CN104387272B - Preparation method of trifluoroacetic acid ester - Google Patents
Preparation method of trifluoroacetic acid ester Download PDFInfo
- Publication number
- CN104387272B CN104387272B CN201410697369.2A CN201410697369A CN104387272B CN 104387272 B CN104387272 B CN 104387272B CN 201410697369 A CN201410697369 A CN 201410697369A CN 104387272 B CN104387272 B CN 104387272B
- Authority
- CN
- China
- Prior art keywords
- trifluoroacetic acid
- preparation
- organic solvent
- acid ester
- fluoride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of trifluoroacetic acid ester. The preparation method is characterized by comprising the steps of (1) uniformly mixing potassium fluoride and alcohol, adding an organic solvent, and then adding trifluoro-acetyl fluoride to react; (2) filtering potassium fluoride-potassium bifluoride solid from a reaction mixture; (3) rectifying to obtain the trifluoroacetic acid ester, the organic solvent in the step (1) is selected from one or a mixture of C2H4C12 and diethyl ether, and the volume ratio of the organic solvent to the alcohol is 1:0.5 to 1:4. According to the preparation method of the trifluoroacetic acid ester, the preparation process of the trifluoroacetic acid ester is simplified, no waste acid or waste catalysts are generated during reaction, reaction by-products can be recycled and reused, and the environmental protection problem of trifluoroacetic acid ester synthesis is 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 CHCl=CCl2, one of chloroform or its mixture；Organic solvent and alcohol
Volume ratio is 1:0.5～1:4.
Described organic solvent is preferably chloroform and CHCl=CCl2Volume 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 DEG C, and the 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 chloroform, CHCl=CCl2Deng
Organic solvent, can improve yield, shorten the response time, especially when organic solvent is chloroform and CHCl=CCl2Mixed
During compound, better.
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 chloroform, and chloroform and propanol volume ratio are 1:1, then mixture is transferred to one
In the reactor of airtight belt stirrer, start stirring, 11.6 kilograms of trifluoroacetyl fluorine gas are passed into propanol and potassium fluoride
Mixture in reacted, reaction temperature is room temperature (25 DEG C), and the response time controls at 5 hours.Cross after the completion of reaction and filter
Remove KHF2, product is transferred in rectifying column and carries out rectification, obtain 14.9 kilograms of trifluoroacetic acid propyl ester (yield 94.9%).
The KHF removing2, it is solid, is neutralized with KOH, is completely converted into KF, eliminating water is reclaimed as raw material after being dried after water dissolution
Recycle.
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 chloroform and CHCl=CCl2(volume ratio 1:1) organic solvent being blended, chloroform
And CHCl=CCl2The volume of mixed solvent and propanol volume ratio are 1:1, then mixture is transferred to an airtight band stirring
In the reactor of device, start stirring, 11.6 kilograms of trifluoroacetyl fluorine gas are passed in propanol and the mixture of potassium fluoride
Row reaction, reaction temperature is room temperature (25 DEG C), and the response time controlled at 5 hours.It is filtered to remove KHF after the completion of reaction2, will react
Product is transferred in rectifying column and is carried out rectification, obtains 15.5 kilograms of trifluoroacetic acid propyl ester (yield 98.7%).The KHF removing2, its
For solid, neutralized with KOH after water dissolution, be 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 CHCl=CCl2, CHCl=CCl2It is 1 with propanol volume ratio:1, then mixture is transferred to
In the reactor of one airtight belt stirrer, start stirring, 11.6 kilograms of trifluoroacetyl fluorine gas are passed into propanol and fluorine
Reacted in the mixture changing potassium, reaction temperature is room temperature (25 DEG C), the response time controlled at 5 hours.Mistake after the completion of reaction
Filter KHF2, product is transferred in rectifying column and carries out rectification, obtain 14.8 kilograms of trifluoroacetic acid propyl ester (yields
94.2%).The KHF removing2, it is solid, is neutralized with KOH, be completely converted into KF after water dissolution, as raw material after eliminating water is dry
Carry out recycling.
Claims (4)
1. a kind of preparation method of trifluoroacetic acid propyl ester 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 trifluoroacetic acid propyl ester after rectification；
Described organic solvent is 1 with the volume ratio of propanol:0.5～1:4；
Described organic solvent is chloroform and CHCl=CCl2Volume ratio 1:0.5～1:3 mixture.
2. trifluoroacetic acid propyl ester according to claim 1 preparation method it is characterised in that：Described potassium fluoride and trifluoro second
The mol ratio of acyl fluorides is 1：1～2：1.
3. trifluoroacetic acid propyl ester according to claim 1 preparation method it is characterised in that：Trifluoro-acetic fluoride and propanol
Mol ratio is 1：1～1：3.
4. trifluoroacetic acid propyl ester according to claim 1 preparation method it is characterised in that：The reaction temperature of step (1)
For 5～45 DEG C, the response time is 1～5 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410697369.2A CN104387272B (en) | 2014-11-27 | 2014-11-27 | Preparation method of trifluoroacetic acid ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410697369.2A CN104387272B (en) | 2014-11-27 | 2014-11-27 | Preparation method of trifluoroacetic acid ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104387272A CN104387272A (en) | 2015-03-04 |
| CN104387272B true CN104387272B (en) | 2017-02-22 |
Family
ID=52605251
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410697369.2A Active CN104387272B (en) | 2014-11-27 | 2014-11-27 | Preparation method of trifluoroacetic acid ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104387272B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5710317A (en) * | 1994-07-28 | 1998-01-20 | Asahi Glass Company Ltd. | Preparation of difluoroacetic acid fluoride and difluoroacetic acid esters |
| CN1345298A (en) * | 1999-03-23 | 2002-04-17 | 旭硝子株式会社 | Process for producing fluorine compound through liquid phase fluorination |
| CN102167358A (en) * | 2010-12-24 | 2011-08-31 | 浙江司太立制药股份有限公司 | Method for recycling fluorine elements in fluoroquinolone production |
| 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 ester |
-
2014
- 2014-11-27 CN CN201410697369.2A patent/CN104387272B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5710317A (en) * | 1994-07-28 | 1998-01-20 | Asahi Glass Company Ltd. | Preparation of difluoroacetic acid fluoride and difluoroacetic acid esters |
| CN1345298A (en) * | 1999-03-23 | 2002-04-17 | 旭硝子株式会社 | Process for producing fluorine compound through liquid phase fluorination |
| CN102471217A (en) * | 2009-08-03 | 2012-05-23 | 罗地亚经营管理公司 | Method for preparing difluoroacetic acid ester |
| CN102167358A (en) * | 2010-12-24 | 2011-08-31 | 浙江司太立制药股份有限公司 | Method for recycling fluorine elements in fluoroquinolone production |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104387272A (en) | 2015-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6144204B2 (en) | Recovery of toluenediamine from tar waste residue discharged from the synthesis process of toluene diisocyanate | |
| CN104829415B (en) | A kind of method synthesizing hexafluoro-1,3-butadiene | |
| CN106748712B (en) | The preparation method of hyptafluorobutyric acid and its derivative | |
| CN102030729B (en) | Preparation method of alpha-acetyl-gamma-butyrolactone | |
| CN102351694A (en) | Preparation method of trifluoroacetic acid ethyl ester | |
| CN108658051A (en) | Recovery method, device and its sulfuric acid of recycling of nitrating wasting acid | |
| CN104402714B (en) | Preparation method of trifluoroacetate | |
| CN104387272B (en) | Preparation method of trifluoroacetic acid ester | |
| CN114181118B (en) | Synthesis process of fatty acyl taurate | |
| CN102741217B (en) | Hydrocarbon feed flexible high pressure nitration plant design | |
| CN113444039B (en) | Method for preparing 2,2, 4-trimethyl-1, 2-dihydroquinoline by using ionic liquid | |
| CN107652180A (en) | The production method of tributyrin | |
| CN109336822A (en) | A kind of metronidazole production method | |
| CN104478747B (en) | A kind of method utilizing organic solvent to produce glycine | |
| CN104370739B (en) | A kind of preparation method of trifluoro-acetate | |
| CN1962064A (en) | Method for processing waste catalyst in production of pentafluoro ethane | |
| CN102627561B (en) | Preparation process for plasticizer-tributyl citrate | |
| CN103382193B (en) | Glycidyl methacrylate or the manufacture method of glycidyl acrylate | |
| CN106187691B (en) | A method of recycling hexafluoroisopropanol from the gaseous mixture containing hexafluoroisopropanol and hydrogen | |
| CN101781217B (en) | Method for high-selectivity co-production of nitrocyclohexane and adipic acid | |
| CN107216234B (en) | Method for preparing monofluorodichloroethane by catalytic fluorination of vinylidene chloride | |
| CN101412677B (en) | Clean method for chlorobenzene liquid phase selective nitration | |
| EP0367050B1 (en) | Process for the preparation of carboxylic-acid chlorides | |
| CN104402665B (en) | Preparation method of trichlorotrifluoroethane | |
| CN109912423A (en) | A kind of green synthesis process of 3,5- dinitro -4- methyl benzoic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |