CN102633639A - Synthesis process for trifluoroacetic acid ethyl ester - Google Patents
Synthesis process for trifluoroacetic acid ethyl ester Download PDFInfo
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- CN102633639A CN102633639A CN2012100987334A CN201210098733A CN102633639A CN 102633639 A CN102633639 A CN 102633639A CN 2012100987334 A CN2012100987334 A CN 2012100987334A CN 201210098733 A CN201210098733 A CN 201210098733A CN 102633639 A CN102633639 A CN 102633639A
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- trifluoroacetic acid
- ethyl ester
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Abstract
A synthesis process for trifluoroacetic acid ethyl ester includes: by using trifluoroacetic acid and absolute ethyl alcohol as main raw materials and a molecular sieve as catalyst, dropwise adding the absolute ethyl alcohol by being supplemented with a permeable separator, so that generated water after reaction can be timely removed; and utilizing water consumption as a basis to judge ending of reaction, filtering the molecular sieves after reaction ends, rinsing and drying by inorganic salt solution, and finally obtaining the trifluoroacetic acid ethyl ester with the purity of higher than 99.5% after two-time distillation. The synthesis process has the advantages of simplicity and convenience in operation, high yield, low environmental pollution and the like, and is applicable to industrial mass production.
Description
One, technical field
The present invention relates to a kind of is main raw material with trifluoroacetic acid and absolute ethyl alcohol, and molecular sieve is that the method for catalyzer prepares Trifluoroacetic Acid Ethyl Ester, belongs to the Fine Organic Chemical field.
Two, background technology
Trifluoroacetic Acid Ethyl Ester is a kind of important Organic Chemicals, and industries such as, agricultural chemicals synthetic at the organofluorine compound thing, medicine, dyestuff and liquid crystal have purposes widely.China has superiority on raw material owing to be the main output state of fluorite (a kind of raw material that contains fluorine element), makes China become the main output state of fluorochemicals.The industrial process of Trifluoroacetic Acid Ethyl Ester is under the catalysis of the vitriol oil, to generate the Trifluoroacetic Acid Ethyl Ester bullion with trifluoroacetic acid and absolute ethyl alcohol at present; The used vitriol oil is except having katalysis; Still dewatering agent in the reaction can impel reaction to carry out towards positive dirction.But the easy etching apparatus of the vitriol oil, and aftertreatment trouble.2005 the 6th phases " Beijing University of Chemical Technology's journal " point out can the catalyzer of Trifluoroacetic Acid Ethyl Ester be made into the D072 strongly acidic cationic exchange resin, add the dehydration resin as siccative.It is main raw material that Chinese patent CN101397249A proposes with trifluoroacetic acid and absolute ethyl alcohol on this basis; With strongly acidic cationic exchange resin as catalyzer; Be lower than 50 ℃ with the following dropping absolute ethyl alcohol of normal pressure; In the drying tower that is filled with solid particulate silica gel, remove water seal,, collect 58 ℃ of-64 ℃ of cuts in distillation.Though more than two kinds of methods the vitriol oil in the traditional technology is substituted with Zeo-karb because resin is utilizing the wash-out in the process need use a large amount of solvents again, so in industry, be difficult to application.
Three, summary of the invention
It is main raw material with trifluoroacetic acid and absolute ethyl alcohol that the present invention provides a kind of, and molecular sieve is that the method for catalyzer prepares Trifluoroacetic Acid Ethyl Ester, can be applicable to the suitability for industrialized production of Trifluoroacetic Acid Ethyl Ester.
The technical scheme that the present invention adopted is: with Trifluoroacetic Acid Ethyl Ester and absolute ethyl alcohol is main raw material; With the acidic molecular sieve is catalyzer; Carry out towards forward in order to make reaction; Introduce permeable separator, the water that is generated in the esterification is in time drawn,, distillatory method dry again through extraction, drying, extraction obtains highly purified Trifluoroacetic Acid Ethyl Ester.Method difference is: 1, the molar ratio range of trifluoroacetic acid and absolute ethyl alcohol is 1: 1.2-1: 5, and the quality of trifluoroacetic acid and sieve catalyst is 1 than scope: 0.2-1: 0.5; 2, the end of esterification is to collect about 98% (the having no reaction can reach 100% yield) that the water yield is a calculated value in the permeable separator; 3, it is to be cooled to room temperature that reaction finishes the back, filters out sieve catalyst, in reaction solution, adds inorganic salt solution, preferred saturated aqueous sodium carbonate; Wash once more with inorganic salt solution more afterwards, preferred saturated sodium-chloride water solution is again after the yellow soda ash drying; Distill the cut when collecting 60-62 °, use acid siccative again, after preferred Vanadium Pentoxide in FLAKES carries out drying; Carry out the distillation second time, the cut when collecting 60-62 ° obtains purity at 99.5% above Trifluoroacetic Acid Ethyl Ester.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 Acid Ethyl Ester reaction equation:
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
11.4 kilograms of trifluoroacetic acids are put into reaction kettle, open and stir, the operation of lowering the temperature, slow Dropwise 5 .53 kilogram absolute ethyl alcohol in reaction kettle, the dropping time is 0.5 hour, adds 3.42 kilograms AlPO then
4Sieve catalyst is added dropwise to complete the back and in reacting kettle jacketing, adds steam, makes its temperature reach 48-50 ℃, keeps watch on the water-content in the permeable separator, and when it reached 1.76 liters of left and right sides, stopped reaction was reduced to room temperature, elimination AlPO
4Molecular sieve obtains the Trifluoroacetic Acid Ethyl Ester bullion.The saturated aqueous sodium carbonate that in the Trifluoroacetic Acid Ethyl Ester bullion, adds its volume and be 4 times of reaction solutions extracts; Remove trifluoroacetic acid, water and the ethanol that possibly have, the saturated sodium-chloride water solution with 2 times of reaction solution volumes washs again, air distillation after an amount of solid carbonic acid potassium drying; Collect 60-62 ° of cut; Normal temperature carries out air distillation with the Vanadium Pentoxide in FLAKES drying down again, collects 60-62 ° of cut, 12.07 kilograms of last Trifluoroacetic Acid Ethyl Esters; Molar yield is 85%, and Trifluoroacetic Acid Ethyl Ester purity reaches more than 99.7%.
Embodiment 2
11.4 kilograms of trifluoroacetic acids are put into reaction kettle, open and stir, the operation of lowering the temperature slowly drips 6.91 kilograms of absolute ethyl alcohols in reaction kettle, and the dropping time is 1 hour, adds 4.56 kilograms SiO then
2/ Al
2O
3(V
SiO2: V
Al2O3=2: 3) sieve catalyst, be added dropwise to complete the back and in reacting kettle jacketing, add steam, make its temperature reach 48-50 ℃, keep watch on the water-content in the permeable separator, when it reached 1.76 liters of left and right sides, stopped reaction was reduced to room temperature, elimination SiO
2/ Al
2O
3Molecular sieve obtains the Trifluoroacetic Acid Ethyl Ester bullion.The saturated aqueous sodium carbonate that in the Trifluoroacetic Acid Ethyl Ester bullion, adds its volume and be 3.7 times of reaction solutions extracts; Remove trifluoroacetic acid, water and the ethanol that possibly have, the saturated sodium-chloride water solution with 2.4 times of reaction solution volumes washs again, air distillation after an amount of solid carbonic acid potassium drying; Collect 60-62 ° of cut; Normal temperature carries out air distillation with the Vanadium Pentoxide in FLAKES drying down again, collects 60-62 ° of cut, 11.51 kilograms of last Trifluoroacetic Acid Ethyl Esters; Molar yield is 82%, and Trifluoroacetic Acid Ethyl Ester purity reaches more than 99.7%.
Embodiment 2
11.4 kilograms of trifluoroacetic acids are put into reaction kettle, open and stir, the operation of lowering the temperature, slow Dropwise 5 .98 kilogram absolute ethyl alcohol in reaction kettle, the dropping time is 0.6 hour, adds 3.45 kilograms SiO then
2/ Al
2O
3(V
SiO2: V
Al2O3=5: 1) sieve catalyst, be added dropwise to complete the back and in reacting kettle jacketing, add steam, make its temperature reach 48-50 ℃, keep watch on the water-content in the permeable separator, when it reached 1.76 liters of left and right sides, stopped reaction was reduced to room temperature, elimination SiO
2/ Al
2O
3Molecular sieve obtains the Trifluoroacetic Acid Ethyl Ester bullion.The saturated aqueous sodium carbonate that in the Trifluoroacetic Acid Ethyl Ester bullion, adds its volume and be 3 times of reaction solutions extracts; Remove trifluoroacetic acid, water and the ethanol that possibly have, the saturated sodium-chloride water solution with 3 times of reaction solution volumes washs again, air distillation after an amount of solid carbonic acid potassium drying; Collect 60-62 ° of cut; Normal temperature carries out air distillation with the Vanadium Pentoxide in FLAKES drying down again, collects 60-62 ° of cut, 11.37 kilograms of last Trifluoroacetic Acid Ethyl Esters; Molar yield is 80%, and Trifluoroacetic Acid Ethyl Ester purity reaches more than 99.7%.
Claims (7)
1. the present invention relates to a kind of synthesis technique of Trifluoroacetic Acid Ethyl Ester, it is characterized in that, comprise the steps:
(1) trifluoroacetic acid is put into reaction kettle; Open and stir, the operation of lowering the temperature slowly drips the ethanol that measures in reaction kettle; Add an amount of sieve catalyst then; Be added dropwise to complete the back and in reacting kettle jacketing, add steam, make its temperature reach temperature of reaction, finishing with question response in the reaction promptly obtains the Trifluoroacetic Acid Ethyl Ester bullion;
(2) in the Trifluoroacetic Acid Ethyl Ester bullion, adding inorganic salt solution extracts; Remove trifluoroacetic acid, water and ethanol,, after dry, distill again with the saturated sodium-chloride water solution washing; Collect middle runnings; Normal temperature distills with acid siccative down again, collects middle runnings, and the Trifluoroacetic Acid Ethyl Ester purity of gained is more than 99.5%.
2. the present invention relates to a kind of compound method of Trifluoroacetic Acid Ethyl Ester, it is characterized in that in claim 1 step (1), carry out towards positive dirction, load permeable separator, the water of drawing esterification timely and being generated on the reaction kettle next door for guaranteeing esterification.
3. the present invention relates to a kind of compound method of Trifluoroacetic Acid Ethyl Ester, it is characterized in that the sieve catalyst of claim 1 step (1) indication comprises AlPO
4, different ratios SiO
2/ Al
2O
3Deng.
4. the present invention relates to a kind of compound method of Trifluoroacetic Acid Ethyl Ester, it is characterized in that the temperature of reaction of claim 1 step (1) indication is 48-50 ℃.
5. the present invention relates to a kind of compound method of Trifluoroacetic Acid Ethyl Ester, it is characterized in that the inorganic salt solution that claim 1 step (2) is proposed refers to saturated aqueous sodium carbonate, saturated sodium bicarbonate aqueous solution, unsaturated carbonate aqueous solutions of potassium etc.
6. the present invention relates to a kind of compound method of Trifluoroacetic Acid Ethyl Ester, it is characterized in that the acid siccative that claim 1 step (2) is proposed is a Vanadium Pentoxide in FLAKES.
7. the present invention relates to a kind of compound method of Trifluoroacetic Acid Ethyl Ester, it is characterized in that SiO in the claim 3
2/ Al
2O
3Volume ratio be 1: 1～20.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012100987334A CN102633639A (en) | 2012-04-06 | 2012-04-06 | Synthesis process for trifluoroacetic acid ethyl ester |
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| CN2012100987334A CN102633639A (en) | 2012-04-06 | 2012-04-06 | Synthesis process for trifluoroacetic acid ethyl ester |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108530295A (en) * | 2018-04-28 | 2018-09-14 | 江苏新东风化工科技有限公司 | A kind of technique of the acrylic acid N-butyl from waste oil |
| CN110343043A (en) * | 2018-04-04 | 2019-10-18 | 浙江蓝天环保高科技股份有限公司 | A kind of purification process of Trifluoroacetic Acid Ethyl Ester |
| CN113912499A (en) * | 2021-11-29 | 2022-01-11 | 八叶草健康产业研究院(厦门)有限公司 | 4-fluoro-5-hydroxy-2-nitrobenzoic acid methyl ester |
-
2012
- 2012-04-06 CN CN2012100987334A patent/CN102633639A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110343043A (en) * | 2018-04-04 | 2019-10-18 | 浙江蓝天环保高科技股份有限公司 | A kind of purification process of Trifluoroacetic Acid Ethyl Ester |
| CN108530295A (en) * | 2018-04-28 | 2018-09-14 | 江苏新东风化工科技有限公司 | A kind of technique of the acrylic acid N-butyl from waste oil |
| CN113912499A (en) * | 2021-11-29 | 2022-01-11 | 八叶草健康产业研究院(厦门)有限公司 | 4-fluoro-5-hydroxy-2-nitrobenzoic acid methyl ester |
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Application publication date: 20120815 |