CN103694119A - Preparation method of ethyl 4,4,4-trifluoroacetoacetate - Google Patents
Preparation method of ethyl 4,4,4-trifluoroacetoacetate Download PDFInfo
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- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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Abstract
The invention discloses a preparation method of ethyl 4,4,4-trifluoroacetoacetate. With an ethanol solution of sodium ethoxide as a catalyst and in the presence of an organic solvent, ethyl trifluoroacetate and ethyl acetate are subjected to a Claisen condensation reaction, and ethyl 4,4,4-trifluoroacetoacetate is synthesized. The method provided by the invention has the advantages of mild conditions, simple operation, relatively high conversion rate of raw materials, relatively high product selectivity, easy separation of the product, low energy consumption and the like, and is suitable for industrialized production. The prepared ethyl 4,4,4-trifluoroacetoacetate is an important pesticide and medicine intermediate, can be used for preparation of thifluzamide, fluacrypyrim, thiazopyr and other pesticides, and also can be used for preparation of befloxatone and other medicines.
Description
Technical field
The present invention relates to a kind of 4,4, the preparation method of 4-trifluoroacetic ethyl acetoacetate.
Background technology
[0002] 4,4,4-trifluoroacetic ethyl acetoacetate (hereinafter to be referred as trifluoroacetic ethyl acetoacetate), English name ethyl 4,4,4-trifluoroacetoacetate, is for No. CAS 372-31-6.Molecular formula is C
6h
7f
3o
3, molecular weight is 184.11, and density is 1.259, and fusing point is-39 ℃, and boiling point is 129.5 ℃ (760 mmHg), and specific refractory power is 1.375-1.378, and flash-point is 28 ℃, and in water, solubleness is 10 g/L (20 ℃).Trifluoroacetic ethyl acetoacetate has two configurations, and enol form and keto-acid, generally can freely change, and concrete structure is as follows:
Trifluoroacetic ethyl acetoacetate is a kind of important agricultural chemicals and medicine intermediate, can be used for preparing the agricultural chemicals such as thiophene fluorine bacterium amine, Fluacrypyrim, thiazopyr, also can be for the preparation of medicine such as befloxatones.Its synthetic method is mainly to make through claisen condensation reaction with Trifluoroacetic Acid Ethyl Ester and ethyl acetate.The principle of reaction is as follows:
In prior art 4,4, it is raw material that Trifluoroacetic Acid Ethyl Ester and ethyl acetate are take in the preparation of 4-trifluoroacetic ethyl acetoacetate, and the hexanaphthene of take is synthetic through claisen condensation reaction as solvent, has following report:
US Patent No. 4647689 has been reported following method: at sodium hydride, (content is 60%, be dispersed in mineral oil) exist under, take hexanaphthene as solvent, Trifluoroacetic Acid Ethyl Ester and ethyl acetate react, add hydrogen chloride gas acidifying to obtain reacting coarse product, again after filtration, after rectifying, obtain 4,4,4-trifluoroacetic ethyl acetoacetate product.Product purity is 94.0%, and yield is 75%.This reaction system: produce a large amount of hydrogen, have potential safety hazard in suitability for industrialized production; Use anhydrous hydrogen chloride gas acidifying, be difficult to accurately control acidifying terminal during operation, the anhydrous hydrogen chloride gas of effusion needs relatively large alkali lye neutralization, and quantity of three wastes is increased; Use a large amount of hexanaphthenes, can make system component separation difficulty, thereby increase energy consumption and operational cycle; The membership that adds of trifluoroacetyl chloride increases the operation steps of reacting, thereby extends the operating time of single still reaction.
US Patent No. 4883904 has been reported following method: sodium Metal 99.5 and ethanol are prepared sodium ethylate, adding cyclohexane give is solvent, after cooling, add Trifluoroacetic Acid Ethyl Ester, after intensification, add anhydrous ethyl acetate reaction, precipitation, adds hexanaphthene, anhydrous formic acid and ethyl acetate acidifying, more after filtration, after rectification under vacuum, obtain 4 under atmospheric distillation, underpressure distillation, 140 mmHg vacuum tightnesss, 4,4-trifluoroacetic ethyl acetoacetate.Product purity is 99.1%, and yield is 74.7%.In this production technique: solid alkali sodium is violent in reinforced process heat release, reinforced process is wayward, easily causes dust pollution; Use sodium Metal 99.5 and ethanol to prepare sodium ethylate and can produce a large amount of hydrogen, in suitability for industrialized production, have potential safety hazard; Twice azeotropic dealcoholysis, energy consumption is large, and dealcoholysis process endpoint is difficult to be controlled, so that technique is unstable; A large amount of hexanaphthenes are used in dealcoholysis, cause the increase of recovery energy consumption, the reaction times of solvent to increase.
Summary of the invention
The object of the present invention is to provide and a kind ofly prepare 4,4, the method of 4-trifluoroacetic ethyl acetoacetate, the feature such as have reaction conditions gentleness, simple to operate, the transformation efficiency of raw material and the selectivity of product is higher, target product trifluoroacetic ethyl acetoacetate is easily separated, energy consumption is low, is applicable to suitability for industrialized production.
It is raw material that the present invention uses Trifluoroacetic Acid Ethyl Ester and ethyl acetate, and the ethanolic soln of sodium ethylate of take is catalyzer, under organic solvent exists, through claisen condensation reaction, prepares trifluoroacetic ethyl acetoacetate, and reaction conditions is gentle, reacts required energy consumption lower.Reaction formula is as follows:
Preparation 4,4 of the present invention, the method for 4-trifluoroacetic ethyl acetoacetate, comprises the following steps:
(1), toward the ethanolic soln and the ethyl acetate that add organic solvent, sodium ethylate in reactor, described organic solvent is selected from a kind of, more than two or three combination in dehydrated alcohol, hexanaphthene, tetrahydrofuran (THF), diethylene glycol dimethyl ether, methyl tertiary butyl ether, ethyl acetate and Meta Dichlorobenzene;
(2) cooling reacting liquid temperature to 5～10 ℃, drip Trifluoroacetic Acid Ethyl Ester, and during dropping, controlling reacting liquid temperature is 10～20 ℃, and after dropwising, controlling reacting liquid temperature is 10～65 ℃, reacts 0.5～6.0 hour;
(3) cooling reacting liquid temperature to 10～15 ℃, drip acid, and during dropping, controlling reacting liquid temperature is 20～30 ℃, and after dropwising, controlling reacting liquid temperature is 10～60 ℃, reacts 0.5～6.0 hour;
(4) 4,4,4-trifluoroacetic ethyl acetoacetate will be obtained after reacting liquid filtering, washing, underpressure distillation.
The ethanolic soln of the sodium ethylate that the present invention uses, its concentration range should be to be greater than 0 between saturation concentration.Be preferably 10%～20%.
Mole proportion optimization of sodium ethylate of the present invention and Trifluoroacetic Acid Ethyl Ester is 1.0:1.0～2.5:1.0, more preferably 1.1:1.0～1.5:1.0.
Mole proportion optimization of ethyl acetate of the present invention and Trifluoroacetic Acid Ethyl Ester is 1.0:1.0～3.0:1.0, more preferably 1.1:1.0～2.0:1.0.
In step of the present invention (3) acidification reaction, the acid of use is a kind of, more than two or three combination in the vitriol oil, concentrated hydrochloric acid, acetic acid, anhydrous formic acid and methylsulfonic acid preferably, more preferably concentrated hydrochloric acid and/or anhydrous formic acid; Acid is 1.0:1.0～2.5:1.0, more preferably 1.2:1.0～1.7:1.0 with mole proportion optimization of Trifluoroacetic Acid Ethyl Ester.
The organic solvent that the present invention uses is preferably dehydrated alcohol and/or ethyl acetate.
Of the present invention 4,4, the detailed preparation process of 4-trifluoroacetic ethyl acetoacetate is as follows:
In the reactor that whipping appts, constant pressure funnel and thermometer are housed, first add organic solvent, then add the ethanolic soln of sodium ethylate, add a certain amount of ethyl acetate after starting stirring.Cooling reaction solution to 5～10 ℃, slowly drip Trifluoroacetic Acid Ethyl Ester, control temperature at 10～20 ℃.After dropwising, under design temperature, react some hours.Wherein preferred temperature of reaction is 10～65 ℃, more preferably 40～60 ℃; The preferred reaction times is 0.5～6.0 hour, more preferably 1.0～3.0 hours.After condensation reaction, reaction solution is cooled to 10～15 ℃, then slowly drips acid, control temperature at 20～30 ℃.After dripping off, under design temperature, react the some time, preferred temperature of reaction is 10～60 ℃, more preferably 30～50 ℃; The preferred reaction times is 0.5～6.0 hour, more preferably 1.0～2.5 hours.After acidifying, obtain dirty solution, solids removed by filtration is also collected filtrate, and filter cake washs by ethyl acetate, obtains the mixed solution that contains trifluoroacetic ethyl acetoacetate.Mixed solution obtains trifluoroacetic ethyl acetoacetate through rectification under vacuum.
The present invention, than prior art, has the following advantages:
(1) preparation process is novel, and preparation process does not produce hydrogen, and process safety is reliable;
(2) take the ethanolic soln of sodium ethylate is catalyzer, and reaction system is homogeneous phase, makes reaction more complete, and yield is higher;
(3) adopt liquid alcohol sodium alcohol solution as catalyzer, to avoid the problems such as the wayward and dust pollution of violent, the reinforced process of heat release in the reinforced process of solid alkali, make reaction be more suitable for suitability for industrialized production;
(4) removed the processing step of azeotropic dealcoholysis in existing technique, made energy consumption lower, the operational cycle shortens;
(5) raw material is conveniently easy to get, and technique is simple, and reaction conditions is gentle, is applicable to suitability for industrialized production.
Embodiment
Below in conjunction with specific embodiment, the present invention is further described, but does not limit the invention to these embodiments.One skilled in the art would recognize that the present invention contained all alternativess, improvement project and the equivalents that within the scope of claims, may comprise.
embodiment 1
At 25 ℃, in reactor, will add 200 mL dehydrated alcohols, then add 510 g (1.5 mol), 20% alcohol sodium alcohol solution, then add 105.6 g (1.2mol) ethyl acetate.Cooling reaction solution to 5～10 ℃, then start to drip 142 g (1.0 mol) Trifluoroacetic Acid Ethyl Ester, control 10～20 ℃ of temperature.After adding, be warming up to 60 ℃ of reactions 2 hours, then cooling reaction solution to 10～15 ℃.In reaction solution, drip 166.6g (1.7mol) vitriol oil, control 20～30 ℃ of temperature, drip off at latter 30 ℃ and react 2.5 hours, obtain the sedimentary dirty solution of contains sodium sulfate.
Sodium sulfate throw out is by removing by filter, and filter cake washs by ethyl acetate, and the filtrate obtaining is carried out rectification under vacuum, obtains 157.0 g trifluoroacetic ethyl acetoacetates, and yield is 85.3% (in Trifluoroacetic Acid Ethyl Ester), and purity is 95.2%.
embodiment 2
At 25 ℃, in reactor, will add 100 mL hexanaphthenes, then add 374 g (0.55 mol), 10% alcohol sodium alcohol solution, then add 57.2 g (0.65 mol) ethyl acetate.Cooling reaction solution to 5～10 ℃, then start to drip 71 g (0.5 mol) Trifluoroacetic Acid Ethyl Ester, control 15～20 ℃ of temperature.After adding, be warming up to 50 ℃ of reactions 3 hours, then cooling reaction solution to 10～15 ℃.In reaction solution, drip 59.2 g (0.6 mol), 37% concentrated hydrochloric acid, control 20～30 ℃ of temperature, drip off at latter 40 ℃ and react 1.5 hours, obtain the sedimentary dirty solution of sodium chloride-containing.
Sodium chloride deposit thing is by removing by filter, and filter cake washs by ethyl acetate, and the filtrate obtaining is carried out rectification under vacuum, obtains 75.6 g trifluoroacetic ethyl acetoacetates, and yield is 82.2% (in Trifluoroacetic Acid Ethyl Ester), and purity is 95.2%.
embodiment 3
At 25 ℃, in reactor, will add 100 mL tetrahydrofuran (THF)s, then add 385.3 g (0.85 mol), 15% alcohol sodium alcohol solution, then add 70.4 g (0.8 mol) ethyl acetate.Cooling reaction solution to 5～10 ℃, then start to drip 99.4 g (0.7 mol) Trifluoroacetic Acid Ethyl Ester, control 10～20 ℃ of temperature.After adding, be warming up to 40 ℃ of reactions 4 hours, then cooling reaction solution to 10～15 ℃.In reaction solution, drip 54 g (0.9 mol) acetic acid, control 20～30 ℃ of temperature, drip off at latter 35 ℃ and react 2.0 hours, obtain containing the sedimentary dirty solution of sodium acetate.
Sodium acetate throw out is by removing by filter, and filter cake washs by ethyl acetate, and the filtrate obtaining is carried out rectification under vacuum, obtains 107.4 g trifluoroacetic ethyl acetoacetates, and yield is 83.4% (in Trifluoroacetic Acid Ethyl Ester), and purity is 95.5%.
embodiment 4
At 25 ℃, in reactor, will add 200 mL methyl tertiary butyl ethers, then add 544 g (1.6 mol), 20% alcohol sodium alcohol solution, then add 140.8 g (1.6 mol) ethyl acetate.Cooling reaction solution to 5～10 ℃, then start to drip 113.6 g (0.8 mol) Trifluoroacetic Acid Ethyl Ester, control 10～20 ℃ of temperature.After adding, be warming up to 45 ℃ of reactions 2.5 hours, then cooling reaction solution to 10～15 ℃.In reaction solution, drip 78.2 g (1.7 mol) anhydrous formic acid, control 20～30 ℃ of temperature, drip off at latter 50 ℃ and react 1.0 hours, obtain containing the sedimentary dirty solution of sodium formiate.
Sodium formiate throw out is by removing by filter, and filter cake washs by ethyl acetate, and the filtrate obtaining is carried out rectification under vacuum, obtains 127.0 g trifluoroacetic ethyl acetoacetates, and yield is 86.3% (in Trifluoroacetic Acid Ethyl Ester), and purity is 94.7%.
embodiment 5
At 25 ℃, in reactor, will add 200 mL Meta Dichlorobenzenes, then add 510 g (1.5 mol), 20% alcohol sodium alcohol solution, then add 123.2 g (1.4 mol) ethyl acetate.Cooling reaction solution to 5～10 ℃, then start to drip 170.4 g (1.2 mol) Trifluoroacetic Acid Ethyl Ester, control 10～20 ℃ of temperature.After adding, be warming up to 55 ℃ of reactions 2.0 hours, then cooling reaction solution to 10～15 ℃.In reaction solution, drip 78.2 g (1.6 mol) methylsulfonic acid, control 20～30 ℃ of temperature, drip off at latter 30 ℃ and react 2.5 hours, obtain containing the sedimentary dirty solution of methanesulfonic sodium.
Sodium formiate throw out is by removing by filter, and filter cake washs by ethyl acetate, and the filtrate obtaining is carried out rectification under vacuum, obtains 189.0 g trifluoroacetic ethyl acetoacetates, and yield is 85.6% (in Trifluoroacetic Acid Ethyl Ester), and purity is 96.7%.
From above-described embodiment, provided by the invention 4,4,4-trifluoroacetic ethyl acetoacetate process of preparing, compared with prior art, yield obviously improves, all more than 82%.
Claims (9)
1. a method of preparing 4,4,4-trifluoroacetic ethyl acetoacetate, is characterized in that comprising the following steps:
Toward the ethanolic soln and the ethyl acetate that add organic solvent, sodium ethylate in reactor, described organic solvent is selected from a kind of, more than two or three combination in dehydrated alcohol, hexanaphthene, tetrahydrofuran (THF), diethylene glycol dimethyl ether, methyl tertiary butyl ether, ethyl acetate and Meta Dichlorobenzene;
Cooling reacting liquid temperature to 5～10 ℃, drip Trifluoroacetic Acid Ethyl Ester, and during dropping, controlling reacting liquid temperature is 10～20 ℃, and after dropwising, controlling reacting liquid temperature is 10～65 ℃, 0.5～6.0 hour reaction times;
Cooling reacting liquid temperature to 10～15 ℃, drip acid, and during dropping, controlling reacting liquid temperature is 20～30 ℃, and after dropwising, controlling reacting liquid temperature is 10～60 ℃, 0.5～6.0 hour reaction times;
4,4,4-trifluoroacetic ethyl acetoacetate will be obtained after reacting liquid filtering, washing, underpressure distillation.
2. according to preparation 4 claimed in claim 1,4, the method of 4-trifluoroacetic ethyl acetoacetate, is characterized in that the concentration of ethanolic soln of described sodium ethylate is for being greater than 0 to saturation concentration, and mole proportioning of described sodium ethylate and Trifluoroacetic Acid Ethyl Ester is 1.0:1.0～2.5:1.0.
3. according to preparation 4,4 claimed in claim 2, the method for 4-trifluoroacetic ethyl acetoacetate, the concentration that it is characterized in that the ethanolic soln of described sodium ethylate is 10%～20%, mole proportioning of described sodium ethylate and Trifluoroacetic Acid Ethyl Ester is 1.1:1.0～1.5:1.0.
4. according to preparation 4,4 claimed in claim 1, the method for 4-trifluoroacetic ethyl acetoacetate, mole proportioning that it is characterized in that described ethyl acetate and Trifluoroacetic Acid Ethyl Ester is 1.0:1.0～3.0:1.0.
5. according to preparation 4,4 claimed in claim 4, the method for 4-trifluoroacetic ethyl acetoacetate, mole proportion optimization that it is characterized in that described ethyl acetate and Trifluoroacetic Acid Ethyl Ester is 1.1:1.0～2.0:1.0.
6. according to preparation 4 claimed in claim 1,4, the method of 4-trifluoroacetic ethyl acetoacetate, it is characterized in that the acid of using in described step (3) is selected from a kind of, more than two or three combination in the vitriol oil, concentrated hydrochloric acid, acetic acid, anhydrous formic acid and methylsulfonic acid, acid is 1.0:1.0～2.5:1.0 with mole proportioning of Trifluoroacetic Acid Ethyl Ester.
7. according to preparation 4,4 claimed in claim 6, the method for 4-trifluoroacetic ethyl acetoacetate, is characterized in that the acid of using in described step (3) is selected from concentrated hydrochloric acid and/or anhydrous formic acid, and acid is 1.2:1.0～1.7:1.0 with mole proportioning of Trifluoroacetic Acid Ethyl Ester.
8. according to preparation 4,4 claimed in claim 1, the method for 4-trifluoroacetic ethyl acetoacetate, is characterized in that the organic solvent using in described step (1) is dehydrated alcohol and/or ethyl acetate.
9. according to preparation 4,4 claimed in claim 1, the method for 4-trifluoroacetic ethyl acetoacetate, after it is characterized in that dripping Trifluoroacetic Acid Ethyl Ester in described step (2) adds, controlling reacting liquid temperature is 40～65 ℃, 1.0～3.0 hours reaction times; After step (3) drips acid, controlling reacting liquid temperature is 30～50 ℃, 1.0～2.5 hours reaction times.
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| CN201210367583.2A CN103694119A (en) | 2012-09-28 | 2012-09-28 | Preparation method of ethyl 4,4,4-trifluoroacetoacetate |
| CN201610909136.3A CN106565475A (en) | 2012-09-28 | 2012-09-28 | Preparing method for ethyl 4,4,4-trifluoroacetoacetate |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105985253A (en) * | 2015-02-06 | 2016-10-05 | 浙江蓝天环保高科技股份有限公司 | Method for preparing 3-amino-4,4,4-trifluorocrotonate |
| CN108218703A (en) * | 2016-12-21 | 2018-06-29 | 浙江蓝天环保高科技股份有限公司 | A kind of preparation method of 4,4- difluoros ethyl acetoacetate |
| CN108325556A (en) * | 2018-05-12 | 2018-07-27 | 长乐智高生物科技有限公司 | A kind of synthetic method of intermediate 2,6- dihydroxy -3- cyano -4- trifluoromethyl pyridines |
| CN108558749A (en) * | 2018-05-12 | 2018-09-21 | 长乐智高生物科技有限公司 | It is a kind of synthesis 2,6- dihydroxy -3- cyano -4- trifluoromethyl pyridines catalyst and its application |
| CN113024353A (en) * | 2019-12-09 | 2021-06-25 | 浙江蓝天环保高科技股份有限公司 | Preparation method of sodium formate |
| CN115286509A (en) * | 2022-08-30 | 2022-11-04 | 山东华安新材料有限公司 | Method for co-producing ethyl trifluoroacetate and trifluoroethanol |
| CN116063178A (en) * | 2021-11-03 | 2023-05-05 | 宁夏常晟药业有限公司 | Synthesis method of ethyl trifluoroacetoacetate |
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| US4883904A (en) * | 1985-06-14 | 1989-11-28 | Rhone-Poulenc Specialites Chimiques | Process for the preparation of ethyltrifluoroacetoacetate |
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- 2012-09-28 CN CN201610909136.3A patent/CN106565475A/en active Pending
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| US4883904A (en) * | 1985-06-14 | 1989-11-28 | Rhone-Poulenc Specialites Chimiques | Process for the preparation of ethyltrifluoroacetoacetate |
Non-Patent Citations (1)
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| 张国华 等: "三氟乙酰乙酸乙酯的合成", 《农药》, vol. 46, no. 12, 31 December 2007 (2007-12-31), pages 823 - 824 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105985253A (en) * | 2015-02-06 | 2016-10-05 | 浙江蓝天环保高科技股份有限公司 | Method for preparing 3-amino-4,4,4-trifluorocrotonate |
| CN108218703A (en) * | 2016-12-21 | 2018-06-29 | 浙江蓝天环保高科技股份有限公司 | A kind of preparation method of 4,4- difluoros ethyl acetoacetate |
| CN108325556A (en) * | 2018-05-12 | 2018-07-27 | 长乐智高生物科技有限公司 | A kind of synthetic method of intermediate 2,6- dihydroxy -3- cyano -4- trifluoromethyl pyridines |
| CN108558749A (en) * | 2018-05-12 | 2018-09-21 | 长乐智高生物科技有限公司 | It is a kind of synthesis 2,6- dihydroxy -3- cyano -4- trifluoromethyl pyridines catalyst and its application |
| CN113024353A (en) * | 2019-12-09 | 2021-06-25 | 浙江蓝天环保高科技股份有限公司 | Preparation method of sodium formate |
| CN116063178A (en) * | 2021-11-03 | 2023-05-05 | 宁夏常晟药业有限公司 | Synthesis method of ethyl trifluoroacetoacetate |
| CN115286509A (en) * | 2022-08-30 | 2022-11-04 | 山东华安新材料有限公司 | Method for co-producing ethyl trifluoroacetate and trifluoroethanol |
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Application publication date: 20140402 |