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CN1097191A - A kind of synthetic method of fluorine-containing alkyl sulfonate - Google Patents

A kind of synthetic method of fluorine-containing alkyl sulfonate Download PDF

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CN1097191A
CN1097191A CN 93112483 CN93112483A CN1097191A CN 1097191 A CN1097191 A CN 1097191A CN 93112483 CN93112483 CN 93112483 CN 93112483 A CN93112483 A CN 93112483A CN 1097191 A CN1097191 A CN 1097191A
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fluorine
reaction
sulfonate
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containing hydrocarbon
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黄维垣
谢银保
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Shanghai Institute of Organic Chemistry of CAS
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Shanghai Institute of Organic Chemistry of CAS
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Abstract

本发明涉及一种从氟卤烷烃或含氟烯烃，在脱卤 磺化试剂、氮原子上带有弧对电子的有机胺化合物和 溶剂存在下合成含氟烃基磺酸盐的方法。The present invention relates to a kind of from fluorohaloalkane or fluorine-containing olefin, in dehalogenation Sulfonated reagents, organic amine compounds with arc pair electrons on nitrogen atoms and A method for synthesizing fluorine-containing hydrocarbon group sulfonate in the presence of a solvent.

本发明的方法不仅方法简便，操作简单，条件温 和，转化率高，有机胺和溶剂均可回收利用，产物便于 分离提纯，而且适合于工业化生产。The method of the present invention is not only simple in method, simple in operation, and And, the conversion rate is high, both organic amine and solvent can be recycled, and the product is convenient Separation and purification, and suitable for industrial production.

Description

A kind of synthetic method of fluorine-containing hydrocarbyl sulfonate
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
Figure 931124832_IMG3
Figure 931124832_IMG4
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:
Figure 931124832_IMG6
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、一种合成含氟烃基磺酸盐的方法，包括脱卤磺化试剂和溶剂存在下的反应，其特征是氟卤烷烃或含氟烯烃，在一种带有弧对电子的有机胺化合物存在下与脱卤磺化试剂反应，其中氟卤烷烃或含氟烯烃、脱卤磺化试剂和氮原子上带有弧对电子的有机胺化合物的克分子比为1∶0.2-10∶0.2-20，所述的氟卤烷烃或含氟烯烃具有1. A method for synthesizing fluorine-containing alkyl sulfonate, comprising the reaction in the presence of a dehalogenation sulfonation reagent and a solvent, characterized in that a fluorohaloalkane or a fluorine-containing alkene, in an organic amine compound with an arc pair electron Reaction with dehalogenating sulfonating reagents in the presence, wherein the molar ratio of fluorohalogenated alkanes or fluorine-containing olefins, dehalogenating sulfonating reagents and organic amine compounds with arc pair electrons on nitrogen atoms is 1:0.2-10:0.2- 20. The fluorohaloalkane or fluorine-containing olefin has
Figure 931124832_IMG1
Figure 931124832_IMG1
 其中Z=X、W(CF2)n或W(CF2)mO(CF2)m，X=F、Cl、Br或I，Y=Cl、Br或I，W=X、H，Rf=CnH2n+1，W(CF2)n、Q(CF2)mO(CF2)m或Cl(CFClCF2)p、Rf 1或Rf 11=F、CF3或C2F5，n=0-20，m=1-10，W=H或Y，Q=W或SO2F，P=0-3，U=2-4，所述的脱卤磺化试剂是MHSO3或M2S2O5，其中M是一价金属或铵离子，所述的氮原子上带弧对电子的有机胺化合物是伯、仲或叔胺的杂环化合物，如RNH2，RR1NH，RR1R11，NH2R111NH2，R1111 2N(CF2)hNR11111，吡啶、哌啶、吗啡啉、吡咯、四氢吡咯、肼、其中，R、R1或R11=C1-12的烷基或芳基，R111或R1111=C1-6的烷基，h=2-8。Where Z=X, W(CF 2 ) n or W(CF 2 ) m O(CF 2 ) m , X=F, Cl, Br or I, Y=Cl, Br or I, W=X, H, R f =C n H 2n+1 , W(CF 2 ) n , Q(CF 2 ) m O(CF 2 ) m or Cl(CFClCF 2 ) p , R f 1 or R f 11 =F, CF 3 or C 2 F 5 , n=0-20, m=1-10, W=H or Y, Q=W or SO 2 F, P=0-3, U=2-4, said dehalogenation sulfonation reagent It is MHSO 3 or M 2 S 2 O 5 , where M is a monovalent metal or ammonium ion, and the organic amine compound with arc pair electrons on the nitrogen atom is a heterocyclic compound of primary, secondary or tertiary amine, such as RNH 2 , RR 1 NH, RR 1 R 11 , NH 2 R 111 NH 2 , R 1111 2 N(CF 2 ) h NR 11111 , pyridine, piperidine, morpholine, pyrrole, tetrahydropyrrole, hydrazine, among them, R, R 1 or R 11 =C1-12 alkyl or aryl, R 111 or R 1111 =C1-6 alkyl, h=2-8. 2、如权利要求1所述的一种合成含氟烃基磺酸盐的方法，其特征是所述的氟卤烷烃或含氟烯烃、脱卤磺化试剂和氮原子上带弧对电子的有机胺化合物的克分子比是1∶1-5∶1-10。2. A method for synthesizing fluorine-containing hydrocarbon-based sulfonates as claimed in claim 1, characterized in that said fluorohalogenated alkanes or fluorine-containing olefins, dehalogenation sulfonation reagents and organic compounds with arc pair electrons on nitrogen atoms The molar ratio of the amine compound is 1:1-5:1-10. 3、如权利要求1所述的一种合成含氟烃基磺酸盐的方法，其特征是反应温度为-40-80℃，推荐反应温度为-20-40℃。3. A method for synthesizing fluorine-containing hydrocarbon sulfonate as claimed in claim 1, characterized in that the reaction temperature is -40-80°C, and the recommended reaction temperature is -20-40°C. 4、如权利要求1所述的一种合成含氟烃基磺酸盐的方法，其特征是反应时间0.5-5.0小时，推荐反应时间为2-10小时。4. A method for synthesizing fluorine-containing hydrocarbon sulfonate as claimed in claim 1, characterized in that the reaction time is 0.5-5.0 hours, and the recommended reaction time is 2-10 hours. 5、如权利要求1所述的一种合成含氟烃基磺酸盐的方法，其特征是所述的溶剂是一种或一种以上的溶剂，推荐为极性溶剂。5. A method for synthesizing fluorine-containing hydrocarbon sulfonate as claimed in claim 1, characterized in that said solvent is one or more solvents, preferably polar solvents. 6、如权利要求1、2、3或4所述的一种合成含氟烃基磺酸盐的方法，其特征是所述的含氟烃基磺酸盐是ZHXC-CXFSO3M，其中Z＝X，W（CF2）n，W（CF2）mO（CF2）m，X＝F、Cl、Br或I，W＝X、H，M是一价金属或铵离子。6. A method for synthesizing fluorine-containing hydrocarbon sulfonate as claimed in claim 1, 2, 3 or 4, characterized in that said fluorine-containing hydrocarbon sulfonate is ZHXC-CXFSO 3 M, wherein Z=X , W(CF 2 ) n , W(CF 2 ) m O(CF 2 ) m , X=F, Cl, Br or I, W=X, H, M is a monovalent metal or ammonium ion. 7、如权利要求1、2、3或4所述的一种合成含氟烃其磺酸盐的方法，其特征是所述的含氟烃基磺酸盐是具有RfR1 fCHCR11 fXSO3M、7. A method for synthesizing fluorine-containing hydrocarbons and their sulfonates as claimed in claim 1, 2, 3 or 4, characterized in that said fluorine-containing hydrocarbons sulfonates have R f R 1 f CHCR 11 f XSO 3 M,
Figure 931124832_IMG2
Figure 931124832_IMG2
 的含氟烃基磺酸盐，其中Rf＝H，CnF2n+1、W（CF2）u、Q（CF2）mO（CF2）m或Cl（CFClCF2）p，R1 f或R11 f＝F、CH3或C2F5，n＝0-20，m＝1-10，W＝H或Y，Q＝W或SO2F，P＝0-3，U＝2-4，Y＝Cl、Br或I，M是一价金属或铵离子。Fluorine-containing hydrocarbon sulfonates, where R f = H, C n F 2n+1 , W(CF 2 )u, Q(CF 2 ) m O(CF 2 ) m or Cl(CFClCF 2 ) p , R 1 f or R 11 f =F, CH 3 or C 2 F 5 , n=0-20, m=1-10, W=H or Y, Q=W or SO 2 F, P=0-3, U= 2-4, Y=Cl, Br or I, M is a monovalent metal or ammonium ion.
CN 93112483 1993-07-08 1993-07-08 A kind of synthetic method of fluorine-containing alkyl sulfonate Pending CN1097191A (en)

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Cited By (5)

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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
WO2014020614A3 (en) * 2012-07-30 2014-03-20 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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* Cited by examiner, † Cited by third party
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
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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