CN104402714B - Preparation method of trifluoroacetate - Google Patents
Preparation method of trifluoroacetate Download PDFInfo
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- CN104402714B CN104402714B CN201410697239.9A CN201410697239A CN104402714B CN 104402714 B CN104402714 B CN 104402714B CN 201410697239 A CN201410697239 A CN 201410697239A CN 104402714 B CN104402714 B CN 104402714B
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- trifluoro
- preparation
- organic solvent
- fluoride
- trifluoroacetate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a preparation method of trifluoroacetate. The preparation method of trifluoroacetate is characterized by comprising the following steps: (1) uniformly mixing potassium fluoride with alcohol, adding an organic solvent and then adding trifluoroacetyl fluoride to react; (2) filtering potassium fluoride-potassium hydrofluoride solid out of a reaction mixture; (3) rectifying to obtain trifluoroacetate, wherein the organic solvent in the step (1) is selected from one or mixture of both of C2H4C12 and ethyl ether; the volume ratio of the organic solvent to the alcohol is (1:0.5)-(1:4). By virtue of the method, the preparation process of the trifluoroacetate is simplified; waste acid and waste catalyst are not generated in the reaction process; reaction byproducts can be recycled and reused; the problem of the environmental protection of synthesis of the trifluoroacetate can be solved.
Description
Technical field
The present invention relates to field of fine chemical is and in particular to a kind of preparation method of trifluoro-acetate.
Background technology
Trifluoro-acetate is a kind of important Organic fluoride intermediate, and it is synthesizing multiple fluorine-containing medicines, pesticide, liquid crystal, combustion
It is widely used on the products such as material, for example, be used for synthesizing cardiovascular medicament-Lenno Puli.
The traditional preparation methods of trifluoro-acetate are with trifluoroacetic acid as raw material, are esterified with alcohol under sulphuric acid catalysis
Reaction obtains, and the method synthesis yield is relatively low, and produces the more waste water containing Waste Sulfuric Acid；Occur in that in recent years and use highly acid
Cation exchange resin replaces concentrated sulphuric acid as the technique of catalyst, and such as Authorization Notice No. is CN101397249A, invention name
Referred to as in the Chinese patent of " a kind of preparation method of trifluoro-acetate ", disclose one kind and use storng-acid cation exchange resin
As the method for catalyst preparation trifluoro-acetate, decrease spent acid discharge, but yet suffer from the process problem of dead catalyst,
And using the trifluoroacetic acid of severe corrosive in technique, the requirement to equipment and materials is higher.In publication number CN102351694A
Disclose a kind of preparation method of Trifluoroacetic Acid Ethyl Ester, but it use aminated compoundss as acid binding agent, make in reaction
Organic amine has zest foul odour, the work situation of impact R＆D and production personnel.
Content of the invention
Technical problem solved by the invention is that offer one kind can be cost-effective, simplifies program, simple to operate, yield
Height, will not produce spent acid, dead catalyst, and the by-product that reaction produces processes convenient trifluoro-acetate preparation method.
The technical solution adopted in the present invention is：A kind of preparation method of trifluoro-acetate is it is characterised in that include as follows
Step：
(1), after potassium fluoride being mixed homogeneously with alcohol, add organic solvent, add trifluoro-acetic fluoride and reacted；
(2) reactant mixture is filtered fluorinated potassium-potassium hydrogen fluoride solid；
(3) obtain trifluoro-acetate after rectification.
Described organic solvent is selected from C2H4Cl2, one of ether or its mixture；Organic solvent with the volume ratio of alcohol is
1:0.5～1:4.
Described organic solvent is preferably C2H4Cl2With ether volume ratio 1:0.5～1:3 mixture.
In the distillation process of step (2), organic solvent is also removed.
Preferably,
Described potassium fluoride is 1 with the mol ratio of trifluoro-acetic fluoride：1～2：1.
Described trifluoro-acetic fluoride is 1 with the mol ratio of alcohol：1～1：3.
The reaction temperature of step (1) is 5～45, and DEG C response time is 1～5 hour.
Described alcohol is selected from methanol, ethanol, propanol or isopropanol, and prepared described trifluoro-acetate phase should be trifluoroacetic acid first
Ester, Trifluoroacetic Acid Ethyl Ester, trifluoroacetic acid propyl ester or trifluoroacetic acid isopropyl ester.
In the present invention, trifluoro-acetic fluoride and alcohol react generation trifluoro-acetate, and fluohydric acid gas (HF), fluohydric acid gas (HF) with
Potassium fluoride (KF) is combined into KHF2, it is solid, can with KOH and after, be completely converted into KF, carry out reclaiming again as raw material
Using, or use as fluorization agent.
This invention simplifies the synthesis technique of trifluoro-acetate, and the compound involved by course of reaction is almost corrosion-free
Property, the requirement to consersion unit is relatively low, reduces production safety risk, course of reaction will not produce spent acid, dead catalyst, reaction
Produced by-product energy recycling, solves the environmental protection problem of trifluoroacetic acid Lipase absobed.
And inventor is found surprisingly that in research process, step (1) adds C2H4Cl2, ether etc. organic molten
Agent, can improve yield, shorten the response time, especially when organic solvent is C2H4Cl2During with the mixture of ether, effect is more
Good.
Specific embodiment
With reference to specific embodiment, the present invention will be further described：
Comparative example 1
In the reactor of a belt stirrer, add 12 kilograms of propanol, under agitation, be slowly added into 5.8 kilograms of fluorinations
Potassium, makes the two mix homogeneously, the mixture of propanol and potassium fluoride is transferred in the reactor of an airtight belt stirrer, opens
Dynamic stirring, 11.6 kilograms of trifluoroacetyl fluorine gas is passed in propanol and the mixture of potassium fluoride and is reacted, reaction temperature
For room temperature (about 25 DEG C), the response time controlled at 5 hours.It is filtered to remove KHF after the completion of reaction2, product is transferred to essence
Evaporate in tower and carry out rectification, obtain 14.2 kilograms of trifluoroacetic acid propyl ester (yield 91.0%).The KHF removing2, it is solid, uses water
After dissolving, with KOH neutralization, it is completely converted into KF, after drying and dehydrating, becomes anhydrous potassium fluoride.
Embodiment 1
In the reactor of a belt stirrer, add 12 kilograms of propanol, under agitation, be slowly added into 5.8 kilograms of fluorinations
Potassium, makes the two mix homogeneously, adds C2H4Cl2, C2H4Cl2It is 1 with propanol volume ratio:1, then by mixture transfer to one airtight
The reactor of belt stirrer in, start stirring, 11.6 kilograms of trifluoroacetyl fluorine gas be passed into the mixed of propanol and potassium fluoride
Reacted in compound, reaction temperature is room temperature (25 DEG C), the response time controlled at 5 hours.It is filtered to remove after the completion of reaction
KHF2, product is transferred in rectifying column and carries out rectification, obtain 14.9 kilograms of trifluoroacetic acid propyl ester (yield 95.5%).Remove
The KHF going2, it is solid, is neutralized with KOH, is completely converted into KF, eliminating water carries out reclaiming as raw material after being dried again after water dissolution
Using.
Embodiment 2
In the reactor of a belt stirrer, add 12 kilograms of propanol, under agitation, be slowly added into 5.8 kilograms of fluorinations
Potassium, makes the two mix homogeneously, adds C2H4Cl2With ether (volume ratio 1:1) organic solvent being blended, C2H4Cl2With ether mixing
The volume of solvent and propanol volume ratio are 1:1, then mixture is transferred in the reactor of an airtight belt stirrer, start
Stirring, 11.6 kilograms of trifluoroacetyl fluorine gas is passed in propanol and the mixture of potassium fluoride and is reacted, reaction temperature is
Room temperature (25 DEG C), the response time controlled at 5 hours.It is filtered to remove KHF after the completion of reaction2, product is transferred to rectifying column
In carry out rectification, obtain 15.5 kilograms of trifluoroacetic acid propyl ester (yield 99.4%).The KHF removing2, it is solid, after water dissolution
With KOH neutralization, it is completely converted into KF, eliminating water carries out recycling as raw material after being dried.
Embodiment 3
In the reactor of a belt stirrer, add 12 kilograms of propanol, under agitation, be slowly added into 5.8 kilograms of fluorinations
Potassium, makes the two mix homogeneously, adds ether, and ether and propanol volume ratio are 1:1, then mixture is transferred to an airtight band
In the reactor of agitator, start stirring, 11.6 kilograms of trifluoroacetyl fluorine gas are passed into the mixture of propanol and potassium fluoride
In reacted, reaction temperature is room temperature (25 DEG C), and the response time controls at 5 hours.It is filtered to remove KHF after the completion of reaction2, will
Product is transferred in rectifying column and is carried out rectification, obtains 14.8 kilograms of trifluoroacetic acid propyl ester (yield 94.8%).Remove
KHF2, it is solid, is neutralized with KOH, be completely converted into KF after water dissolution, and eliminating water carries out reclaiming profit again as raw material after being dried
With.
Claims (4)
1. a kind of preparation method of trifluoro-acetate is it is characterised in that comprise the steps：
(1), after potassium fluoride being mixed homogeneously with propanol, add organic solvent, add trifluoro-acetic fluoride and reacted；
(2) reactant mixture is filtered fluorinated potassium-potassium hydrogen fluoride solid；
(3) obtain trifluoro-acetate after rectification；
Described organic solvent is 1 with the volume ratio of propanol:0.5～1:4；
Described organic solvent is C2H4Cl2With ether volume ratio 1:0.5～1:3 mixture.
2. trifluoro-acetate according to claim 1 preparation method it is characterised in that：Described potassium fluoride and trifluoroacetyl
The mol ratio of fluorine is 1：1～2：1.
3. trifluoro-acetate according to claim 1 preparation method it is characterised in that：Trifluoro-acetic fluoride is rubbed with propanol
That ratio is 1：1～1：3.
4. trifluoro-acetate according to claim 1 preparation method it is characterised in that：The reaction temperature of step (1) is 5
～45 DEG C, the response time is 1～5 hour.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410697239.9A CN104402714B (en) | 2014-11-27 | 2014-11-27 | Preparation method of trifluoroacetate |
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| CN201410697239.9A CN104402714B (en) | 2014-11-27 | 2014-11-27 | Preparation method of trifluoroacetate |
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| CN104402714A CN104402714A (en) | 2015-03-11 |
| CN104402714B true CN104402714B (en) | 2017-02-22 |
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| CN108911982B (en) * | 2018-07-19 | 2022-08-26 | 徐州博康信息化学品有限公司 | Environment-friendly method for synthesizing acyloxy-substituted styrene compound |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1447784A (en) * | 2000-08-30 | 2003-10-08 | 旭硝子株式会社 | Process for prepn. of fluorinated ketones |
| CN102351694A (en) * | 2011-10-17 | 2012-02-15 | 三明市海斯福化工有限责任公司 | Preparation method of trifluoroacetic acid ethyl ester |
| CN102471217A (en) * | 2009-08-03 | 2012-05-23 | 罗地亚经营管理公司 | Method for preparing difluoroacetic acid esters |
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2014
- 2014-11-27 CN CN201410697239.9A patent/CN104402714B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1447784A (en) * | 2000-08-30 | 2003-10-08 | 旭硝子株式会社 | Process for prepn. of fluorinated ketones |
| CN102471217A (en) * | 2009-08-03 | 2012-05-23 | 罗地亚经营管理公司 | Method for preparing difluoroacetic acid esters |
| CN102351694A (en) * | 2011-10-17 | 2012-02-15 | 三明市海斯福化工有限责任公司 | Preparation method of trifluoroacetic acid ethyl ester |
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