: the treatment temperature is 65-120 ℃, and the treatment time is 1-3 hours.
2. The separation method according to claim 1, wherein the temperature of the heat treatment is a temperature of solvent reflux.
3. The separation method according to claim 1, wherein the cooling is performed to 5 to 35 ℃.
4. The separation method according to claim 1, wherein the content of the isomers of quinmerac in the crude product is 15% by weight or less.
5. The separation method according to claim 1, wherein the content of the isomers of quinmerac in the crude product is 10% by weight or less.
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| CN201911259796.1A CN112939858B (en) | 2019-12-10 | 2019-12-10 | Process for separating quinmerac and its isomer |
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| CN112939858A CN112939858A (en) | 2021-06-11 |
| CN112939858B true CN112939858B (en) | 2023-03-28 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0282778A1 (en) * | 1987-03-03 | 1988-09-21 | BASF Aktiengesellschaft | Process for the preparation of 7-chloro-quinoline-8-carboxylic acids |
| US4845226A (en) * | 1987-02-03 | 1989-07-04 | Basf Aktiengesellschaft | Preparation of 8-bromomethyl-3-methylquinoline compounds |
| CN102942524A (en) * | 2012-11-21 | 2013-02-27 | 北京法盖银科技有限公司 | Preparation method of quinoline derivative |
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2019
- 2019-12-10 CN CN201911259796.1A patent/CN112939858B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4845226A (en) * | 1987-02-03 | 1989-07-04 | Basf Aktiengesellschaft | Preparation of 8-bromomethyl-3-methylquinoline compounds |
| EP0282778A1 (en) * | 1987-03-03 | 1988-09-21 | BASF Aktiengesellschaft | Process for the preparation of 7-chloro-quinoline-8-carboxylic acids |
| CN102942524A (en) * | 2012-11-21 | 2013-02-27 | 北京法盖银科技有限公司 | Preparation method of quinoline derivative |
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