CN111377831A - Preparation method of herbicide cyhalofop-butyl - Google Patents
Preparation method of herbicide cyhalofop-butyl Download PDFInfo
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- CN111377831A CN111377831A CN201811640116.6A CN201811640116A CN111377831A CN 111377831 A CN111377831 A CN 111377831A CN 201811640116 A CN201811640116 A CN 201811640116A CN 111377831 A CN111377831 A CN 111377831A
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Abstract
The invention discloses a preparation method of herbicide cyhalofop-butyl, which particularly relates to the field of biological pharmacy and specifically comprises the following steps: step one, selecting a clean double-neck flask, adding an organic solvent into the double-neck flask, and dissolving (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid in the organic solvent; and step two, continuously adding solid inorganic base into the double-neck flask, heating to 50 ℃, preserving the temperature, and reacting for 0.5-1 hour in the double-neck flask. According to the invention, (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid is dissolved in an organic solvent, solid inorganic base is added, the temperature is raised to reflux and water-carrying reaction, and HPLC tracking reaction is carried out, so that the reaction steps of cyhalofop-butyl are shorter, the operation is simple and convenient, reaction byproducts are less, the control is easy, no harm is caused, the safety risk is small, the product yield and the optical purity are improved, and part of raw materials in the reaction process can be recycled, so that the cost is low, and the industrial production is facilitated.
Description
Technical Field
The invention relates to the field of biological pharmacy, in particular to a preparation method of herbicide cyhalofop-butyl.
Background
Cyhalofop-butyl, sold under the trade name of Qianjin, and chemically (R) -butyl 2- [4- (4-cyano-2-fluorophenoxy) phenoxy ] propionate, is an acetyl-CoA carboxylase inhibitor developed by the Dow agricultural sciences company, USA. The herbicide is used as a paddy field herbicide with high efficiency, low toxicity and good selectivity, is mainly used for preventing and killing important gramineous weeds, is high in efficiency on moleplant seeds and various barnyard grasses, can also prevent and kill crab grass, paspalum distichum, green bristlegrass, eleusine indica, alopecurus, and the like, and particularly has excellent effect of preventing and controlling the moleplant seeds with serious harm in the paddy field. Cyhalofop-butyl has excellent selectivity to rice, the selectivity is based on different metabolic rates, and cyhalofop-butyl can be rapidly degraded into a diacid state without activity to acetyl coenzyme A carboxylase in rice bodies, so that the cyhalofop-butyl has high safety to rice. Because it degrades rapidly in soil and in typical paddy field water, it is safe for succeeding crops.
The synthetic method of cyhalofop-butyl mainly comprises the following steps: in patent document CN102584627, (R) -2- (4-hydroxyphenoxy) propionic acid is reacted with 3, 4-difluorobenzonitrile to obtain ether, (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid, which is then reacted with phosgene to produce an acid chloride intermediate, which is finally reacted with butanol to produce cyhalofop-butyl. In the route, a virulent raw material phosgene is used, hydrogen chloride gas is generated in the esterification reaction, and the residual phosgene and hydrogen chloride gas need to be removed in the post-treatment, so that the operation is complicated and the safety risk is high; in patent document CN105601538, an (R) -2- (4-hydroxyphenoxy) propionic acid is reacted with 3, 4-difluorobenzonitrile, and then dehydrated and esterified with butanol under acid catalysis to generate cyhalofop-butyl, in the method, an organic base, an acid-binding agent and a phase transfer catalyst are used in an etherification reaction, so that the method has the advantages of high cost, complex operation, more three wastes generation and slow esterification reaction; patent document CN107686454 uses 3, 4-dichlorobenzonitrile as a raw material, and obtains cyhalofop-butyl through etherification, esterification and fluorination reactions, wherein the fluorination reaction byproducts are many and are not easy to control; patent document CN107673995 uses potassium (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionate obtained after etherification to react with bromobutane to obtain a product, but bromobutane is expensive and not favorable for industrial production.
Disclosure of Invention
In order to overcome the defects in the prior art, the embodiment of the invention provides a preparation method of herbicide cyhalofop-butyl, which is characterized in that (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid is dissolved in an organic solvent, solid inorganic base is added, the temperature is raised to reflux and water-carrying reaction, and HPLC tracking reaction is carried out, so that the reaction steps of cyhalofop-butyl are shorter, the operation is simple and convenient, reaction byproducts are less, the control is easy, no harm is caused, the safety risk is small, the product yield and the optical purity are improved, excessive chlorobutane in a solvent can be evaporated and recycled in the reaction production process, inorganic salt generated in the solvent is filtered, part of raw materials in the reaction process are recycled, the cost is low, and the preparation method is beneficial to industrial production.
In order to achieve the purpose, the invention provides the following technical scheme: the medicine for treating neuroendocrine tumor specifically comprises the following steps:
step one, selecting a clean double-neck flask, adding an organic solvent into the double-neck flask, and dissolving (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid in the organic solvent;
continuously adding solid inorganic base into the double-neck flask, heating to 50 ℃, keeping the temperature, reacting for 0.5-1 hour in the double-neck flask, and obtaining carboxylate after the reaction;
continuously adding chlorobutane into the double-mouth flask, heating to reflux and carrying out water-carrying reaction, and carrying out HPLC tracking reaction;
and step four, evaporating the solvent after the reaction is finished, recovering and recycling excessive chlorobutane in the solvent pool, cooling, filtering inorganic salt generated in the solvent, and removing the solvent to obtain the product cyhalofop-butyl.
In a preferred embodiment, in the first step, the organic solvent is one of dimethylsulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
In a preferred embodiment, in the second step, the solid inorganic base is one of sodium hydroxide, potassium carbonate and sodium carbonate.
In a preferred embodiment, the molar ratio of chlorobutane to (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid in step three is 2-3: 1.
in a preferred embodiment, the molar ratio of the solid inorganic base to (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propanoic acid is from 0.5 to 1.0: 1.
the invention has the technical effects and advantages that:
1. dissolving (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid in an organic solvent, adding solid inorganic base, heating to reflux and carrying out water reaction, and carrying out HPLC tracking reaction, so that the reaction step of cyhalofop-butyl is shorter, the operation is simple and convenient, reaction byproducts are fewer, the control is easy, no harm is caused, the safety risk is small, and the product yield and the optical purity are improved;
2. in the reaction production process, the excessive chlorobutane in the solvent pool can be distilled out for recycling, and the inorganic salt generated in the solvent is filtered out, so that part of raw materials in the reaction process are recycled, the cost is low, and the industrial production is facilitated;
3. the method has the advantages of simple process, low equipment requirement, strong operability and good social popularization and application.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of herbicide cyhalofop-butyl specifically comprises the following steps:
step one, selecting a clean double-neck flask, adding 300ml of dimethyl sulfoxide into the double-neck flask, and dissolving 100g (0.33mol) of (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid in 300ml of dimethyl sulfoxide;
step two, continuously adding 18.5g (0.33mol) of potassium hydroxide into the double-neck flask, heating to 50 ℃, preserving heat, reacting in the double-neck flask for 1 hour, and obtaining carboxylate after reaction;
step three, continuously adding 61g (0.66mol) of chlorobutane into the double-mouth flask, heating to reflux and carrying out reaction with water for 5 hours, and detecting complete conversion by HPLC;
and step four, evaporating the solvent after the reaction is finished, recovering and recycling excessive chlorobutane in the solvent pool, cooling, filtering out potassium chloride generated in the solvent, and removing the solvent to obtain 112g of cyhalofop-butyl (yield 95%, content 98% and optical purity 98%) of a product.
In the above technical scheme, the molar ratio of chlorobutane to (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propanoic acid is 2: 1, the molar ratio of solid inorganic base to (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid is 0.5: 1.
example 2
A preparation method of herbicide cyhalofop-butyl specifically comprises the following steps:
step one, selecting a clean double-neck flask, adding 300ml of dimethyl sulfoxide into the double-neck flask, and dissolving 100g (0.33mol) of (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid in 300ml of dimethyl sulfoxide;
step two, continuously adding 22.8g (0.16mol) of potassium carbonate into the double-mouth flask, heating to 50 ℃, keeping the temperature, reacting in the double-mouth flask for 1 hour to obtain carboxylate;
step three, continuously adding 61g (0.66mol) of chlorobutane into the double-mouth flask, heating to reflux and reacting for 8 hours with water, and detecting the conversion rate by HPLC (high performance liquid chromatography) to be 99%;
and step four, evaporating excessive chlorobutane out of the solvent pool after the reaction is finished, recycling the excessive chlorobutane, cooling, filtering potassium chloride generated in the solvent, and removing the solvent to obtain 108g of cyhalofop-butyl (yield 92%, content 97%, optical purity 96%).
In the technical scheme, the molar ratio of chlorobutane to (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid is 3: 1, the molar ratio of solid inorganic base to (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid is 1.0: 1.
example 3
A preparation method of herbicide cyhalofop-butyl specifically comprises the following steps:
step one, selecting a clean double-neck flask, adding 300ml of N, N-dimethylformamide into the double-neck flask, and dissolving 100g (0.33mol) of (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid in 300ml of N, N-dimethylformamide;
step two, continuously adding 18.5g (0.33mol) of potassium hydroxide into the double-neck flask, heating to 50 ℃, preserving heat, reacting in the double-neck flask for 1 hour, and obtaining carboxylate after reaction;
step three, continuously adding 61g (0.66mol) of chlorobutane into the double-mouth flask, heating to reflux and carrying out reaction with water for 5 hours, and detecting complete conversion by HPLC;
and step four, evaporating the solvent after the reaction is finished, recovering and recycling excessive chlorobutane in the solvent pool, cooling, filtering out potassium chloride generated in the solvent, and removing the solvent to obtain 110g of cyhalofop-butyl (yield 94%, content 98% and optical purity 97%).
In the above technical scheme, the molar ratio of chlorobutane to (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propanoic acid is 2: 1, the molar ratio of solid inorganic base to (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid is 0.5: 1.
example 4
A preparation method of herbicide cyhalofop-butyl specifically comprises the following steps:
step one, selecting a clean double-neck flask, adding 300ml of dimethyl sulfoxide into the double-neck flask, and dissolving 100g (0.33mol) of (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid in 300ml of dimethyl sulfoxide;
step two, continuously adding 20.3g (0.36mol) of potassium hydroxide into the double-neck flask, heating to 50 ℃, preserving heat, reacting in the double-neck flask for 1 hour, and obtaining carboxylate after reaction;
step three, continuously adding 61g (0.66mol) of chlorobutane into the double-mouth flask, heating to reflux and carrying out reaction with water for 5 hours, and detecting complete conversion by HPLC;
and step four, evaporating excessive chlorobutane out of the solvent pool after the reaction is finished, recycling the excessive chlorobutane, cooling, filtering potassium chloride generated in the solvent, and removing the solvent to obtain 106g of cyhalofop-butyl (yield 90%, content 96.5% and optical purity 95%) of the product.
In the technical scheme, the molar ratio of chlorobutane to (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid is 3: 1, the molar ratio of solid inorganic base to (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid is 1.0: 1.
example 5
A preparation method of herbicide cyhalofop-butyl specifically comprises the following steps:
step one, selecting a clean double-neck flask, adding 300ml of dimethyl sulfoxide into the double-neck flask, and dissolving 100g (0.33mol) of (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid in 300ml of dimethyl sulfoxide;
step two, continuously adding 18.5g (0.33mol) of potassium hydroxide into the double-neck flask, heating to 50 ℃, preserving heat, reacting in the double-neck flask for 1 hour, and obtaining carboxylate after reaction;
step three, continuously adding 76g (0.82mol) of chlorobutane into the double-mouth flask, heating to reflux and carrying out reaction with water for 5 hours, and detecting complete conversion by HPLC;
and step four, evaporating the solvent after the reaction is finished, recovering and recycling excessive chlorobutane in the solvent pool, cooling, filtering out potassium chloride generated in the solvent, and removing the solvent to obtain 113g of cyhalofop-butyl (yield is 96%, content is 98%, and optical purity is 97%).
In the above technical scheme, the molar ratio of chlorobutane to (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propanoic acid is 2: 1, the molar ratio of solid inorganic base to (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid is 0.5: 1.
through the five groups of embodiments, five herbicides of cyhalofop-butyl can be obtained, the five herbicides of cyhalofop-butyl are respectively subjected to performance tests, and then the herbicide of cyhalofop-butyl subjected to a common production process is subjected to performance tests, so that the capability of the herbicide of cyhalofop-butyl in the five groups of embodiments is improved differently, and the (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid is dissolved in an organic solvent, solid inorganic alkali is added, the temperature is raised to reflux water-carrying reaction, HPLC tracking reaction is carried out, so that the reaction step of cyhalofop-butyl is shorter, the operation is simple and convenient, reaction byproducts are less, the control is easy, no harm is caused, the safety risk is small, the product yield and the optical purity are improved, and in the reaction production process, excessive chlorobutane in a solvent pool can be distilled out for recycling and applying, and the inorganic salt generated in the solvent is filtered, so that part of raw materials in the reaction process are recycled, the cost is low, and the method is favorable for industrial production.
Table 1 shows a comparison table of the quality parameters of each raw material in examples 1 to 5.
Table 2 is a comparison table of various basic parameters of cyhalofop-butyl in the products of examples 1-5
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments or portions thereof without departing from the spirit and scope of the invention.
Claims (5)
1. A preparation method of herbicide cyhalofop-butyl is characterized by comprising the following steps:
step one, selecting a clean double-neck flask, adding an organic solvent into the double-neck flask, and dissolving (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid in the organic solvent;
continuously adding solid inorganic base into the double-neck flask, heating to 50 ℃, keeping the temperature, reacting for 0.5-1 hour in the double-neck flask, and obtaining carboxylate after the reaction;
continuously adding chlorobutane into the double-mouth flask, heating to reflux and carrying out water-carrying reaction, and carrying out HPLC tracking reaction;
and step four, evaporating the solvent after the reaction is finished, recovering and recycling excessive chlorobutane in the solvent pool, cooling, filtering inorganic salt generated in the solvent, and removing the solvent to obtain the product cyhalofop-butyl.
2. The process for producing a herbicide cyhalofop-butyl according to claim 1, characterized in that: in the first step, the organic solvent is one of dimethyl sulfoxide, N-dimethylformamide and N, N-dimethylacetamide.
3. The process for producing a herbicide cyhalofop-butyl according to claim 1, characterized in that: in the second step, the solid inorganic base is one of sodium hydroxide, potassium carbonate and sodium carbonate.
4. The process for producing a herbicide cyhalofop-butyl according to claim 1, characterized in that: in the third step, the molar ratio of chlorobutane to (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid is 2-3: 1.
5. the process for producing a herbicide cyhalofop-butyl according to claim 1, characterized in that: the molar ratio of the solid inorganic base to (R) -2- [4- (2-fluoro-4-cyanophenoxy) phenoxy ] propionic acid is 0.5-1.0: 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115490617A (en) * | 2022-10-14 | 2022-12-20 | 江苏丰山集团股份有限公司 | Preparation process of low-cost high-light pure content cyhalofop-butyl |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107253912A (en) * | 2017-05-02 | 2017-10-17 | 江苏永凯化学有限公司 | The synthetic method of cyhalofop-butyl |
| CN107673995A (en) * | 2017-08-23 | 2018-02-09 | 连云港世杰农化有限公司 | A kind of method for synthesizing cyhalofop-butyl |
| CN107698461A (en) * | 2017-09-26 | 2018-02-16 | 连云港世杰农化有限公司 | A kind of method for synthesizing cyhalofop-butyl |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107253912A (en) * | 2017-05-02 | 2017-10-17 | 江苏永凯化学有限公司 | The synthetic method of cyhalofop-butyl |
| CN107673995A (en) * | 2017-08-23 | 2018-02-09 | 连云港世杰农化有限公司 | A kind of method for synthesizing cyhalofop-butyl |
| CN107698461A (en) * | 2017-09-26 | 2018-02-16 | 连云港世杰农化有限公司 | A kind of method for synthesizing cyhalofop-butyl |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115490617A (en) * | 2022-10-14 | 2022-12-20 | 江苏丰山集团股份有限公司 | Preparation process of low-cost high-light pure content cyhalofop-butyl |
| CN115490617B (en) * | 2022-10-14 | 2024-03-26 | 江苏丰山生化科技有限公司 | Preparation process of cyhalofop-butyl with low cost and high optical purity content |
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