CN108947834A - A kind of synthetic method of Trifluoroacetic Acid Ethyl Ester - Google Patents
A kind of synthetic method of Trifluoroacetic Acid Ethyl Ester Download PDFInfo
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- CN108947834A CN108947834A CN201810785698.0A CN201810785698A CN108947834A CN 108947834 A CN108947834 A CN 108947834A CN 201810785698 A CN201810785698 A CN 201810785698A CN 108947834 A CN108947834 A CN 108947834A
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- trifluoroacetic acid
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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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- 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
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- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention relates to a kind of synthetic method of Trifluoroacetic Acid Ethyl Ester, the raw material in synthetic method is trifluoroacetic acid and dehydrated alcohol, and catalyst is solid acid catalyst.Present invention process is simple, and equipment requirement is simple, and thoroughly, purity is 99.5% or more for reaction, and molar yield is 98.0% or more, and solid acid catalyst can be recycled after drying, and activity is not decreased obviously, and the dosage of catalyst is few；Overall cost control of the present invention is relatively low, is suitble to industrialized production.
Description
Technical field
The present invention relates to a kind of synthetic methods of Trifluoroacetic Acid Ethyl Ester, belong to chemosynthesis technical field.
Background technique
Trifluoroacetic Acid Ethyl Ester, F3CCOOCH2CH3It is a kind of important Organic Chemicals, is mainly used for synthesizing organic fluoride
It closes and object and prepares pesticide, medicine, dyestuff, the industrial chemicals such as liquid crystal are widely used.In medicine for manufacturing treatment rheumatoid
Property arthritis and osteoarthritis anti-inflammatory agent and for treat knot, the carcinoma of the rectum antineoplastic.For manufacturing born of the same parents' division on pesticide
Inhibitor is used for cotton, removes grass family herbicide standing grain broadleaf weeds to peanut.Development and application prospect is wide, and supply falls short of demand in market.
In the prior art, the synthetic method of Trifluoroacetic Acid Ethyl Ester is mainly the following.
(1) it is reacted and is obtained with dehydrated alcohol with sulphuric acid catalysis trifluoroacetic acid, but this method environmental pollution is big, production is set
Standby seriously corroded, the sulfuric acid after catalysis are difficult to be recycled.
(2) it is reacted, is flowed back 2 hours, drying is distilled with dehydrated alcohol with Catalyzed by p-Toluenesulfonic Acid trifluoroacetic acid
Trifluoroacetic Acid Ethyl Ester, yield only have 75.9%.
(3) using trifluoroacetic acid and dehydrated alcohol as primary raw material, using storng-acid cation exchange resin as catalyst, pass through
It is added dropwise, esterification, cold filtration catalyst, silica dehydrator, desired product is made in distillation key step.Then this method is with acid
Property cation exchange resin be catalyst, it is every to be declined to a great extent using primary activity although can be recycled after processing,
New cation exchange resin, which must be added, can be only achieved ideal esterification effect.
Separately there are trifluoro-acetic fluoride and ethyl alcohol, fluorination nak response to prepare Trifluoroacetic Acid Ethyl Ester, the method trifluoro-acetic fluoride raw material
Seldom, and hazard of gas is big, is not suitable for industrialized production, generating a large amount of potassium bifluoride solid can not be handled.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of synthetic method of Trifluoroacetic Acid Ethyl Ester, synthetic method operation letter
It is single, easily controllable, safety and environmental protection, high income, purity is high, and production cost is low.Technical scheme is as follows:
A kind of synthetic method of Trifluoroacetic Acid Ethyl Ester, raw material are trifluoroacetic acid and dehydrated alcohol, and catalyst is solid acid.Institute
Stating solid catalyst is phosphoric acid and sulfonic acid+SiO2(manufacturer: Suzhou Huan Ke new material Co., Ltd, sour load value is about
0.8mmol/g), i.e. the mixture of phosphoric acid and sulfonic acid is carried on silica.
Steps are as follows:
Trifluoroacetic acid and dehydrated alcohol are the mixing of 1:1.05-1.1 ratio in molar ratio, and solid acid catalysis is added and is esterified, three
The molar ratio 1:0.002-0.008 of fluoroacetic acid and solid acid catalyst；Reaction generates trifluoroacetic acid second under the conditions of 20-50 DEG C
Ester；Its reaction equation is as follows:
Specific step is as follows:
Trifluoroacetic acid and dehydrated alcohol are the ratio mixing of 1:1.05-1.1 in molar ratio, and solid acid catalysis esterification is added,
The molar ratio of trifluoroacetic acid and solid acid catalyst is 1:0.005, under the conditions of 20-50 DEG C, is reacted to the content of trifluoroacetic acid
It less than 0.5% (mass fraction), stands, removes moisture content；It adds solid acid catalyst and carries out catalytic esterification, trifluoro second before reacting
Acid is 1:0.002 with the molar ratio for adding solid acid catalyst, is reacted to the content of trifluoroacetic acid less than 0.1% (quality point
Number), end of reaction carries out rectifying, receives 60-62 DEG C of product, i.e. Trifluoroacetic Acid Ethyl Ester.
Further, trifluoroacetic acid and ethyl alcohol are mixed in 1:1.05 ratio；Reaction temperature is 30 DEG C.
Solid acid can be recycled after drying and dehydrating activates in the present invention.
Compared with the prior art, the present invention has the following advantages:
Present invention process is simple, and equipment requirement is simple, and thoroughly, purity is 99.5% or more, and molar yield is (with trifluoro for reaction
Acetometer) it is 98.0% or more, solid acid catalyst can be recycled after drying, and activity is not decreased obviously, catalyst
Dosage it is few；Overall cost control of the present invention is relatively low, is suitble to industrialized production.
Specific embodiment
The invention will now be further described with reference to specific embodiments, the advantages and features of the present invention will be with description and
It is apparent.But examples are merely exemplary, and it is not intended to limit the scope of the present invention in any way.Those skilled in the art answer
It should be appreciated that without departing from the spirit and scope of the invention can details to technical solution of the present invention and form repair
Change or replace, but these modifications and replacement are fallen within the protection scope of the present invention.
Reaction equation of the invention are as follows:
A kind of synthetic method of the Trifluoroacetic Acid Ethyl Ester of example 1
100 grams of (0.877mol) trifluoroacetic acids are thrown, 42.5 grams of dehydrated alcohol (0.922mol), three mouthfuls in 500 milliliters are burnt
In bottle, 5.5 grams of reinforcing body acid catalyst (4.4mmol, every gram of solid acid catalyst molal quantity are 0.8mmol) opens stirring 20
DEG C insulation reaction 8 hours, sample detection, trifluoroacetic acid 0.48% stopped stirring, removed lower part moisture content using separatory funnel,
The top bed of material is transferred in three-necked flask, puts into 2.2 grams of solid acid catalyst, and opening 20 DEG C of stirring, the reaction was continued 1 hour, sampling inspection
It surveys, trifluoroacetic acid 0.08%, end of reaction is poured into feed liquid in another 500 milliliters of three-necked flask, and flask assembles 40 centimetres
The rectifying column (glass spring filler) of 24# bore, starting stirring, heat up rectifying；The distillate for receiving 60-62 DEG C, obtains trifluoro second
122.7 grams of acetoacetic ester (molar yield 98.5%), purity 99.5% has been distilled, and a small amount of residue is mainly that ethyl alcohol is applied in kettle
Lower batch.Solid acid catalyst is put into 100 DEG C of drying box drying, is recycled.
A kind of synthetic method of the Trifluoroacetic Acid Ethyl Ester of example 2
100 grams of (0.877mol) trifluoroacetic acids are thrown, 42.5 grams of dehydrated alcohol (0.922mol), three mouthfuls in 500 milliliters are burnt
In bottle, 5.5 grams of reinforcing body acid catalyst, opens and stir 30 DEG C insulation reaction 4 hours, sample detection, trifluoroacetic acid 0.42% (is wanted
It asks less than 0.5%), stopping to stir, pours into separatory funnel point and remove lower part water, the top bed of material is transferred in three-necked flask, puts into solid acid
2.2 grams of catalyst, opening 20 DEG C of stirring, the reaction was continued 1 hour, sample detection, trifluoroacetic acid 0.05% (it is required that less than 0.1%),
End of reaction is poured into feed liquid in another 500 milliliters of three-necked flask, and flask assembles the rectifying column (glass of 40 centimetres of 24# bores
Spring filler), starting stirring, heat up rectifying；The distillate for receiving 60-62 DEG C obtains 122.8 grams of Trifluoroacetic Acid Ethyl Ester (mole receipts
Rate 98.5%), purity 99.6% has been distilled, and a small amount of residue is mainly that ethyl alcohol is applied down batch in kettle.Solid acid catalyst is put into
100 DEG C of drying box drying, are recycled.
A kind of synthetic method of the Trifluoroacetic Acid Ethyl Ester of example 3
100 grams of (0.877mol) trifluoroacetic acids are thrown, 42.5 grams of dehydrated alcohol (0.922mol), three mouthfuls in 500 milliliters are burnt
In bottle, 8.0 grams of reinforcing body acid catalyst, opens and stir 30 DEG C insulation reaction 2 hours, sample detection, trifluoroacetic acid 0.45% (is wanted
It asks less than 0.5%), stopping to stir, pours into separatory funnel point and remove lower part water, the top bed of material is transferred in three-necked flask, puts into solid acid
2.2 grams of catalyst, opening 20 DEG C of stirring, the reaction was continued 1 hour, sample detection, trifluoroacetic acid 0.04% (it is required that less than 0.1%),
End of reaction is poured into feed liquid in another 500 milliliters of three-necked flask, and flask assembles the rectifying column (glass of 40 centimetres of 24# bores
Spring filler), starting stirring, heat up rectifying；The distillate for receiving 60-62 DEG C obtains 123.0 grams of Trifluoroacetic Acid Ethyl Ester (mole receipts
Rate 98.6%), purity 99.6% has been distilled, and a small amount of residue is mainly that ethyl alcohol is applied down batch in kettle.Solid acid catalyst is put into
100 DEG C of drying box drying, are recycled.
A kind of synthetic method of the Trifluoroacetic Acid Ethyl Ester of example 4
100 grams of (0.877mol) trifluoroacetic acids are thrown, 44.5 grams of dehydrated alcohol (0.966mol), three mouthfuls in 500 milliliters are burnt
In bottle, 5.5 grams of reinforcing body acid catalyst, opens and stir 30 DEG C insulation reaction 3 hours, sample detection, trifluoroacetic acid 0.45% (is wanted
It asks less than 0.5%), stopping to stir, pours into separatory funnel point and remove lower part water, the top bed of material is transferred in three-necked flask, puts into solid acid
2.2 grams of catalyst, opening 30 DEG C of stirring, the reaction was continued 1 hour, sample detection, trifluoroacetic acid 0.03% (it is required that less than 0.1%),
End of reaction is poured into feed liquid in another 500 milliliters of three-necked flask, and flask assembles the rectifying column (glass of 40 centimetres of 24# bores
Spring filler), starting stirring, heat up rectifying；The distillate for receiving 60-62 DEG C obtains 123.2 grams of Trifluoroacetic Acid Ethyl Ester (mole receipts
Rate 98.7%), purity 99.2% has been distilled, and a small amount of residue is mainly that ethanol impurity is applied down batch in kettle.Solid acid catalyst
100 DEG C of drying box drying are put into, are recycled.
A kind of synthetic method of the Trifluoroacetic Acid Ethyl Ester of example 5
100 grams of (0.877mol) trifluoroacetic acids are thrown, 42.5 grams of dehydrated alcohol (0.922mol), three mouthfuls in 500 milliliters are burnt
In bottle, 4.0 grams of reinforcing body acid catalyst, opens and stir 50 DEG C insulation reaction 2 hours, sample detection, trifluoroacetic acid 0.47% (is wanted
It asks less than 0.5%), stopping to stir, pours into separatory funnel point and remove lower part water, the top bed of material is transferred in three-necked flask, puts into solid acid
2.2 grams of catalyst, opening 30 DEG C of stirring, the reaction was continued 1 hour, sample detection, trifluoroacetic acid 0.05% (it is required that less than 0.1%),
End of reaction is poured into feed liquid in another 500 milliliters of three-necked flask, and flask assembles the rectifying column (glass of 40 centimetres of 24# bores
Spring filler), starting stirring, heat up rectifying；The distillate for receiving 60-62 DEG C obtains 121.1 grams of Trifluoroacetic Acid Ethyl Ester (mole receipts
Rate 97.2%), purity 99.2% has been distilled, and a small amount of residue is mainly that ethyl alcohol is applied down batch in kettle.
Solid acid catalyst is put into 100 DEG C of drying box drying, is recycled；Activity through detecting solid acid catalyst does not have
It is decreased obviously.
Claims (7)
1. a kind of synthetic method of Trifluoroacetic Acid Ethyl Ester, which is characterized in that raw material in synthetic method be trifluoroacetic acid with it is anhydrous
Ethyl alcohol, catalyst are solid acid catalyst.
2. synthetic method according to claim 1, which is characterized in that the solid catalyst is phosphoric acid and sulfonic acid+SiO2,
Wherein, i.e. the mixture of phosphoric acid and sulfonic acid is carried on silica.
3. synthetic method according to claim 1, which is characterized in that the sour load value of the solid catalyst is 0.8mmol/
g。
4. synthetic method according to claim 1-3, which is characterized in that steps are as follows:
Trifluoroacetic acid and dehydrated alcohol are the mixing of 1:1.05-1.1 ratio in molar ratio, and solid acid catalysis esterification, trifluoro second is added
The molar ratio 1:0.002-0.008 of acid and solid acid catalyst；Reaction generates Trifluoroacetic Acid Ethyl Ester under the conditions of 20-50 DEG C；Its
Reaction equation is as follows:
5. synthesis technology according to claim 4, which is characterized in that specific step is as follows:
Trifluoroacetic acid and dehydrated alcohol are the ratio mixing of 1:1.05-1.1 in molar ratio, and solid acid catalysis esterification, trifluoro is added
The molar ratio of acetic acid and solid acid catalyst is 1:0.005, under the conditions of 20-50 DEG C, reacts to the content of trifluoroacetic acid and is less than
0.5% (mass fraction) is stood, and removes moisture content；Add solid acid catalyst carry out catalytic esterification, react before trifluoroacetic acid with
The molar ratio for adding solid acid catalyst is 1:0.002, reacts the content to trifluoroacetic acid less than 0.1% (mass fraction),
End of reaction carries out rectifying, receives 60-62 DEG C of product, i.e. Trifluoroacetic Acid Ethyl Ester.
6. synthetic method according to claim 5, which is characterized in that trifluoroacetic acid and ethyl alcohol are mixed by 1:1.05 molar ratio
It closes.
7. synthetic method according to claim 5, which is characterized in that reaction temperature is 30 DEG C.
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| CN201810785698.0A CN108947834A (en) | 2018-07-17 | 2018-07-17 | A kind of synthetic method of Trifluoroacetic Acid Ethyl Ester |
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| CN201810785698.0A CN108947834A (en) | 2018-07-17 | 2018-07-17 | A kind of synthetic method of Trifluoroacetic Acid Ethyl Ester |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021179458A1 (en) * | 2020-03-13 | 2021-09-16 | 湘潭大学 | Inorganic solid silicon-based sulfonic acid and/or phosphoric acid catalyst, preparation method therefor, and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4879407A (en) * | 1986-10-16 | 1989-11-07 | Rhone-Poulenc Chimie | Process for the preparation of ethyl trifluoroacetate |
| CN1208032A (en) * | 1997-08-13 | 1999-02-17 | 中国石化齐鲁石油化工公司 | Preparation of acrylate or higher methyl acrylate |
| CN106431908A (en) * | 2016-09-19 | 2017-02-22 | 南通宝凯化工有限公司 | Ethyl trifluoroacetate preparation method |
-
2018
- 2018-07-17 CN CN201810785698.0A patent/CN108947834A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4879407A (en) * | 1986-10-16 | 1989-11-07 | Rhone-Poulenc Chimie | Process for the preparation of ethyl trifluoroacetate |
| CN1208032A (en) * | 1997-08-13 | 1999-02-17 | 中国石化齐鲁石油化工公司 | Preparation of acrylate or higher methyl acrylate |
| CN106431908A (en) * | 2016-09-19 | 2017-02-22 | 南通宝凯化工有限公司 | Ethyl trifluoroacetate preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 黄小磊 等: "一种三氟乙酸乙酯的制备工艺", 《浙江化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021179458A1 (en) * | 2020-03-13 | 2021-09-16 | 湘潭大学 | Inorganic solid silicon-based sulfonic acid and/or phosphoric acid catalyst, preparation method therefor, and application thereof |
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Application publication date: 20181207 |