CN106632232A - Preparation method of fluorosultone - Google Patents
Preparation method of fluorosultone Download PDFInfo
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- CN106632232A CN106632232A CN201610750489.3A CN201610750489A CN106632232A CN 106632232 A CN106632232 A CN 106632232A CN 201610750489 A CN201610750489 A CN 201610750489A CN 106632232 A CN106632232 A CN 106632232A
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- acid lactone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
- C07D327/04—Five-membered rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
- C07D327/06—Six-membered rings
Abstract
The invention relates to generation of a sodium dihydroxyl sulfonate compound by a substitution reaction of a saturated aqueous solution of sodium sulfite and a chloro dihydroxy compound; a dehydration reaction is carried out for the sodium dihydroxyl sulfonate compound obtained by the step and excess dehydrating agents, after the reaction, excess dehydrating agents are removed; residual sodium dihydroxyl sulfonate is removed by washing and extracting the reaction products; drying and purification are carried out in order to obtain a hydroxy substituted sultone compound; a fluorination reaction is carried out for the obtained hydroxy substituted sultone compound and a fluorating agent, underpressure distillation and purification are carried out, and the fluorosultone compound is obtained. The method has the advantages of cheap raw material, easy purchase, simple operation steps, mild reaction conditions, short reaction steps, easy purification, and high purity of produced products.
Description
Technical field
The invention belongs to the synthetic method technical field of organic compound, more particularly in a kind of flurosulphonic acid
The preparation method of ester.
Background technology
Lithium rechargeable battery is in civilian mobile device, and the market on electrokinetic cell obtains rapidly in last decade
Development.Sultones class compound, as the conventional film for additive of lithium-ion battery electrolytes, can significantly improve lithium two
Life-span (Leggesse, E.G.and J.-C.Jiang (2012). " the Theoretical Study of the of primary cell
Reductive Decomposition of 1,3-Propane Sultone:SEI Forming Additive in
Lithium-ion Batteries."RSC Advances.).In recent years, flurosulphonic acid lactone compound is in lithium ion secondary
The common all reports of Jing on the application in the field such as battery and nonaqueous electrolyte material periodical at home and abroad.It can be seen that this kind of compound tool
Have important application prospect (Jung, H.M., S.-H.Park, et al. (2013). " Fluoropropane sultone as
an SEI-forming additive that outperforms vinylene carbonate."Journal of
Materials Chemistry A 1(38):11975-11981.)。
Shown in the general structure of flurosulphonic acid lactone such as formula (IV)：
In formula, M is CnH2n, wherein, n=1～4.
It is considerably less about the report of the preparation of flurosulphonic acid lactone in prior art, it is in flurosulphonic acid the reason for possible
Ester, the reaction for incorporating fluorine atoms into is more difficult, and synthetic yield is low, it is difficult to separating-purifying.
In view of this, it is necessory to providing a kind of operating procedure simply and can obtaining in the flurosulphonic acid of high-purity product
The preparation method of ester.
The content of the invention
The present invention provides a kind of preparation method of flurosulphonic acid lactone, and this method has that operating procedure is simple, reaction condition
Gently, the features such as easily separated purification of with low cost, product, high purity and high yield.
In order to achieve the above object, the present invention is adopted the following technical scheme that：
A kind of preparation method of flurosulphonic acid lactone, at least comprises the following steps：
(1), occur to replace instead with the saturated sodium sulfite aqueous solution and the chloro dihydroxy compounds with formula (I) structure
Should, the dihydroxy sulfonate sodium compound with formula (II) structure is generated,
In formula (I) and formula (II), M is CnH2n+1, wherein, n=1～4；
(2) the dihydroxy sulfonate sodium compound of gained in step (1) is dehydrated instead by carrying out with excessive dehydrating agent
Should, excessive dehydrating agent is removed after reaction, product is carried out to wash the dihydroxy sulfonate sodium that extraction removes residual, then Jing
It is dried purification and obtains the hydroxyl substituted sulfonic acid lactone compound with formula (III) structure
M is CnH2n+1, wherein, n=1～4；
(3) the hydroxyl substituted sulfonic acid lactone compound of gained in step (2) and fluorization agent are carried out into fluorination reaction, generates fluorine
For sultone compounds.Then vacuum distillation purification.
In formula, M is CnH2n+1, wherein, n=1～4.
As the preparation method of flurosulphonic acid lactone of the present invention, it is characterised in that：In step (1), the sulfurous
Sour sodium is (1～4) with the mol ratio of the chloro dihydroxy compounds:1, preferably (1.2～2.2):1.
As the preparation method of flurosulphonic acid lactone of the present invention, it is characterised in that：Replacement described in step (1)
Reaction is the saturated sodium sulfite aqueous solution and the dibromoalkane hydrocarbon to be added in reactor, and is entered at 80～130 DEG C
Row backflow, the backflow duration is more than or equal to 4 hours.
As the preparation method of flurosulphonic acid lactone of the present invention, it is characterised in that：Dehydration described in step (2)
Agent is SOCl2And/or COCl2And/or SO2Cl2And/or P2O5。
As the preparation method of flurosulphonic acid lactone of the present invention, it is characterised in that：Dehydration described in step (2)
Reaction is gained hydroxyl substituted sulfonic acid lactone compound in step (2) to be added in reactor, and 80 with the dehydrating agent of excess
Flowed back at～130 DEG C, the backflow duration is more than or equal to 4 hours.
As the preparation method of flurosulphonic acid lactone of the present invention, it is characterised in that：Wash described in step (2) and adopt
Washing extractant is at least one in ether, dioxane and glycol dimethyl ether, toluene.
As the preparation method of flurosulphonic acid lactone of the present invention, it is characterised in that the fluorization agent described in step (3)
Including fluorides such as sodium fluoride, potassium fluoride, antimony trifluoride, hydrogen fluoride.
As the preparation method of flurosulphonic acid lactone of the present invention, it is characterised in that：The temperature of the fluorination reaction
For 40 DEG C～120 DEG C.The temperature of the vacuum distillation is 80 DEG C～120 DEG C
Relative to prior art, the present invention at least has the advantages that：
First, raw material is inexpensively easily bought.
Second, operating procedure is simple, reaction condition is gentle.
3rd, reactions steps are short, are easily purified, and obtained product purity is high.
Specific embodiment
The preparation method of part of compounds involved in the present invention is set forth below, to make further details of theory to the present invention
It is bright, but the present invention is not restricted to the preparation of the compound cited by embodiment.
(1) specific embodiment
A kind of preparation method of flurosulphonic acid lactone, it is characterised in that comprise the following steps：
(1), occur to replace instead with the saturated sodium sulfite aqueous solution and the chloro dihydroxy compounds with formula (I) structure
Should, the dihydroxy sulfonate sodium compound with formula (II) structure is generated,
M in formula (I) and formula (II) is CnH2n+1, wherein, n=1～4；
(2) the dihydroxy sulfonate sodium compound of gained in step (1) is dehydrated instead by carrying out with excessive dehydrating agent
Should, excessive dehydrating agent is removed after reaction, product is carried out to wash the dihydroxy sulfonate sodium that extraction removes residual, then Jing
It is dried purification and obtains the hydroxyl substituted sulfonic acid lactone compound with formula (III) structure
The M of formula (III) is CnH2n+1, wherein, n=1～4；
(3) the hydroxyl substituted sulfonic acid lactone compound of gained in step (2) is carried out into fluorination reaction with fluorization agent, is then subtracted
Pressure distilation, obtains the flurosulphonic acid lactone compound with formula (IV) structure,
The M of formula (IV) is CnH2n+1, wherein, n=1～4.
The sodium sulfite is 1～4 with the mol ratio of the chloro dihydroxy compounds:1.
Substitution reaction described in step (1) is to add the saturated sodium sulfite aqueous solution and the dibromoalkane hydrocarbon
In reactor, and flowed back at 80～130 DEG C, the backflow duration is more than or equal to 4 hours.
Dehydration described in step (2) is by gained hydroxyl substituted sulfonic acid lactone compound and excess in step (2)
Dehydrating agent add in reactor, and flowed back at 80～130 DEG C, the backflow duration is more than or equal to 4 hours.
Described dehydrating agent is SOCl2、COCl2、SO2Cl2Or P2O5In the mixing of one or more arbitrary proportions.
The washing extractant that washing extraction described in step (2) is adopted is for ether, dioxane and glycol dimethyl ether, first
One or more arbitrary proportion mixing in benzene.
Fluorization agent described in step (3) is sodium fluoride, potassium fluoride, antimony trifluoride or hydrogen fluoride.
The temperature of the fluorination reaction is 40 DEG C～120 DEG C, and the temperature of the vacuum distillation is 80 DEG C～120 DEG C.
(2) specific embodiment
Embodiment 1
The fluoro- PSs of 2-
Reaction equation is as follows：
Its preparation method comprises the steps：
(1), with the saturated sodium sulfite aqueous solution and 3- chlorine-1,2-propylene glycols, 2,3- dihydroxy-propanesulfonate is generated.Tool
Body, 33.2g (0.3mol) 3- chlorine-1,2-propylene glycols are slowly added dropwise to filling sodium sulfite aqueous solution (wherein, sodium sulfite
Quality be 45.4g, mole is 0.36mol) reactor in, 4 hours are then refluxed at 110 DEG C, until system
Become homogeneous, obtain the solution containing 2,3- dihydroxy-propanesulfonate.By the solution of 2, the 3- dihydroxy-propanesulfonate of gained
Carry out being concentrated to give saturated solution, then crystallize the solid product (hydrate) of 2,3- dihydroxy-propanesulfonate of attaining the Way.
(2) gained 2,3- dihydroxy-propanesulfonate in step (1) and the dehydrating agent of excess are carried out into dehydration condensation.
Specifically, by the solid of 2,3- dihydroxy-propanesulfonate, in adding reactor, then it is slowly added dropwise 47.6g in reactor
(0.4mol) thionyl chloride.After completion of dropping, flow back 8 hours at 85 DEG C.After completion of the reaction, product is added into ice
In water.Then add ethyl acetate in reaction system, after being sufficiently stirred for separatory funnel separate organic phase (product 2- hydroxyls-
1,3 propane sultone is extracted in organic phase), organic phase is washed 2～3 times with frozen water, obtain product 2- hydroxyl -1,3 third
The solution of sultones.
(3) 2- hydroxyl -1 for obtaining step (2), 3 propane sultones are dissolved in organic solvent, in the guarantor of inert gas
Shield is lower to add fluorization agent anhydrous potassium fluoride, and 6 hours are then stirred at reflux under 80 degree.Filter after completion of the reaction, by reactant
Solution carries out vacuum distillation (pressure 1mmHg), collects 100～120 degree of cut, obtains in fluoro- 1,3 propane sulfonic acid of target product 2-
Ester 30.1g (total recovery 71%).
Embodiment 2：Fluoro- Isosorbide-5-Nitrae-the butyl sultones of 3-
Reaction equation is as follows：
Its preparation method comprises the steps：
(1), with the saturated sodium sulfite aqueous solution and the chloro- 1,3-BDOs of 4-, 2,4- dihydroxy-fourth sodium sulfonate is generated.Tool
Body, the chloro- 1,3-BDOs of 37.4g (0.3mol) 4- are slowly added dropwise to filling sodium sulfite aqueous solution (wherein, sodium sulfite
Quality be 45.4g, mole is 0.36mol) reactor in, 4 hours are then refluxed at 110 DEG C, until system
Become homogeneous, obtain the solution containing 2,4- dihydroxy-fourth sodium sulfonate.By the solution of 2, the 4- dihydroxy-fourth sodium sulfonate of gained
Carry out being concentrated to give saturated solution, then crystallize the solid product (hydrate) of 2,4- dihydroxy-fourth sodium sulfonate of attaining the Way.
(2) gained 2,4- dihydroxy-fourth sodium sulfonate in step (1) and the dehydrating agent of excess are carried out into dehydration condensation.
Specifically, by the solid of 2,4- dihydroxy-fourth sodium sulfonate, in adding reactor, then it is slowly added dropwise 47.6g in reactor
(0.4mol) thionyl chloride.After completion of dropping, flow back 8 hours at 85 DEG C.After completion of the reaction, product is added into ice
In water.Then add ethyl acetate in reaction system, after being sufficiently stirred for separatory funnel separate organic phase (product 3- hydroxyls-
Isosorbide-5-Nitrae-butyl sultone is extracted in organic phase), organic phase is washed 2～3 times with frozen water, obtain product 3- hydroxyl-Isosorbide-5-Nitraes-
The solution of butyl sultone.
(3) the 3- hydroxyls-Isosorbide-5-Nitrae-butyl sultone for obtaining step (2) is dissolved in organic solvent, in inert gas
Protection is lower to add fluorization agent anhydrous potassium fluoride, and 6 hours are then stirred at reflux under 80 degree.Filter after completion of the reaction, will react
Thing solution carries out vacuum distillation (pressure 1mmHg), collects 100～120 degree of cut, obtains the fluoro- Isosorbide-5-Nitraes of target product 3--fourth sulphur
Acid lactone 29.6g (total recovery 64%).
It should be noted that the announcement and teaching of book according to the above description, those skilled in the art in the invention may be used also
So that above-mentioned embodiment is changed and changed.Therefore, the invention is not limited in disclosed and described above being embodied as
Mode, some equivalent modifications and change to the present invention should also be as falling into the scope of the claims of the present invention.Additionally,
Although some specific terms used in this specification, these terms merely for convenience of description, not to structure of the present invention
Into any restriction.
Claims (8)
1. a kind of preparation method of flurosulphonic acid lactone, it is characterised in that comprise the following steps：
(1), there is substitution reaction with the saturated sodium sulfite aqueous solution and the chloro dihydroxy compounds with formula (I) structure, it is raw
Into the dihydroxy sulfonate sodium compound with formula (II) structure,
M in formula (I) and formula (II) is CnH2n, wherein, n=1～4；
(2) by the dihydroxy sulfonate sodium compound of gained in step (1) by carrying out dehydration with excessive dehydrating agent, instead
Excessive dehydrating agent should be afterwards removed, product is carried out to wash the dihydroxy sulfonate sodium that extraction removes residual, then drying
Purification obtains the hydroxyl substituted sulfonic acid lactone compound with formula (III) structure
The M of formula (III) is CnH2n, wherein, n=1～4；
(3) the hydroxyl substituted sulfonic acid lactone compound of gained in step (2) is carried out into fluorination reaction with fluorization agent, then decompression is steamed
Purification is evaporated, the flurosulphonic acid lactone compound with formula (IV) structure is obtained,
The M of formula (IV) is CnH2n, wherein, n=1～4.
2. the preparation method of flurosulphonic acid lactone according to claim 1, it is characterised in that：In step (1), the sulfurous
Sour sodium is 1～4 with the mol ratio of the chloro dihydroxy compounds:1.
3. the preparation method of flurosulphonic acid lactone according to claim 1, it is characterised in that：Taking described in step (1)
Generation reaction is the saturated sodium sulfite aqueous solution and the dibromoalkane hydrocarbon to be added in reactor, and at 80～130 DEG C
Flowed back, the backflow duration is more than or equal to 4 hours.
4. the preparation method of flurosulphonic acid lactone according to claim 1, it is characterised in that：It is de- described in step (2)
Water reaction is gained hydroxyl substituted sulfonic acid lactone compound in step (2) to be added in reactor with the dehydrating agent of excess, and
Flowed back at 80～130 DEG C, the backflow duration is more than or equal to 4 hours.
5. the preparation method of the flurosulphonic acid lactone according to claim 1 or 4, it is characterised in that：Described dehydrating agent is
SOCl2、COCl2、SO2Cl2Or P2O5In the mixing of one or more arbitrary proportions.
6. the preparation method of flurosulphonic acid lactone according to claim 1, it is characterised in that：Wash described in step (2)
The washing extractant that extraction is adopted is for one or more any ratios in ether, dioxane and glycol dimethyl ether, toluene
Example mixing.
7. the preparation method of flurosulphonic acid lactone according to claim 1, it is characterised in that the fluorination described in step (3)
Agent is sodium fluoride, potassium fluoride, antimony trifluoride or hydrogen fluoride.
8. the preparation method of flurosulphonic acid lactone according to claim 1, it is characterised in that：The temperature of the fluorination reaction
For 40 DEG C～120 DEG C, the temperature of the vacuum distillation is 80 DEG C～120 DEG C.
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| CN201610750489.3A CN106632232A (en) | 2016-08-29 | 2016-08-29 | Preparation method of fluorosultone |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108321434A (en) * | 2018-03-23 | 2018-07-24 | 安普瑞斯（无锡）有限公司 | A kind of high-voltage lithium-ion battery electrolyte |
| CN108484567A (en) * | 2018-03-19 | 2018-09-04 | 东莞市航盛新能源材料有限公司 | A kind of preparation method of the fluoro- 1,3- propane sultones of 1- |
| CN110105326A (en) * | 2019-02-26 | 2019-08-09 | 武汉松石科技股份有限公司 | A kind of preparation method of 1,3- propane sultone |
| KR20200001137A (en) * | 2018-06-27 | 2020-01-06 | 삼화페인트공업주식회사 | Method for preparing sultone derivatives |
| CN111499547A (en) * | 2020-03-03 | 2020-08-07 | 江汉大学 | Preparation method and application of alkyl ether sulfonyl fluoride compound |
| CN115433109A (en) * | 2022-07-27 | 2022-12-06 | 厦门威亮光学涂层技术有限公司 | Preparation method of organic sulfonic acid amine salt |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108484567A (en) * | 2018-03-19 | 2018-09-04 | 东莞市航盛新能源材料有限公司 | A kind of preparation method of the fluoro- 1,3- propane sultones of 1- |
| CN108321434A (en) * | 2018-03-23 | 2018-07-24 | 安普瑞斯（无锡）有限公司 | A kind of high-voltage lithium-ion battery electrolyte |
| KR20200001137A (en) * | 2018-06-27 | 2020-01-06 | 삼화페인트공업주식회사 | Method for preparing sultone derivatives |
| KR102070028B1 (en) | 2018-06-27 | 2020-01-29 | 삼화페인트공업주식회사 | Method for preparing sultone derivatives |
| US11180469B2 (en) * | 2018-06-27 | 2021-11-23 | Samhwa Paints Industries Co., Ltd. | Method for preparing sultone derivatives |
| CN110105326A (en) * | 2019-02-26 | 2019-08-09 | 武汉松石科技股份有限公司 | A kind of preparation method of 1,3- propane sultone |
| CN111499547A (en) * | 2020-03-03 | 2020-08-07 | 江汉大学 | Preparation method and application of alkyl ether sulfonyl fluoride compound |
| CN115433109A (en) * | 2022-07-27 | 2022-12-06 | 厦门威亮光学涂层技术有限公司 | Preparation method of organic sulfonic acid amine salt |
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