CN111606807A - Preparation method of fomesafen technical intermediate acifluorfen - Google Patents
Preparation method of fomesafen technical intermediate acifluorfen Download PDFInfo
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- CN111606807A CN111606807A CN202010597326.2A CN202010597326A CN111606807A CN 111606807 A CN111606807 A CN 111606807A CN 202010597326 A CN202010597326 A CN 202010597326A CN 111606807 A CN111606807 A CN 111606807A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/16—Separation; Purification; Stabilisation; Use of additives
Abstract
The invention provides a preparation method of fomesafen as a raw pesticide intermediate, namely acifluorfen, and belongs to the technical field of pesticides. The method adopts a low-temperature nitration mode, can slowly release nitre milling ions, enables the reaction to tend to be smooth, enhances the selective competitive power of a target product, inhibits multi-nitration and ectopic nitration by-products, and effectively improves the content of intermediate acifluorfen. The method provided by the invention can be effectively applied to the production and application of fomesafen technical.
Description
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a preparation method of fomesafen as a technical intermediate of fomesafen.
Background
The fomesafen is also named as sanwei, has a chemical name of 5- [ 2-chloro-4- (trifluoromethyl) phenoxy ] -N-methylsulfonyl-2-nitrobenzamide, belongs to a fluorine-containing diphenyl ether herbicide, is a protoporphyrinogen oxidase inhibitor, and is a high-efficiency, low-toxicity and broad-spectrum dry field herbicide.
Acifluorfen is an intermediate in the synthesis of fomesafen technical material, and the quality of the acifluorfen technical material directly influences the quality of the fomesafen technical material. Therefore, the production of high-content acifluorfen is the subject of domestic enterprise research. At present, 3- [ 2-chloro-4- (trifluoromethyl) phenoxy ] benzoic acid is mostly adopted as an initial raw material in domestic synthesis and is obtained by high-temperature nitration. However, the synthesis route has high reaction temperature, low safety and low content yield, and the main reasons are as follows: under the reaction condition, the nitration reaction temperature is high, the side reaction is more, the selectivity is poor, and the content is lower.
Disclosure of Invention
The invention provides a preparation method of fomesafen as a raw drug intermediate of fomesafen, which adopts a low-temperature nitration mode, can slowly release nitre milling ions, enables the reaction to tend to be gentle, enhances the selective competitiveness of a target product, inhibits multi-nitration and ectopic nitration by-products, and effectively improves the content of the intermediate of the fomesafen.
In order to achieve the purpose, the invention provides a preparation method of fomesafen as a technical intermediate of fomesafen, which comprises the following steps:
putting the measured 3- [ 2-chloro-4- (trifluoromethyl) phenoxy ] benzoic acid into a reaction kettle, adding the measured solvent, slowly cooling to 50-60 ℃, adding the catalyst, continuously and slowly cooling, and slowly dropwise adding mixed acid prepared by 98% nitric acid and 98% sulfuric acid in proportion under the temperature control;
after the dropwise addition is finished, naturally heating to 20-25 ℃, and then carrying out heat preservation reaction for 1-2 hours;
after the reaction is finished, dropwise adding a certain amount of water under the controlled temperature to dilute the sulfuric acid to 60-70%, stirring for 25-40 minutes under the controlled temperature after dropwise adding is finished, fully standing and layering, and discharging lower-layer waste acid to a waste acid storage tank;
after the waste acid is removed, adding a certain amount of water into the materials to clean free acid, then heating to 55-60 ℃, stirring for 1 hour, fully standing for layering to remove the solvent, cooling to 40-45 ℃, performing suction filtration, centrifuging, and drying to obtain the intermediate acifluorfen.
The reaction equation is as follows:
side reaction 1 (polynitro by-product):
side reaction 2 (ectopic nitro by-product):
preferably, the solvent is 1, 2-dichloroethane. It is understood that the present application screens the solvent, ultimately to the selection of dichloroethane only, primarily from the cost, safety and commercial operability aspects. In the selection of the solvent, the methylene chloride used in the prior art has been considered, but its boiling point is too low to be suitable for the incubation temperature of the reaction of the invention, and similarly, chloroform has also been considered, also screened for the reasons mentioned above; for other solvents, the solvents are difficult to be applied to the nitration environment based on experimental results based on various considerations such as cost, safety, operability and the like.
Preferably, the catalyst is acetic anhydride or propionic anhydride. It can be understood that the invention selects acetic anhydride or propionic anhydride as the catalyst, on one hand, the invention can absorb the water produced in the reaction process, ensure the concentration of the mixed acid not to be diluted and ensure the nitration capability; on the other hand, the activity of nitric acid for dissociating nitre milling ions can be ensured under the condition of low temperature, and the reaction is ensured, so that the dosage of sulfuric acid is effectively reduced.
Preferably, the molar ratio of the 3- [ 2-chloro-4- (trifluoromethyl) phenoxy ] benzoic acid added to the catalyst is 1 (2-3.5). It can be understood that the key point of the invention lies in that the dosage of the mixed acid, especially the dosage of the sulfuric acid is reduced by increasing the dosage of the catalyst, and the nitric milling ions can be slowly generated under the condition of low temperature, thereby ensuring the timely participation of the generated nitric milling ions in the reaction and enhancing the competitiveness of the main reaction.
Preferably, the molar ratio of the 3- [ 2-chloro-4- (trifluoromethyl) phenoxy ] benzoic acid to nitric acid added is 1: (1.2-2.4), wherein the ratio of the added 98% nitric acid to 98% sulfuric acid is 1:
(1-2)。
preferably, the mixed acid is slowly dropped at the temperature of-5 to 20 ℃ for 1 to 1.5 hours. It can be understood that the main point of the invention is to adopt the low-temperature nitrification mode for treatment, which has the advantages that the dissociated nitre milling ions are slow and uniform, the reaction is carried out along with the generation, the low-temperature condition does not reach the potential energy for initiating the side reaction, the phase transformation enhances the competitiveness of the main reaction, the conversion selectivity is improved, the side reaction is inhibited, and the amount of the side products is reduced.
Preferably, a certain amount of water is added dropwise while controlling the temperature at 40-60 deg.C, and the solution is stirred and layered while controlling the temperature at 55-60 deg.C. It can be understood that the purpose of adding a fixed amount of water under controlled temperature is to dilute the sulfuric acid concentration to 60-70%, so the specific amount of water added can be determined according to the target dilution concentration, the adding time is also determined by the time for reaching the target dilution concentration, and the actual production can be controlled to be about 15-20 minutes.
Preferably, the content of the obtained acifluorfen is more than or equal to 78 percent and the total yield is more than or equal to 80 percent based on the 3- [ 2-chloro-4- (trifluoromethyl) phenoxy ] benzoic acid.
Compared with the prior art, the invention has the advantages and positive effects that:
the preparation method of the fomesafen original drug intermediate acifluorfen provided by the invention adopts a low-temperature nitration mode, can slowly release nitre milling ions, and simultaneously properly increases the consumption of acetic anhydride, so that the reaction tends to be gentle, the selective competitiveness of a target product is enhanced, multi-nitration and ectopic nitration by-products are inhibited, and the content of the intermediate acifluorfen is effectively improved;
the preparation method provided by the invention can effectively reduce the nitration temperature, improve the controllability, facilitate safe production, have high safety and are easy to realize industrialization;
the content of acifluorfen which is a raw drug intermediate of fomesafen prepared by the low-temperature preparation method provided by the invention is more than or equal to 78 percent, and the yield is more than or equal to 80 percent (calculated by 3- [ 2-chloro-4- (trifluoromethyl) phenoxy ] benzoic acid).
Detailed Description
Example 1
Weighing 31.6g (actual feeding amount) of 3- [ 2-chloro-4- (trifluoromethyl) phenoxy ] benzoic acid with the content of 90.6 percent, putting the weighed material into a 500ml reaction bottle, adding 170ml of dichloroethane, stirring, heating to dissolve, cooling to about 55 ℃, adding 30.6g of acetic anhydride, continuously cooling to 0 ℃, beginning to dropwise add 28.3g of mixed acid (0.16 mol of concentrated nitric acid and 0.18mol of concentrated sulfuric acid), wherein the temperature is not more than 5 ℃ in the dropwise adding process. After the dripping is finished, naturally raising the temperature to 20-25 ℃, and preserving the heat for 1.5 hours to carry out reaction. After the reaction is finished, 10ml of water is dripped at the temperature of 50-55 ℃, and after the dripping is finished, the temperature is controlled to be 55-60 ℃, the mixture is stirred for 30 minutes, and the mixture is kept stand for layering and waste acid is removed. After the waste acid is separated, 100ml of water is added to control the temperature to be 55-60 ℃, stirred and washed for 1 hour, layered, added with water to remove dichloroethane, cooled, filtered, centrifuged and dried. The final acifluorfen was obtained in 34.1g, content 78.72% and yield 82%.
Example 2
Weighing 31.6g (actual feeding amount) of 3- [ 2-chloro-4- (trifluoromethyl) phenoxy ] benzoic acid with the content of 90.6 percent, putting the weighed material into a 500ml reaction bottle, adding 170ml of dichloroethane, stirring, heating to dissolve, cooling to about 55 ℃, adding 30.6g of acetic anhydride, continuing to cool to 5 ℃, starting to dropwise add 28.3g of mixed acid (0.16 mol of concentrated nitric acid and 0.18mol of concentrated sulfuric acid), wherein the temperature is not more than 10 ℃ in the dropwise adding process. After the dripping is finished, naturally raising the temperature to 20-25 ℃, and preserving the heat for 1.5 hours to carry out reaction. After the reaction is finished, 10ml of water is dripped at the temperature of 50-55 ℃, and after the dripping is finished, the temperature is controlled to be 55-60 ℃, the mixture is stirred for 30 minutes, and the mixture is kept stand for layering and waste acid is removed. After the waste acid is separated, 100ml of water is added to control the temperature to be 55-60 ℃, stirred and washed for 1 hour, layered, added with water to remove dichloroethane, cooled, filtered, centrifuged and dried. The final acifluorfen was obtained in 33.84g, content 78.45% and yield 81.06%.
Example 3
Weighing 31.6g (actual feeding amount) of 3- [ 2-chloro-4- (trifluoromethyl) phenoxy ] benzoic acid with the content of 90.6 percent, putting the weighed material into a 500ml reaction bottle, adding 170ml of dichloroethane, stirring, heating to dissolve, cooling to about 55 ℃, adding 27.8g of acetic anhydride, continuously cooling to 0 ℃, beginning to dropwise add 28.3g of mixed acid (0.16 mol of concentrated nitric acid and 0.18mol of concentrated sulfuric acid), wherein the temperature is not more than 5 ℃ in the dropwise adding process. After the dripping is finished, naturally raising the temperature to 20-25 ℃, and preserving the heat for 1.5 hours to carry out reaction. After the reaction is finished, 10ml of water is dripped at the temperature of 50-55 ℃, and after the dripping is finished, the temperature is controlled to be 55-60 ℃, the mixture is stirred for 30 minutes, and the mixture is kept stand for layering and waste acid is removed. After the waste acid is separated, 100ml of water is added to control the temperature to be 55-60 ℃, stirred and washed for 1 hour, layered, added with water to remove dichloroethane, cooled, filtered, centrifuged and dried. The final acifluorfen yield was 33.8g, 78.1% yield 80.8%.
Example 4
Weighing 31.6g (actual feeding amount) of 3- [ 2-chloro-4- (trifluoromethyl) phenoxy ] benzoic acid with the content of 90.6 percent, putting the weighed material into a 500ml reaction bottle, adding 170ml of dichloroethane, stirring, heating to dissolve, cooling to about 55 ℃, adding 32.5g of acetic anhydride, continuously cooling to 0 ℃, beginning to dropwise add 28.3g of mixed acid (0.16 mol of concentrated nitric acid and 0.18mol of concentrated sulfuric acid), wherein the temperature is not more than 5 ℃ in the dropwise adding process. After the dripping is finished, naturally raising the temperature to 20-25 ℃, and preserving the heat for 1.5 hours to carry out reaction. After the reaction is finished, 10ml of water is dripped at the temperature of 50-55 ℃, and after the dripping is finished, the temperature is controlled to be 55-60 ℃, the mixture is stirred for 30 minutes, and the mixture is kept stand for layering and waste acid is removed. After the waste acid is separated, 100ml of water is added to control the temperature to be 55-60 ℃, stirred and washed for 1 hour, layered, added with water to remove dichloroethane, cooled, filtered, centrifuged and dried. The final acifluorfen gave 33.87g, content 78.5%, yield 81.3%.
Example 5
Weighing 31.6g (actual feeding amount) of 3- [ 2-chloro-4- (trifluoromethyl) phenoxy ] benzoic acid with the content of 90.6 percent, putting the weighed material into a 500ml reaction bottle, adding 170ml of dichloroethane, stirring, heating to dissolve, cooling to about 55 ℃, adding 32.5g of acetic anhydride, continuously cooling to 0 ℃, beginning to dropwise add 22.1g of mixed acid (0.135 mol of concentrated nitric acid and 0.135mol of concentrated sulfuric acid), wherein the temperature is not more than 5 ℃ in the dropwise adding process. After the dripping is finished, naturally raising the temperature to 20-25 ℃, and preserving the heat for 1.5 hours to carry out reaction. After the reaction is finished, 10ml of water is dripped at the temperature of 50-55 ℃, and after the dripping is finished, the temperature is controlled to be 55-60 ℃, the mixture is stirred for 30 minutes, and the mixture is kept stand for layering and waste acid is removed. After the waste acid is separated, 100ml of water is added to control the temperature to be 55-60 ℃, stirred and washed for 1 hour, layered, added with water to remove dichloroethane, cooled, filtered, centrifuged and dried. The final acifluorfen yield was 33.7g, 78.0% yield 80.4%.
Example 6
Weighing 31.6g (actual feeding amount) of 3- [ 2-chloro-4- (trifluoromethyl) phenoxy ] benzoic acid with the content of 90.6 percent, putting the weighed material into a 500ml reaction bottle, adding 170ml of dichloroethane, stirring, heating to dissolve, cooling to about 55 ℃, adding 27.8g of acetic anhydride, continuously cooling to 0 ℃, beginning to dropwise add 38.6g of mixed acid (0.18 mol of concentrated nitric acid and 0.27mol of concentrated sulfuric acid), wherein the temperature is not more than 5 ℃ in the dropwise adding process. After the dripping is finished, naturally raising the temperature to 20-25 ℃, and preserving the heat for 1.5 hours to carry out reaction. After the reaction is finished, 10ml of water is dripped at the temperature of 50-55 ℃, and after the dripping is finished, the temperature is controlled to be 55-60 ℃, the mixture is stirred for 30 minutes, and the mixture is kept stand for layering and waste acid is removed. After the waste acid is separated, 100ml of water is added to control the temperature to be 55-60 ℃, stirred and washed for 1 hour, layered, added with water to remove dichloroethane, cooled, filtered, centrifuged and dried. The final acifluorfen yield was 33.8g, 78.1% yield 80.7%.
Comparative example 1 (method used in CN 103787890A)
Weighing 3- [ 2-chloro-4- (trifluoromethyl) phenoxy ] with the content of 90.6 percent]31.6g of benzoic acid (actual amount) was put into a 500ml reaction flask, and 56.6ml of chloroform was added to dissolve the benzoic acid in the flask. Preparing mixed acid, weighing 3.03ml acetic acid, slowly dropping into 4.8ml 92% nitric acid at low temperature, then dropping into sulfuric acid, n (etherate): n (HNO)3)＝1:1.2，n(HNO3):n(H2SO4) 1: 0.5. After dissolving the etherate, the mixed acid is dripped, and the temperature is controlled to be about 10 ℃. The addition time was about 20min and the reaction was continued at 10 ℃ for 2 h. The final acifluorfen gave 33.8g, a content of 71.4% and a yield of 73.8%.
Comparative example 2
Weighing 31.6g (actual feeding amount) of 3- [ 2-chloro-4- (trifluoromethyl) phenoxy ] benzoic acid with the content of 90.6 percent, putting the weighed material into a 500ml reaction bottle, adding 170ml of dichloroethane, stirring, heating to dissolve, cooling to about 55 ℃, adding 18g of acetic anhydride, continuously cooling to 0 ℃, beginning to dropwise add 28.3g of mixed acid (0.16 mol of concentrated nitric acid and 0.18mol of concentrated sulfuric acid), wherein the temperature in the dropwise adding process is not more than 5 ℃. After the dripping is finished, naturally raising the temperature to 20-25 ℃, and preserving the heat for 3 hours to carry out reaction. After the reaction is finished, 10ml of water is dripped at the temperature of 50-55 ℃, and after the dripping is finished, the temperature is controlled to be 55-60 ℃, the mixture is stirred for 30 minutes, and the mixture is kept stand for layering and waste acid is removed. After the waste acid is separated, 100ml of water is added to control the temperature to be 55-60 ℃, stirred and washed for 1 hour, layered, added with water to remove dichloroethane, cooled, filtered, centrifuged and dried. The final acifluorfen yield was 33.1g, 78.0% yield 78.9%.
Comparative example 3
Weighing 31.6g (actual feeding amount) of 3- [ 2-chloro-4- (trifluoromethyl) phenoxy ] benzoic acid with the content of 90.6 percent, putting the weighed material into a 500ml reaction bottle, adding 170ml dichloroethane, stirring, heating to dissolve, cooling to about 55 ℃, adding 30.6g of acetic anhydride, continuously cooling to 0 ℃, beginning to dropwise add 60g of mixed acid (0.227 mol of concentrated nitric acid and 0.453mol of concentrated sulfuric acid), wherein the temperature is not more than 5 ℃ in the dropwise adding process. After the dripping is finished, naturally raising the temperature to 20-25 ℃, and preserving the heat for 1.5 hours to carry out reaction. After the reaction is finished, 10ml of water is dripped at the temperature of 50-55 ℃, and after the dripping is finished, the temperature is controlled to be 55-60 ℃, the mixture is stirred for 30 minutes, and the mixture is kept stand for layering and waste acid is removed. After the waste acid is separated, 100ml of water is added to control the temperature to be 55-60 ℃, stirred and washed for 1 hour, layered, added with water to remove dichloroethane, cooled, filtered, centrifuged and dried. The final acifluorfen yield was 33.7g, 76.1% yield 79.4%.
Comparative example 4
Weighing 31.6g (actual feeding amount) of 3- [ 2-chloro-4- (trifluoromethyl) phenoxy ] benzoic acid with the content of 90.6 percent, putting the weighed material into a 500ml reaction bottle, adding 170ml of dichloroethane, stirring, heating to dissolve, cooling to about 55 ℃, adding 30.6g of acetic anhydride, continuously cooling to 20 ℃, beginning to dropwise add 28.3g of mixed acid (0.16 mol of concentrated nitric acid and 0.18mol of concentrated sulfuric acid), wherein the temperature is not more than 30 ℃ in the dropwise adding process. After the dripping is finished, naturally raising the temperature to 20-25 ℃, and preserving the heat for 1.5 hours to carry out reaction. After the reaction is finished, 10ml of water is dripped at the temperature of 50-55 ℃, and after the dripping is finished, the temperature is controlled to be 55-60 ℃, the mixture is stirred for 30 minutes, and the mixture is kept stand for layering and waste acid is removed. After the waste acid is separated, 100ml of water is added to control the temperature to be 55-60 ℃, stirred and washed for 1 hour, layered, added with water to remove dichloroethane, cooled, filtered, centrifuged and dried. The final acifluorfen yield was 33.9g, 76.7% yield 79.5%.
As can be seen from the data of the examples 1-6 and the comparative examples 1-4, the low-temperature nitration method of the present invention is adopted to properly increase the catalyst dosage, so that the reaction tends to be smooth, the selective competitive power of the target product is enhanced, the multi-nitration and the heterotopic nitration by-products are inhibited, the content of the intermediate acifluorfen is more than or equal to 78%, the yield is more than or equal to 80% (calculated by 3- [ 2-chloro-4- (trifluoromethyl) phenoxy ] benzoic acid), the controllability and the safety are high, and the industrialization is easy to realize. In contrast, comparative examples 1-4 are relatively poor in technical effect, mainly because: the solvent added in comparative example 1 is acetic acid instead of acetic anhydride or propionic anhydride, and since it has no ability to absorb moisture, it dilutes the mixed acid, reduces the concentration of the mixed acid, and reduces the nitrification ability; comparative example 2 the use amount of acetic anhydride is reduced at low temperature, so the dissociation activity of nitromilled ions is reduced, the concentration of the nitromilled ions is reduced, the reaction period is prolonged, the conversion rate is poor, and the yield is relatively low; comparative example 3 the amount of mixed acid is increased at low temperature, especially the amount of sulfuric acid is increased, the dissociation capability of nitric acid and the nitre milling ion concentration are improved, and the nitration capability is improved, so that the amount of multi-nitro by-products is increased, and the content of target products is influenced; in comparative example 4, since the reaction temperature was increased to enhance the competitiveness of each side reaction, various byproducts were simultaneously increased to affect the content of the objective product.
Claims (8)
1. The preparation method of fomesafen technical intermediate acifluorfen is characterized by comprising the following steps:
putting the measured 3- [ 2-chloro-4- (trifluoromethyl) phenoxy ] benzoic acid into a reaction kettle, adding the measured solvent, slowly cooling to 50-60 ℃, adding the catalyst, continuously and slowly cooling, and slowly dropwise adding mixed acid prepared by 98% nitric acid and 98% sulfuric acid in proportion under the temperature control;
after the dropwise addition is finished, naturally heating to 20-25 ℃, and then carrying out heat preservation reaction for 1-2 hours;
after the reaction is finished, dropwise adding a certain amount of water under the controlled temperature to dilute the sulfuric acid to 60-70%, stirring for 25-40 minutes under the controlled temperature after dropwise adding is finished, fully standing and layering, and discharging lower-layer waste acid to a waste acid storage tank;
after the waste acid is removed, adding a certain amount of water into the materials to clean free acid, then heating to 55-60 ℃, stirring for 1-2 hours, fully standing for layering to remove the solvent, cooling to 40-45 ℃, performing suction filtration, centrifuging, and drying to obtain the intermediate acifluorfen.
2. The method according to claim 1, wherein the solvent is 1, 2-dichloroethane.
3. The method according to claim 1, wherein the catalyst is acetic anhydride or propionic anhydride.
4. The process according to claim 3, wherein the molar ratio of the 3- [ 2-chloro-4- (trifluoromethyl) phenoxy ] benzoic acid added to the catalyst is 1 (2-3.5).
5. The method according to claim 1, wherein the molar ratio of the 3- [ 2-chloro-4- (trifluoromethyl) phenoxy ] benzoic acid to nitric acid added is 1: (1.2-2.4), wherein the ratio of the added 98% nitric acid to the 98% sulfuric acid is 1 (1-2).
6. The method according to claim 1, wherein the mixed acid is slowly added dropwise at a temperature of-5 to 20 ℃ for 1 to 1.5 hours.
7. The method according to claim 1, wherein a fixed amount of water is added dropwise while controlling the temperature at 40 to 60 ℃, and the solution is stirred and layered while controlling the temperature at 55 to 60 ℃.
8. The process according to claim 1, wherein the resulting acifluorfen is contained in an amount of 78% or more and the total yield of 80% or more based on 3- [ 2-chloro-4- (trifluoromethyl) phenoxy ] benzoic acid.
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|---|---|---|---|---|
| CN112358400A (en) * | 2020-10-22 | 2021-02-12 | 烟台大学 | Method for synthesizing acifluorfen by nitration in microreactor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1234786A (en) * | 1996-11-01 | 1999-11-10 | 曾尼卡有限公司 | Nitrification process |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1234786A (en) * | 1996-11-01 | 1999-11-10 | 曾尼卡有限公司 | Nitrification process |
Non-Patent Citations (1)
| Title |
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| 王保安等: "CuI 促进下乙羧氟草醚的合成", 《化学工程师》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112358400A (en) * | 2020-10-22 | 2021-02-12 | 烟台大学 | Method for synthesizing acifluorfen by nitration in microreactor |
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