CN1032814C - Preparation method of polyhalogen alkyl sulfonite - Google Patents
Preparation method of polyhalogen alkyl sulfonite Download PDFInfo
- Publication number
- CN1032814C CN1032814C CN 91107533 CN91107533A CN1032814C CN 1032814 C CN1032814 C CN 1032814C CN 91107533 CN91107533 CN 91107533 CN 91107533 A CN91107533 A CN 91107533A CN 1032814 C CN1032814 C CN 1032814C
- Authority
- CN
- China
- Prior art keywords
- sulfonite
- reaction
- preparation
- polyhalogen
- water
- 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.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for preparing polyhalogen alkyl sulfonite. A sulfinatodehalogenation reaction of bisulfite which is used as sulfination reagents and polyhalogen paraffin hydrocarbon is reacted in mixed solvents of polar solvents and water to make polyhalogen alkyl sulfonite. The present invention has the advantages of high conversion rate and yield, mild condition, short reacting time, easy purification of products, low productive cost, etc., and is suitable for commercial production.
Description
The present invention relates to a kind of preparation method of many halogen organic compound, specifically a kind of preparation method of polyhalogen alkyl sulfonite.
Polyhalogen alkyl sulfonite, particularly polyfluoro or perfluoroalkyl-sulfinate are important organic halogen compound of a class and fluorine-containing organic intermediate.Perfluor or Polyfluoroalkyl-sulfinate can be used for preparing the very important fluorinated organic compound of a big class---perfluor or Polyfluoroalkyl-sulfinic acid, sulfonic acid and derivative thereof, extensive application on organic synthesis and industrial production is used for organic synthesis as trifluoromethanesulfonic acid as organic proton super acids; Perfluorooctane sulfonate and derivative thereof are good fluorochemical surfactants, are a kind of important industrial auxiliary agents; Perfluorinated sulfonic resin is applied to chlorine industry.Simultaneously, perfluor or polyfluoro-sulfinate are a kind of good fluoroalkylation reagent.
Preparation method about polyhalogen alkyl sulfonite reports a lot, present hydrocarbon alkyl sulfonyl chloride of industrial main employing or sulfonic acid fluoride, carry out electrofluorination with anhydrous hydrofluoric acid, generate perfluoroalkyl sulfonyl fluoride, further change into perfluoroalkyl-sulfinic acid, sulfonic acid and derivative thereof (T.Gramstd and R.N.Haszeldine again, J.Chem.Soc, 1957,2640).This method shortcoming is to prepare the perfluoroalkyl-sulfinate, and technical difficulty is big, requires height, and the perfluorination productive rate obviously reduces with the growth of carbon bond.NaHSO such as Huang Weiyuan
3/ Ce
4+Redox system carry out sulfinatodehalogenation and prepare-sulfinate (Huang Weiyuan, Chen Jianlong, chemical journal, 1986,44,484), this reaction must be reacted under acid bar, the productive rate temperature influence is very big, difficult control, and suitability for industrialized production still has certain difficulty.Therefore seek one simple and easy and be applicable to that effectively the preparation method of the polyhalogen alkyl sulfonite of suitability for industrialized production is still the problem that people make earnest efforts studying.
For this reason, the object of the invention provides a kind of productive rate height, and cost is low, the reaction conditions gentleness, and the reaction times is short, and product is easy to purifying and is suitable for the preparation method of the polyhalogen alkyl sulfonite of suitability for industrialized production.
Preparation method of the present invention is to be raw material with the polyhalid alkane, carries out sulfinatodehalogenation with sulfination reagent hydrosulphite and generate polyhalogen alkyl sulfonite in the mixed solvent of polar solvent and water.Method of the present invention, available following reaction formula is represented:
B is F, Cl, Br, I, H, SO in the formula
2F, SO
2Na, SO
3Na, COOH, COONa, CONH
2, CON (Me)
2, CON (Et)
2, PO (OEt)
2,
R is (CH
2)
2n, (CF
2)
2m-1, (CF
1)
d-O-(CF
2)
2m-1,
M=1-5 wherein, n=0-5, d=1-2,
X is F, Cl, Br, I,
Y is F, Cl, Br, I,
Z is Cl, Br, I
If when B was I or Br substituting group, B also became SO in reaction process
2Na (being B ' in the formula),
If B is SO
2During F, then B is hydrolyzed into SO in reaction process
3When Na (being B ' in the formula), B were above-mentioned other substituting groups, unaffected under reaction conditions, B ' was identical with B.
Sulfination reagent is a class hydrosulphite, as sodium bisulfite, Potassium hydrogen sulfite, ammonium bisulfite etc.The mole ratio of polyhalid alkane and hydrosulphite is 1: 1-10, the polar solvent of forming mixed solvent with water can be N, dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO), acetonitrile, alcohols (methyl alcohol, ethanol, Virahol etc.), acetone etc., the volume ratio of polar solvent and water is 0.1-5: 1, and per 10 millimole polyhalid alkanes 5-50 milliliter mixed solvent.
Temperature of reaction is the reflux temperature from the room temperature to the reaction solvent, and the reaction times becomes with temperature of reaction, is to be 0.5-20 hour.Transformation efficiency is 100%, and productive rate can reach 70-95%.
As mentioned above, the inventive method can singly be converted into polyhalogen alkyl sulfonite to polyhalid alkane, the reaction conditions gentleness with one step of cheap hydrosulphite, reaction times is short, the easy purifying that is easy to of product separation method, productive rate height, cost is low, does not need special equipment, is suitable for suitability for industrialized production.
In order to understand the present invention better, now be exemplified below:
Embodiment 1
Polyfluoro or perfluoroalkyl iodides (bromine) are for the sulfinatodehalogenation of alkane
In 5 milliliters of mixed solvents of forming by polar solvent and water, add 5 millimole polyfluoros or perfluoroalkyl iodides (bromine) for alkane and a certain amount of sodium bisulfite, react certain hour at a certain temperature,
19F-NMR follows the tracks of reaction.After reaction is all over, removal of solvent under reduced pressure, remaining solid ethyl acetate extraction.Get white solid, recrystallization in Virahol or water after removing ethyl acetate.Products therefrom
19F-NMR, IR and physical constant are all consistent with bibliographical information.The preparation of various polyfluoros or perfluoroalkyl-sulfinic acid sodium sees Table I.
Embodiment 2
Have the sulfinatodehalogenation of the Polyfluoroalkyl iodine (bromine) of polar group replacement for alkane
In 20 milliliters of mixed solvents of forming by polar solvent and water, add 10 millimoles and have Polyfluoroalkyl sulphur (bromine) that polar group replaces for alkane and a certain amount of sodium bisulfite, react certain hour at a certain temperature.
19F-NMR follow the tracks of detection reaction fully after, decompression removes down and desolvates, the remaining solid ethyl acetate extraction gets white solid after removing ethyl acetate.With Virahol or water recrystallization, products therefrom
19F-NMR, IR and physical constant are consistent with bibliographical information.The preparation of various-sulfinic acid sodium salts sees Table II.
Embodiment 3
α, ω perfluoroalkyl diiodo-(bromine) is for the sulfinatodehalogenation of alkane
In 50 milliliters of mixed solvents of forming by polar solvent and water, add 10 millimole α, ω-perfluoroalkyl diiodo-(bromine) reacts certain hour at a certain temperature for alkane and a certain amount of hydrosulphite.
19F-NMR follows the tracks of reaction.After reacting completely, removal of solvent under reduced pressure, behind the hcl acidifying, with ether extraction three times (3 * 30 milliliters), the ether extracted liquid anhydrous magnesium sulfate drying.Remove ether, drip potassium hydroxide aqueous solution to neutral.Decompression removes and anhydrates, and water or Virahol recrystallization get product.Product
19F-NMR, IR and physical constant are consistent with bibliographical information.The preparation of various-sulfinic acid sylvite sees Table III.
Embodiment 4
The preparation of trichloromethyl-sulfinic acid sodium
With 10 millimole tetra sulfur chlorides, 20 millimole sodium bisulfites reached the mixed solvent of being made up of 10 milliliters of DMF and 5 ml waters and put into reaction flask, 80 ℃ of reactions 15 hours.Removal of solvent under reduced pressure, the remaining solid ethyl acetate extraction.After extracting solution is removed ethyl acetate, use the Virahol recrystallization, get product trichloromethyl-sulfinic acid sodium 1.40 grams, productive rate is 70%.The physical constant of product is consistent with bibliographical information.
Table I polyfluoro or perfluoroalkyl iodides (bromine) are for the sulfinatodehalogenation of alkane
The Polyfluoroalkyl iodine (bromine) that Table II band rubbish group replaces is for the sulfinatodehalogenation of alkane
Table III α, ω-perfluoroalkyl diiodo-(bromine) is for the sulfinatodehalogenation of alkane
Claims (4)
1. the preparation method of a polyhalogen alkyl sulfonite is characterized in that with hydrosulphite and molecular formula be the polyhalid alkane of B-R-CXY-Z, and carrying out sulfinatodehalogenation generation molecular formula in the mixed solvent of polar solvent and water is B '-R-CXY-SO
2The polyhalogen alkyl sulfonite of Na, B is F, Cl, Br, I, H, SO in the formula
2F, SO
2Na, SO
3Na, COOH, COONa, CONH
2, CON (Me)
2, CON (Et)
2, PO (OEt)
2,
R is (CH
2)
2n, (CF
2)
2m-1, (CF
2) d-O-(CF
2)
2m-1,
M=1-5 wherein, n=0-5, d=1-2,
X is F, Cl, Br, I,
Y is F, Cl, Br, I,
Z is Cl, Br, I
When B was I or Br, B ' was SO
2Na
When B is SO
2During F, B ' is SO
2Na
When B was above-mentioned other substituting group, then B ' was identical with B,
The mole ratio of polyhalid alkane and hydrosulphite is 1: 1-10, the volume ratio that polar solvent and water are formed mixed solvent is 0.1-5: 1, per 10 millimole polyhalid alkanes are with 5-50 milliliters of mixed solvents, temperature of reaction is the reflux temperature from the room temperature to the reaction solvent, and the reaction times is to be 0.5-20 hours.
2. by the described preparation method of claim 1, it is characterized in that hydrosulphite is sodium bisulfite, Potassium hydrogen sulfite or ammonium bisulfite.
3. by the described preparation method of claim 1, the polar solvent that it is characterized in that forming with water mixed solvent can be N, dinethylformamide, dimethyl sulfoxide (DMSO), acetonitrile, alcohols and acetone.
4. by the described preparation method of claim 3, it is characterized in that used alcohols is methyl alcohol, ethanol, Virahol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91107533 CN1032814C (en) | 1991-11-19 | 1991-11-19 | Preparation method of polyhalogen alkyl sulfonite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91107533 CN1032814C (en) | 1991-11-19 | 1991-11-19 | Preparation method of polyhalogen alkyl sulfonite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1072407A CN1072407A (en) | 1993-05-26 |
| CN1032814C true CN1032814C (en) | 1996-09-18 |
Family
ID=4908869
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91107533 Expired - Fee Related CN1032814C (en) | 1991-11-19 | 1991-11-19 | Preparation method of polyhalogen alkyl sulfonite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1032814C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU5805598A (en) * | 1997-12-22 | 1999-07-12 | Minnesota Mining And Manufacturing Company | Process for preparation of fluorinated sulfinates |
| JP4930690B2 (en) * | 2005-05-13 | 2012-05-16 | 株式会社豊田中央研究所 | Ion conductive polymers and imide monomers |
| EP3611195A1 (en) | 2010-12-17 | 2020-02-19 | 3M Innovative Properties Co. | Partially fluorinated sulfinic acid monomers and their salts |
| CN102911087A (en) * | 2012-11-19 | 2013-02-06 | 江西国化实业有限公司 | Preparation method of trifluoro methanesulfonic acid |
| CN105693567B (en) * | 2016-01-06 | 2017-12-08 | 四川大学 | A kind of method for preparing arylsulfinate |
| CN117263174B (en) * | 2023-11-21 | 2024-02-02 | 新乡学院 | Sulfonic acid graphene electrode material and synthesis method thereof |
-
1991
- 1991-11-19 CN CN 91107533 patent/CN1032814C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1072407A (en) | 1993-05-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1032814C (en) | Preparation method of polyhalogen alkyl sulfonite | |
| CN1884259A (en) | Process for preparing 2-methoxyl-5-amino sulfonyl methyl benzoate | |
| CA2813834C (en) | Method for the preparation of (3s,3s') 4,4'-disulfanediylbis (3-aminobutane 1-sulfonic acid) | |
| KR101431926B1 (en) | Method for producing perfluorosulfonic acid having ether structure and derivative thereof, and surfactant containing fluorine-containing ether sulfonic acid compound and derivative thereof | |
| US4128572A (en) | Process for preparing phenylacetic acid | |
| CN1120833C (en) | Method of preparing fluorine-containing alkyl sulfinate from fluorine-containing alkyl chloromethane | |
| US7781612B2 (en) | Process for producing fluorinated sulfonyl fluoride | |
| JPH083130A (en) | Production of 4-fluorothiophenol | |
| CN102105442B (en) | Aqueous methods for making fluorinated sulfonate esters | |
| JP5018067B2 (en) | Method for producing fluorine-containing alkane esters | |
| US7019163B2 (en) | Process for producing perfluorovinylcarboxylic acid ester | |
| CN100509776C (en) | Method for synthesis of hydrogenofluoromethylenesulphonyl radical derivatives | |
| CA1253877A (en) | Process for the preparation of carboxylic acid esters of hydroxy sulfonates | |
| US4866190A (en) | Process for the preparation of perhaloalkanesulfinic and -sulfonic acids, perhaloalkanesulfinic and -sulfonic acid salts and other derivatives of these acids | |
| CN1238349C (en) | Synthesis method of L-ascorbic acid multiester compound | |
| Okazoe et al. | An entirely new methodology for synthesizing perfluorinated compounds: synthesis of perfluoroalkanesulfonyl fluorides from non-fluorinated compounds | |
| JP4318803B2 (en) | Method for producing bis (perfluoroalkylsulfonyl) methane | |
| JP2001322975A (en) | Method for producing perfluoroalkylsulfonic acid salt | |
| CA2026593A1 (en) | Process for preparing sulfonyl acids | |
| KR810000581B1 (en) | Process for the preparation of 2-aryl-propionic acid by direct-coupling utilizing | |
| CN1289462C (en) | Trifluoromethyl benzols, preparing process and application thereof | |
| CN106631770B (en) | A kind of synthetic method of beta-halogen tetrafluoro propionyl fluoride | |
| JP3624478B2 (en) | Process for producing polyfluoroalkyl ester compound | |
| CN118546051A (en) | Preparation method of perfluoroalkyl ethanol | |
| CN112079750A (en) | Preparation method of methanesulfonic acid |
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 | ||
| C15 | Extension of patent right duration from 15 to 20 years for appl. with date before 31.12.1992 and still valid on 11.12.2001 (patent law change 1993) | ||
| OR01 | Other related matters | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |