CN105418415A - Method for preparing 3,3,3-trifluoro ethyl propionate - Google Patents
Method for preparing 3,3,3-trifluoro ethyl propionate Download PDFInfo
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- CN105418415A CN105418415A CN201510731098.2A CN201510731098A CN105418415A CN 105418415 A CN105418415 A CN 105418415A CN 201510731098 A CN201510731098 A CN 201510731098A CN 105418415 A CN105418415 A CN 105418415A
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- China
- Prior art keywords
- trifluoroacetic acid
- acid ethyl
- ethyl ester
- ethanol
- ethyl propionate
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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
Abstract
The invention provides a method for preparing 3,3,3-trifluoro ethyl propionate. According to the method, 3,3,3-trifluoro ethyl propionate is synthesized from 3,3,3-trifluoro propionic acid and ethanol, which serve as raw materials, under the catalysis of a tungsten-containing compound. The method is environment-friendly and is free of pollution caused by waste gases, waste water and waste residues, the catalytic selectivity is high, and the catalyst is easy to separate and can be recovered, so that the method has a good industrial application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of 3,3,3-trifluoroacetic acid ethyl ester, with 3,3,3-trifluoroacetic acid with ethanol for raw material, synthesis 3,3,3-trifluoroacetic acid ethyl ester under Tungstenic compound katalysis.
Background technology
Fluorinated organic compound has unique physics, chemical property and physiologically active, is thus widely used in fields such as medicine, agricultural chemicals.By fluoro-building block to introducing a kind of common method that fluorine atom is synthesis fluorinated organic compound in organic molecule.In recent years, containing CF
3the C of group
3fluoro-building block obtains very fast development, and wherein 3,3,3-trifluoroacetic acid ethyl esters are as a kind of novel fluoro-building block, is applied in the synthesis of fluorine-containing medicines, agricultural chemicals gradually, has become one of important fluoro-containing intermediate.
The prior synthesizing method of 3,3,3-trifluoroacetic acid ethyl ester be with 3,3,3-trifluoroacetic acid and ethanol for raw material, prepare when being catalyzer when catalyst-free or with the vitriol oil.During catalyst-free, the transformation efficiency of 3,3,3-trifluoroacetic acid is lower.When taking the vitriol oil as catalyzer, catalytic activity is higher, but there is following shortcoming: the vitriol oil has strong corrodibility, corrosive equipment; The vitriol oil, as homogeneous catalyst, is not easy to be separated, is difficult to recycling, and the spent acid produced easily causes environmental pollution; The strong oxidizing property of the vitriol oil and dehydration property can cause the generation of the side reactions such as sulfuric ester, ether or unsaturated compound, and 3,3,3-trifluoroacetic acid ethyl ester selectivity are about 97%, thus bring difficulty for further refining with raw materials recovery.Therefore, be necessary that searching is a kind of efficiently, green, novel 3,3, the 3-trifluoroacetic acid ethyl ester preparation methods of environmental protection.
Summary of the invention
In order to solve shortcomings and deficiencies of the prior art, the invention provides a kind of environmental friendliness, three-waste free pollution, catalytic selectivity is high, and catalyzer is easy to be separated and the preparation method of returnable 3,3,3-trifluoroacetic acid ethyl esters.
In order to realize object of the present invention, the present invention is with 3,3,3-trifluoroacetic acid and ethanol for raw material, and under Tungstenic compound katalysis, synthesize 3,3,3-trifluoroacetic acid ethyl ester, wherein Tungstenic compound is tungsten oxide, can be selected from WO
3, WO
3h
2o, WO
30.33H
2o, WO
2.90or WO
2.72in one or more.
In the present invention, the mass ratio of catalyzer and 3,3,3-trifluoroacetic acid is 0.01 ~ 0.1:1; The mol ratio of 3,3,3-trifluoroacetic acid and ethanol is 1:1.0 ~ 1.5; Temperature of reaction is 55 ~ 95 DEG C, is preferably 70 ~ 90 DEG C; Reaction times is 4 ~ 24h, is preferably 6 ~ 8h.
Catalyzer involved in the present invention is applicable to 3,3,3-trifluoroacetic acid and ethanol synthesizes 3,3,3-trifluoroacetic acid ethyl ester.Reaction terminates rear catalyst can adopt method and the product separations such as centrifugal, suction filtration or standing decant.
Compared with prior art, beneficial effect of the present invention is as follows:
(1) the present invention is without the need to using the vitriol oil as catalyzer, environmental friendliness, three-waste free pollution; (2) catalyzer used herein exists in reaction system in solid form, just can be realized separation and the recovery of catalyzer by simple solid-liquid separation; (3) selectivity of product 3,3,3-trifluoroacetic acid ethyl ester of the present invention is greater than 99.9%, 3,3,3-trifluoroacetic acid transformation efficiency and is greater than 80.8%.
Embodiment
The invention will be further described by the following examples, but the present invention is not by the restriction of the following example.
Embodiment 1
Add 0.08gWO successively in the reactor
3, 6.40g trifluoroacetic acid and 3.50g ethanol, controlling stirring velocity 600r/min, stirring 10min to mixing, be warmed up to 85 DEG C, be cooled to room temperature after reaction 7h, by gained reaction solution high speed centrifugation, incline to obtain clear liquid, 3,3,3-trifluoroacetic acid transformation efficiency is 88.0%, 3,3,3-trifluoroacetic acid ethyl ester selectivity is 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, this material is 3,3,3-trifluoroacetic acid ethyl ester really.
Embodiment 2
0.64gWO is added successively to reactor
2.72, in 6.40g trifluoroacetic acid and 3.50g ethanol, controlling stirring velocity 400r/min, stirring 30min to mixing, be warmed up to 55 DEG C, be cooled to room temperature after reaction 24h, decant left standstill to gained reaction solution, gets its clear liquid, 3,3,3-trifluoroacetic acid transformation efficiency is 82.0%, 3,3,3-trifluoroacetic acid ethyl ester selectivity is 99.9%.
Embodiment 3
Add 0.06gWO successively in the reactor
2.72and 0.06gWO
3, 6.40g trifluoroacetic acid and 3.50g ethanol, control stirring velocity 800r/min, be stirred to and mix, be warmed up to 70 DEG C, be cooled to room temperature after reaction 8h, by gained reaction solution high speed centrifugation, get its clear liquid, 3,3,3-trifluoroacetic acid transformation efficiency is 82.3%, 3,3,3-trifluoroacetic acid ethyl ester selectivity is 99.9%.
Embodiment 4
Get about 150g sodium wolframate and 225g water in there-necked flask, after being heated to 90 DEG C, slowly add the dense HCl of 120ml, after stirring 24h, generate bright yellow solid, centrifugal after using hot water to disperse also sedimentation washing for several times, be placed in 120 DEG C of constant temperature drying 12h, take out after Temperature fall, grind to 200 order powdered samples, be WO
30.33H
2o catalyzer.
Add the catalyzer of the above-mentioned preparation of 0.32g, 6.40g trifluoroacetic acid and 2.30g ethanol in the reactor successively, control stirring velocity 600r/min, stirring 10min to mixing, being warmed up to 95 DEG C, room temperature is cooled to after reaction 4h, by gained reaction solution high speed centrifugation, get its clear liquid, 3,3-trifluoroacetic acid transformation efficiency is 77.4%, 3,3,3-trifluoroacetic acid ethyl ester selectivity is 99.9%.
Embodiment 5
Add catalyzer WO prepared by 0.32g embodiment 2 in the reactor successively
2.90, 6.40g trifluoroacetic acid and 3.50g ethanol, control stirring velocity 600r/min, stir, be warmed up to 90 DEG C, be cooled to room temperature after reaction 4h, by gained reaction solution high speed centrifugation, get its clear liquid, 3,3,3-trifluoroacetic acid transformation efficiency is 81.3%, 3,3,3-trifluoroacetic acid ethyl ester selectivity is 99.9%.
Embodiment 6
By isolated for embodiment 5 catalyzer after washing with alcohol, oven dry, then roasting 6h reuses in 500 DEG C of air atmospheres.3,3,3-trifluoroacetic acid transformation efficiency is 80.8%, 3,3,3-trifluoroacetic acid ethyl ester selectivity is 99.9%, and activity does not have obvious reduction, illustrates that this catalyzer is reusable.
Claims (3)
1. the preparation method of a trifluoroacetic acid ethyl ester, is characterized in that with 3,3,3-trifluoroacetic acid and ethanol for raw material, synthesizes 3,3,3-trifluoroacetic acid ethyl ester under Tungstenic compound katalysis; Reaction conditions is the mass ratio of catalyzer and 3,3,3-trifluoroacetic acid is 0.01 ~ 0.1:1; The mol ratio of 3,3,3-trifluoroacetic acid and ethanol is 1:1.0 ~ 1.5; Temperature of reaction is 55 ~ 95 DEG C; Reaction times is 4 ~ 24h.
2. the preparation method of 3,3,3-trifluoroacetic acid ethyl esters according to claim 1, is characterized in that Tungstenic compound is tungsten oxide, can be selected from WO
3, WO
3h
2o, WO
30.33H
2o, WO
2.90or WO
2.72in one or more.
3. the preparation method of 3,3,3-trifluoroacetic acid ethyl esters according to claim 1, is characterized in that temperature of reaction is 70 ~ 90 DEG C; Reaction times is 6 ~ 8h.
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| CN201510731098.2A CN105418415B (en) | 2015-11-02 | 2015-11-02 | A kind of preparation method of 3,3,3 trifluoroacetic acid ethyl ester |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109534991A (en) * | 2018-11-02 | 2019-03-29 | 浙江皇马科技股份有限公司 | A kind of preparation method of two isotridecanol of decanedioic acid |
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| US20060152930A1 (en) * | 2005-01-10 | 2006-07-13 | Delta Electronics, Inc. | Adjustable light-emitting device for projection system |
| 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 |
-
2015
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060152930A1 (en) * | 2005-01-10 | 2006-07-13 | Delta Electronics, Inc. | Adjustable light-emitting device for projection system |
| 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 |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109534991A (en) * | 2018-11-02 | 2019-03-29 | 浙江皇马科技股份有限公司 | A kind of preparation method of two isotridecanol of decanedioic acid |
| CN109534991B (en) * | 2018-11-02 | 2021-07-23 | 浙江皇马科技股份有限公司 | Preparation method of diisotridecyl sebacate |
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