CN105418415B - A kind of preparation method of 3,3,3 trifluoroacetic acid ethyl ester - Google Patents
A kind of preparation method of 3,3,3 trifluoroacetic acid ethyl ester Download PDFInfo
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- CN105418415B CN105418415B CN201510731098.2A CN201510731098A CN105418415B CN 105418415 B CN105418415 B CN 105418415B CN 201510731098 A CN201510731098 A CN 201510731098A CN 105418415 B CN105418415 B CN 105418415B
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- trifluoroacetic acid
- acid ethyl
- trifluoroacetic
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- 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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Abstract
The present invention provides a kind of preparation method of 3,3,3 trifluoroacetic acid ethyl ester.This method, for raw material, synthesizes 3,3,3 trifluoroacetic acid ethyl esters with 3,3,3 trifluoroacetic acids and ethanol under Tungstenic compound catalytic action.Environment-friendly, three-waste free pollution of the invention, catalytic selectivity is high, and catalyst is easily isolated and recyclable, with good industrial applications prospect.
Description
Technical field
It is original with 3,3,3- trifluoroacetic acids and ethanol the present invention relates to a kind of preparation method of 3,3,3- trifluoroacetic acid ethyl esters
Material, synthesizes 3,3,3- trifluoroacetic acid ethyl esters under Tungstenic compound catalytic action.
Background technology
Fluorinated organic compound has unique physics, chemical property and physiologically active, thus in fields such as medicine, agricultural chemicals
It is widely used.It is a kind of normal of synthesis fluorinated organic compound to introduce fluorine atom into organic molecule by fluoro-building block
Use method.In recent years, containing CF3The C of group3Fluoro-building block obtains development quickly, wherein 3,3,3- trifluoroacetic acid ethyl esters are used as one
New fluoro-building block is planted, gradually applied in fluorine-containing medicines, the synthesis of agricultural chemicals, it has also become one of important fluoro-containing intermediate.
The prior synthesizing method of 3,3,3- trifluoroacetic acid ethyl esters is, for raw material, to be urged in nothing with 3,3,3- trifluoroacetic acids and ethanol
Prepared when during agent or using the concentrated sulfuric acid as catalyst.During without catalyst, the conversion ratio of 3,3,3- trifluoroacetic acids is relatively low.With dense
When sulfuric acid is catalyst, catalytic activity is higher, but has the following disadvantages：The concentrated sulfuric acid has strong corrosivity, corrosive equipment；
The concentrated sulfuric acid is not easy to separation, it is difficult to recycling as homogeneous catalyst, and the spent acid produced easily causes environmental pollution；It is dense
The strong oxidizing property and dehydration property of sulfuric acid can cause the generation of the side reactions such as sulfuric ester, ether or unsaturated compound, 3,3,3- trifluoros
Ethyl propionate is selectively 97% or so, so as to bring difficulty for further refined and raw materials recovery.Therefore, it is necessary to find
A kind of new 3,3,3- trifluoroacetic acids ethyl ester preparation method efficiently, green, environmentally friendly.
The content of the invention
In order to solve shortcomings and deficiencies of the prior art, the present invention provides a kind of environment-friendly, three-waste free pollution, catalysis choosing
Selecting property is high, and catalyst is easily isolated and recyclable 3, the preparation method of 3,3- trifluoroacetic acid ethyl esters.
In order to realize the purpose of the present invention, the present invention with 3,3,3- trifluoroacetic acids and ethanol for raw material, in Tungstenic compound
3,3,3- trifluoroacetic acid ethyl esters are synthesized under catalytic action, wherein Tungstenic compound is tungsten oxide, may be selected from WO3、WO3·H2O、
WO3·0.33H2O、WO2.90Or WO2.72In one or more.
In the present invention, catalyst and 3, the mass ratio of 3,3- trifluoroacetic acids is 0.01~0.1:1；3,3,3- trifluoroacetic acids with
The mol ratio of ethanol is 1:1.0~1.5；Reaction temperature is 55~95 DEG C, preferably 70~90 DEG C；Reaction time is 4~24h,
Preferably 6~8h.
Catalyst involved in the present invention synthesizes 3,3,3- trifluoroacetic acid ethyl esters with ethanol suitable for 3,3,3- trifluoroacetic acids.Instead
Rear catalyst, which should be terminated, to be separated using methods such as centrifugation, suction filtration or standing decantations with product.
Compared with prior art, beneficial effects of the present invention are as follows：
(1) present invention without using the concentrated sulfuric acid as catalyst, environment-friendly, three-waste free pollution；(2) it is used herein
Catalyst exists in reaction system in solid form, and the separation and recovery of catalyst are achieved that by simple separation of solid and liquid；
(3) selectivity of the trifluoroacetic acid ethyl ester of product 3,3,3- of the present invention is more than 99.9%, and 3,3,3- trifluoroacetic acid conversion ratios are more than
80.8%.
Embodiment
The invention will be further described by the following examples, but the present invention is not limited by the following example.
Embodiment 1
0.08g WO are sequentially added in the reactor3, 6.40g trifluoroacetic acids and 3.50g ethanol, control mixing speed
600r/min, stirring 10min are cooled to room temperature to well mixed after being warming up to 85 DEG C, reaction 7h, by gained reaction solution at a high speed from
The heart, incline to obtain clear liquid, and 3,3,3- trifluoroacetic acid conversion ratios are 88.0%, and 3,3,3- trifluoroacetic acid ethyl esters are selectively 99.9%.
Product structure is identified：
MS, m/z：157 (M+), 111 (100).
IR (KBr), υ/cm-1：3479,2990,1753.
Said structure appraising datum confirms that the material is strictly 3,3,3- trifluoroacetic acid ethyl esters.
Embodiment 2
0.64g WO are sequentially added to reactor2.72, in 6.40g trifluoroacetic acids and 3.50g ethanol, control mixing speed
400r/min, stirring 30min are cooled to room temperature after being warming up to 55 DEG C, reaction 24h, gained reaction solution are stood to well mixed
Decantation, takes its clear liquid, and 3,3,3- trifluoroacetic acid conversion ratios are 82.0%, and 3,3,3- trifluoroacetic acid ethyl esters are selectively 99.9%.
Embodiment 3
0.06g WO are sequentially added in the reactor2.72And 0.06g WO3, 6.40g trifluoroacetic acids and 3.50g ethanol, control
Mixing speed 800r/min, stirring is cooled to room temperature to well mixed after being warming up to 70 DEG C, reaction 8h, and gained reaction solution is high
Speed centrifugation, takes its clear liquid, and 3,3,3- trifluoroacetic acid conversion ratios are 82.3%, and 3,3,3- trifluoroacetic acid ethyl esters are selectively
99.9%.
Embodiment 4
Take about 150g sodium tungstates and 225g water in three-necked flask, be heated to after 90 DEG C, be slowly added to the dense HCl of 120ml, stir
Mix after 24h, generate bright yellow solid, disperse and settle washing to centrifuge afterwards for several times using hot water, be placed in 120 DEG C of constant temperature drying 12h,
Take out, ground to 200 mesh powder samples, as WO after Temperature fall3·0.33H2O catalyst.
The catalyst, 6.40g trifluoroacetic acids and 2.30g ethanol of the above-mentioned preparations of 0.32g are sequentially added in the reactor, are controlled
Mixing speed 600r/min, stirring 10min are cooled to room temperature after being warming up to 95 DEG C, reaction 4h, gained are reacted to well mixed
Liquid high speed centrifugation, takes its clear liquid, and 3,3- trifluoroacetic acid conversion ratios are 77.4%, and 3,3,3- trifluoroacetic acid ethyl esters are selectively
99.9%.
Embodiment 5
The catalyst WO of the preparation of 0.32g embodiments 2 is sequentially added in the reactor2.90, 6.40g trifluoroacetic acids and 3.50g
Ethanol, controls mixing speed 600r/min, stirs, and room temperature is cooled to after being warming up to 90 DEG C, reaction 4h, by gained reaction solution
High speed centrifugation, takes its clear liquid, and 3,3,3- trifluoroacetic acid conversion ratios are 81.3%, and 3,3,3- trifluoroacetic acid ethyl esters are selectively
99.9%.
Embodiment 6
The catalyst that embodiment 5 is isolated washs through ethanol, dry after, 6h weights are calcined in 500 DEG C of air atmospheres
Use again.3,3,3- trifluoroacetic acid conversion ratios are 80.8%, and 3,3,3- trifluoroacetic acid ethyl esters are selectively 99.9%, and activity does not have
Substantially reduction, illustrates that this catalyst is reusable.
Claims (2)
1. one kind 3,3, the preparation method of 3- trifluoroacetic acid ethyl esters, it is characterised in that with 3,3,3- trifluoroacetic acids and ethanol be original
Material, synthesizes 3,3,3- trifluoroacetic acid ethyl esters under Tungstenic compound catalytic action；Reaction condition is catalyst and 3,3,3- trifluoros
The mass ratio of propionic acid is 0.01~0.1:1；The mol ratio of 3,3,3- trifluoroacetic acids and ethanol is 1:1.0~1.5；Reaction temperature is
55~95 DEG C；Reaction time is 4~24h；Wherein Tungstenic compound is WO3、WO3·H2O、WO3·0.33H2O、WO2.90Or
WO2.72In one or more.
2. the preparation method of according to claim 13,3,3- trifluoroacetic acid ethyl esters, it is characterised in that reaction temperature is 70
~90 DEG C；Reaction time is 6~8h.
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| CN105418415B true CN105418415B (en) | 2017-08-08 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104326915A (en) * | 2014-09-30 | 2015-02-04 | 扬州大学 | Method for synthesizing ethyl p-hydroxybenzoate through catalysis of modified metal oxide type solid super acid |
| WO2015068487A1 (en) * | 2013-11-07 | 2015-05-14 | 関東電化工業株式会社 | Ester having 3,3,3-trifluoropropionate group and method for producing same |
| CN104710308A (en) * | 2015-02-10 | 2015-06-17 | 南京齐正化学有限公司 | Synthesis method of ethyl trifluoroacetate |
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| TWM275434U (en) * | 2005-01-10 | 2005-09-11 | Delta Electronics Inc | Adjustable light source apparatus for projection system |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015068487A1 (en) * | 2013-11-07 | 2015-05-14 | 関東電化工業株式会社 | Ester having 3,3,3-trifluoropropionate group and method for producing same |
| CN104326915A (en) * | 2014-09-30 | 2015-02-04 | 扬州大学 | Method for synthesizing ethyl p-hydroxybenzoate through catalysis of modified metal oxide type solid super acid |
| CN104710308A (en) * | 2015-02-10 | 2015-06-17 | 南京齐正化学有限公司 | Synthesis method of ethyl trifluoroacetate |
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