CN1097191A - A kind of synthetic method of fluorine-containing hydrocarbyl sulfonate - Google Patents
A kind of synthetic method of fluorine-containing hydrocarbyl sulfonate Download PDFInfo
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Abstract
The present invention relates to a kind of from fluorohaloparaffin or Fluorine containing olefine, the method for synthetic fluorine-containing hydrocarbyl sulfonate in the presence of organic amine compound that has lone pair electron on dehalogenation sulfonated reagent, the nitrogen-atoms and solvent.
Method of the present invention not only method is easy, and is simple to operate, mild condition, and the transformation efficiency height, all recyclable utilization of organic amine and solvent, product is convenient to separate and is purified, and is suitable for suitability for industrialized production.
Description
The present invention relates to a kind of method from fluorohaloparaffin or the synthetic fluorine-containing hydrocarbyl sulfonate of Fluorine containing olefine.Specifically under the organic amine compound and solvent system that have lone pair electron on dehalogenation sulfonated reagent, the nitrogen-atoms, fluorohaloparaffin or fluorine-containing haloolefin are prepared the method for fluorine-containing hydrocarbyl sulfonate, in other words, also be a kind of dehalogenation sulfonation and sulfonation reaction.
At Synthetic Organic Chemistry and medicine, in dyestuff synthetic, the fluorine-containing alkylsulphonic acid of short chain is used very extensive, and they can be used as the catalyzer and the reaction reagent of many organic reactions.Especially trifluoromethane sulfonic acid can carry out various gentlenesses as strong acid reagent, efficiently reaches spatial selectivity organic transformation preferably, provides possibility for realizing many new building-up reactionss.At present, the way of electrofluorination is adopted in the preparation of trifluoromethane sulfonic acid or perfluoro alkyl sulfonic acid mostly, this method cost height, toxicity are big, and concerning β-hydrogen perfluoro alkyl sulfonic acid, the normal alkali aqueous solution that adopts Fluorine containing olefine and sodium bisulfite causes by superoxide in high temperature, autoclave and prepares.This process exists severe reaction conditions, and productive rate is low, and the reaction specificity is not strong, shortcomings such as cost height.
Once reported [U.S.P.2403207(1946); U.S.P.2409274(1947)] addition reaction of tetrafluoroethylene, perfluoro propylene and sodium bisulfite excessively, but the conditional request of reaction is relatively harsher, contain a large amount of boraxs in the requirement system, and temperature of reaction to need also superoxide to cause between 100-120 ℃.Produce the tetrafluoroethylene polymerization problem in the reaction process, the sulfonate of Sheng Chenging hydrolysis easily with this understanding then, and have the side reaction of tetrafluoroethylene and water addition, the HCF of generation a great deal of in the reaction product
2CNa causes difficulty for the separation of product.Thereby the preparation method of research fluorine carbon sulfonate, seek under mild conditions fluorine-containing hydrocarbyl sulfonate of high productivity synthesizing new and derivative thereof and be still a research topic highly significant.
The purpose of this invention is to provide a kind of fluorohaloparaffin with cheapness, fluorine-containing haloolefin is a raw material, has the organic amine compound of lone pair electron on nitrogen-atoms, dehalogenation sulfonated reagent and solvent exist down, prepare the method for fluorine-containing hydrocarbyl sulfonate.This salt can obtain derivatives such as fluorine-containing hydrocarbyl sulfonic and fluorine-containing sulfonic acid chloride thereof respectively again through acidifying and chloride.
Fluorohaloparaffin described in the present invention has the molecular formula of ZCXYCXYF, and fluorine-containing haloolefin is having except that CFCl=CFCl
Molecular formula, wherein Z=F, W(CF
2)
nOr W(CF
2)
mO(CF
2)
m, X=F, Cl, Br or I, Y=Cl, Br or I, R
f=H, C
nH
2n+1, W(CF
2)
n, Q(CF
2)
mO(CF
2)
mOr Cl(CFCLCF
2)
p, R
1 fOr R
11 f=F, CF
3Or C
2F
5, n=0-20, m=1-10, W=H or Y, Q=W or SO
2F, P=0-3, U=2-4.
Dehalogenation sulfonated reagent described in the present invention is MHSO
3Or M
2S
2O
5, wherein M is monovalence metal or ammonium ion, as Li, Na, K, NH
4Plasma.
On the nitrogen-atoms described in the present invention the organic amine compound of band lone pair electron be have alkyl or aryl primary, the second month in a season or tertiary amine and heterogeneous ring compound.As RNH
2, RR
1NH, RR
1R
11, NH
2R
111NH
2, R
1111 2N(CF
2)
hNR
11111 2, morphine quinoline, piperidines, hydrazine, Pyrrolidine, hexahydropyridine, diethylamine, dibutylamine, two-amino dodecane, triethylamine, trioctylamine etc., wherein R, R
1Or R
11The alkyl or aryl of=C1-12, R
111Or R
1111The alkyl of=C1-6, h=2-8.
Method of the present invention is in solvent, the mole ratio that has the organic amine compound of lone pair electron on many halogen fluothane hydrocarbon or fluorine-containing haloolefin, dehalogenation sulfonated reagent and the nitrogen-atoms is 1: 0.2-10: 0.2-10, adopt the organic amine compound that has lone pair electron on more dehalogenation sulfonated reagent or the nitrogen-atoms to not influence of reaction result.The mole ratio of recommending above-mentioned reactant is 1: 1-5: 1-10.
In the method for the invention, temperature of reaction and time are with the boiling point of different fluorochemicalss and actively decide, and temperature of reaction be-40-80 ℃ usually, and temperature is too low, and speed of response is too slow, and temperature too high yield reduces, and generally reacts and at room temperature just can carry out.So recommended temperature is-20-40 ℃.Reaction times is 0.5-50 hour, is recommended as 2-10 hour.
The solvent that adopts among the present invention is one or more polarity or non-polar solvent, as the alcohol of low carbon chain or cave, ethyl acetate, tetrahydrofuran (THF), dioxane, sherwood oil, cyclohexane, benzene, toluene, tetracol phenixin, chloroform, methylene dichloride, acetonitrile, dimethyl formamide, phenyl ether, N-methyl-2-tetramethyleneimine cave etc.But for well, contain water in the solvent and will help reaction and carry out with polar solvent.
When adopting method of the present invention, if adopt CFCl
2CFCl
2As the fluorohaloparaffin raw material, reaction product is mainly the olefin reduction product, and it is few to contain fluoroalkyl sulfonate accordingly.And when being raw material as fluorine halogen alkene, almost can not obtain to contain accordingly fluoroalkyl sulfonate with CFCl-CFCl.
Method of the present invention, when with the fluorohaloparaffin being the synthetic fluorine-containing hydrocarbyl sulfonate of raw material, normally " one kettle way " directly obtains containing the fluoroalkyl sulfonate product.Reaction may be to have experienced dehalogenation and two step of sulfonation addition course:
ZCXYCXYF→ZCX-CXF→ZCXHCXFSO
3M
Along with the variation of this body structure of fluorohaloparaffin, have organic amine compound and the solvent and the variation of lone pair electron on the nitrogen-atoms, reaction also can realize step by step.
Adopt method of the present invention to synthesize and have ZHXCCXFSO from above-mentioned fluorohaloparaffin
3The fluorine-containing hydrocarbyl sulfonate of M, Z=X wherein, W(CF
2)
n, W (CF
2)
mO(CF
2)
m, X=F, Cl, Br or I, W=X, H, M are monovalence metal or ammonium ion, also can be from the synthetic R of above-mentioned fluorine-containing haloolefin
fR
1 fCHCR
11 fXSO
3M,
Fluorine-containing hydrocarbyl sulfonate, R wherein
f=H, C
nF
2n+1, W(CF
2)
u, Q(CF
2)
mO(CF
2)
mOr Cl(CFClCF
2)
p, R
1 fOr R
11 f=F, CH
3Or C
2F
5, n=0-20, m=1-10, W=H or Y, Q=W or SO
2F, P=0-3, U=2-4, Y=Cl, Br or I, M are monovalence metal or ammonium ion.When synthesizing fluorine-containing hydrocarbyl sulfonate by fluorine-containing haloolefin, primary product is as above described, but with the initiator structural changes, also can produce the sulfonate of defluorinate product.
Adopt method of the present invention, use
19FNMR follows the tracks of the reaction and display transformation efficiency and reaches 100%, and specificity is greater than 90%.Isolated yield is subjected to speed of response, the airtight degree of system and Temperature Influence bigger.If reaction is very low with the Fluorine containing olefine boiling point, preferably change in tube sealing or the autoclave and carry out, can improve reaction yield like this.But the improper productive rate that also can cause of aftertreatment reduces.
The fluorine-containing hydrocarbyl sulfonate that adopts method of the present invention to obtain can have ZHXCCXFSO
3The molecular formula of M, Z=X wherein, W(CF
2)
n, W(CF
2)
mO(CF
2)
m, X=F, Cl, Br or I, W=X, H, M be the monovalence metal in or ammonium ion.As CF
2ClCFCl
2(F113) Quantitative yield is HClFCCF
2SO
3CF
2=CF
2, CF
3CF=CF
2Can change into HCF respectively
2CF
2SO
3M or CF
3CFHCF
2SO
3M and CF
3CF=CFSO
3M.After reactant removes by filter inorganic salt,,, can obtain corresponding fluorine-containing hydrocarbyl sulfonic with excessive mineral acid or mineral acid and methyl alcohol or the acidifying of alcoholic acid solution, distillation preferably again through concentrating.Fluorine-containing hydrocarbyl sulfonic is through acyl chloride reaction, as with PCl
5Reaction produces fluorine-containing sulfonic acid chloride.If the β carbon atom of fluorine-containing hydrocarbyl sulfonate has hydrogen atom to connect, through with alkali reaction after acidifying again, can obtain the perfluoroalkyl sulfonic acid of β-carboxyl or carbonyl.
Method of the present invention not only provides the synthetic method of a kind of perfluoroalkyl sulfonate and derivative thereof, has also opened up an approach for the utilization in fluorine Lyons.
Adopt method of the present invention, solvent, organic amine compound and inorganic salt are all recyclable, and cost is low, sulfonate purity can reach greater than 98%.
Adopt method of the present invention and system, activity that can corresponding raising fluorinated organic compound has reduced sulfonation temperature, and speed of response is fast, mild condition, and the reaction specificity is strong, the transformation efficiency height, product is easy to purifying, and is easy and simple to handle, is convenient to suitability for industrialized production.
To further help to understand the present invention by following embodiment, but not limit content of the present invention.
Embodiment 1:HClFC-CF
2SO
3Na's is synthetic
Method one, 18.8g(0.1mol) CF
2Cl-CFCl
2, the NaHSO of 0.2mol
3, the n-Butyl Amine 99 of 0.3mol, the DMF of 100ml mix the back and stirred 12 hours under room temperature.Filter, take out and desolvate, ethyl acetate extraction is used in alkalization, the anhydrous sodium sulfate drying extraction liquid, and decompression is taken out and is desolvated, and drying gets white solid 15.6g, productive rate 77%.
The BrCF of method two, 0.1mol
2CFClBr, the Na of 0.2mol
2S
2O
5, the Pyrrolidine of 0.2mol, the methylene dichloride of 100ml mix the back and reacted 10 hours down in 5 ℃.By method one aftertreatment, get white solid 17.9g, productive rate 81%.
The NaHSO of method three, 0.25mol
3, the triethylamine of 0.4mol, the DMF of 150ml, 10ml water is mixed in the autoclave, feeds the CF of 0.1mol
2=CFCl
3, reacted 10 hours.The reaction solution aftertreatment is with method one, productive rate 80%.
The product analysis result:
19The F(TFA external standard, D
2O), δ :+41.0(AB, J
AB=256HZ, 2F)
+73.5（dt，J
HF＝58HZ，1F）
1The H(TMS external standard, D
2O), δ: 6.72(ddd, J
HF=58HZ, J
3 HF=19.8HZ)
IR：νmax（cm
-1）：3500（s），1150（m），1060（ms）
Ultimate analysis calculated value: C 10.06; H 1.26; F 23.90; S 13.42
HClFC-CF
2SO
3NaH
2O measured value: C 10.58; H 1.12; F 24.25; S 13.67
Embodiment 2:HClFC-CF
2SO
3H's is synthetic
Method one, take by weighing 4.4gHClFC-CF
2SO
3Na, the dense H of adding 96%
2SO
410ml, underpressure distillation gets the 2.5g colourless viscous liquid, productive rate 58%, b.p.92 ℃/0.2mmHg(HClFC-CF
2SO
3HH
2O).
Method two, take by weighing 7.5gHClFC-CF
2SO
3Na adds the 35ml anhydrous methanol, feeds HCl gas, 50 ℃ of reactions 5 hours down, filter NaCl1.6g, take out methyl alcohol and get the 7.1g crude product.
The product analysis result:
19F（CD
3COCD
3），δ：+40.6（AB，J
AB＝256HZ，2F）
+72.76（dt，J
HF＝58HZ）
1H（CD
3COCD
3），δ：6.72（ddd，J
HF＝58HZ，19.8，3.6HZ）
8.30（S，SO
3H）
IR：νmax（cm
-1）1140（s），1090，1060（m），ν3200-3400
Ultimate analysis calculated value: C 11.09; H 1.85; F 26.33; S 14.78
HCFCl-CF
2SO
3HH
2O measured value: C 11.49; H 2.05; F 26.18; S 14.80
Embodiment 3:HClFC-CF
2SO
2Cl's is synthetic
Take by weighing 14gPCl
5, put into dropping funnel is housed, in the 50ml three-necked bottle of prolong, add the fluoroalkyl sulfonic acid crude product 7.1g that makes by embodiment 2 method twos, drip sulfonic acid in 1 hour, be warming up to 90 ℃, continue reaction 3 hours.With reaction solution washing, P
2O
5Drying, distill colourless liquid 4.1g, boiling point 52-53 ℃, overall yield 55%.
The product analysis result:
19F（CDCl
3），δ：+29.6（AB，J
AB＝219HZ，2F），+75.0（dt，J
HF＝58HZ，1F）
1H（CDCl
3），δ：6.6（ddd，J
2 HF＝58HZ，J
3 HF＝19.8，3.6HZ）
IR：νmax（cm
-1）1185（s），1405（s，SO
2Cl）
MS：218（M
++1，4.67），149（M
+-CF
2H，17.3）
Ultimate analysis calculated value: C 11.06; H 0.46; F 26.27; S 14.75
Measured value: C 11.13; H 0.40; F 26.91; S 14.87
Embodiment 4:HCF
2CF
2SO
3Na's is synthetic
The NaHSO of method one, 0.4mol
30.4mol hexahydropyridine, after the commercial product acetonitrile of 120ml mixes, drip 26.3g(0.1mol) ICF
2CF
2Cl solution keeps temperature of reaction about 0-5 ℃, and after dripping, continuation reaction 20 hours is filtered, and takes out and desolvates, and the alkalization resistates is used ethyl acetate extraction, the anhydrous sodium sulfate drying extraction liquid, and decompression is taken out and is desolvated, and gets white solid 12.2g, productive rate 59%.
The diethylamine of method two, 0.5mol, 5ml water after the trichloromethane of 150ml and the sodium bisulfite of 0.3mol mix, drips 26g(0.1mol) BrCF
2CF
2Br solution keeps temperature of reaction between 0-5 ℃, drips the back and continues reaction 20 hours, and aftertreatment gets white solid 12.5g, productive rate 62% with method one.
The product analysis result:
19F（CD
3COCD
3），δ：+48（S，CF
2SO
3Na），+60（d，J＝54HZ，HCF
2-）
1H（CD
3COCD
3），δ：5.85（tt，J
HF＝54HZ，5HZ）
IR：νmax（cm
-1）1145（m），1040（ms）
Embodiment 5:HCF
2CF
2SO
3H's is synthetic
Method one, with embodiment 2 methods one, productive rate 62%, boiling point 109-112 ℃/3mmHg, 110 ℃/3mmHg of literature value.
Method two, with embodiment 2 method twos, warp
19F NMR is accredited as HCF
2CF
2SO
3H, 0.5CH
3OH, b.p.94-96 ℃/2.3mmHg.
The product analysis result:
19F（D
2O），δ：+45.0（S，-CF
2SO
3H），+59.0（d，J
HF＝52HZ，-CF
2H）
1H（D
2O），δ：6.3（tt，J
HF＝52HZ，5HZ）
IR：νmax（cm
-1）3200-3400（s），1140（s），1090（s）
MS：183（M
++1，83.53），165（M
+-OH，10.17），102（M-SO
3，100）
Embodiment 6:HCF
2CF
2SO
2Cl's is synthetic
With embodiment 3, overall yield 64%, boiling point 39-41 ℃.
The product analysis result:
19F（CDCl
3），δ：+34.7（S，CF
2SO
2Cl），+58.1（d，J
HF＝52HZ，-CF
2H）
1H（CDCl
3），δ：6.45（tt，J
HF＝52HZ，5HZ）
IR：νmax（cm
-1）1410（S，SO
2Cl）
MS（m/z）：200（M
+，13.70），199（M
+-1，1.32），149（M
+-CF
2H，13.91）44（100）
Ultimate analysis calculated value: C 11.97; H 0.50; F 37.91; S 15.96
Measured value: C 11.86; H 0.65; F 38.01; S 15.73
Embodiment 7:CF
3CFHCF
2SO
3Na's is synthetic
The CF of method one, 0.1mol
3CFBrCF
2Br, the NaHSO of 0.2mol
3, the sec-butylamine of 0.4mol, the acetonitrile of 120ml mix the back and stirred 5 hours down in 0-5 ℃.Filter, take out and desolvate, alkalization, ethyl acetate extraction, the anhydrous sodium sulfate drying extraction liquid, underpressure distillation is taken out and is desolvated, white solid 26.7g(with
19F NMR detects, and contains 11% CF
3CF=CFSO
3Na), overall yield 76%.
Method two, take by weighing 13g(0.13mol) NaHSO
3, triethylamine 13g(0.125mol), 40ml acetonitrile, 1.2ml H
2O packs them into and cools off in the autoclave, adds refrigerative perfluoro propylene 5.7g(0.038mol by the reinforced method of liquid then), recover (8 ℃) after the room temperature, reacted 7 hours, drive still,
19F detects 100% and transforms, and post-treating method gets white solid 10.5g, productive rate-100% with method one.(
19F detects and includes 21.1%CF
3CF=CFSO
3Na).
The product analysis result:
（1）CF
3-CFH-CF
2SO
3Na
19F（CD
3COCD
3），δ：-0.5（S，3F），+43（AB，J
AB＝272HZ，2F）
+135（d，J
2 HF＝27HZ，1F）
1H（CD
3COCD
3），δ：5.3（dm，J
2 HF＝27HZ）
IR：νmax（cm
-1）1180（m），1090（m），1060（w）
（2）CF
3CF＝CFSO
3Na
19F（CD
3COCD
3），δ：-7.0（S，3F），+66.6（dm，J
FF＝137HZ，＝CFCF
3）
+88.6（dm，J
FF＝137HZ，＝CFSO
3Na）
Embodiment 8:Cl(CF
2)
10CFHCF
2SO
3The preparation of Na
The Cl(CF of method one, 0.1mol
2)
10CF=CF
2, the NaHSO of 0.15mol
3, the morphine quinoline of 0.8mol, the DMSO of 100ml stirred 10 hours after mixing.Filter, take out low-boiling-point substance, alkalization, washing, anhydrous sodium sulfate drying gets white solid, and water and ethyl alcohol recrystallization get 53.7g, productive rate 82%.
Method two, with method one, reaction substrate is Cl(CF
2)
10CFCl-CF
2Cl.
The product analysis result:
19F（CD
3COCD
3），δ：-10.3（t，2F，CF
2Cl），+4.11（m，2F，CF
2CF
2Cl）
+42.6（m，2F，CF
2CFH），
+43.8（AB，J＝260HZ，2F，-CF
2SO
3Na）
+ 44.9-46.5(m, other, 10F)
+131（dm，J
HF＝25HZ，CFH）
1H（CD
3COCD
3），δ：5.0（m，-CFH）
IR（KBr）：νmax（cm
-1）1060（m），1140（m）
Ultimate analysis calculated value: C 19.99; H 0.14; F 60.65; S 4.44
Measured value: C 20.26; H 0.09; F 60.12; S 4.09
Embodiment 9:NaO
3SCF
2CF
2O(CF
2)
8CFHCF
2SO
3Na's is synthetic
The FO of method one, 0.1mol
2SCF
2CF
2O(CF
2)
8CF=CF
2, the NaHSO of 0.2mol
3, the diethylamine of 0.3mol after the acetonitrile of 100ml mixes, adds 10ml water, stirs 12 hours.Filter, take out low-boiling-point substance, alkalization, ethyl acetate extraction is used in washing, and anhydrous sodium sulfate drying is taken out and is desolvated, and gets white solid 54.9g, productive rate 70%.
Method two, with method one, substrate is FO
2SCF
2CF
2O(CF
2)
8CFBr-CF
2Br.
The product analysis result:
19F（CD
3COCD
3），δ：+6.7（m，4F，CF
2OCF
2），+37.4（S，2F，CF
2CF
2SO
3Na）
+42.1（AB，J
AB＝256HZ，2F，-CFHCF
2SO
3Na）
+44.5-48.2（m，other，7×CF
2）
+134（dm，J
HF＝21HZ，CFH）
1H（CD
3COCD
3），δ：5.13（m，CFH）
IR（KBr）：νmax（cm
-1）1060（m），1160（m）
Ultimate analysis calculated value: C 17.91; H 0.12; F 54.35; S 7.96
Measured value: C 17.56; H 0.16; F 53.90; S 8.14
Embodiment 10:
Synthetic
0.5mol triethylamine, after the S-WAT of 150ml commercial product acetonitrile and 0.3mol mixes, drip 0.1mol's
Solution reacted 5 hours down at 18 ℃, and aftertreatment gets white solid 29.2g, productive rate 80% with embodiment 4.
Claims (7)
1, a kind of method of synthetic fluorine-containing hydrocarbyl sulfonate, comprise the reaction under the existence of dehalogenation sulfonated reagent and solvent, it is characterized in that fluorohaloparaffin or Fluorine containing olefine, in the presence of a kind of organic amine compound that has a lone pair electron, react with the dehalogenation sulfonated reagent, the mole ratio that wherein has the organic amine compound of lone pair electron on fluorohaloparaffin or Fluorine containing olefine, dehalogenation sulfonated reagent and the nitrogen-atoms is 1: 0.2-10: 0.2-20, described fluorohaloparaffin or Fluorine containing olefine have
Wherein Z=X, W (CF
2)
nOr W (CF
2)
mO (CF
2)
m, X=F, Cl, Br or I, Y=Cl, Br or I, W=X, H, R
f=C
nH
2n+1, W (CF
2)
n, Q (CF
2)
mO (CF
2)
mOr Cl (CFClCF
2)
p, R
f 1Or R
f 11=F, CF
3Or C
2F
5, n=0-20, m=1-10, W=H or Y, Q=W or SO
2F, P=0-3, U=2-4, described dehalogenation sulfonated reagent is MHSO
3Or M
2S
2O
5, wherein M is monovalence metal or ammonium ion, on the described nitrogen-atoms organic amine compound of band lone pair electron be primary, the heterogeneous ring compound of the second month in a season or tertiary amine, as RNH
2, RR
1NH, RR
1R
11, NH
2R
111NH
2, R
1111 2N (CF
2)
hNR
11111, pyridine, piperidines, morphine quinoline, pyrroles, Pyrrolidine, hydrazine, wherein, R, R
1Or R
11The alkyl or aryl of=C1-12, R
111Or R
1111The alkyl of=C1-6, h=2-8.
2, the method for a kind of synthetic fluorine-containing hydrocarbyl sulfonate as claimed in claim 1 is characterized in that the mole ratio of the organic amine compound of band lone pair electron on described fluorohaloparaffin or Fluorine containing olefine, dehalogenation sulfonated reagent and the nitrogen-atoms is 1: 1-5: 1-10.
3, the method for a kind of synthetic fluorine-containing hydrocarbyl sulfonate as claimed in claim 1 is characterized in that temperature of reaction is-40-80 ℃, the recommendation response temperature is-and 20-40 ℃.
4, the method for a kind of synthetic fluorine-containing hydrocarbyl sulfonate as claimed in claim 1 is characterized in that reaction times 0.5-5.0 hour, and the recommendation response time is 2-10 hour.
5, the method for a kind of synthetic fluorine-containing hydrocarbyl sulfonate as claimed in claim 1 is characterized in that described solvent is one or more solvent, is recommended as polar solvent.
6, as the method for claim 1,2,3 or 4 described a kind of synthetic fluorine-containing hydrocarbyl sulfonates, it is characterized in that described fluorine-containing hydrocarbyl sulfonate is ZHXC-CXFSO
3M, Z=X wherein, W(CF
2)
n, W(CF
2)
mO(CF
2)
m, X=F, Cl, Br or I, W=X, H, M are monovalence metal or ammonium ion.
7,, it is characterized in that described fluorine-containing hydrocarbyl sulfonate is to have R as the method for claim 1,2,3 or 4 described a kind of synthetic its sulfonate of hydrocarbon compoud containing fluorine
fR
1 fCHCR
11 fXSO
3M,
Fluorine-containing hydrocarbyl sulfonate, R wherein
f=H, C
nF
2n+1, W(CF
2) u, Q(CF
2)
mO(CF
2)
mOr Cl(CFClCF
2)
p, R
1 fOr R
11 f=F, CH
3Or C
2F
5, n=0-20, m=1-10, W=H or Y, Q=W or SO
2F, P=0-3, U=2-4, Y=Cl, Br or I, M are monovalence metal or ammonium ion.
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|---|---|---|---|
| CN 93112483 CN1097191A (en) | 1993-07-08 | 1993-07-08 | A kind of synthetic method of fluorine-containing hydrocarbyl sulfonate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 93112483 CN1097191A (en) | 1993-07-08 | 1993-07-08 | A kind of synthetic method of fluorine-containing hydrocarbyl sulfonate |
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| CN1097191A true CN1097191A (en) | 1995-01-11 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100376553C (en) * | 2004-10-15 | 2008-03-26 | 肖进新 | Full halothane sulfonic acid salts, preparation method and application |
| US7683209B2 (en) | 2005-06-07 | 2010-03-23 | E.I. Du Pont De Nemours And Company | Manufacture of hydrofluoroalkanesulfonic acids |
| CN102070494A (en) * | 2010-12-25 | 2011-05-25 | 锦州惠发天合化学有限公司 | Preparation method of fluorine-containing sulfoacid |
| WO2014020614A2 (en) * | 2012-07-30 | 2014-02-06 | Srf Limited | Process for the synthesis of tetrafluoroethanesulfonic acid |
| KR20190070989A (en) * | 2016-11-03 | 2019-06-21 | 메르크 파텐트 게엠베하 | Fluorinated surfactant |
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1993
- 1993-07-08 CN CN 93112483 patent/CN1097191A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100376553C (en) * | 2004-10-15 | 2008-03-26 | 肖进新 | Full halothane sulfonic acid salts, preparation method and application |
| US7683209B2 (en) | 2005-06-07 | 2010-03-23 | E.I. Du Pont De Nemours And Company | Manufacture of hydrofluoroalkanesulfonic acids |
| US7897807B2 (en) | 2005-06-07 | 2011-03-01 | E. I. Du Pont De Nemours And Company | Manufacture of hydrofluoroalkanesulfonic acids |
| US8283492B2 (en) | 2005-06-07 | 2012-10-09 | E I Du Pont De Nemours And Company | Manufacture of hydrofluoroalkanesulfonic acids |
| CN102070494A (en) * | 2010-12-25 | 2011-05-25 | 锦州惠发天合化学有限公司 | Preparation method of fluorine-containing sulfoacid |
| CN102070494B (en) * | 2010-12-25 | 2013-07-17 | 锦州海森堡石化科技有限公司 | Preparation method of fluorine-containing sulfoacid |
| WO2014020614A2 (en) * | 2012-07-30 | 2014-02-06 | Srf Limited | Process for the synthesis of tetrafluoroethanesulfonic acid |
| WO2014020614A3 (en) * | 2012-07-30 | 2014-03-20 | Srf Limited | Process for the synthesis of tetrafluoroethanesulfonic acid |
| US20150259281A1 (en) * | 2012-07-30 | 2015-09-17 | Srf Limited | Process for the synthesis of tetrafluoroethanesulfonic acid |
| US9376379B2 (en) * | 2012-07-30 | 2016-06-28 | Srf Limited | Process for the synthesis of tetrafluoroethanesulfonic acid |
| KR20190070989A (en) * | 2016-11-03 | 2019-06-21 | 메르크 파텐트 게엠베하 | Fluorinated surfactant |
| JP2019532994A (en) * | 2016-11-03 | 2019-11-14 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Fluorinated surfactant |
| JP7116726B2 (en) | 2016-11-03 | 2022-08-10 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | fluorinated surfactant |
| US11535589B2 (en) | 2016-11-03 | 2022-12-27 | Merck Patent Gmbh | Fluorinated tensides |
| KR102560815B1 (en) * | 2016-11-03 | 2023-07-27 | 메르크 파텐트 게엠베하 | Fluorinated Surfactants |
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