CN105985253A - Method for preparing 3-amino-4,4,4-trifluorocrotonate - Google Patents
Method for preparing 3-amino-4,4,4-trifluorocrotonate Download PDFInfo
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- CN105985253A CN105985253A CN201510063344.1A CN201510063344A CN105985253A CN 105985253 A CN105985253 A CN 105985253A CN 201510063344 A CN201510063344 A CN 201510063344A CN 105985253 A CN105985253 A CN 105985253A
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- amino
- trifluoroacetic ethyl
- ammonia
- acetic acid
- crotonates
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Abstract
The invention discloses a method for preparing 3-amino-4,4,4-trifluorocrotonate with high raw material utilization rate. According to the invention, 4,4,4-trifluoroacetyl ethyl acetate and excessive ammonium acetate are subjected to an amination reaction to obtain a reaction solution, then the reaction solution is separated to an organic phase and an aqueous phase, ammoniacal liquor is added in the aqueous phase to obtain ammonium acetate, and finally ammonium acetate is cycled to continuous reaction.
Description
Technical field
The present invention relates to a kind of 3-amino-4, the preparation method of 4,4-trifluoroacetic ethyl crotonates, utilize particularly to a kind of high raw material
The preparation method of the 3-amino-4,4,4-trifluoroacetic ethyl crotonate of rate.
Background technology
3-amino-4,4,4-trifluoroacetic ethyl crotonates are reactive intermediates in pesticide, medicine and other industrial chemical building-up process,
It is particularly useful for making the substituted heterocyclic compound of trifluoromethyl, as uracil derivant, thiazole derivative, oxazines class are spread out
Biology and pyridine derivatives.
For 3-amino-4, the preparation of 4,4-trifluoroacetic ethyl crotonates, typically with 4,4,4-trifluoroacetic ethyl acetoacetates and ammonium acetate
For raw material, prepared by aminating reaction.The method can produce substantial amounts of by-product, i.e. containing acetic acid and the mixture of water, and existing skill
Art generally uses four kinds of method separating acetic acids and water: conventional distillation method, azeotropic distillation, extraction fractional distillation, extraction-azeotropic couple
Rectification method.For conventional distillation method, owing to the relative volatility of acetic acid and water is close to 1, need the more number of plates and bigger
Reflux ratio, in terms of equipment investment and energy consumption, the most do not have economy.For azeotropic distillation, owing to adding entrainer, institute
Need the number of plates less and separation efficiency is higher, but when acetic acid concentration is relatively low in charging, azeotropic distillation needs greater energy consumption, and sets
Standby input is big, there is entrainer and supplements and recovery problem.For extraction fractional distillation, can obtain higher by adding extractant
Strength acetic acid solution, but equipment investment is big, there is extractant and supplements and recovery problem.For extraction-azeotropic coupling rectification method,
By extracting rectifying and azeotropic distillation being coupled, cost of material that acetic acid reclaims and energy consumption cost can be made to reduce further.
A kind of the mixed of separating acetic acid that 3-amino-4,4,4-trifluoroacetic ethyl crotonate produces and water can be applicable to it is thus desirable to develop
The method of compound.
Summary of the invention
It is an object of the invention to provide a kind of method preparing 3-amino-4,4,4-trifluoroacetic ethyl crotonate of high raw material availability.
For reaching goal of the invention the technical solution used in the present invention it is:
One prepares 3-amino-4, the method for 4,4-trifluoroacetic ethyl crotonates, comprises the following steps:
(1) at reaction temperature is 60～120 DEG C, making 4,4,4-trifluoroacetic ethyl acetoacetates carry out amine with the ammonium acetate of excess
Change reaction and obtain the reactant liquor containing 3-amino-4,4,4-trifluoroacetic ethyl crotonate；
(2) make reactant liquor be cooled to 30～80 DEG C, be separated into rich in 3-amino-4, the organic facies of 4,4-trifluoroacetic ethyl crotonates and
Rich in the aqueous phase of acetic acid, organic facies obtains 3-amino-4,4,4-trifluoroacetic ethyl crotonates after purifying further；
(3) in aqueous phase, add ammonia, make acetic acid react with ammonia and obtain ammonium acetate, by acetic acid after removed under reduced pressure water and ammonia
Ammonium is recycled to step (1) and continues reaction.
Reaction equation is as follows:
As preferred mode, in above-mentioned steps (1), ammonium acetate and 4, the mol ratio of 4,4-trifluoroacetic ethyl acetoacetates is preferred
It is 1.0～2.5:1, and more preferably 1.8～2.1:1；Reaction temperature is preferably 80～110 DEG C.
As preferred mode, in above-mentioned steps (2), reactant liquor is cooled to 30～60 DEG C, is separated into rich in 3-amino-4,4,4-
The organic facies of trifluoroacetic ethyl crotonate and the aqueous phase rich in acetic acid, acetic acid mass content in aqueous phase is 30～80%.Wherein second
Acid mass content in aqueous phase more preferably 40～60%.
As preferred mode, in above-mentioned steps (3), the mass content of ammonia is preferably 10～28%, and more preferably
15～25%；The mol ratio of ammonia and acetic acid is preferably 1.0～1.8:1, and more preferably 1.2～1.5:1；Removed under reduced pressure
The temperature of water and ammonia is preferably 30～100 DEG C, and more preferably 70～90 DEG C, vacuum is preferably-100～-50KPa,
And more preferably-95～-75KPa.
Compared with prior art, the invention have the advantages that
(1) raw material 4,4,4-trifluoroacetic ethyl acetoacetate and ammonium acetate utilization rate are high；
(2) product 3-amino-4,4,4-trifluoroacetic ethyl crotonate content is high, yield is high；
(3) acetic acid and laden water separation process are efficient, it is not necessary to investment rectifying device and interpolation extractant or entrainer, cost economy.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further described, but does not limit the invention to these and be embodied as
Mode.One skilled in the art would recognize that and present invention encompasses potentially included in Claims scope all alternative
Scheme, improvement project and equivalents.
Embodiment 1
Aminating reaction kettle amasss as 1000L, is furnished with stirring, thermometer, measuring tank and condenser.By measuring tank toward reactor
Middle addition 368.0kg (2.0kmol) 4,4,4-trifluoroacetic ethyl acetoacetate, is warming up to 90 DEG C after adding.Then 323.4 are put into
Kg (4.2kmol) ammonium acetate, finishes and is incubated 3 hours at latter 90 DEG C.Cooling reacting liquid temperature, to 30 DEG C, stops stirring, stands
30 minutes.Reactant liquor divides two-layer, and lower floor is organic facies, and weight is 359.6kg, product 3-amino-4,4,4-trifluoro .beta.-methylacrylic acids
The content of ethyl ester is 98.2%, yield 96.5%；Upper strata is aqueous phase, and aqueous phase weight 330.6kg, in aqueous phase, the content of acetic acid is 36.3%.
The 359.6kg aqueous phase of gained is transferred in the neutralization reactor of 1000L, neutralize reactor be furnished with stirring, thermometer,
Measuring tank and condenser.After opening stirring, dripping 20% ammonia after being warming up to 40 DEG C, dripping quantity is that 204.0kg (is equivalent to second
1.2 equivalents of acid).After dropping, system temperature is increased to 70 DEG C, the water in vacuum-95KPa removing system
With unnecessary ammonia.Finally obtaining the ammonium acetate solid of 318.2kg white, purity is 98.2%, and the response rate is 96.6%.
Embodiment 2
Aminating reaction kettle amasss as 1000L, is furnished with stirring, thermometer, measuring tank and condenser.By measuring tank toward reactor
Middle addition 368.0kg (2.0kmol) 4,4,4-trifluoroacetic ethyl acetoacetate, is warming up to 100 DEG C after adding.Then 308.0 are put into
Kg (4.0kmol) ammonium acetate, finishes and is incubated 4 hours at latter 80 DEG C.Cooling reacting liquid temperature, to 40 DEG C, stops stirring, stands
30 minutes.Reactant liquor divides two-layer, and lower floor is organic facies, and weight is 357.6kg, product 3-amino-4,4,4-trifluoro .beta.-methylacrylic acids
The content of ethyl ester is 97.7%, yield 95.4%；Upper strata is aqueous phase, and aqueous phase weight 317.5kg, in aqueous phase, the content of acetic acid is 38.5%.
The 317.5kg aqueous phase of gained is transferred in the neutralization reactor of 1000L, neutralize reactor be furnished with stirring, thermometer,
Measuring tank and condenser.After opening stirring, dripping 25% ammonia after being warming up to 50 DEG C, dripping quantity is that 175.3kg (is equivalent to second
1.3 equivalents of acid).After dropping, system temperature is increased to 80 DEG C, the water in vacuum-85KPa removing system
With unnecessary ammonia.Finally obtaining the ammonium acetate solid of 302.5kg white, purity is 97.6%, and the response rate is 95.9%.
Embodiment 3
Aminating reaction kettle amasss as 1000L, is furnished with stirring, thermometer, measuring tank and condenser.By measuring tank toward reactor
Middle addition 414.0kg (2.25kmol) 4,4,4-trifluoroacetic ethyl acetoacetate, is warming up to 95 DEG C after adding.Then 366.0 are put into
Ammonium acetate solid (weight respectively accounts for 50%) obtained by the embodiment 1 of kg (4.75kmol) and embodiment 2, finishes latter 95 DEG C
Lower insulation 3 hours.Cooling reacting liquid temperature, to 35 DEG C, stops stirring, stands 30 minutes.Reactant liquor divides two-layer, and lower floor is for having
Machine phase, weight is 403.5kg, product 3-amino-4, and the content of 4,4-trifluoroacetic ethyl crotonates is 98.2%, yield 96.2%；
Upper strata is aqueous phase, and aqueous phase weight 375.4kg, in aqueous phase, the content of acetic acid is 36.8%.
The 403.5kg aqueous phase of gained is transferred in the neutralization reactor of 1000L, neutralize reactor be furnished with stirring, thermometer,
Measuring tank and condenser.After opening stirring, dripping 25% ammonia after being warming up to 60 DEG C, dripping quantity is that 187.7kg (is equivalent to second
1.2 equivalents of acid).After dropping, system temperature is increased to 90 DEG C, the water in vacuum-80KPa removing system
With unnecessary ammonia.Finally obtaining the ammonium acetate solid of 359.2kg white, purity is 98.0%, and the response rate is 96.2%.
Claims (9)
1. prepare 3-amino-4 for one kind, the method for 4,4-trifluoroacetic ethyl crotonates, it is characterised in that comprise the following steps:
(1) at reaction temperature is 60～120 DEG C, making 4,4,4-trifluoroacetic ethyl acetoacetates carry out amine with the ammonium acetate of excess
Change reaction and obtain the reactant liquor containing 3-amino-4,4,4-trifluoroacetic ethyl crotonate；
(2) make reactant liquor be cooled to 30～80 DEG C, be separated into rich in 3-amino-4, the organic facies of 4,4-trifluoroacetic ethyl crotonates and
Rich in the aqueous phase of acetic acid, organic facies obtains 3-amino-4,4,4-trifluoroacetic ethyl crotonates after purifying further；
(3) in aqueous phase, add ammonia, make acetic acid react with ammonia and obtain ammonium acetate, by acetic acid after removed under reduced pressure water and ammonia
Ammonium is recycled to step (1) and continues reaction.
2. according to preparation 3-amino-4 described in claim 1, the method for 4,4-trifluoroacetic ethyl crotonates, it is characterised in that described step
Suddenly, in (1), ammonium acetate and 4, the mol ratio of 4,4-trifluoroacetic ethyl acetoacetates is 1.0～2.5:1, and reaction temperature is 80～110 DEG C.
3. according to preparation 3-amino-4 described in claim 2, the method for 4,4-trifluoroacetic ethyl crotonates, it is characterised in that described step
Suddenly, in (1), ammonium acetate and 4, the mol ratio of 4,4-trifluoroacetic ethyl acetoacetates is 1.8～2.1:1.
4. according to preparation 3-amino-4 described in claim 1, the method for 4,4-trifluoroacetic ethyl crotonates, it is characterised in that described step
Suddenly in (2), reactant liquor is cooled to 30～60 DEG C, is separated into rich in 3-amino-4, the organic facies of 4,4-trifluoroacetic ethyl crotonates
With the aqueous phase rich in acetic acid, acetic acid mass content in aqueous phase is 30～80%.
5. according to preparation 3-amino-4 described in claim 4, the method for 4,4-trifluoroacetic ethyl crotonates, it is characterised in that described step
(2), in, acetic acid mass content in aqueous phase is 40～60%.
6. according to preparation 3-amino-4 described in claim 1, the method for 4,4-trifluoroacetic ethyl crotonates, it is characterised in that described step
Suddenly in (3), the mass content of ammonia is 10～28%, and ammonia is 1.0～1.8:1 with the mol ratio of acetic acid.
7. according to claim, preparation 3-amino-4 described in 6, the method for 4,4-trifluoroacetic ethyl crotonates, it is characterised in that described step
Suddenly, in (3), the mass content of ammonia is 15～25%.Ammonia is 1.2～1.5:1 with the mol ratio of acetic acid.
8. according to preparation 3-amino-4 described in claim 1, the method for 4,4-trifluoroacetic ethyl crotonates, it is characterised in that described step
Suddenly, in (3), the temperature of removed under reduced pressure water and ammonia is 30～100 DEG C, vacuum is-100～-50KPa.
9. according to preparation 3-amino-4 described in claim 11, the method for 4,4-trifluoroacetic ethyl crotonates, it is characterised in that described step
Suddenly, in (3), the temperature of removed under reduced pressure water and ammonia is 70～90 DEG C, vacuum is-95～-75KPa.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4100189A (en) * | 1975-04-24 | 1978-07-11 | Rhone-Poulenc Industries | Recovery of acetic acid from dilute aqueous solutions thereof |
| WO1991007392A1 (en) * | 1989-11-17 | 1991-05-30 | Uniroyal Chemical Ltd./Uniroyal Chemical Ltee | Pesticidal pyrimidinyl benzoic acids and esters |
| JPH06321877A (en) * | 1993-05-12 | 1994-11-22 | Nissan Chem Ind Ltd | Production of 3-substituted amino-4,4,4-trifluorocrotonic ester |
| CN1172103A (en) * | 1996-05-22 | 1998-02-04 | 罗姆和哈斯公司 | Method for preparing 3-amino substituted crotonates |
| CA2222831A1 (en) * | 1997-05-19 | 1999-05-28 | Showa Denko Kabushiki Kaisha | Process for producing saturated aliphatic carboxylic acid amide |
| US6423866B1 (en) * | 1997-11-07 | 2002-07-23 | Solvaytflour Und Derivate Gmbh | Production of aminohalogencrotonates |
| CN101838215A (en) * | 2010-05-25 | 2010-09-22 | 刘伟斌 | Process for separating acetic acid from DMAC azeotrope |
| CN103694119A (en) * | 2012-09-28 | 2014-04-02 | 中化蓝天集团有限公司 | Preparation method of ethyl 4,4,4-trifluoroacetoacetate |
-
2015
- 2015-02-06 CN CN201510063344.1A patent/CN105985253A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4100189A (en) * | 1975-04-24 | 1978-07-11 | Rhone-Poulenc Industries | Recovery of acetic acid from dilute aqueous solutions thereof |
| WO1991007392A1 (en) * | 1989-11-17 | 1991-05-30 | Uniroyal Chemical Ltd./Uniroyal Chemical Ltee | Pesticidal pyrimidinyl benzoic acids and esters |
| JPH06321877A (en) * | 1993-05-12 | 1994-11-22 | Nissan Chem Ind Ltd | Production of 3-substituted amino-4,4,4-trifluorocrotonic ester |
| CN1172103A (en) * | 1996-05-22 | 1998-02-04 | 罗姆和哈斯公司 | Method for preparing 3-amino substituted crotonates |
| CA2222831A1 (en) * | 1997-05-19 | 1999-05-28 | Showa Denko Kabushiki Kaisha | Process for producing saturated aliphatic carboxylic acid amide |
| US6423866B1 (en) * | 1997-11-07 | 2002-07-23 | Solvaytflour Und Derivate Gmbh | Production of aminohalogencrotonates |
| CN101838215A (en) * | 2010-05-25 | 2010-09-22 | 刘伟斌 | Process for separating acetic acid from DMAC azeotrope |
| CN103694119A (en) * | 2012-09-28 | 2014-04-02 | 中化蓝天集团有限公司 | Preparation method of ethyl 4,4,4-trifluoroacetoacetate |
Non-Patent Citations (2)
| Title |
|---|
| 董延军 等: "利用奥沙新母液制备乙酸铵", 《佳木斯医学院学报》 * |
| 蒋强 等: "3-氨基-4,4,4-三氟巴豆酸乙酯的应用进展", 《有机氟工业》 * |
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