FR2823205A1 - COMPOSITION BASED ON AN AMINO COMPOUND AND AMMONIUM BIFLUORIDE AND USE THEREOF - Google Patents

Abstract

The invention relates to a composition comprising at least one amine-containing compound and ammonium bifluoride, the use thereof as a fluorinating agent and a method for preparing perfluoroalkanesulphonyl fluoride using said fluorinating agent.

Description

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The present invention relates to a composition comprising at least one amine and ammonium bifluoride, the use of this composition as a fluoran agent and a process for the preparation of perfluoroalkanesulfonyl fluoride using this fluorinating agent.

 In particular, US Pat. No. 2,732,398 describes an electrochemical fluorination process (called ECF) which allows the synthesis of perfluoroalkanesulfonic acid fluoride and these derivatives from alkane sulphonic acid chloride or carbohydrogenated sulphone. However, the products resulting from these syntheses are mixtures of perfluorinated chain isomers (CnF2n + 1, n> 1) which are variously branched.

 In US Pat. Nos. 2,809,990, 845,573 and 3,403,122 of the 3M Company, these perfluoroalkanesulfonic acid fluorides are described as intermediates in the synthesis of textile, leather and paper processing derivatives. They can especially be used to obtain perfluoroalkanesulfonamides finding application as paper treatment agents or insecticides. The sulfonic acids prepared by hydrolysis of perfluoroalkanesulfonyl fluorides are precursors of superacids used as catalysts in carbocationic synthesis.

 It has been described the synthesis of n-perfluoroalkylsulfonyl fluoride from n-perfluoroalkylsulfonyl chloride by a nucleophilic substitution reaction of chlorine with a fluorine in a dissociating solvent (formamide or sulfolan) (S. Bénéfice-Malouet, H. Blancou , R. Teissedre and A. Commeyras, Journal of Fluorine Chemistry, 31 (1986) 319-332).

 The main known fluorinating agents (see A. Lantz, Engineering Technique, Treaty Process Engineering, J5 670 1-8), such as (NEt3.3HF), (NH4F · HF), NaF, KF, do not give no satisfactory results. More particularly, with NaF and KF, the reactivity is weak, with NEt3. 3HF or NH4F. HF reaction causes corrosion problems. In addition, the use of these reagents involves a separation step of the products obtained, difficult to implement, expensive and often incompatible with high yields.

 It has been unexpectedly found that this exchange can be remarkably effected in biphasic medium (H 2 O-methylene chloride (CH 2 Cl 2) or H 2 O / 4-methyl-2-pentanone ((CH 3) 2 CHCH 2 COCH 3) using of the

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 new fluoran mixtures prepared from amines (primary, secondary or tertiary) and ammonium bifluoride (NH4F, HF).

 The present invention therefore aims to provide new high performance fluorans agents.

 It also aims to propose a process for the preparation of fluorinated compounds using these fluoran mixtures having very satisfactory yields and kinetics.

 These processes using these fluorinating mixtures make it possible to limit the corrosion of the materials (reactors) used. It is also possible to change scale in production. Purification of the final product obtained is also made extremely easy and efficient by these methods.

 These and other objects can be achieved by the present invention which relates to a composition comprising at least one amino compound and ammonium bifluoride (NH4F, HF).

 More particularly, the amine compound is a primary, secondary or tertiary amine of formula (1) NH 3-x (R 1 in which x represents 1, 2 or 3, R 1 represents a linear or branched, saturated or unsaturated C 1 -C 20 alkyl radical. or forms a ring with the nitrogen atom, optionally aromatic.

 Among the linear or branched C1-C20 alkyl radicals, there may be mentioned especially the methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl and hexyl, heptyl, octyl, nonyl, dodecyl and pentadecyl radicals.

 The C 1 -C 4 alkyl radical and more particularly the methyl, ethyl, propyl or butyl radical are preferred.

 When R1 forms a ring with nitrogen, the amine compound can be cyclic saturated C2-C8, such as in particular cyclohexylamine or piperidine, or unsaturated. It is then advantageously aromatic, such as in particular pyridine, pyrimidine or imidazole.

 Advantageously, the composition according to the invention is an aqueous composition.

 The molar ratio of the amine compound and the ammonium bifluoride is advantageously between 0.8 and 1.2; preferentially it is 1.

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 The pH of the composition may vary to a large extent depending on the nature and amounts of the compounds present. Generally, it is between 4 and 8, advantageously between 5 and 7.5.

 The composition according to the invention may be prepared by simple mixing of the constituents. According to a particular mode, the amine compound is brought into contact with water, the ammonium bifluoride is then added, advantageously by fraction.

 Advantageously, the process for preparing the composition according to the invention is carried out at a temperature of between 0 and room temperature (20-30 ° C.). Preferably, this temperature is between 5 and 20oC.

 The present invention also relates to the use of the previously described composition as fluoran agent.

 Thus, this use is particularly suitable for a process for the preparation of perfluoroalkanesulfonyl fluoride.

 It therefore relates to a process for preparing perfluoroalkanesulfonyl fluoride, characterized in that it comprises the reaction between the composition according to the invention and at least one perfluoroalkanesulfonyl halide.

 The process according to the invention has the advantage of making possible the synthesis of n-perfluoroalkylsulfonyl fluoride, that is to say with a linear alkyl chain.

 The perfluoroalkanesulfonyl halides may be chosen from iodides, bromides and preferably perfluoroalkanesulfonyl chlorides.

 The perfluoroalkanesulfonyl halides are preferably compounds of formula RfSO2X where X represents a halogen atom and Rf represents a linear or branched perfluorinated chain containing from 1 to 12 carbon atoms. Advantageously, the perfluorinated chain is linear. It preferably has 2,4,6 or 8 carbon atoms.

 The perfluoroalkanesulfonyl halides may in particular be obtained according to the methods described by P. J. Stang et al. in Synthesis 1982,85,

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 by R. N. Haszeldine et al. in J. Chem. Soc. 1955, 2901, or in FR 76 06303 and US 3732398.

 The perfluoroalkanesulfonyl halides may also be obtained by contacting the alkali metal salt, preferably sodium salt, with the corresponding perfluoroalkanesulfonic acid with at least one halogenating agent, preferably a chlorate agent, such as in particular the chlorine or sulfuryl chloride. This step may in particular be carried out in an aqueous medium or, surprisingly, in a halogenated organic solvent, more particularly chlorinated, such as in particular dichloromethane or dichloroethane.

 Said reaction between the composition according to the invention and at least one perfluoroalkanesulfonyl halide of the process according to the invention is advantageously carried out in a biphasic medium.

 Thus, preferably, the solvents used correspond to a mixture of water and at least one non-water-soluble organic solvent, such as, in particular, methylene chloride or ethylene chloride, 4-methyl-2-pentanone or chloroform.

 Thus, in the case where the perfluoroalkanesulfonyl chloride used was obtained by chlorination in a solvent such as dichloromethane or dichloroethane as described above, the process according to the invention has the advantage of not necessarily proceeding with separation step of the perfluoroalkanesulfonyl chloride obtained before being contacted with the fluoran agent.

 In order to carry out a quantitative reaction, the perfluoroalkanesulfonyl halide and the ammonium bifluoride present in the composition according to the invention are advantageously used in an amount close to the stoichiometry of the reaction, ie to a molar ratio between perfluoroalkanesulfonyl halide and ammonium bifluoride, preferably 1, 2, 2.

 The amounts of solvents that can be used are excessively variable and depend on the solubilities of the compounds used in said solvents. The

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 The quantities used are in general between 500 ml and 1000 ml of solvents per mole of perfluoroalkanesulfonyl halide.

 The temperature of the reaction of the process according to the invention can vary to a large extent. In practice, the temperature is generally from 0 to 40OC. Advantageously, the temperature is maintained at room temperature (between about 20 and 300C).

 It is generally carried out at atmospheric pressure. Of course, pressures above or below atmospheric pressure are not excluded.

 The perfluoroalkanesulfonyl fluoride thus obtained can be recovered by any suitable means, for example by simple decantation. Indeed, the present invention has the advantage of allowing a very effective separation of perfluoroalkanesulfonyl fluoride by simple decantation, a phase separation can be observed at the end of the reaction.

 The perfluoroalkanesulfonyl fluoride thus obtained can then be contacted with at least one amine compound to prepare a perfluorosulfonamide.

 Thus, the present invention finally relates to a process for the preparation of perfluorosulfonamide, characterized in that the perfluoroalkanesulfonyl fluoride obtained according to the process described above is brought into contact with at least one amine compound.

 According to a particular procedure, this step is carried out under anhydrous conditions. This mode makes it possible in particular to obtain perfluorosulfonamides with a linear perfluorinated chain.

 In this step, the amino compound is preferably a compound of the formula NH3-y (R) y, wherein y represents 1 or 2, R represents a linear or branched C1-C20 alkyl radical. Preferably, y is 1.

 Among the linear or branched C1-C20 alkyl radical, mention may especially be made of the methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl and hexyl, heptyl, octyl, nonyl, dodecyl and pentadecyl radicals.

 For perfluoroalkanesulfonyl, the perfluoroalkyl radical of Cl-Cl 2 as defined above is preferred, more particularly the perfluorohexyl or perfluorooctyl radical.

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The following examples illustrate the invention without, however, limiting its scope.

EXAMPLES Example No. 1 a / Preparation of the fluorination reagent 111.1 g (1.1 mol) of triethylamine (N (C2H5) 3) is added to 200 ml of H20, the temperature of the medium is maintained between 15 and 20 ° C. . 62.7 g (1.1 moles) of ammonium bifluoride (NH4F, HF) are subsequently added in a fraction of 15 g, the final pH of the medium is between 5.6 and 5.8. b / fluorination reaction.

A solution of 518 g (1 mole) of C8F17SO2Cl in 250 mL of CH2Cl2 is added over 15 minutes to the aqueous solution of "NH4 + F-, F-NH + (C2H5) 3" prepared previously. The temperature of the medium is maintained between 20 and 30 C for 60 minutes.

The lower phase of the reaction medium which consists of 451 g of CsF17SO2F is then recovered by decantation.

 Yield: 85-90%.

 19F NMR Characteristics: -CF2-SO2F: d = -111.9 ppm.

 Boiling point: 155OC.

 Spectral and physical characteristic identical to that of an authentic sample.

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EXAMPLE 2 Preparation of the Fluorination Reagent A 87.6 g (1.2 mole) of diethylamine (NH (C 2 H 5) 2) in solution in 150 ml of H 2 O is added in 15 g portions while maintaining a temperature. 15-20 C, 68.4 g (1.2 mol) of ammonium bifluoride (NH4F, HF), the final pH of the medium is between 7 and 7.5. b / fluoridation reaction
A solution of 518 g (1 mole) of C8F17SO2Cl in 250 ml of CH2Cl2 is added over 15 minutes to the aqueous solution of "NH4 + F-, F-NH2 + (C2H5) 2" prepared above. The temperature of the medium is maintained between 30 and 35 C for 90 minutes.

 The lower phase of the reaction medium which consists of 476 g of CgF17SO2F is then recovered by decantation.

 Yield: 92-95%.

 19F NMR Characteristics: -CF2-S02F: d = -111.9 ppm.

 Boiling point: 155OC.

authentique. Spectral and physical characteristic identical to that of a sample

authentic.

Example 3 Preparation of the Fluorination Reagent To an aqueous solution containing 1.5 moles of ethylamine (NH 2 C 2 H 5) is added in 15 g fractions, maintaining a temperature of between 5 and 10 C, 85.5 g (1). 5 mol) of ammonium bifluoride (NH4 + F- H + F-), the final pH of the medium is between 6 and 7.

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b/réaction de fluoration.

b / fluorination reaction.

A solution of 518 g (1 mole) of C8F17SO2Cl in 250 mL of CH2Cl2 is added over 15 minutes to the aqueous solution of "NH4 + F-, F-NH3 + C2H5" prepared above. The temperature of the medium is maintained between 45 and 50 C for 120 minutes.

The lower phase of the reaction medium which consists of 400 g of C8F17SO2F is then recovered by decantation.

Yield: 80%.

19F NMR Characteristics: -CF2-S02F: d = -111.9 ppm.

Boiling point: 155OC.

Spectral and physical characteristic identical to that of an authentic sample.

Example 4a / Preparation of the Fluorination Reagent 203.9 g (1.1 mol) of tributylamin (N (C4H9) 3) is added to 400 ml of H20, the temperature of the medium is maintained between 15 and 20oC. 62.7 g (1.1 moles) of ammonium bifluoride (NH4F, HF) are then added in portions of g), the final pH of the medium is between 6 and 7. b / fluorination reaction
A solution of 518 g (1 mole) of C8F17SO2Cl in 250 mL of CH2Cl2 is added over 15 minutes to the aqueous solution of "NH4F, NH (C2H5) 3F" prepared previously. The temperature of the medium is maintained at 20 ° C for 60 minutes.

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The lower phase of the reaction medium which consists of 451 g of C8F17SO2F is then recovered by decantation.

Yield: 85-90%.

19F NMR Characteristics: -CF2-SO2F: d = -111.9 ppm.

Boiling point: 155OC.

Spectral and physical characteristic identical to that of an authentic sample.

EXAMPLE 5 Preparation of Fluoride of 1. 1, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 6 Tridecafluoro hexane-1-sulphonyl The procedure is as in Examples 1, 2 and 3 but by replacing the fluoride of 1, 1, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8 heptadecafluoro-octane-1-sulfonyl with fluoride of 1, 1,2,3,3,4,4,5,5,6,6,6 tridecafluoro hexane-1-sulfonyl.

Yield: 80-95%.

19F NMR Characteristics: -CF2-S02F: d = -111.9 ppm.

Spectral and physical characteristic identical to that of an authentic sample.

Example No. 6 Preparation of fluorides of n-perfluoroalkanesulfonyl 8El7SOgF and C6F1SO2F) in other solvents.

The procedure is as in the preceding examples, with the fluorination agent mixtures consisting of an amine and ammonium bifluoride.

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(NH2C2H5/NH4F, HF ou NH (C2H5) 2/NH4F, HF ou N (C2H5) 3/NH4F, HF) dans différents solvants comme la méthylisobutylcétone ou le sulfolane, dans ce cas, les rendements varient de 70 à 85 %.

(NH2C2H5 / NH4F, HF or NH (C2H5) 2 / NH4F, HF or N (C2H5) 3 / NH4F, HF) in various solvents such as methyl isobutyl ketone or sulfolane, in this case the yields vary from 70 to 85%.

Example 7 Preparation of N-hexyl 1. 1. 2. 2. 3, 3. 4. 4. 5, 5, 6. 6. 7. 7. 8. 8. 8 heptadecafluorooctane-1-sulfonamide A 103 g (0, 2 M) fluoride of 1, 1, 2, 3, 3, 4, 4, 5, 5, 6, 7, 7, 8, 8, 8 heptadecafluoro hexane-1-anhydrous sulfonyl, 106 g (0.4 M) of anhydrous hexylamine are added.

 The temperature of the reaction is maintained at 50 ° C. for 1/2 hour, with stirring and protected from ambient humidity. At the end of the reaction, crystals appear in the reaction medium. While maintaining the medium at the same temperature, the product is solubilized in 200 mL of ethyl acetate.

After washing the organic phase with 100 ml of aqueous 2N HCl solution, the solvent is distilled off under reduced pressure; 116 g of crystals are obtained (purity 95%).

 The product is then purified by crystallization from a solvent mixture: dichloromethane / methanol (80/20, v / v).

 Yield: 90%.

 19F NMR Characteristics: -CF2-SO2NR: d = -111.9 ppm. 1H NMR: d ppm 0.85 (t, 3H-CH 3), 1.3 (m, 6H (CH 2) 3), 1.6 (m, 2H-CH 2), 3.3 (t, 2H CH 2 -NH ).

 Melting point = 88 OC.

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Example No. 8 Preparation of N-octyl 1. 1. 2, 2. 3. 3. 4, 4. 5. 5. 6. 6, 6 heptadecafluorooctane-1-sulfonamide
The procedure is as in the preceding example, replacing the hexylamine with 106 g (0.4 M) of octylamine. 122 g of crystals (purity 95%) are obtained.

 The product is then purified by crystallization from a solvent mixture: dichloromethane / methanol (80/20, v / v).

 Yield: 90%.

 19F NMR Characteristics: -CF2-SO2NR: d = -111.9 ppm. 1H NMR: d ppm 0.85 (t, 3H-CH 3), 1.3 (m, 10H (CH 2) 5), 1.6 (m, 2H-CH 2), 3.3 (t, 2H CH 2 -NH ).

Exact calculated mass: 582.0396; exact mass found: 582.0439 (Err-mmu = 4.3)
Melting point = 91 C.

Example No. 9 Preparation of N-dodecyl 1, 1, 2, 2, 3, 4, 5, 6, 6, 7, 7, 8, 8, 8 heptadecafluorooctane-1-sulfonamide A 70 g (0, 37 M) of anhydrous dodecylamine 95 g (0.19 M) of n-perfluorooctylsulfonyl fluoride are added rapidly. The temperature of the reaction is brought to 60 ° C. for 1 hour with stirring and protected from ambient humidity.

At the end of the reaction, crystals appear in the reaction medium. While maintaining the medium at the same temperature, the product is solubilized in 200 mL of ethyl acetate. After washing the organic phase with 100 ml of aqueous 2N HCl solution, the solvent is distilled under reduced pressure; 129.2 g of crystals are obtained (purity 95
The product is then purified by crystallization in a solvent mixture: dichloromethane / methanol (70/30, v / v).

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 Yield: 90%.

 19F NMR Characteristics: -CF2-SO2NR: d = -111.9 ppm. 1H NMR: d ppm 0.85 (t, 3H-CH 3), 1.3 (m, 18H (CH 2) 9), 1.6 (m, 2H-CH 2), 3.3 (t, 2H CH 2 -NH ).

Exact calculated mass: 610.0709; exact mass found: 610.0636 (Err-mmu = 7.3)
Melting point = 93.3OC.

Préparation du N-hexadécvl 1, 1, 2. 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7. 8. 8, 8 heptadécafluoro octane-1-sulfonamide A 243 g (0, 4 M) d'hexadécylamine anhydre, on additionne 103 g (0, 2 M) de fluorure de n-perfluorooctylsulfonyle. La température de la réaction est amenée à 60oC, pendant 1 H, sous agitation et à l'abri de l'humidité ambiante. À la fin de la réaction, des cristaux apparaissent dans le milieu réactionnel. En maintenant le milieu réactionnel à la même température, on solubilise le produit dans 400 mL d'acétate d'éthyle. Après lavage de la phase organique par 100 mL de solution aqueuse d'HCI 2N, le solvant est distillé sous pression réduite ; il est obtenu 144 g de cristaux (pureté 95 %). Example 10

Preparation of N-hexadecyl 1,1,2,2,3,3,4,5,5,6,6,7,8,8,8,8-heptadecafluorooctane-1-sulfonamide A 243 g 4 M) of anhydrous hexadecylamine is added 103 g (0.2 M) of n-perfluorooctylsulfonyl fluoride. The temperature of the reaction is brought to 60 ° C., for 1 hour, with stirring and protected from ambient humidity. At the end of the reaction, crystals appear in the reaction medium. While maintaining the reaction medium at the same temperature, the product is solubilized in 400 ml of ethyl acetate. After washing the organic phase with 100 ml of aqueous 2N HCl solution, the solvent is distilled under reduced pressure; 144 g of crystals are obtained (purity 95%).

 The product is then purified by crystallization in a solvent mixture: dichloromethane / methanol (70/30, v / v).

 Yield: 95%.

 19F NMR Characteristics: -CF2-SO2NR: d = -111.9 ppm. 1H NMR: d ppm 0.85 (t, 3H-CH 3), 1.3 (m, 26H (CH 2) 13), 1, 6 (m, 2H-CH 2), 3.3 (t, 2H CH 2 -NH ).

Exact calculated mass: 722.1912; exact mass found: 722.1961 (Err-mmu = -4, 8)
Melting point = 92.4 oc.

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Example Na 11 Preparation of N-butyl. 1. 2. 2. 3. 3, 4, 4, 5. 5. 6, 6. 6 tridecafluoro hexane-1-sulfonamide 103 g (0.2 M) of hexane-1-sulfonyl fluoride 1.1 , 2.2, 3.3, 4.4, 5.5, 6.6, 6 tridecafluoro anhydrous, 29.2 g (0.4 M) of anhydrous n-butylamine are added.

 The temperature of the reaction is maintained at 50 ° C. for 1/2 hour with stirring and protected from ambient humidity. At the end of the reaction, crystals appear in the reaction medium. While maintaining the medium at the same temperature, the product is solubilized in 200 mL of ethyl acetate. After washing the organic phase with 100 ml of aqueous 2N HCl solution, the solvent is distilled under reduced pressure, 430 g of crystals are obtained (95% purity).

 Yield: 90%.

 19F NMR Characteristics: -CF2-SO2NR: d = -111.9 ppm. 1 H NMR: d ppm 0.85 (t, 3H-CH 3), 1.3 (m, 2H-CH 2), 1.6 (m, 2H-CH 2), 3.3 (t, 2H CH 2 -NH) .

 Identification by spectral comparison with an authentic sample.

Claims (18)

 1-Composition, characterized in that it comprises at least one amino compound and ammonium bifluoride.  2-Composition according to the preceding claim, characterized in that the amine compound is an amine of formula (1) NH3-x (R1) x, in which x represents 1,2 or 3, R1 represents an alkyl radical, saturated or unsaturated of linear Cl- C20, branched or forms a ring with nitrogen.  3-Composition according to claim 2, characterized in that the amine compound has a C1-C4 alkyl radical and more particularly the methyl, ethyl, propyl or butyl radical.  4-Composition according to any one of the preceding claims, characterized in that it is an aqueous composition.  5-Composition according to any one of the preceding claims, characterized in that the molar ratio of the amine compound and ammonium bifluoride is between 0.8 and 1.2.  6-Composition according to any one of the preceding claims, characterized in that the pH is between 4 and 8.  7-Composition according to the preceding claim, characterized in that the pH is between 5 and 7.5.  8-Use of the composition defined according to any one of

 preceding claims as a fluoran agent. 9-Process for the preparation of perfluoroalkanesulfonyl fluoride, characterized in that it comprises the reaction between the composition defined according to <Desc / Clms Page number 15>  any of claims 1 to 7 and at least one perfluoroalkanesulfonyl halide.  10-Process according to the preceding claim, characterized in that the perfluoroalkanesulfonyl halides are chosen from iodides, bromides and perfluoroalkanesulfonyl chlorides.  11-Process according to any one of claims 9 or 10, characterized in that the perfluoroalkanesulfonyl halides are obtained beforehand by contacting the alkali metal salt of the corresponding perfluoroalkane sulfonic acid with at least one halogenating agent preferably a chlorate agent.  12-Process according to the preceding claim, characterized in that the step of obtaining the perfluoroalkanesulfonyl halides is carried out in a halogenated organic solvent.  13-Process according to any one of claims 9 to 12, characterized in that said reaction between the composition and at least one perfluoroalkanesulfonyl halide is carried out in a biphasic medium.  14-Process according to claim 13, characterized in that the solvents used correspond to a mixture of water and at least one non-water soluble organic solvent.  15-Process according to the preceding claim, characterized in that the non-water-soluble organic solvent is selected from methylene chloride or ethylene, 4-methyl-2-pentanone or chloroform.  16-Process according to one of claims 9 to 15, characterized in that the perfluoroalkanesulfonyl halide and ammonium bifluoride present in said composition are used in an amount close to stoichiometry. <Desc / Clms Page number 16>  17-Process for the preparation of perfluoroalkanesulfonamide, characterized in that the perfluoroalkanesulfonyl fluoride obtained according to the process described in one of Claims 9 to 16 is brought into contact with at least one amine compound.  18-Process according to claim 17, characterized in that this step is carried out under anhydrous conditions.