CN109824551A - A method of trimethyl fluoride sulfonyl fluorine is prepared by trimethyl fluoride sulfonyl chlorine - Google Patents
A method of trimethyl fluoride sulfonyl fluorine is prepared by trimethyl fluoride sulfonyl chlorine Download PDFInfo
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- CN109824551A CN109824551A CN201910273954.2A CN201910273954A CN109824551A CN 109824551 A CN109824551 A CN 109824551A CN 201910273954 A CN201910273954 A CN 201910273954A CN 109824551 A CN109824551 A CN 109824551A
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- fluoride sulfonyl
- trimethyl fluoride
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- trimethyl
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Abstract
The method of the trimethyl fluoride sulfonyl fluorine reaction is prepared by trimethyl fluoride sulfonyl chlorine it is divided into two steps the invention discloses a kind of: (1) under the conditions of nitrogen protection; trimethyl fluoride sulfonyl chlorine is instilled in the solution containing potassium fluoride and 18- crown- 6; when dropping liquid, reaction system is placed in ice-water bath.(2) after dropping liquid, continue 2 hours.After reaction, it can be collected in cold-trap and obtain trimethyl fluoride sulfonyl fluorine liquid.The present invention has many advantages, such as that synthetic route is short, and process flow is simple, reaction safety is high.
Description
Technical field
The invention belongs to organic chemical industry fields, and in particular to one kind prepares trimethyl fluoride sulfonyl fluorine by trimethyl fluoride sulfonyl chlorine
Method, the present invention has many advantages, such as that synthetic route is short, and process flow is simple, reaction safety is high.
Background technique
Trimethyl fluoride sulfonyl fluorine is a kind of important organic intermediate, can be used for preparing trifluoromethane sulfonic acid, trifluoromethyl
The important organic compounds such as sulfonate, two (trimethyl fluoride sulfonyl) inferior amine salts and many pharmaceutical compounds, organic catalyst
Synthesize indispensable base stock.Meanwhile based on literature survey as a result, it is also that one kind potentially can be used for high voltage transmission
In environmentally friendly insulating gas.As a kind of important fine-chemical intermediate, both at home and abroad very to trimethyl fluoride sulfonyl fluorine demand
Greatly, it is increasingly becoming the hot spot product in fine-chemical intermediate field.Its research and production are concentrated mainly on the U.S., Japan at present
Regional with European Union etc., the country starts late to the research of this compound, and there are the high requirements on the equipment, peaces for most of synthesis technology
The problems such as overall coefficient is lower.
Patent CN 101842348A discloses a kind of manufacturing method of trifluoro Fumette.This method is to pass through depositing in water
Under, make trifluoromethanesulfchloride chloride (CF3SO2Cl it) is reacted with metal fluoride, to manufacture trifluoro Fumette (CF3SO2F).It should
Method has problems in that no matter raw material trimethyl fluoride sulfonyl chlorine or product trimethyl fluoride sulfonyl fluorine are all to water sensitive
Compound, extremely stringent to the control requirement of the amount of water, experiment serious forgiveness is low.Meanwhile when raw material or product react with water
When, amount of heat and HF and HCl toxic gas can be generated.
Summary of the invention
In order to solve the above-mentioned technical problems, the present invention provides one kind to prepare trimethyl fluoride sulfonyl by trimethyl fluoride sulfonyl chlorine
The method of fluorine.
The problem of method provided by the invention carries out under water-less environment, reacts there is no raw material and target product and water,
Certainly amount of heat will not be generated, HF or HCl toxic gas will not be also generated.Present invention employs 18- crown-s 6 as catalysis
Agent can be effectively reduced reaction energy barrier, improve reaction speed and production efficiency；Using the potassium fluoride of drying type technical spray,
Further increase reaction speed and efficiency.The present invention is low for equipment requirements, is not necessarily to hyperbaric environment, and low energy consumption, without additional heating.
Method synthetic route provided by the invention is simple, and reaction safety is high, and serious forgiveness is high.Confirmation about proportion can be opened up briefly
It opens.
The present invention is using trimethyl fluoride sulfonyl chlorine as raw material, and the molar ratio with potassium fluoride is 1:3, in the catalysis of 18- crown- 6
It is reacted under effect, reaction condition is low temperature ice-water bath, by nitrogen protection inside system, produces the trifluoromethyl of high-purity
Sulfuryl fluoride, and without other harmful poisonous by-products.
Synthetic route of the invention is as follows:
Scheme provided by the invention is as follows:
A method of trimethyl fluoride sulfonyl fluorine is prepared by trimethyl fluoride sulfonyl chlorine, which comprises the following steps:
(1) potassium fluoride and catalyst are dissolved in solvent and obtain solution A；
(2) under nitrogen protection, trimethyl fluoride sulfonyl chlorine is instilled in solution A；
(3) it is collected after fully reacting through condensation and obtains trimethyl fluoride sulfonyl fluorine liquid.
Specifically, the reaction temperature of above-mentioned reaction system is 0 DEG C.
Specifically, the temperature for condensing collection after above-mentioned reaction system fully reacting is -78 DEG C.
Specifically, above-mentioned potassium fluoride is the dry potassium fluoride of technical spray, partial size is 1.0~15 μm.
Specifically, above-mentioned catalyst is 18- crown- 6, quality is 1%~5wt% of potassium fluoride.
Specifically, above-mentioned solvent is selected from the mixed of one or more of dimethylformamide, tetrahydrofuran and anhydrous acetonitrile
It closes, quality is 2~5 times of potassium fluoride.
Specifically, the molar ratio of above-mentioned trimethyl fluoride sulfonyl chlorine and potassium fluoride is 1:3.
Another object of the present invention is to provide the reaction unit of benefit with the aforedescribed process, including reaction unit, gas washing dress
It sets and tail gas collecting device.
The reaction unit includes two-mouth bottle；A bite of two-mouth bottle connects dropping funel, another mouthful of connection condenser pipe；
Air-washer is made of two cold-traps or drexel bottle；
Tail gas collecting device is gas buffer bag；
Condenser pipe, air-washer and the tail gas collecting device of the reaction unit are sequentially connected；
The cold-trap connecting with condenser pipe or drexel bottle are equipped with silicone oil.
Specifically, the temperature of refrigerant is less than -10 DEG C in the condenser pipe.
Specifically, the cold-trap connecting with tail gas collecting device or the control of the temperature of drexel bottle are at -78 DEG C.
Shown in preparation facilities Fig. 1.
Beneficial effects of the present invention:
(1) reaction is water-less environment, effectively avoids contact of the raw material with water, will not generate HF and HCl toxic gas, is improved
React serious forgiveness and safety；
(2) catalyst is used as using 18- crown- 6, reaction energy barrier can be effectively reduced, potassium fluoride is spray drying type, is mentioned
High reaction speed and production efficiency；
(3) yield is higher, and prepared product purity is high；
(4) synthetic route is simple, and equipment requirement is low, is not necessarily to hyperbaric environment, and low energy consumption, without additional heating.
Detailed description of the invention
Fig. 1 is the schematic diagram of reaction unit of the present invention, wherein 1,2 is cold-trap (or drexel bottle) device.
Specific embodiment
It is further described below with reference to technical solution of the example to invention.
Following embodiments carry out preparing trimethyl fluoride sulfonyl fluorine using device shown in FIG. 1.The device includes reaction dress
It sets, air-washer and tail gas collecting device.The reaction unit includes two-mouth bottle；A bite of two-mouth bottle connects dropping funel, separately
Connection condenser pipe flatly.Air-washer is made of two cold-traps, and No. 1 cold-trap connects condenser pipe, and No. 2 cold-traps are connected to No. 1 cold-trap.
Tail gas collecting device is gas buffer bag.Condenser pipe, air-washer and the tail gas collecting device of the reaction unit are sequentially connected.
The cold-trap connecting with condenser pipe is equipped with silicone oil.The temperature of refrigerant is less than -10 DEG C in the condenser pipe.Described and tail gas collecting device
The temperature of the cold-trap of connection is controlled at -78 DEG C.
Embodiment 1
10g potassium fluoride and 0.1g 18- crown- 6 are added in the anhydrous acetonitrile of 30mL, the three of 10g is added dropwise into solution
Methyl fluoride sulfonic acid chloride, solution are placed in ice-water bath, and temperature remains 0 DEG C.After being added dropwise, kept for 2 hours.Reaction terminates
Afterwards, 3.48g trimethyl fluoride sulfonyl fluorine, yield 40%, purity 94.0% can be collected into No. 2 cold-traps.
Embodiment 2
100g potassium fluoride and 5g 18- crown- 6 are added in the anhydrous acetonitrile of 400mL, are added dropwise 100g's into solution
Trimethyl fluoride sulfonyl chlorine, solution are placed in ice-water bath, and temperature remains 0 DEG C.After being added dropwise, kept for 2 hours.Reaction terminates
Afterwards, 56.55g trimethyl fluoride sulfonyl fluorine, yield 65%, purity 98.4% can be collected into No. 2 cold-traps.
Embodiment 3
50g potassium fluoride and 1.25g 18- crown- 6 are added in the anhydrous acetonitrile of 200mL, are added dropwise 50g's into solution
Trimethyl fluoride sulfonyl chlorine, solution are placed in ice-water bath, and temperature remains 0 DEG C.After being added dropwise, kept for 2 hours.Reaction terminates
Afterwards, 28.00g trimethyl fluoride sulfonyl fluorine, yield 64%, purity 98.0% can be collected into No. 2 cold-traps.
Embodiment 4
It is as follows that compound map prepared by embodiment 1-3 confirms data:
Nuclear-magnetism model: temperature 298K, model Bruker Advance-III 500MHz, probe model 5mm BBFO, fluorine spectrum
Frequency is 470.59MHz.
F19NMR(470.59MHz,CDCl3): δ=- 38.70 (dd, F), -72.10 (dd, 3F).
Mass spectrum: instrument model: TQ Mass Spectrometer:Varian 320-MS
MS(EI)m/z:base peak 69[CF3]+,67[SOF]+,64[SO2]+,48[SO]+,31[CF]+。
The foregoing is only a preferred embodiment of the present invention, but the scope of protection of the invention be not limited thereto,
Any modification that anyone skilled in the art is made in the technical scope disclosed by the present invention, equivalent replacement and
Improve etc., it should be included within the protection scope of invention.
Claims (10)
1. a kind of method for preparing trimethyl fluoride sulfonyl fluorine by trimethyl fluoride sulfonyl chlorine, which comprises the following steps:
(1) potassium fluoride and catalyst are dissolved in solvent and obtain solution A；
(2) under nitrogen protection, trimethyl fluoride sulfonyl chlorine is instilled in solution A；
(3) it is collected after fully reacting through condensation and obtains trimethyl fluoride sulfonyl fluorine liquid.
2. according to the method described in claim 1, it is characterized by: the reaction temperature of the reaction system is 0 DEG C.
3. according to the method described in claim 1, it is characterized by: condensing the temperature of collection after the reaction system fully reacting
It is -78 DEG C.
4. according to the method described in claim 1, it is characterized by: the potassium fluoride is the dry potassium fluoride of technical spray,
Partial size is 1.0~15 μm.
5. according to the method described in claim 1, quality is potassium fluoride it is characterized by: the catalyst is 18- crown- 6
1%~5wt%.
6. according to the method described in claim 1, it is characterized by: the solvent be selected from dimethylformamide, tetrahydrofuran and
The mixing of one or more of anhydrous acetonitrile, quality are 2~5 times of potassium fluoride.
7. according to the method described in claim 1, it is characterized by: the molar ratio of the trimethyl fluoride sulfonyl chlorine and potassium fluoride is
1:3。
8. the reaction unit of method described in claim 1, it is characterised in that:
Including reaction unit, air-washer and tail gas collecting device；
The reaction unit includes two-mouth bottle；A bite of two-mouth bottle connects dropping funel, another mouthful of connection condenser pipe；
Air-washer is made of two cold-traps or drexel bottle；
Tail gas collecting device is gas buffer bag；
Condenser pipe, air-washer and the tail gas collecting device of the reaction unit are sequentially connected；
The cold-trap connecting with condenser pipe or drexel bottle are equipped with silicone oil.
9. device according to claim 8, it is characterised in that: the temperature of refrigerant is less than -10 DEG C in the condenser pipe.
10. device according to claim 8, it is characterised in that: the cold-trap or gas washing being connect with tail gas collecting device
The temperature of bottle is controlled at -78 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112661676A (en) * | 2020-12-15 | 2021-04-16 | 中船重工（邯郸）派瑞特种气体有限公司 | Method for preparing methanesulfonyl fluoride from methanesulfonyl chloride |
| CN112724047A (en) * | 2020-12-15 | 2021-04-30 | 中船重工（邯郸）派瑞特种气体有限公司 | Device and method for preparing trifluoromethanesulfonyl fluoride |
| CN115724774A (en) * | 2022-12-16 | 2023-03-03 | 山东华安新材料有限公司 | Preparation method of trifluoromethyl sulfonyl chloride |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112661676A (en) * | 2020-12-15 | 2021-04-16 | 中船重工（邯郸）派瑞特种气体有限公司 | Method for preparing methanesulfonyl fluoride from methanesulfonyl chloride |
| CN112724047A (en) * | 2020-12-15 | 2021-04-30 | 中船重工（邯郸）派瑞特种气体有限公司 | Device and method for preparing trifluoromethanesulfonyl fluoride |
| CN112661676B (en) * | 2020-12-15 | 2022-11-25 | 中船(邯郸)派瑞特种气体股份有限公司 | Method for preparing methanesulfonyl fluoride from methanesulfonyl chloride |
| CN112724047B (en) * | 2020-12-15 | 2023-10-17 | 中船(邯郸)派瑞特种气体股份有限公司 | Device and method for preparing trifluoro methanesulfonyl fluoride |
| CN115724774A (en) * | 2022-12-16 | 2023-03-03 | 山东华安新材料有限公司 | Preparation method of trifluoromethyl sulfonyl chloride |
| CN115724774B (en) * | 2022-12-16 | 2023-12-26 | 山东华安新材料有限公司 | Preparation method of trifluoromethyl sulfonyl chloride |
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Application publication date: 20190531 |