CN105601538A - Preparation method of cyhalofop-butyl - Google Patents
Preparation method of cyhalofop-butyl Download PDFInfo
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Abstract
The invention relates to a preparation method of cyhalofop-butyl. The method comprises the following steps: by using (R)-2-(4-hydroxyphenoxy)propionic acid and 3,4-difluorobenzonitrile as raw materials and an inorganic alkali as an acid-binding agent, adding an organic alkali and a phase-transfer catalyst, carrying out etherification reaction under milder conditions within a short time to generate an intermediate (R)-2-[4-(2-fluoro-4-cyano)-phenoxy]-propionic acid, and carrying out esterification reaction for dehydration, wherein the total yield of the two reactions can reach 94% or above, and the optical purity is greater than 99%. The method lowers the etherification reaction temperature, shortens the etherification reaction time, enhances the reaction selectivity, completely maintains the chirality, and increases the product yield, thereby saving the energy consumption and lowering the cost. Besides, in the esterification reaction, the used dehydration solvent can lower the byproduct content, thereby omitting the refinement operation of the product, reducing the discharge amount of three wastes, and being beneficial to environmental protection.
Description
Technical field
The invention belongs to herbicide production field, be specifically related to a kind of preparation method of cyhalofop-butyl.
Background technology
Cyhalofop-butyl is one and weeds is presented to very high activity and optionally rice field at very low dosePost-emergence herbicide, is mainly used in preventing and kill off important grassy weed, especially barnyard grass (is comprised to above the average age for marriage barnyard grassGrass), moleplant seed, amur foxtail, moderately well-off grass, lady's-grass, Paspalum distichum, green bristlegrass, eleusine indica etc. haveRemarkable effect, very safe to rice class crop, and it has the feature of low toxicity, low-residual. Paddy riceTanaka's moleplant seed harm is more serious, and the moleplant seed of cyhalofop-butyl before to 4 leaf phases shows high killingGrass is active, and other medicament cannot be by comparison.
Therefore, apply cyhalofop-butyl and will will bring into play important work to the increasing both production and income of national cropsWith, exploitation highy potent herbicide cyhalofop-butyl will have good development prospect.
Cyhalofop-butyl, English common name: cyhalofopbutyl, trade name: a thousand pieces of gold (clincher),Chemical name: (R)-2-[4-(4-cyano group-2-fluorophenoxy) phenoxy group] butyl propionate, English name:Butyl (R)-2-[4-(4-cyano-2-fluorophenoxy) phenoxy] propionate is LG-DOW agricultureThe phenoxy carboxylic acid herbicides of industry scientific company exploitation. Structural formula is:
Sterling is white crystals body, 50 DEG C of fusing points, and vapour pressure is 1.2 × 10-6Pa (20 DEG C), in waterSolubility is 0.7mg/L (20 DEG C, pH=7); Stable when pH=4, when pH=7, decompose slowly,PH is 1～2 or decomposes rapidly for 9 o'clock.
Cyhalofop-butyl is unique in fragrant phenoxy phenoxy propionic acid herbicide paddy rice (transplant and live) to be hadThe kind of tight security, has good selectively to paddy rice etc., it is good selectively based on cyanogenFluorine grass ester has different accretion rates in paddy rice body He in weeds body, in paddy rice body, and cyanogen fluorine grassEster can be degraded to rapidly the diacid state to acetyl-CoA carboxylase non-activity, thereby paddy rice is hadThe security of height; And the accretion rate of cyhalofop-butyl in weeds body is slower, can effectively suppress weedsGrowth, because the degraded of cyhalofop-butyl in soil and in typical paddy field water is rapid, therefore, to rearStubble crop safety.
At present, the main synthetic method of cyhalofop-butyl has following several:
Taking (S)-methyl lactate as raw material, first synthetic (S)-tolysulfonyl methyl lactate, more same to benzeneDiphenol reaction obtains intermediate, then obtains (R)-2-(4-hydroxy benzenes through hydrolysis, ethyl esterification reactionOxygen base) ethyl propionate, finally react with 3,4-difluorobenzonilyile again, obtain (R)-2-[4-(4-cyano group-2-fluorinePhenoxy group) phenoxy group] ethyl propionate, then be hydrolyzed into acid, acid generates by esterification with n-butanol againCyhalofop-butyl. This process route is long, and complex operation has a large amount of waste water to generate, and generate to firstBenzene sulfonic acid accessory substance cannot reclaim, and is difficult to process (" pesticide research and application " the 11st volume in 2007The 1st phase).
Hydroquinones and the reaction of 3,4-difluorobenzonilyile obtain the fluoro-4-of 3-(4-hydroxyphenoxy) cyanophenyl, then(S)-tolysulfonyl lactate reaction generates cyhalofop-butyl; Be subject to the impact of raw material and reaction condition,There is racemization phenomenon in reaction, actual (the R)-isomers that only can obtain 80-90%, meanwhile, from becoming weFace considers, 3,4-difluorobenzonilyile with in the reacting of biphenol generation, to two of biphenol phenolic hydroxyl groupsAll can participate in reaction, generate accessory substance, increase the consumption of 3,4-difluorobenzonilyile, and 3,4-difluorobenzeneNitrile is expensive, therefore this route cost costliness, and the post processing of p-methyl benzenesulfonic acid need be used micro-lifeThing degraded is done in-depth and is processed, therefore industrial this synthetic route (" agricultural chemicals " 2010 that generally do not adoptThe 49th the 5th phase of volume of year).
Chinese patent CN104803883A discloses a kind of synthetic method of cyhalofop-butyl, with PfansteihlButyl ester and paratoluensulfonyl chloride are the L-that raw material first carries out the protection of condensation reaction generation p-toluenesulfonylButyl lactate, then under alkali condition, carry out etherification reaction generation (R)-4-hydroxy benzenes with hydroquinonesOxygen base propionic acid, etherification product carries out condensation with 3,4-difluorobenzonilyile in organic solvent, under alkali conditionReaction generates cyhalofop-butyl, taking (R)-4-hydroxyphenoxy butyl propionate of generating as raw material, and reactionTemperature be 100-110 DEG C, first reflux dewatering obtains cyanogen fluorine grass with 3,4-difluorobenzonilyile etherification reaction againEster, it uses potassium hydroxide is raw material, products obtained therefrom color is darker, and side reaction easily occurs, as cyanogenBase hydrolysis; Etherification reaction temperature is greater than 100 DEG C, under alkali condition, easily makes the configuration of product occurRacemization, affects product quality.
Summary of the invention
The preparation method who the object of the present invention is to provide a kind of cyhalofop-butyl, the method has reduced etherificateReaction temperature, has shortened the etherification reaction time, has improved reaction selectivity, and chirality keeps completely,Improve product yield, thereby saved energy consumption, reduced cost; On the other hand, reduced by-productThing content, saves the purification operations of product, reduces three wastes discharge amount, is conducive to environmental protection.
In order to achieve the above object, technical scheme of the present invention is as follows:
A preparation method for cyhalofop-butyl, comprises the steps:
1) etherification reaction
In non-proton organic solvent, add acid binding agent, organic base and phase transfer catalyst, then divideCriticize and add (R)-2-(4-hydroxyphenoxy) propionic acid, then add 3,4-difluorobenzonilyile, be heated to 60～90DEG C, insulation reaction 2～4 hours, reaction finishes rear desolvation, is down to room temperature, is dissolved in water, and usesAcid for adjusting pH to 3～5, stir, and separate out solid, filter, and obtain intermediate (R)-2-[4-(2-Fluorine-4-nitrile)-phenoxy group]-propionic acid; Wherein, (R)-2-(4-hydroxyphenoxy) propionic acid and 3,4-The mol ratio of difluorobenzonilyile is 1:1～1.5; Described acid binding agent is inorganic base;
2) dehydration esterification
By step 1) obtain intermediate (R)-2-[4-(2-fluorine-4-nitrile)-phenoxy group]-propionic acid andN-butanol, dehydrated solvent and bronsted acid catalyst add reaction vessel, add hot reflux, and point water is to nothingMoisture goes out, and reaction finishes, and obtains reactant liquor, and reactant liquor is washed to neutrality, and desolvation obtains cyanogenFluorine grass ester; Described dehydrated solvent refers to that not alkanes or the ketone non-proton property miscible with water are organic moltenAgent;
Reaction equation is as follows:
Preferably, step 1) described organic base is selected from triethylene diamine, hexa, twoAt least one in azabicyclo, organic base with the mass ratio of (R)-2-(4-hydroxyphenoxy) propionic acid is0.01～0.2：1。
Preferably, step 1) described phase transfer catalyst is 18-hat-6, TBAB, threeAt least one in ethyl Bian amine, the matter of phase transfer catalyst and (R)-2-(4-hydroxyphenoxy) propionic acidAmount is than being 0.005～0.2:1.
Preferably, step 1) non-proton organic solvent described in etherification reaction and (R)-2-(4-Hydroxyphenoxy) mass ratio of propionic acid is 2～10:1, non-proton organic solvent is selected from dimethyl formylAt least one in amine, dimethylacetylamide, dimethyl sulfoxide (DMSO) and 1-METHYLPYRROLIDONE.
Preferably, step 1) acid binding agent described in etherification reaction be selected from NaOH, potassium hydroxide,At least one in sodium carbonate, potash, cesium carbonate and potassium phosphate, acid binding agent and (R)-2-(4-hydroxylPhenoxyl) mass ratio of propionic acid is 1.5～3:1.
Further, etherification reaction post processing first adds aqueous solvent, then to be acidified to pH with acid be 3～5, instituteWith acid can be at least one in sulfuric acid, hydrochloric acid, phosphoric acid and oxalic acid.
Preferably, step 2) described in dehydrated solvent be selected from cyclohexane, n-hexane and butanoneAt least one, dehydrated solvent and step 1) in the mass ratio of (R)-2-(4-hydroxyphenoxy) propionic acid be5～15:1.
Preferably, step 2) esterification bronsted acid catalyst used is selected from sulfuric acid, hydrochloric acid, nitreAcid, at least one in p-methyl benzenesulfonic acid and phosphoric acid, bronsted acid catalyst and step 1) in (R)-2-(4-Hydroxyphenoxy) mass ratio of propionic acid is 0.01～0.1:1.
In etherification reaction of the present invention, acid binding agent and organic base and phase transfer catalyst are used in conjunction with,In etherification reaction, add organic base and phase transfer catalyst, its effect is: reaction substrate (R)-2-(4-Hydroxyphenoxy) propionic acid and acid binding agent be two phase reaction, adds the organic base of catalytic amount can make (R)-2-(4-Hydroxyphenoxy) propionic acid and acid binding agent react rapidly in homogeneous system, generates reactive intermediate, be conducive toThe carrying out of etherification reaction, effectively improves reaction rate; Meanwhile, the phase transfer catalyst adding, can takeWith acid binding agent with react in organic alkali salt fast reaction of generating, make organic base free out, dissociateThe organic base coming can carry out next one circulation and continue reaction, reduces the needed temperature of etherification reaction, contractingThe short reaction time, improve reaction selectivity.
Catalytic reaction process is shown below:
Compared to the prior art, the invention has the beneficial effects as follows:
1) the present invention uses inorganic base as acid binding agent, and organic base, as catalyst, adds phase simultaneouslyTransfer catalyst, under comparatively gentle condition, in the short period, reaction generates intermediate (R)-2-[4-(2-fluorine-4-nitrile)-phenoxy group]-propionic acid, shorten the etherification reaction time, reduce etherification reaction requiredThe temperature of wanting, has improved reaction selectivity, and chirality keeps completely, has improved product yield.
2) the present invention is organic molten in esterification environment for use close friend's alkanes or the non-proton property of ketoneAgent is as the dehydrated reagent of esterification, and reaction temperature is low, and selectively good, two-step reaction total recovery canReach 94%, optical purity is greater than 99%, and by-products content reduces, and can save the purification operations of product,Reduce three wastes discharge amount, be conducive to environmental protection, the recycled solvent in course of reaction, cleanGreen, cost-saving.
Brief description of the drawings
Fig. 1 is the HPLC of the absolute configuration content of the cyhalofop-butyl product that obtains of the embodiment of the present invention 1Spectrogram.
Fig. 2 is the HPLC spectrogram of the absolute configuration content of the cyhalofop-butyl product that obtains of comparative example 2.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is done to a step explanation.
The preparation method of 1 one kinds of cyhalofop-butyls of embodiment, comprises the following steps:
1) etherification reaction
To drop in 250mL four-hole boiling flask DMA 100mL, potash 50g,Triethylene diamine 5g and phase transfer catalyst 18-hat-60.3g, then drop into (R)-2-(4-hydroxyl in batchesPhenoxyl) propionic acid 26g (0.14mol), there are a large amount of Bubble formations; Treat (R)-2-(4-hydroxy benzenes oxygenBase) propionic acid feeds intake completely, then drops into 3,4-difluorobenzonilyile 20g (0.14mol), is then warming up to 60DEG C, insulation reaction 3 hours, reaction finishes. Decompression distillation is steamed and is desolventized, and is down to the room temperature 150mL that adds waterDissolve, with 15% watery hydrochloric acid adjusting pH value to 4～5, stir and separate out solid, filter to obtain (R)-2-[4-(2-fluorine-4-nitrile)-phenoxy group]-propionic acid is for subsequent use.
2) esterification
In 500mL four-hole boiling flask, drop into above-mentioned intermediate (R)-2-[4-(2-fluorine-4-nitrile)-benzeneOxygen base] concentrated sulfuric acid 1g of-propionic acid, 200mL cyclohexane, n-butanol 18g (0.24mol) and catalytic amount,Temperature rising reflux divides water to separating without moisture, and reaction finishes.
After esterification finishes, reactant liquor washing three times to pH be 7, separate organic phase, decompression is steamedDry solvent obtains product, chemical content 97%, and optical purity is greater than 99%, its absolute configuration contentAs shown in Figure 1, as shown in Figure 1, absolute configuration R type is 99.84% to HPLC spectrogram, absolute configurationS type is 0.16%, two-step reaction total recovery 94% (in (R)-4-hydroxyphenoxy propionic acid), and outward appearance isWhite solid.
The preparation method of 2 one kinds of cyhalofop-butyls of embodiment, comprises the following steps:
1) etherification reaction
To drop in 250mL four-hole boiling flask DMA 100mL, potash 40g,Hexa 0.3g and phase transfer catalyst TBAB 3g, more in batches drop into (R)-2-(4-hydroxyphenoxy) propionic acid 26g (0.14mol), has a large amount of Bubble formations; Treat (R)-2-(4-Hydroxyphenoxy) propionic acid feeds intake completely, then drops into 3,4-difluorobenzonilyile 22g (0.16mol), thenBe warming up to 90 DEG C, insulation reaction 2 hours, reaction finishes. Decompression distillation is steamed and is desolventized, and is down to chamberThe temperature 250mL that adds water dissolves, and regulates pH value to 3～4 with 30wt.% dilute sulfuric acid, and solid is separated out in stirring,Filtering to obtain (R)-2-[4-(2-fluorine-4-nitrile)-phenoxy group]-propionic acid is for subsequent use.
2) esterification
In 500mL four-hole boiling flask, drop into above-mentioned intermediate (R)-2-[4-(2-fluorine-4-nitrile)-benzeneOxygen base]-propionic acid, 200mL cyclohexane, n-butanol 18g (0.24mol) and catalytic amount to toluene sulphurAcid 0.5g, temperature rising reflux divides water to separating without moisture, and reaction finishes.
After esterification finishes, reactant liquor washing three times to pH be 7, separate organic phase, decompression is steamedDry solvent obtains product, chemical content 97.3%, and optical purity is greater than 99%, two-step reaction total recovery93.5% (in (R)-4-hydroxyphenoxy propionic acid), outward appearance is white solid.
The preparation method of 3 one kinds of cyhalofop-butyls of embodiment, comprises the following steps:
1) etherification reaction
To drop in 250mL four-hole boiling flask DMA 100mL, potash 40g,Diazabicyclo 1g and phase transfer catalyst benzyl triethyl ammonium amine 0.5g, then drop into (R)-2-(4-in batchesHydroxyphenoxy) propionic acid 26g (0.14mol), there are a large amount of Bubble formations; Treat (R)-2-(4-hydroxy benzenesOxygen base) propionic acid feeds intake completely, then drops into 3,4-difluorobenzonilyile 20g (0.14mol), is then warming up to 85DEG C, insulation reaction 2 hours, reaction finishes. Decompression distillation is steamed and is desolventized, and is down to the room temperature 250mL that adds waterDissolve, with 30% phosphoric acid,diluted adjusting pH value to 3～4, stir and separate out solid, filter to obtain (R)-2-[4-(2-fluorine-4-nitrile)-phenoxy group]-propionic acid is for subsequent use.
2) esterification
In 500mL four-hole boiling flask, drop into above-mentioned intermediate (R)-2-[4-(2-fluorine-4-nitrile)-benzeneOxygen base] the phosphatase 11 g of-propionic acid, 300mL cyclohexane, n-butanol 20g (0.27mol) and catalytic amount,Temperature rising reflux divides water to separating without moisture, and reaction finishes.
After esterification finishes, reactant liquor washing three times to pH be 7, separate organic phase, decompression is steamedDry solvent obtains product, chemical content 97.5%, and optical purity is greater than 99%, two-step reaction total recovery94.1% (in (R)-4-hydroxyphenoxy propionic acid), outward appearance is white solid.
The preparation method of 4 one kinds of cyhalofop-butyls of embodiment, comprises the following steps:
1) etherification reaction
To drop in 250mL four-hole boiling flask DMA 100mL, potash 40g,Hexa 1.5g and phase transfer catalyst benzyl triethyl ammonium amine 0.15g, more in batches drop into (R)-2-(4-hydroxyphenoxy) propionic acid 26g (0.14mol), has a large amount of Bubble formations; Treat (R)-2-(4-Hydroxyphenoxy) propionic acid feeds intake completely, then drops into 3,4-difluorobenzonilyile 20g (0.14mol), thenBe warming up to 80 DEG C, insulation reaction 2 hours, reaction finishes, and decompression distillation is steamed and is desolventized, and is down to chamberThe temperature 150mL that adds water dissolves, and regulates pH value to 3～4 with 30wt.% dilute sulfuric acid, and solid is separated out in stirring,Filtering to obtain (R)-2-[4-(2-fluorine-4-nitrile)-phenoxy group]-propionic acid is for subsequent use.
2) esterification
In 500mL four-hole boiling flask, drop into above-mentioned intermediate (R)-2-[4-(2-fluorine-4-nitrile)-benzeneOxygen base] the phosphatase 11 g of-propionic acid, 200mL cyclohexane, n-butanol 16g (0.21mol) and catalytic amount,Temperature rising reflux divides water to separating without moisture, and reaction finishes.
After esterification finishes, reactant liquor washing three times to pH be 7, separate organic phase, decompression is steamedDry solvent obtains product, chemical content 97%, and optical purity is greater than 99%, two-step reaction total recovery 94%(in (R)-4-hydroxyphenoxy propionic acid), outward appearance is white solid.
The preparation method of 1 one kinds of cyhalofop-butyls of comparative example, comprises the following steps:
1) etherification reaction
To drop in 250mL four-hole boiling flask DMA 100mL, potash 60g,Hexa 1.5g, then drop into (R)-2-(4-hydroxyphenoxy) propionic acid 26g (0.14 in batchesMol), there are a large amount of Bubble formations; Treat that (R)-2-(4-hydroxyphenoxy) propionic acid feeds intake complete, then drop into3,4-difluorobenzonilyile 20g (0.14mol), is then warming up to 80 DEG C, and insulation reaction 7 hours is anti-Should finish. Decompression distillation steam desolventize, be down to room temperature add water 150mL dissolve, use 30% dilute sulfuric acidRegulate pH value to 3～4, stir and separate out solid, filter to obtain (R)-2-[4-(2-fluorine-4-nitrile)-benzeneOxygen base]-propionic acid is for subsequent use.
2) esterification
In 500mL four-hole boiling flask, drop into above-mentioned intermediate (R)-2-[4-(2-fluorine-4-nitrile)-benzeneOxygen base] the sulfuric acid 1g of-propionic acid, 200mL cyclohexane, n-butanol 16g (0.21mol) and catalytic amount,Temperature rising reflux divides water to separating without moisture, and reaction finishes, by reactant liquor washing three times to pH be 7,Separate organic phase, evaporated under reduced pressure solvent obtains product, chemical content 96.8%, and optical purity 98.2%,Two-step reaction total recovery 91% (in (R)-4-hydroxyphenoxy propionic acid), outward appearance is white solid.
Comparative example 2
1) etherification reaction
In 250mL four-hole boiling flask, drop into DMA 100mL, potash 40G (0.29mol) drops into (R)-2-(4-hydroxyphenoxy) propionic acid 26g (0.14mol) in batches, feeds intakeAfter, then drop into 3,4-difluorobenzonilyile 20g (0.14mol), be then warming up to 100 DEG C, insulationReact 12 hours, reaction finishes. Decompression distillation steam desolventize, be down to room temperature add water 150mL dissolve,With 30wt.% dilute sulfuric acid adjusting pH value to 4～5, stir and separate out solid, filter to obtain (R)-2-[4-(2-fluorine-4-nitrile)-phenoxy group]-propionic acid is for subsequent use.
2) esterification
In 500mL four-hole boiling flask, drop into above-mentioned intermediate (R)-2-[4-(2-fluorine-4-nitrile)-benzeneOxygen base]-propionic acid, 200mL benzene, n-butanol 18g (0.24mol) and concentrated sulfuric acid 1g, temperature rising reflux dividesWater, reaction is to separating without moisture, and reaction finishes. By reactant liquor washing three times to pH be 7, separateOrganic phase, evaporated under reduced pressure solvent obtains product, and two-step reaction total recovery 89% is (with (R)-4-hydroxyphenoxyPropionic acid meter), chemical content is 95%, optical purity 97.6%, the HPLC spectrum of its absolute configuration contentAs shown in Figure 2, as shown in Figure 2, absolute configuration R type is 98.82% to figure, and absolute configuration S type is 1.18％。
Claims (10)
1. a preparation method for cyhalofop-butyl, comprises the steps:
1) etherification reaction
In non-proton organic solvent, add acid binding agent, organic base and phase transfer catalyst, thenAdd (R)-2-(4-hydroxyphenoxy) propionic acid in batches, then add 3,4-difluorobenzonilyile, be heated to60～90 DEG C, insulation reaction 2～4 hours, reaction finishes rear desolvation, is down to room temperature, adds waterDissolve, with acid for adjusting pH to 3～5, stir, separate out solid, filter, obtain intermediate (R)-2-[4-(2-fluorine-4-nitrile)-phenoxy group]-propionic acid; Wherein, (R)-2-(4-hydroxyphenoxy) thirdAcid and 3, the mol ratio of 4-difluorobenzonilyile is 1:1～1.5; Described acid binding agent is inorganic base;
2) dehydration esterification
By step 1) obtain intermediate (R)-2-[4-(2-fluorine-4-nitrile)-phenoxy group]-propionic acidAdd reaction vessel with n-butanol, dehydrated solvent and bronsted acid catalyst, add hot reflux, point waterTo anhydrous separating, reaction finishes, and obtains reactant liquor, reactant liquor is washed to neutrality, desolvationObtain cyhalofop-butyl;
Described dehydrated solvent refers to that not alkanes or the ketone non-proton property miscible with water are organic moltenAgent;
Reaction equation is as follows:
2. the preparation method of cyhalofop-butyl according to claim 1, is characterized in that step 1) instituteThe organic base of stating is selected from least one in triethylene diamine, hexa, diazabicycloKind.
3. the preparation method of cyhalofop-butyl according to claim 1 and 2, is characterized in that step 1)Described organic base is 0.01～0.2:1 with the mass ratio of (R)-2-(4-hydroxyphenoxy) propionic acid.
4. according to the preparation method of the cyhalofop-butyl described in claims 1 to 3 any one, it is characterized in that,
Step 1) described phase transfer catalyst is selected from 18-hat-6, TBAB, triethyl group BianAt least one in amine.
5. according to the preparation method of the cyhalofop-butyl described in claim 1 or 4, it is characterized in that step 1)Described phase transfer catalyst with the mass ratio of (R)-2-(4-hydroxyphenoxy) propionic acid is0.005～0.2：1。
6. the preparation method of cyhalofop-butyl according to claim 1, is characterized in that step 1) etherChange the matter of the non-proton organic solvent described in reaction and (R)-2-(4-hydroxyphenoxy) propionic acidAmount is than being 2～10:1, non-proton organic solvent be selected from dimethyl formamide, dimethylacetylamide,At least one in dimethyl sulfoxide (DMSO) and 1-METHYLPYRROLIDONE.
7. the preparation method of cyhalofop-butyl according to claim 1, is characterized in that step 1) etherChange the acid binding agent described in reaction be selected from NaOH, potassium hydroxide, sodium carbonate, potash,At least one in cesium carbonate and potassium phosphate, acid binding agent and (R)-2-(4-hydroxyphenoxy) propionic acidMass ratio be 1.5～3:1.
8. the preparation method of cyhalofop-butyl according to claim 1, is characterized in that, etherification reactionIn regulate while carrying out post processing pH acid used be in sulfuric acid, hydrochloric acid, phosphoric acid and oxalic acid at leastA kind of.
9. according to the preparation method of the cyhalofop-butyl described in claim 1-8 any one, it is characterized in that stepRapid 2) dehydrated solvent described in is selected from least one in cyclohexane, n-hexane and butanone, instituteState dehydrated solvent and step 1) in the mass ratio of (R)-2-(4-hydroxyphenoxy) propionic acid be 5～15:1。
10. the preparation method of cyhalofop-butyl according to claim 1, is characterized in that step 2) esterChange reaction bronsted acid catalyst used and be selected from sulfuric acid, hydrochloric acid, nitric acid, p-methyl benzenesulfonic acid and phosphorusAt least one in acid, described bronsted acid catalyst and step 1) in (R)-2-(4-hydroxy benzenes oxygenBase) mass ratio of propionic acid is 0.01～0.1:1.
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| CN107628967A (en) * | 2017-08-23 | 2018-01-26 | 连云港世杰农化有限公司 | A kind of method for synthesizing 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 |
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| CN109651140A (en) * | 2018-12-12 | 2019-04-19 | 江苏中旗科技股份有限公司 | A kind of synthetic method of cyhalofop-butyl active compound |
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| CN109942460A (en) * | 2019-04-24 | 2019-06-28 | 湖南速博生物技术有限公司 | A method of synthesis cyhalofop-butyl |
| CN110003051A (en) * | 2019-05-06 | 2019-07-12 | 湖南速博生物技术有限公司 | A kind of preparation method of cyhalofop-butyl standard items |
| CN113767911A (en) * | 2021-09-17 | 2021-12-10 | 维讯化工（南京）有限公司 | Herbicide composition containing cyhalofop-butyl and preparation method thereof |
| EP4209486A1 (en) * | 2022-01-07 | 2023-07-12 | Adama Agan Ltd. | Process for the preparation of aryloxyphenoxypropionic acid derivatives in a non polar solvent with a tertiary amine catalyst |
| WO2023131947A1 (en) * | 2022-01-07 | 2023-07-13 | Adama Agan Ltd. | Process for the preparation of aryloxyphenoxypropionic acid derivatives in a non polar solvent with a tertiary amine catalyst |
| 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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