CN107686454A - A kind of method for synthesizing cyhalofop-butyl - Google Patents

A kind of method for synthesizing cyhalofop-butyl Download PDF

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Publication number
CN107686454A
CN107686454A CN201710788145.6A CN201710788145A CN107686454A CN 107686454 A CN107686454 A CN 107686454A CN 201710788145 A CN201710788145 A CN 201710788145A CN 107686454 A CN107686454 A CN 107686454A
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cyhalofop
reaction
butyl
mass ratio
qualified
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不公告发明人
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Lianyungang Shijie Agrochemical Co Ltd
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Lianyungang Shijie Agrochemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of method for synthesizing cyhalofop-butyl, and with R 2 (4 hydroxyphenoxy) propionic acid and 3,4 dichlorobenzonitriles are raw material by obtaining cyhalofop-butyl into salt, etherificate, neutralization, esterification, fluorination reaction and post processing.The synthetic method of the present invention, with 3,4 dichlorobenzonitriles for raw material, cost of material is greatly reduced, reaction scheme is simple, acyl chloride reaction is needed not move through, reduces the requirement to equipment, it is easy to operate, and solvent and catalyst are recyclable applies mechanically, three wastes discharge amount is few, and reaction condition is gentle, is advantageous to extend to industrialized production.

Description

A kind of method for synthesizing cyhalofop-butyl
Technical field
The present invention relates to herbicide preparing technical field, specially a kind of method for synthesizing cyhalofop-butyl.
Background technology
Cyhalofop-butyl is herbicide for paddy field efficient, less toxic and that selectivity is high, is had to barnyard grass, moleplant seed, amur foxtail etc. Remarkable effect, it is very safe to rice class crop, therefore a kind of simple efficient synthetic route is developed to prepare cyhalofop-butyl, it is right Technique is amplified and industrialized production has huge directive significance.Its chemical structural formula is as follows：
In a variety of synthetic technologys announced at present, have with 3,4- difluorobenzonilyiles and hydroquinones for raw material, by being etherified, The reactions such as substitution obtain cyhalofop-butyl, but this synthetic route is influenceed by raw material and reaction condition, and reaction has racemization phenomenon, different Structure body is more, and side reaction can increase by 3,4- difluorobenzonilyile unit consumption, and 3,4- difluorobenzonilyiles are expensive, therefore general route is complicated And cost is higher；Also have with R-2- (4- hydroxyphenoxies) propionic acid and 3,4- difluorobenzonilyile for raw material, by condensation, photochemical reaction Intermediate R-2- (4- (2- fluorine-4-nitriles)-phenoxy group)-propionyl chloride is generated, finally carrying out esterification with n-butanol obtains cyanogen Fluorine grass ester, but this route needs to carry out acyl chloride reaction, has used phosgene or thionyl chloride poisonous, that corrosivity is strong during reaction Deng raw material, very high is required to equipment and operation, it is dangerous high.
The content of the invention
It is an object of the invention to provide a kind of method for synthesizing cyhalofop-butyl, with R-2- (4- hydroxyphenoxies) propionic acid and 3,4- dichlorobenzonitriles pass through into salt, etherificate, neutralization, esterification, fluorination reaction and post processing for raw material obtains cyhalofop-butyl, with solution The problem of being proposed in certainly above-mentioned background technology.
To achieve the above object, the present invention provides following technical scheme：A kind of method for synthesizing cyhalofop-butyl, with R-2- (4- hydroxyphenoxies) propionic acid and 3,4- dichlorobenzonitrile be raw material by into salt, etherificate, neutralization, esterification, fluorination reaction and after Processing obtains cyhalofop-butyl.
The further technical scheme of the present invention, comprises the following steps：
(1) salt-forming reaction
Quantitative solvent DMF is put into reactor, adds a certain amount of R- (+) -2- (4- hydroxyphenoxies) propionic acid；Often Temperature stirring 0.5 hour, after be slowly added to a certain amount of sodium carbonate, have carbon dioxide generation in course of reaction, risen after terminating Warm to 100~110 DEG C are incubated 1 hour, and the mixed liquor for obtaining intermediate 1 is treated to react in next step.
Wherein, the intermediate 1 is C9H8Na2O4, product C9H8Na2O4, carbon dioxide CO2With water H2O；C9H8Na2O4、 Carbon dioxide CO2With water H2O mass ratio is 226: 44: 18.
(2) etherification reaction
Quantitative 3,4- dichlorobenzonitriles are added drop-wise in previous step reaction mixture, time for adding about 0.5 hour, dripped Finishing sampling analysis after being incubated 2~2.5 hours at 100~110 DEG C, material content ＜ 0.3% is qualified, otherwise extends soaking time, Untill qualified, the mixed liquor of intermediate 2 is obtained, treats to react in next step.
Wherein, the intermediate 2 is C16H11ClNNaO4, product C16H11ClNNaO4, sodium chloride nacl； C16H11ClNNaO4, sodium chloride nacl mass ratio be 635: 117.
(3) neutralization reaction
The mixed liquor of intermediate 2 is cooled to room temperature, and quantitative hydrochloric acid is added dropwise thereto, neutralization reaction liquid to faintly acid, obtains The mixed liquor of intermediate 3 is treated to react in next step.
Wherein, the intermediate 3 is C16H12ClNO4, product C16H12ClNO4, sodium chloride nacl；C16H12ClNO4, chlorine The mass ratio for changing sodium NaCl is 678: 117.
(4) esterification
A certain amount of n-butanol, time for adding is added dropwise into the mixed liquor of intermediate 3 in the range of 50-55 DEG C in temperature control About 0.5 hour, it is added dropwise and is incubated 2~2.5 hours at 50-55 DEG C, sampling analysis, the content ＜ 0.3% of intermediate 3 is qualified, Otherwise continue insulation untill qualified, obtain the mixed liquor of intermediate 4 and treat to react in next step.
Wherein, the intermediate 4 is C20H20ClNO4, product C20H20ClNO4, water H2O；C20H20ClNO4, water H2O matter Amount is than being 747: 117.
(5) fluorination reaction
Quantitative KF is slowly added in the mixed liquor of intermediate 4, adds catalyst A and catalyst B, intermediate 4 and KF occurs Fluorination reaction, KF feed intake end after be incubated 2~2.5 hours at 100-105 DEG C, sampling analysis, product content ＞ more than 98% It is as qualified, otherwise continue insulation untill qualified.
(6) wash
After reaction terminates, control temperature is less than 60 DEG C, negative pressure abjection DMF, recovery, and precipitation is warming up to 55 after terminating~ 60 DEG C, add a certain amount of water washing, layering twice in this temperature range, obtain organic phase, secondary washing water is applied mechanically, once washed Water enters wastewater treatment.
(7) it is dehydrated
Organic phase was entered into micro porous filtration and enters dehydrating kettle, at 55~60 DEG C, vacuum is less than 10 millis for dehydration temperaturre control Meter mercury column(unit of pressure), it is dehydrated 2 hours, detection moisture is qualified less than 0.2%, otherwise continues dehydration untill qualified, and after qualified, cooling is solid Change, obtain cyhalofop-butyl finished product and packed.
Preferably, in step (1), R- (+) -2- (4- hydroxyphenoxies) the propionic acid C9H10O4, sodium carbonate Na2CO3's Mass ratio is 182: 106.
Preferably, in step (2), the intermediate 1C9H8Na2O4, 3,4- dichlorobenzonitriles C7H3Cl2N mass ratio is 226∶172。
Preferably, in step (3), the intermediate 2C16H11ClNNaO4, hydrochloric acid HCl mass ratio be 679: 73.
Preferably, in step (4), the intermediate 3C16H12ClNO4, n-butanol C4H10O mass ratio is 635: 148.
Preferably, in step (5), the intermediate 4C20H20ClNO4, potassium fluoride KF mass ratio be 747: 116.
Preferably, in step (1-5), salt-forming reaction, etherification reaction, neutralization reaction, esterification, turn of fluorination reaction Rate is all higher than 99.5%.
Compared with prior art, the beneficial effects of the invention are as follows：
1st, the present invention synthesis cyhalofop-butyl method, with 3,4- dichlorobenzonitriles for raw material, relative to the preparation announced Technique, for raw material, greatly reduces cost of material with 3, the 4- difluorobenzonilyiles of costliness.
2nd, the method for present invention synthesis cyhalofop-butyl, esterification uses n-butanol as raw material, cheap and easy to get.
3rd, the method for present invention synthesis cyhalofop-butyl, using DMF solvent, price is low, and can be direct by simple precipitation Recovery, it is simple to operate, reduce cost.
4th, the method for present invention synthesis cyhalofop-butyl, avoids acyl chloride reaction, without poisonous, severe corrosive raw material, safety Property is higher, and process route is shorter, and easy to operate, it is easy to accomplish large-scale production.
Brief description of the drawings
Fig. 1 is the cyhalofop-butyl synthetic reaction equation of the present invention；
Fig. 2 is the salt-forming reaction equation of the present invention；
Fig. 3 is the etherification reaction equation of the present invention；
Fig. 4 is the neutralization reaction equation of the present invention；
Fig. 5 is the esterification equation of the present invention；
Fig. 6 is the fluorination reaction equation of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.It is based on Embodiment in the present invention, those of ordinary skill in the art are obtained every other under the premise of creative work is not made Embodiment, belong to the scope of protection of the invention.
Referring to Fig. 1, a kind of method for synthesizing cyhalofop-butyl, with R-2- (4- hydroxyphenoxies) propionic acid and 3,4- dichloro-benzenes Nitrile is raw material by obtaining cyhalofop-butyl into salt, etherificate, neutralization, esterification, fluorination reaction and post processing.
The further technical scheme of the present invention, comprises the following steps：
(1) salt-forming reaction
Quantitative solvent DMF is put into reactor, adds a certain amount of R- (+) -2- (4- hydroxyphenoxies) propionic acid；Often Temperature stirring 0.5 hour, after be slowly added to a certain amount of sodium carbonate, have carbon dioxide generation in course of reaction, risen after terminating Warm to 100~110 DEG C are incubated 1 hour, and the mixed liquor for obtaining intermediate 1 is treated to react in next step.
Wherein, the intermediate 1 is C9H8Na2O4, product C9H8Na2O4, carbon dioxide CO2With water H2O；C9H8Na2O4、 Carbon dioxide CO2With water H2O mass ratio is 226: 44: 18.
Wherein, R- (+) -2- (4- hydroxyphenoxies) the propionic acid C9H10O4, sodium carbonate Na2CO3Mass ratio be 182: 106。
(2) etherification reaction
Quantitative 3,4- dichlorobenzonitriles are added drop-wise in previous step reaction mixture, time for adding about 0.5 hour, dripped Finishing sampling analysis after being incubated 2~2.5 hours at 100~110 DEG C, material content ＜ 0.3% is qualified, otherwise extends soaking time, Untill qualified, the mixed liquor of intermediate 2 is obtained, treats to react in next step.
Wherein, the intermediate 2 is C16H11ClNNaO4, product C16H11ClNNaO4, sodium chloride nacl； C16H11ClNNaO4, sodium chloride nacl mass ratio be 635: 117.
Wherein, the intermediate 1C9H8Na2O4, 3,4- dichlorobenzonitriles C7H3Cl2N mass ratio is 226: 172.
(3) neutralization reaction
The mixed liquor of intermediate 2 is cooled to room temperature, and quantitative hydrochloric acid is added dropwise thereto, neutralization reaction liquid to faintly acid, obtains The mixed liquor of intermediate 3 is treated to react in next step.
Wherein, the intermediate 3 is C16H12ClNO4, product C16H12ClNO4, sodium chloride nacl；C16H12ClNO4, chlorine The mass ratio for changing sodium NaCl is 678: 117.
Wherein, the intermediate 2C16H11ClNNaO4, hydrochloric acid HCl mass ratio be 679: 73.
(4) esterification
A certain amount of n-butanol, time for adding is added dropwise into the mixed liquor of intermediate 3 in the range of 50-55 DEG C in temperature control About 0.5 hour, it is added dropwise and is incubated 2~2.5 hours at 50-55 DEG C, sampling analysis, the content ＜ 0.3% of intermediate 3 is qualified, Otherwise continue insulation untill qualified, obtain the mixed liquor of intermediate 4 and treat to react in next step.
Wherein, the intermediate 4 is C20H20ClNO4, product C20H20ClNO4, water H2O；C20H20ClNO4, water H2O matter Amount is than being 747: 117.
Wherein, the intermediate 3C16H12ClNO4, n-butanol C4H10O mass ratio is 635: 148.
(5) fluorination reaction
Quantitative KF is slowly added in the mixed liquor of intermediate 4, adds catalyst A and catalyst B, intermediate 4 and KF occurs Fluorination reaction, KF feed intake end after be incubated 2~2.5 hours at 100-105 DEG C, sampling analysis, product content ＞ more than 98% It is as qualified, otherwise continue insulation untill qualified.
Wherein, the intermediate 4C20H20ClNO4, potassium fluoride KF mass ratio be 747: 116.
(6) wash
After reaction terminates, control temperature is less than 60 DEG C, negative pressure abjection DMF, recovery, and precipitation is warming up to 55 after terminating~ 60 DEG C, add a certain amount of water washing, layering twice in this temperature range, obtain organic phase, secondary washing water is applied mechanically, once washed Water enters wastewater treatment.
(7) it is dehydrated
Organic phase was entered into micro porous filtration and enters dehydrating kettle, at 55~60 DEG C, vacuum is less than 10 millis for dehydration temperaturre control Meter mercury column(unit of pressure), it is dehydrated 2 hours, detection moisture is qualified less than 0.2%, otherwise continues dehydration untill qualified, and after qualified, cooling is solid Change, obtain cyhalofop-butyl finished product and packed.
In step (1-5), salt-forming reaction, etherification reaction, neutralization reaction, esterification, the conversion ratio of fluorination reaction are equal More than 99.5%.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto, Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.

Claims (8)

  1. A kind of 1. method for synthesizing cyhalofop-butyl, it is characterised in that：With R-2- (4- hydroxyphenoxies) propionic acid and 3,4- dichloro-benzenes Nitrile is raw material by obtaining cyhalofop-butyl into salt, etherificate, neutralization, esterification, fluorination reaction and post processing.
  2. 2. the synthetic method of cyhalofop-butyl according to claim 1, it is characterised in that：Synthetic method comprises the following steps：
    (1) salt-forming reaction
    Quantitative solvent DMF is put into reactor, adds a certain amount of R- (+) -2- (4- hydroxyphenoxies) propionic acid；Normal temperature stirs Mix 0.5 hour, after be slowly added to a certain amount of sodium carbonate, have carbon dioxide generation in course of reaction, be warming up to after terminating 100~110 DEG C are incubated 1 hour, and the mixed liquor for obtaining intermediate 1 is treated to react in next step.
    Wherein, the intermediate 1 is C9H8Na2O4, product C9H8Na2O4, carbon dioxide CO2With water H2O；C9H8Na2O4, dioxy Change carbon CO2With water H2O mass ratio is 226: 44: 18.
    (2) etherification reaction
    Quantitative 3,4- dichlorobenzonitriles are added drop-wise in previous step reaction mixture, time for adding about 0.5 hour, are added dropwise 100~110 DEG C insulation 2~2.5 hours after sampling analysis, material content ＜ 0.3% is qualified, otherwise extends soaking time, until Untill qualified, the mixed liquor of intermediate 2 is obtained, treats to react in next step.
    Wherein, the intermediate 2 is C16H11ClNNaO4, product C16H11ClNNaO4, sodium chloride nacl；C16H11ClNNaO4、 The mass ratio of sodium chloride nacl is 635: 117.
    (3) neutralization reaction
    The mixed liquor of intermediate 2 is cooled to room temperature, and quantitative hydrochloric acid is added dropwise thereto, neutralization reaction liquid to faintly acid, obtains centre The mixed liquor of body 3 is treated to react in next step.
    Wherein, the intermediate 3 is C16H12ClNO4, product C16H12ClNO4, sodium chloride nacl；C16H12ClNO4, sodium chloride NaCl mass ratio is 678: 117.
    (4) esterification
    A certain amount of n-butanol, time for adding about 0.5 are added dropwise into the mixed liquor of intermediate 3 in the range of 50-55 DEG C for temperature control Hour, be added dropwise and be incubated 2~2.5 hours at 50-55 DEG C, sampling analysis, the content ＜ 0.3% of intermediate 3 is qualified, otherwise after Continuation of insurance temperature obtains the mixed liquor of intermediate 4 and treats to react in next step untill qualified.
    Wherein, the intermediate 4 is C20H20ClNO4, product C20H20ClNO4, water H2O；C20H20ClNO4, water H2O mass ratio For 747: 117.
    (5) fluorination reaction
    Quantitative KF is slowly added in the mixed liquor of intermediate 4, adds catalyst A and catalyst B, intermediate 4 and KF is fluorinated Reaction, KF feed intake end after be incubated 2~2.5 hours at 100-105 DEG C, sampling analysis, product content ＞ more than 98% as It is qualified, otherwise continue insulation untill qualified.
    (6) wash
    After reaction terminates, control temperature is less than 60 DEG C, negative pressure abjection DMF, and recovery, precipitation is warming up to 55~60 after terminating DEG C, add a certain amount of water washing, layering twice in this temperature range, obtain organic phase, secondary washing water is applied mechanically, a washing water Into wastewater treatment.
    (7) it is dehydrated
    Organic phase was entered into micro porous filtration and enters dehydrating kettle, dehydration temperaturre is controlled at 55~60 DEG C, and vacuum is less than 10 millimeters of mercury Post, it is dehydrated 2 hours, detection moisture is qualified less than 0.2%, otherwise continues dehydration untill qualified, after qualified, cooling solidification, Cyhalofop-butyl finished product is obtained to be packed.
  3. 3. the synthetic method of cyhalofop-butyl according to claim 2, it is characterised in that：In step (1), the R- (+)- 2- (4- hydroxyphenoxies) propionic acid C9H10O4, sodium carbonate Na2CO3Mass ratio be 182: 106.
  4. 4. the synthetic method of cyhalofop-butyl according to claim 2, it is characterised in that：In step (2), the intermediate 1C9H8Na2O4, 3,4- dichlorobenzonitriles C7H3Cl2N mass ratio is 226: 172.
  5. 5. the synthetic method of cyhalofop-butyl according to claim 2, it is characterised in that：In step (3), the intermediate 2C16H11ClNNaO4, hydrochloric acid HCl mass ratio be 679: 73.
  6. 6. the synthetic method of cyhalofop-butyl according to claim 2, it is characterised in that：In step (4), the intermediate 3C16H12ClNO4, n-butanol C4H10O mass ratio is 635: 148.
  7. 7. the synthetic method of cyhalofop-butyl according to claim 2, it is characterised in that：In step (5), the intermediate 4C20H20ClNO4, potassium fluoride KF mass ratio be 747: 116.
  8. 8. the synthetic method of cyhalofop-butyl according to claim 2, it is characterised in that：It is anti-into salt in step (1-5) Should, etherification reaction, neutralization reaction, esterification, the conversion ratio of fluorination reaction be all higher than 99.5%.
CN201710788145.6A 2017-08-23 2017-08-23 A kind of method for synthesizing cyhalofop-butyl Pending CN107686454A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101885703A (en) * 2010-07-08 2010-11-17 湖南化工研究院 N-oxyaryloxyphenoxy carboxylic acid amide compound with bioactivity and preparation method thereof
CN105601538A (en) * 2016-02-02 2016-05-25 江苏丰山集团股份有限公司 Preparation method of cyhalofop-butyl

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101885703A (en) * 2010-07-08 2010-11-17 湖南化工研究院 N-oxyaryloxyphenoxy carboxylic acid amide compound with bioactivity and preparation method thereof
CN105601538A (en) * 2016-02-02 2016-05-25 江苏丰山集团股份有限公司 Preparation method of cyhalofop-butyl

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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