CN107628939A - A kind of synthetic method of 2,3,3,3 tetrafluoro propionic acid - Google Patents
A kind of synthetic method of 2,3,3,3 tetrafluoro propionic acid Download PDFInfo
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- CN107628939A CN107628939A CN201710918455.5A CN201710918455A CN107628939A CN 107628939 A CN107628939 A CN 107628939A CN 201710918455 A CN201710918455 A CN 201710918455A CN 107628939 A CN107628939 A CN 107628939A
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- propionic acid
- tetrafluoro propionic
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Abstract
The invention provides a kind of preparation method of compound, and in particular to a kind of preparation method of 2,3,3,3 tetrafluoro propionic acid, specific method are：In the basic conditions, N, the fluoroalanine of N diethyl 2,3,3,3 four are put into solvent, heating hydrolysis, carries out low temperature crystallization after the completion of hydrolysis, you can 2,3,3,3 tetrafluoro propionic acid are made.1st, to contain N in the present invention, the waste liquid of the fluoroalanine of N diethyl 2,3,3,3 four is as raw material, it is not necessary to which, using catalyst, 2,3,3,3 tetrafluoro propionic acid are prepared in hydrolysis in the basic conditions.Because hydrolysis is to carry out in the basic conditions, therefore hydrolysis rate is fast, it is not necessary to using metallic catalyst, does not pollute the environment.2nd, after the completion of the characteristics of maximum in the application is hydrolysis, hydrolysate is collected using the method for low temperature crystallization, compared to the method for distillation, product purity is high, technique is simple, shortens the production cycle, reduces production cost.
Description
Technical field
The invention provides a kind of preparation method of compound, and in particular to a kind of preparation side of 2,3,3,3- tetrafluoro propionic acid
Method, belong to chemical products preparing technical field.
Background technology
2,3,3,3- tetrafluoro propionic acid be it is a kind of be widely used in medicine, the important fluoro-containing intermediate of pesticide field, fusing point is
28.2 DEG C, the document report about its synthetic route is less.
Hemer, I et al. (Journal of Fluorine Chemistry, 34 (2), 241-50；1986) with 1,1- bis-
Bromo- 1,2,2,2- tetrafluoropropanes or the bromo- 1- of 1- chloro- 1,2,2,2- tetrafluoropropanes are raw material, first react to form zincon with zinc powder,
Again with CO2Reaction introduces carboxyl, and finally debrominate or chlorine synthesize 2,3,3,3- tetrafluoro propionic acid under zinc powder effect.Used in this method
Initiation material is not easy to obtain, and seriously pollutes environment using a large amount of zinc powders, and yield is very low.
Yamauchi, Akiyoshi et al. (JP2008280304) with 1,1,2,3,3,3- hexafluoropropene for raw material, in alkali
Property under the conditions of reacted with benzylalcohol into ester, then hydrolyze generation 2,3,3,3- tetrafluoro propionic acid, the yield of this method is 63%, but 1,1,
2,3,3,3- hexafluoropropenes are expensive.
Zhang Zhiguo et al. (CN103254058A) and Zhao Lei et al. (CN103508875A) is with N, N- diethyl -2,3,3,3-
Four fluoroalanines are initiation material, and reaction 2,3,3,3- tetrafluoro propionic acid of synthesis are hydrolyzed in acid condition using catalyst.
Yield can reach 90% or so, but reaction needs to use catalyst, can cause environmental pollution, and be steamed using normal pressure
Evaporate to obtain 2,3,3,3- tetrafluoro propionic acid.
N, N- diethyl -1,1,2,3,3,3- hexafluoro propylamine are a kind of fluorination reagents, are widely used in chemical industry, pharmacy production
Industry, the reagent is just needed to use to be fluorinated in the building-up process of veterinary antibiotic Florfenicol.N, N- diethyl -2,3,3,3-
Four fluoroalanines are N, N- diethyl -1,1, and 2,3,3,3- hexafluoro propylamine carry out the accessory substance after fluorination reaction, and the accessory substance is not
It is degradable, if directly discharge will seriously pollute environment.In order to alleviate N, the fluoroalanines of N- diethyl -2,3,3,3- four are to life
The pressure of enterprise and environment is produced, is developed a kind of simple to operate, free from environmental pollution with N, N- diethyl -2,3,3,3- tetrafluoros third
Acid amides is the technique that raw material prepares 2,3,3,3- tetrafluoro propionic acid, turns waste into wealth, environmental protection, increases the benefit, and has very much reality
Meaning.
The content of the invention
The invention provides a kind of synthetic method of 2,3,3,3- tetrafluoro propionic acid, prior art this method solve not
Foot, the N being effectively utilized in waste liquid, N- diethyl -2,3,3,3- tetra- fluoroalanines, turned waste into wealth, can environmental protection,
The performance of enterprises is improved again.
Technical scheme is used by realizing above-mentioned purpose of the present invention：
A kind of synthetic method of 2,3,3,3- tetrafluoro propionic acid, in the basic conditions, by N, N- diethyl -2,3,3,3- tetrafluoros
In propionamide input solvent, heating is hydrolyzed, and low temperature crystallization is carried out after the completion of hydrolysis, you can 2,3,3,3- tetrafluoros third are made
Acid, reaction equation are as follows：
Described solvent is combination more than one or both of water, methanol, ethanol, toluene and dimethylbenzene.
The mass volume ratio of the fluoroalanines of the N, N- diethyl -2,3,3,3- four and solvent is：1:7~20g/mL.
Alkali used is sodium hydroxide, potassium hydroxide, sodium methoxide or caustic alcohol in described alkalescence condition.
The mol ratio of the fluoroalanines of the N, N- diethyl -2,3,3,3- four and alkali is 1：5~10.
The heating-up temperature of the hydrolysis is 70~140 DEG C, and the reaction time is 12~24 hours.
The temperature of described low temperature crystallization is 0~20 DEG C.
Compared with prior art, there is advantages below in the application：1st, to contain N in the present invention, N- diethyl -2,3,3,
The waste liquid of the fluoroalanines of 3- tetra- is as raw material, it is not necessary to which, using catalyst, hydrolysis in the basic conditions is prepared 2,3,3,3-
Tetrafluoro propionic acid.Because hydrolysis is to carry out in the basic conditions, therefore hydrolysis rate is fast, it is not necessary to using metallic catalyst,
Do not pollute the environment.2nd, after the completion of the characteristics of maximum in the application is hydrolysis, hydrolysis is collected using the method for low temperature crystallization
Product.In fact, Chinese patent《A kind of synthetic methods of 2,3,3,3- tetrafluoros propionic acid (I) of the A of CN 103508875》With《CN
A kind of synthetic methods of 2,3,3,3- tetrafluoros propionic ester of 106278887 A》In refer in the claims in alkalescence condition
Lower hydrolysis, however, in its patent Example, but the hydrolyzed under acidic conditions being to provide entirely without exception, then uses and steams
The mode evaporated is to obtain product.The embodiment not being hydrolyzed in the basic conditions, present inventor are special more than
When the method that profit is provided is hydrolyzed, find in the basic conditions, being using the method for distillation after hydrolysis can not be smooth
Obtain product 2,3,3,3- tetrafluoro propionic acid.Present inventor has done substantial amounts of research work on this basis, exists finally
Under one accidental chance, discovery can be collected with the mode of low temperature crystallization to the product after hydrolyzed under basic conditions.And
And due to using the technique of low temperature crystallization in the application, compared to the method for distillation, product purity is high, technique is simple, shortens
Production cycle, reduce production cost.
Embodiment
The present invention is explained with example, it should be understood that example is to be used to illustrate the present invention, is not to this hair below
Bright limitation, the scope of the present invention are determined with core content according to claims.
Embodiment 1
60g sodium hydroxides, 200ml water, 350ml methanol and the fluoroalanine 60.3g of N, N- diethyl -2,3,3,3- four are thrown
Entering in there-necked flask, stirring is warming up to 100 DEG C of backflows, and methanol is evaporated off in normal pressure after reacting 20 hours, and reaction solution is down into 1 DEG C or so,
There is mass crystallization precipitation, centrifuge, obtain product 41.6g, molar yield 95%, GC purity is 99.5%.
Embodiment 2
96g sodium hydroxides, 450ml water and the fluoroalanine 60.3g of N, N- diethyl -2,3,3,3- four are put into there-necked flask
In, backflow is warming up to, reaction solution is down to 5 DEG C or so by quick stirring reaction after 22 hours, there is mass crystallization precipitation, centrifugation point
From obtaining product 39.7g, molar yield 90.6%, GC purity is 99.7%.
Embodiment 3
72g potassium hydroxide, 250ml water, 450ml toluene and the fluoroalanine 60.3g of N, N- diethyl -2,3,3,3- four are thrown
Entering in there-necked flask, stirring is warming up to 110 DEG C of backflows, and reaction removes toluene under reduced pressure after 14 hours, reaction solution is down into 8 DEG C or so,
There is mass crystallization precipitation, centrifuge, obtain product 42.4g, molar yield 96.8%, GC purity is 99.5%.
Embodiment 4
By 84g sodium hydroxides, 270ml water, 400ml dimethylbenzene and the fluoroalanine 60.3g of N, N- diethyl -2,3,3,3- four
Put into there-necked flask, stirring is warming up to 90 DEG C of backflows, and reaction removes dimethylbenzene under reduced pressure after 12 hours, reaction solution is down into 5 DEG C of left sides
The right side, there is mass crystallization precipitation, centrifuge, obtain product 42.8g, molar yield 97.7%, GC purity is 99.6%.
Claims (7)
1. the synthetic method of the tetrafluoro propionic acid of one kind 2,3,3,3-, it is characterised in that：In the basic conditions, by N, N- diethyl -2,
In 3,3,3- tetra- fluoroalanines input solvent, heating is hydrolyzed, and low temperature crystallization is carried out after the completion of hydrolysis, you can 2,3,3 are made,
3- tetrafluoro propionic acid, reaction equation are as follows：
2. the synthetic method of according to claim 12,3,3,3- tetrafluoro propionic acid, it is characterised in that：Described solvent is
Combination more than one or both of water, methanol, ethanol, toluene and dimethylbenzene.
3. the synthetic method of according to claim 1 or 22,3,3,3- tetrafluoro propionic acid, it is characterised in that：The N, N- bis-
The mass volume ratio of the fluoroalanines of ethyl -2,3,3,3- four and solvent is：1:7~20g/mL.
4. the synthetic method of according to claim 12,3,3,3- tetrafluoro propionic acid, it is characterised in that：Described alkalescence condition
In used alkali be sodium hydroxide, potassium hydroxide, sodium methoxide or caustic alcohol.
5. the synthetic method of 2 according to claim 1 or 4,3,3,3- tetrafluoro propionic acid, it is characterised in that：The N, N- bis-
The mol ratio of the fluoroalanines of ethyl -2,3,3,3- four and alkali is 1：5~10.
6. the synthetic method of according to claim 12,3,3,3- tetrafluoro propionic acid, it is characterised in that：The hydrolysis
Heating-up temperature is 70~140 DEG C, and the reaction time is 12~24 hours.
7. the synthetic method of according to claim 12,3,3,3- tetrafluoro propionic acid, it is characterised in that：Described low temperature crystallization
Temperature be 0~20 DEG C.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2795601A (en) * | 1956-01-03 | 1957-06-11 | Minnesota Mining & Mfg | Fluorinated 2-alkenoic acids, esters and amides |
| CN103254058A (en) * | 2013-04-19 | 2013-08-21 | 京山瑞生制药有限公司 | Process for synthesizing 2, 3, 3, 3-tetrafluoropropionic acid |
| CN103508875A (en) * | 2012-06-25 | 2014-01-15 | 赵磊 | 2,3,3,3-tetrafluoro propionic acid (I) synthesis method |
| CN104072357A (en) * | 2014-07-04 | 2014-10-01 | 太仓博亿化工有限公司 | Synthetic method for difluoroethanoic acid |
| CN106278887A (en) * | 2016-08-15 | 2017-01-04 | 赵满良 | A kind of synthetic method of 2,3,3,3 tetrafluoro propionic esters |
-
2017
- 2017-09-30 CN CN201710918455.5A patent/CN107628939A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2795601A (en) * | 1956-01-03 | 1957-06-11 | Minnesota Mining & Mfg | Fluorinated 2-alkenoic acids, esters and amides |
| CN103508875A (en) * | 2012-06-25 | 2014-01-15 | 赵磊 | 2,3,3,3-tetrafluoro propionic acid (I) synthesis method |
| CN103254058A (en) * | 2013-04-19 | 2013-08-21 | 京山瑞生制药有限公司 | Process for synthesizing 2, 3, 3, 3-tetrafluoropropionic acid |
| CN104072357A (en) * | 2014-07-04 | 2014-10-01 | 太仓博亿化工有限公司 | Synthetic method for difluoroethanoic acid |
| CN106278887A (en) * | 2016-08-15 | 2017-01-04 | 赵满良 | A kind of synthetic method of 2,3,3,3 tetrafluoro propionic esters |
Non-Patent Citations (2)
| Title |
|---|
| 李广洲 等: "《学科教学详解 初中化学》", 31 July 2015, 湖南教育出版社 * |
| 金杭丹 等: "2,3,3,3-四氟丙酸的制备及其应用", 《浙江化工》 * |
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Application publication date: 20180126 |