CN105601538B - A kind of preparation method of cyhalofop-butyl - Google Patents
A kind of preparation method of cyhalofop-butyl Download PDFInfo
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Abstract
A kind of preparation method of cyhalofop-butyl, with（R）2 (4 hydroxyphenoxy) propionic acid and 3,4 difluorobenzonilyiles are raw material, using inorganic base as acid binding agent, add organic base and phase transfer catalyst, and etherification reaction generation intermediate occurs under conditions of more gently, in the short period（R）‑2‑[4‑（The cyano group of 2 fluorine 4）Phenoxy group] propionic acid, then dehydration esterification reaction is carried out, two-step reaction total recovery can reach more than 94%, and optical purity is more than 99%.Present invention reduces etherification reaction temperature, the etherification reaction time is shortened, reaction selectivity, and chiral holding completely is improved, improves product yield, so as to save energy consumption, reduce cost；In addition, the present invention is in the esterification reaction, the dehydrated solvent used can reduce the content of accessory substance, eliminate the purification operations of product, reduce three wastes discharge amount, be advantageous to environmental protection.
Description
Technical field
The invention belongs to herbicide production field, and in particular to a kind of preparation method of cyhalofop-butyl.
Background technology
Cyhalofop-butyl is a rice field post-emergence herbicide that weeds are presented with very high activity and selectivity in very low dose,
It is mainly used in preventing and kill off important grassy weed, especially to barnyard grass (including above the average age for marriage barnyard grass), moleplant seed, amur foxtail, moderately well-off grass, horse
Tang, Paspalum distichum, green bristlegrass, eleusine indica etc. have brilliance effect, it is very safe to rice class crop, and its have it is less toxic, low residual
The characteristics of staying.Moleplant seed harm is more serious in rice terrace, and cyhalofop-butyl shows high herbicide to the moleplant seed before 4 leaf phases
Activity, other medicaments can not be by comparison.
Therefore, popularization and application cyhalofop-butyl will play a significant role the increasing both production and income to national crops, and exploitation is efficient
Herbicide cyhalofop-butyl is by with 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- fluorophenoxies) phenoxy group] butyl propionate, English name：butyl(R)-2-[4-(4-cyano-
2-fluorophenoxy) phenoxy] propionate is the phenoxy carboxylic acid weeding that LG-DOW agricultural sciences company develops
Agent.Structural formula is：
Sterling is white crystalline body, 50 DEG C of fusing point, and vapour pressure is 1.2 × 10-6Pa (20 DEG C), and solubility is in water
0.7mg/L (20 DEG C, pH=7)；During pH=4 stably, decompose during pH=7 slowly, decomposed rapidly when pH is 1~2 or 9.
Cyhalofop-butyl is that uniquely have tight security to rice (transplanting and live) in fragrant phenoxy phenoxy propionic acid herbicide
Kind, there is excellent selectivity to rice etc., its excellent selectivity is based on cyhalofop-butyl in rice body and weeds body
Interior to have different accretion rates, in rice body, cyhalofop-butyl can be degraded quickly to be inactive to acetyl-CoA carboxylase
Two acid-state, thus there is the security of height to rice；, can be effective and accretion rate of the cyhalofop-butyl in weeds body is slower
Suppress the growth of weeds, the degraded because of cyhalofop-butyl in soil and in typical paddy field water is rapid, and therefore, succession crop is pacified
Entirely.
At present, the primary synthetic methods of cyhalofop-butyl have following several：
Using (S)-methyl lactate as raw material, (S)-tolysulfonyl methyl lactate is synthesized first, then react with hydroquinones
Obtain intermediate, then by hydrolysis, ethanol esterification obtain (R) -2- (4- hydroxyphenoxies) ethyl propionate, finally again with
3,4- difluorobenzonilyiles react, and obtain (R) -2- [4- (4- cyano group -2- fluorophenoxies) phenoxy group] ethyl propionate, then are hydrolyzed into acid,
Acid generates cyhalofop-butyl with n-butanol by esterification again.This process route is grown, cumbersome, has substantial amounts of waste water to generate,
And the p-methyl benzenesulfonic acid accessory substance of generation can not reclaim, it is difficult to handle (《Pesticide research and application》The 1st phase of volume 11 in 2007).
Hydroquinones and 3,4- difluorobenzonilyile react to obtain the fluoro- 4- of 3- (4- hydroxyphenoxies) cyanophenyl, then and (S)-right
Tosyl lactate reaction generation cyhalofop-butyl；Influenceed by raw material and reaction condition, reaction has racemization phenomenon, and reality is only
80-90% (R)-isomers can be obtained, meanwhile, from the aspect of cost, 3,4- difluorobenzonilyiles with biphenol is occurred it is anti-
Ying Zhong, two phenolic hydroxyl groups of biphenol each may participate in reaction, generate accessory substance, increase the dosage of 3,4- difluorobenzonilyiles, and 3,
4- difluorobenzonilyiles are expensive, therefore the route is costly, also, the post processing of p-methyl benzenesulfonic acid need to be made of microbial degradation
In-depth is handled, thus it is industrial general do not use this synthetic route (《Agricultural chemicals》The 5th phase of volume 49 in 2010).
Chinese patent CN104803883A discloses a kind of synthetic method of cyhalofop-butyl, with Pfansteihl butyl ester and to toluene
Sulfonic acid chloride is that raw material first carries out the Pfansteihl butyl ester that condensation reaction generates p-toluenesulfonyl protection, then with hydroquinones in alkalescence
Under the conditions of carry out etherification reaction generation (R) -4- hydroxyphenoxypropanoic acids, etherification product in organic solvent, under alkalescence condition with
3,4- difluorobenzonilyiles carry out condensation reaction generation cyhalofop-butyl, using (R) -4- hydroxyphenoxypropanoic acids butyl ester of generation as raw material,
The temperature of reaction is 100-110 DEG C, and first reflux dewatering obtains cyhalofop-butyl with 3,4- difluorobenzonilyile etherification reactions again, and it uses hydrogen
Potassium oxide is raw material, and products obtained therefrom color is deeper, and side reaction easily occurs, such as cyan-hydrolysis；Etherification reaction temperature is more than 100
DEG C, under alkalescence condition, easily make the configuration of product that racemization occur, influence product quality.
The content of the invention
It is an object of the invention to provide a kind of preparation method of cyhalofop-butyl, etherification reaction temperature is this method reduce,
The etherification reaction time is shortened, reaction selectivity, and chiral holding completely is improved, product yield is improved, so as to save
Energy consumption, reduce cost；On the other hand, by-products content is reduced, saves the purification operations of product, reduces three wastes discharge amount,
Be advantageous to environmental protection.
In order to achieve the above object, technical scheme is as follows：
A kind of preparation method of cyhalofop-butyl, comprises the following steps：
1) etherification reaction
Acid binding agent, organic base and phase transfer catalyst are added into non-proton organic solvent, be then added portionwise (R)-
2- (4- hydroxyphenoxies) propionic acid, adds 3,4- difluorobenzonilyiles, is heated to 60~90 DEG C, insulation reaction 2~4 hours, reacts
Desolvation after end, is down to room temperature, is dissolved in water, and with acid for adjusting pH to 3~5, stirring, separates out solid, filtering, obtains centre
Body (R) -2- [4- (the fluoro- 4- cyano group of 2-)-phenoxy group]-propionic acid；Wherein, (R) -2- (4- hydroxyphenoxies) propionic acid and 3,4- difluoro
The mol ratio of cyanophenyl is 1:1~1.5；Described acid binding agent is inorganic base；
2) dehydration esterification
Intermediate (R) -2- [4- (the fluoro- 4- cyano group of 2-)-phenoxy group]-propionic acid that step 1) is obtained and n-butanol, dehydration
Solvent and bronsted acid catalyst add reaction vessel, are heated to reflux, divide water to be separated to anhydrous, and reaction terminates, and obtains reaction solution,
Reaction solution is washed to neutrality, desolvation obtains cyhalofop-butyl；Described dehydrated solvent refers to water-immiscible alkanes
Or ketone non-proton organic solvent；
Reaction equation is as follows：
Preferably, the organic base described in step 1) in triethylene diamine, hexa, diazabicyclo extremely
The mass ratio of few one kind, organic base and (R) -2- (4- hydroxyphenoxies) propionic acid is 0.01~0.2：1.
Preferably, the phase transfer catalyst described in step 1) is in 18- crown-s 6, TBAB, triethyl group benzyl ammonium
The mass ratio of at least one, phase transfer catalyst and (R) -2- (4- hydroxyphenoxies) propionic acid is 0.005~0.2：1.
Preferably, the non-proton organic solvent described in step 1) etherification reaction and (R) -2- (4- hydroxyphenoxies) third
The mass ratio of acid is 2~10：1, non-proton organic solvent is selected from dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO)
At least one of with 1-METHYLPYRROLIDONE.
Preferably, the acid binding agent described in step 1) etherification reaction be selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
The mass ratio of at least one of cesium carbonate and potassium phosphate, acid binding agent and (R) -2- (4- hydroxyphenoxies) propionic acid is 1.5~3：
1。
Further, etherification reaction post processing first adds aqueous solvent, then it is 3~5 to be acidified to pH with acid, and acid used can be sulphur
At least one of acid, hydrochloric acid, phosphoric acid and oxalic acid.
Preferably, the dehydrated solvent described in step 2) is selected from least one of hexamethylene, n-hexane and butanone, dehydration
The mass ratio of (R) -2- (4- hydroxyphenoxies) propionic acid is in solvent and step 1) 5~15：1.
Preferably, the bronsted acid catalyst used in step 2) esterification is selected from sulfuric acid, hydrochloric acid, nitric acid, p-methyl benzenesulfonic acid
At least one of with phosphoric acid, the mass ratio of bronsted acid catalyst and (R) -2- (4- hydroxyphenoxies) propionic acid in step 1) is
0.01~0.1：1.
In the etherification reaction of the present invention, acid binding agent and organic base and phase transfer catalyst are used cooperatively, in etherification reaction
Adding organic base and phase transfer catalyst, its effect is：Reaction substrate (R) -2- (4- hydroxyphenoxies) propionic acid is with acid binding agent
Two phase reaction, adding the organic base of catalytic amount can make (R) -2- (4- hydroxyphenoxies) propionic acid and acid binding agent rapid in homogeneous system
Reaction, reactive intermediate is generated, is advantageous to the progress of etherification reaction, effectively improves reaction rate；Meanwhile the phase transfer of addition is urged
Agent, acid binding agent and the organic alkali salt fast reaction generated in reaction can be carried, makes organic base separate out, separate out has
Machine alkali, which can carry out next circulation, to be continued to react, and is reduced the temperature required for etherification reaction, is shortened the reaction time, improves reaction choosing
Selecting property.
Catalytic reaction process is shown below：
Compared to the prior art, the beneficial effects of the invention are as follows：
1) present invention uses inorganic base organic base adds phase transfer catalyst as catalyst as acid binding agent,
Under conditions of more gentle, reaction generation intermediate (R) -2- [4- (the fluoro- 4- cyano group of 2-)-phenoxy group]-propionic acid in the short period,
The etherification reaction time is shortened, reduces the temperature required for etherification reaction, improves reaction selectivity, and chiral holding completely,
Improve product yield.
2) present invention is used as esterification in the friendly alkanes of esterification use environment or ketone non-proton organic solvent
The dehydrated reagent of reaction, reaction temperature is low, and selectivity is good, and two-step reaction total recovery can reach 94%, and optical purity is more than 99%,
By-products content reduces, and can save the purification operations of product, reduces three wastes discharge amount, is advantageous to environmental protection, in course of reaction
Recycled solvent, cleaning green, it is cost-effective.
Brief description of the drawings
Fig. 1 is the HPLC spectrograms of the absolute configuration content for the cyhalofop-butyl product that the embodiment of the present invention 1 obtains.
Fig. 2 is the HPLC spectrograms of the absolute configuration content for the cyhalofop-butyl product that comparative example 2 obtains.
Embodiment
One step explanation is made to the present invention below in conjunction with specific embodiment.
A kind of preparation method of 1 cyhalofop-butyl of embodiment, comprises the following steps：
1) etherification reaction
DMAC N,N' dimethyl acetamide 100mL, potassium carbonate 50g, triethylene diamine 5g and phase are put into 250mL four-hole boiling flasks
The 0.3g of transfer catalyst 18- crown-s 6, then (R) -2- (4- hydroxyphenoxies) propionic acid 26g (0.14mol) is put into batches, have a large amount of
Bubble produces；Treat that propionic acid feeds intake and finished (R) -2- (4- hydroxyphenoxies), then puts into 3,4- difluorobenzonilyiles 20g (0.14mol), so
After be warming up to 60 DEG C, insulation reaction 3 hours, reaction terminates.Solvent is evaporated off in vacuum distillation, is down to room temperature and adds water 150mL to dissolve, uses
15% watery hydrochloric acid adjusts pH value to 4~5, and stirring separates out solid, filters (R) -2- [4- (the fluoro- 4- cyano group of 2-)-phenoxy group]-the third
Acid is standby.
2) esterification
Put into 500mL four-hole boiling flasks above-mentioned intermediate (R) -2- [4- (the fluoro- 4- cyano group of 2-)-phenoxy group]-propionic acid,
The concentrated sulfuric acid 1g of 200mL hexamethylenes, n-butanol 18g (0.24mol) and catalytic amount, temperature rising reflux divide water to no moisture to separate, instead
It should terminate.
After esterification terminates, reaction solution washing is three times 7 to pH, separates organic phase, and evaporated under reduced pressure solvent obtains product, is changed
Content 97% is learned, optical purity is more than 99%, and the HPLC spectrograms of its absolute configuration content are as shown in figure 1, as shown in Figure 1, definitely
Configuration R types are 99.84%, and absolute configuration S types are 0.16%, and two-step reaction total recovery 94% is (with (R) -4- hydroxyphenoxies third
Acid meter), outward appearance is white solid.
A kind of preparation method of 2 cyhalofop-butyl of embodiment, comprises the following steps：
1) etherification reaction
DMAC N,N' dimethyl acetamide 100mL, potassium carbonate 40g, hexa 0.3g are put into 250mL four-hole boiling flasks
With phase transfer catalyst TBAB 3g, then in batches put into (R) -2- (4- hydroxyphenoxies) propionic acid 26g (0.14mol),
There are a large amount of bubbles to produce；Treat that propionic acid feeds intake and finished (R) -2- (4- hydroxyphenoxies), then puts into 3,4- difluorobenzonilyiles 22g
(0.16mol), 90 DEG C are then heated to, insulation reaction 2 hours, reaction terminates.Solvent is evaporated off in vacuum distillation, is down to room temperature and adds water
250mL dissolves, and adjusts pH value to 3~4 with 30wt.% dilute sulfuric acids, stirring separates out solid, filters (R) -2- [4- (fluoro- 4- of 2-
Cyano group)-phenoxy group]-propionic acid is standby.
2) esterification
Put into 500mL four-hole boiling flasks above-mentioned intermediate (R) -2- [4- (the fluoro- 4- cyano group of 2-)-phenoxy group]-propionic acid,
The p-methyl benzenesulfonic acid 0.5g of 200mL hexamethylenes, n-butanol 18g (0.24mol) and catalytic amount, temperature rising reflux divide water to no moisture point
Go out, reaction terminates.
After esterification terminates, reaction solution washing is three times 7 to pH, separates organic phase, and evaporated under reduced pressure solvent obtains product, is changed
Content 97.3% is learned, optical purity is more than 99%, two-step reaction total recovery 93.5% (in terms of (R) -4- hydroxyphenoxypropanoic acids),
Outward appearance is white solid.
A kind of preparation method of 3 cyhalofop-butyl of embodiment, comprises the following steps：
1) etherification reaction
DMAC N,N' dimethyl acetamide 100mL, potassium carbonate 40g, diazabicyclo 1g and phase are put into 250mL four-hole boiling flasks
Transfer catalyst benzyl triethyl ammonium amine 0.5g, then (R) -2- (4- hydroxyphenoxies) propionic acid 26g (0.14mol) is put into batches, have
A large amount of bubbles produce；Treat that propionic acid feeds intake and finished (R) -2- (4- hydroxyphenoxies), then puts into 3,4- difluorobenzonilyiles 20g
(0.14mol), 85 DEG C are then heated to, insulation reaction 2 hours, reaction terminates.Solvent is evaporated off in vacuum distillation, is down to room temperature and adds water
250mL dissolves, and adjusts pH value to 3~4 with 30% phosphoric acid,diluted, stirring separates out solid, filters (R) -2- [4- (fluoro- 4- cyanogen of 2-
Base)-phenoxy group]-propionic acid is standby.
2) esterification
Put into 500mL four-hole boiling flasks above-mentioned intermediate (R) -2- [4- (the fluoro- 4- cyano group of 2-)-phenoxy group]-propionic acid,
The phosphatase 11 g of 300mL hexamethylenes, n-butanol 20g (0.27mol) and catalytic amount, temperature rising reflux divide water to no moisture to separate, reaction
Terminate.
After esterification terminates, reaction solution washing is three times 7 to pH, separates organic phase, and evaporated under reduced pressure solvent obtains product, is changed
Content 97.5% is learned, optical purity is more than 99%, two-step reaction total recovery 94.1% (in terms of (R) -4- hydroxyphenoxypropanoic acids),
Outward appearance is white solid.
A kind of preparation method of 4 cyhalofop-butyl of embodiment, comprises the following steps：
1) etherification reaction
DMAC N,N' dimethyl acetamide 100mL, potassium carbonate 40g, hexa 1.5g are put into 250mL four-hole boiling flasks
With phase transfer catalyst benzyl triethyl ammonium amine 0.15g, then input (R) -2- (4- hydroxyphenoxies) propionic acid 26g in batches
(0.14mol), there are a large amount of bubbles to produce；Treat that propionic acid feeds intake and finished (R) -2- (4- hydroxyphenoxies), then puts into 3,4- difluorobenzenes
Nitrile 20g (0.14mol), 80 DEG C are then heated to, insulation reaction 2 hours, reaction terminates, and solvent is evaporated off, is down to room
Wen Jiashui 150mL dissolve, and adjust pH value to 3~4 with 30wt.% dilute sulfuric acids, stirring separates out solid, filters (R) -2- [4- (2-
Fluoro- 4- cyano group)-phenoxy group]-propionic acid is standby.
2) esterification
Put into 500mL four-hole boiling flasks above-mentioned intermediate (R) -2- [4- (the fluoro- 4- cyano group of 2-)-phenoxy group]-propionic acid,
The phosphatase 11 g of 200mL hexamethylenes, n-butanol 16g (0.21mol) and catalytic amount, temperature rising reflux divide water to no moisture to separate, reaction
Terminate.
After esterification terminates, reaction solution washing is three times 7 to pH, separates organic phase, and evaporated under reduced pressure solvent obtains product, is changed
Content 97% is learned, optical purity is more than 99%, two-step reaction total recovery 94% (in terms of (R) -4- hydroxyphenoxypropanoic acids), outward appearance
For white solid.
A kind of preparation method of 1 cyhalofop-butyl of comparative example, comprises the following steps：
1) etherification reaction
DMAC N,N' dimethyl acetamide 100mL, potassium carbonate 60g, hexa are put into 250mL four-hole boiling flasks
1.5g, then (R) -2- (4- hydroxyphenoxies) propionic acid 26g (0.14mol) is put into batches, there are a large amount of bubbles to produce；Treat (R) -2-
(4- hydroxyphenoxies) propionic acid feeds intake and finished, then puts into 3,4- difluorobenzonilyiles 20g (0.14mol), then heats to 80 DEG C, insulation
Reaction 7 hours, reaction terminates.Solvent is evaporated off in vacuum distillation, is down to room temperature and adds water 150mL to dissolve, and pH is adjusted with 30% dilute sulfuric acid
For value to 3~4, stirring separates out solid, and it is standby to filter (R) -2- [4- (the fluoro- 4- cyano group of 2-)-phenoxy group]-propionic acid.
2) esterification
Put into 500mL four-hole boiling flasks above-mentioned intermediate (R) -2- [4- (the fluoro- 4- cyano group of 2-)-phenoxy group]-propionic acid,
The sulfuric acid 1g of 200mL hexamethylenes, n-butanol 16g (0.21mol) and catalytic amount, temperature rising reflux divide water to no moisture to separate, reaction
Terminate, be three times 7 to pH by reaction solution washing, separate organic phase, evaporated under reduced pressure solvent obtains product, chemical content 96.8%, light
Purity 98.2% is learned, two-step reaction total recovery 91% (in terms of (R) -4- hydroxyphenoxypropanoic acids), outward appearance is white solid.
Comparative example 2
1) etherification reaction
DMA 100mL, potassium carbonate 40g (0.29mol) are put into 250mL four-hole boiling flasks, is thrown in batches
Enter (R) -2- (4- hydroxyphenoxies) propionic acid 26g (0.14mol), after feeding intake, then put into 3,4- difluorobenzonilyiles 20g
(0.14mol), 100 DEG C are then heated to, insulation reaction 12 hours, reaction terminates.Solvent is evaporated off in vacuum distillation, is down to room temperature and adds
Water 150mL dissolves, and adjusts pH value to 4~5 with 30wt.% dilute sulfuric acids, stirring separates out solid, and filtering (R) -2-, [(2- is fluoro- by 4-
4- cyano group)-phenoxy group]-propionic acid is standby.
2) esterification
Put into 500mL four-hole boiling flasks above-mentioned intermediate (R) -2- [4- (the fluoro- 4- cyano group of 2-)-phenoxy group]-propionic acid,
200mL benzene, n-butanol 18g (0.24mol) and concentrated sulfuric acid 1g, temperature rising reflux divide water, react to no moisture and separate, reaction terminates.
It is three times 7 to pH by reaction solution washing, separates organic phase, evaporated under reduced pressure solvent obtains product, two-step reaction total recovery 89% (with
(R) -4- hydroxyphenoxypropanoic acids meter), chemical content 95%, optical purity 97.6%, the HPLC spectrums of its absolute configuration content
For figure as shown in Fig. 2 as shown in Figure 2, absolute configuration R types are 98.82%, absolute configuration S types are 1.18%.
Claims (7)
1. a kind of preparation method of cyhalofop-butyl, comprises the following steps：
1) etherification reaction
Acid binding agent, organic base and phase transfer catalyst are added into non-proton organic solvent, (R) -2- (4- are then added portionwise
Hydroxyphenoxy) propionic acid, 3,4- difluorobenzonilyiles are added, are heated to 60~90 DEG C, insulation reaction 2~4 hours, after reaction terminates
Desolvation, be down to room temperature, be dissolved in water, with acid for adjusting pH to 3~5, stirring separates out solid, filtering, obtain intermediate (R)-
2- [4- (the fluoro- 4- cyano group of 2-)-phenoxy group]-propionic acid；
Wherein, the mol ratio of (R) -2- (4- hydroxyphenoxies) propionic acid and 3,4- difluorobenzonilyile is 1:1~1.5；Described is organic
The mass ratio of alkali and (R) -2- (4- hydroxyphenoxies) propionic acid is 0.01~0.2：1；Described acid binding agent is inorganic base；
The organic base is selected from least one of triethylene diamine, hexa, diazabicyclo；
The phase transfer catalyst is selected from least one of 18- crown-s 6, TBAB, triethyl group benzyl ammonium；
2) dehydration esterification
Intermediate (R) -2- [4- (the fluoro- 4- cyano group of 2-)-the phenoxy group]-propionic acid and n-butanol, dehydrated solvent that step 1) is obtained
And bronsted acid catalyst adds reaction vessel, is heated to reflux, divides water to be separated to anhydrous, reaction terminates, and obtains reaction solution, will be anti-
Liquid is answered to be washed to neutrality, desolvation obtains cyhalofop-butyl；
Described dehydrated solvent is selected from least one of hexamethylene, n-hexane and butanone；
Reaction equation is as follows：
2. the preparation method of cyhalofop-butyl according to claim 1, it is characterised in that the phase transfer catalysis (PTC) described in step 1)
The mass ratio of agent and (R) -2- (4- hydroxyphenoxies) propionic acid is 0.005~0.2：1.
3. the preparation method of cyhalofop-butyl according to claim 1, it is characterised in that described in step 1) etherification reaction
The mass ratio of non-proton organic solvent and (R) -2- (4- hydroxyphenoxies) propionic acid is 2~10：1, non-proton organic solvent
Selected from least one of dimethylformamide, dimethyl acetamide, dimethyl sulfoxide (DMSO) and 1-METHYLPYRROLIDONE.
4. the preparation method of cyhalofop-butyl according to claim 1, it is characterised in that described in step 1) etherification reaction
Acid binding agent is selected from least one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate and potassium phosphate, acid binding agent with
(R) mass ratio of -2- (4- hydroxyphenoxies) propionic acid is 1.5~3：1.
5. the preparation method of cyhalofop-butyl according to claim 1, it is characterised in that when being post-processed in etherification reaction
The acid adjusted used in pH is at least one of sulfuric acid, hydrochloric acid, phosphoric acid and oxalic acid.
6. the preparation method of the cyhalofop-butyl according to claim any one of 1-5, it is characterised in that taken off described in step 2)
The mass ratio of (R) -2- (4- hydroxyphenoxies) propionic acid is in aqueous solvent and step 1) 5~15：1.
7. the preparation method of cyhalofop-butyl according to claim 1, it is characterised in that the matter used in step 2) esterification
Sub- acid catalyst is selected from sulfuric acid, hydrochloric acid, nitric acid, at least one of p-methyl benzenesulfonic acid and phosphoric acid, the bronsted acid catalyst with
The mass ratio of (R) -2- (4- hydroxyphenoxies) propionic acid is 0.01~0.1 in step 1)：1.
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| CN107183028A (en) * | 2017-07-08 | 2017-09-22 | 北京燕化永乐生物科技股份有限公司 | A kind of ethyl（2R）‑2‑[4‑（The fluorophenoxy of 4 cyano group 2）Phenoxy group] propionic ester and preparation and application |
| CN107686454A (en) * | 2017-08-23 | 2018-02-13 | 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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