CN108424363A - 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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- CN108424363A CN108424363A CN201710076369.4A CN201710076369A CN108424363A CN 108424363 A CN108424363 A CN 108424363A CN 201710076369 A CN201710076369 A CN 201710076369A CN 108424363 A CN108424363 A CN 108424363A
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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
- C07C67/08—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
- 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 provides a kind of preparation methods of 2,4 dichlorphenoxyacetic acids, include the following steps：A) monohydric alcohol of C2 or more and halogenated acetic acids reaction, obtain halogenated acetic acids ester；B) halogenated acetic acids ester and 2,4 Dichlorophenol reactant salts obtain 2,4 dichlorphenoxyacetic acid esters；C) 2,4 dichlorphenoxyacetic acid ester hydrolysis reactions, obtain 2,4 dichlorphenoxyacetic acids.Halogenated acetic acids ester intermediate is obtained by the reaction by the monohydric alcohol and halogenated acetic acids of C2 or more in the present invention, and the intermediate stability is good, and byproduct of reaction is few, high income；And then with 2,4 Dichlorophenol reactant salts obtain 2,4 dichlorphenoxyacetic acid esters, and final hydrolysis obtains 2,4 dichlorphenoxyacetic acids.Specific reaction route through the invention makes the purity that 2,4 dichlorphenoxyacetic acids are finally prepared and yield higher, and by-product is few, and reaction route is simple, is conducive to apply.
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) monohydric alcohol of C2 or more and halogenated acetic acids reaction, obtain halogenated acetic acids ester；
B) halogenated acetic acids ester and 2,4- Dichlorophenol reactant salts obtain 2,4- dichlorphenoxyacetic acid esters；
C) 2,4- dichlorphenoxyacetic acids ester hydrolysis reaction obtains 2,4- dichlorphenoxyacetic acids.
Preferably, the monohydric alcohol of the C2 or more is the monohydric alcohol of C2~C20.
Preferably, the halogenated acetic acids is selected from one or more of monoxone, bromoacetic acid and iodoacetic acid；The 2,4- bis-
Diclofenac salt be selected from 2,4- sodium dichlorophenol indophenols, 2,4- Dichlorophenols potassium, 2,4- Dichlorophenols calcium, 2,4- Dichlorophenols magnesium, 2,4- Dichlorophenols zinc and
One or more of 2,4- Dichlorophenol aluminium.
Preferably, the step A) reaction temperature be 50~200 DEG C；Reaction time is 1~10h.
Preferably, the molar ratio of the monohydric alcohol of the C2 or more and halogenated acetic acids is (1~1.5):1.
Preferably, the step B) reaction temperature be 70~200 DEG C；Reaction time is 1~7h.
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 step C) reaction temperature be 50~200 DEG C；Reaction time is 1~10h.
Preferably, the step C) hydrolysis catalyst be selected from polyethers, crown ether, quaternary ammonium salt, tertiary amine, quaternary phosphonium salt, pyrrole
It is one or more in pyridine, titanate esters, inorganic acid, organic acid.
Preferably, the step C) catalyst of hydrolysis accounts for the mass percent of 2, the 4- dichlorphenoxyacetic acids ester
It is 1 ‰~1%.
Compared with prior art, the present invention provides the preparation methods of one kind 2,4- dichlorphenoxyacetic acids, including walk as follows
Suddenly：A) monohydric alcohol of C2 or more and halogenated acetic acids reaction, obtain halogenated acetic acids ester；B) halogenated acetic acids ester and 2,4- dichloro phenates are anti-
It answers, obtains 2,4- dichlorphenoxyacetic acid esters；C) 2,4- dichlorphenoxyacetic acids ester hydrolysis reaction obtains 2,4- dichlorphenoxyacetic acids.
Halogenated acetic acids ester intermediate is obtained by the reaction by the monohydric alcohol and halogenated acetic acids of C2 or more in the present invention, and the intermediate stability is good,
Byproduct of reaction is few, high income；And then 2,4- dichlorphenoxyacetic acid esters are obtained with 2,4- Dichlorophenol reactant salts, final hydrolysis obtains
2,4- dichlorphenoxyacetic acids.Specific reaction route through the invention so that the pure of 2,4- dichlorphenoxyacetic acids is finally prepared
Degree and yield are higher, and by-product is few, and reaction route is simple, is conducive to apply.
Specific implementation mode
The present invention provides the preparation methods of one kind 2,4- dichlorphenoxyacetic acids, include the following steps：
A) monohydric alcohol of C2 or more and halogenated acetic acids reaction, obtain halogenated acetic acids ester；
B) halogenated acetic acids ester and 2,4- Dichlorophenol reactant salts obtain 2,4- dichlorphenoxyacetic acid esters；
C) 2,4- dichlorphenoxyacetic acids ester hydrolysis reaction obtains 2,4- dichlorphenoxyacetic acids.
The present invention first reacts the monohydric alcohol of C2 or more and halogenated acetic acids, obtains halogenated acetic acids ester.It is preferred that specific C2
Above monohydric alcohol and halogenated acetic acids is mixed under the effect of the catalyst, and dehydration obtains halogenated acetic acids ester.The present invention
For the stirring concrete mode without limit, 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 is preferably selected from the concentrated sulfuric acid or butyl titanate；The solvent
Preferably toluene, dimethylbenzene, ether, DMF or NMP.
Wherein, the molar ratio of the monohydric alcohol of the C2 or more and halogenated acetic acids is preferably (1~1.5):1；More preferably (1
~1.2):1；Most preferably (1~1.1):1；The additive amount of the catalyst is preferably 1 ‰~1%.The step A) reaction
Temperature is 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.
After obtaining halogenated acetic acids ester intermediate, halogenated acetic acids ester and 2,4- Dichlorophenol reactant salts obtain 2,4- Dichlorophenoxies
Acetic acid esters.It is preferred that being specially：Halogenated acetic acids ester and 2,4- dichloro phenates are stirred to react, and filtering obtains 2,4- dichlorphenoxyacetic acids
Ester.The present invention for the stirring concrete mode without limit, agitating mode well known to those skilled in the art.This
Invention for the filtering concrete mode without limit, filter type well known to those skilled in the art.
In the present invention, halogenated acetic acids ester is preferably selected from one kind or several in chloracetate, bromacetate and Alkyl Iodoacetates
Kind；The 2,4- dichloros phenates is preferably selected from 2,4- sodium dichlorophenol indophenols, 2,4- Dichlorophenols potassium, 2,4- Dichlorophenols calcium, 2,4- Dichlorophenols
One or more of magnesium, 2,4- Dichlorophenols zinc and 2,4- Dichlorophenol aluminium.
The molar ratio of the halogenated acetic acids ester and 2,4- dichloro phenates is preferably (0.9~1.1)：(0.9~1.1)；It is more excellent
It is selected as (0.9~1.0)：(0.9~1.0)；The step B) reaction temperature be 70~200 DEG C；More preferably 80~180 DEG C；
Most preferably 90~160 DEG C；The reaction time is preferably 1~7h；More preferably 2~6h；Most preferably 3~5h.
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%~
50%；The mass ratio of the 2,4 dichlorophenoxyacetic acid ester and aqueous slkali is preferably 1:(2~2.5)：
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 concentration of the acid is preferably 10%~100%；More preferably
30%~60%；The additive amount of the acid is preferably 2,4 dichlorophenoxyacetic acid ester 0.5%~10%.
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.
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.
Wherein, the catalyst of the hydrolysis is preferably selected from polyethers, crown ether, quaternary ammonium salt, tertiary amine, quaternary phosphonium salt, pyridine, titanium
It is one or more in acid esters, inorganic acid, organic acid；More preferably polyethers, crown ether, quaternary ammonium salt, tertiary amine, quaternary phosphonium salt, pyridine, titanium
Two or more in acid esters, inorganic acid, organic acid；Most preferably polyethers, crown ether, quaternary ammonium salt, tertiary amine, quaternary phosphonium salt and pyrrole
One or more mixing in one or more and titanate esters, inorganic acid, organic acid in pyridine.Wherein, the crown ether is preferred
For crown ether or cyclic crown ether；The quaternary ammonium salt includes but not limited to tetrabutylammonium bromide；The polyethers includes but not limited to poly- second
Glycol dialkyl ether；The quaternary phosphonium salt includes but not limited to tetrabutyl phosphonium bromide phosphine；The tertiary amine includes but not limited to triethylamine；Institute
It includes but not limited to sulfuric acid, hydrochloric acid to state inorganic acid；The organic acid includes but not limited to p-methyl benzenesulfonic acid, formic acid and acetic acid.
The mass percent that the catalyst of the hydrolysis accounts for 2,4 dichlorophenoxyacetic acid ester is preferably 1 ‰~1%；More
Preferably 2 ‰~8 ‰；Most preferably 3 ‰~7 ‰.
Under the catalytic action of above-mentioned composite catalyst, hydrolysis is crystallized, is filtered, being dried to obtain 2,4- Dichlorophenoxies
Acetic acid.
Wherein, reaction temperature is 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 reaction is preferably back flow 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 provides the preparation methods of one kind 2,4- dichlorphenoxyacetic acids, include the following steps：A) the one of C2 or more
First alcohol and halogenated acetic acids reaction, obtain halogenated acetic acids ester；B) halogenated acetic acids ester and 2,4- Dichlorophenol reactant salts, obtains 2,4- dichloros
Phenoxy acetic acid ester；C) 2,4- dichlorphenoxyacetic acids ester hydrolysis reaction obtains 2,4- dichlorphenoxyacetic acids.The present invention passes through C2 or more
Monohydric alcohol and halogenated acetic acids halogenated acetic acids ester intermediate is obtained by the reaction, the intermediate stability is good, and byproduct of reaction is few, yield
It is high；And then 2,4- dichlorphenoxyacetic acid esters are obtained with 2,4- Dichlorophenol reactant salts, final hydrolysis obtains 2,4- dichlorphenoxyacetic acids.
Specific reaction route through the invention makes the purity that 2,4- dichlorphenoxyacetic acids are finally prepared and yield higher, secondary
Product is few, and reaction route is simple, is conducive to apply.
Present invention preferably employs using high performance liquid chromatography to 2, the 4- dichlorphenoxyacetic acids purity and yield that are prepared
It is measured.
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.2,4- sodium dichlorophenol indophenols 186g (1mol), 80 DEG C of insulated and stirred 3h are added, it is solid to filter out the sodium chloride that reaction generates
Body, filtrate precipitation go out ethyl alcohol, obtain 2,4- dichlorphenoxyacetic acid ethyl esters, and 125g32% sodium hydroxide solutions, 100 DEG C of heat preservations are added
2h is stirred, 50% sulfuric acid 100g is added, 1h is crystallized at 10 DEG C, filters, filtration cakes torrefaction obtains 2,4- dichlorphenoxyacetic acid solids
221g, purity 99.5%, yield 99.5%.
Embodiment 2
32g propyl alcohol, 95g (1mol) monoxone, 50g toluene and 0.1g butyl titanates are mixed, 180 DEG C of precipitation dehydrations
6h obtains propyl chloroacetate.2,4- sodium dichlorophenol indophenols 186g (1mol), 180 DEG C of insulated and stirred 4h are added, filter out what reaction generated
Solid sodium chloride, filtrate precipitation go out toluene, obtain 2,4- dichlorphenoxyacetic acid second diester, and it is molten that 125g32% sodium hydroxides are added
Liquid, 100 DEG C of insulated and stirred 3h are added 50% sulfuric acid 100g, 1h are crystallized at 10 DEG C, filter, and filtration cakes torrefaction obtains 2,4- dichloro-benzenes
Fluoroacetic acid solid 221g, purity 99.3%, yield 99.3%.
Embodiment 3
200g n-butanols, 95g (1mol) monoxones and the 0.1g concentrated sulfuric acids are mixed, 120 DEG C of precipitations are dehydrated 5h, obtain
Solid acid n-butyl chloroacete.2,4- sodium dichlorophenol indophenols 186g (1mol), 120 DEG C of insulated and stirred 3h are added, filter out the chlorination that reaction generates
Sodium solid, filtrate precipitation go out n-butanol, obtain 2,4- dichlorphenoxyacetic acid N-butyls, and 125g32% sodium hydroxide solutions are added,
100 DEG C of insulated and stirred 3h are added 50% sulfuric acid 100g, 1h are crystallized at 10 DEG C, filter, and filtration cakes torrefaction obtains 2,4- Dichlorophenoxies
Acetic acid solid 221g, purity 99.5%, yield 99.5%.
Embodiment 4
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.2,4- Dichlorophenol potassium 202g (1mol), 180 DEG C of insulated and stirred 4h are added, filter out the bromine that reaction generates
Change potassium solid, filtrate precipitation goes out isooctanol, obtains the different monooctyl ester ester of 2,4- dichlorphenoxyacetic acids, and 100g30wt% hydrochloric acid is added, and returns
6h is stirred in stream dehydration, and 1h is crystallized at 10 DEG C, is filtered, and filtration cakes torrefaction obtains 2,4- dichlorphenoxyacetic acid solid 222g, purity
99.2%, yield 99.6%.
Embodiment 5
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.123g ethyl chloroacetates (1mol) and 2,4- sodium dichlorophenol indophenols 186g (1mol) are mixed, 80 DEG C of insulated and stirred 3h, mistake
The solid sodium chloride that reaction generates is filtered, 2,4- dichlorphenoxyacetic acid ethyl esters are obtained.Addition 0.1g dialkylethers,
The 0.1g concentrated sulfuric acids, 50g water, reflux dealcoholysis 5h crystallize 1h at 10 DEG C, filter, filtration cakes torrefaction, it is solid to obtain 2,4- dichlorphenoxyacetic acids
Body 221g, purity 99.5%, yield 99.5%.
Embodiment 6
200g n-butanols, 95g (1mol) monoxones and the 0.1g concentrated sulfuric acids are mixed, 120 DEG C of precipitations are dehydrated 5h, obtain
Solid acid n-butyl chloroacete.151g Solid acid n-butyl chloroacetes (1mol) and 2,4- sodium dichlorophenol indophenols 186g (1mol) are mixed, 120 DEG C of heat preservations are stirred
3h is mixed, the solid sodium chloride that reaction generates is filtered out, obtains 2,4- dichlorphenoxyacetic acid N-butyls.Addition 0.1g18 crown ethers,
0.1g p-methyl benzenesulfonic acid, 50g water, reflux dealcoholysis 6h crystallize 1h at 10 DEG C, filter, filtration cakes torrefaction obtains 2,4- Dichlorophenoxy second
Sour solid 221g, purity 99.3%, yield 99.3%.
Embodiment 7
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.207g Isooctyl chloroacetates (1mol) and 2,4- Dichlorophenol potassium 202g (1mol) are mixed, 180 DEG C of heat preservations
3h is stirred, the solid potassium chloride that reaction generates is filtered out, obtains the different monooctyl ester of 2,4- dichlorphenoxyacetic acids.0.1g tetrabutyl bromines are added
Change ammonium, 0.1g30wt% hydrochloric acid, 50g water, reflux dealcoholysis 7h crystallizes 1h at 10 DEG C, filters, filtration cakes torrefaction obtains 2,4- dichloros
Phenoxy acetic acid solid 221g, purity 99.5%, yield 99.5%.
Embodiment 8
200g ethyl alcohol, 95g (1mol) bromoacetic acids and the 0.1g concentrated sulfuric acids are mixed, 80 DEG C of precipitations are dehydrated 5h, obtain bromine
Ethyl acetate.168g bromoacetates (1mol) and 2,4- Dichlorophenol calcium 183g (1mol) are mixed, 80 DEG C of insulated and stirred 3h, mistake
The calcium chloride solid that reaction generates is filtered, 2,4- dichlorphenoxyacetic acid ethyl esters are obtained.0.1g pyridines, 0.1g formic acid, 50g is added
Water, reflux dealcoholysis 5h crystallize 1h at 10 DEG C, filter, filtration cakes torrefaction obtains 2,4- dichlorphenoxyacetic acid solid 221g, purity
99.3%, yield 99.3%.
Embodiment 9
200g amylalcohols, 95g (1mol) bromoacetic acids and the 0.1g concentrated sulfuric acids are mixed, 120 DEG C of precipitations are dehydrated 5h, obtain bromine
Pentyl acetate.210g bromoacetic acids pentyl ester (1mol) and 2,4- Dichlorophenol magnesium 175g (1mol) are mixed, 160 DEG C of insulated and stirred 3h,
The magnesium chloride solids that reaction generates are filtered out, 2,4- dichlorphenoxyacetic acid pentyl esters are obtained.0.1g tetrabutyl phosphonium bromides phosphine, 0.1g is added
Acetic acid, 50g water, reflux dealcoholysis 6h crystallize 1h at 10 DEG C, filter, filtration cakes torrefaction obtains 2,4- dichlorphenoxyacetic acid solids
221g, purity 99.4%, yield 99.4%.
Embodiment 10
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.2,4- Dichlorophenol potassium 202g (1mol), insulated and stirred 4h is added, it is solid to filter out the potassium bromide that reaction generates
Body, filtrate precipitation go out isooctanol, obtain the different monooctyl ester ester of 2,4- dichlorphenoxyacetic acids, and 0.1g triethylamines, 0.1g30wt% salt is added
Acid, reflux dewatering stir 6h, crystallize 1h at 10 DEG C, filter, filtration cakes torrefaction, obtain 2,4- dichlorphenoxyacetic acid solids 222g, pure
Degree 99.2%, yield 99.6%.
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) monohydric alcohol of C2 or more and halogenated acetic acids reaction, obtain halogenated acetic acids ester；
B) halogenated acetic acids ester and 2,4- Dichlorophenol reactant salts obtain 2,4- dichlorphenoxyacetic acid esters；
C) 2,4- dichlorphenoxyacetic acids ester hydrolysis reaction obtains 2,4- dichlorphenoxyacetic acids.
2. preparation method according to claim 1, which is characterized in that the monohydric alcohol of the C2 or more is the one of C2~C20
First alcohol.
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 2,4- dichloros phenates is selected from 2,4- sodium dichlorophenol indophenols, 2,4- Dichlorophenols potassium, 2,4- Dichlorophenols
One or more of calcium, 2,4- Dichlorophenols magnesium, 2,4- Dichlorophenols zinc and 2,4- Dichlorophenol aluminium.
4. preparation method according to claim 1, which is characterized in that the step A) reaction temperature be 50~200 DEG C；
Reaction time is 1~10h.
5. preparation method according to claim 1, which is characterized in that the monohydric alcohol of the C2 or more and rubbing for halogenated acetic acids
You are than being (1~1.5):1.
6. preparation method according to claim 1, which is characterized in that the step B) reaction temperature be 70~200 DEG C；
Reaction time is 1~7h.
7. 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).
8. preparation method according to claim 1, which is characterized in that the step C) reaction temperature be 50~200 DEG C；
Reaction time is 1~10h.
9. preparation method according to claim 1, which is characterized in that the step C) catalyst of hydrolysis be selected from it is poly-
It is one or more in ether, crown ether, quaternary ammonium salt, tertiary amine, quaternary phosphonium salt, pyridine, titanate esters, inorganic acid, organic acid.
10. preparation method according to claim 9, which is characterized in that the step C) catalyst of hydrolysis accounts for institute
The mass percent for stating 2,4 dichlorophenoxyacetic acid ester is 1 ‰~1%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008104524A1 (en) * | 2007-02-28 | 2008-09-04 | Smithkline Beecham Corporation | Thiadiazole derivatives, inhibitors of stearoyl-coa desaturase |
| CN106242971A (en) * | 2016-08-04 | 2016-12-21 | 山东省化工研究院 | A kind of chloracetate synthesis in water technology and the new method of preparation 2,4 D esters thereof |
-
2017
- 2017-02-13 CN CN201710076369.4A patent/CN108424363A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008104524A1 (en) * | 2007-02-28 | 2008-09-04 | Smithkline Beecham Corporation | Thiadiazole derivatives, inhibitors of stearoyl-coa desaturase |
| CN106242971A (en) * | 2016-08-04 | 2016-12-21 | 山东省化工研究院 | A kind of chloracetate synthesis in water technology and the new method of preparation 2,4 D esters thereof |
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