CN112390752B - Chloromethylquinolinic acid and its preparing method - Google Patents
Chloromethylquinolinic acid and its preparing method Download PDFInfo
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- C07—ORGANIC CHEMISTRY
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- 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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Abstract
The invention relates to the field of herbicide synthesis, and in particular relates to chloroquine acid and a preparation method thereof. The method can avoid the generation of a large amount of waste acid and waste water, is green and environment-friendly, and greatly reduces the treatment cost of three wastes; moreover, the reaction condition is mild, the post-treatment is simple, the product purity and yield are high, and the method is very suitable for industrial production.
Description
Technical Field
The invention relates to the field of herbicide synthesis, and particularly relates to chloroquinolinic acid and a preparation method thereof.
Background
Clomazone is a selective herbicide of the quinoline carboxylic acid hormone type, used for controlling cleavers, speedwell and other weeds in cereal crops, rapes and beet fields, and in addition, the umbelliferae crops are very sensitive to the clomazone. The structural formula is as follows:
the oxidation of methyl to carboxylic acid is a key step in the synthesis of chloroquinolinic acid. Patent US5006659 discloses the preparation of chloroquinolinic acid by oxidation of 3, 8-dimethyl-7-chloroquinoline with dilute nitric acid in sulfuric acid. However, the method generates a large amount of waste acid and waste water, the intermediate needs extraction and distillation, the operation steps are multiple, the yield is moderate, and the method is not suitable for industrial production.
Patent US4845226 discloses a process for preparing chloroquinolinic acid by using 3, 8-dimethyl-7-chloroquinoline as raw material, 1, 2-dichlorobenzene and sodium acetate aqueous solution as solvent, azodiisobutyronitrile as initiator, brominating with bromine, extracting with 70% sulfuric acid, adding manganese dioxide directly, oxidizing with nitric acid. The method has the advantages of high yield, high product purity, long reaction steps, high operation difficulty, generation of a large amount of waste acid, use of bromine and other organic solvents, troublesome post-treatment and difficult industrial production.
Disclosure of Invention
The invention aims to solve the problems of large amount of waste acid and waste water generated in the synthesis process, difficult industrialization and the like in the prior art, and provides a method for preparing chloroquinolinic acid by adopting liquid-phase catalytic oxidation and chloroquinolinic acid prepared by the method; moreover, the reaction condition is mild, the post-treatment is simple, the product purity and yield are high, and the method is very suitable for industrial production.
In order to achieve the above object, one aspect of the present invention provides a method for preparing chloroquinolinic acid, which comprises performing an oxidation reaction using 3, 8-dimethyl-7-chloroquinoline as a raw material, a carboxylic acid as a solvent, and an oxygen-containing gas as an oxidant in the presence of a catalyst, wherein the catalyst is one or more of a cobalt-based metal compound, a manganese-based metal compound, and a vanadium-based metal compound.
Preferably, the mass ratio of the 3, 8-dimethyl-7-chloroquinoline to the carboxylic acid is 1: 1-10.
Preferably, the molar ratio of 3, 8-dimethyl-7-chloroquinoline to oxygen-containing gas, calculated as oxygen, is 1: 2-10.
Preferably, the molar ratio of the 3, 8-dimethyl-7-chloroquinoline to the catalyst is 1: 0.001-1.
Preferably, the carboxylic acid is selected from one or more of acetic acid, propionic acid and butyric acid.
Preferably, the catalyst is one or more of cobalt acetate, manganese acetate, cobalt chloride, manganese chloride and vanadium pentoxide.
Preferably, the oxygen-containing gas is ozone or a mixed gas of ozone and air.
More preferably, the volume ratio of ozone to air is 1: 1-20.
Preferably, the conditions of the oxygen reaction include: the reaction temperature is 20-200 deg.C, and the reaction time is 4-20 hr.
Preferably, the method further comprises solid-liquid separating the oxidation product to obtain chloroquinolinic acid and a liquid phase, and using the liquid phase obtained by the solid-liquid separation as the reaction liquid in the oxidation reaction.
The invention also provides chloromethylquinolinic acid prepared by the method.
The method adopts a liquid phase catalytic oxidation method to prepare the chloroquinolinic acid, avoids the mass production of waste acid and waste water, is green and environment-friendly, and greatly reduces the treatment cost of three wastes. In addition, the preparation method has the advantages of low reaction temperature, less side reaction, high product conversion rate and high purity, and the oxidant is the mixed gas of ozone and air. Furthermore, the liquid phase (mother liquor) obtained by solid-liquid separation of the reaction liquid can be recycled, so that the time cost is reduced, and the method is suitable for 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.
According to one aspect of the present invention, there is provided a process for producing chloroquinolinic acid, which comprises carrying out an oxidation reaction using 3, 8-dimethyl-7-chloroquinoline as a raw material, a carboxylic acid as a solvent, and an oxygen-containing gas as an oxidizing agent in the presence of a catalyst, wherein the catalyst is one or more of a cobalt-based metal compound, a manganese-based metal compound, and a vanadium-based metal compound.
According to the invention, the liquid-phase catalytic oxidation method is adopted to prepare the chloroquinolinic acid, so that a large amount of waste acid and waste water is avoided, the method is green and environment-friendly, and the three-waste treatment cost is greatly reduced.
Further, by carrying out the oxidation by the above-mentioned method, the post-treatment is extremely simple, and chloroquinolinic acid of high purity can be obtained only by cooling to room temperature (e.g., 10 to 40 ℃ C.), solid-liquid separation and drying after the completion of the oxidation reaction. The method of the temperature reduction, solid-liquid separation and drying is not particularly limited, and a method generally used in the art may be employed, and for example, the temperature reduction may be carried out by air cooling, the solid-liquid separation may be carried out by filtration, centrifugation or the like, and the drying may be carried out by drying at 60 to 100 ℃ for 4 to 12 hours.
According to the invention, the amount of 3, 8-dimethyl-7-chloroquinoline and carboxylic acid is preferably 1: 1-10, more preferably 1: 2 to 8, and more preferably 1:3 to 6.
According to the present invention, the oxygen-containing gas as the oxidizing agent is used in excess, for example, the oxygen-containing gas is continuously fed until the end of the reaction during the reaction, and the feeding rate of the oxygen-containing gas is not particularly limited and may be carried out according to the conditions usual in the art, for example, the feeding rate of the oxygen-containing gas may be 100-300mL/min, more preferably 150-250mL/min, relative to a 1L reactor. Further, the molar ratio of the compound of the structure represented by the formula (1) to the oxygen-containing gas in terms of oxygen may be, for example, 1: 2-10, preferably 1: 3-7.
According to the invention, 3, 8-dimethyl-7-chloroquinoline and the catalyst are preferably used in a molar ratio of 1: 0.001-1, more preferably 1: 0.001 to 0.5, more preferably 1: 0.01 to 0.1, more preferably 1: 0.02 to 0.07, more preferably 1: 0.03 to 0.06, particularly preferably 1:0.04 to 0.06.
According to the present invention, preferably, the carboxylic acid is selected from one or more of acetic acid, propionic acid and butyric acid; more preferably, the carboxylic acid is acetic acid.
According to the present invention, preferably, the catalyst is one or more of cobalt acetate, manganese acetate, cobalt chloride, manganese chloride and vanadium pentoxide; more preferably, the catalyst is one or more of cobalt acetate, manganese acetate and vanadium pentoxide.
According to the present invention, preferably, the oxidation reaction is carried out in the presence of a bromide salt.
The amount of the bromide salt can be selected according to the amount of 3, 8-dimethyl-7-chloroquinoline, and preferably, the molar ratio of the 3, 8-dimethyl-7-chloroquinoline to the bromide salt is 1: 0.001-0.5, more preferably 1: 0.001 to 0.25, more preferably 1: 0.01 to 0.05, more preferably 1: 0.01-0.03.
The bromide salt is preferably sodium bromide and/or potassium bromide, more preferably sodium bromide.
According to the present invention, preferably, the oxygen-containing gas is ozone, or a mixed gas of ozone and air. More preferably, in the mixed gas of ozone and air, the volume ratio of ozone to air is 1: 1-20, more preferably 1: 4-16.
By using the mixed gas of ozone and air as the oxidant, the method is clean and environment-friendly, and the liquid phase obtained by solid-liquid separation contains almost all the catalyst, so that the method preferably further comprises the steps of carrying out solid-liquid separation on the oxidation product to obtain a solid phase (chloroquinolinic acid) and a liquid phase, and using the liquid phase obtained by solid-liquid separation as the reaction liquid in the oxidation reaction, namely, recycling the liquid phase obtained by solid-liquid separation for the oxidation reaction system.
Preferably, the recycling and reusing times are 1-100 times; more preferably, the recycling and reusing times are 5-50 times; further preferably, the recycling and reusing times are 5-20 times.
Further, since a small amount of the catalyst may be adsorbed on the surface of the solid phase of the solid-liquid separation, it is preferable that the small amount of the catalyst can be separated from the solid phase by washing. The washing solvent is preferably a reaction solvent used in the oxidation reaction, that is, it is preferable in the method of the present invention to further include: and washing the solid phase obtained by the solid-liquid separation with a solvent used in the oxidation reaction.
In addition, in order to further reduce the cost, it is preferable that the liquid phase obtained by the solid-liquid separation and the washing liquid after the washing are used as the reaction liquid in the oxidation reaction.
The amount of the solvent used for the washing is preferably 0.1 to 10 times by weight, more preferably 0.2 to 4 times by weight, based on the amount of the solvent used for the oxidation reaction, in view of the yield obtained and the concentration of the catalyst when the solvent is reused together with the liquid phase obtained by the solid-liquid separation.
According to the present invention, preferably, the conditions of the oxygen reaction include: the reaction temperature is 20-200 ℃, and the reaction time is 4-20 hours; more preferably, the conditions of the oxygen reaction include: the reaction temperature is 40-180 ℃, and the reaction time is 6-18 hours; further preferably, the oxygen reaction conditions include: the reaction temperature is 60-120 deg.C, and the reaction time is 8-16 hr.
According to a second aspect of the present invention, chloroquinolinic acid prepared by the process of the present invention is provided.
The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.
In the following examples, 3, 8-dimethyl-7-chloroquinoline was purchased from Henan Agrochemistry, Inc. of Zhongnong.
Example 1
1) In a 2L four-neck glass flask, 200 g of 3, 8-dimethyl-7-chloroquinoline, 800g of acetic acid, 9.26 g (0.05 equivalent) of cobalt acetate and 2.7 g (0.025 equivalent) of sodium bromide are added, the temperature is raised to 100 ℃, when the solid is completely dissolved, mixed gas of ozone and air is introduced for 0.4L/min, and liquid phase detection reaction is carried out. After the reaction is carried out for 12 hours, the temperature is reduced to 25 ℃, solid is separated out, the solid is filtered, 30g of acetic acid is leached, the solid is dried, and the filtrate is applied to the next batch of reaction. Chloroquinolinic acid solid 214.7 g (nuclear magnetic data below) was obtained with a purity of 98.9 wt.% and a yield of 91.8%. The filtered mother liquor is added with corresponding 3, 8-dimethyl-7-chloroquinoline, and then the reaction is continued.
1 H-NMR(500MHz,d6-DMSO)δ:8.819(s,1H),8.128(s,1H),7.761-7.743(d,1H,J＝9Hz),7.581-7.563(d,1H,J＝9Hz),2.763(s,3H),2.497(s,3H)。
The first application is as follows: 200 g of 3, 8-dimethyl-7-chloroquinoline and 800g of solvent (793 g of the last batch of filtrate and 7 g of acetic acid) are added into a 2L four-neck glass flask, the temperature is raised to 100 ℃, when the solid is completely dissolved, mixed gas of ozone and air is introduced for 0.4L/min, and liquid phase detection reaction is carried out. After the reaction is carried out for 12 hours, the temperature is reduced to 25 ℃, the solid is separated out, the solid is filtered and dried, and the filtrate is applied to the next batch of reaction. Chloroquinolinic acid solid 216.8 g, purity 98.8 wt%, yield 92.6%. The filtered mother liquor is reused for the next batch to continue the reaction.
3) The second time to the nineteenth time: the same procedure was followed for the first use except that the mother liquor obtained in the previous use was used (the amount of the mother liquor was less than 800g and was made up to 800g with acetic acid), and the yield and purity were as shown in Table 1.
TABLE 1
| Product yield (%) | Purity of the product (% by weight) | |
| First reaction | 91.8 | 98.9 |
| For the first time | 92.6 | 98.8 |
| For the second time | 92.8 | 98.8 |
| For the third time | 92.3 | 98.7 |
| For the fourth time | 92.5 | 98.8 |
| For the fifth use | 92.4 | 98.7 |
| For the sixth time | 92.7 | 98.7 |
| For the seventh time | 92.8 | 98.9 |
| For the eighth application | 92.8 | 98.6 |
| For the ninth time | 92.5 | 98.9 |
| For the tenth application | 92.2 | 98.6 |
| For the eleventh application | 92.1 | 98.5 |
| For the twelfth application | 92.3 | 98.7 |
| For the thirteenth application | 92.4 | 98.6 |
| For the fourteenth application | 92.1 | 98.9 |
| For the fifteenth application | 92.6 | 98.6 |
| For the sixteenth application | 92.7 | 98.7 |
| For the seventeenth time | 92.5 | 98.7 |
| For the eighteenth application | 92.3 | 98.8 |
| Used for the nineteenth time | 92.2 | 98.7 |
Example 2
1) 200 g of 3, 8-dimethyl-7-chloroquinoline, 1000 g of acetic acid, 14 g (0.05 equivalent) of manganese acetate and 2.7 g (0.025 equivalent) of sodium bromide are added into a 2L four-neck glass flask, the temperature is raised to 100 ℃, when the solid is completely dissolved, 0.4L/min of mixed gas of ozone and air is introduced, and the reaction is detected by a liquid phase. After the reaction is carried out for 12 hours, the temperature is reduced to 25 ℃, solid is separated out, the solid is filtered, 50g of acetic acid is leached, the solid is dried, and the filtrate is applied to the next batch of reaction. 215.8 g of chloromethylquinolinic acid solid is obtained, the purity is 98.9 percent by weight, and the yield is 92.2 percent. The filtered mother liquor is added with corresponding 3, 8-dimethyl-7-chloroquinoline, and then the reaction is continued.
The first application is as follows: adding 200 g of 3, 8-dimethyl-7-chloroquinoline and 1010.4 g of filtrate into a 2L four-neck glass flask, heating to 100 ℃, introducing 0.4L/min of mixed gas of ozone and air when the solid is completely dissolved, and carrying out liquid phase detection reaction. After the reaction is carried out for 12 hours, the temperature is reduced to 25 ℃, the solid is separated out, the solid is filtered and dried, and the filtrate is applied to the next batch of reaction. The chloroquinolinic acid solid 217 g was obtained with a purity of 98.6% by weight and a yield of 92.5%. The filtered mother liquor is added with corresponding 3, 8-dimethyl-7-chloroquinoline, and then the reaction is continued.
3) The second time to the nineteenth time: the same procedure was followed for the first use except that the mother liquor obtained in the previous use was used (the amount of mother liquor was less than 1000 g and was made up to 1000 g with acetic acid), and the yield and purity were as shown in Table 2.
TABLE 2
Example 3
1) 200 g of 3, 8-dimethyl-7-chloroquinoline, 1000 g of acetic acid, 9.3 g (0.05 equivalent) of vanadium pentoxide and 2.7 g (0.025 equivalent) of sodium bromide are added into a 2L four-neck glass flask, the temperature is raised to 80 ℃, mixed gas of ozone and air is introduced for 0.6L/min after all solids are dissolved, and liquid phase detection reaction is carried out. After the reaction is carried out for 12 hours, the temperature is reduced to 25 ℃, solid is separated out and filtered, 50g of acetic acid is used for leaching, the solid is dried, and the filtrate is used for the next batch of reaction. 214 g of chloromethylquinolinic acid solid is obtained, the purity is 98.7 weight percent, and the yield is 91.3 percent. The filtered mother liquor is added with corresponding 3, 8-dimethyl-7-chloroquinoline, and then the reaction is continued.
For the first time, the application is as follows: 200 g of 3, 8-dimethyl-7-chloroquinoline and 1008.8 g of filtrate are added into a 2L four-neck glass flask, the temperature is raised to 80 ℃, when the solid is completely dissolved, mixed gas of ozone and air is introduced for 0.6L/min, and liquid phase detection reaction is carried out. After the reaction is carried out for 12 hours, the temperature is reduced to 25 ℃, the solid is separated out, the solid is filtered and dried, and the filtrate is applied to the next batch of reaction. The chloroquinolinic acid solid obtained was 214.5 g, purity 98.9% by weight, yield 91.7%. The filtered mother liquor is added with corresponding 3, 8-dimethyl-7-chloroquinoline, and then the reaction is continued.
3) The second time to the nineteenth time: the same procedure was followed for the first use except that the mother liquor obtained in the previous use was used (the amount of mother liquor was less than 1000 g and was made up to 1000 g with acetic acid), and the yield and purity were as shown in Table 3.
TABLE 3
| Product yield (%) | Purity of the product (% by weight) | |
| First reaction | 91.3 | 98.7 |
| For the first time | 91.7 | 98.9 |
| For the second time | 91.5 | 98.7 |
| For the third time | 91.6 | 98.9 |
| For the fourth time | 91.7 | 98.6 |
| For the fifth use | 91.4 | 98.7 |
| For the sixth time | 91.5 | 98.9 |
| For the seventh application | 91.3 | 98.3 |
| For the eighth application | 91.1 | 98.9 |
| For the ninth application | 91.8 | 98.8 |
| For the tenth application | 91.7 | 98.5 |
| For the eleventh application | 91.3 | 98.6 |
| For the twelfth application | 91.5 | 98.8 |
| For the thirteenth application | 91.5 | 98.7 |
| For the fourteenth application | 91.4 | 98.8 |
| For the fifteenth application | 91.2 | 98.7 |
| For the sixteenth application | 91.5 | 98.8 |
| For the seventeenth time | 91.8 | 98.3 |
| For the eighteenth application | 91.4 | 98.7 |
| Used for the nineteenth time | 91.6 | 98.6 |
Comparative example 1
The procedure is as in example 1, except that the acetic acid is replaced with DMF solvent to give chloroquinolinic acid as a solid 81.1 g with a purity of 96.2% by weight and a yield of 33.7%.
Comparative example 2
The procedure is as in example 1, except that the acetic acid is replaced with chlorobenzene solvent, to give chloroquinolinic acid as a solid 27.8 g, 95.7% purity by weight and 11.5% yield.
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 (8)
1. A preparation method of chlorochloroquinolinic acid is characterized in that the method comprises the steps of taking 3, 8-dimethyl-7-chloroquinoline as a raw material, carboxylic acid as a solvent and oxygen-containing gas as an oxidant in the presence of a catalyst to carry out oxidation reaction, wherein the catalyst is one or more of cobalt acetate, manganese acetate, cobalt chloride, manganese chloride and vanadium pentoxide,
wherein the method also comprises the steps of carrying out solid-liquid separation on the oxidation product to obtain chloroquinolinic acid and a liquid phase, and using the liquid phase obtained by the solid-liquid separation as the reaction liquid of the oxidation reaction.
2. The method according to claim 1, wherein the mass ratio of the 3, 8-dimethyl-7-chloroquinoline to the carboxylic acid is 1: 1-10.
3. The process according to claim 1, wherein the molar ratio of 3, 8-dimethyl-7-chloroquinoline to oxygen-containing gas, calculated as oxygen, is from 1: 2-10.
4. The process of claim 1, wherein the molar ratio of 3, 8-dimethyl-7-chloroquinoline to the catalyst is from 1: 0.001-1.
5. The process according to any one of claims 1 to 4, wherein the carboxylic acid is selected from one or more of acetic acid, propionic acid and butyric acid.
6. The method according to any one of claims 1 to 4, wherein the oxygen-containing gas is ozone or a mixed gas of ozone and air.
7. The method of claim 6, wherein the volume ratio of ozone to air is 1: 1-20.
8. The method of any one of claims 1-4, wherein the conditions of the oxygen reaction comprise: the reaction temperature is 20-200 deg.C, and the reaction time is 4-20 hr.
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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 |
| US5006659A (en) * | 1987-03-03 | 1991-04-09 | Basf Aktiengesellschaft | Preparation of 7-chloroquinoline-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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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 |
| US5006659A (en) * | 1987-03-03 | 1991-04-09 | Basf Aktiengesellschaft | Preparation of 7-chloroquinoline-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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