CN1165807A - Absolute trifluoro acetate and absolute trifluoro acetic acid prepn. - Google Patents
Absolute trifluoro acetate and absolute trifluoro acetic acid prepn. Download PDFInfo
- Publication number
- CN1165807A CN1165807A CN 97106461 CN97106461A CN1165807A CN 1165807 A CN1165807 A CN 1165807A CN 97106461 CN97106461 CN 97106461 CN 97106461 A CN97106461 A CN 97106461A CN 1165807 A CN1165807 A CN 1165807A
- Authority
- CN
- China
- Prior art keywords
- absolute
- trifluoro
- sulfuric acid
- reaction
- acetic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The anhydrous trifluoroacetic acid and anhydrous trifluoroacetate are prepared through the oxidation of trifloroalcohol as raw material in aqueous solution of sulfuric acid containing oxidant. The process has advantages of high selectivity and yield, shorter reaction time and low reaction temp.
Description
The invention relates to preparation of fluoric acid and salt thereof, namely preparation of anhydrous trifluoroacetic acid and anhydrous trifluoroacetate.
Anhydrous trifluoroacetic acid is an important chemical raw material. It is a good solvent for polymer and polypeptide, and at the same time it is a raw material for preparing fluorine-containing medicine (medicine and pesticide), so that it possesses extensive application. There are many reports in the literature on the preparation of anhydrous trifluoroacetic acid. The electrolytic fluorination of acetic acid derivatives is reported in J.Fluor ine chem.1987, 35(3)557 with a yield of 36-45%, and the synthesis of trifluorobromomethane and carbon dioxide under the action of metal powder or electrolysis is reported in Fr.Demante FR 2,564,829 USSR SU1,699,993. Jpn. Kokai Tokkyo Koho JP 60,239,435; jpn. Kokai Tokkyo Koho JP 60,239,437; jpn. Kokai Tokkyo JP 58,159,440 reported by CF3CHCl2The method of oxidative hydrolysis of (1). Ger. Offen DE 3,326,210 reports on the conversion of CF3CH2NO2Hydrolysis in 90% aqueous sulfuric acid. CF (compact flash)3CCl3Offen DE 3,509,911 proposes the use of transition metal catalystsHydrolysis under hydrolysis and RuO of Perfluoroalkylethylene in J.fluorine chem.1979, 13(2)1754Synthesis under oxidizing conditions. But the synthesis method with mild reaction conditions, high reaction yield and less pollution is a target which is always pursued by people.
The invention aims to provide a simple, convenient, efficient and high-selectivity preparation method.
The invention is realized by the following scheme that: trifluoroacetic acid and salt thereof are prepared by oxidizing inorganic oxidant with trifluoroethanol as raw material, and the reaction formula is as follows:
wherein the oxidant is MMnO4，M2Cr2O7，MIO4(M＝K，Na)，CrO3The sulfuric acid concentration of the aqueous sulfuric acid solution is from 1M to 8M. Inorganic salts (e.g., CuSO) may also be added to the oxidant system4，CuCl2，CuBr2) As a catalyst to increase the reaction rate, lower the reaction temperature or increase the reaction yield. The temperature range during the reaction is from room temperature to 140 ℃. The specific synthesis method is to add the oxidant into the sulfuric acid solution with a certain concentration slowly in batches, and stir to dissolve the oxidant. Then, a certain amount of trifluoroethanol wasadded in portions to the reaction system. The reaction system is kept stirring for several hours at a certain temperature, and then azeotropic distillation is carried out to distill off CF3CO2H and water. Distilling off the fraction with alkali metalNeutralizing with hydroxide water solution (concentration 10-40%) to pH 7, and removing water under reduced pressure to obtain white powdered CF3CO2M (K, Na) solid. The solid is dried for several hours under vacuum condition, and then anhydrous trifluoroacetate can be obtained. Distilling the trifluoroacetate under the condition of concentrated sulfuric acid to obtain anhydrous trifluoroacetic acid.
Compared with other methods, the method for preparing trifluoroacetate and trifluoroacetic acid has good selectivity which can reach 100%; high yield, up to 95%; short reaction time, low reaction temperature and the like, and the reduced product of the inorganic oxidant can be recycled without polluting the environment.
The following examples are helpful in understanding the present invention, but are not intended to be limiting thereof.
Example 1
Oxidizing agent CrO3The solution was added slowly in portions to a solution of sulfuric acid of a certain concentration (table below) and stirred to dissolve it. Then, a certain amount of trifluoroethanol was added in portions to the reaction system. The reaction system is kept stirring for 4-8 hours under the conditions of 110-120 ℃, then azeotropic distillation is carried out to distill off CF3CO2H and water. Distilling off the distillate, neutralizing with aqueous solution of alkali metal hydroxide (concentration 10-40%) until system pH is about 7, and removing water under reduced pressure to obtain white powdered CF3CO2M (K, Na)solid. The solid is dried for several hours under vacuum condition, and then anhydrous trifluoroacetate can be obtained. Distilling the trifluoroacetate under the condition of concentrated sulfuric acid to obtain anhydrous trifluoroacetic acid. The results are as follows:
| CF3CH2OH(g) | H2O(ml)/98％H2SO4 (ml) | CrO3(g) | time of stirring (h) | Temperature of agitation (℃) | Yield (%) |
| 10 | 40/5 | 15 | 4 | 110-120 | 50 |
| 10 | 40/5 | 14 | 6 | 110-120 | 44 |
| 10 | 40/5 | 14 | 8 | 110-120 | 50 |
| 10 | 40/10 | 14 | 4 | 110-120 | 93 |
| 10 | 40/10 | 14 | 8 | 110-120 | 95 |
Example 2
The specific experimental procedure was the same as in example 1, the stirring time was 4 hours, and the temperature change affected the present invention, with the following results:
| CF3CH2OH(g) | H2O(ml)/98％H2SO4 (ml) | CrO3(g) | time of stirring (h) | Temperature of agitation (℃) | Yield (%) |
| 10 | 40/5 | 15 | 4 | 110-120 | 50 |
| 10 | 40/ 5 | 14 | 4 | 80 | 51 |
| 10 | 40/10 | 14 | 4 | 110-120 | 93 |
| 10 | 40/10 | 14 | 4 | 80 | 86 |
| 10 | 40/10 | 14 | 4 | Without heating | 68 |
Example 3
The specific experimental procedure is the same as that of example 1, the stirring time is 4 hours, the temperature is 80 ℃ or 110 ℃ and 120 ℃, and the change of the concentration of the sulfuric acid aqueous solution has the following effect on the invention:
| CF3CH2OH(g) | H2O(ml)/98％H2SO4 (ml) | CrO3(g) | time of stirring (h) | Temperature of agitation (℃) | Yield (%) |
| 10 | 40/5 | 15 | 4 | 110-120 | 50 |
| 10 | 40/10 | 14 | 4 | 110-120 | 93 |
| 10 | 40/5 | 14 | 4 | 80 | 51 |
| 10 | 40/10 | 14 | 4 | 80 | 86 |
Example 4
The specific experimental procedure was the same as in example 1, with stirring time of 4 hours and temperature of 80 ℃ or room temperature, and inorganic salts were added to the reaction system, and the results of the inorganic salts affecting the present invention are as follows:
a adding 2.5g of CuSO4·5H2Ob 2.2g of CuBr2
| CF3CH2OH(g) | H2O(ml)/98％H2SO4 (ml) | CrO3(g) | time of stirring (h) | Temperature of agitation (℃) | Yield (%) |
| 10 | 40/10 | 14 | 4 | Without heating | 68 |
| 10 | 40/10 | 14 | 4 | Without heating | 71(a) |
| 10 | 40/10 | 14 | 4 | 80 | 86 |
| 10 | 40/10 | 14 | 4 | 80 | 61(b) |
Example 5
In the following reactions, the amounts of trifluoroethanol used were all 10g, the reaction time was 4 hours, the reaction temperature was 80 ℃, and different oxidants affected the present invention, with the following results:
| H2O(ml)/98％H2SO4(ml) | oxidant (g) | Yield (%) |
| 40/10 | CrO3 14 | 86 |
| 40/14 | K2Cr2O7 20.6 | 76 |
| 40/5 | KMnO4 22 | 30 |
| 40/13 | NaIO4 21.4 | 5 |
Claims (3)
1. A process for preparing trifluoroacetic acid and its salt features that under the condition of ordinary temp to 140 deg.C, the oxidizing reaction of trifluoroethanol in the aqueous solution of sulfuric acid containing oxidant (KMnO) takes place for 4-8 hr4、K2Cr2O7、NaIO4、CrO3(ii) a The concentration of the aqueous sulfuric acid solution is 1M to 8M.
2. The process according to claim 1, wherein an inorganic salt is added as a catalyst to the oxidation system, and the inorganic salt is CuSO4，CuCl2，CuBr2。
3. The process according to claim 1, wherein the reaction temperature is from 80 to 120 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106461A CN1049421C (en) | 1997-06-11 | 1997-06-11 | Absolute trifluoro acetate and absolute trifluoro acetic acid prepn. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106461A CN1049421C (en) | 1997-06-11 | 1997-06-11 | Absolute trifluoro acetate and absolute trifluoro acetic acid prepn. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1165807A true CN1165807A (en) | 1997-11-26 |
| CN1049421C CN1049421C (en) | 2000-02-16 |
Family
ID=5168700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97106461A Expired - Fee Related CN1049421C (en) | 1997-06-11 | 1997-06-11 | Absolute trifluoro acetate and absolute trifluoro acetic acid prepn. |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1049421C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759551B (en) * | 2009-12-30 | 2011-02-09 | 济南大学 | Method for preparation of dodecafluoroheptanoic acid |
| WO2018209842A1 (en) * | 2017-05-13 | 2018-11-22 | 南通宝凯化工有限公司 | Preparation process for trifluoroacetic acid |
| CN111333499A (en) * | 2018-12-19 | 2020-06-26 | 中蓝晨光化工研究设计院有限公司 | Process for producing fluorine-containing carboxylic acid |
| CN111333501A (en) * | 2018-12-19 | 2020-06-26 | 中蓝晨光化工研究设计院有限公司 | Preparation method of fluorine-containing carboxylic acid |
| CN113045380A (en) * | 2019-12-26 | 2021-06-29 | 中蓝晨光化工研究设计院有限公司 | Method for preparing fluorine-containing dihydric alcohol from fluorine-containing cycloolefin |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60197635A (en) * | 1984-03-21 | 1985-10-07 | Central Glass Co Ltd | Preparation of trifluoroacetic acid derivative |
| DE3564257D1 (en) * | 1984-05-15 | 1988-09-15 | Asahi Glass Co Ltd | Process for producing trifluoroacetic acid and trifluoroacetyl chloride |
| SU1699993A1 (en) * | 1989-07-18 | 1991-12-23 | Институт Физической Химии Им.Л.В.Писаржевского | Method of producing trifluoroacetic acid and its salts |
-
1997
- 1997-06-11 CN CN97106461A patent/CN1049421C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759551B (en) * | 2009-12-30 | 2011-02-09 | 济南大学 | Method for preparation of dodecafluoroheptanoic acid |
| WO2018209842A1 (en) * | 2017-05-13 | 2018-11-22 | 南通宝凯化工有限公司 | Preparation process for trifluoroacetic acid |
| CN111333499A (en) * | 2018-12-19 | 2020-06-26 | 中蓝晨光化工研究设计院有限公司 | Process for producing fluorine-containing carboxylic acid |
| CN111333501A (en) * | 2018-12-19 | 2020-06-26 | 中蓝晨光化工研究设计院有限公司 | Preparation method of fluorine-containing carboxylic acid |
| CN111333501B (en) * | 2018-12-19 | 2022-11-04 | 中蓝晨光化工研究设计院有限公司 | Preparation method of fluorine-containing carboxylic acid |
| CN111333499B (en) * | 2018-12-19 | 2023-02-10 | 中蓝晨光化工研究设计院有限公司 | Process for producing fluorine-containing carboxylic acid |
| CN113045380A (en) * | 2019-12-26 | 2021-06-29 | 中蓝晨光化工研究设计院有限公司 | Method for preparing fluorine-containing dihydric alcohol from fluorine-containing cycloolefin |
| CN113045380B (en) * | 2019-12-26 | 2023-03-14 | 中蓝晨光化工研究设计院有限公司 | Method for preparing fluorine-containing dihydric alcohol from fluorine-containing cycloolefin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1049421C (en) | 2000-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108503531B (en) | Preparation method of 3, 3-dimethyl-2-oxobutyric acid | |
| ZA200309058B (en) | Process of preparing halogenated esters. | |
| US5637741A (en) | Process for producing 2-methyl-1,4-naphthoquinone | |
| CN111440051A (en) | Synthesis method of 4-chloro-3, 5-dimethylphenol | |
| CN1165807A (en) | Absolute trifluoro acetate and absolute trifluoro acetic acid prepn. | |
| CN114805033A (en) | Synthesis method of chlorophenol compound | |
| US6746653B2 (en) | Process for recovering catalyst transition metals from salt-containing reaction mixtures | |
| CN113372204A (en) | Method for preparing aromatic aldehyde | |
| CN111825590A (en) | Preparation method of tert-butyl peroxybenzoate | |
| JP2761761B2 (en) | Industrial production of aqueous solutions of glyoxylic acid | |
| CN115583878A (en) | Preparation method of 4,4,4-trifluorobutyric acid | |
| US4400325A (en) | Process for the preparation of pure, saturated perfluoroalkane-1-carboxylic acids from 1-iodoperfluoroalkanes | |
| JP3836518B2 (en) | Method for producing 3-mercaptopropionitrile and 3-mercaptopropionic acid | |
| CN113318730B (en) | δ-MnO2Catalyst, preparation method and application thereof | |
| EP0438143B1 (en) | Process for the preparation of dodecanedioic acid | |
| CN112321399B (en) | Preparation method of chemical intermediate | |
| EP0872468A1 (en) | Method for producing 3,3-dichloro-1,1,1-trifluoroacetone | |
| JPH021833B2 (en) | ||
| CN112159340A (en) | Preparation method of hydroxyethyl sulfonic acid | |
| JPH06234691A (en) | Continuous preparation of aromatic aldehyde | |
| GB782430A (en) | Improvements in the oxidation of organic aldehydes | |
| CN112142603A (en) | Preparation method of 2, 4, 6-trichloroaniline | |
| CS268849B2 (en) | Method of 4,4-dinitrostilbene-2,2-disulphonic acid production | |
| CN102190575B (en) | Method for recovering binary acid from waste alkali liquor in cyclohexane oxidation | |
| HUE029452T2 (en) | Novel carboxylic acid ester, use of the same, and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20000216 |