CN102295566A - Preparation method of tetrafluoroethyl dimethyl amine - Google Patents
Preparation method of tetrafluoroethyl dimethyl amine Download PDFInfo
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- CN102295566A CN102295566A CN2011101978075A CN201110197807A CN102295566A CN 102295566 A CN102295566 A CN 102295566A CN 2011101978075 A CN2011101978075 A CN 2011101978075A CN 201110197807 A CN201110197807 A CN 201110197807A CN 102295566 A CN102295566 A CN 102295566A
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- dimethyl amine
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- tetrafluoroethylene
- ethyl dimethyl
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Abstract
The invention discloses a preparation method of tetrafluoroethyl dimethyl amine. The tetrafluoroethyl dimethyl amine is expressed in a formula [1], wherein R1 and R2 are expressed as methyl. The method comprises a first-stage reaction and a subsequent second-stage reaction, wherein the pressure generated when tetrafluoroethylene and dimethylamine are reacted can be decreased by adopting the continuously-fed tetrafluoroethylene in the first-stage reaction, and the reaction temperature is increased to continue the reaction in the second-stage reaction on the basis of the first-stage reaction. Through the method disclosed by the invention, the auto-polymerization danger of the tetrafluoroethylene under a high pressure is reduced, the reaction rate is uniform, and byproducts are fewer.
Description
Technical field
The present invention relates to a kind of preparation method of fluorizating agent, particularly a kind of preparation method who can selectivity fluoridizes the compound fluorizating agent that has chiral hydroxyl group.
Background technology
Up to now, the technology of effectively fluorine atom being introduced matrix mainly contains: use element fluorine (F
2) directly fluoridize (patent documentation 1); An alkali metal salt that uses HF or fluorine is to halogen atom compound permutoid reaction (patent documentation 2); Use IF, FF
5The method of iodine such as (patent documentation 3) high price; Also can use HF and pyridine (non-patent literature 1) or triethylamine Lewis bases such as (non-patent literatures 2) to form the molecule-type compound and carry out halogen fluorine permutoid reaction.In addition, can use SF
4, SO
2F
2(patent documentation 4), DAST (patent documentation 5), alkylamine type reagent (non-patent literature 3) etc. all can be replaced as fluorine atom with the particular functional group.
As the important intermediate of medicine and agricultural chemicals, the fluorine substitution compound with chirality acquires a special sense.And utilize fluorizating agent to introduce the method for fluorine atom to the compound privileged site, high purity and obtain but difficulty very of chiral fluorinated thing with high yield.
Put down in writing application fluoro-alkyl amine tetrafluoro ethyl dimethyl amine stereoselectivity synthesis of chiral fluoropropionic acid ester in the patent documentation 6, because method therefor has very high ee and transformation efficiency, allow present inventors see the wide new prospect that tetrafluoro ethyl dimethyl amine is used in the synthetic fluorochemicals of stereoselectivity.
Non-patent literature 4 has been reported fluoro-alkyl amine tetrafluoro ethyl diethylamide (HCF
2CF
2N (C
2H
5)
2) the preparation method, on this basis, non-patent literature 5 has been reported its improved tetrafluoro ethyl dimethyl amine (HCF that can be used for fluoride fat alcohol
2CF
2N (CH
3)
2, preparation method TFEDMA).For the manufacture method of record in the non-patent literature 4, the yield of tetrafluoro ethyl diethylamide is no more than 60%; And according to the method for putting down in writing in the non-patent literature 5, reaction process adopts one kettle way, and tetrafluoroethylene hypertonia in the pressurized vessel almost reaches 3Mpa when causing reacting initial, has explosion hazard if deal with improperly; And the pressure of tetrafluoroethylene descends gradually in reaction process; become very slow in reaction later stage speed; it is not a process comparatively at the uniform velocity; these reasons cause this method to need a lot of difficult problems of customer service in the words of industrial application, therefore are starved of method a kind of economy of exploitation and that be easy to industrial implementation and prepare tetrafluoro ethyl dimethyl amine.
Patent documentation 1: the Japanese Patent spy opens bulletin clear 53-1827 number
Patent documentation 2: Chinese patent 101061090A specification sheets
Patent documentation 3: Chinese patent 1436159A specification sheets
Patent documentation 4: Chinese patent 101484405A specification sheets
Patent documentation 5: No. 3976691 specification sheets of United States Patent (USP)
Patent documentation 6: Chinese patent 101528662A specification sheets
Non-patent literature 1:J.Org.Chem., 1979,44,3872
Non-patent literature 2:Aldrichimia Acta., 1995,28,31
Non-patent literature 3:Bull.Chem.Soc.Jpn., 1979,52,3377
Non-patent literature 4:J.Am.Chem.Soc., 1960,82,5116
Non-patent literature 5:J.Fluorine Chem., 2001,109,25
Summary of the invention
Technical problem to be solved by this invention provides that a kind of reaction pressure is low, and speed of response is even, the preparation method of the tetrafluoro ethyl dimethyl amine that by product is few.
In order to solve above-mentioned technical problem, technical scheme of the present invention is: a kind of preparation method of tetrafluoro ethyl dimethyl amine, and described tetrafluoro ethyl dimethyl amine is represented suc as formula [1]:
R wherein
1, R
2The expression methyl, present method comprises fs reaction and the reaction of subordinate phase subsequently, described fs temperature of reaction of reaction is-30-10 ℃, feed the tetrafluoroethylene of 0.1-2.0MPa by the tetrafluoroethylene storage tank continuously to reactor, and under stirring condition, react with dimethylamine; Described subordinate phase is reflected on the fs reaction basis, temperature of reaction is increased to 10-60 ℃ continues reaction.
Method of the present invention can be carried out having under the situation of solvent, however the inventive method preferably do not have solvent in the presence of react.
Method of the present invention can be carried out under standard pressure, but method of the present invention also can carry out adding to depress, usually between 0.1 to 1.5MPa, and preferred 0.2-1.0MPa.
Comprise a tetrafluoroethylene storage tank that tetrafluoroethylene can be provided continuously to reactor in the method for the present invention in reaction process, and the pressure of gaseous tetrafluoroethylene is higher than reaction pressure in the reactor all the time in this storage tank.
The temperature of reaction that relates in the method for the present invention can be carried out in the larger context, but lower temperature of reaction is selected in fs reaction, usually between-15 to 0 ℃, and preferred-5 to 0 ℃; And higher temperature of reaction is selected in subordinate phase reaction, usually between 10～50 ℃, and preferred 20～30 ℃.
Manufacture method of the present invention adopts the tetrafluoroethylene reduction tetrafluoroethylene reaction pressure of continuously feeding low, has reduced the tetrafluoroethylene danger of autohemagglutination under high pressure, and operation is convenient more; In the different steps of reaction, adopt the generation of different controlling reaction temperature speed of reaction and minimizing by product.
Embodiment
Compound analysis uses following instrument to carry out in the embodiment of the invention:
(NMR) measured in the nucleus magnetic resonance POP
1H?NMR(500MHz)：Bruker?AV-500
19F?NMR(470MHz)：Bruker?AV-500
Embodiment 1
The 2L stainless steel cauldron is cooled to-5 ℃ and vacuumize, add 450g (10.0mol) dimethylamine under vacuum condition, stir then and pass through the tetrafluoroethylene storage tank down, keep temperature of reaction to be controlled at 0 to 10 ℃ of scope, and reaction pressure keeps 1-1.5MPa to the lasting tetrafluoroethylene of introducing of reactor.React after 12 hours, temperature of reaction system risen to 30-50 ℃ and kept 0.5 hour, products therefrom by rectifying (bp 76-77 ℃/760mmHg), the yield with 82.6% obtains main distillate fraction.
Embodiment 2
The 2L stainless steel cauldron is cooled to-5 ℃ and vacuumize, add 450g (10.0mol) dimethylamine under vacuum condition, stir then down and continue to introduce tetrafluoroethylene to reactor by the tetrafluoroethylene storage tank, keep temperature of reaction to be controlled at-30 to-15 ℃ of scopes, and reaction pressure keep 1.5-2.0MPa.React after 12 hours, temperature of reaction system risen to 50-60 ℃ and kept 0.5 hour, products therefrom by rectifying (bp76-77 ℃/760mmHg), the yield with 81.1% obtains main distillate fraction.
Embodiment 3
The 2L stainless steel cauldron is cooled to-5 ℃ and vacuumize, add 450g (10.0mol) dimethylamine under vacuum condition, stir then down and continue to introduce tetrafluoroethylene to reactor by the tetrafluoroethylene storage tank, keep temperature of reaction to be controlled at-15 to-5 ℃ of scopes, and reaction pressure keep 0.1-0.2MPa.React after 12 hours, temperature of reaction system risen to 10-20 ℃ and kept 0.5 hour, products therefrom by rectifying (bp 76-77 ℃/760mmHg), the yield with 84.2% obtains main distillate fraction.
Embodiment 4
The 2L stainless steel cauldron is cooled to-5 ℃ and vacuumize, add 450g (10.0mol) dimethylamine under vacuum condition, stir then down and continue to introduce tetrafluoroethylene to reactor by the tetrafluoroethylene storage tank, keep temperature of reaction to be controlled at-5 to 0 ℃ of scope, and reaction pressure keep 0.2-1.0MPa.React after 12 hours, temperature of reaction system risen to 20-30 ℃ and kept 0.5 hour, products therefrom by rectifying (bp 76-77 ℃/760mmHg), the yield with 86.9% obtains main distillate fraction.
The foregoing description does not limit the present invention in any way, and every employing is equal to replaces or technical scheme that the mode of equivalent transformation obtains all drops in protection scope of the present invention.
Claims (8)
1. the preparation method of a tetrafluoro ethyl dimethyl amine, described tetrafluoro ethyl dimethyl amine is represented suc as formula [1]:
R wherein
1, R
2The expression methyl, it is characterized in that comprising fs reaction and the reaction of subordinate phase subsequently, the temperature of reaction of described fs reaction is-30～10 ℃,, react with dimethylamine under stirring condition to the continuous tetrafluoroethylene that feeds 0.1～2.0MPa of reactor by the tetrafluoroethylene storage tank; Described subordinate phase is reflected on the fs reaction basis, temperature of reaction is increased to 10～60 ℃ continues reaction.
2. the preparation method of tetrafluoro ethyl dimethyl amine according to claim 1 is characterized in that: the reaction of described fs, subordinate phase reaction all do not have solvent in the presence of carry out.
3. the preparation method of tetrafluoro ethyl dimethyl amine according to claim 1 is characterized in that: the reaction pressure of described tetrafluoroethylene is 0.1～1.5MPa.
4. the preparation method of tetrafluoro ethyl dimethyl amine according to claim 3 is characterized in that: the reaction pressure of described tetrafluoroethylene is 0.2～1.0MPa.
5. the preparation method of tetrafluoro ethyl dimethyl amine according to claim 1 is characterized in that: described fs temperature of reaction is-15～0 ℃.
6. the preparation method of tetrafluoro ethyl dimethyl amine according to claim 5 is characterized in that: described fs temperature of reaction is-5～0 ℃.
7. the preparation method of tetrafluoro ethyl dimethyl amine according to claim 1 is characterized in that: described subordinate phase temperature of reaction is 10～50 ℃.
8. the preparation method of tetrafluoro ethyl dimethyl amine according to claim 7 is characterized in that: described subordinate phase temperature of reaction is 20～30 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101978075A CN102295566A (en) | 2011-07-14 | 2011-07-14 | Preparation method of tetrafluoroethyl dimethyl amine |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101978075A CN102295566A (en) | 2011-07-14 | 2011-07-14 | Preparation method of tetrafluoroethyl dimethyl amine |
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| CN102295566A true CN102295566A (en) | 2011-12-28 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113220A (en) * | 2013-01-29 | 2013-05-22 | 巨化集团技术中心 | Synthesis method of difluoroacetate ester |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3976691A (en) * | 1972-12-11 | 1976-08-24 | E. I. Du Pont De Nemours And Company | Dialkylaminosulfur trifluorides as fluorinating agents |
| CN101061090A (en) * | 2004-11-05 | 2007-10-24 | 国立大学法人北海道大学 | Process for producing alpha, alpha-difluoroamine |
| CN101720317A (en) * | 2007-06-15 | 2010-06-02 | 巴斯夫欧洲公司 | Method for producing difluoromethyl-substituted pyrazole compounds |
-
2011
- 2011-07-14 CN CN2011101978075A patent/CN102295566A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3976691A (en) * | 1972-12-11 | 1976-08-24 | E. I. Du Pont De Nemours And Company | Dialkylaminosulfur trifluorides as fluorinating agents |
| CN101061090A (en) * | 2004-11-05 | 2007-10-24 | 国立大学法人北海道大学 | Process for producing alpha, alpha-difluoroamine |
| CN101720317A (en) * | 2007-06-15 | 2010-06-02 | 巴斯夫欧洲公司 | Method for producing difluoromethyl-substituted pyrazole compounds |
Non-Patent Citations (3)
| Title |
|---|
| AKIO TAKAOKA等: "F-Propene-Dialkylamine Reaction Prodycts as Fluorinating Agents", 《BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN》, vol. 52, no. 11, 31 December 1979 (1979-12-31), pages 3377 - 3380, XP002971347 * |
| D.C.ENGLAND: "Nucleophilic Reactions of Fluoroolefins", 《NUCLEOPHILIC REACTIONS OF FLUOROOLEFINS》, vol. 82, 5 October 1962 (1962-10-05), pages 5116 - 5122 * |
| VIACHESLAV A. PETROV等: "1,1,2,2-Tetrafluoroethyl-N,N-dimethylamine: a new selective fluorinating agent", 《JOURNAL OF FLUORINE CHEMISTRY》, 31 December 2001 (2001-12-31), pages 25 - 31 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113220A (en) * | 2013-01-29 | 2013-05-22 | 巨化集团技术中心 | Synthesis method of difluoroacetate ester |
| CN103113220B (en) * | 2013-01-29 | 2015-03-18 | 巨化集团技术中心 | Synthesis method of difluoroacetate ester |
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Application publication date: 20111228 |