CN108424347A - A kind of preparation method of 2,4 dichlorophenoxyacetic acid - Google Patents
A kind of preparation method of 2,4 dichlorophenoxyacetic acid Download PDFInfo
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- CN108424347A CN108424347A CN201710076370.7A CN201710076370A CN108424347A CN 108424347 A CN108424347 A CN 108424347A CN 201710076370 A CN201710076370 A CN 201710076370A CN 108424347 A CN108424347 A CN 108424347A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
Abstract
The present invention relates to technical field of organic synthesis, and the present invention provides a kind of preparation methods of 2,4 dichlorphenoxyacetic acids, include the following steps：A) under the conditions of existing for phase transfer catalyst, halogenated acetic acids ester and 2,4 Dichlorophenol reactant salts obtain 2,4 dichlorphenoxyacetic acid esters；B) 2,4 dichlorphenoxyacetic acid ester hydrolysis, obtain 2,4 dichlorphenoxyacetic acids.The present invention is under phase transfer catalyst, and using the halogenated acetic acids ester of oil phase and 2,2,4 dichlorphenoxyacetic acid esters are prepared in 4 Dichlorophenol reactant salts, and 2,4 dichlorphenoxyacetic acids and corresponding alcohol are obtained using hydrolysis.The present invention is under phase transfer catalyst effect, and hydrolysis by-product is few in reaction process, and reaction speed is fast, and conversion ratio and yield are higher, and the wastewater flow rate of generation is few, is conducive to industrial applications.
Description
Technical field
The present invention relates to technical field of organic synthesis, more particularly, to the preparation method of one kind 2,4- dichlorphenoxyacetic acids.
Background technology
2,4- dichlorphenoxyacetic acid class compounds are a kind of very important compounds, are that usage history is longest in the world
Organic synthesis herbicide kind, is still being widely used now.Wherein, 2,4- dichlorphenoxyacetic acids are a kind of synthesis plant growths
Element is agriculturally being used as herbicide and plant growth substance, is being widely used.
The synthetic method of 2,4- dichlorphenoxyacetic acids disclosed in the prior art mainly uses Williamson condensation methods, production
Technique can be divided into chloro and first two kinds of chloro after-condensation after first condensation.Wherein, specifically, chloro after being first condensed, i.e. phenol are first
It is condensed to yield sodiumphenoxyacetate, then chloro with sodium chloroacetate, obtains 2,4- dichlorphenoxyacetic acids.
Both existing techniques are reacted including phenates with chloracetate, and reaction system is aqueous phase system, there is reaction
It is not thorough, the problems such as hydrolysising by-product is more, and product yield is low, and product purity is low.
Invention content
In view of this, the technical problem to be solved in the present invention is to provide the preparation side of one kind 2,4- dichlorphenoxyacetic acids
Method, 2, the 4- dichlorphenoxyacetic acids purity that preparation method provided by the invention is prepared is high, high income.
The present invention provides the preparation methods of one kind 2,4- dichlorphenoxyacetic acids, include the following steps：
A) in the presence of a phase transfer catalyst, halogenated acetic acids ester and 2,4- Dichlorophenol reactant salts, obtains 2,4- Dichlorophenoxies
Acetic acid esters；
B) 2, the 4- dichlorphenoxyacetic acids ester hydrolysis, obtains 2,4- dichlorphenoxyacetic acids.
Preferably, the one kind or several of the phase transfer catalyst in polyethers, crown ether, quaternary ammonium salt, tertiary amine and quaternary phosphonium salt
Kind.
Preferably, the dosage of the phase transfer catalyst is the 0.1%~0.5% of 2,4- dichlorphenoxyacetic acid ester quality.
Preferably, the halogenated acetic acids ester is selected from one or more of chloracetate, bromacetate and Alkyl Iodoacetates.
Preferably, 2, the 4- dichloros phenates is selected from 2,4- sodium dichlorophenol indophenols, 2,4- Dichlorophenols potassium, 2,4- Dichlorophenols calcium, 2,
One or more of 4- Dichlorophenols magnesium, 2,4- Dichlorophenols zinc and 2,4- Dichlorophenol aluminium.
Preferably, 2, the 4- dichloros phenates is selected from 2,4- sodium dichlorophenol indophenols or 2,4- Dichlorophenol potassium.
Preferably, the reaction temperature of the step a) is 70~200 DEG C；Reaction time is 0.5~7h.
Preferably, the molar ratio of the halogenated acetic acids ester and 2,4- dichloro phenates is (0.9~1.1)：(0.9~1.1).
Preferably, the halogenated acetic acids ester is prepared by the following method：Alcohol and halogenated acetic acids reaction, obtain halogenated acetic acids ester.
Preferably, 2, the 4- dichloros phenates is prepared by the following method：2,4- Dichlorophenols are reacted with alkali, obtain 2,4- dichloros
Phenates
Compared with prior art, the present invention provides the preparation methods of one kind 2,4- dichlorphenoxyacetic acids, including walk as follows
Suddenly：In the presence of a phase transfer catalyst, halogenated acetic acids ester and 2,4- Dichlorophenol reactant salts obtain 2,4- dichlorphenoxyacetic acid esters；
2,4- dichlorphenoxyacetic acid ester hydrolysis, obtain 2,4- dichlorphenoxyacetic acids.The present invention uses oil phase under phase transfer catalyst
2,4- dichlorphenoxyacetic acid esters are prepared in halogenated acetic acids ester and 2,4- Dichlorophenol reactant salts, and 2,4- dichloros are obtained using hydrolysis
Phenoxy acetic acid and corresponding alcohol.The present invention is under phase transfer catalyst effect, and hydrolysis by-product is few in reaction process, reaction speed
Soon, conversion ratio and yield are higher, and the wastewater flow rate of generation is few.
Specific implementation mode
The present invention provides the preparation methods of one kind 2,4- dichlorphenoxyacetic acids, include the following steps：
A) in the presence of a phase transfer catalyst, halogenated acetic acids ester and 2,4- Dichlorophenol reactant salts, obtains 2,4- Dichlorophenoxies
Acetic acid esters；
B) 2, the 4- dichlorphenoxyacetic acids ester hydrolysis, obtains 2,4- dichlorphenoxyacetic acids.
Preparation method provided by the invention can overcome reaction existing in the prior art to be not thorough, and hydrolysising by-product is more, production
The problems such as product yield is low, and product purity is low, and consumption of raw materials amount is big, and waste water yield is big, and exhaust gas discharge is not easy to control.
In embodiments of the present invention, the halogenated acetic acids ester in chloracetate, bromacetate and Alkyl Iodoacetates one
Kind is several, preferably chloracetate or bromacetate.
Halogenated acetic acids ester is prepared in the embodiment of the present invention first, can prepare by the following method：Alcohol and halogenated acetic acids reaction,
Obtain halogenated acetic acids ester.Wherein, the alcohol can be methanol and other monohydric alcohols.
In the present invention, the preparation method of the halogenated acetic acids ester is preferably specially：By the monohydric alcohol of C2 or more and halogenated
Acetic acidreaction obtains halogenated acetic acids ester.The monohydric alcohol and halogenated acetic acids of more preferably specific C2 or more is under the effect of the catalyst
It is mixed, dehydration obtains halogenated acetic acids ester.The present invention for the stirring concrete mode without limit, this field
Agitating mode known to technical staff.
The monohydric alcohol of C2 the or more more than monohydric alcohol of C2 or more of the present invention namely two carbon atoms；Preferably C2
The monohydric alcohol of~C20；The more preferably monohydric alcohol of C2~C10；The most preferably monohydric alcohol of C3~C9.The halogenated acetic acids is preferred
Selected from one or more of monoxone, bromoacetic acid and iodoacetic acid；The alcohol and the catalyst of halogenated acetic acids reaction are preferably selected from
The concentrated sulfuric acid, toluene and butyl titanate.Wherein, the molar ratio of the monohydric alcohol of the C2 or more and halogenated acetic acids be preferably (1~
1.5):1；More preferably (1~1.2):1；Most preferably (1~1.1):1；The additive amount of the catalyst be preferably 1wt ‰~
1wt%.
Halogenated acetic acids ester intermediate can be prepared in the present invention, and the intermediate stability is good, and byproduct of reaction is few, yield
It is high；And then provide good condition for the yield and purity subsequently prepared.
In addition, 2,4- dichloro phenates can be prepared in the embodiment of the present invention, such as 2,4- chlorophenesic acids are reacted with alkali, obtain 2,
4- dichloro phenates.The present invention is not particularly limited the preparation of 2, the 4- dichloros phenates, the alkali may be used sodium hydroxide,
The alkaline substance solutions such as potassium hydroxide or solid；The temperature of the reaction can be 70~95 DEG C.
In an embodiment of the present invention, 2, the 4- dichloros phenates is selected from 2,4- sodium dichlorophenol indophenols, 2,4- Dichlorophenols potassium, 2,4-
Dichlorophenol calcium, 2,4- Dichlorophenols magnesium, 2,4- Dichlorophenols zinc and 2, one or more of 4- Dichlorophenol aluminium, preferably 2,4- dichloros
Phenol sodium or 2,4- Dichlorophenol potassium.
The present invention uses the halogenated acetic acids ester and 2 of oil phase, and 4- dichloro phenates, under phase transfer catalyst effect, reaction is made
It is standby to obtain 2,4- dichlorphenoxyacetic acid esters, it can make to hydrolyze that by-product is few, and reaction speed is fast, conversion ratio and yield in entire reaction process
Higher, the wastewater flow rate of generation is few.
In the present invention, the phase transfer catalyst preferably is selected from one in polyethers, crown ether, quaternary ammonium salt, tertiary amine and quaternary phosphonium salt
Kind is several, more preferably quaternary ammonium salt, crown ether, tertiary amine or quaternary phosphonium salt.The crown ether such as cyclic crown ether；In the preferred reality of the present invention
It applies in example, the phase transfer catalyst is tetrabutylammonium bromide, 18 crown ethers, triethylamine or tetrabutyl phosphonium bromide phosphine.The phase transfer
The dosage of catalyst is the 0.1%~0.5% of 2,4 dichlorophenoxyacetic acid ester quality.
In an embodiment of the present invention, phase transfer catalyst is added into 2,4- dichloro phenate solutions, is then added halogenated
Acetic acid esters is stirred to react, and layering, gained 2,4- dichlorphenoxyacetic acid esters are in upper oil phase.Wherein, the halogenated acetic acids ester and 2,
The molar ratio of 4- dichloro phenates can be (0.9~1.1)：(0.9~1.1).The present invention for the stirring concrete mode not into
Row limits, agitating mode well known to those skilled in the art.The temperature of the reaction is preferably 70~200 DEG C, more preferably
It is 80~100 DEG C；Reaction time is preferably 0.5~7h, more preferably 0.5h~3h.
After obtaining 2,4- dichlorphenoxyacetic acid esters, the present invention is transferred to hydrolysis reactor and is hydrolyzed, and obtains 2,4- bis-
Chlorophenoxyacetic acid.
After obtaining 2,4- dichlorphenoxyacetic acid esters, one of which method is preferably specially：
2,4- dichlorphenoxyacetic acid esters and aqueous slkali mixed hydrolysis, stirring, then mixed with acid, finally obtain 2,4- dichloro-benzenes
Fluoroacetic acid；More preferably it is specially：2,4- dichlorphenoxyacetic acid esters and aqueous slkali mixed hydrolysis, stirring, then mixed with acid, crystallization,
Filtering, drying, finally obtain 2,4- dichlorphenoxyacetic acids.
Wherein, alkali is preferably one kind in sodium hydroxide, potassium hydroxide；The concentration of the aqueous slkali is preferably 30%~
40%.The reaction temperature is preferably 90~110 DEG C；More preferably 100~110 DEG C；The reaction time is preferably 2~4h；
The present invention for the stirring concrete mode without limit, agitating mode well known to those skilled in the art.
The acid is preferably sulfuric acid, hydrochloric acid or nitric acid；The mass concentration of the acid is preferably 10%~100%；More preferably
It is 30%~60%.The crystallization temperature is preferably 10~20 DEG C；More preferably 10~15 DEG C；The crystallization time is preferably 1
~1.5h；More preferably 1~1.2h.The present invention is for the filtering and dry concrete mode without restriction, this field skill
Filtering and drying mode known to art personnel.
After obtaining 2,4- dichlorphenoxyacetic acid esters, another method is preferably specially：
2,4- dichlorphenoxyacetic acid esters hydrolysis under the effect of the catalyst, obtains 2,4- dichlorphenoxyacetic acids.
In the present invention, it is carried out under the conditions of the hydrolysis can be existing for catalyst.The catalyst of the hydrolysis selects
From one or more in polyethers, crown ether, quaternary ammonium salt, tertiary amine, quaternary phosphonium salt, pyridine, titanate esters, inorganic acid, organic acid；Preferably
Two or more in polyethers, crown ether, quaternary ammonium salt, tertiary amine, quaternary phosphonium salt, pyridine, titanate esters, inorganic acid, organic acid；It is more excellent
It is selected as in the one or more and titanate esters in polyethers, crown ether, quaternary ammonium salt, tertiary amine, quaternary phosphonium salt and pyridine, inorganic acid, organic acid
One or more mixing.Wherein, the crown ether is preferably crown ether or cyclic crown ether；The quaternary ammonium salt includes but not limited to four
Butylammonium bromide；The polyethers includes but not limited to dialkylethers；The quaternary phosphonium salt includes but not limited to the tetrabutyl
Bromide phosphine；The tertiary amine includes but not limited to triethylamine；The inorganic acid includes but not limited to sulfuric acid, hydrochloric acid；The organic acid
Including but not limited to p-methyl benzenesulfonic acid, formic acid and acetic acid.
In an embodiment of the present invention, the catalyst of the hydrolysis accounts for the quality percentage of 2,4- dichlorphenoxyacetic acid esters
Than being preferably 1 ‰~1%；More preferably 2 ‰~8 ‰；Most preferably 3 ‰~7 ‰.The preferred embodiment of the present invention is above-mentioned multiple
Under the catalytic action for closing catalyst, hydrolysis is crystallized, is filtered, being dried to obtain 2,4- dichlorphenoxyacetic acids.
Wherein, the reaction temperature of the hydrolysis is preferably 50~200 DEG C；More preferably 60~180 DEG C；Most preferably 70~
170℃；The reaction time is preferably 1~10h；More preferably 2~9h；Most preferably 4~8h.The reaction preferably flows back
Reaction.
The crystallization temperature is preferably 10~20 DEG C；More preferably 10~15 DEG C；The crystallization time is preferably 1~
1.5h；More preferably 1~1.2h.The present invention is for the filtering and dry concrete mode without restriction, art technology
Filtering and drying mode known to personnel.
The present invention uses the high performance liquid chromatography of this field routine, to 2, the 4- dichlorphenoxyacetic acid purity being prepared
It is measured with yield.
In conclusion preparation method provided by the invention is under phase transfer catalyst, using oil phase halogenated acetic acids ester with
2,4- dichlorphenoxyacetic acid esters are prepared in 2,4- Dichlorophenol reactant salts, and 2,4- dichlorphenoxyacetic acids and right are obtained using hydrolysis
The alcohol answered.The present invention is under phase transfer catalyst effect, and hydrolysis by-product is few in reaction process, and reaction speed is fast, conversion ratio and receipts
Rate is higher, and the wastewater flow rate of generation is few, is conducive to apply.
In order to further illustrate the present invention, with reference to embodiments to the system of 2,4- dichlorphenoxyacetic acids provided by the invention
Preparation Method is described in detail.
Embodiment 1
200g ethyl alcohol, 95g (1mol) monoxones and the 0.1g concentrated sulfuric acids are mixed, 80 DEG C of precipitations are dehydrated 5h, obtain chlorine
Ethyl acetate.
The sodium hydrate aqueous solution 125g (1mol) of 2,4 dichloro phenol 164g (1mo1), mass fraction 32% is mixed and is stirred
It mixes, is warming up to 70 DEG C, obtain 2,4- sodium dichlorophenol indophenol solution.
Tetrabutylammonium bromide 0.1g is added to 2, the 4- sodium dichlorophenol indophenols solution, is then added at one time the chlorine being prepared
Ethyl acetate, after 80 DEG C are stirred 0.5h, layering, the upper oil phase that will contain 2,4- dichlorphenoxyacetic acid esters is transferred to hydrolysis reactor,
Sodium hydrate aqueous solution 125g (1mol) return stirring 0.5h of mass fraction 32% is added, the hydrochloric acid of mass concentration 30% is added
130g crystallizes 1h at 10 DEG C, filters, and filtration cakes torrefaction obtains 2,4- dichlorphenoxyacetic acid solid 221g, purity 99.5%, yield
99.5%.
Embodiment 2
200g methanol, 95g (1mol) monoxones and the 0.1g concentrated sulfuric acids are mixed, 100 DEG C of precipitations are dehydrated 5h, obtain chlorine
Methyl acetate.
The potassium hydroxide aqueous solution 113g (1mol) of 2,4 dichloro phenol 164g (1mo1), mass fraction 50% is mixed and is stirred
It mixes, is warming up to 90 DEG C, obtain 2,4- Dichlorophenol potassium solutions.
18 crown ether 0.1g are added to 2, the 4- Dichlorophenols potassium solution, are then added at one time the monoxone first being prepared
Ester, after 90 DEG C are stirred 0.5h, upper oil phase is transferred to hydrolysis reactor, the hydrochloric acid 130g of mass concentration 30% is added, returned by layering
Dealcoholysis 3h is flowed, 1h is crystallized at 10 DEG C, is filtered, filtration cakes torrefaction, obtains 2,4- dichlorphenoxyacetic acid solid 219g, purity 99.2%,
Yield 98.3%.
Embodiment 3
300g isooctanol, 140g (1mol) bromoacetic acids and the 0.1g concentrated sulfuric acids are mixed, 180 DEG C of precipitations are dehydrated 4h, obtain
To the different monooctyl ester of bromoacetic acid.
The sodium hydrate aqueous solution 125g (1mol) of 2,4 dichloro phenol 164g (1mo1), mass fraction 32% is mixed and is stirred
It mixes, is warming up to 80 DEG C, obtain 2,4- sodium dichlorophenol indophenol solution.
Triethylamine 0.1g is added to 2, the 4- Dichlorophenols potassium solution, it is different to be then added at one time the bromoacetic acid being prepared
Monooctyl ester, after 100 DEG C are stirred 0.5h, upper oil phase is transferred to hydrolysis reactor, concentrated sulfuric acid 20g is added by layering, and flow back dealcoholysis 3h,
1h is crystallized at 10 DEG C, is filtered, and filtration cakes torrefaction obtains 2,4- dichlorphenoxyacetic acid solid 221g, purity 99.3%, yield
99.3%.
Embodiment 4
200g butanol, 95g (1mol) monoxones and the 0.1g concentrated sulfuric acids are mixed, 120 DEG C of precipitations are dehydrated 5h, obtain chlorine
Butyl acetate.
2,4- chlorophenesic acids 164g (1mo1), calcium hydroxide solid 21g (0.5mol) and water are mixed, are warming up to 80
DEG C, obtain 2,4- Dichlorophenol calcium solutions.
0.1g tetrabutyl phosphonium bromide phosphines are added to 2, the 4- Dichlorophenols calcium solution, are then added at one time the chlorine being prepared
Butyl acetate, after 150 DEG C are stirred 0.5h, upper oil phase is transferred to hydrolysis reactor, the hydrogen-oxygen of mass fraction 32% is added by layering
Change sodium water solution 125g (1mol) return stirring 0.5h, 30% hydrochloric acid 130g be added, 1h is crystallized at 10 DEG C, filters, filtration cakes torrefaction,
Obtain 2,4- dichlorphenoxyacetic acid solid 221g, purity 99.2%, yield 99.2%.
Embodiment 5
It is mixed by 150g propyl alcohol, 95g (1mol) monoxone, with the 0.1g concentrated sulfuric acids, 80 DEG C of precipitations are dehydrated 7h, obtain chlorine
Propyl acetate.
The potassium hydroxide aqueous solution 113g (1mol) of 2,4 dichloro phenol 164g (1mo1), mass fraction 50% is mixed and is stirred
It mixes, is warming up to 90 DEG C, obtain 2,4- Dichlorophenol potassium solutions.
Glycol dialkyl ether 0.5g is added to 2, the 4- Dichlorophenols potassium solution, is then added at one time and is prepared
The different monooctyl ester of bromoacetic acid, after 100 DEG C are stirred 0.5h, upper oil phase is transferred to hydrolysis reactor by layering, and concentrated sulfuric acid 20g, reflux is added
Dealcoholysis 3h crystallizes 1h at 10 DEG C, filters, filtration cakes torrefaction, obtain 2,4- dichlorphenoxyacetic acid solid 221g, purity 99.3% is received
Rate 99.3%.
Embodiment 6
200g butanol, 95g (1mol) monoxones and the 0.1g concentrated sulfuric acids are mixed, 120 DEG C of precipitations are dehydrated 5h, obtain chlorine
Butyl acetate.
The potassium hydroxide aqueous solution 113g (1mol) of 2,4 dichloro phenol 164g (1mo1), mass fraction 50% is mixed and is stirred
It mixes, is warming up to 90 DEG C, obtain 2,4- Dichlorophenol potassium solutions.
0.1gDMF is added to 2, the 4- Dichlorophenols potassium solution, is then added at one time the butyl chloroacetate being prepared,
After 150 DEG C of stirring 0.5h, upper oil phase is transferred to hydrolysis reactor by layering, and the sodium hydroxide that mass fraction 32% is added is water-soluble
Liquid 125g (1mol) return stirring 0.5h is added 30% hydrochloric acid 130g, 1h is crystallized at 10 DEG C, filters, and filtration cakes torrefaction obtains 2,4-
Dichlorphenoxyacetic acid solid 221g, purity 99.3%, yield 99.3%.
As seen from the above embodiment, preparation method provided by the invention uses the halogenated of oil phase under phase transfer catalyst
2,4- dichlorphenoxyacetic acid esters are prepared in acetic acid esters and 2,4- Dichlorophenol reactant salts, and 2,4- Dichlorophenoxies are obtained using hydrolysis
Acetic acid and corresponding alcohol；Product purity is 99% or more, and yield is 98% or more.The result shows that the present invention is in phase transfer catalysis (PTC)
Under agent effect, hydrolysis by-product is few in reaction process, and reaction speed is fast, and conversion ratio and yield are higher, and the wastewater flow rate of generation is few, favorably
In application.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. one kind 2, the preparation method of 4- dichlorphenoxyacetic acids, include the following steps：
A) in the presence of a phase transfer catalyst, halogenated acetic acids ester and 2,4- Dichlorophenol reactant salts, obtains 2,4- dichlorphenoxyacetic acids
Ester；
B) 2, the 4- dichlorphenoxyacetic acids ester hydrolysis, obtains 2,4- dichlorphenoxyacetic acids.
2. preparation method according to claim 1, which is characterized in that the phase transfer catalyst is selected from polyethers, crown ether, season
One or more of ammonium salt, tertiary amine and quaternary phosphonium salt.
3. preparation method according to claim 1, which is characterized in that the dosage of the phase transfer catalyst is 2,4- dichloros
The 0.1%~0.5% of phenoxy acetic acid ester quality.
4. preparation method according to claim 1, which is characterized in that the halogenated acetic acids ester is selected from chloracetate, bromine second
One or more of acid esters and Alkyl Iodoacetates.
5. preparation method according to claim 1, which is characterized in that 2, the 4- dichloros phenates is selected from 2,4- Dichlorophenols
One kind in sodium, 2,4- Dichlorophenols potassium, 2,4- Dichlorophenols calcium, 2,4- Dichlorophenols magnesium, 2,4- Dichlorophenols zinc and 2,4- Dichlorophenol aluminium
Or it is several.
6. preparation method according to claim 4, which is characterized in that 2, the 4- dichloros phenates is selected from 2,4- sodium dichlorophenol indophenols
Or 2,4- Dichlorophenol potassium.
7. preparation method according to claim 1, which is characterized in that the reaction temperature of the step a) is 70~200 DEG C；
Reaction time is 0.5~7h.
8. preparation method according to claim 1, which is characterized in that the halogenated acetic acids ester and 2,4- dichloro phenates rubs
You are than being (0.9~1.1)：(0.9~1.1).
9. preparation method according to claim 1, which is characterized in that the halogenated acetic acids ester is prepared by the following method：Alcohol
It is reacted with halogenated acetic acids, obtains halogenated acetic acids ester.
10. preparation method according to claim 1, which is characterized in that 2, the 4- dichloros phenates is prepared by the following method：
2,4- Dichlorophenols are reacted with alkali, obtain 2,4- dichloro phenates.
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| CN109748797A (en) * | 2018-12-18 | 2019-05-14 | 内蒙古世杰化工有限公司 | A method of synthesis fluoro- 2,4 2,4-dinitrophenoxy of 2-(5-) acetic acid esters |
| CN109776301A (en) * | 2019-03-26 | 2019-05-21 | 黑龙江大学 | The synthetic method of one kind 2,4- dichlorphenoxyacetic acid compound |
| CN109942445A (en) * | 2019-02-26 | 2019-06-28 | 山东瑞弘生物科技有限公司 | Beet alkali hydrochlorate synthetic method |
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| CN109748797A (en) * | 2018-12-18 | 2019-05-14 | 内蒙古世杰化工有限公司 | A method of synthesis fluoro- 2,4 2,4-dinitrophenoxy of 2-(5-) acetic acid esters |
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| CN109776301B (en) * | 2019-03-26 | 2021-11-16 | 黑龙江大学 | Synthesis method of 2, 4-dichlorophenoxyacetic acid compound |
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Application publication date: 20180821 |