CN108424348A - 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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- CN108424348A CN108424348A CN201710076406.1A CN201710076406A CN108424348A CN 108424348 A CN108424348 A CN 108424348A CN 201710076406 A CN201710076406 A CN 201710076406A CN 108424348 A CN108424348 A CN 108424348A
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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
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
- C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
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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
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Abstract
The present invention provides a kind of preparation methods of 2,4 dichlorphenoxyacetic acids, include the following steps, first by after alcohol and halogenated acetic acids reaction, obtain halogenated acetic acids ester；After 2,4 Dichlorophenols are reacted with alkali, 2,4 dichloro phenates are obtained；Then the halogenated acetic acids ester and 2 above-mentioned steps obtained, 4 dichloro phenates are reacted, and 2,4 dichlorphenoxyacetic acid esters are obtained；Reaction is hydrolyzed in above-mentioned steps are obtained again 2,4 dichlorphenoxyacetic acid esters, obtains 2,4 dichlorphenoxyacetic acids and alcohol；The alcohol that above-mentioned steps obtain finally is back to abovementioned steps, is recycled；The alcohol is the alcohol that C atomicities are more than or equal to 2.Adjusting process route of the present invention, is improved on the basis of, and reaction process cleaning, the wastewater flow rate generated are few, and hydrolysising by-product is few, and product purity is high, and conversion ratio and yield are higher；And process raw material is Ke Xunhuanliyong, is suitble to large-scale industrial production.
Description
Technical field
The invention belongs to benzene oxycarboxylic acid esters synthesis technical fields, are related to the preparation side of one kind 2,4- dichlorphenoxyacetic acids
The preparation method of method more particularly to a kind of Ke Xunhuanliyong 2, the 4- dichlorphenoxyacetic acids of process raw material.
Background technology
2,4- dichlorphenoxyacetic acids also known as 2,4-D, (2,4- dichlorophenoxy) acetic acid or 2,4-D acid etc., molecular formula are
C8H6Cl2O3, fusing point is 140.5 DEG C, and boiling point is 160 DEG C, and it is most of organic molten to be dissolved in alcohol, ether or ketone etc. for white diamond crystallization
Agent is practically insoluble in water.
2,4- dichlorphenoxyacetic acid class compounds are a kind of very important compounds, are usage history longests in the world
Organic synthesis herbicide kind, be still widely used, be agriculturally mainly used for as herbicide or plant growth now
Agent uses, and in analysis field, the standard etc. of carbon and hydrogen is measured for organic microanalysis.
As herbicide, 2,4- dichlorphenoxyacetic acids in 500ppm or more high concentrations be used for cauline leaf process, can wheat,
The broad leaved weeds such as lamb's-quarters, amaranth and budding period grassy weed are prevented and kill off in the crop fields such as rice, corn, sugarcane, can be entered from root, stem, leaf
In plant, degradation is slow, therefore can accumulate a certain concentration, to interfere plant hormone in vivo to balance, destroys nucleic acid and protein
Metabolism, promotes or inhibits certain organ growths, so that weeds cauline leaf is distorted, stem foot is thicker, swells and splits；With Atrazine, prometryn
Equal herbicide mixtures, or it is mixed with the acidic fertiliziers such as ammonium sulfate, herbicide effect can be increased, but to safety of human and livestock.
As auxin, 2,4- dichlorphenoxyacetic acids are representative synthetic auxins (auxin), are a kind of
Auxin analog.High activity is shown in common auximone sizing technique, but is using auximone standard
In the oat elongation test of sizing technique, effect is quite low.Many synthetic auxins centered on 2,4 dichlorophenoxyacetic acid
There is rapid development applied to agricultural, by large-scale for preventing fruit early fallout agent etc..
Just because of this, 2,4- dichlorphenoxyacetic acids have the larger market demand, but its preparation process always exists
The synthetic method of many defects, 2,4- dichlorphenoxyacetic acids disclosed in the prior art mainly uses Williamson condensation methods, raw
Production. art particularly may be divided into chloro and first two kinds of chloro after-condensation after first condensation.But two kinds of techniques are phenates and chloracetate
Reaction, reaction system is aqueous phase system, and there are reactions to be not thorough, and hydrolysising by-product is more, and product yield is low, and product purity is low, former
Expect that consumption is big, waste water yield is big, and exhaust gas discharges the problems such as not easy to control, serious to affect 2,4- Dichlorophenoxy second
The production of acid does not meet the developing direction for the green energy conservation that country advocates yet.
Therefore, a kind of preparation method of more suitable 2,4- dichlorphenoxyacetic acids how is found, above-mentioned technology is overcome to lack
It falls into, is always many line research staff and poly-talented manufacturer widely focus of attention.
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, especially a kind of preparation method of recyclable 2,4- dichlorphenoxyacetic acids, preparation process provided by the invention, technique
Simply, mild condition, reaction process cleaning, the wastewater flow rate generated are few, and hydrolysising by-product is few, environmentally protective, and reactant purity is high,
Conversion ratio and yield are higher, and process raw material is Ke Xunhuanliyong, are suitble to large-scale industrial production.
The present invention provides the preparation methods of one kind 2,4- dichlorphenoxyacetic acids, include the following steps：
A alcohol and halogenated acetic acids) are subjected to esterification, obtain halogenated acetic acids ester；
After 2,4- Dichlorophenols are reacted with alkali, 2,4- dichloro phenates is obtained；
B) the halogenated acetic acids ester and 2 for obtaining above-mentioned steps, 4- dichloro phenates are reacted, and 2,4- Dichlorophenoxy second is obtained
Acid esters；
C reaction) is hydrolyzed in 2, the 4- dichlorphenoxyacetic acid esters that above-mentioned steps obtain, obtains 2,4- dichlorphenoxyacetic acids
And alcohol；
D the alcohol that above-mentioned steps obtain) is back to step A), it recycles；
The alcohol is the alcohol that C atomicities are more than or equal to 2.
Preferably, the alcohol is the alcohol of C2~C20；
The alcohol includes monohydric alcohol.
Preferably, the halogenated acetic acids includes one or more in monoxone, bromoacetic acid and iodoacetic acid；
The 2,4- dichloros phenates includes 2,4- sodium dichlorophenol indophenols, 2,4- Dichlorophenols potassium, 2,4- Dichlorophenols calcium, 2,4- Dichlorophenols
It is one or more in magnesium, 2,4- Dichlorophenols zinc and 2,4- Dichlorophenol aluminium.
Preferably, the reaction promoter of the esterification includes the concentrated sulfuric acid；
The temperature of the esterification is 50~200 DEG C；The time of the esterification is 1~10h；
The temperature that the 2,4- Dichlorophenols are reacted with alkali is 10~100 DEG C；The time that the 2,4- Dichlorophenols are reacted with alkali
For 0.1~2h h.
Preferably, the molar ratio of the alcohol and halogenated acetic acids is (1~1.5):1；
The molar ratio of the 2,4- Dichlorophenols and alkali is 1：(1~1.5).
Preferably, the step B) in, the temperature of the reaction is 70~200 DEG C；
The time of the reaction 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) be specially：
Under the effect of the catalyst, reaction is hydrolyzed in 2, the 4- dichlorphenoxyacetic acid esters that above-mentioned steps obtain, obtained
2,4 dichlorophenoxyacetic acid and alcohol.
Preferably, the temperature of the hydrolysis is 50~200 DEG C；
The time of the hydrolysis is 1~10h.
Preferably, the catalyst includes polyethers, crown ether, quaternary ammonium salt, tertiary amine, quaternary phosphonium salt, pyridine, titanate esters, inorganic acid
With it is one or more in organic acid；
The percentage that the quality of the catalyst accounts for the 2,4 dichlorophenoxyacetic acid ester quality is 0.1%~1%.
The present invention provides the preparation methods of one kind 2,4- dichlorphenoxyacetic acids, include the following steps, first by alcohol and halogen
After acetic acidreaction, halogenated acetic acids ester is obtained；After 2,4- Dichlorophenols are reacted with alkali, 2,4- dichloro phenates is obtained；It then will be upper
The halogenated acetic acids ester and 2 that step obtains is stated, 4- dichloro phenates is reacted, and 2,4- dichlorphenoxyacetic acid esters are obtained；It again will be above-mentioned
Reaction is hydrolyzed in 2, the 4- dichlorphenoxyacetic acid esters that step obtains, and obtains 2,4- dichlorphenoxyacetic acids and alcohol；It finally will be above-mentioned
The alcohol that step obtains is back to step A), it recycles；The alcohol is the alcohol that C atomicities are more than or equal to 2.With prior art phase
Than for chloro or first chloro after-condensation after existing first condensation, both are reacted using phenates with chloracetate, are deposited the present invention
Be not thorough in reaction, hydrolysising by-product is more, and product yield is low, and product purity is low, and consumption of raw materials amount is big, waste water yield it is big and
Exhaust gas discharge problem not easy to control.Adjusting process route of the present invention, carries out inventive improvements on the basis of, first uses alcohol and halogen
Halogenated acetic acids ester is prepared for acetic acid, then with 2, the 4- Dichlorophenol reactant salts of preparation, prepares 2,4- dichlorphenoxyacetic acid esters, then pass through
Cross hydrolysis obtain 2,4- dichlorphenoxyacetic acids and alcohol, the alcohol hydrolyzed again can reuse with prepare halogenated acetic acids ester during,
Realize recycling for process raw material.Preparation process provided by the invention, reaction process cleaning, the wastewater flow rate generated are few, water
It is few to solve by-product, product purity is high, and conversion ratio and yield are higher；And process raw material is Ke Xunhuanliyong, is suitble to large-scale industry
Metaplasia is produced.The experimental results showed that 2,4- dichlorphenoxyacetic acids prepared by the present invention, purity can reach 99.5%, yield energy
Enough reach 99.5%.
Specific implementation mode
For a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment, still
It should be appreciated that these descriptions are intended merely to the feature and advantage further illustrated the present invention, rather than to invention claim
Limitation.
All raw materials of the present invention, are not particularly limited its source, buying on the market or according to people in the art
It is prepared by conventional method known to member.
All raw materials of the present invention, are not particularly limited its purity, and present invention preferably employs analyze pure or organic synthesis neck
The conventional purity used in domain.
The present invention provides the preparation methods of one kind 2,4- dichlorphenoxyacetic acids, include the following steps：
A alcohol and halogenated acetic acids) are subjected to esterification, obtain halogenated acetic acids ester；
After 2,4- Dichlorophenols are reacted with alkali, 2,4- dichloro phenates is obtained；
B) the halogenated acetic acids ester and 2 for obtaining above-mentioned steps, 4- dichloro phenates are reacted, and 2,4- Dichlorophenoxy second is obtained
Acid esters；
C reaction) is hydrolyzed in 2, the 4- dichlorphenoxyacetic acid esters that above-mentioned steps obtain, obtains 2,4- dichlorphenoxyacetic acids
And alcohol；
D the alcohol that above-mentioned steps obtain) is back to step A), it recycles；
The alcohol is the alcohol that C atomicities are more than or equal to 2.
Alcohol and halogenated acetic acids are carried out esterification by the present invention, obtain halogenated acetic acids ester；2,4- Dichlorophenols are reacted with alkali
Afterwards, 2,4- dichloro phenates is obtained.
Alcohol of the present invention is the alcohol that C atomicities are more than or equal to 2, and the present invention especially limits the alcohol without other, with
Routine C atomicities well known to those skilled in the art are more than or equal to 2 alcohol, and those skilled in the art can be according to practical life
Production situation, product requirement and quality requirement are selected and are adjusted, and alcohol of the present invention is preferably the alcohol of C2~C20, more preferably
For the alcohol of C3~C10, the most preferably alcohol of C4~C8.Alcohol of the present invention preferably includes monohydric alcohol.
The halogenated acetic acids is not particularly limited in the present invention, with conventional halogenated acetic acids well known to those skilled in the art
, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The bright halogenated acetic acids preferably includes one or more in monoxone, bromoacetic acid and iodoacetic acid, more preferably monoxone, bromine second
Acid or iodoacetic acid, most preferably monoxone or bromoacetic acid.
The dosage of the alcohol and halogenated acetic acids is not particularly limited in the present invention, with well known to those skilled in the art similar
The conventional amount used of reaction, those skilled in the art can carry out according to practical condition, product requirement and quality requirement
The molar ratio of selection and adjustment, alcohol and halogenated acetic acids of the present invention is preferably (1~1.5):1, more preferably (1.1~1.4):
1, most preferably (1.3~1.3):1.
The temperature of the esterification is not particularly limited in the present invention, with conventional ester well known to those skilled in the art
Change reaction temperature, those skilled in the art can select according to practical condition, product requirement and quality requirement
And adjustment, the temperature of esterification of the present invention is preferably 50~200 DEG C, more preferably 75~175 DEG C, most preferably 100
~150 DEG C.The time of the esterification is not particularly limited in the present invention, with conventional ester well known to those skilled in the art
Change the reaction time, those skilled in the art can select according to practical condition, product requirement and quality requirement
And adjustment, the time of esterification of the present invention is preferably 1~10h, more preferably 3~8h, most preferably 5~6h.
The detailed process of the esterification is not particularly limited in the present invention, with routine well known to those skilled in the art
Esterification reaction process, those skilled in the art can carry out according to practical condition, product requirement and quality requirement
Selection and adjustment, esterification of the present invention is particularly preferred as, and under conditions of reaction promoter, alcohol and halogenated acetic acids are carried out
Esterification obtains halogenated acetic acids ester.
The reaction promoter is not particularly limited in the present invention, with conventional reaction promoter well known to those skilled in the art
, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The bright reaction promoter is preferably the concentrated sulfuric acid.The addition of the reaction promoter is not particularly limited in the present invention, with this field
The addition of popular response auxiliary agent known to technical staff, those skilled in the art can be according to practical condition, productions
Product require and quality requirement is selected and adjusted.
Above-mentioned steps of the present invention have obtained intermediate halogenated acetic acids ester, and the intermediate stability is good, and byproduct of reaction is few, receive
Rate is high, and then provides good condition for the follow-up yield for preparing 2,4- dichlorphenoxyacetic acids and purity.
The alkali is not particularly limited in the present invention, with alkali of the routine well known to those skilled in the art containing metallic element
, those skilled in the art can select and adjust, this hair according to practical condition, product requirement and quality requirement
The metallic element contained in the bright alkali preferably include it is one or more in sodium, potassium, calcium, magnesium, zinc and aluminium, more preferably sodium,
Potassium, calcium, magnesium, zinc or aluminium, most preferably sodium or potassium.Alkali of the present invention preferably include sodium hydroxide, potassium hydroxide, sodium carbonate,
Potassium carbonate, sodium bicarbonate, saleratus, calcium hydroxide, calcium carbonate, calcium bicarbonate, aluminium hydroxide, magnesium hydroxide and zinc hydroxide
In one or more, more preferably sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus, hydrogen-oxygen
Change calcium, calcium carbonate, calcium bicarbonate, aluminium hydroxide, magnesium hydroxide or zinc hydroxide, most preferably sodium hydroxide, potassium hydroxide, carbon
Sour sodium, potassium carbonate, sodium bicarbonate or saleratus.
2, the 4- dichloros phenates is not particularly limited in the present invention, with well known to those skilled in the art conventional 2,4-
Dichloro phenates, the selection correspondence based on above-mentioned alkali obtain, and those skilled in the art can be according to actual production feelings
Condition, product requirement and quality requirement are selected and are adjusted, and 2,4- dichloros phenates of the present invention preferably includes 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 a variety of, more preferably 2,4- sodium dichlorophenol indophenols, 2,4- Dichlorophenols potassium, 2,4- Dichlorophenols calcium, 2,4- Dichlorophenols magnesium, 2,4- Dichlorophenols
Zinc or 2,4- Dichlorophenol aluminium, most preferably 2,4- sodium dichlorophenol indophenols or 2,4- Dichlorophenol potassium.
The dosage of 2, the 4- Dichlorophenols and alkali is not particularly limited in the present invention, with class well known to those skilled in the art
Like the conventional amount used of reaction, those skilled in the art can according to practical condition, product requirement and quality requirement into
Row selection and adjustment, the molar ratio of 2,4- Dichlorophenols and alkali of the present invention is preferably 1：(1~1.5), more preferably 1：(1.1
~1.4), most preferably 1：(1.2~1.3).
The reaction temperature that the present invention reacts 2, the 4- Dichlorophenols with alkali is not particularly limited, with those skilled in the art
The temperature of well known similar reaction, those skilled in the art can want according to practical condition, product requirement and quality
It asks and is selected and adjusted, the temperature that 2,4- Dichlorophenols of the present invention are reacted with alkali is preferably 10~100 DEG C, more preferably 30
~80 DEG C, most preferably 50~60 DEG C.The reaction time that the present invention reacts 2, the 4- Dichlorophenols with alkali is not particularly limited,
With the reaction time of similar reaction well known to those skilled in the art, those skilled in the art can be according to actual production feelings
Condition, product requirement and quality requirement are selected and are adjusted, and the time that 2,4- Dichlorophenols of the present invention are reacted with alkali is preferably
0.1~2h, more preferably 0.5~1.5h, most preferably 0.8~1.2h.
Then halogenated acetic acids ester and 2 that the present invention obtains above-mentioned steps, 4- dichloro phenates are reacted, and 2,4- bis- is obtained
Chlorophenoxyacetic acid ester.
The condition of 2, the 4- dichloros phenates is not particularly limited in the present invention, with routine well known to those skilled in the art
2,4- dichloro phenates condition, based on above-mentioned alkali selection correspondence obtains, those skilled in the art can root
It is selected and is adjusted according to practical condition, product requirement and quality requirement, 2,4- dichloros phenates of the present invention is preferably
2,4- dichloro phenates solids.
The present invention is to the halogenated acetic acids ester and 2, and the addition of 4- dichloro phenates is not particularly limited, with art technology
The conventional amount used of similar reaction known to personnel, those skilled in the art can be according to practical condition, product requirement
And quality requirement is selected and is adjusted, halogenated acetic acids ester of the present invention and 2, the molar ratio of 4- dichloro phenates is preferably (0.9
~1.1)：(0.9~1.1), more preferably (0.94~1.06)：(0.9~1.1), more preferably (0.98~1.02)：(0.9~
1.1), more preferably (0.9~1.1)：(0.94~1.06), more preferably (0.9~1.1)：(0.98~1.02), most preferably
1:1。
The temperature of the reaction is not particularly limited in the present invention, with the temperature of similar reaction well known to those skilled in the art
Degree, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement, this
The temperature for inventing the reaction is preferably 70~200 DEG C, more preferably 90~180 DEG C, more preferably 110~160 DEG C, most preferably
It is 130~140 DEG C.The time of the reaction is not particularly limited in the present invention, with well known to those skilled in the art similar anti-
The reaction time answered, those skilled in the art can select according to practical condition, product requirement and quality requirement
It selects and adjusts, the time of reaction of the present invention is preferably 1~7h, more preferably 2~6h, most preferably 3~5h.
Again reaction is hydrolyzed in 2, the 4- dichlorphenoxyacetic acid esters that above-mentioned steps obtain by the present invention, obtains 2,4- dichloro-benzenes
Fluoroacetic acid and alcohol.
The temperature of the hydrolysis is not particularly limited in the present invention, with similar reaction well known to those skilled in the art
Temperature, those skilled in the art can select and adjust according to practical condition, product requirement and quality requirement
Whole, the temperature of hydrolysis of the present invention is preferably 50~200 DEG C, more preferably 70~180 DEG C, more preferably 90~160
DEG C, most preferably 110~140 DEG C.The time of the hydrolysis is not particularly limited in the present invention, with those skilled in the art
In the reaction time of well known similar reaction, those skilled in the art can be according to practical condition, product requirement and matter
Amount requires to be selected and adjusted, and the time of hydrolysis of the present invention is preferably 1~10h, and more preferably 3~8h is optimal
It is selected as 5~6h.
The detailed process of the hydrolysis is not particularly limited in the present invention, with hydrolysis well known to those skilled in the art
The process of reaction, those skilled in the art can select according to practical condition, product requirement and quality requirement
And adjustment, the detailed process of hydrolysis of the present invention, i.e., the described step C) it is particularly preferred as：
Under the effect of the catalyst, reaction is hydrolyzed in 2, the 4- dichlorphenoxyacetic acid esters that above-mentioned steps obtain, obtained
2,4 dichlorophenoxyacetic acid and alcohol.
The dosage of the catalyst is not particularly limited in the present invention, with similar reaction well known to those skilled in the art
Conventional amount used, those skilled in the art can be selected according to practical condition, product requirement and quality requirement and
Adjustment, the percentage that the quality of catalyst of the present invention accounts for 2, the 4- dichlorphenoxyacetic acids ester quality is preferably 0.1%~
1%, more preferably 0.3%~0.8%, most preferably 0.5%~0.6%.
The selection of the catalyst is not particularly limited in the present invention, anti-with similar hydrolysis well known to those skilled in the art
The catalyst answered, those skilled in the art can select according to practical condition, product requirement and quality requirement
And adjustment, catalyst of the present invention preferably include polyethers, crown ether, quaternary ammonium salt, tertiary amine, quaternary phosphonium salt, pyridine, titanate esters, inorganic
It is one or more in acid and organic acid, more preferably polyethers, crown ether, quaternary ammonium salt, tertiary amine, quaternary phosphonium salt, pyridine, titanate esters, nothing
Machine acid or organic acid, more preferably composite catalyst, 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
It is one or more in pyridine, with one or more mixtures in titanate esters, inorganic acid and organic acid.Wherein, the crown ether
Preferably crown ether or cyclic crown ether；The quaternary ammonium salt includes but not limited to tetrabutylammonium bromide；The polyethers includes but not limited to
Dialkylethers；The quaternary phosphonium salt includes but not limited to tetrabutyl phosphonium bromide phosphine；The tertiary amine includes but not limited to three second
Amine；The inorganic acid includes but not limited to sulfuric acid, hydrochloric acid；The organic acid includes but not limited to p-methyl benzenesulfonic acid, formic acid and second
Acid.
The present invention is to improve the integrality and operability of technique, ensures the purity and yield of product, the hydrolysis
After the completion, preferably further include post-processing step.
The detailed process and parameter of the post-processing step is not particularly limited in the present invention, ripe with those skilled in the art
The conventional post-processing step known, those skilled in the art can be according to practical condition, product requirement and quality requirements
Selected and adjusted, post-processing step of the present invention preferably include crystallization, filtering and it is dry in it is one or more, it is more excellent
It is selected as crystallization, filtering and drying.The parameter of above-mentioned specific steps is not particularly limited in the present invention, ripe with those skilled in the art
The conventional parameter of crystallization, filtering and the drying known, those skilled in the art can be according to practical condition, product requirements
And quality requirement is selected and is adjusted.
The present invention is to improve the integrality and operability of technique, more specifically, the step C) be specifically as follows it is following
Step：
2,4- dichlorphenoxyacetic acid esters hydrolysis under the effect of the catalyst, crystallizes, filters, being dried to obtain 2,4- dichloros
Phenoxy acetic acid.
Wherein, the temperature of the hydrolysis is preferably 50~200 DEG C, more preferably 70~180 DEG C, more preferably 90~
160 DEG C, most preferably 110~140 DEG C；The time of the hydrolysis is preferably 1~10h, more preferably 3~8h, most preferably
For 5~6h；The hydrolysis 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.
Or：
It by 2,4- dichlorphenoxyacetic acids ester and aqueous slkali mixed hydrolysis, stirring, then is mixed with acid, finally obtains 2,4- dichloros
Phenoxy acetic acid；More preferably it is specially：2,4- dichlorphenoxyacetic acid esters and aqueous slkali mixed hydrolysis, stirring, then mixed with acid, it ties
Brilliant, 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 mass ratio of the 2,4 dichlorophenoxyacetic acid ester and aqueous slkali is preferably 1：(1~1.5), more preferably 1：(1.1~
1.4), most preferably 1：(1.2~1.3).
The reaction temperature is preferably 90~110 DEG C；More preferably 95~105 DEG C；The reaction time is preferably 2~
4h, more preferably 2.5~3.5h；The present invention for the stirring concrete mode without limiting, those skilled in the art are ripe
The agitating mode known.
The acid is preferably sulfuric acid, hydrochloric acid or nitric acid；The concentration of the acid is preferably 10%~100%；More preferably
30%~60%；More preferably 40%~50%；The additive amount of the acid is preferably 0.1%~5%, more preferably 0.5%~
4%, most preferably 1%~3%.
The crystallization temperature is preferably 10~20 DEG C, more preferably 12~18 DEG C, more preferably 14~16 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 limit
It is fixed, filtering well known to those skilled in the art and drying mode.
The alcohol that above-mentioned steps obtain finally is back to step A by the present invention), to realize the cycle of process raw material -ol
Recycling.
Above-mentioned steps of the present invention provide the preparation method of 2,4- dichlorphenoxyacetic acids, adjusting process route of the present invention, from
On the basis of carry out inventive improvements, first alcohol and halogenated acetic acids is used to prepare halogenated acetic acids ester, then with 2, the 4- Dichlorophenols of preparation
Reactant salt prepares 2,4- dichlorphenoxyacetic acid esters, and the intermediate stability is good, and byproduct of reaction is few, high income, and then is follow-up
The yield and purity for preparing 2,4- dichlorphenoxyacetic acids provide good condition, and 2,4- Dichlorophenoxy second is obtained using hydrolysis
Acid and alcohol, the alcohol hydrolyzed again can reuse with prepare halogenated acetic acids ester during, realize recycling for process raw material.
Preparation process provided by the invention, reaction process cleaning, the wastewater flow rate generated are few, and hydrolysising by-product is few, and product purity is high, conversion
Rate and yield are higher；And process raw material is Ke Xunhuanliyong, is suitble to large-scale industrial production.The experimental results showed that the present invention
2, the 4- dichlorphenoxyacetic acids prepared, purity can reach 99.5%, and yield can reach 99.5%.
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, but it is to be understood that these embodiments are carried out lower based on the technical solution of the present invention
Implement, give detailed embodiment and specific operating process, be only the feature and advantage further illustrated the present invention,
Rather than limiting to the claimed invention, protection scope of the present invention are also not necessarily limited to following embodiments.
Embodiment 1
200g isopropanols, 95g (1mol) monoxones and the 0.1g concentrated sulfuric acids are mixed, precipitation is dehydrated 5h, obtains chloroethene
Isopropyl propionate.
The sodium hydrate aqueous solution 125g (1mol) of 2,4 dichloro phenol 164g (1mo1), mass fraction 32% is mixed and is stirred
It mixes, obtains 2,4- sodium dichlorophenol indophenols.
In the isopropyl chloracetate that 2,4- sodium dichlorophenol indophenols input is prepared, after stirring 0.5h, filters out reaction and generate
Sodium chloride, filtrate is put into hydrolysis reactor, sodium hydrate aqueous solution 125g (1mol) reflux of mass fraction 32% is added
0.5h is stirred, collects the obtained isopropanol 80g of precipitation, 30% hydrochloric acid 130g is added in concentrate, crystallizes 1h at 10 DEG C, filters, filter
Biscuit is dry, obtains 2,4- dichlorphenoxyacetic acid solids 221g.
The product prepared to the embodiment of the present invention 1 is detected and counts, purity 99.5%, yield 99.5%.
Embodiment 2
The isopropanol 80g recycled in embodiment 1, new isopropanol 150g, 95g (1mol) monoxone and 0.1g is dense
Sulfuric acid is mixed, and precipitation is dehydrated 5h, obtains isopropyl chloracetate.
The potassium hydroxide aqueous solution 113g (1mol) of 2,4 dichloro phenol 164g (1mo1), mass fraction 50% is mixed and is stirred
It mixes, obtains 2,4- Dichlorophenol potassium.
In the isopropyl chloracetate that 2,4- Dichlorophenol potassium input is prepared, after stirring 0.5h, filters out reaction and generate
Potassium chloride, filtrate is put into hydrolysis reactor, 30% hydrochloric acid 130g is added, flow back dealcoholysis 3h, and the alcohol of recycling is used to prepare chlorine
Acetic acid esters crystallizes 1h at 10 DEG C of concentrate, filters, and filtration cakes torrefaction obtains 2,4- dichlorphenoxyacetic acid solids 220g.
The product prepared to the embodiment of the present invention 2 is detected and counts, purity 99.3%, yield 98.9%.
Embodiment 3
300g isooctanol, 140g (1mol) bromoacetic acids and the 0.1g concentrated sulfuric acids are mixed, precipitation is dehydrated 4h, obtains bromine second
The different monooctyl ester of acid.
The sodium hydrate aqueous solution 125g (1mol) of 2,4- chlorophenesic acids 164g (1mo1), 32% are mixed, obtained
2,4- sodium dichlorophenol indophenols.
In the different monooctyl ester of bromoacetic acid that 2,4- sodium dichlorophenol indophenols input is prepared, after stirring 0.5h, filters out reaction and generate
Sodium chloride, filtrate is put into hydrolysis reactor, concentrated sulfuric acid 20g is added, flow back dealcoholysis 3h, and collection obtains isooctanol 131g, dense
1h is crystallized at 10 DEG C of contracting liquid, is filtered, filtration cakes torrefaction obtains 2,4- dichlorphenoxyacetic acid solids 221g.
The product prepared to the embodiment of the present invention 3 is detected and counts, purity 99.5%, yield 99.5%.
Embodiment 4
The isooctanol recycled in embodiment 3, new isooctanol 150g, 95g (1mol) monoxone are mixed with the 0.1g concentrated sulfuric acids
Stirring, precipitation are dehydrated 5h, obtain Isooctyl chloroacetate.
2,4- chlorophenesic acids 164g (1mo1), calcium hydroxide solid 21g (0.5mol) are mixed, 2,4- dichloros are obtained
Phenol calcium solid.
In the Isooctyl chloroacetate that 2,4- Dichlorophenol calcium input is prepared, after stirring 0.5h, filters out reaction and generate
Calcium chloride, filtrate is put into hydrolysis reactor, sodium hydrate aqueous solution 125g (1mol) reflux of mass fraction 32% is added
0.5h is stirred, isooctanol 130g is collected, concentrate is added 30% hydrochloric acid 130g, 1h is crystallized at 10 DEG C, filters, and filtration cakes torrefaction obtains
To 2,4 dichlorophenoxyacetic acid solid 221g.
The product prepared to the embodiment of the present invention 4 is detected and counts, purity 99.4%, yield 99.4%.
Above to a kind of preparation method of the Ke Xunhuanliyong 2,4 dichlorophenoxyacetic acid of process raw material provided by the invention
It is described in detail, principle and implementation of the present invention are described for specific case used herein, above
The explanation of embodiment is merely used to help understand the method and its core concept of the present invention, including best mode, and but also
Any person skilled in the art can put into practice the present invention, including manufacture and use any device or system, and implement any
In conjunction with method.It should be pointed out that for those skilled in the art, in the premise for not departing from the principle of the invention
Under, it can be with several improvements and modifications are made to the present invention, these improvement and modification also fall into the protection of the claims in the present invention
In range.The range of patent protection of the present invention is defined by the claims, and may include those skilled in the art it is conceivable that
Other embodiment.If these other embodiments have the structural element for being not different from claim character express, or
If they include and equivalent structural elements of the character express of claim without essence difference, these other embodiments
Should include within the scope of the claims.
Claims (10)
1. one kind 2, the preparation method of 4- dichlorphenoxyacetic acids, which is characterized in that include the following steps：
A alcohol and halogenated acetic acids) are subjected to esterification, obtain halogenated acetic acids ester；
After 2,4- Dichlorophenols are reacted with alkali, 2,4- dichloro phenates is obtained；
B) the halogenated acetic acids ester and 2 for obtaining above-mentioned steps, 4- dichloro phenates are reacted, and 2,4- dichlorphenoxyacetic acids are obtained
Ester；
C reaction) is hydrolyzed in 2, the 4- dichlorphenoxyacetic acid esters that above-mentioned steps obtain, obtain 2,4- dichlorphenoxyacetic acids and
Alcohol；
D the alcohol that above-mentioned steps obtain) is back to step A), it recycles；
The alcohol is the alcohol that C atomicities are more than or equal to 2.
2. preparation method according to claim 1, which is characterized in that the alcohol is the alcohol of C2~C20；
The alcohol includes monohydric alcohol.
3. preparation method according to claim 1, which is characterized in that the halogenated acetic acids include monoxone, bromoacetic acid and
It is one or more in iodoacetic acid；
The 2,4- dichloros phenates include 2,4- sodium dichlorophenol indophenols, 2,4- Dichlorophenols potassium, 2,4- Dichlorophenols calcium, 2,4- Dichlorophenols magnesium,
It is one or more in 2,4- Dichlorophenols zinc and 2,4- Dichlorophenol aluminium.
4. preparation method according to claim 1, which is characterized in that the reaction promoter of the esterification includes dense sulphur
Acid；
The temperature of the esterification is 50~200 DEG C；The time of the esterification is 1~10h；
The temperature that the 2,4- Dichlorophenols are reacted with alkali is 10~100 DEG C；The time that the 2,4- Dichlorophenols are reacted with alkali is 0.1
~2h.
5. preparation method according to claim 1, which is characterized in that the molar ratio of the alcohol and halogenated acetic acids be (1~
1.5):1；
The molar ratio of the 2,4- Dichlorophenols and alkali is 1：(1~1.5).
6. preparation method according to claim 1, which is characterized in that the step B) in, the temperature of the reaction is 70
~200 DEG C；
The time of the reaction 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) be specially：
Under the effect of the catalyst, reaction is hydrolyzed in 2, the 4- dichlorphenoxyacetic acid esters that above-mentioned steps obtain, obtains 2,4-
Dichlorphenoxyacetic acid and alcohol.
9. preparation method according to claim 1, which is characterized in that the temperature of the hydrolysis is 50~200 DEG C；
The time of the hydrolysis is 1~10h.
10. preparation method according to claim 1, which is characterized in that the catalyst include polyethers, crown ether, quaternary ammonium salt,
It is one or more in tertiary amine, quaternary phosphonium salt, pyridine, titanate esters, inorganic acid and organic acid；
The percentage that the quality of the catalyst accounts for the 2,4 dichlorophenoxyacetic acid ester quality is 0.1%~1%.
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