CN109748831A - A kind of preparation method of trifluoromethanesulfonic acid trifluoro ethyl ester - Google Patents
A kind of preparation method of trifluoromethanesulfonic acid trifluoro ethyl ester Download PDFInfo
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- CN109748831A CN109748831A CN201910129449.0A CN201910129449A CN109748831A CN 109748831 A CN109748831 A CN 109748831A CN 201910129449 A CN201910129449 A CN 201910129449A CN 109748831 A CN109748831 A CN 109748831A
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- ethyl ester
- trifluoromethanesulfonic acid
- preparation
- trifluoro ethyl
- water
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Abstract
The present invention relates to a kind of preparation method of trifluoromethanesulfonic acid trifluoro ethyl ester, which includes the following steps: that (1) synthesizes: triethylamine, trifluoroethanol and trifluoro Fumette being synthesized, synthesis material is obtained；(2) it hydrolyzes: synthesis material is hydrolyzed；(3) rectifying: the organic matter that hydrolysis is obtained is sent into the rectifying still of 300L, is heated with steam, and the fraction for collecting 89 DEG C of boiling points of tower top temperature is target product trifluoromethanesulfonic acid trifluoro ethyl ester.The present invention has the advantages that the preparation method of trifluoromethanesulfonic acid trifluoro ethyl ester of the present invention enables the trifluoromethanesulfonic acid trifluoro ethyl ester content prepared to reach 98% or more, can be used for organic synthesis by selecting suitable raw material and effectively controlling reaction condition.
Description
Technical field
The invention belongs to organic synthesis intermediate preparation technical field, in particular to a kind of trifluoromethanesulfonic acid trifluoro ethyl ester
Preparation method.
Background technique
Trifluoromethanesulfonic acid trifluoro ethyl ester, alias 2,2,2- trifluoroethyl trifluoromethayl sulfonic acid ester, English name are
TRIFLUOROMETHANESULFONIC ACID, No. CAS is 6226-25-1, molecular formula C3H2F6O3S, is used for organic synthesis
Intermediate.
But the preparation method of related trifluoromethanesulfonic acid trifluoro ethyl ester is not retrieved at present.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation methods of trifluoromethanesulfonic acid trifluoro ethyl ester, prepare
Trifluoromethanesulfonic acid trifluoro ethyl ester can be used in organic synthesis.
In order to solve the above technical problems, the technical solution of the present invention is as follows: a kind of preparation side of trifluoromethanesulfonic acid trifluoro ethyl ester
Method, innovative point are: the preparation method includes the following steps:
Step 1: synthesis: triethylamine being added in the 200L kettle of dried and clean, and cooling water is opened under stirring, and control temperature exists
10-20 DEG C, then trifluoroethanol is added dropwise in kettle, control temperature is at 20-30 DEG C, time for adding 0.5-1.5h, after dripping off
15-25min is stirred, then is cooled to 10 DEG C of temperature < with brine ice, is then slowly passed through trifluoro Fumette wherein, temperature control
For system at 6-10 DEG C, the time is 4.5-6 hours, and first four hour is subject to the speed of emission-free releasing, per hour about 6-7kg, after
Face velocity is slow；Stirring 3-4 hours after having led to, at 10-15 DEG C, synthesis terminates temperature；
Step 2: hydrolysis: being cooled to 8-12 DEG C for the material that step 1 synthesis obtains, and then instills hydrolysis water wherein,
Temperature is controlled at 15-25 DEG C, stirs 5-10mn, is stood 0.4-0.6h, is separated following organic layer, then being passed through water scouring water will be above-mentioned
The organic layer stirring washing 8-12min separated, stands 0.5-1.5h, separates organic layer, it is ensured that without obvious droplet, then add
Natrium carbonicum calcinatum stirs 15-25min, and stands 0.5-1.5h, filters off solids after being repeated twice, and takes limpid organic matter essence
It evaporates；
Step 3: rectifying: the organic matter that step 2 is obtained is sent into the rectifying still of 300L, is heated with steam, collects tower top
The fraction of 89 DEG C of boiling points of temperature is target product trifluoromethanesulfonic acid trifluoro ethyl ester.
Further, the mass ratio of triethylamine and trifluoroethanol in step 1 is 1:0.98-0.99, step in the step 1
The mass ratio of triethylamine and trifluoro Fumette in step 1 is 1:1.56-1.58 in 1.
Further, trifluoro Fumette and the mass ratio of hydrolysis water in step 2 are 1:1.35- in the step 1
1.37, the mass ratio of water scouring water is 1.5:1 in hydrolysis water and step 2 in step 2, natrium carbonicum calcinatum and step 1 in step 2
The mass ratio of middle triethylamine is 1:30.
The present invention has the advantages that the preparation method of trifluoromethanesulfonic acid trifluoro ethyl ester of the present invention, suitable former by selecting
Material and effectively control reaction condition, enable the trifluoromethanesulfonic acid trifluoro ethyl ester content prepared to reach 98% or more, can use
In organic synthesis.
Specific embodiment
The following examples can make professional and technical personnel that the present invention be more fully understood, but therefore not send out this
It is bright to be limited among the embodiment described range.
Embodiment
The preparation method of the present embodiment trifluoromethanesulfonic acid trifluoro ethyl ester, the preparation method include the following steps:
Step 1: synthesis: the triethylamine of 21kg being added in the 200L kettle of dried and clean, and cooling water, control temperature are opened under stirring
Then the trifluoroethanol of 20.6kg is added dropwise in kettle by degree at 10-20 DEG C, control temperature at 25 DEG C, time for adding 1h is dripped off
After stir 20min, then be cooled to 10 DEG C of temperature < with brine ice, be then slowly passed through the trifluoro Fumette of 33kg wherein,
At 6-10 DEG C, the time is 4.5-6 hours for temperature control, and first four hour is subject to the speed of emission-free releasing, per hour about 6-
7kg, behind speed it is slow；Stirring 3-4 hours after having led to, at 10-15 DEG C, synthesis terminates temperature；
Step 2: hydrolysis: the material that step 1 synthesis obtains being cooled to 10 DEG C, the hydrolysis of 45kg is then instilled it with water
In, temperature is controlled at 20 DEG C, stirs 5-10mn, is stood 0.5h, is separated following organic layer, then being passed through the water scouring water of 30kg will be upper
The organic layer stirring washing 10min separated is stated, 1h is stood, separates organic layer, it is ensured that without obvious droplet, then add 0.7kg
Natrium carbonicum calcinatum, stir 20min, and stand 1h, filter off solids after being repeated twice, take limpid organic matter rectifying；
Step 3: rectifying: the organic matter that step 2 is obtained is sent into the rectifying still of 300L, is heated with steam, collects tower top
The fraction of 89 DEG C of boiling points of temperature is the target product trifluoromethanesulfonic acid trifluoro ethyl ester of 28-32kg, and content is up to 98% or more.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The skill of the industry
Art personnel it should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (3)
1. a kind of preparation method of trifluoromethanesulfonic acid trifluoro ethyl ester, it is characterised in that: the preparation method includes the following steps:
Step 1: synthesis: triethylamine being added in the 200L kettle of dried and clean, and cooling water is opened under stirring, controls temperature in 10-20
DEG C, then trifluoroethanol is added dropwise in kettle, controls temperature at 20-30 DEG C, time for adding 0.5-1.5h is stirred after dripping off
15-25min, then 10 DEG C of temperature < are cooled to brine ice, then slowly trifluoro Fumette is passed through wherein, temperature control exists
6-10 DEG C, the time is 4.5-6 hour, and first four hour is subject to the speed of emission-free releasing, per hour about 6-7kg, behind it is fast
Degree is slow；Stirring 3-4 hours after having led to, at 10-15 DEG C, synthesis terminates temperature；
Step 2: hydrolysis: being cooled to 8-12 DEG C for the material that step 1 synthesis obtains, and then instills hydrolysis water wherein, temperature
Control stirs 5-10mn at 15-25 DEG C, stands 0.4-0.6h, separates following organic layer, then be passed through water scouring water and separate above-mentioned
Organic layer stirring washing 8-12min, stand 0.5-1.5h, separate organic layer, it is ensured that without obvious droplet, then add anhydrous
Sodium carbonate stirs 15-25min, and stands 0.5-1.5h, filters off solids after being repeated twice, takes limpid organic matter rectifying；
Step 3: rectifying: the organic matter that step 2 is obtained is sent into the rectifying still of 300L, is heated with steam, collects tower top temperature
The fraction of 89 DEG C of boiling points is target product trifluoromethanesulfonic acid trifluoro ethyl ester.
2. the preparation method of trifluoromethanesulfonic acid trifluoro ethyl ester according to claim 1, it is characterised in that: in the step 1
The mass ratio of trifluoroethanol is 1:0.98-0.99 in triethylamine and step 1, triethylamine and trifluoro methylsulfonyl in step 1 in step 1
The mass ratio of fluorine is 1:1.56-1.58.
3. the preparation method of trifluoromethanesulfonic acid trifluoro ethyl ester according to claim 1, it is characterised in that: in the step 1
The mass ratio of hydrolysis water is 1:1.35-1.37 in trifluoro Fumette and step 2, hydrolysis water and water in step 2 in step 2
The mass ratio of scouring water is 1.5:1, and the mass ratio of natrium carbonicum calcinatum and triethylamine in step 1 is 1:30 in step 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2018115421444 | 2018-12-17 | ||
| CN201811542144 | 2018-12-17 |
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| CN109748831A true CN109748831A (en) | 2019-05-14 |
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| CN201910129449.0A Pending CN109748831A (en) | 2018-12-17 | 2019-02-21 | A kind of preparation method of trifluoromethanesulfonic acid trifluoro ethyl ester |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3419595A (en) * | 1965-03-05 | 1968-12-31 | Minnesota Mining & Mfg | Fluorocarbon fluoroalkanesulfonates |
| US4263311A (en) * | 1976-09-27 | 1981-04-21 | Smithkline Corporation | 5,6-Phenyl-2,3-dihydroimidazo [2,1-b] thiazoles |
| JPS62221695A (en) * | 1986-03-24 | 1987-09-29 | Microbial Chem Res Found | Tylosin oxide derivative and production thereof |
| US5550273A (en) * | 1993-09-30 | 1996-08-27 | Minnesota Mining And Manufacturing Company | Process for preparing fluorocarbon fluoroalkanesulfonates |
| CN1188403C (en) * | 2000-05-22 | 2005-02-09 | 比奥维特罗姆股份公司 | Inhibitors of 11-beta-hydroxy steroid dehydrogenase type 1 |
| JP2005314356A (en) * | 2004-03-30 | 2005-11-10 | Central Glass Co Ltd | Method for production of fluoroalykylfluoroalkane-sulfonate |
| CN102076658A (en) * | 2008-05-29 | 2011-05-25 | 罗地亚管理公司 | Method for the sulphonylation of a hydroxylated organic compound |
-
2019
- 2019-02-21 CN CN201910129449.0A patent/CN109748831A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3419595A (en) * | 1965-03-05 | 1968-12-31 | Minnesota Mining & Mfg | Fluorocarbon fluoroalkanesulfonates |
| US4263311A (en) * | 1976-09-27 | 1981-04-21 | Smithkline Corporation | 5,6-Phenyl-2,3-dihydroimidazo [2,1-b] thiazoles |
| JPS62221695A (en) * | 1986-03-24 | 1987-09-29 | Microbial Chem Res Found | Tylosin oxide derivative and production thereof |
| US5550273A (en) * | 1993-09-30 | 1996-08-27 | Minnesota Mining And Manufacturing Company | Process for preparing fluorocarbon fluoroalkanesulfonates |
| CN1188403C (en) * | 2000-05-22 | 2005-02-09 | 比奥维特罗姆股份公司 | Inhibitors of 11-beta-hydroxy steroid dehydrogenase type 1 |
| JP2005314356A (en) * | 2004-03-30 | 2005-11-10 | Central Glass Co Ltd | Method for production of fluoroalykylfluoroalkane-sulfonate |
| CN102076658A (en) * | 2008-05-29 | 2011-05-25 | 罗地亚管理公司 | Method for the sulphonylation of a hydroxylated organic compound |
Non-Patent Citations (2)
| Title |
|---|
| J. BURDON等: "TRIFLUOROMFTHANESULPHONATE ESTERS AND THEIR ALKYLATING PROPERTIES", 《TETRAHEDRON》 * |
| SHUICHI SAKAMOTO等: "SYNTHESES OF 23-DEOXY-23-N-ETHYL-23-(2-FLUORO-, 2,2-DIFLUORO-, AND 2,2,2-TRIFLUOROETHYL)AMINO DERIVATIVES OF MYCAMINOSYL TYLONOLIDE AND 4"-DEOXYMYCAMINOSYL TYLONOLIDE", 《THE JOURNAL OF ANTIBIOTICS》 * |
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Application publication date: 20190514 |