CN108424360A - The preparation method of one kind 2,4- dichlorphenoxyacetic acids - Google Patents
The preparation method of one kind 2,4- dichlorphenoxyacetic acids Download PDFInfo
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- CN108424360A CN108424360A CN201710076223.XA CN201710076223A CN108424360A CN 108424360 A CN108424360 A CN 108424360A CN 201710076223 A CN201710076223 A CN 201710076223A CN 108424360 A CN108424360 A CN 108424360A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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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
- C07C67/307—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 halogen; by substitution of halogen atoms by other halogen atoms
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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
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Abstract
The present invention provides a kind of preparation methods of 2,4 dichlorphenoxyacetic acids, including：A) halogenated acetic acids ester is obtained by the reaction with alcohol in halogenated acetic acids；Phenolate is obtained by the reaction with alkali in phenol；B) phenoxy acetic acid ester is obtained by the reaction with phenolate in halogenated acetic acids ester；C) chlorination obtains 2,4 dichlorphenoxyacetic acid esters to phenoxy acetic acid ester under the effect of the catalyst；The catalyst is selected from one or more of ferric trichloride, alchlor, boron trifluoride, columbium pentachloride, fluoroform sulphonate, aluminium oxide, di-iron trioxide, diboron trioxide, niobium pentaoxide, diphenyl ether, diphenylsulfide, diphenyl disulfide, dimethyl sulfide and dimethyl disulfide D) 2,4 dichlorphenoxyacetic acid ester hydrolysis obtain 2,4 dichlorphenoxyacetic acids.The present invention uses specific catalyst using specific reaction route and chlorination, and good reaction selectivity, by-product is few, high income.
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 acids are a kind of synthetic auxins, are agriculturally being used as herbicide and plant growth substance,
It has a wide range of applications.
The synthetic method of 2,4- dichlorphenoxyacetic acids disclosed in the prior art mainly uses condensation method, can be divided into and first be condensed
Chloro and first chloro are condensed two kinds again again.Specifically, it is first condensed again chloro i.e. phenol and is first condensed to yield benzene oxygen with sodium chloroacetate
Sodium acetate, then chloro obtain 2,4- dichlorphenoxyacetic acids.This method advantage is that monoxone hydrolysis is few, chloro high selectivity, still
The disadvantage is that quantity of three wastes is handled greatly very much；The method that first chloro is condensed again, phenol chloro is selectively poor, is obtaining 2,4- Dichlorophenols
Meeting by-product 2,6- Dichlorophenols etc. simultaneously.Cause by-product separation difficult.And above two method yield 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 and yield that the preparation methods of 2,4- dichlorphenoxyacetic acids provided by the invention is prepared
It is high.
The present invention provides the preparation methods of one kind 2,4- dichlorphenoxyacetic acids, include the following steps：
A) halogenated acetic acids ester is obtained by the reaction with alcohol in halogenated acetic acids；
Phenolate is obtained by the reaction with alkali in phenol；
B) phenoxy acetic acid ester is obtained by the reaction with phenolate in halogenated acetic acids ester；
C) chlorination obtains 2,4- dichlorphenoxyacetic acid esters to phenoxy acetic acid ester under the effect of the catalyst；The catalyst is selected from
Ferric trichloride, alchlor, boron trifluoride, columbium pentachloride, fluoroform sulphonate, aluminium oxide, di-iron trioxide, three oxidations two
One kind in boron, niobium pentaoxide, diphenyl ether, diphenylsulfide, diphenyl disulfide, dimethyl sulfide and dimethyl disulfide or
It is several
D) 2,4- dichlorphenoxyacetic acids ester hydrolysis obtains 2,4- dichlorphenoxyacetic acids.
Preferably, the step A) in the molar ratio of halogenated acetic acids and alcohol be 1：(1~1.5)；The phenol is reacted with alkali
Molar ratio be 1：(1~1.1).
Preferably, the halogenated acetic acids is selected from one or more of monoxone, bromoacetic acid and iodoacetic acid；The alcohol is C2
Above monohydric alcohol；The one kind of the alkali in sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and zinc hydroxide
Or it is several.
Preferably, the reaction temperature of the halogenated acetic acids and alcohol is 50~200 DEG C；The phenol is 50 with alkali reaction temperature
~120 DEG C.
Preferably, the molar ratio of the halogenated acetic acids ester and phenol reactant salt is (1~1.2)：1；The step B) reaction
Temperature is 50~200 DEG C.
Preferably, the step C) catalyst be selected from ferric trichloride, alchlor, boron trifluoride, columbium pentachloride, trifluoro
Mesylate, aluminium oxide, di-iron trioxide, diboron trioxide, niobium pentaoxide, diphenyl ether, diphenylsulfide, diphenyl disulfide
Two or more in ether, dimethyl sulfide and dimethyl disulfide.
Preferably, the step C) catalyst be selected from ferric trichloride, alchlor, boron trifluoride, columbium pentachloride, trifluoro
One or more of mesylate, aluminium oxide, di-iron trioxide, diboron trioxide and niobium pentaoxide and diphenyl ether, hexichol
The mixing of one or more of base thioether, diphenyl disulfide, dimethyl sulfide and dimethyl disulfide.
Preferably, the step C) catalyst account for the phenoxy acetic acid ester molar content be 0.1%~1%.
Preferably, the step C) chlorination temperature be 0~100 DEG C.
Preferably, the step D) hydrolysis catalyst be alkali or acid；The alkali is sodium hydroxide or potassium hydroxide；
A concentration of the 30%~40% of the aqueous slkali；The mass ratio of 2, the 4- dichlorphenoxyacetic acids ester and aqueous slkali is 1:1~2；
The acid is selected from one or more of sulfuric acid, hydrochloric acid, p-methyl benzenesulfonic acid, formic acid and acetic acid；The acid accounts for 2,4- Dichlorophenoxies
Acetic acid esters mass percent is 0.5%~10%.
Compared with prior art, the present invention provides the preparation methods of one kind 2,4- dichlorphenoxyacetic acids, including walk as follows
Suddenly：A) halogenated acetic acids ester is obtained by the reaction with alcohol in halogenated acetic acids；Phenolate is obtained by the reaction with alkali in phenol；B) halogenated acetic acids ester and phenol
Reactant salt obtains phenoxy acetic acid ester；C) chlorination obtains 2,4- dichlorphenoxyacetic acid esters to phenoxy acetic acid ester under the effect of the catalyst；
The catalyst is selected from ferric trichloride, alchlor, boron trifluoride, columbium pentachloride, fluoroform sulphonate, aluminium oxide, three oxidations
Two iron, diboron trioxide, niobium pentaoxide, diphenyl ether, diphenylsulfide, diphenyl disulfide, dimethyl sulfide and dimethyl two
One or more of thioether D) 2,4- dichlorphenoxyacetic acid ester hydrolysis obtains 2,4- dichlorphenoxyacetic acids.The present invention by using
Phenoxy acetic acid ester is obtained by the reaction in phenolate and halogenated acetic acids ester, after obtain 2,4- bis- through superchlorination under the action of special catalyst
Chlorophenoxyacetic acid ester, 2,4- dichlorphenoxyacetic acid esters obtain 2,4- dichlorphenoxyacetic acids by hydrolysis.The present invention using price compared with
Low raw material, phenoxy acetic acid ester chlorination use specific catalyst, and at low cost, good reaction selectivity, by-product is few, high income,
Process safety.
Specific implementation mode
The present invention provides the preparation methods of one kind 2,4- dichlorphenoxyacetic acids, include the following steps：
A) halogenated acetic acids ester is obtained by the reaction with alcohol in halogenated acetic acids；
Phenolate is obtained by the reaction with alkali in phenol；
B) phenoxy acetic acid ester is obtained by the reaction with phenolate in halogenated acetic acids ester；
C) chlorination obtains 2,4- dichlorphenoxyacetic acid esters to phenoxy acetic acid ester under the effect of the catalyst；The catalyst is selected from
Ferric trichloride, alchlor, boron trifluoride, columbium pentachloride, fluoroform sulphonate, aluminium oxide, di-iron trioxide, three oxidations two
One kind in boron, niobium pentaoxide, diphenyl ether, diphenylsulfide, diphenyl disulfide, dimethyl sulfide and dimethyl disulfide or
It is several
D) 2,4- dichlorphenoxyacetic acids ester hydrolysis obtains 2,4- dichlorphenoxyacetic acids.
First halogenated acetic acids ester is obtained by the reaction in halogenated acetic acids and alcohol by the present invention.It is preferred that specifically, by halogenated acetic acids and alcohol
It is stirred to react to obtain halogenated acetic acids ester under the effect of the catalyst.The present invention for the stirring concrete mode without limit
It is fixed, agitating mode well known to those skilled in the art.
The monohydric alcohols more than monohydric alcohol of C2 or more of the present invention namely two carbon atoms；Preferably C2~C20's
Monohydric alcohol；The more preferably monohydric alcohol of C2~C10；The most preferably monohydric alcohol of C3~C9.The halogenated acetic acids is preferably selected from chlorine
One or more of acetic acid, bromoacetic acid and iodoacetic acid；The catalyst be preferably selected from the concentrated sulfuric acid, toluene and butyl titanate,
The molar ratio of the alcohol and halogenated acetic acids is preferably (1~1.5):1；More preferably (1.1~1.4):1；Most preferably
For (1.2~1.4):1；The additive amount of the catalyst is preferably 1 ‰~1%.The step A) reaction temperature be preferably 50
~200 DEG C；More preferably 60~180 DEG C；Most preferably 70~170 DEG C；The reaction time is preferably 1~10h；More preferably
2~9h；Most preferably 4~8h.
The halogenated acetic acids ester intermediate that the present invention obtains, the intermediate stability is good, and byproduct of reaction is few, high income；Into
And the yield and purity subsequently to prepare provide good condition.
Phenolate is obtained by the reaction in phenol and alkali by the present invention.It is preferred that benzene specifically is obtained by the reaction in phenol and alkali mixing
Phenates.The present invention for the stirring concrete mode without limit, agitating mode well known to those skilled in the art.
In the present invention, the alkali is preferably selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and hydroxide
One or more of zinc.The molar ratio that the phenol is reacted with alkali is preferably 1：(1~1.1).The phenol reacts temperature with alkali
Preferably 50~120 DEG C of degree；More preferably 60~110 DEG C；Most preferably 70~100 DEG C.
After obtaining halogenated acetic acids ester and phenolate, phenoxy acetic acid ester is obtained by the reaction in halogenated acetic acids ester and phenolate.It is preferred that
Specially halogenated acetic acids ester and phenolate are stirred to react, and layering hydrolyzes upper oil phase.
Wherein, the molar ratio of the halogenated acetic acids ester and phenol reactant salt is preferably (1~1.2)：1；More preferably (1.1
~1.2)：1；The reaction temperature is preferably 50~200 DEG C；More preferably 60~180 DEG C；Most preferably 70~170 DEG C；It is described
Reaction time is preferably 0.5~1h；More preferably 0.5~0.9h；Most preferably 0.5~0.8h.
After obtaining phenoxy acetic acid ester, by phenoxy acetic acid ester, chlorination obtains 2,4- dichlorphenoxyacetic acids under the effect of the catalyst
Ester；It is preferred that being specially：Phenoxy acetic acid ester is added in solvent, obtains 2,4- bis- with chlorination reagent chlorination under the effect of the catalyst
Chlorophenoxyacetic acid ester.
Wherein, the chlorination carries out preferably in chlorination reactor, and the solvent is preferably dimethyl disulfide, four chlorinations
One or more of carbon and dichloroethanes；The chlorination reagent is selected from one or more of chlorine and sulfonic acid chloride；The benzene
The molar ratio of fluoroacetic acid and chlorination reagent is preferably 1：(2~2.5).
The catalyst is preferably selected from ferric trichloride, alchlor, boron trifluoride, columbium pentachloride, fluoroform sulphonate, oxygen
Change aluminium, di-iron trioxide, diboron trioxide, niobium pentaoxide, diphenyl ether, diphenylsulfide, diphenyl disulfide, dimethyl sulfide
One or more of with dimethyl disulfide；More preferably be selected from ferric trichloride, alchlor, boron trifluoride, columbium pentachloride,
Fluoroform sulphonate, aluminium oxide, di-iron trioxide, diboron trioxide, niobium pentaoxide, diphenyl ether, diphenylsulfide, hexichol two
Two or more in thioether, dimethyl sulfide and dimethyl disulfide；Be most preferably selected from ferric trichloride, alchlor,
One in boron trifluoride, columbium pentachloride, fluoroform sulphonate, aluminium oxide, di-iron trioxide, diboron trioxide and niobium pentaoxide
One or more of kind or several and diphenyl ether, diphenylsulfide, diphenyl disulfide, dimethyl sulfide and dimethyl disulfide
Mixing；The most it is preferably ferric trichloride, alchlor, boron trifluoride, columbium pentachloride, fluoroform sulphonate, aluminium oxide, three oxygen
Change one kind and diphenyl ether, diphenylsulfide, diphenyl disulfide, dimethyl disulfide in two iron, diboron trioxide and niobium pentaoxide
A kind of mixing in ether and dimethyl disulfide.
The molar percentage that the additive amount of the catalyst accounts for phenoxy acetic acid ester is preferably 0.1%~1%；More preferably
0.2%~0.9%；Most preferably 0.3%~0.8%.
The temperature of the chlorination reaction is preferably 0~100 DEG C；More preferably 10~90 DEG C；Most preferably 30~70 DEG C.Institute
It is preferably 3~7h to state the reaction time；More preferably 5~7h.
After obtaining 2,4- dichlorphenoxyacetic acid esters, 2,4- dichlorphenoxyacetic acid ester hydrolysis is obtained into 2,4- Dichlorophenoxy second
Acid.
The hydrolysis is divided into basic hydrolysis or sour water solution；It specifically, preferably can be by 2,4- Dichlorophenoxies in basic hydrolysis
Acetic acid esters first with aqueous slkali mixed hydrolysis, stirs, then is mixed with acid, finally obtains phenoxy acetic acid；More preferably it is specially：2,4- bis-
Chlorophenoxyacetic acid ester and aqueous slkali mixed hydrolysis, stirring, then mixed with acid, crystallization filters, is dry, finally obtains 2,4- dichloros
Phenoxy acetic acid.
The alkali is sodium hydroxide or potassium hydroxide；The concentration of the aqueous slkali is preferably 30%~40%；Described 2,4-
The mass ratio of dichlorphenoxyacetic acid ester and aqueous slkali is preferably 1:1~2；The hydrolysising reacting temperature is preferably 70~200 DEG C；More
Preferably 80~180 DEG C；Most preferably 100~150 DEG C；The reaction time is preferably 2~4h；The present invention is 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 concentration of the acid is preferably 10%~100%；More preferably
30%~60%；The additive amount of the acid is preferably 0.1~5%.
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.
In sour water solution, the acid is selected from one or more of sulfuric acid, hydrochloric acid, p-methyl benzenesulfonic acid, formic acid and acetic acid；Institute
It is preferably 0.5%~10% to state acid and account for 2,4- dichlorphenoxyacetic acid ester mass percents；More preferably 1%~8%；Most preferably
2%~6%；In the acid, sulfuric acid, p-methyl benzenesulfonic acid, formic acid and acetic acid are pure acid solution；The concentration of hydrochloric acid is preferably
30%~50%；The hydrolysising reacting temperature is preferably 70~200 DEG C；More preferably 80~180 DEG C；Most preferably 100~150
℃；The reaction time is preferably 2~4h.
After reaction, solvent is removed, crystallizes, filter, being dried to obtain 2,4- dichlorphenoxyacetic acids.
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 provides the preparation methods of one kind 2,4- dichlorphenoxyacetic acids, include the following steps：A) halogenated acetic acids with
Halogenated acetic acids ester is obtained by the reaction in alcohol；Phenolate is obtained by the reaction with alkali in phenol；B) benzene oxygen is obtained by the reaction with phenolate in halogenated acetic acids ester
Acetic acid esters；C) chlorination obtains 2,4- dichlorphenoxyacetic acid esters to phenoxy acetic acid ester under the effect of the catalyst；The catalyst is selected from
Ferric trichloride, alchlor, boron trifluoride, columbium pentachloride, fluoroform sulphonate, aluminium oxide, di-iron trioxide, three oxidations two
One kind in boron, niobium pentaoxide, diphenyl ether, diphenylsulfide, diphenyl disulfide, dimethyl sulfide and dimethyl disulfide or
Several D) 2,4- dichlorphenoxyacetic acid ester hydrolysis obtains 2,4- dichlorphenoxyacetic acids.The present invention is by using phenolate and halogenated second
Phenoxy acetic acid ester is obtained by the reaction in acid esters, after obtain 2,4- dichlorphenoxyacetic acid esters through superchlorination under the action of special catalyst,
2,4 dichlorophenoxyacetic acid ester obtains 2,4 dichlorophenoxyacetic acid by hydrolysis.The present invention uses the lower raw material of price, benzene oxygen
Acetic acid esters chlorination uses specific catalyst, and at low cost, good reaction selectivity, by-product is few, high income, process safety.
Present invention preferably employs high performance liquid chromatography to 2, the 4- dichlorphenoxyacetic acids purity that is prepared and yield into
Row measures.
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, 70 DEG C of precipitations are dehydrated 5h, obtain chlorine
Ethyl acetate.The sodium hydrate aqueous solution 125g (1mol) of phenol 94.3g (1mo1), mass fraction 32% is mixed, is risen
Temperature obtains phenol sodium solution to 70 DEG C or so.It is added at one time the ethyl chloroacetate being prepared to phenol sodium phenolate solution, stirs
After 0.5h, upper oil phase is transferred to chlorination reactor, iron chloride 0.5g, dimethyl disulfide 0.3g is added by layering, after at 70 DEG C
Logical chlorine 5h down obtains 2,4- dichlorphenoxyacetic acid ethyl esters.2,4- dichlorphenoxyacetic acid ethyl esters are transferred to hydrolysis reactor, matter is added
Sodium hydrate aqueous solution 125g (1mol) return stirring 0.5h of score 32% is measured, 30% hydrochloric acid 130g is added, is crystallized at 10 DEG C
1h, filtering, filtration cakes torrefaction obtain 2,4- dichlorphenoxyacetic acid solid 221g, purity 99.5%, yield 99.5%.
Embodiment 2
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 potassium hydroxide aqueous solution 113g (1mol) of phenol 94.3g (1mo1), 50% will be mixed, be risen
Temperature obtains phenol potassium solution to 80 DEG C or so.It is added at one time the different monooctyl ester of the bromoacetic acid being prepared into phenol potassium solution, stirs
After mixing 0.5h, upper oil phase is transferred to chlorination reactor, alundum (Al2O3) 0.5g, diphenyl ether 0.3g is added by layering, after at 70 DEG C
Logical chlorine 5h down obtains the different monooctyl ester of 2,4- dichlorphenoxyacetic acids.The different monooctyl ester of 2,4- dichlorphenoxyacetic acids is transferred to hydrolysis reactor, is added
Enter concentrated sulfuric acid 20g, reflux dealcoholysis 3h crystallizes 1h at 10 DEG C, filters, filtration cakes torrefaction obtains 2,4- dichlorphenoxyacetic acid solids
221g, purity 99.3%, yield 99.3%.
Embodiment 3
300g butanol, 95g (1mol) monoxones and the 0.1g concentrated sulfuric acids are mixed, 120 DEG C of precipitations are dehydrated 4h, obtain chlorine
Butyl acetate.The potassium hydroxide aqueous solution 113g (1mol) of phenol 94.3g (1mo1), 50% will be mixed, and be warming up to 80
DEG C or so, obtain phenol potassium solution.It is added at one time the Isooctyl chloroacetate being prepared into phenol potassium solution, stirs 0.5h
Afterwards, be layered, upper oil phase be transferred to chlorination reactor, niobium pentaoxide 0.5g, diphenyl sulfide 0.3g is added, after at 30 DEG C plus
Enter sulfonic acid chloride 275g, be stirred to react 5h, obtains 2,4- dichlorobenzene oxygen butyl acetates.2,4 dichlorophenoxyacetic acid butyl ester is transferred to water
Reactor is solved, is added concentrated sulfuric acid 20g, reflux dealcoholysis 3h crystallizes 1h at 10 DEG C, filters, filtration cakes torrefaction obtains 2,4- Dichlorophenoxies
Acetic acid solid 221g, purity 99.3%, yield 99.3%.
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) halogenated acetic acids ester is obtained by the reaction with alcohol in halogenated acetic acids；
Phenolate is obtained by the reaction with alkali in phenol；
B) phenoxy acetic acid ester is obtained by the reaction with phenolate in halogenated acetic acids ester；
C) chlorination obtains 2,4- dichlorphenoxyacetic acid esters to phenoxy acetic acid ester under the effect of the catalyst；The catalyst is selected from trichlorine
Change iron, alchlor, boron trifluoride, columbium pentachloride, fluoroform sulphonate, aluminium oxide, di-iron trioxide, diboron trioxide, five
Aoxidize one or more of two niobiums, diphenyl ether, diphenylsulfide, diphenyl disulfide, dimethyl sulfide and dimethyl disulfide
D) 2,4- dichlorphenoxyacetic acids ester hydrolysis obtains 2,4- dichlorphenoxyacetic acids.
2. preparation method according to claim 1, which is characterized in that the step A) in halogenated acetic acids and alcohol molar ratio
It is 1：(1~1.5)；The molar ratio that the phenol is reacted with alkali is 1：(1~1.1).
3. preparation method according to claim 1, which is characterized in that the halogenated acetic acids be selected from monoxone, bromoacetic acid and
One or more of iodoacetic acid；The alcohol is the monohydric alcohol of C2 or more；The alkali is selected from sodium hydroxide, potassium hydroxide, hydrogen-oxygen
Change one or more of calcium, magnesium hydroxide and zinc hydroxide.
4. preparation method according to claim 1, which is characterized in that the reaction temperature of the halogenated acetic acids and alcohol be 50~
200℃；The phenol is 50~120 DEG C with alkali reaction temperature.
5. preparation method according to claim 1, which is characterized in that mole of the halogenated acetic acids ester and phenol reactant salt
Than for (1~1.2)：1；The step B) reaction temperature be 50~200 DEG C.
6. preparation method according to claim 1, which is characterized in that the step C) catalyst be selected from ferric trichloride,
Alchlor, boron trifluoride, columbium pentachloride, fluoroform sulphonate, aluminium oxide, di-iron trioxide, diboron trioxide, five oxidations two
Two or more in niobium, diphenyl ether, diphenylsulfide, diphenyl disulfide, dimethyl sulfide and dimethyl disulfide.
7. preparation method according to claim 6, which is characterized in that the step C) catalyst be selected from ferric trichloride,
Alchlor, boron trifluoride, columbium pentachloride, fluoroform sulphonate, aluminium oxide, di-iron trioxide, diboron trioxide and five oxidations
One or more of two niobiums in diphenyl ether, diphenylsulfide, diphenyl disulfide, dimethyl sulfide and dimethyl disulfide
One or more of mixing.
8. preparation method according to claim 1, which is characterized in that the step C) catalyst account for the phenoxy acetic acid
The molar content of ester is 0.1%~1%.
9. preparation method according to claim 1, which is characterized in that the step C) chlorination temperature be 0~100 DEG C.
10. preparation method according to claim 1, which is characterized in that the step D) catalyst of hydrolysis is alkali
Or acid；The alkali is sodium hydroxide or potassium hydroxide；A concentration of the 30%~40% of the aqueous slkali；2, the 4- Dichlorophenoxies
The mass ratio of acetic acid esters and aqueous slkali is 1:1~2；The acid is in sulfuric acid, hydrochloric acid, p-methyl benzenesulfonic acid, formic acid and acetic acid
It is one or more of；It is 0.5%~10% that the acid, which accounts for 2,4- dichlorphenoxyacetic acid ester mass percents,.
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| CN102336654A (en) * | 2011-07-14 | 2012-02-01 | 大连化工研究设计院 | Chloration method for phenoxyacetic acid and derivatives thereof |
| CN106278862A (en) * | 2016-08-04 | 2017-01-04 | 山东省化工研究院 | A kind of new technique for synthesizing of 2,4 dichlorphenoxyacetic acids |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336654A (en) * | 2011-07-14 | 2012-02-01 | 大连化工研究设计院 | Chloration method for phenoxyacetic acid and derivatives thereof |
| CN106278862A (en) * | 2016-08-04 | 2017-01-04 | 山东省化工研究院 | A kind of new technique for synthesizing of 2,4 dichlorphenoxyacetic acids |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11040933B2 (en) * | 2018-03-19 | 2021-06-22 | Shandong Rainbow Biotech Co., Ltd. | Preparation method of phenoxycarboxylic acid herbicides |
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