CN115160136A - Preparation method of ethyl trifluoroacetate - Google Patents
Preparation method of ethyl trifluoroacetate Download PDFInfo
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- CN115160136A CN115160136A CN202211043964.5A CN202211043964A CN115160136A CN 115160136 A CN115160136 A CN 115160136A CN 202211043964 A CN202211043964 A CN 202211043964A CN 115160136 A CN115160136 A CN 115160136A
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- ethyl trifluoroacetate
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
- C07C67/42—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of secondary alcohols or ketones
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Abstract
A preparation method of ethyl trifluoroacetate, belonging to the technical field of organic fluorine chemical industry. The invention takes 1, 1-trifluoro-2-butanone as raw material, and prepares ethyl trifluoroacetate through Bayer-Virgiger oxidation rearrangement reaction. The preparation method comprises the following steps: 1) Mixing 1, 1-trifluoro-2-butanone, a phase transfer catalyst and a solvent, adding the mixture into a reactor, dropwise adding a peroxyacetic acid aqueous solution, carrying out heat preservation reaction after the dropwise adding is finished, and separating liquid; 2) Washing the organic phase obtained by liquid separation in the step 1) with water to obtain a crude product of the ethyl trifluoroacetate, and purifying the crude product to obtain a pure product of the ethyl trifluoroacetate; 3) And adding alkali into the water phase obtained by separating the liquid in the step 1) to obtain an acetate solution, and concentrating to obtain an acetate solid. The preparation method of the ethyl trifluoroacetate has the advantages of low raw material consumption, simple and controllable operation, less three-waste discharge, low cost, high conversion rate, simple synthetic route, high product purity, easy realization of reaction conditions and the like.
Description
Technical Field
The invention relates to a preparation method of ethyl trifluoroacetate, belonging to the technical field of organic fluorine chemical industry.
Background
The trifluoroacetic acid ethyl ester has a boiling point of 60-62 ℃, and is a volatile colorless liquid with pungent odor. Is commonly used as analytical reagent, solvent, catalyst, dehydration condensation agent and protective agent for hydroxyl and amino trifluorphthalination, and is an important raw material for preparing organic fluorine fine chemicals, medicines and pesticides.
The preparation method of the ethyl trifluoroacetate in the prior art is obtained by taking trifluoroacetic acid as a raw material and carrying out esterification reaction with ethanol under the catalysis of concentrated sulfuric acid, but the concentrated sulfuric acid in the process has the advantages of good catalytic effect, low price and the like. But the defects brought by the concentrated sulfuric acid are not negligible, and the concentrated sulfuric acid has the problems of more byproducts, poor product selectivity, low purity, serious equipment corrosion, incapability of recycling, more waste water containing waste sulfuric acid, environmental pollution and the like in the catalytic esterification process. A process for preparing ethyl trifluoroacetate from trifluoroacetic acid and absolute alcohol as main raw materials and solid superacid as catalyst includes heating reflux to obtain coarse product; zhang Jian et al, synthesis of ethyl trifluoroacetate [ J ]. Hebei chemical industry, 2012, discloses a method for preparing a crude product by heating and refluxing trifluoroacetic acid and absolute ethyl alcohol which are used as main raw materials and p-toluenesulfonic acid which is used as a catalyst. Although these methods use concentrated sulfuric acid as a catalyst, there is a problem that the catalyst needs to be filtered and dried.
Patent CN 10139249A discloses a preparation method of ethyl trifluoroacetate, which uses trifluoroacetic acid and absolute ethyl alcohol as main raw materials, uses strong acid ion exchange resin as a catalyst, and dropwise adds absolute ethyl alcohol at a temperature lower than 50 ℃ and under normal pressure and keeps the reaction for a period of time to be complete. Filtering out the catalyst, drying in a drying tower filled with solid particle silica gel to remove the residual water, distilling at normal pressure, and collecting the distillate at the temperature of 58-64 ℃ to obtain the target product. The strong acid cation resin is used as the catalyst, so that the problem of treatment of the waste catalyst exists, and the resin is high in activation cost, has a plurality of phenomena of performance reduction after activation, is not generally recycled, but is directly abandoned, so that resource waste and environmental pollution are caused. Patent CN102351694A discloses a preparation method of ethyl trifluoroacetate, which is mixing amine compound and ethanol uniformly according to a molar ratio of 0.2-2. The target product is obtained after rectification, the method uses an amine compound as an acid-binding agent, and organic amine used in the reaction has pungent odor and influences the environment.
Patent CN103864615B discloses a method for preparing ethyl trifluoroacetate by a continuous non-catalytic method, which does not solve two problems: (1) The yield of the ethyl trifluoroacetate prepared by using the continuous non-catalytic reaction of trifluoroacetyl chloride and ethanol is still not high, and the highest yield is only 97.86 percent; (2) The application problem of the by-product hydrochloric acid is not solved, the effective utilization of the by-product hydrochloric acid is not concerned, and the waste of the whole process is easily caused. A new synthesis method of Wangmingin ethyl trifluoroacetate researches on [ J ] organic fluorine industry, 2017,000 (003): 11-12,15, discloses a preparation method of ethyl trifluoroacetate, wherein trifluoroacetyl fluoride reacts with ethanol and potassium fluoride to prepare ethyl trifluoroacetate, a trifluoroacetyl fluoride raw material is difficult to obtain, gas is dangerous, the method is not suitable for industrial production, and a large amount of solid potassium bifluoride cannot be treated. European patent EP1070702 discloses a preparation method of ethyl trifluoroacetate, wherein trifluoroacetyl chloride and absolute ethyl alcohol are used as main raw materials, ethyl trifluoroacetate is used as a solvent to prepare ethyl trifluoroacetate, and the purity of ethyl trifluoroacetate obtained after reaction is high. After the reaction, the system is heated to room temperature, the hydrogen chloride gas generated in the system is discharged, and the discharged hydrogen chloride gas is absorbed by a sodium hydroxide solution. However, the reaction needs to be carried out under the condition of low temperature, the reaction temperature is-30 ℃ to-20 ℃, trifluoroacetyl chloride is firstly condensed into liquid under the low temperature state, and then ethanol is dripped for esterification reaction. The low-temperature reaction requires high energy consumption, and only intermittent operation of the ethyl trifluoroacetate can be carried out under the process state, so that continuous production is difficult to realize.
US patent No. 4916256 discloses a method for preparing ethyl trifluoroacetate by using trifluoroacetyl chloride and anhydrous ethanol as main raw materials and reacting ethanol and trifluoroacetyl chloride into gas; continuous production of ethyl trifluoroacetate can be realized by taking trifluoroacetyl chloride and ethanol as raw materials through gas phase reaction, but the ethanol is gasified into gas in advance and then reacts through a gas phase reaction tube, so that the reaction energy consumption is high, the reaction is not economical, and the purity of the obtained product is low.
The preparation method of the ethyl trifluoroacetate in the prior art has the defects that a catalyst needs to be filtered and dried, the reaction condition is harsh, the required energy consumption is high, the yield is low, and the purity of the obtained product is low.
Disclosure of Invention
The invention aims to provide a method for preparing ethyl trifluoroacetate by using 1, 1-trifluoro-2-butanone as a raw material through Bayer-Virgiger oxidation rearrangement reaction aiming at the defects that a catalyst needs to be filtered and dried, the reaction condition is harsh, the required energy consumption is high, the yield is low and the product purity is low in the preparation method of the ethyl trifluoroacetate in the prior art.
The technical scheme adopted by the invention for achieving the aim of the invention is as follows: a preparation method of ethyl trifluoroacetate comprises the following steps:
(1) Mixing 1, 1-trifluoro-2-butanone, a phase transfer catalyst and a solvent, and adding the mixture into a reactor; firstly, controlling the temperature to be 0-20 ℃, then dropwise adding a peracetic acid aqueous solution into the reactor, controlling the temperature to be 0-30 ℃ in the dropwise adding process, and then carrying out heat preservation reaction at 0-40 ℃ after the dropwise adding is finished; the dropping of the aqueous solution of peroxyacetic acid is kept at a constant speed, and the duration of the dropping process is at least 4.0 hours. After the reaction was completed, the reaction mixture was separated.
(2) And (2) washing the organic phase prepared in the step (1) with water to obtain a crude product of the ethyl trifluoroacetate, and purifying the crude product to obtain a pure product of the ethyl trifluoroacetate.
(3) And (2) adding alkali into the water phase prepared in the step (1), controlling the pH value to be 7-12 to obtain an acetate solution, and concentrating to obtain an acetate solid.
The synthetic route is as follows:
preferably, the solvent in step (1) is water, and the weight of the water is 0.5-2.0 times of that of the 1, 1-trifluoro-2-butanone.
Preferably, the phase transfer catalyst in step (1) is: tetrabutylammonium bromide, tetrabutylammonium chloride, PEG400 or triethylbenzylammonium chloride.
Preferably, in the step (1), the mass percentage of the peroxyacetic acid in the aqueous peroxyacetic acid solution is 5-40%, and the mass ratio of the 1, 1-trifluoro-2-butanone to the aqueous peroxyacetic acid solution is 1.
Preferably, the mass ratio of the 1, 1-trifluoro-2-butanone to the phase transfer catalyst in the step (1) is 1:0.05 to 0.15.
Preferably, the time of the incubation reaction in step (1) is 6 to 12 hours.
Preferably, the organic phase is washed with water more than three times in step (2), the volume of water used for each washing is 1/4 to 1/2 of that of the organic phase, and the water phase after washing can be used as the water for 2 (1) reaction.
Preferably, the step (3) is performed by using any one of potassium hydroxide and sodium hydroxide.
Preferably, the pH value in step (3) is controlled to be 8 to 10.
Preferably, the concentrated solution in step (3) is concentrated under reduced pressure.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the preparation method of the ethyl trifluoroacetate, water is used as a solvent to carry out heterogeneous reaction, so that the reaction speed can be effectively reduced, the over-fast reaction and the rapid temperature rise are prevented, and the safety risk is avoided; the layering is more thorough after the reaction is finished, and the yield is improved.
2. The preparation method of the ethyl trifluoroacetate adopts the peroxyacetic acid as the oxidant, controls the adding speed by dripping, and simultaneously controls the dripping temperature, so that the generation of impurities can be effectively reduced, and the purity of the obtained product is over 99 percent.
3. The preparation method of the ethyl trifluoroacetate has the advantages of low raw material consumption, simple and controllable operation, less three-waste discharge, low cost, high conversion rate, simple synthetic route, high product purity, easy realization of reaction conditions and the like.
Detailed Description
The invention is further described with reference to the following examples, which are intended to illustrate the invention but are not intended to limit the scope of the invention. The conditions in the embodiments can be further adjusted according to specific conditions, and simple modifications of the method of the present invention based on the concept of the present invention are within the scope of the claimed invention.
Example 1
A1000 ml four-necked flask was charged with 126.21g of 1, 1-trifluoro-2-butanone, 1.20g of tetrabutylammonium bromide and 100g of water; firstly controlling the temperature to be 5-10 ℃, then dropwise adding 308.10g of 25% peracetic acid aqueous solution into the flask, controlling the temperature to be 5-10 ℃ in the dropwise adding process, ending the dropwise adding within about 4 hours, and keeping the temperature at 20-30 ℃ for reacting for 0.5 hour after the dropwise adding is ended;
standing for 0.5h, layering, adjusting pH of the water phase to 8 with alkali, and concentrating to obtain acetate solid. The organic phase was washed with distilled water three times to obtain a crude product of ethyl trifluoroacetate. The purification yielded 135.2g of ethyl trifluoroacetate with a purity of 99.51% and a yield of 94.59%.
Example 2
The reaction temperature was changed from 0 ℃ to 5 ℃ on the basis of example 1, and the reaction results were shown in Table 1, except that the reaction conditions were the same as in example 1.
Example 3
The reaction conditions were the same as in example 1 except that the dropping time of peracetic acid was changed to 6 hours based on example 1, and the reaction results are shown in Table 1.
Example 4
The concentration of peracetic acid was changed to 35% based on example 1, and the mass was 219.32g, and the reaction conditions were the same as in example 1, and the reaction results are shown in Table 1.
Example 5
The stirring time after the dropwise addition of the peracetic acid solution was prolonged to 2 hours based on example 1, the reaction conditions were the same as in example 1, and the reaction results are shown in table 1.
Example 6
Based on example 1, the surfactant was changed to triethylbenzylammonium chloride, and the reaction conditions were the same as in example 1, and the reaction results are shown in table 1.
The yield and purity of the ethyl trifluoroacetate prepared in examples 1 to 6 were measured, respectively, and the results are shown in table 1 below.
Table 1 examples 1 to 6 yield and purity test results
From the above table, it can be seen that 1, 1-trifluoro-2-butanone is used as a raw material, and ethyl trifluoroacetate is prepared through a bayer-viliger oxidation rearrangement reaction, and the result shows that the yield of the prepared ethyl trifluoroacetate reaches over 93%, the utilization rate of the raw material is improved, and the production cost can be reduced. The purity of the obtained product is more than 99 percent, and the method has the characteristics of simple and controllable operation, less discharge of three wastes, high conversion rate, simple synthetic route, high product purity, easy realization of reaction conditions and the like.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A preparation method of ethyl trifluoroacetate is characterized in that 1, 1-trifluoro-2-butanone is used as a raw material, and the ethyl trifluoroacetate is prepared through Bayer-Virgiger oxidation rearrangement reaction.
2. A process for the preparation of ethyl trifluoroacetate of claim 1, comprising the steps of:
1) Mixing 1, 1-trifluoro-2-butanone, a phase transfer catalyst and a solvent according to the proportion, adding the mixture into a reactor, controlling the temperature to be between 0 and 20 ℃, dropwise adding a peroxyacetic acid aqueous solution into the reactor, controlling the temperature to be between 0 and 30 ℃ in the dropwise adding process, and keeping the temperature to react at the temperature of between 0 and 40 ℃ after the dropwise adding is finished; dropwise adding the peroxyacetic acid aqueous solution at a constant speed, keeping the duration of the dropwise adding process at least 4.0 hours, and separating liquid after the reaction is finished;
2) Washing the organic phase obtained by liquid separation in the step 1) with water to obtain a crude product of the ethyl trifluoroacetate, and purifying the crude product to obtain a pure product of the ethyl trifluoroacetate;
3) Adding alkali into the water phase obtained by separating the liquid in the step 1), controlling the pH value to be 7-12 to obtain an acetate solution, and concentrating to obtain an acetate solid.
3. A process for the preparation of ethyl trifluoroacetate according to claim 2, which comprises: the solvent in the step 1) is water, and the weight of the water is 0.5-2.0 times of that of the 1, 1-trifluoro-2-butanone.
4. A process for the preparation of ethyl trifluoroacetate according to claim 2, which comprises: the phase transfer catalyst in the step 1) is any one of tetrabutylammonium bromide, tetrabutylammonium chloride, PEG400 or triethylbenzylammonium chloride.
5. A process for the preparation of ethyl trifluoroacetate according to any one of claims 2 or 4, which comprises: the mass ratio of the 1, 1-trifluoro-2-butanone to the phase transfer catalyst in the step 1) is 1.
6. A process for the preparation of ethyl trifluoroacetate according to claim 2, comprising: the mass percentage of the peroxyacetic acid in the peroxyacetic acid aqueous solution in the step 1) is 5-40%, and the mass ratio of the 1, 1-trifluoro-2-butanone to the peroxyacetic acid aqueous solution is 1.
7. A process for the preparation of ethyl trifluoroacetate according to claim 2, which comprises: the reaction time of the heat preservation reaction after dripping the aqueous solution of the peroxyacetic acid in the step 1) is 6 to 12 hours.
8. A process for the preparation of ethyl trifluoroacetate according to claim 2, comprising: the frequency of washing the organic phase in the step 2) is more than three times, and the volume of water for washing each time is 1/4-1/2 of that of the organic phase.
9. A process for the preparation of ethyl trifluoroacetate according to claim 2, comprising: the alkali in the step 3) is any one of potassium hydroxide or sodium hydroxide.
10. A process for the preparation of ethyl trifluoroacetate according to claim 2, which comprises: the pH value in the step 3) is controlled to be 8-10.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694118A (en) * | 2013-12-30 | 2014-04-02 | 联化科技(上海)有限公司 | Preparation method of trifluoroacetic acid ethyl ester and preparation method of intermediate of trifluoroacetic acid ethyl ester |
| CN109705083A (en) * | 2019-01-29 | 2019-05-03 | 安徽华业香料合肥有限公司 | A kind of synthetic method of ε-decalactone fragrance |
| CN110003002A (en) * | 2019-04-26 | 2019-07-12 | 济南万兴达化工有限公司 | A kind of production technology of high yield Trifluoroacetic Acid Ethyl Ester |
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- 2022-08-30 CN CN202211043964.5A patent/CN115160136A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694118A (en) * | 2013-12-30 | 2014-04-02 | 联化科技(上海)有限公司 | Preparation method of trifluoroacetic acid ethyl ester and preparation method of intermediate of trifluoroacetic acid ethyl ester |
| CN109705083A (en) * | 2019-01-29 | 2019-05-03 | 安徽华业香料合肥有限公司 | A kind of synthetic method of ε-decalactone fragrance |
| CN110003002A (en) * | 2019-04-26 | 2019-07-12 | 济南万兴达化工有限公司 | A kind of production technology of high yield Trifluoroacetic Acid Ethyl Ester |
Non-Patent Citations (1)
| Title |
|---|
| 张湛赋等: "《有机化学反应类型概论》", pages: 282 - 283 * |
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