CN107183028A - A kind of ethyl（2R）‑2‑[4‑（The fluorophenoxy of 4 cyano group 2）Phenoxy group] propionic ester and preparation and application - Google Patents
A kind of ethyl（2R）‑2‑[4‑（The fluorophenoxy of 4 cyano group 2）Phenoxy group] propionic ester and preparation and application Download PDFInfo
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- CN107183028A CN107183028A CN201710553405.1A CN201710553405A CN107183028A CN 107183028 A CN107183028 A CN 107183028A CN 201710553405 A CN201710553405 A CN 201710553405A CN 107183028 A CN107183028 A CN 107183028A
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
- A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
- A01N39/04—Aryloxy-acetic acids; Derivatives thereof
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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
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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Abstract
It is an object of the invention to provide a kind of herbicides compounds for being used to prevent and kill off rice terrace grassy weed, the herbicides compounds are ethyl (2R) 2 [4 (fluorophenoxy of 4 cyano group 2) phenoxy group] propionic ester, the preparation method of the wherein described herbicides compounds for preventing and kill off rice terrace grassy weed includes hydroquinones and Williamson etherification reactions occurs in the basic conditions with (S) () 2 chloropropionic acid, obtains (R) 2 [4 hydroxyphenoxy] propionic acid；React, obtain after (R) 2 [4 (fluorophenoxy of 4 cyano group 2) phenoxy group] propionic acid with highly basic again；Reacted with highly basic, obtain ethyl (2R) 2 [4 (fluorophenoxy of 4 cyano group 2) phenoxy group] propionic ester.Synthetic method craft of the present invention is simple, reacts more gentle, without high-temperature and high-pressure conditions, the reaction time is shorter, high income；Herbicides compounds are efficient to moleplant seed, can also prevent and kill off lady's-grass, Paspalum distichum, green bristlegrass, eleusine indica, amur foxtail etc..Preferably, consumption is less compared with cyhalofop-butyl for antagonism barnyard grass preventive effect.
Description
Technical field
The invention belongs to chemical pesticide field, and in particular to a kind of ethyl (2R) -2- [4- (4- cyano group 2- fluorophenoxies) -
Phenoxy group] propionic ester and preparation and application.
Background technology
Due to the development and the rise of cost of labor of science and technology, the use of herbicide becomes more and more frequently, Ren Menye
Gradually depend on herbicide.The unreasonable use of existing most of herbicide has stronger selection pressure to weeds, weeds it is anti-
The property of medicine also becomes more and more stronger.The continuous enhancing of herbicide resistance, the reasonable development of herbicide are caused using chemical herbicide
Become increasingly serious with utilizing.
Cyhalofop-butyl, chemical name (R) -2- [4 (4- cyano group -2- fluorophenoxies) phenoxy group]-butyl propionate, is fragrant oxygen benzene
The only kind to paddy rice with tight security in oxygen phenoxy propionic acid herbicide, is also that interior inhale passes as such other kind
The property led herbicide.Absorbed by the blade and leaf sheath of plant, bast conduction accumulates the meristem zone in plant, resisted
Acetyl-CoA carboxylase (ACCase), makes aliphatic acid synthesis stopping, and the growth division of cell can not be normally carried out, membranous system etc.
Structure containing fat is destroyed, and finally results in Plant death.Weeds Mortality Ratio is absorbed into from cyhalofop-butyl slower, generally require 1-3
Week.The symptom of weeds after administration is as follows：The tender shoots atrophy of four leaf stage, causes death.The old leaf of two leaf stage is changed very little, and is kept
Green.However, cyhalofop-butyl has risen to 225-450g ai/ to the consumption of moleplant seed from initial 75-150g ai/hm2
Hm2, and cyhalofop-butyl is invalid to partial resistance moleplant seed.
The content of the invention
In view of this, it is an object of the invention to provide a kind of weeding chemical combination for being used to prevent and kill off rice terrace grassy weed
Thing, the herbicides compounds are ethyl (2R) -2- [4- (4- cyano group 2- fluorophenoxies)-phenoxy group] propionic ester.
Preferably, the present invention has following structural formula for preventing and kill off the herbicides compounds of rice terrace grassy weed：
Another object of the present invention is used for the preparation method for the herbicides compounds for preventing and kill off rice terrace grassy weed for offer,
Comprise the following steps：
1), with (S)-(-) -2- chloropropionic acids Williamson etherification reactions occur in the basic conditions for hydroquinones, water-soluble
The hydroquinones of property generates hydroquinones sodium salt in alkaline aqueous solution, with attack (S)-(-) -2- chloropropionic acids, is taken through SN2 nucleophilics
Generation reaction obtains (R) 2- [4- Hydroxy-phenoxies] propionic acid；
2), (R) 2- [4- Hydroxy-phenoxies] propionic acid and highly basic react, and generate its carboxylate to increase its nucleophilicity,
SN2 reactions (bimolecular nucleophilic subsititution) occur for its carboxylate attack 3,4 carbon of the fluorobenzonitriles of 4- bis-, and reaction obtains (R) 2-
[4- (4- cyano group 2- fluorophenoxies)-phenoxy group] propionic acid；
3), (R) 2- [4- (4- cyano group 2- fluorophenoxies)-phenoxy group] propionic acid and highly basic react, and generate its carboxylate
To increase its nucleophilicity, attack bromoethane necleophilic reaction obtains ethyl (2R) -2- [4- (4- cyano group 2- fluorophenoxies)-phenoxy group]
Propionic ester；
Preferably, in the preparation method for the herbicides compounds for preventing and kill off rice terrace grassy weed of the present invention, institute
State step 1) described in hydroquinones be water miscible hydroquinones, in alkaline aqueous solution generate hydroquinones sodium salt, to enter
(S)-(-) -2- chloropropionic acids are attacked, are replaced through SN2 necleophilic reactions, (S)-(-) -2- chloropropionic acid configurations are overturn, reaction obtains (R)
2- [4- Hydroxy-phenoxies] propionic acid；It is highly preferred that the step 1) in SN2 nucleophilic substitutions condition be back flow reaction,
SN2 nucleophilic substitutions temperature is 100 DEG C~120 DEG C；Most preferably, the SN2 nucleophilic substitutions temperature is 110 DEG C.More
Preferably, the step 1) described in then optional 3 times~10 times of benzenediol and (S)-(-) -2- chloropropionic acids equivalent proportion, preferably
5.5 times of equivalents；Preferably, it is increase hydroquinones nucleophilicity, first makes benzenediol phenol sodium corresponding with alkali reaction generation, institute
With the equivalent of several 0.8 equivalents of alkali equivalence unit~2, it is highly preferred that the alkali equivalence unit number is 0.9 equivalent；It is highly preferred that described
Alkali is sodium hydroxide.Because start material and product are water solubility, Gu Fanyingxuanzeshui is as solvent, and amount used is to make
Hydroquinones sodium salt dissolves with reaction product, the optional water of scope：1~50 times of hydroquinones (mass ratio), preferably 1.8
Times.Preferably, the step 1) described in nucleophilic substitution be generated as the sodium salt of (R) 2- [4- Hydroxy-phenoxies] propionic acid, institute
The sodium salt for stating (R) 2- [4- Hydroxy-phenoxies] propionic acid is soluble in water, and it is highly acid that inorganic acid regulation Ph values, which can be used, is made described
(R) 2- [4- Hydroxy-phenoxies] propionic acid is separated out, and makes described (R) 2- [4- Hydroxy-phenoxies] propionic acid separate out through filtering.
Preferably, in the preparation method for the herbicides compounds for preventing and kill off rice terrace grassy weed of the present invention,
The step 2) described in SN2 reaction can be carried out in intensive polar solvent；It is highly preferred that the intensive polar solvent is such as acetonitrile,
DMF, methanol, ethanol, the one or more of water；Most preferably, the intensive polar solvent is acetonitrile, described
The consumption of acetonitrile is 1~20 times of (R) 2- [4- Hydroxy-phenoxies] propionic acid, most preferably, and the consumption of the acetonitrile is (R) 2-
8 times of [4- Hydroxy-phenoxies] propionic acid.Preferably, in the weeding chemical combination for being used to prevent and kill off rice terrace grassy weed of the present invention
In the preparation method of thing, in the step 2) described in SN2 reactions alkali used by (R) 2- [4- Hydroxy-phenoxies] propionic acid PKa values
Determine, to ensure to make it to generate carboxylate；It is highly preferred that the alkali is sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, hydrogen
Change the one or more of sodium；Most preferably, the alkali is potassium carbonate；Preferably, the consumption of the alkali is alkali：(R) 2- [4- hydroxyls
Base-phenoxy group] propionic acid 1~3 times of equivalent, most preferably 1.05 equivalents.It is highly preferred that in the step 2) described in SN2 reaction
Condition be backflow, to promote the positive of reaction to occur, the range of reaction temperature is 82~95 DEG C, most preferably 85 DEG C.It is more excellent
Selection of land, in the step 2) described in SN2 start materials (R) 2- [4- Hydroxy-phenoxies] propionic acid：3,4- bis- fluorobenzonitriles are rubbed
Preferably 0.9~5 times of ratio of that, most preferably 1.2 times.
Preferably, in the preparation method for the herbicides compounds for preventing and kill off rice terrace grassy weed of the present invention,
The step 3) described in the preferred sodium hydroxide of alkali, potassium hydroxide, sodium carbonate, potassium carbonate, the one or more of sodium hydride；It is optimal
Selection of land, the alkali is potassium hydroxide.Preferably, the consumption of the alkali is (R) 2- [4- (4- cyano group 2- fluorophenoxies)-phenoxy group]
1~5 times of equivalent of propionic acid, most preferably 1.05 times.Preferably, the bromoethane and (R) 2- [4- (4- cyano group 2- fluorophenoxies)-
Phenoxy group] propionic acid equivalence ratio range be 1：3, most preferably 1.5 times.
The step 3) in SN necleophilic reactions solvent for use be polar non-solute, it is preferable that the aprotic, polar
Solvent is DMF, and DMA, acetonitrile, the one or more of 1-METHYLPYRROLIDONE are optimal
Selection of land, the polar non-solute is DMF.The SN necleophilic reactions can be carried out at 20 DEG C~60 DEG C, most
Preferably in 40 DEG C of progress.Reaction should keep system closed, to prevent raw material bromoethane from volatilizing.Reaction terminates, to make product second
Base (2R) -2- [4- (4- cyano group 2- fluorophenoxies)-phenoxy group] propionic ester is separated out, and a large amount of water can be added in system, afterwards mistake
Filter.Preferably, the water of DMF equivalent volumes is added in the present invention.The other effect for adding water is to make instead
The KBr that should be generated is dissolved in system.Preferably, for ensure its be completely dissolved can after adding water heating systems, most preferably
Ground, the temperature that the present invention is heated is 60 DEG C.Taking the mode of heat filtering afterwards makes product dissociate.
The present invention can obtain ethyl (2R) -2- [4- (4- cyano group 2- fluorophenoxies)-phenoxy group] propionic ester of high-purity, its
Containing a small amount of inorganic impurity and organic impurities, the inorganic impurity can be washed away with organic impurities with water or polar solvent, it is preferable that
The polar solvent is ethanol.
Preferably, in the preparation method of the present invention for the herbicides compounds for preventing and kill off rice terrace grassy weed, institute
State step 1) it is described reaction terminate after can also be extracted with organic solvent, vacuum distillation, after being recrystallized with water, washing dry obtain
(R) 2- [4- Hydroxy-phenoxies] propionic acid.
Preferably, in the preparation method of the present invention for the herbicides compounds for preventing and kill off rice terrace grassy weed, institute
State step 1) organic solvent be Ethyl formate, ethyl acetate, ethyl butyrate, 2- methyltetrahydrofurans, methylisobutylketone, just
The one or more of butanol.
Preferably, in the preparation method of the present invention for the herbicides compounds for preventing and kill off rice terrace grassy weed, institute
State step 2) described in reaction to carry out in the basic conditions.
Preferably, in the preparation method of the present invention for the herbicides compounds for preventing and kill off rice terrace grassy weed, institute
State step 2) described in reaction terminate after extracted with organic solvent, acidizing crystal filters to take precipitation, after washing dry acquisition (R)
2- [4- (4- cyano group 2- fluorophenoxies)-phenoxy group] propionic acid.
Preferably, in the preparation method of the present invention for the herbicides compounds for preventing and kill off rice terrace grassy weed, institute
State step 3) described in reaction be alkalescence condition, reaction temperature be 110 DEG C；After reaction terminates, added water filtering, and drying is obtained after washing
Obtain ethyl (2R) -2- [4- (4- cyano group 2- fluorophenoxies)-phenoxy group] propionic ester.
Present invention also offers herbicides compounds prepared by the above method, and it is preventing and kill off rice terrace grassy weed
Purposes.
Compared with prior art, the present invention has advantages below to the present invention：
1), synthetic method craft of the present invention is simple, reacts more gentle, without high-temperature and high-pressure conditions, the reaction time is shorter,
High income (80%), and cyhalofop-butyl yield is low (48%), and the reaction time is long；
2) careless ethyl ester (i.e. ethyl (2R) -2- [4- (4- cyano group 2- fluorophenoxies)-benzene oxygen of the cyanogen fluorine of synthetic method of the present invention
Base] propionic ester) it is efficient to moleplant seed, it can also prevent and kill off lady's-grass, Paspalum distichum, green bristlegrass, eleusine indica, amur foxtail etc..Antagonism barnyard grass
Preferably, consumption is less compared with cyhalofop-butyl for careless preventive effect.
Embodiment
Below in conjunction with the embodiment in the present invention, the technical scheme in the present invention is clearly and completely described.It is aobvious
So, described embodiment is only a part of embodiment of the invention, rather than whole embodiments.Based on the reality in the present invention
Example is applied, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made all belongs to
In the scope of protection of the invention.
The synthesis of embodiment 1 (R) 2- [4- Hydroxy-phenoxies] propionic acid
At room temperature, into the NaOH solution of 134g mass percentage concentrations 15% add hydroquinones (60g,
544.90mmol), (S)-(-) -2- chloropropionic acids (10.3g, 94.91mmol).System is warming up to backflow, gas-chromatography after 3 hours
Detection reaction is completed.Cooling, ice bath is down to 0 DEG C, and watery hydrochloric acid is added dropwise to PH=6.0.After methylisobutylketone extraction, aqueous phase is acidified to
PH=1.0, system to muddiness, methylisobutylketone is extracted twice, every all over 100ml.Organic phase vacuum distillation is to dry, 40 DEG C of residue
Constant weight is dried under vacuum to, brown solid is obtained.Recrystallized with water, the washing of wet product cold water, 60 DEG C are dried under reduced pressure to constant weight, obtain
10.8g (98%) off-white powder, i.e. (R) 2- [4- Hydroxy-phenoxies] propionic acid.Yield 61.2%.
M.p.141 DEG C~145 DEG C, [a]D 18=+56.83 ° (C=1, CH3COCH3)；H1NMRδ:1.53(d,3H),
4.69(q,1H),6.75(m,4H)
The synthesis of embodiment 2 (R) 2- [4- (4- cyano group 2- fluorophenoxies)-phenoxy group] propionic acid
Addition (R) 2- [4- Hydroxy-phenoxies] propionic acid (10.0g, 54.89mmol) in 100ml acetonitriles, potassium carbonate (8.0g,
57.31mmol), it is stirred at room temperature 30 minutes.The fluorobenzonitriles of 3,4- bis- (9g, 64.70mmol) are added, backflow is heated to, insulation 6 is small
When, high performance liquid chromatography detection reaction is completed.Temperature is down to room temperature, adds 250ml water, twice, every time is extracted with ethyl acetate
50ml.Water layer ice bath is cooled to 0 DEG C, and dilute hydrochloric acid solution is added dropwise to pH value 3-4, gradually there is a solid precipitation, 0-10 DEG C of keeping temperature after
Continuous stirring 1 hour, filtering, filter cake 50ml cold water is washed twice, and 50 degree are dried under vacuum to constant weight, obtain 13.5g (content 96%) class
White solid, is (R) 2- [4- (4- cyano group 2- fluorophenoxies)-phenoxy group] propionic acid.Yield 78.4%.
1H-NMR(DMSO-D6)δ:2.63 (1H, d, J=6.8Hz), δ:4.56 (1H, d, J=6.8Hz), δ:7.04(2H,
Dd, J=8.1,1.7Hz), δ:7.28 (2H, dd, J=8.1,1.7Hz), δ:7.32 (1H, dd, J=7.6,0.7Hz), δ:7.65
(1H,dd,7.6,1.5Hz),δ:8.01 (1H, dd, J=1.5,0.7Hz), δ:12.65(1H,S)
The synthesis of the ethyl of embodiment 3 (2R) -2- [4- (4- cyano group 2- fluorophenoxies)-phenoxy group] propionic ester
In 150mlN, dinethylformamide, (R) 2- [4- (4- cyano group 2- fluorophenoxies)-phenoxy group] propionic acid is added
(13.5g, 96%, 43.02mmol), potassium hydroxide (2.64g, 45.17mmol), 1ml water stirs 30min.System is warming up to 40
DEG C, the 20mlN of bromoethane (7.0g, 64.53mmol), dinethylformamide solution is added dropwise.This temperature is kept, is reacted 3 hours,
High performance liquid chromatography detection reaction is completed.60 DEG C are warming up to, 150ml water is added dropwise, afterwards heat filtering, filter cake water, ice ethanol is washed
Wash, 45 DEG C are dried under vacuum to constant weight, obtain 12.0g (99%) off-white powder, as ethyl (2R) -2- [4- (4- cyano group 2- fluorine
Phenoxy group)-phenoxy group] propionic ester.Yield 83.9%.
1H-NMR(DMSO-D6)δ:1.18 (3H, t, J=7.0Hz), δ:1.51 (3H, d, J=6.8Hz), δ:4.15(2H,
M, J=7.0Hz), δ:4.96 (1H, q, J=6.8Hz), δ:6.96 (1H, dd, J=1.6Hz, J=2.0Hz), δ:6.98(2H,
D, J=6.4Hz), δ:7.11 (2H, d, J=6.4Hz), δ:7.64 (1H, dd, J=1.6Hz, J=8.8Hz), δ:8.0(1H,
Dd, J=2.0Hz, J=8.8Hz)
The different agents of embodiment 4 prevent and treat the test of pesticide effectiveness of rice terrace grassy weed
Experimental method：The careless ethyl ester EC of 10% cyanogen fluorine, the cyhalofop-butyl EC of equivalent 10% and high dose are spray applied to rice terrace
10% cyhalofop-butyl EC, experiment totally 5 processing, each three repetitions of processing, cell random alignment, plot area 50m2.Carry out
After the spraying of cauline leaf, medicine 14 days and the fresh weight preventive effect of each medicament is observed within 30 days respectively.Respondent is the barnyard grass in field, a thousand pieces of gold
Paddy rice occurs son, 3 kinds of weeds of amur foxtail, visual test medicament without poisoning.
Processing 1：Use careless ethyl ester (ethyl (2R) -2- [4- (the 4- cyano group 2- fluorophenoxies)-phenoxy group] propionic acid of 95% cyanogen fluorine
Ester) 10%, 500#5%, 1601#1.5%, 600#1.5%, dimethylbenzene supplies, and is prepared into 10% cyanogen fluorine grass ethyl ester EC (missible oil),
It is 75 grams/ha wherein to apply active ingredient amount.
Processing 2：Use careless ethyl ester (ethyl (2R) -2- [4- (the 4- cyano group 2- fluorophenoxies)-phenoxy group] propionic acid of 95% cyanogen fluorine
Ester) 10%, 500#5%, 1601#1.5%, 600#1.5%, dimethylbenzene supplies, and is prepared into 10% cyanogen fluorine grass ethyl ester EC (missible oil),
It is 90 grams/ha wherein to apply active ingredient amount.
Processing 3：Use careless ethyl ester (ethyl (2R) -2- [4- (the 4- cyano group 2- fluorophenoxies)-phenoxy group] propionic acid of 95% cyanogen fluorine
Ester) 10%, 500#5%, 1601#1.5%, 600#1.5%, dimethylbenzene supplies, and is prepared into 10% cyanogen fluorine grass ethyl ester EC (missible oil)
It is 120 grams/ha wherein to apply active ingredient amount.
Processing 4：Use 10% cyhalofop-butyl EC ((R) -2- [4 (4- cyano group -2- fluorophenoxies) phenoxy group]-propionic acid fourths
Ester), wherein it is 150 grams/ha to apply active ingredient amount.
As a result it is as follows：
It can be seen that careless ethyl ester (i.e. ethyl (2R) -2- [4- (4- cyano group 2- the fluorophenoxies)-benzene of the cyanogen fluorine of synthetic method of the present invention
Epoxide] propionic ester) it is efficient to moleplant seed, preferably, consumption is less compared with cyhalofop-butyl for antagonism barnyard grass preventive effect.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of herbicides compounds for being used to prevent and kill off rice terrace grassy weed, it is characterised in that the herbicides compounds have
Ethyl (2R) -2- [4- (4- cyano group 2- fluorophenoxies)-phenoxy group] propionic ester.
2. herbicides compounds according to claim 1, it is characterised in that the herbicides compounds have following structural formula：
3. a kind of preparation method for being used to prevent and kill off the herbicides compounds of rice terrace grassy weed, it is characterised in that including following
Step：
1), with (S)-(-) -2- chloropropionic acids Williamson etherification reactions occur in the basic conditions for hydroquinones, through SN2 nucleophilics
Substitution reaction obtains (R) 2- [4- Hydroxy-phenoxies] propionic acid；
2), (R) 2- [4- Hydroxy-phenoxies] propionic acid and highly basic react, (R) 2- [4- Hydroxy-phenoxies] third described in generation
The carboxylate of acid is to increase its nucleophilicity, and (R) 2- [4- Hydroxy-phenoxies] the propionic acid carboxylates and the fluorobenzonitrile of 3,4- bis- occur
SN2 reacts, and obtains (R) 2- [4- (4- cyano group 2- fluorophenoxies)-phenoxy group] propionic acid；
3), (R) 2- [4- (4- cyano group 2- fluorophenoxies)-phenoxy group] propionic acid and highly basic react, and generate its carboxylate to increase
Plus its nucleophilicity, attack bromoethane generation SN necleophilic reaction acquisition ethyl (2R) -2- [4- (4- cyano group 2- fluorophenoxies)-benzene oxygen
Base] propionic ester.
4. the preparation method according to claim 3 for being used to prevent and kill off the herbicides compounds of rice terrace grassy weed, it is special
Levy and be, the step 1) described in alkaline solution be sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, one kind of sodium hydride
Or it is several, contained alkaline matter and benzenediol equivalent proportion are 0.8 times~2 times, most preferably 0.9 times equivalent in the alkali lye；
The benzenediol and (S)-(-) -2- chloropropionic acids equivalent proportion then preferably 3 times~10 times equivalents, most preferably 5.5 times equivalents；Preferably,
The SN necleophilic reactions temperature is 110 DEG C.
5. the preparation method according to claim 3 for being used to prevent and kill off the herbicides compounds of rice terrace grassy weed, it is special
Levy and be, the step 1) reaction extracts after terminating with organic solvent, and vacuum distillation after being recrystallized with water, washs drying
(R) 2- [4- Hydroxy-phenoxies] propionic acid described in acquisition.
6. the preparation method according to claim 3 for being used to prevent and kill off the herbicides compounds of rice terrace grassy weed, it is special
Levy and be, the step 1) organic solvent is Ethyl formate, ethyl acetate, ethyl butyrate, 2- methyltetrahydrofurans, methyl
Isobutyl ketone, the one or more of n-butanol.
7. the preparation method according to claim 3 for being used to prevent and kill off the herbicides compounds of rice terrace grassy weed, it is special
Levy and be, the step 2) described in reaction to carry out in the basic conditions.
8. the preparation method according to claim 7 for being used to prevent and kill off the herbicides compounds of rice terrace grassy weed, it is special
Levy and be, the step 2) described in reaction terminate after extracted with organic solvent, acidizing crystal filters to take precipitation, dry after washing
Dry acquisition (R) 2- [4- (4- cyano group 2- fluorophenoxies)-phenoxy group] propionic acid.
9. the preparation method according to claim 7 for being used to prevent and kill off the herbicides compounds of rice terrace grassy weed, it is special
Levy and be, the step 3) described in reaction be alkalescence condition, reaction temperature is 20 DEG C~60 DEG C；After reaction terminates, added water
Filter, dries after washing and obtains ethyl (2R) -2- [4- (4- cyano group 2- fluorophenoxies)-phenoxy group] propionic ester.
10. herbicides compounds prepared by method according to claims 1 to 9, and it is preventing and kill off rice terrace grassy weed
Purposes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710553405.1A CN107183028A (en) | 2017-07-08 | 2017-07-08 | A kind of ethyl（2R）‑2‑[4‑（The fluorophenoxy of 4 cyano group 2）Phenoxy group] propionic ester and preparation and application |
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| CN201710553405.1A CN107183028A (en) | 2017-07-08 | 2017-07-08 | A kind of ethyl（2R）‑2‑[4‑（The fluorophenoxy of 4 cyano group 2）Phenoxy group] propionic ester and preparation and application |
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| CN107183028A true CN107183028A (en) | 2017-09-22 |
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| 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 |
| 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 |
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