CN102633644A - Synthesis process of trifluoroacetyl ethyl acetate - Google Patents
Synthesis process of trifluoroacetyl ethyl acetate Download PDFInfo
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- CN102633644A CN102633644A CN2012100987349A CN201210098734A CN102633644A CN 102633644 A CN102633644 A CN 102633644A CN 2012100987349 A CN2012100987349 A CN 2012100987349A CN 201210098734 A CN201210098734 A CN 201210098734A CN 102633644 A CN102633644 A CN 102633644A
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- Prior art keywords
- ethyl acetate
- inorganic salt
- trifluoroacetic
- ethyl ester
- trifluoroacetic acid
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Abstract
The invention discloses a synthesis process of trifluoroacetyl ethyl acetate. The invention provides a synthesis process of high-purity trifluoroacetyl ethyl acetate. The synthesis process comprises the following steps: reacting for a period of time by taking trifluoroacetyl ethyl acetate and ethyl acetate as primary raw materials and a molecular sieve as a catalyst; filtering out the molecular sieve; washing with an inorganic salt aqueous solution and extracting; and putting the obtained product from the former step into a rectifying tower to distill so as to obtain high-purity trifluoroacetyl ethyl acetate. The process has the characteristics that operation is simple and convenient, yield is high, environmental pollution is little and the like, and can be applicable to industrial large-scale production.
Description
One, technical field
The present invention relates to a kind of is main raw material with Trifluoroacetic Acid Ethyl Ester and ETHYLE ACETATE, and molecular sieve is that the method for catalyzer prepares trifluoroacetic ethyl acetoacetate, belongs to the Fine Organic Chemical field.
Two, background technology
Trifluoroacetic ethyl acetoacetate is a kind of important Organic Chemicals, and industries such as, agricultural chemicals synthetic at organofluorine compound, medicine, dyestuff and liquid crystal have purposes widely.China is the main output state of fluorite (a kind of raw material that contains fluorine element), on raw material, has superiority, and makes China become the major country of production of fluorochemicals.The industrial process of trifluoroacetic ethyl acetoacetate is under the catalysis of sodium Metal 99.5, to generate the trifluoroacetic ethyl acetoacetate bullion with Trifluoroacetic Acid Ethyl Ester and ETHYLE ACETATE at present, and there is bigger danger in used sodium Metal 99.5 in transportation and use.2007 the 12nd phases " agricultural chemicals " point out and can impel Trifluoroacetic Acid Ethyl Ester and ETHYLE ACETATE to carry out Claisen condensation reaction as catalyzer with solid sodium ethanol; Yet solid sodium ethanol and sodium Metal 99.5 belong to high-risk transportation article equally; In use, can cause more serious injury to human body if any improper.
Three, summary of the invention
It is main raw material with Trifluoroacetic Acid Ethyl Ester and ETHYLE ACETATE that the present invention provides a kind of, and molecular sieve is that the method for catalyzer prepares trifluoroacetic ethyl acetoacetate, can be applicable to the suitability for industrialized production of trifluoroacetic ethyl acetoacetate.
The technical scheme that the present invention adopted is: with Trifluoroacetic Acid Ethyl Ester, ETHYLE ACETATE, sieve catalyst, organic solvent adds in the reaction kettle, stirred for several hour; Filtering recovering catalyst adds organic acid for adjusting pH value in the filtrating, add saturated inorganic salt solution and extract; Ester matter layer is dry with inorganic salt; The rectifying of tower still, the trifluoroacetic ethyl acetoacetate molar yield rate that obtains is 68-75%, purity is more than 99.5%.Molecular sieve can reuse according to circumstances, or through utilizing after ethanol, the washing of acetone equal solvent, repetition rate can reach more than 99%, and simple to operate, is suitable for suitability for industrialized production again.
The trifluoroacetic ethyl acetoacetate reaction equation:
F
3CCOOC
2H
5+CH
3COOC
2H
5→CF
3COCH
2COOC
2H
5+C
2H
5OH
Four, description of drawings
The operational path that Fig. 1 the present invention adopts
Five, embodiment
Below in conjunction with instance technical scheme of the present invention is described in further detail, but embodiment of the present invention is not limited thereto.Method described in the instance, general industry technician all can understand.
Embodiment 1
With 14.2kg Trifluoroacetic Acid Ethyl Ester, 17.6kg ETHYLE ACETATE, 2.84kgKF-Al
2O
3, 30L N, dinethylformamide add in the reaction kettle, stir, and behind the about 12h of reflux, filtered and recycled KF-Al
2O
3, add about an amount of first acid for adjusting pH value to 7 in the filtrating, add 2 times of saturated nacl aqueous solutions and carry out separatory to the reaction solution volume; Ester matter layer is used an amount of anhydrous sodium sulfate drying, the rectifying of tower still, and wherein rectification temperature is 80 ℃; Pressure 0.2MPa; The trifluoroacetic ethyl acetoacetate 12.5kg that obtains, molar yield are 68.5%, and purity is 99.7%.
Embodiment 2
With 13.2g ETHYLE ACETATE, 4g KF-Al
2O
3, an amount of N, dinethylformamide add in the there-necked flask, and reflux stirs, and drips the 14.2g Trifluoroacetic Acid Ethyl Ester, and about 0.5h is added dropwise to complete, and continues reflux 10h, cooling, filtered and recycled KF-Al
2O
3It is about 7 that filtrating adding acetate is neutralized to pH, adds 3 times to the saturated sodium carbonate solution of above-mentioned reaction solution volume, separatory; Ester matter layer with an amount of anhydrous magnesium sulfate drying after, filter, filtrating gets into the rectifying of tower still; Rectification temperature is 78 ℃, and pressure 0.15MPa gets trifluoroacetic ethyl acetoacetate 13.2g; Molar yield 74%, purity 99.8%.
Embodiment 3
With 14.2kg Trifluoroacetic Acid Ethyl Ester, 26.4 ETHYLE ACETATE, 2.84kgKF-Al
2O
3, add in the reaction kettle, stir, behind the about 14h of reflux, filter, reclaim KF-Al
2O
3, add about an amount of first acid for adjusting pH value to 7 in the filtrating, add 1.5 times of saturated nacl aqueous solutions and carry out separatory to the reaction solution volume; Ester matter layer is used an amount of anhydrous sodium sulfate drying, the rectifying of tower still, and wherein rectification temperature is 80 ℃; Pressure 0.2MPa; The trifluoroacetic ethyl acetoacetate 13.6g that obtains, molar yield are 72%, and purity is 99.6%.
Claims (7)
1. the present invention relates to a kind of technology of synthetic trifluoroacetic ethyl acetoacetate, specifically comprise:
(1) Trifluoroacetic Acid Ethyl Ester, ETHYLE ACETATE, sieve catalyst, organic solvent are added in the reaction kettle, stir, after reflux is passed through certain reaction times, filtering recovering catalyst;
(2) regulate filtrating pH value, add inorganic salt solution solution and carry out separatory, ester matter layer is dry with inorganic salt;
(3) will in dried Trifluoroacetic Acid Ethyl Ester bullion inflow tower still, carry out rectifying, obtain purity at the trifluoroacetic ethyl acetoacetate more than 99.5%.
2. the sieve catalyst of indication refers to KF-Al in claim 1 step (1)
2O
3
3. the molar mass ratio of Trifluoroacetic Acid Ethyl Ester and ETHYLE ACETATE is 1: 1.5～4 in claim 1 step (1);
4. the reaction times of claim 1 step (1) indication is 10-15 hour.
5. the inorganic salt solution that proposed of claim 1 step (2) refers to saturated aqueous sodium carbonate, saturated sodium-chloride water solution, and inorganic salt refer to SODIUM SULPHATE ANHYDROUS 99PCT, anhydrous magnesium sulfate.
6. regulating the used reagent of pH value in claim 1 step (2) is formic acid, acetate.
7. the top temperature of rectifying tower is 80 ℃ in claim 1 step (3), and pressure is 0.1～0.5MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100987349A CN102633644A (en) | 2012-04-06 | 2012-04-06 | Synthesis process of trifluoroacetyl ethyl acetate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012100987349A CN102633644A (en) | 2012-04-06 | 2012-04-06 | Synthesis process of trifluoroacetyl ethyl acetate |
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| CN102633644A true CN102633644A (en) | 2012-08-15 |
Family
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| CN2012100987349A Pending CN102633644A (en) | 2012-04-06 | 2012-04-06 | Synthesis process of trifluoroacetyl ethyl acetate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214355A (en) * | 2012-11-02 | 2013-07-24 | 江苏中丹药物研究有限公司 | Method for preparing fluorine-containing methyl or alkylaryl ketones |
| CN104829455A (en) * | 2015-04-29 | 2015-08-12 | 衢州学院 | Catalytic synthesis method of ethyl trifluoroacetoacetate |
| CN109456192A (en) * | 2018-12-18 | 2019-03-12 | 深圳市第二人民医院 | The synthetic method of oxiracetam intermediate 4- chloroacetyl acetacetic ester |
| CN112574039A (en) * | 2020-12-25 | 2021-03-30 | 湖南海利化工股份有限公司 | Synthesis method of ethyl difluoroacetoacetate |
-
2012
- 2012-04-06 CN CN2012100987349A patent/CN102633644A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214355A (en) * | 2012-11-02 | 2013-07-24 | 江苏中丹药物研究有限公司 | Method for preparing fluorine-containing methyl or alkylaryl ketones |
| CN103214355B (en) * | 2012-11-02 | 2016-02-17 | 江苏中丹药物研究有限公司 | A kind of method prepared containing methyl fluoride or aryl alkyl ketone |
| CN104829455A (en) * | 2015-04-29 | 2015-08-12 | 衢州学院 | Catalytic synthesis method of ethyl trifluoroacetoacetate |
| CN109456192A (en) * | 2018-12-18 | 2019-03-12 | 深圳市第二人民医院 | The synthetic method of oxiracetam intermediate 4- chloroacetyl acetacetic ester |
| CN109456192B (en) * | 2018-12-18 | 2022-04-01 | 深圳市第二人民医院 | Synthetic method of oxiracetam intermediate 4-ethyl chloroacetoacetate |
| CN112574039A (en) * | 2020-12-25 | 2021-03-30 | 湖南海利化工股份有限公司 | Synthesis method of ethyl difluoroacetoacetate |
| CN112574039B (en) * | 2020-12-25 | 2022-12-16 | 湖南海利化工股份有限公司 | Synthesis method of ethyl difluoroacetoacetate |
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| C06 | Publication | ||
| PB01 | Publication | ||
| DD01 | Delivery of document by public notice |
Addressee: Huayuan Medical Research Institute Co., Ltd. Document name: Notification that Application Deemed to be Withdrawn |
|
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120815 |