FR2903693A1 - AROMATIC SULFONYL SULFINATES AND HALOGENIDES, AND THEIR PREPARATION. - Google Patents

Abstract

The invention relates to aromatic sulfinates and sulphonyl halides, and their preparation. The sulphonylimides and sulfinates have the formulas Ar-Z- (CF2) n-CFR <f> -SO2Y (I) and [Ar-Z-, respectively. (CF2) n-CFR <f> -SO2] m M in which Z represents a sulphide, sulfinyl or sulphonyl group; n is 0 or 1; R <f> represents F or a perfluoroalkyl group; Ar represents an aromatic group; Y represents Cl, Br or F; M represents H, an alkali metal cation, an alkaline earth metal cation, a trivalent or tetravalent metal cation, or an organic cation.Sulfinates are useful for the preparation of sulfonyl halides, which are useful for the preparation. sulfonates and sulfonylimides useful as salts for an electrolyte.

Description

791 FR 2903693 1 The present invention relates to sulfinates,

sulfonyl halides, and their preparation. The sulfonyl halides are compounds useful for obtaining sulfonylimides and sulfonates used for the constitution of electrolytes, in particular for lithium batteries and for fuel cells. Conventionally, the sulfonyl halides are prepared either by the action of a halogenating agent (for example PC15) on the corresponding acid, or from the corresponding sulfinates. The process using a sulfinate must be carried out under reaction conditions such that it is necessary to separate the sulfinates from the by-products present in solution in the reaction medium, before converting them into sulphonyl halides. Now, sulfinates are very hygroscopic compounds which are insufficiently thermally stable to be able to be easily dehydrated. Their isolation is therefore a source of moisture input into the halogenation reaction medium, which greatly affects the yield of formation of sulfonyl halides. To resolve this drawback, the invention provides novel sulphonyl halides, the synthesis of which, which involves obtaining the corresponding sulfinates, avoids the isolation of the sulfinates during the reaction.

Accordingly, the present invention relates to sulfonyl halides, a process for preparing them, and the obtained sulfinates as intermediates. A sulfonyl halide according to the present invention has the formula Ar-Z- (CF2) n-CFRf-SO2Y (I) in which: • Z represents a carbonyl, sulfide, sulfinyl, sulfonyl, phosphine oxide, phosphonate group. aryl or amino; • n is 0 or 1; • Rf is F or or a linear or branched perfluoroalkyl group having 1 to 8 carbon atoms; • Y is Cl, Br or F; • Ar is an aromatic group chosen from the group consisting of monocyclic aromatic groups optionally bearing one or more substituents; o polycyclic aromatic groups having condensed or non-condensed rings, said rings optionally carrying one or more substituents; o heterocyclic aromatic groups, bicyclic with condensed or non-condensed rings, or monocyclic, and optionally bearing one or more substituents; it being understood that said aromatic group may be part of a repeating unit of a polymer chain. The substituents of an aromatic group Ar can be chosen from the group consisting of: o halogen atoms, Cl-CH2-, and Ql-O-CH2-groups in which Q1 is H, an alkyl group or a group Acyl; o A hydroxyl group protected in the form of Q2-O- ether, in the form of the carboxylic ester Q2C (0) 0- or in the form of a sulfonate Q2-SO2-O-, Q2 representing an alkyl group or an aryl group, [ for example benzyl ether PhCH2O-, trityl ether Ph3CO-, methyl ether CH30-, benzoyl ester PhC (0) 0- and acetyl ester CH3C (0) 0 -]; o aliphatic or aromatic groups possessing an unsaturation which may originate from a vinyl unit (CH = CH2-), from an allyl unit (CH2 = CH-CH2-) or from an acryloyloxy unit (CH2 = CH-C (0) -O-), optionally substituted; o protected amino groups Q3-NH- in which Q3 represents an alkyl group, an aryl group, an arylalkyl group or an acyl group, [for example CH3C (O) NH- or PhCH2NH-); o trialkylsilyl groups; o oxirane groups; o electron-withdrawing groups such as perfluoroalkyl groups, alkylsulfonyl or arylsulfonyl groups, sulfonyl halide groups, ester, nitrile, cyclic carbonate or nitro groups. A group Z of the carbonyl, sulphide, sulfinyl or sulphonyl type is represented respectively by the formulas - 0 (0) -, -S-, -S (0) - or -S (0) 2-. An aryl phosphonate group Z is represented by the formula -OP (0) (OR1) - and a phosphine oxide type Z group is represented by the formula -P (0) (R ') -, R1 being preferably selected from the groups defined for Ar. A Z group of the amino type is represented by the formula - N (R2) - in which R2 represents H or a linear or branched alkyl group preferably having 1 to 4 carbon atoms. carbon, or an aryl group, for example as defined for Ar. The following compounds can be cited as examples of sulfonyl halides according to the present invention: - compounds Ar-CO- (CF2), - CFRf-SO2Y which are hereinafter designated by Ico-y; the compounds Ar-S- (CF2), - CFRf-SO2Y which are designated below by Is_y; the compounds Ar-SO- (CF2), - CFRf-SO2Y which are hereinafter referred to as Iso_y; - the compounds Ar-SO2- (CF2), - CFRf-S02Y which are hereinafter referred to as I S02-Y • the compounds Ar-CD-P (0) (OR1) - (CF2) n-CFRf-S02Y which are designated below by IpOR-Y • 25 - the compounds Ar-P (0) (R1) - (CF2) n-CFRf-SO2Y which are designated below by IpR-y. the compounds Ar-N (R2) - (CF2) n-CFRf-SO2Y which are designated below by IN_y. Mention may in particular be made of compounds in which Ar represents a phenyl group without a substituent, or a phenyl group bearing a halogen substituent (for example Br, Cl or F) or a trialkylsilyl group (for example trimethylsilyl). Mention may also be made of compounds in which Ar represents a heterocyclic aromatic group, in particular a pyridine group. Mention may also be made of the compounds in which Rf is F. A sulfonyl halide (I) according to the present invention is obtained by a process comprising a step of pre- paration of a sulfinate [Ar-Z- (CF2) n-CFRf-SO2] mM (II), and a step of converting the sulfinate into sulphonyl halide (I), Ar, Z and n having the preceding meaning, M being a cation of valence m (m being 1 or 2) , selected from alkali metal or alkaline earth metal cations, and organic ammonium, phosphonium, imidazolium and pyridinium cations, said organic cation optionally bearing one or more substituents. The substituent (s) of an organic cation can be independently selected from the group consisting of: • hydrogen; • the alkyl chains; • monocyclic aromatic groups; polycyclic aromatic groups with fused rings (for example a naphthyl or anthracenyl group) or not condensed (for example the biphenyl or ter-phenyl group); heterocyclic aromatic groups in which the heteroatom is a nitrogen atom, said heterocyclic groups being polycyclic with condensed or non-condensed rings, or monocyclic. The [Ar-Z- (CF2) n-CFRf-SO2] mM (II) sulfinates defined above constitute another subject of the present invention. Sulfinates can be useful radical generators in various methods of synthesizing chemical compounds. The methods of carrying out the sulfinate preparation step depend on the desired sulfinate, and in particular on the nature of Z of the Ar-Z group that it contains. A sulfinate [Ar-S- (CF2) n-CFRf-SO2] m M (hereinafter referred to as IIs) in which Ar, - (CF2) n-CFRf-, M and m have the meaning given above. can be obtained by a process comprising: - a first step consisting in reducing a halide Ar- 35 S- (CF2) n-CFRf-X in which X represents Br or Cl, by an excess of magnesium in the presence of trimethylsilyl chloride ( TMSC1) to obtain a compound Ar-S- (CF2) n-CFRf-Si- (CH3) 3; 80791 FR 2903693 5 - a second step during which the compound Ar-S- (CF2) n-CFRf-Si- (CH3) 3 is reacted with a fluoride of the cation M in the presence of SO2 to obtain the sulfinate. This process can be represented by the following reaction scheme: Step 1: Ar-S- (CF2), - CFRf-X + Mg + TMSC1û * Ar-S- (CF2), - CFRf-SiMe3 + MgC1X Step 2: m Ar-S- (CF2) n-CFRf-SiMe3 + MF + SO2 -3 IIs + Me3SiF The 1st step is preferably carried out in THF, and the 2nd step preferably in MeCN. The sulfinates corresponding to the formula They constitute another subject of the present invention. The process for preparing sulfinate They is advantageously carried out with an MF fluoride in which M is an alkali metal cation or an ammonium cation. A sulfinate of a different cation can then be obtained by ion exchange. A compound of the Ar-S- (CF2), -CFCRf-Br type can be obtained by reacting the thiol Ar-SH with a Br- (CF2) n-CFRf-Br dibromide using the excess dibromide. An [Ar-SO2- (CF2) n-CFRf-SO2] mM sulfinate (hereinafter referred to as pr IIso) or a [Ar-SO2- (CF2) n-CFRf-SO2] mM sulfinate (hereinafter referred to as IIS02 ) can be obtained by a process comprising - a step consisting in reducing an Ar-S- (CF2) n-CFRf-X halide in which X represents F, Br or Cl, by an excess of magnesium in the presence of chloride trimethylsilyl (TMSCl) to obtain a compound Ar-S- (CF2), - CFRf-Si- (CH3) 3; a 2nd step during which the compound Ar-S- (CF2), - CFRf-Si- (CH3) 3 is oxidized using excess metachloroperbenzoic acid (m-CPBA), the amount of acid being chosen according to the degree of oxidation [(IV) or (VI)] which it is desired to achieve for the S atom, the oxidation being advantageously carried out in anhydrous dichloromethane; - a 3rd stage during which the silane obtained at the end of the 2nd stage is condensed with sulfur dioxide in the presence of MF. Another object of the present invention is the sulfinates corresponding to the formula IIs and IIso2. A sulfinate corresponding to formula II in which Z is CO and n = 0, that is to say a sulfinate corresponding to the formula [Ar-CO-CFRf-SO2] mM (hereinafter referred to as Ilco-o) in which Ar, Rf and M and m have the meaning given above, can be obtained by a process comprising: - a first step consisting in reducing a halide Ar-CO-CFXRf in which X represents F, Br or Cl, with an excess of magnesium in the presence of TMSC1 to obtain a silylated enol ether TMSO-C (Ar) = CFRF; - a second step during which the compound TMSO-C (Ar) = CFRF is reacted with a fluoride of the cation M in the presence of SO 2 to obtain the sulfinate IIco. This process can be represented by the following reaction scheme: Step 1: Ar-CO-CFRf-X + Mg + TMSC1 -> TMSO-C (Ar) = CFRF Step 2: m TMSO-C (Ar) = CFRF + MF + SO2 - * IIco The 1st step is preferably carried out in THF, and the 2nd step preferably in MeCN or in THF. Another object of the present invention is IIco sulfinates. The process is advantageously carried out with an MF fluoride in which M is an alkali metal cation or an ammonium cation. A sulfinate of a different cation can then be obtained by ion exchange. Many Ar-CO-CFRf-X halides useful as a starting material for the preparation of IIco sulfinates are commercially available. By way of examples, mention may be made of Ph-C (0) -CF2C1, and the following compounds, sold in particular by the companies Aldrich, Acros and Oakwood: B0791FR 2903693 7 OO Cl OO CF3 CF3 CF3 Cl Cl CF3 Cl CF3 OOO CF3 MeO O OMe CF3 CF3 CF3 O CF3 An Ar-CO-CFRf-X halide can be prepared by a process of treating an anhydride (X-CFRf-CO) 2O, an acyl halide X-CFRf-C (0) X1 (X1 = halogen) or an ester of X-CFRf-CO2R 'by the compound ArH under the conditions of a Friedel-Crafts reaction, or by an aryl metal derived from ArH (for example ArLi or ArMgBr). A sulfinate corresponding to the formula II in which Z is CO and n = 1, that is to say to the formula [Ar-CO-CF2-CFRf-SO2] mM (hereinafter referred to as IICO_1), can be obtained by a process comprising: - A 1st step consisting in reducing a halide Ar-COCF2-CFRf-X with X = Br, Cl with a hydride donor to obtain the compound Ar-CH (OH) -CF2-CFRf- X; 15 - A 2nd step consisting in protecting the alcohol Ar-CH (OH) -CF2-CFRf-X with a so-called orthogonal group to the trimethylsilyl group (for example benzyl) to obtain the compound Ar-CH (OE) -CF2-CFRf -X, E being a protecting group; 20 - A 3rd step consisting in reducing the halide Ar-CH (EO) -CF2-CFRf-X, (X being Br, Cl) by an excess of magnesium in the presence of TMSC1 to obtain the compound Ar-CH (EO) -CF2-CFRf-SiMe3; - A 4th step consisting in deprotecting the alcohol Ar-CH (EO) -25 CF2-CFRf-SiMe3; - A 5th step consisting in oxidizing the alcohol to the ketone Ar-CO-CF2-CFRf-SiMe3; A 6th step during which the compound Ar-CO-CF2-CFRf-SiMe3 is reacted with a fluoride of the cation M in the presence of SO2 to obtain the sulfinate [Ar-COCF2-CFRf-SO2] mM. In another embodiment, the [Ar-C (0) -CF2-CFRf-SO2] mM sulfinate can be obtained by a process comprising the following steps: a step consisting in protecting the carbonyl group of Ar- C (0) -CF2CF2Br as 1,3-dioxolane- or 1, 3-dioxane-Ar-C (OR) 2-CF2CF2Br, [C (OR) 2 representing a -O-CH2CH2-0 ring or -OCH2CH2CH2-0-]; - a 2nd step consisting in reducing Ar-C (OR) 2-CF2CF2Br with magnesium in the presence of Me3SiC1 to obtain Ar-C (OR) 2-CF2CF2-SiMe3; - a 3rd step consisting in reacting Ar-C (OR) 2-CF2CF2-SiMe3 with a fluoride MF and SO2 to obtain Ar-C (OR) 2-CF2CF2-S (0) OM; a 4th step consisting in protecting Ar-C (OR) 2-CF2CF2- S (0) OM by the action of benzyl bromide to obtain the benzyl sulfone Ar-C (OR) 2-CF2CF2-S (0) 2- CH2Ph; a 5th step consisting in regenerating the carbonyl function by the action of boron tribromide BBr3 at moderate temperature; a 6th step consisting in deprotecting the sulfinate function by hydrogenation (hydrogen / palladium or platinum catalyst) to finally obtain the desired product. This process is analogous to that described by C. AUBERT, et al., Journal of Fluorine Chemistry, 1989, 44, 377-394. An [Ar-OP (0) (OR1) - (CF2) n-CFRf-SO2] mM sulfinate (hereinafter referred to as IIpoR) wherein Ar, (CF2) n-CFRf, R1, M and m have the meaning given above, can be obtained by a process comprising: a first step consisting in reducing a halide Ar-OP (0) (OR1) - (CF2) n-CFRf-X in which X represents F if n = 0 and X represents Br or Cl when n = 1, by an excess of magnesium in the presence of TMSC1 to obtain the compound Ar-OP (0) (OR1) - (CF2) n-CFRf-Si (CH3) 3; 80791 FR 2903693 9 a second step during which the said compound Ar-OP (0) (OR1) - (CF2) nùCFRf-Si (CH3) 3 is reacted with a fluoride of the cation M in the presence of SO2 to obtain the sulfinate IIpoR. This process can be represented by the following reaction scheme. Step 1: Ar-OP (0) (OR1) - (CF2) nùCFRf-X + Mg + TMSCl -> Ar-0-P (0) (OR1) - (CF2) n-CFRf-Si (CH3) 3 Step 2: m Ar-OP (0) (OR1) - (CF2) nùCFRf-Si (CH3) 3 + MF + 10 S02 - * IIPOR The 1st stage is preferably carried out in THF, and the 2nd stage preferably in MeCN or in THF. The IIpoR sulfinates constitute another object of the present invention. The process is advantageously carried out with an MF fluoride in which M is an alkali metal cation or an ammonium cation. A sulfinate of a different cation can then be obtained by ion exchange. The Ar-OP (0) (OR1) - (CF2) nùCFRf-X halides useful as a starting material for the preparation of IIpoR sulfinates can be prepared by a process comprising reacting a diarylphoshite (ArO) 2P-OH or a triarylphosphite (ArO) 3P with a compound X- (CF2) nY (Y = Br, Cl). A sulfinate [Ar-P (0) (R1) - (CF2) n-CFRf-SO2J mM (hereinafter referred to as IIpR) in which Ar, (CF2) n-CFRf, R1, M and m have the meaning given above, can be obtained by a process comprising: - a first step consisting in reducing a halide Ar-P (R1) - (CF2) n-CFRf-X in which X represents Br or Cl, by an excess of magnesium in the presence of trimethylsilyl chloride (TMSC1) to obtain a compound Ar-P (R1) - (CF2) n-CFRf-Si- (CH3) 3 - a second step during which the compound Ar-P ( R1) - (CF2) n-CFRf-Si- (CH3) 3 using excess metachloroperbenzoic acid (m-CPBA), the oxidation being advantageously carried out in anhydrous dichloromethane; - a step during which the silane obtained at the end of the 2nd step is condensed with sulfur dioxide. Another object of the present invention is IIPR sulfinates. The process is advantageously carried out with an MF fluoride in which M is an alkali metal cation or an ammonium cation. A sulfinate of a different cation can then be obtained by ion exchange. The Ar-P (R1) - (CF2) n-CFRf-X halides useful as a starting material for the preparation of IIPR sulfinates can be prepared by a process of reacting an Ar (R1) PH phosphine with the agent. alkylating X- (CF2) n-CFRf-X in the presence of a base. A sulfinate [Ar-N (R2) - (CF2) n-CFRf-SO2] m M (hereinafter referred to as IIN) in which Ar, n, Rf-, R2, M and m have the meaning given below. above, can be obtained by a process comprising: - a first step consisting in reducing a halide Ar-NR2- (CF2) n-CFRf-X in which X represents Br or Cl, by an excess of magnesium in the presence of chloride of trimethylsilyl (TMSCl) to obtain a compound Ar-NR2- (CE2) n-CFRf-Si- (CH3) 3; a second step during which the compound Ar-NR2- (CF2) n-CFRf-Si- (CH3) 3 is reacted with a fluoride of the cation M in the presence of SO2 to obtain the sulfinate IIN. This process can be represented by the following reaction scheme: Step 1: Ar-NR2- (CF2) n-CFRf-X + Mg + TMSCl-> Ar-NR2-30 (CF2) n-CFRf-SiMe3 Step 2: m Ar -NR2- (CF2) n-CFRf-SiMe3 + MF + SO2 - * IIN The 1st step is preferably carried out in THF, and the 2nd step preferably in MeCN. Another object of the present invention is the sulfinates of the formula IIN. The process for preparing the IIN sulfinate is advantageously carried out with an MF fluoride in which M is an alkali metal cation or an ammonium cation. A sulfinate of a different cation can then be obtained by ion exchange. A compound of the Ar-NR2- (CF2) n-CFRf-Br type can be obtained by reacting an Ar-NR2H aniline with a Br-5 (CF2) n-CFRf-Br dibromide using the excess dibromide. It is particularly advantageous to prepare a sulfinate in the acetonitrile solvent. It is then possible to use the sulfinate for the preparation of the sulphonyl halide without isolating it from the reaction medium. This characteristic is particularly important in view of the highly hygroscopic nature of sulfinates, as well as their moderate, or even low, thermal stability which constitutes a handicap for their drying. The methods of carrying out the step of obtaining a sulfonyl halide from a sulfinate depend on the sulfonyl halide targeted, in particular on the nature of Z of the Ar-Z group that it contains. and of the nature of the halogen designated as Y in the general formula I. A sulfonyl chloride Herein can be obtained by reacting the corresponding sulfinate II with SO2C12. The reaction can be carried out using sulfinate dissolved in the solvent in which it was obtained, if said solvent is acetonitrile. This process can be carried out advantageously to obtain the following sulfonyl chlorides: - Ar-CO- (CF2) n-CFRf-SO2C1 (Ico-cl) Ar-S-CF2-CFRf-SO2C1 (Is-cl) Ar -SO- (CF2) n-CFRf-SO2C1 (Iso-cl) Ar-SO2- (CF2) n-CFRf-SO2C1 (Iso2-cl) 30 - Ar-OP (0) (OR ') - (CF2) n -CFRf-SO2C1 (IpoR-cl) - Ar-P (0) (Ri) - (CF2) n-CFRf-SO2Cl (IpR-cl) Ar-N (R2) - (CF2) n-CFRf-SO2C1 (IN -cl) A sulfonyl fluoride IF can be obtained by reacting the corresponding sulfinate II with F-TEDA. The reaction can be carried out using sulfinate in solution in the solvent in which it was obtained, if said solvent is acetonitrile. B0791 FR 2903693 12 The compound F-TEDA is commercially available under the name Selectfluor and it can be represented by the formula 5 Said process can be carried out advantageously by making 10 ù to obtain the sulfonyl chlorides Ar-CO- ( CF2) n-CFRf-SO2F (Ico-F) -Ar-S- (CF2) n-CFRf-SOIF (Is_F) - Ar-SO- (CF2) n-CFRf-SO2F (Iso-F) Ar-S02- (CF2) n-CFRf-SO2F (Iso2-F) - Ar-OP (0) (OR1) (CF2) n-CFRf-SO2F -Ar-P (0) (R1) - (CF2) n-CFRf-SO2F (IpR-F) - Ar-N (R2) (CF2) n-CFRf-SO2F (IN-F) A sulfonyl fluoride IF can be obtained (IPoR-F) following. corresponding sulfonyl with KF in advantageously carried out 15 to react the chloride CH3CN. This process can be used to obtain the following sulfonyl fluorides: - Ar-CO- (CF2) n-CFRf-S02F (Ico-F) 20 _ Ar-S-CF2-CFRf-SO2F (Is-F) Ar-SO- (CF2) n-CFRf-SO2F (Iso-F) Ar-S02- (CF2) n-CFRf-S02F (Iso2-F) - Ar-OP (0) (OR1) - (CF2) n-CFRf-S02F ( I POR-F) Iso-Y and IsO2-Y can be obtained from the halides The oxidation is advantageously carried out with the aid of metachloroperbenzoic acid (m-CPBA) in excess, the quantity of acid being chosen by depending on the degree of oxidation (IV) or (VI)] which it is desired to achieve for the S atom. The process for preparing a sulfonyl halide Ico is described in more detail below, with reference to a representative compound in which Ar is a phenyl group, - Ar-P (0) (R1) - (CF2) n-CFRf-SO2F (IpR-F) 25 - Ar-N (R2) - (CF2) nùCFRf-SO2F (IN-F) Sulfonyl halides 80791 FR 2903693 13 n = 0 and Rf is F, and Y is fluorine. The process is of course transposable to other compounds. Said process comprises: a 1st step consisting in reducing the α, α, α-trifluoroacetophenone PhCOCF3 with an excess of magnesium, in the presence of TMSC1 at a temperature close to 0 C, to obtain the enol ether silyl which is then treated with an excess of fluoride and an excess of sulfur dioxide SO2 to obtain a sulfinate; 10 - a 2nd step consisting in halogenating the sulfinate. The 1st step can be represented by the following reaction scheme. Mg (2 eq)! ~ 'TF (1.1 eq) TMSO F S02 (3 eq) e; , 1 PhCOCF3 TMSC1 (4eq). I> PhCOCF2SO2 M THF Ph F CH3CN or THF The reaction of the silylated enol ether is carried out at a temperature below 0 C, for example between -40 C and 0 C when MF is CsF, and between -70 C and 0 C when MF is tetrabutylammonium fluoride. A sulfonyl chloride Ico-ci can be obtained during the 2nd step (halogenation of the sulfinate) by reacting the sulfinate with the sulfuryl chloride SO2C12r according to the following reaction scheme:. D 802012 (1.2 eq) PhCOCF2SO2 M PhCOCF2S02C1 Pentane./CH1CN This reaction is carried out at a temperature between -10 ° C. and room temperature, in a pentane / acetonitrile mixture. A sulfonyl fluoride Ico_F can be obtained during the 2nd step (halogenation of the sulfinate) by reacting the sulfinate with the fluorinating agent F-TEDA between -20 C and room temperature, according to the following reaction scheme: B0791EN 2903693 14 F-TEDA (1 e) PhCOCF2SO2F CH3CN A sulfonyl fluoride Ico-F can further be obtained from a sulfonyl chloride Ico-ci, by subjecting said chloride to a reaction with an excess of anhydrous KF, to 5 room temperature, according to the following reaction scheme: [Phcocr2so2cl] Anhydrous KF (4.7 eq) PhCOCF2SO2F When the sulfonyl chloride used is obtained by the process described above, it is not necessary to isolate it before it is used. use for the preparation of the corresponding fluoride 10, which constitutes an important advantage in view of the hydrolyzable nature of said chloride. Detail of the preparation of an Is_F compound The process for the preparation of a sulfonyl halide Is is described in more detail below, with reference to a representative compound in which Ar is a phenyl group, the group - (CF2). n-CFRf- is a group (CF2) n and Y is fluorine. The process is of course transposable to other compounds. Said process comprises: a 1st step consisting in reducing a compound Ph-S- 20 (CF2) mBr with an excess of magnesium, in the presence of TMSC1, to obtain Ph-S- (CF2) m-Si (CH3) 3, then reacting this intermediate with an excess of fluoride and an excess of sulfur dioxide SO2 to obtain a sulfinate; - a 2nd step consisting in halogenating the sulfinate. The 1st step can be represented by the following reaction scheme: Mg (2 eq) CsF (1.1 eq) TMSCI (4 eq) PhS- (CF2) mSiMe3 S02 eq) (3. PhS- (CF2) mBr THF isolated CH3CN [PhS (CF2) mSO2 [PhcoCF2so2 80791 FR 2903693 15 CsF could be replaced by a quaternary ammonium fluoride A sulfonyl chloride Is_cl can be obtained in the 2nd step (halogenation of the sulfinate) by reacting the sulfinate with sulfuryl chloride S02C12, according to the following reaction scheme: I PhS- (CF2) 2S02 'S02C12 (1.2 eq) PentanefCH3CN PhS- (CF2) 2S02CI This reaction is carried out at a temperature between 10 C and room temperature, in a mixture pentane / 10 acetonitrile. A sulfonyl fluoride Is_F can be obtained during the 2nd step (halogenation of the sulfinate) by reacting the sulfinate with the fluorinating agent F-TEDA at a temperature between -20 C and room temperature, according to the following reaction scheme: [PhSCF2) mSO F-TEDA (1 eq) CH3CN PhS- (CF2) mS02F Lo rsque m = 2, the sulfonyl fluoride IS_F can also be obtained from a sulfonyl chloride Is_cl, by subjecting said chloride to a reaction with an excess of anhydrous KF 20, at room temperature, according to the following reaction scheme: PhS- (CF2) 2So201 KF anhydrous (4.7 eq) .. PhS- (CF2) 2S02F When the sulfonyl chloride used is obtained by the method described above, it is not necessary to isolate it before 'use for the preparation of fluoride corresponds, which constitutes an important advantage in view of the hydrolyzable nature of said chloride. A compound Iso_y and IS02_Y can be obtained by oxidation of the corresponding compound Is_y, using metachloro-perbenzoic acid (m-CPBA) in excess, the amount of acid being chosen according to the degree of oxidation (IV) or (VI)] which it is desired to achieve for the S atom. The oxidation is advantageously carried out in anhydrous dichloromethane. The reaction is relatively slow, 1 to 5 days at room temperature. This oxidation can however be accelerated, at least in a certain number of cases, by operating under reflux of the dichloromethane. For example, from 2 to 3 equivalents of m-CPBA per equivalent of fluorosulfonyl Is_F can be used to obtain a compound Iso_F, and about 8 equivalents to obtain a compound IsO2-F. Similarly, a compound Iso-Ci or Iso2-c1 can be obtained by oxidation using m-CPBA, used in the appropriate amount to achieve the desired degree of oxidation. Further, an Iso-F OR IsO2-F compound can be obtained from an Iso-ci or Iso2-ci compound, by halogen exchange using KF in acetonitrile at room temperature. Of course, the processes described above for the different types of compounds can be carried out by choosing the starting halides Ar-Z-Y corresponding to the desired final sulfonyl halide. The sulfonyl halides IN_y, IpR_y and IpOR_y can be obtained according to a process analogous to that described above for the preparation of Is_y. The present invention is illustrated by the concrete examples described below, to which it is however not limited. Example 1 Preparation of n-tetrabutylammonium 1,1-difluoro-2-oxo-2-phenylethanesulfinate The ntetrabutylammonium 1,1-difluoro-2-oxo-2-phenylethanesulfinate was obtained from 2,2-Difluoro- 1-phenyl-vinyloxy) -trimethyl-silane. 80791 FR 2903693 17 Preparation of (2,2-Difluoro-1-phenyl-vinyloxy) -trimethylsilane (1) M = 228.31 g.mol-1 6 In a solution of magnesium turnings (0.2 g, 5 8 , 3 mmol) and trimethylsilyl chloride (2 mL, 16 mmol) in anhydrous THF (10 mL), maintained at 0 C with stirring, 2,2,2-trifluoroacetophenone (560 pL, 4 mmol). The mixture was further stirred at 0 C for 2 h then concentrated. The resulting solid was washed with petroleum ether. The organic phase was evaporated in vacuo to provide the silylated enol ether 1 as a colorless liquid (0.92 g, yield> 99%). TLC: Rf 0.7 (7/3 petroleum ether / dichloromethane) 19F NMR (280 MHz, CDCl3): 8 -100.4 (d, 1F, 2JF_F = 68.0 15 Hz), -112.2 (d , 1F, 2JF_F = 68.0 Hz) 1H and 19F NMR are in agreement with the literature (GK Surya Prakash et al., J. Fluorine Chem., 2001, 112, 357-362). Preparation of n-tetrabutylammonium 1,1-difluoro-2-oxo-2-phenylethanesulfinate M = 461.65 g.mol-1 Bu4NG O / CS FFO 20 A solution of sulfur dioxide is prepared by bubbling sulfur dioxide ( 2.3 g, 36 mmol) in anhydrous acetonitrile solution (20 mL) at room temperature. This solution is added to silylated enol ether 1 (11.2 mmol) and stirred at -40 ° C. under an inert atmosphere. The n-tetrabutylammonium fluoride (11.3 mmol) is then added, with stirring, to the reaction mixture maintained at -40 C for 1 h, then brought to room temperature for 1 h. The reaction is followed by TLC and by 19F NMR (CDCl3) until disappearance of the enol ether. After evaporation of the solvents, the desired sulfinate is obtained in the form of a yellow oil. 19F NMR (280 MHz, CDCl3): 8 -112.18 (s, 2F) 1H NMR (300 MHz, CDCl3): 8.93 (t, 12H, CH3CH2, 3JH-H = 7.3 Hz), 1 , 26-1.34 (m, 8H, CH3CH2CH2), 1.73-1.78 (m, 10 8H, CH2CH2CH2), 3.16 (t, 8H, CH2CH2N, 3JH-H = 8.5Hz), 7.51 (t, 2H, Jortho = 7.5Hz), 7.63 (t, 1H, Jortho = 7.5Hz), 8.05 (d, 2H, Jortho = 7.5Hz). MS (ESI / H20-MeOH): m / z = 236.8 (M + H20) (mass of the hydrate form of the structure). Example 2 1,1-Difluoro-2-oxo-2-phenylethanesulfonyl fluoride, direct preparation M = 238.18 g.mol-1 Sulfur dioxide solution is prepared by bubbling sulfur dioxide (2,3 g, 36 mmol) in anhydrous acetonitrile solution (20 mL) at room temperature. This solution is added to the silylated enol ether 1 (11.2 mmol) prepared according to the process of Example 1, and stirred at -40 under an inert atmosphere. Anhydrous CsF 25 (1.7 g, 11.3 mmol) is then added, with stirring, to the reaction mixture maintained at -40 C for 1 h then brought to room temperature for 1 h. The reaction is followed by TLC and by 19F NMR (CDCl3) until disappearance of the enol ether. F-TEDA (4.0 g, 11.3 mmol) is then added to the mixture which is stirred for 1 h at room temperature. The final solution is concentrated in vacuo and the solid residue is washed with anhydrous ethyl ether (10 x 50 mL). The filtrate is evaporated and the product purified by ball oven distillation. The sulfonyl fluoride is obtained in the form of a colorless liquid (1.79 g, yield 67%). 5 TLC Rf 0.6 (petroleum ether / dichloromethane, 9/1) 19F NMR (280 MHz, CDC13) 8 41.61 (t, 1F, -SO2F, 3JF-F 2.3 Hz), -95, 98 (d, 2F, CF2, 3JF-F = 2.3Hz). 1H NMR (300 MHz, CDCl3) 8 7.60 (dd, 2H, H2, 3JH2-H3 3JH2-H1 = 7.7 Hz), 7.79 (tt, 1H, H1, 3JH1-H2 = 7.7 Hz, 4JH1 -H3 10 = 1.1Hz), 8.10 (dd, 2H, H3, 3JH3-H2 = 7.7Hz, 4JH1-H3 = 1.1Hz). 13C NMR (75 MHz, CDC13) 8,116.58 (td, 1C, CF2, 1JF_c = - 309.3 Hz, 2JF_c = 28.0 Hz), 129.58 (s, 2C, C2), 129.8 ( td, 1C, C4, 3JF-C = 4JF-C = 2.6 Hz), 130.46 (t, 2C, 15 C3, 4JF-c = 2.7 Hz), 136.76 (s, 1C, C1 ), 181.13 (td, 1C, C5r 2J, -c = 23.9Hz, 3JF-c = 1.7Hz). Example 3 1,1-Difluoro-2-oxo-2-phenylethanesulfonyl chloride 20 M = 254.64 g.mol-1 A sulfur dioxide solution is prepared by bubbling sulfur dioxide (1.7 g, 26, 5 mmol) in anhydrous acetonitrile solution (15 mL) at room temperature. This solution is added, with stirring and under an inert atmosphere, to the silylated enol 1 ether (66 mmol) prepared according to the procedure of Example 1 and maintained at -40 ° C. The anhydrous CsF (1.0 g, 6.6 mmol) is then added to the reaction mixture which is stirred at -40 C for 1 h then at room temperature for 1 h. The reaction is followed by TLC and 19F NMR (CDCl3) until disappearance of the silylated enol ether. A solution of sulfuryl chloride (540 pL, 6.6 mol) in pentane (1 mL) is then added to the reaction mixture at -10 C. This solution is further stirred at -10 C for 30 min, then brought to room temperature for 30 min. The mixture is concentrated and the product is purified by ball oven distillation. The sulfonyl chloride is obtained in the form of a pale yellow liquid (54%). 19F NMR (282 MHz, CDC13) 8 -93.47 (s, 1F, CF2) 10 1H NMR (300 MHz, CDC13) 8 7.59 (dd, 2H, H2, 3JH2-H3 3JH2-Hi = 7.9 Hz) , 7.77 (tt, 1H, H1, 3JH1-H2 = 7.9Hz, 1.2Hz), 8.11 (dd, 2H, H3, 3JH2-H3 = 7.9Hz, 1.2Hz). 13C NMR (75 MHz, CDC13) 8,117.49 (t, 1C, CF2, 15,315.1 Hz), 129.43 (s, 2C, C2), 130, 50 (t, 1C, C4r 3JF-c = 2.2 Hz), 130.88 (t, 2C, C3, 4JF_c = 3.0 Hz), 136, 57 (s, 1C, C1), 180.63 (t, 1C, c5 r 2 JF-C 23 , 1 Hz). Example 4 1,1-Difluoro-2-oxo-2-phenylethanesulfonyl fluoride from 1,1-difluoro-2-oxo-2-phenylethanesulfonyl chloride. A solution of sulfur dioxide is prepared by bubbling sulfur dioxide (480 g, 7.5 mmol) in a solution of anhydrous acetonitrile (5 mL) at room temperature. This solution is added to the silylated enol ether 1 (1.4 mmol) and stirred at -40 ° C. under an inert atmosphere. Anhydrous CsF (250 mg, 1.65 mmol) is then added to the reaction mixture which is stirred at -40 C 30 for 1 h then at room temperature for 1 h. The reaction is followed by TLC and by 19F NMR (CDCl3) until disappearance of the silylated enol ether. A solution of sulfuryl chloride (140 pL, 1.65 mmol) in pentane (1 mL) is then added to the reaction mixture maintained at 35 -10 C. This solution is further stirred at -10 C for 30 min then at temperature. room temperature for 30 min. JH1-H3 JH1-H3 1 _ JF-C 4 4 B0791EN 2903693 21 Anhydrous KF (380 mg, 6.55 mmol) is then added to the mixture which is stirred at room temperature for 1 h. The final suspension is concentrated and the product is purified by ball oven distillation. The sulfonyl fluoride 5 is obtained as a pale yellow liquid (0.141 g, 45%). Example 5 [(Bromodifluoromethyl) sulfanyl] benzene M = 239.08 g.mol-1 10 In a three-necked flask placed under a nitrogen atmosphere, surmounted by a dry ice condenser and a dropping funnel, thiophenol (10 , 2 mL, 100 mmol) is added dropwise, over 40 min at 0 C, to a suspension of NaH (6 g, 150 mmol) in anhydrous DMF (100 mL). The mixture is then stirred at 0 ° C. for 30 min then cooled to -50 ° C. Dibromodifluoromethane (27 mL, 300 mmol) is then added at -50 ° C. The mixture is then stirred for 3 h at this temperature then 30 min. at room temperature. Water (100 mL) is added to the reaction mixture and then the product is extracted with ethyl ether (3 x 100 mL). The organic phases are washed with water (3 × 100 mL) and dried over MgSO4. After evaporation of the solvent, the residue is distilled under reduced pressure (97 C / 34mmHg) to provide the [(Bromodifluoromethyl) sulfanyl] benzene in the form of a colorless liquid (15.3 g, 60%) TLC: Rf 0, 7 (pentane) 19F NMR (282 MHz, CDCl3): S -22.53 (s, 2F) 1H NMR (300 MHz, CDCl3): 87.43 (m, 2H, H2), 7.52 (m, 1H , H1), 7.66 (d, 2H, H3, 3JH2-H3 = 7.4Hz). 30 13C NMR (75 MHz, CDC13): 8,119.41 (t, 1C, CF2, 1JF_C = 336.0 Hz), 127.30 (t, 1C, C Ar 4, 3JF_c = 1.1 Hz), 129 , 58 (s, 2C, CAr 2), 131,18 (s, 1C, CAr 1), 136,52 (s, 2C, CAr 3) B0791EN 2903693 22 The carbons CAr 1, CAr 2 and CAr 3 are determined on the 2D NMR spectra by analogy with products of the same family. Example 6 5 4 (difluoro- (phenylsulfanyl) -methyl] trimethylsilane M = 232.37 g.mol-1 2 3 // 4 S-CF2SiMe3 5 2 3 Under an inert atmosphere, PhSCF2Br (4.8 g, 20 mmol) is added dropwise to a suspension of magnesium turnings (960 mg, 40 mmol), trimethylsilyl chloride 10 (10.2 mL, 80 mmol) and anhydrous THF (50 mL) cooled to 0 C. The mixture is still stirred at 0 ° C. for 1 h then at room temperature for 1 h The mixture is then concentrated and the resulting solid is washed with petroleum ether The organic phase is evaporated in vacuo to give difluoro- (phenylsulfanyl) - methyl] trimethylsilane as a yellow liquid (4.3 g, 92%) TLC: Rf 0.5 (pentane) 19F NMR (282 MHz, CDCl3): 8 -88.01 (s, 2F) 1H NMR (300 MHz, CDCl3): 80.25 (s, 9H, Si (CH3) 3), 7.35-7-40 (m, 3H, H2 and HI), 7.58-7.61 (m, 2H, H3) .13C NMR (75 MHz,: 8 -4.08 (t, 3C, Si (CH 3 r 3) rr 3) 3r JF-C = 1.3 Hz), 126.44 (t, 1C , CAr 4, 3JF_ ~ = 4.1 Hz), 128.93 (s, 2C, CAr 2), 129.40 (s, 1C, C Ar 1), 25 134, 10 (t, 1C, CF2, 1JF_c = 300.2 Hz), 136.30 (t, 2C, CAr 3, 4JF_C = 1.1 Hz). The CAr1 and CAr2 carbons are determined on the 2D NMR spectra by analogy with products of the same family. 19F, 1H, 13C are determined according to the method described by G. K. 30 Surya Prakash, J. Hu, G. A. Olah, J. Org. Chem., 2003, 68, 11, 4457-4463. 80791 FR 2903693 23 Example 7 Cesium difluoro- (phenylsulfanyl) -methanesulfinate M = 356.15 g.mol-1 A solution of sulfur dioxide is prepared by bubbling sulfur dioxide (160 mg, 2.5 mmol) in anhydrous acetonitrile solution (2 mL) at room temperature. This solution is added to PhSCF2SiMe3 (0.5 mmol) and stirred at room temperature under an inert atmosphere. Anhydrous CsF (150 mg, 1 mmol) is then added to the reaction mixture which is stirred at room temperature for 6 h. The reaction is followed by TLC and by 19F NMR (CDCl3) until disappearance of PhSCF2SiMe3. The mixture is filtered and the solid residue washed with acetonitrile. The filtrate is evaporated and the residue washed with acetonitrile. After drying under vacuum, cesium difluoro- (phenylsulfanyl) -methanesulfinate is obtained in the form of a white solid (0.18 g, quantitative). TLC: Rf 0 (pentane) PF = 127 C 20 19F NMR (282 MHz, acetone-d6): 8 -85.62 (s, 2F, SCF2SO2), 1H NMR (300 MHz, acetone-d6) 87.35- 7-38 (m, 3H, H2 and H1), 7.58-7.61 (m, 2H, H3) 13C NMR (75 MHz, DMSO): 8127.77 (t, 1C, CAr 4.3 JF -c = 1.9 Hz), 128.95 (s, 2C, CAr 2), 129.05 (s, 1C, CAr 1) 25 135.66 (s, 2C, CAr 3), 136.72 (t , 1C, CF2, 1JF_c = 334.0 Hz) The carbons CAr 1, CAr 2 and CAr 3 are determined on the 2D NMR spectra by analogy with products of the same family. B0791EN 2903693 24 Example 8 Difluoro- (phenylsulfanyl) -methanesulfonyl fluoride 2 3S-CF2SO2F 5 M = 242.24 g.mol-1 A solution of sulfur dioxide is prepared by bubbling 5 sulfur dioxide (3.9 g, 61 mmol) in anhydrous acetonitrile solution (20 mL) at room temperature. This solution is added to PhSCF2SiMe3 (4.3 g, 18.4 mmol) and stirred at room temperature under an inert atmosphere. Anhydrous CsF (2.8 g, 18.5 mmol) is then added to the reaction mixture which is stirred at room temperature overnight. The reaction is followed by TLC and by 19F NMR (CDCl3) until disappearance of PhSCF2SiMe3. F-TEDA (7.15 g, 20 mmol) is added to the mixture at -20 ° C. which is then stirred for 1 h at room temperature. The mixture is concentrated and the solid residue washed with ethyl ether (10 x 50 mL). The filtrate is evaporated and the product purified by ball oven distillation. Difluoro- (phenylsulfanyl) -methanesulfonyl fluoride is obtained as a colorless liquid (2.5 g, 57%). 20 TLC: Rf 0.6 (pentane) 19F NMR (282 MHz, CDCl3): 8 35.06 (t, 1F, SO2F, 3JF-F = 4.6 Hz), -76.08 (d, 2F, - SCF2-, 3JF_F = 4.6Hz). 1H NMR (300 MHz, CDCl3): 87.46 (dd, 2H, H2, 3JH2-H1 = 3JH2-H3 = 7.5Hz), 7.56 (t, 1H, H ,, 3JH1-H2 = 7, 5Hz), 7.71 (d, 2H, H3, 3JH3-H2 = 7.5Hz). 13C NMR (75 MHz, CDC13): 8121.83 (t, 1C, C Ar 4r 3 JF-C - 3.0 Hz), 126.56 (td, 1C, CF2, 1JF-c = 323.3 Hz , 2JF_c = 32.9 Hz), 129.95 (s, 2C, CAr 2), 132.13 (s, 1C, CAr i), 137.52 (t, 2C, CAr 3, 9JF-C = 1.1 Hz). The carbons CAr 1, CAr 2 and CAr 3 are determined on the 2D NMR spectra by analogy with products of the same family. Example 9 [(2-Bromo-1,1,2,2-Tetrafluoroethyl) sulfanyl] benzene M = 289.09 g.mol-1 In a three-necked flask placed under nitrogen, surmounted by a dry ice condenser and a dropping funnel, thiophenol (10.2 mL, 100 mmol) is added dropwise (30 min) at 0 C to a suspension of NaH (6 g, 150 mmol) in anhydrous DMF (100 mL ). The mixture is then stirred at this temperature for 20 min then cooled to -50 ° C. 1,2-dibromo-1,1,2,2-tetrafluoroethane (15 mL, 125 mmol) is then added dropwise - 50 C in 10 min. The mixture is then stirred for 2 h at this temperature then 1 h at room temperature. Water (150 mL) is added to the reaction mixture and then the product is extracted with ethyl ether (3 x 100 mL). The phases

organic products are washed with water (3 x 100 mL) and dried over MgSO4. After evaporation of the solvent, the residue is purified by distillation under reduced pressure (99 C / 40mmHg). [(2-Bromo-1,1,2,2-Tetrafluoroethyl) sulfanyl] benzene is then obtained in the form of a colorless liquid (26.07 g, 90%). TLC: Rf 0.8 (pentane) 19F NMR (282 MHz, CDCl3): 8 -62.61 (t, 2F, CF2Br, 3JF-F = 8.0 Hz), -85, 57 (t, 2F, SCF2 , 3JF_F = 8.0Hz).

1H NMR (300 MHz, CDCl3): 67.38-7.44 (m, 2H, H2), 7.47-7.52 (m, 1H, H1), 7.64-7.66 (d, 2H, H3, 3JH2-H3 = 7.1Hz). 13C NMR (75 MHz, CDCl3). 8,116.93 (tt, 1C, CF2, 1JF_c = 312, 9 Hz, 2JF_c = 40.6 Hz), 122.78 (tt, 1C, CF2, 1JF_c = 290.7 Hz, 2JF_c = 33.8 Hz) , 123, 6 (t, 1C, C Ar 4, 30 3JF_c = 2.7 Hz), 129.53 (s, 2C, CAr 2), 131.09 (s, 1C, CAr 1), 137.42 ( s, 2C, CAr 3) B0791 FR 2903693 26 The carbons CAr 1, CAr 2 and CAr 3 are determined on the 2D NMR spectra by analogy with products of the same family. Example 10 5 ((2 phenylsulfanyl) -1,1,2,2-tetrafluoroethyl] trimethylsilane M = 282.37 g.mol-1 Under an inert atmosphere, PhSCF2CF2Br (3.7 g, 12.8 mmol) is added dropwise to drop to a suspension of magnesium turnings (615 mg, 25.6 mmol), trimethylsilyl chloride (6.5 mL, 61 mmol) and anhydrous THF (25 mL), cooled to -20 ° C. The mixture is stirred at -20 C for 1 h then at room temperature for 5 h then concentrated The resulting solid is washed with pentane and the filtrate is evaporated to give [(2-phenylsulfanyl) -1,1,2,2 -tetrafluoroethyl] trimethylsilane as a yellow liquid (3.3 g, 90%) TLC: Rf 0.7 (pentane) 19F NMR (282 MHz, CDCl3): 6 -82.88 (t, 2F, SCF2, 3JF-F = 4.6Hz), -122.56 (t, 2F, CF2Si, 3JF_F = 4.6Hz).

1H NMR (300 MHz, CDCl3): 80.27 (s, 9H, Si (CH3) 3), 7.36-7.48 (m, 3H, H2 and H1), 7.64-7.66 ( m, 2H, H3). 13C NMR (75 MHz, CDC13): 6 -398 (m, 3C, Si (CH3) 3), 123.01 (tt, 1C, CF2, 1JF_c = 273.2 Hz, 3JF_c = 45.3 Hz), 124.63 (m, 1C, C Ar 4), 127.54 (tt, 1C, CF2, 1JF_c = 25,281.8 Hz, 3JF_c = 32.5 Hz), 129.21 (s, 2C, CAr 2) , 130, 29 (s, 1C, CAr i), 137.31 (s, 2C, CAr 3). (Carbon not assigned precisely, but by analogy with products of the same family.) S-CF2CF2SiMe3 5 6 2 B0791 FR 2903693 27 Example 11 2- (Phenylsulfanyl) -1,1,2,2-cesium tetrafluoroethanesulfinate M = 406 , 15 g.mol-1 5 A sulfur dioxide solution is prepared by bubbling sulfur dioxide (0.2 g, 3.1 mmol) in an anhydrous acetonitrile solution (5 mL) at room temperature. This solution is added to PhSCF2CF2SiMe3 (0.2 g, 1.03 mmol) and stirred at room temperature under an inert atmosphere. Anhydrous CsF (165 mg, 1.09 mmol) is then added to the reaction mixture which is stirred at room temperature overnight. The reaction is followed by TLC and by 19F NMR (CDCl3) until disappearance of PhSCF2CF2SiMe3. The mixture is filtered and the solid residue washed with acetonitrile. The filtrate is evaporated and the residue washed with ethyl ether. After drying under vacuum, cesium 2- (Phenylsulfanyl) -1,1,2,2-tetrafluoroethanesulfinate is obtained in the form of a white solid (91%). Rf 0 (pentane) = 100-104 C (282 MHz, DMSO) 8 -85.23 (t, 2F, SCF2, 3JF-F 6.3 Hz), -127.30 (t, 2F, CF2SO2, 3JF_F = 6.3 Hz). (300 MHz, DMSO) 87.44-7.51 (m, 3H, H2 and H1), 7.60 (d, 2H, H3, 3JH2-H3 = 6.8Hz). (75 MHz, DMSO) 8 123.00 (tt, 1C, CF2, 1JF-c = 288.7 Hz, 2JF_c = 32.1 Hz), 124.16 (t, 1C, C Ar 4, 3 JF-C - 2.2 Hz), 128.80 (tt, 1C, CF2, 1JF_c = 292.8 Hz, 2JF_c = 37.3 Hz), 129.43 (s, 2C, CAr 2), 130.45 (s, 1C, CAr 1), 136.58 (s, 2C, CAr 3) S-CF2CF2SO ~ Cs 5 6 2 3 (0.25 g, 20 CCM PF NMR 19F NMR 1H 25 NMR 13C 30 B0791FR 2903693 28 CAr 3 is determined by 2D NMR; CAr 1 and CAr 2r are compared to 2D NMR spectra of products of the same family Example 12 5 2- (Phenylsulfanyl) -1,1,2,2-tetrafluoroethanesulfonyl fluoride M = 292.25 g.mol-1 A solution of sulfur dioxide is prepared by bubbling sulfur dioxide (1.02 g, 16 mmol) in a solution of anhydrous acetonitrile (20 mL) at room temperature. This solution is added on PhSCF2CF2SiMe3 (8 mmol) and stirred at room temperature under an inert atmosphere. Anhydrous CsF (1.4 g, 9 mmol) is then added to the reaction mixture which is stirred at room temperature overnight. The reaction is followed. e by TLC and by 19F NMR (CDCl3) until disappearance of PhSCF2CF2SiMe3. F-TEDA (2.9 g, 8.2 mmol) is added to the mixture which is stirred for 1 h at room temperature. The mixture is concentrated and the solid residue washed with ethyl ether (10 x 20 50 mL). The filtrate is evaporated and the product purified by ball oven distillation. 2- (Phenylsulfanyl) -1,1,2,2-tetrafluoroethanesulfonyl fluoride is obtained as a colorless liquid (1.86 g, 79%). TLC: Rf 0.7 (pentane) 19F NMR (282 MHz, CDCl3): 8 45.93-46.02 (m, 1F, SO2F), -86.52-86.59 (m, 2F, SCF2) , -105.567 (m, 2F, CF2SO2F). 1H NMR (300 MHz, CDCl3): S 7.44 (dd, 2H, H2, 3JH2-H3 = 3JH2-H1 --7.4 Hz), 7.54 (t, 1H, H1, 3JH1-H2 = 7.4 Hz) , 7.67 (d, 2H, H3, 3JH2-H3 = 7.4Hz). 13C NMR (75 MHz, CDC13): S 116.15 = - 300.6 (ttd, 1C, C6, 1JF-C Hz, 2JF_c = 40.8 Hz, 2JF_c = 32.6 Hz), 121.78 B0791FR 2903693 29 ( ttd, 1C, C5, 1JF-c = 290.9 Hz, 2 JF-C = 31.7 Hz, 3 JF-C 1.2 Hz), 122.01 (t, 1C, C Ar 4, 3JF-c = 3.6 Hz), 129.80 (s, 2C, CAr 2), 131.68 (s, 1C, CAr 1), 137.53 (s, 2C, CAr 3) 5 CAr 1, CAr 2 and CAr 3 are determined by 2D NMR. Example 13 2-Phenylsulfanyl-1,1,2,2-tetrafluoroethanesulfonyl chloride M = 308.7 g.mol-1 A sulfur dioxide solution is prepared by bubbling sulfur dioxide (500 mg, 7.8 mmol ) in anhydrous acetonitrile solution (5 mL) at room temperature. This solution is added to PhSCF2CF2SiMe3 (574 mg, 2.03 mmol) and stirred at room temperature under an inert atmosphere. Anhydrous CsF (310 mg, 2.05 mmol) is then added to the reaction mixture which is stirred at room temperature overnight. The reaction is followed by TLC and by 19F NMR (CDCl3) until disappearance of PhSCF2CF2SiMe3. A solution of sulfuryl chloride 20 (220 pL, 2.7 mmol) in pentane (1 mL) is added to the reaction mixture at -10 C. This solution is stirred at -10 C for 1 h then at room temperature for 4 h. The mixture is concentrated and the product is purified by ball oven distillation. 2-Phenylsulfanyl-1,1,2,2-tetrafluoroethanesulfonyl chloride is obtained as a pale yellow liquid (0.516 g, 83%). 19F NMR (282 MHz, CDCl3): 8 -84.99 (t, 2F, SCF2, 3JF-F = 5.2 Hz), -102.16 (t, 2F, CF2SO2F, 3JF_F = 5.2 Hz). 1H NMR (300 MHz, CDCl3): 8 7.44 (dd, 2H, H2, 3JH2-H3 = 3 (1H2-H1 = 30 7.3 Hz), 7.53 (t, 1H, H1, 3JH1-H2 = 7 , 3 Hz), 7.68 (d, 2H, H3, 3JH2-H3 = 7.3 Hz). S-CF2CF2SO2CI 5 6 B0791FR 2903693 30 13C NMR (75 MHz, CDC13): $ 117.29 (tt, CF2 , 1JF_c = 308.0 Hz, 2JF-c = 40.7 Hz), 122.60 (t, CAr 4, 3JF-C = 3.0 Hz), 122.64 (tt, 1C, CF2, 1JF-c = 292.4 Hz, 2JF_c = 31.7 Hz), 129.77 (s, 2C, CAr 2), 131, 65 (s, 1C, 5 CAr 1), 137.48 (s, 2C, CAr 3) The carbons CAr 1, CAr 2 and CAr 3 are determined on the 2D NMR spectra by analogy with products of the same family Example 14 Preparation of 2- (Phenylsulfanyl) -1,1,2,2-tetrafluoroethanesulfonyl fluoride from 2-Phenylsulfanyl-1,1,2,2-tetrafluoroethanesulfonyl chloride A solution of sulfur dioxide is prepared by bubbling sulfur dioxide (4 g, 63 mmol) in a solution of anhydrous acetonitrile (30 mL) at room temperature This solution is added to PhSCF2CF2SiMe3 (5.87 g, 20.3 mmol) and stirred at room temperature. iante under an inert atmosphere. Anhydrous CsF (3.2 g, 21 mmol) is then added to the reaction mixture which is stirred at room temperature overnight. The reaction is followed by TLC and by 19F NMR (CDCl3) until disappearance of PhSCF2CF2SiMe3. A solution of sulfuryl chloride (2.0 mL, 25.2 mmol) in pentane (1 mL) is added to the reaction mixture at -10 C. This solution is stirred at 25 -10 C for 1 h then at room temperature. for 4 h. Anhydrous KF (6 g, 105 mmol) is then added to the mixture which is stirred at room temperature for 72 h. The mixture is concentrated and the product is purified by ball oven distillation. 2- (Phenylsulfanyl) - 1,1,2,2-tetrafluoroethanesulfonyl is obtained as a pale yellow liquid (3.76 g, 64%). B0791EN 2903693 31 Example 15 Difluoro- (phenylsulfinyl) -methanesulfonyl fluoride M = 258.24 g.mol-1 To a solution of PhSCF2S02F (250 mg, 1 mmol) in anhydrous dichloromethane (5 mL) is added metachloroperbenzoic acid (520 mg, 3.0 mmol). The reaction medium is stirred at room temperature for 3 days (followed by 19F NMR) then filtered through silica gel and washed with CH2Cl2. After evaporation of the solvent, the residue is purified by chromatography on silica gel (Pentane to Pentane / CH2C12, 7/3). Difluoro- (phenylsulfinyl) -methanesulfonyl fluoride is obtained as a colorless liquid (90 mg, 34%). TLC: Rf 0.45 (Pentane / CH2Cl2, 1/1) 19F NMR (282 MHz, CDCl3): 649.78 (dd, 1F, SO2F, 3JF-F = 15 3JF-F = 5.1 Hz), -99.61 (dd, 1F, CF2, 1JF-F = 215.7 Hz, 3JF-F = 5.1 Hz), -105.45 (dd, 1F, CF2, 1JF-F = 215.7 Hz, 3JF_F = 5.1 Hz). 1H NMR (300 MHz, CDCl3): 87.63-7.77 (m, 3H, H2 and H1), 7.86 (d, 2H, H3, 3JH3-H2 = 7.3Hz).

13C NMR (75 MHz, CDC13): 8 123.70 (ddd, 1C, CF2, 1JF-c = 348.9 Hz, 1JF-c = 340.7 Hz, 3J, -c = 24.8 Hz), 126.60 (dd, 2C, C Ar 3, 3JF-C = 3JF-C = 1.1 Hz), 129.90 (s, 2C, CAr 2), 134.09 (dd, 1C, CAr 4, 4JF -C = 4 JF-C 2.5 Hz) 134.67 (s, 1C, CAr 1) Example 16 2- (phenylsulfinyl) -1,1,2,2-tetrafluoroethanesulfonyl fluoride M = 308.25 g. mol-1 B0791EN 2903693 32 To a solution of PhSCF2CF2SO2F (1.15 g, 4 mmol) in anhydrous dichloromethane (40 mL) is added metachloroperbenzoic acid (1.4 g, 8 mmol). The reaction medium is stirred at room temperature for 1 day (followed by 5 19F NMR) then filtered through silica gel and washed with CH2012. After evaporation of the solvent, the residue is purified by chromatography on silica gel (Pentane to Pentane / CH2C12, 3/2). 2- (Phenylsulfinyl) -1,1,2,2-tetrafluoroethanesulfonyl fluoride is obtained as a colorless liquid (700 mg, 57%). TLC: Rf 0.60 (Pentane / CH2Cl2r 1/1) 19F NMR (282 MHz, CDCl3): 846.27-46.39 (m, 1F, SO2F), -106.70; -106.87 (m, 2F), - 110.16 (m, 1/2 system AB, 1F), -121.60 (m, 1/2 system AB, 1F).

1H NMR (300 MHz, CDCl3): 87.71 (dd, 2H, H2, 3JH2-H3 = 3JH2H1 = 7.5Hz), 7.69-7.75 (m, 1H, H1), 7.61-7 , 67 (m, 2H, H3). 13C NMR (75 MHz, CDC13) 8 111.80 - 121.70 (m, 2C, C5, C6), 126.80 (m, 2C, CAr 3), 129.90 (s, 2C, CAr 2), 134.40 20 (s, 1C, CAr 1), 134.70 (t, 1C, CAr 4, 3JF-c = 2.5Hz). Example 17 Difluoro- (phenylsulfonyl) methanesulfonyl fluoride M = 274.24 g.mol-1 To a solution of PhSCF2SO2F (2.23 g, 9.2 mmol) in anhydrous dichloromethane (90 mL) is added. metachloroperbenzoic acid (12 g, 70 mmol). The reaction medium is stirred at room temperature for 3 days (followed by 19F NMR) then filtered through silica gel and washed with CH2Cl2. After evaporation of the solvent, the residue is purified by chromatography on silica gel (Pentane / CH2Cl2, 4/1). Difluoro- (phenylsulfonyl) -methanesulfonyl fluoride is obtained as a colorless liquid (1.88 g, 75%).

2903693 B0791 FR 33 336.3 Hz, 33F-c = 30, 0 Hz), 130.24 (s, 2C, 130.99 (s, 1C, CAr 4), 131.58 (s, 2C, CAr 3) (s, 1C, CAr 1) Example 18 2- (phenylsulfonyl) -1,1,2,2-tetrafluoroethanesulfonyl fluoride M = 324.24 g.mol-1 15 To a solution of PhSCF2CF2S02F (1.32 g , 4.5 mmol) in anhydrous dichloromethane (45 mL) is added metachloroperbenzoic acid (6.25 g, 36 mmol). The reaction mixture is stirred at room temperature for 2 days (followed by 19F NMR) then filtered. on silica gel and washed with CH2C12 After evaporation of the solvent, the residue is purified by chromatography on silica gel (Pentane / CH2C12, 4/1). 2- (phenylsulfonyl) fluoride -1,1,2 , 2tetrafluoroethanesulfonyl is obtained as a colorless liquid (1.15 g, 79%).

TLC: Rf 0.7 (Pentane / CH2Cl2, 1/1) 19F NMR (282 MHz, CDCl3): 846.20-46.30 (m, 1F, SO2F), -106.27; -106.37 (m, 2F), -110.72; -110.83 (m, 2F). 1H NMR (300 MHz, CDCl3): 87.71 (dd, 2H, H2, 3JH2-H3 = 3JH2-H1 = - 7.5Hz), 7.89 (t, 1H, H1, 3JH1-H2 = 7.5 Hz), 8.06 (d, 2H, H3, 3JH2-H3 = 7.5Hz). 19F NMR 1H NMR 5 13C NMR 10 TLC: Rf 0.65 (Pentane / CH2C12r 1/1) (282 MHz, CDCl3): 8 49.28 (t, 1F, SO2F, 3JF-F = 5.7 Hz), -99.40 (d, 2F, CF2, 3JF-F = 5.7Hz). (300 MHz, CDC13) 67.70 (t, 2H, H2, 3JH2-H3 = 3JH2-H1 = 7.6 Hz), 7.90 (t, 1H, H1, 3JH1-H2 = 7.6 Hz), 8, 09 (d, 2H, H3, 3JH2-H3 = 7.6Hz). (75 MHz, CDC13): 8 118.76 (td, 1C, CF2, 1JF-c = CAr 2) r 137.66 B0791 FR 2903693 34 13C NMR (75 MHz, CDC13): 8 113.55 (tt, 1C , C5, 1JF-c = 302.0 Hz, 3JF_C = 35.0 Hz), 115.41 (ttd, 1C, C6, 1JF_c = 302.0 Hz, 3JF-c = 35.0 Hz, 3JF_C = 35, 0 Hz), 130.14 (s, 2C, CAr 2), 131.35 (s, 2C, CAr 3), 131.77 (s, 1C, 5 C Ar 4), 137.20 (s, 1C, CAr l) Example 19 2- (Phenylsulfinyl) 1,1,2,2-tetrafluoroethanesulfonyl chloride M = 324.70 g.mol-1 10 To a solution of PhSCF2CF2S02C1 (1.85 g, 6 mmol) in anhydrous dichloromethane (25 mL) is added metachloroperbenzoic acid (2.1 g, 12 mmol). The reaction medium is stirred at room temperature for 1 day (followed by 19F NMR) then filtered through silica gel and washed with CH2Cl2. After evaporation of the solvent, the residue is purified by chromatography on silica gel (Pentane to Pentane / CH2C12, 3/2). 2- (Phenylsulfinyl) 1,1,2,2-tetrafluoroethanesulfonyl chloride is obtained as a yellow liquid (1.25 g, 64%).

20 TLC: Rf 0.60 (Pentane / CH2C12r 1/1) 19F NMR (282 MHz, CD013): 8 -102 70 (m, 1/2 AB system, 1F), -103, 84 (m, 1/2 system AB, 1F), -109.45 (m, 1/2 system AB, 1F), -119.85 (m, 1/2 system AB, IF).

1H NMR (300 MHz, CDCl3): 87.62-7.67 (m, 2H, H2), 7.68-7.74 (m, 1H, H1), 7.82 (d, 2H, H3, 3JH2-H3 = 7.5 Hz). 13C NMR (75 MHz, CDC13) 8,117.21 (dddd, 1C, CF2r 1JF_c = 309.4 Hz, 1JF_C = 306.7 Hz, 3JF-c = 35.2 Hz, 3 JF-C 35.0 Hz) , 118.23 (dddd, 1C, CF2, 1JF-c = 318.5 Hz, 30 1JF-c = 307.1 Hz, 3JF-c = 34.8 Hz, 3JF-c = 32.0 Hz), 126 , 70 (s, 2C, CAr3), 129.70 (s, 2C, C Ar 2), 134.30 (s, 1C, CAr 1), 134.50 (s, 1C, CAr 4) O S-CF2CF2SO2CI 5 6 2 3 20 25 B0791EN 2903693 35 Example 20 2- (phenylsulfonyl) -1,1,2,2-tetrafluoroethanesulfonyl chloride M = 340.70 g.mol-1 5 To a solution of PhSCF2CF2S02C1 (1.85 g, 6 mmol) in anhydrous dichloromethane (25 mL) is added metachloroperbenzoic acid (2.1 g, 12 mmol). The reaction medium is stirred at room temperature for 1 day (followed by 19F NMR) then filtered through silica gel and washed with CH2Cl2. After evaporation of the solvent, the residue is purified by chromatography on silica gel (Pentane to Pentane / CH2C12, 3/2). 2- (Phenylsulfonyl) -1,1,2,2-tetrafluoroethanesulfonyl chloride is obtained as a yellow liquid (0.35 g, 17%).

15 TLC: Rf 0.7 (Pentane / CH2Cl2, 1/1) 19F NMR (282 MHz, CDCl3): 6 -102.96 (s, 2F), -102.99 (s, 2F) 1H NMR (300 MHz , CDC13): 6 7.70 (dd, 2H, H2, 3JH2-H3 = 33-H2 -H1 = 7.7 Hz), 7.87 (t, 1H, H1, 3JH1-H2 = 7.7 Hz), 8 0.04 (d, 2H, H3, 3JH2-H3 = 7.7Hz). 13C NMR (75 MHz, CDC13) 6 114.31 (tt, 1C, CF2, 1JF_c = -303.1 Hz, 3JF-c = 33.1 Hz), 116.19 (tt, 1C, CF2, 1JF_c = 310 , 1 Hz, 3JF_c = 35.1 Hz), 130.13 (s, 2C, CAr 2), 131.28 (s, 2C, CAr 3), 131.61 (s, 1C, C Ar 4), 137 , 25 (s, 1C, CAr 1) Example 21 [(2-Bromo-1,1,2,2-Tetrafluoroethyl) -sulfanyl] -pyridine M = 290.08 g.mol-1 eS-CF2CF2Br 6 7 3 4 4 B0791EN 2903693 36 In a three-necked flask placed under nitrogen, surmounted by a dry ice condenser and a dropping funnel, 2-mercaptopyridine (1.7 g, 15.2 mmol) dissolved in 5 mL of anhydrous DMF, is added dropwise (45 min) at 5 ° C. to a suspension of NaH (0.9 g, 22.5 mmol) in anhydrous DMF (15 mL). The mixture is then stirred at this temperature for 20 min then cooled to -50 ° C. 1,2-dibromo-1,1,2,2-tetrafluoroethane (2 mL, 16.7 mmol) is then added dropwise. -50 C in 10 min. The mixture is then stirred for 3 h at this temperature and then 2 h at room temperature. Water (50 mL) is added to the reaction mixture then the product is extracted with ethyl ether (3 x 50 mL). The organic phases are washed with water (3 x 50 mL) and dried over MgSO4. After evaporation of the solvent, the residue is purified by chromatography on silica gel (Pentane to Pentane / CH2C12, 1/2). The [(2-Bromo-1,1,2,2-Tetrafluoroethyl) -sulfanyl] -pyridine is then obtained in the form of a yellow liquid (3.75 g, 85%) TLC: Rf 0.2 (Pentane / CH2C12r 1/1) 20 19F NMR (282 MHz, CDC13): 8 -63.12 (t, 2F, CF2Br, 3JF-F = 8.0Hz), -84.55 (t, 2F, SCF2, 3JF- F = 8.0 Hz). 1H NMR (300 MHz, CDCl3) 8 7.36 (ddd, 1H, H2, 3JH2-H3 = 7.3 Hz, 3JH1-H2 = 4.8 Hz, 4JH2-H4 = 1.3 Hz), 7.66-7 , 77 (m, 2H, H3 & H4), 8.64-8.67 (m, 1H, H1).

25 13C NMR (75 MHz, CDC13): 8116.75 (tt, 1C, CF2, 1JF c = 313.0 Hz, 2JF-c = 39.7 Hz), 123, 06 (tt, 1C, CF2, 1JF -c = 292.3 Hz, 2JF-c = 34.3 Hz), 124.46 (s, 1C, C Ar2), 130.85 (s, CAr4), 137.63 (s, CAr3), 148, 02 (m, CAr5) 150.82 (s, 1C, CAri) Example 22 [(2 pyridin-2-ylsulfanyl) -1,1,2,2-tetrafluoroethyl] trimethylsilane 3 4 1 M = 283.36 g. mol-1 B0791EN 2903693 37 Under an inert atmosphere, (C6H4N) -SCF2CF2Br (0.58 g, 2 mmol) is added dropwise to a suspension of magnesium turnings (100 mg, 4 mmol), of trimethylsilyl chloride (1 mL, 8 mmol) and anhydrous THF (5 mL), cooled to -78 ° C. The mixture is stirred at -78 ° C. for 1 h then allowed to warm to room temperature for 5 h then concentrated. The residue is dissolved in dichloromethane. The organic phase is washed with water (3 x 20 mL), dried over MgSO4. After evaporation of the solvent, the [(2-pyridin-2-10 ylsulfanyl) -1,1,2,2-tetrafluoroethyl] trimethylsilane is obtained in the form of an orange liquid (0.43 g, 76%). TLC: Rf 0.5 (pentane / CH2Cl2, 1/2) 19F NMR (282 MHz, CDCl3): 8 -82.15 (t, 2F, SCF2, 3JF-F 4.6 Hz), -122.48 ( t, 2F, CF2Si, 3JF-F = 4.6Hz).

15 1H NMR (300 MHz, CDCl3): 80.28 (s, 9H, Si (CH3) 3), 7.26 (ddd, 1H, H2, 3JH2-H3 = 6.5 Hz, 3JH1-H2 = 4.8 Hz , 4JH2-H4 = 2.2Hz), 7.63-7.71 (m, 2H), 8.68 (ddd, 1H, Hi, 3JH1-H2 = 4.8Hz, 4JH1-H3 = 1.6 Hz, 5JH1-H4 = 1.1 Hz).

20 13C NMR (75 MHz, CDC13) 8 -4.06-4.16 (m, Si (CH3) 3), 122.47 (tt, 1C, CF2, 1JF-c = 273.0 Hz, 2JF_c = 44 , 7 Hz), 127.77 (tt, 1C, CF2, 1JF-c = 283.4 Hz, 2JF_c = 32.4 Hz), 123.46 (s, C Ar), 123.63 (s, CAr) , 137.27 (s, CAr), 149.74-149.79 (m, 1C, CAr5) 150.54 25 (s, CAr) Example 23 2- (Pyridin-2-ylsulfanyl) -1.1 fluoride , 2,2- trafluoroethanesulfonyl M = 293.23 g.mol-1 30 A sulfur dioxide solution is prepared by bubbling sulfur dioxide (0.5 g, 7.8 mmol) in an anhydrous acetonitrile solution (10 mL) at room temperature. This solution is added to (C6H4N) SCF2CF2SiMe3 (0.43 g, 1.5 mmol) and stirred at room temperature under an inert atmosphere. Anhydrous CsF (0.29 g, 1.9 mmol) is then added to the reaction mixture which is stirred at room temperature overnight. The reaction is followed by TLC and by 19F NMR (CDCl3) until disappearance of C6H4NSCF2CF2SiMe3. F-TEDA (0.54 g, 1.5 mmol) is added to the mixture at -40 ° C. which is stirred at -40 ° C. to room temperature for 1 hour 30 minutes. The mixture is concentrated and the solid residue washed with ethyl ether (10 x 50 mL). After evaporation of the solvent, 2- (Pyridin-2-ylsulfanyl) -1,1,2,2-tetrafluoroethanesulfonyl fluoride is obtained in the form of a pale yellow liquid (0.32 g, 72%). 19F NMR (282 MHz, CDCl3): 846.29-46.38 (m, 1F, SO2F), -85.19-85.25 (m, 2F, SCF2), -105.70, -105.77 (m, 2F, CF2SO2F). 1H NMR (300 MHz, CDCl3): 87.41 (ddd, 1H, H2, 3JH2-H3 = 7.5Hz, 3JH1-H2 = 4.8Hz, 4JH2-H4 = 1.2Hz), 7.68-7 , 75 (m, 1H, H4), 7.78 (ddd, 1H, H3, 3JH2-H3 = 3JH3-H4 = 7.5Hz, 4JH1-H3 = 1.9Hz), 8.68 (ddd, 1H , H1, 3JH1-H2 = 4.8 Hz, 4 JH1-H3 = 1.9 Hz, 5JH1-H4 = 0.9 Hz). Example 24 1-Bromo-f (2-Bromo-1,1,2,2-Tetrafluoroethyl) sulfanyl] benzene M = 367.98 g.mol-1 25 In a three-necked flask placed under nitrogen, topped with a condenser at dry ice and a dropping funnel, 4-Bromothiophenol (2.89 g, 15 mmol) dissolved in 5 mL of anhydrous DMF, is added dropwise (30 min) at 0 C to a suspension of NaH (0, 9 g, 22.5 mmol) in anhydrous DMF (15 mL). The mixture is then stirred at this temperature for 30 min then cooled to -50 C. The 1,2-dibromo-1,1,2,2-tetrafluoroethane (2 mL, 16.5 mmol) is then added dropwise by drop at -50 C in 10 min. The mixture is then stirred for 3 h at this temperature and is then allowed to return to room temperature. Water (50 mL) is added to the reaction mixture and then the product is extracted with ethyl ether (3 x 40 mL). The organic phases are washed with water (5 × 30 mL) and dried over MgSO4. After evaporation of the solvent, the residue is purified by chromatography on silica gel (Pentane). 1-Bromo - [(2-Bromo-1,1,2,2-Tetrafluoroethyl) sulfanyl] benzene is obtained as a colorless liquid (5 g, 90%). TLC: Rf 0.8 (pentane) 19F NMR (282 MHz, CDC13) 8 -62 75) (t, 2F, CF2Br, 3 JF-F = 8.0 Hz), -85.59 (t, 2F, SCF2 , 3JF_F = 8.0Hz). 1H NMR (300 MHz, CDCl3): 87A9ù7.57 (m, 4H, HAr).

15 13C NMR (75 MHz, CDC13) 8,116.69 (tt, 1C, CF2, 1JF_c = 312.9 Hz, 2JF_c = 40.2 Hz), 121.99 (tt, 1C, CF2, 1JF_c = 291.2 Hz, 2JF_c = 34.2 Hz), 122.6 (t, 1C, C Ar 4, 3JF_c = 2.7 Hz), 126.35 (s, 1C, CAr 1), 132.83 (s, 2C, CAr), 138.72 (s, 2C, CAr) Example 25 ((2- (4-Bromo-phenylsulfanyl) -1.1, 2, 2-tetrafluoroethyl] trimethylsilane M = 361.27 g.mol-1 Under inert atmosphere, BrC6H4SCF2CF2Br (0.368 g, 1 mmol) is added dropwise to a suspension of magnesium turnings (155 mg, 6.4 mmol), trimethylsilyl chloride (1.5 mL, 11.8 mmol) and of anhydrous THF (5 mL), cooled to -78 ° C. The mixture is stirred at -78 ° C. for 8 h. Water is added to the reaction mixture and then the product is extracted with dichloromethane. The organic phases are washed. with water and dried over Mg504. After evaporation of the solvents, the residue is purified by chromatography on silica gel (Pentane). [(2- (4-Bromo-phenylsulfanyl) -1,1, 2,2-tetrafluoroethyl] trimethyl The silane is obtained as a colorless liquid (90 mg, 25%).

5 TLC: Rf 0.5 (pentane) 19F NMR (282 MHz, CDCl3): 6 -82.81 (t, 2F, SCF2, 3JF-F = 5.2 Hz), -122.40 (t, 2F, CF2Si, 3JF_F = 5.2 Hz). 1H NMR (300 MHz, CDCl3): 80.27 (s, 9H, Si (CH3) 3), 731 (m, 4H, HAr) 13C NMR (75 MHz, CDCl3): 8 -4.02 (m, 3C, Si (CH3) 3), 122.66 (tt, 1C, CF2, 1JF_C = 272.6 Hz, 2JF_C = 45.4 Hz), 123.83 (m, 1C, CAr 4), 125.37 ( s, 1C, CAr 1), 127.03 (tt, 1C, CF2, 1JF-C = 282.1 Hz, 2JF-C = 32.8 Hz), 132.48 (s, 2C, CAr), 138, 68 (s, 2C, CAr).

Example 26 [(2- (4-trimethylsilanyl-phenylsulfanyl) -1,1,2,2-tetrafluoroethyl] trimethylsilane M = 354.55 g.mol-1 Under an inert atmosphere, BrC6H4SCF2CF2Br (0.736 g, 2 mmol) is added dropwise to a suspension of magnesium turnings (60 mg, 2.1 mmol), trimethylsilyl chloride (0.6 mL, 4.8 mmol) and anhydrous THF (5 mL), cooled to -78 C The mixture is stirred at -78 ° C. for 8 h then overnight at room temperature Trimethylsilyl chloride (0.6 mL, 4.8 mmol) and magnesium (100 mg, 4.1 mmol) are added to the mixture. reaction mixture at -78 ° C. which is allowed to return to ambient temperature, then is heated at 50 ° C. for 1 day Water is added to the reaction mixture and then the product is extracted with dichloromethane The organic phases are washed. with water and dried over MgSO 4. After evaporation of the solvents, the residue is purified by chromatography on silica gel (Pentane).

The [(2- (4-trimethylsilanyl-phenylsulfanyl) -1,1,2,2-tetrafluoroethyl] trimethylsilane is obtained in the form of a white solid (200 mg, 28%). TLC: Rf 0 , 5 (pentane) 5 19F NMR (282 MHz, CDCl3): 6 -82.63 (t, 2F, SCF2, 3JF-F 5.2 Hz), -122.51 (t, 2F, CF2Si, 3JF_F = 5 , 2Hz). 1H NMR (300 MHz, CDCl3): 80.29 (m, 18H, Si (OH3) 3), 7.53-7.64 (m, 4H, HAr) 13C NMR (75 MHz, CDCl3) ) 8 -3.95 (m, 3C, CF2Si (CH3) 3), -1.12 (s, 3C, Si (CH3) 3), 122.97 (tt, 1C, CF2, 1JF-C = 272, 3 Hz, 3JF_c = 45.2 Hz), 125.09-125.15 (m, 1C, C Ar 4), 127.64 (tt, 1C, CF2, 1JF_c = 281.8 Hz, 3JF-c = 32 , 5 Hz), 134.12 (s, 2C, CAr), 136.28 (s, 2C, CAr), 143.31 (s, 1C, CAr 1) Example 27 2- (4-Bromophenylsulfanyl) fluoride - 1,1,2,2- tetrafluoroethanesulfonyl M = 371.14 g.mol-1 A solution of sulfur dioxide is prepared by bulking sulfur dioxide (200 mg, 3.1 mmol) in a solution anhydrous acetonitrile (5 mL) at room temperature This solution is added to BrC6H4SCF2CF2SiMe3 (0.9 mmol) and stirred at room temperature under an inert atmosphere. Anhydrous CsF (160 mg, 1 mmol) is then added to the reaction mixture which is stirred at room temperature overnight. The reaction is followed by TLC and by 19F NMR (CDCl3) until disappearance of BrC6H4SCF2CF2SiMe3. F-TEDA (355 mg, 1 mmol) is added to the mixture which is stirred for 2 h at room temperature. The mixture is concentrated and the solid residue washed with ethyl ether. After evaporation of the solvents and distillation in a ball oven, B0791EN 2903693 42 Fluoride of 2- (4-Bromophenylsulfanyl) -1,1,2,2-tetrafluoro-ethanesulfonyl is obtained in the form of a colorless liquid (210 mg, 62 %). 19F NMR (282 MHz, CDCl3): 8 46.01-46.10 (m, 1F, SO2F), 5 -86.56-86.62 (m, 2F, SCF2), -105.69-105.74 (m, 2F, CF2S02F). 1H NMR (300 MHz, CDCl3): 87.51-7.64 (m, 4H, HAr), 13C NMR (75 MHz, CDCl3) 8115.78 (ttd, 1C, C6, 1JF-c = 300.6 Hz, 2JF- c = 40.4 Hz, 2JF-c = 32.9 Hz), 121.04-10 121.15 (m, 1C, C Ar 4), 121.45 (ttd, 1C, Cs, 1JF-c = 291 , 6 Hz, 2JF_c = 30.8 Hz, 3JF_c = 1.0 Hz), 127.07 (s, 1C, CArl), 133.15 (s, 2C, CAr), 138.81 (s, 2C, CAr ). Example 28 2- (4- (trimethylsilyl) Phenylsulfanyl) -1,1,2,2-15 t-trafluoroethanesulfonyl fluoride M = 364.43 g.mol-1 A solution of sulfur dioxide is prepared by bubbling sulfur dioxide (350 mg, 5.4 mmol) in anhydrous acetonitrile solution (5 mL) at room temperature.

This solution is added to Me3SiC6H4SCF2CF2SiMe3 (190 mg, 0.5 mmol) and stirred at room temperature under an inert atmosphere. Anhydrous CsF (90 mg, 0.5 mmol) is then added to the reaction mixture which is stirred at room temperature overnight. The reaction is followed by TLC and by 19F NMR (CDCl3) until disappearance of Me3SiC6H4SCF2CE'2SiMe3. F-TEDA (195 mg, 0.55 mmol) is added to the mixture which is stirred for 2 h at room temperature. The mixture is concentrated and the solid residue washed with ethyl ether (5 x 50 mL). 2- (4- (Tri-methylsilyl) Phenylsulfanyl) -1,1,2,2-tetrafluoroethanesulfo-fluoride is obtained as a colorless liquid (155 mg, 77%). 19F NMR (282 MHz, CDCl3): 8 45.97-46.05 (m, 1F, SOZF), -86.37-86.43 (m, 2F, SCF2), -105.51-105.57 ( m, 2F, 5 CF2SO2F). 1H NMR (300 MHz, CDCl3): 80.29 (s, 9H, Si (CH3) 3), 7.56-7.64 (m, 4H). 13C NMR (75 MHz, CDC13): 8 -1.24 (s, Si (CH3) 3), 115.95 (ttd, 1C, C6, 1JF_C = 300.5 Hz, 2JF_C = 40.8 Hz, 2JF_C = 10 32.6 Hz), 121.85 (ttd, 1C, C5, 1JF_C = 291.0 Hz, 2JF_c = 30.8 Hz, 3JF_C = 1.1 Hz), 122.43 (t, 1C, C Ar 4 , 3JF_C = 3.0Hz), 134, 63 (s, CAr), 136, 49 (s, CAr), 145.44 (s, CAr). Example 29 Preparation of 2- (4- (trimethylsilyl) -Phenylsulfanyl) -1,1,2,2-tetrafluoroethanesulfonyl fluoride from ((2- (4-trimethylsilanyl phenylsulfanyl) -1,1,2,2- tetrafluoroethyl] trimethylsilane A solution of sulfur dioxide is prepared by bulking sulfur dioxide (1.5 g, 24 mmol) in a solution of anhydrous acetonitrile (20 mL) at room temperature. Me3SiC6H4SCF2CF2SiMe3 (6 mmol) and stirred at room temperature under inert atmosphere. Anhydrous CsF (1 g, 6.5 mmol) is then added to the reaction mixture which is stirred at room temperature overnight. The reaction is followed by TLC. and by 19F NMR (CDCl3) until disappearance of Me3SiC6H4SCF2CF2SiMe3 A solution of sulfuryl chloride (600 µL, 7.4 mmol) in pentane (2 mL) is added to the reaction mixture at -20 ° C. This solution is stirred at -20 C for 1 h then at room temperature for 4 h. Anhydrous KF (1.8 g, 31 mmol) is then added to the mixture which is stirred at room temperature for 72 h. The mixture is concentrated and distilled in a boules oven. After chromatography on silica gel (pentane), 2- (4- (trimethylsilyl) Phenylsulfanyl) -1,1,2,2-tetrafluoroethanesulfonyl fluoride is obtained as a colorless liquid (1.05 g, 48%). . B0791EN 2903693 44 Example 30 1-f (2-Bromo-1,1,2,2-Tetrafluoroethyl) sulfanyl] -4-fluoro-benzene M = 307.08 g.mol-1 5 In a three-necked flask placed under nitrogen, surmounted by a dry ice condenser and a dropping funnel, 4Fluorothiophenol (3.2 mL, 30 mmol) is added dropwise (30 min) at 0 C on a suspension of NaH (1.8 g, 45 mmol) in anhydrous DMF (35 mL). The mixture is then stirred at this temperature for 30 min then cooled to -50 ° C. 1,2-dibromo-1,1,2,2-tetrafluoroethane (4 mL, 33 mmol) is then added dropwise - 50 C in 10 min. The mixture is then stirred for 3 h at this temperature and is then allowed to return to room temperature. Water is added to the reaction mixture and then the product is extracted with ethyl ether. The organic phases are washed with water and dried over MgSO4. After evaporation of the solvent, the residue is purified by distillation. 1 - [(2-Bromo-1,1,2,2-Tetrafluoroethyl) sulfanyl] -4-fluoro-benzene is obtained as a colorless liquid (7.7 g, 83%). 19F NMR (282 MHz, CDC13): 8 -62.71 (t, 2F, CF2Br, 3JF-F = 8.0 Hz), -86.02 (t, 2F, SCF2, 3JF_F = 8.0 Hz), -108.92-108.83 (m, 1F, FAr). 1H NMR (300 MHz, CDCl3): 87.08.087.16 (m, 2H, HAr2), 7.62-7.67 (m, 2H, HAr3) 13C NMR (75 MHz, CDCl3): 8116.82 ( tt, 1C, CF2, 1JF-C = 313.4 Hz, 2JF_c = 40.4 Hz), 116, 88 (d, 2C, CAr2, 2JF-c = 22.0 Hz), 118.82-118.95 (m, 1C, C Ar4), 122.12 (ttd, 1C, CF2, 1JF_c = 290.9 Hz, 2JF_c = 34.3 Hz, 6JF-c = 30 1.5 Hz), 139.66 (d, 2C, CAr3, 3JF_C = 9.3 Hz), 164.82 (d, 1C, CAri, 1JF_c = 252.5 Hz).

80791 FR 2903693 45 Example 31 [1,1,2,2-tetrafluoroethyl- (2- (4-fluorophenylsulfanyl) -1 trimethyl silane 2 3 S-CF2CF2S1Me3 2 3 M = 300.36 g.mol-1 5 Under inert atmosphere, FC6H4SCF2CF2Br (615 mg, 2 mmol) is added dropwise to a suspension of magnesium turnings (100 mg, 4 mmol), trimethylsilyl chloride (1 mL, 8 mmol) and anhydrous THF (5 mL) , cooled to -78 ° C. The mixture is then stirred for 3 hours, slowly returning to room temperature, water is added to the reaction mixture and the product is then extracted with dichloromethane The organic phases are washed with 1 ml. 'water and dried over MgSO 4. After evaporation of the solvents, [1,1,2,2-tetrafluor.oethyl- (2- (4-fluoro-phenylsulfanyl) -] trimethylsilane is obtained in the form of a yellow liquid (530 mg, 88%) 19F NMR (282 MHz, CDCl3): 8 -83.29 (t, 2F, SCF2, 3JF-F = 4.6 Hz), -122.52 (t, 2F, CF2Si, 3JF- F = 4.6Hz), -110.50-110.59 (m, 1F, FAr).

1H NMR (300 MHz, CDCl3): 80.27 (s, 9H, Si (CH3) 3), 7.05-7.12 (m, 2H, HAr2), 7.61-7.66 (m, 2H, HAr3) • 13C NMR (75 MHz, CDC13): 8 -4.03 (m, 3C, Si (CH3) 3), 116, 48 (d, 2C, CAr2, 2JF-C = 22.0 Hz), 119.87 -119.98 (m, 1C, C Ar 4), 122.75 (tt, 1C, CF2, 1JF-C = 272.2 Hz, 25 2JF-C = 45.3 Hz), 127.10 (ttd, 1C, CF2, 1JF-C = 281.2 Hz, 2JF-c = 32.9 Hz, 6JF_C = 1.4 Hz), 139.50 (d, 2C, CAr3, 3JF-c = 8.8 Hz), 164.41 (d, 1C, 251.4 Hz).

1 CArlr JF-C B0791EN 2903693 46 Example 32 -2- (4-fluorophenylsulfanyl) -1,1,2,2-tetrafluoroethanesulfonyl fluoride M = 310, 24 g.mol-1 5 A solution of sulfur dioxide is prepared by bubbling sulfur dioxide (200 mg, 3.1 mmol) in a solution of anhydrous acetonitrile (5 mL) at room temperature. This solution is added to FC6H4SCF2CF2SiMe3 (300 mg, 1 mmol) and stirred at room temperature under an inert atmosphere. Anhydrous CsF (160 mg, 1 mmol) is then added to the reaction mixture which is stirred at room temperature overnight. The reaction is followed by TLC and by 19F NMR (CDCl3) until disappearance of FC6H4SCF2CF2SiMe3. F-TEDA (360 mg, 1 mmol) is added to the mixture which is stirred for 2 h at room temperature. The mixture is concentrated and the solid residue washed with ethyl ether. After evaporation of the solvents and ball oven distillation, -2- (4-fluorophenylsulfanyl) -1,1,2,2-tetrafluoroethanesulfonyl fluoride is obtained as a yellow liquid (200 mg, 64%). 19F NMR (282 MHz, CDCl3): 8 45.96-46.06 (m, 1F, SO2F), -86.96-87.02 (m, 2F, SCF2), -105.67-105.72 ( m, 2F, CF2S02F), -107.62-107.72 (m, 1F, FAr). 1H NMR (300 MHz, CDCl3): 87.11-7.18 (m, 2H), 7.64-7.69 (m, 2H). B0791EN 2903693 47 Example 33 Preparation of -2- (4-fluorophenylsulfanyl) -1,1,2,2-tetrafluoroethanesulfonyl fluoride from (1,1,2,2-tetrafluoroethyl- (2- (4-fluoro-phenylsulfanyl) ) -] - 5 trimethylsilane A solution of sulfur dioxide is prepared by bubbling sulfur dioxide (2.6 g, 40 mmol) in a solution of anhydrous acetonitrile (25 mL) at room temperature. FC6H4SCF2CF2SiMe3 (2.7 g, 109 mmol) and stirred at room temperature under an inert atmosphere. Anhydrous CsF (1.6 g, 10.5 mmol) is then added to the reaction mixture which is stirred at room temperature overnight. The reaction is followed by TLC and by 19F NMR (CDCl3) until disappearance of FC6H4SCF2CF2SiMe3.

A solution of sulfuryl chloride (900 µL, 11.2 mmol) in pentane (2 mL) is added to the reaction mixture at -20 C. This solution is stirred at -20 C for 1 h then at room temperature for 4 h. Anhydrous KF (2.9 g, 50 mmol) is then added to the mixture which is stirred at room temperature for 72 h. The mixture is concentrated and distilled in a boules oven. -2- (4-Fluorophenylsulfanyl) -1, 1,2,2-tetrafluoroethanesulfonyl fluoride is obtained in the form of a yellow liquid (2.08 g, 67%). Example 34 25 ((Bromodifluoromethyl) sulfanyl] 4-Fluoro-benzene M = 257.07 g.mol-1 In a three-necked flask placed under a nitrogen atmosphere, surmounted by a dry ice condenser and a dropping funnel, thiophenol (2.2 mL, 20 mmol) is added dropwise over 40 min at 0 C to a suspension of NaH (1.2 g, 30 mmol) in anhydrous DMF (30 mL). is then stirred at 0 C for 30 min then cooled to -50 C. Dibromodifluoromethane (5.5 mL, 60 mmol) is then added at -50 C. The mixture is then stirred for 5 h at this temperature then 1 h at room temperature Water is added to the reaction mixture then the product is extracted with ethyl ether The organic phases are washed with water and dried over MgSO 4 After evaporation of the solvent, the organic phases are washed with water and dried over MgSO 4. residue is distilled off under reduced pressure to provide [(Bromodifluoromethyl) sulfanyl] 4-Fluoro-benzene as a colorless liquid (2.15 g, 42%). 19F NMR (282 MHz, CDCl3) : 8 -23.32 (s, 2F, CF2), -108.51-108.56 (m, 1F, FAr). 1H NMR (300 MHz, CDCl3): 87.09-7.16 (m, 2H, H2), 7.62-7.68 (m, 2H, H3). 13C NMR (75 MHz, CDC13): 8116.90 (d, 2C, CAr2, 2JF-c = 22.0 Hz), 119.52 (td, 1C, CF2, 1JF-c = 338.4 Hz, 6JF_c = 2.8Hz), 122.91-122.97 (m, 1C, CAr4), 138.92 (d, 2C, CAr3, 3JF-c = 8.8Hz), 164.76 (d, 1C, 253.0 Hz). Example 35 (difluoro- (4-Fluorophenylsulfanyl) -methyl] trimethylsilane 1 CArlr JF-C 20 M = 250.36 g.mol-1 Under an inert atmosphere, FC6H4SCF2Br (1.29 g, 5 mmol) is added dropwise. a suspension of magnesium turnings (245 mg, 10 mmol), trimethylsilyl chloride (2.5 mL, 20 mmol) and anhydrous THF (20 mL) cooled to 25 -78 C. The mixture is then stirred for 4 h slowly returning to room temperature Water is added to the reaction mixture and then the product is extracted with dichloromethane The organic phases are washed with water and dried over MgSO 4. After evaporation of the solvents, the [difluoro- (4-Fluorophenylsulfanyl) -methyl] trimethylsilane is obtained in the form of a yellow liquid (1.19 g, 95%).

2903693 B0791EN 49 19F NMR (282 MHz, CDCl3): 8 -88.41 (s, 2F), -112.00-112.12 (m, 1F, FAr) 1H NMR (300 MHz, CDCl3): 80.26, ( s, 9H), 7.02-7.09 (m, 2H, H2), 7.53-7.59 (m, 2H, H3).

5 13C NMR (75 MHz, CDC13) 8 -4.14 (t, Si (CH3) 3, 3JF-c = 1.4 Hz), 116.13 (d, 2C, CAr2, 2JF-C = 21.9 Hz), 121.46 (td, CAr4, 3JF-c = 4.4 Hz, 4JF-c = 3.3 Hz), 133.87 (td, 1C, CF2, 1JF-c = 300.5 Hz, 6JF -c = 1.1 Hz), 138.80 (d, 2C, 2C, CAr 3, 3JF_C = 8.8 Hz), 169.92 (d, 10 1C, CAr 1, 1JF-c = 249.7 Hz ). Example 36 Difluoro- (4-fluorophenylsulfanyl) -methanesulfonyl fluoride M = 260.23 g.mol-1 A solution of sulfur dioxide is prepared by bubbling sulfur dioxide (0.5 g, 7.8 mmol) in anhydrous acetonitrile solution (10 mL) at room temperature. This solution is added to FC6H4SCF2SiMe3 (625 mg, 2.5 mmol) and stirred at room temperature under an inert atmosphere. Anhydrous CsF (390 mg, 2.6 mmol) is then added to the reaction mixture which is stirred at room temperature overnight. The reaction is followed by TLC and by 19F NMR (CDCl3) until disappearance of FC6H4SCF2SiMe3. F-TEDA (890 mg, 2.5 mmol) is added to the mixture at -20 ° C. which is then stirred for 2 h at room temperature. The mixture is concentrated and the solid residue washed with ethyl ether. The filtrate is evaporated and the product purified by ball oven distillation. Difluoro- (4-fluorophenylsulfanyl) -methanesulfonyl fluoride 30 is obtained as a colorless liquid (205 mg, 32%). B0791FR 2903693 50 19F NMR (282 MHz, CDC13): 8 35.16 (t, 1F, SO2F, 3JF-F = 4.6 Hz), -76.80 (d, 2F, 3 = i 2-i JF- F 4.6Hz), -106.68-106.78 (m, 1F, FAr). 1H NMR (300 MHz, CDCl3): 87.13-7.19 (m, 2H, H2), 7.68-7.72 (m, 2H, H3). 13C NMR (75 MHz, CDCl3): 8,117.10 (m, 1C, C Ar 4), 117.37 (d, 2C, CAr2, 2J, -c = 22.5 Hz), 126.72 (tdd, 1C, CF2, 1JF-c = 323.4 Hz, 2JF_c = 32.3 Hz, 6JF_c = 2.4 Hz), 139.86 (d, 2C, 2C, CAr3, 3JF-C = 9.3 Hz), 165.33 (d, 1C, 10 CArl, 1JF_c = 254.7 Hz). B0791FR

Claims (34)

Claims 1. A compound of the formula Ar-Z- (CF2) n-CFRf-SO2Y (I) in which: • Z represents a carbonyl, sulfide, sulfinyl, sulfonyl, phosphine oxide, aryl phosphonate or amino group; • n is 0 or 1; • Rf is F or or a linear or branched perfluoroalkyl group having 1 to 8 carbon atoms; • Y is Cl, Br or F; • Ar is an aromatic group chosen from the group consisting of o monocyclic aromatic groups optionally bearing one or more substituents; O polycyclic aromatic groups having condensed or non-condensed rings, said rings optionally bearing one or more substituents; o heterocyclic aromatic groups, bicyclic with condensed or non-condensed rings, or monocyclic, and optionally bearing one or more substituents; it being understood that said aromatic group can form part of a repeating unit of a polymer chain. 2. Compound according to claim 1, characterized in that the substituents of the aromatic groups which constitute Ar are selected from the group consisting of: o halogen atoms, Cl-CH2-, and Q1-O-CH2- groups. wherein Q1 is H, an alkyl group or an acyl group; o A hydroxyl group protected in the form of an ether Q2-0-, in the form of a carboxylic ester Q2C (O) 0- or in the form of a sulfonate Q2-SO2-0-, Q2 representing an alkyl group or an aryl group; o aliphatic or aromatic groups possessing an ethylenic unsaturation which may originate from a vinyl unit (CH = CH2-), from an allyl unit (CH2 = CH-CH2-) or from an acryloyloxy unit (CH2 = CH-). C (O) -O-), optionally substituted; O protected amino groups Q3-NH- in which Q3 represents an alkyl group, an aryl group, an arylalkyl group or an acyl group; o trialkylsilyl groups; o oxirane groups; o electron-withdrawing groups such as perfluoroalkyl groups, alkylsulfonyl or arylsulfonyl groups, sulfonyl halide groups, ester, nitrile, cyclic carbonate or nitro groups. 3. Compound according to one of claims 1 to 2, characterized in that Z is an aryl phosphonate group corresponding to the formula -OP (0) (OR ') - or a phosphine oxide group corresponding to the formula - P (0) (RI) -, R1 being chosen from the groups defined for Ar. 4. Compound according to one of claims 1 to 2, characterized in that Z is an amino group corresponding to the formula -N (R2) - in which R2 represents H or a linear or branched alkyl group, or an aryl group such as than defined for Ar. 5. Compound according to claim 1, characterized in that it meets one of the following formulas: - Ar-CO- (CF2) n-CFRf-SO2Y (Ico-Y) Ar-S- (CF2) nùCFRf- S02Y (Is-Y) Ar-SO- (CF2) n-CFRf-S02Y (Iso-Y) - Ar-S02 (CF2) nùCFRf-S02Y (Iso2-Y) - Ar-OP (0) (OR ') - (CF2) n-CFRf-SO2Y (IpoR-Y) Ar-P (0) (R1) - (CF2) n-CFRf-S02Y (IPR-Y) - Ar-N (R2) - (CF2) n-CFRf -S02Y (IN_Y) 6. Compound according to one of claims 1 to 5, characterized in that Ar represents a phenyl group without a substituent, or a phenyl group bearing a halogen or a trialkylsilyl group. B0791EN 2903693 53 7. Compound according to one of claims 1 to 5, characterized in that Ar represents a heterocyclic aromatic group. 8. Compound according to one of claims 1 to 7, characterized in that Rf is F. 9. Process for preparing a compound Ar-Z- (CF2) n-CFRf-SO2Y (I) according to claim 1, characterized in that it comprises a step of preparing a sulfinate [Ar-Z- ( CF2) n-CFRf-SO2] mM (II), and a step of converting the sulfinate to sulphonyl halide (I), M being a cation of valence m (m being 1 or 2), chosen from metal cations alkali or alkaline earth metal, and organic ammonium, phosphonium, imidazolium and pyridinium cations, said organic cation optionally bearing one or more substituents. 10. The method of claim 9, characterized in that the substituent (s) of the organic cation is (are) chosen from the group consisting of • hydrogen; • alkyl chains; • monocyclic aromatic groups; polycyclic aromatic groups with condensed or non-condensed rings; heterocyclic aromatic groups in which the heteroatom is a nitrogen atom, said heterocyclic groups being polycyclic with condensed or non-condensed rings, or monocyclic. 11. The method of claim 9, characterized in that the sulfinate meets one of the formulas Ils [Ar-S- (CF2) n-CFRf-SO2] mM or IIN [Ar-N (R2) - (CF2) n -CFRf-SO2] mM, and in that it is obtained by a process comprising: - a first step consisting in reducing a halide Ar-Z- (CF2) n-CFRf-X in which X represents Br or Cl, by an excess of magnesium in the presence of trimethylsilyl chloride (TMSCl); - a second step during which the compound Ar-Z- (CF2) n-CFRf-Si- (CH3) 3 obtained is reacted with an MF fluoride in the presence of SO2; Z being respectively S or N (R2) for the sulfinate Ils or 5 IIN. 12. The method of claim 9, characterized in that the sulfinate corresponds to one of the formulas IIso [Ar-SO- (CF2) n-CFRf-SO2] mM or IIso2 [Ar-SO2- (CF2) n-CFRf -SO2] mM and in that it is obtained by a process comprising 10 - a 1st step consisting in reducing a halide Ar-S- (CF2) n-CFRf-X in which X represents F, Br or Cl, by a excess of magnesium in the presence of trimethylsilyl chloride (TMSCl); a 2nd step during which the compound Ar-S- (CF2) n-CFRf-Si- (CH3) 3 obtained is oxidized, using excess metachloroperbenzoic acid (m-CPBA), the amount of the acid being chosen according to the degree of oxidation [(IV) or (VI)] which it is desired to achieve for the S atom, the oxidation being carried out in anhydrous dichloromethane; a 5th stage during which the silane obtained at the end of the 2nd stage is condensed with sulfur dioxide in the presence of MF. 13. Process according to Claim 9, characterized in that the sulfinate corresponds to the formula IIso-o [Ar-COCFRf-SO2] mM and in that it is obtained by a process comprising: - a first step consisting of reducing an Ar-CO-CFXRf halide in which X represents F, Br or Cl, by excess of magnesium in the presence of TMSC1 to obtain a silylated enol ether TMSO-C (Ar) = CFRF; - a second step during which the compound TMSO-C (Ar) = CFRF is reacted with MF in the presence of SO2. 14. The method of claim 9, characterized in that the sulfinate corresponds to the formula IICO_1 [Ar-CO-35 CF2-CFRf-SO2] mM and in that it is obtained by a process comprising. A 1st step consisting in reducing a halide Ar-COCF2-CFRf-X in which with X = Br, Cl with a hydride donor; - A 2nd step consisting in protecting the alcohol Ar-CH (OH) - 5 CF2-CFRf-X obtained with a so-called orthogonal group to the trimethylsilyl group; - A 3rd step consisting in reducing the halide Ar-CH (EO) -CF2-CFRf-X obtained (in which X is Br or Cl and E is a protecting group), by an excess of magnesium in the presence of TMSC1; A 4th step consisting in deprotecting the alcohol Ar-CH (EO) -CF2-CFRf-SiMe3 obtained; - A 5th step consisting in oxidizing the alcohol obtained by deprotection to the ketone Ar-CO-CF2-CFRf-SiMe3; 15 - A 6th step during which the ketone is reacted with an MF fluoride in the presence of SO2. 15. The method of claim 9, characterized in that the sulfinate corresponds to the formula IIpOR [Ar- 0P (0) (OR1) - (CF2) n-CFRf-SO2] mM and in that it is obtained by 20 a process comprising: a 'first step of reducing an Ar-OP (0) (OR1) - (CF2) n-CFRf-X halide in which X n = 0 and X represents Br or Cl when excess magnesium in the presence of TMSC1; 25 - a 2nd step during which Ar-O-P (0) (OR1) - (CF2) n-CFRf-Si (CH3) 3 fluoride MF in the presence of SO2 is compounded. 16. The method of claim 9, characterized in that the sulfinate corresponds to the formula IIpR [Ar-30 P (0) (R1) - (CF2) n-CFRf-SO2] mM and in that it is obtained by a process comprising: a 'first step consisting in reducing a halide Ar-P (R1) - (CF2) n-CFRf-X in which X represents Br or Cl, by an excess of magnesium in the presence of trimethylsilyl chloride (TMSC1 ); represents F if n = 1, by reacting the obtained, with a 2nd step during which the compound Ar-P (R1) - (0F2) n-CFRf-Si- (CH3) is oxidized 3 obtained using excess metachloroperbenzoic acid (m-CPBA); a 3rd stage during which the silane 5 obtained at the end of the 2nd stage is condensed with sulfur dioxide in the presence of MF. 17. Method according to one of claims 9 to 16, characterized in that it is implemented in acetonitrile. 10 18. The method of claim 9, characterized in that MF is an alkali metal or ammonium fluoride, and in that the sulfinate is modified by cation exchange. 19. A process according to claim 9, characterized in that a sulfonyl chloride IoL is obtained by reaction with SO2C12r of the corresponding sulfinate II. 20. The method of claim 19, characterized in that the sulfinate II is chosen from the following sulfinates. - Ar-CO- (CF2) n-CFRf-S02M (IIoo) 20 _ Ar-S-CF2-CFRf-SO2M (IIs) Ar-SO- (CF2) n-CFRf-SO2M (IIso) -Ar-SO2- (CF2) n-CFRf-S02M (IIso2) - ArùOùP (0) (OR ') ù (CF2) nùCFRfùS02M (IIpoR) - ArùP (0) (R1) ù (CF2) nùCFRfùS02M (IIpR) 25 - Ar-N ( R2) - (CF2) n-CFRf-S02M (IIN) in which M is an alkali metal cation or an ammonium, to obtain respectively the following chlorides - Ar-CO- (CF2) n-CFRf-S02C1 (Ico-cl ) Ar-S-CF2-CFRf-SO2C1 (Is-cl) 30 _ Ar-SO- (CF2) n-CFRf-S02C1 (Iso-ci) Ar-S02- (CF2) n-CFRf-S02C1 (Iso2-cl ) - Ar-OP (0) (OR1) - (CF2) n-CFRf-S02C1 (IpoR-cl) - Ar-P (0) (R1) - (CF2) n-CFRf-S02C1 (IpR-c1) - Ar-N (R2) - (CF2) n-CFRf-S02C1 (IN Cl) B0791FR 2903693 57 21. The method of claim 9, characterized in that a sulfonyl fluoride IF is obtained by reaction of the corresponding sulfinate II with the compound F-TEDA, which corresponds to the formula. 22. The method of claim 21, characterized in that the sulfinate II is chosen from the following sulfinates. - Ar-CO- (CF2) n-CFRf-SO2M (IIco) 10 _ Ar-S- (CF2) n-CFRf-SO2M (IIs) Ar-SO- (CF2) n-CFRf-SO2M (IIso) - Ar -SO2- (CF2) n-CFRf-SO2M (I Iso2) - Ar-OP (0) (OR1) - (CF2) n-CFRf-SO2M (IIpoR) - Ar-P (0) (R1) - (CF2 ) n-CFRf-SO2M (IIpR) 15 - Ar-N (R2) - (CF2) n-CFRf-SO2M (IIN) in which M is an alkali metal cation or an ammonium, to obtain respectively the following fluorides - Ar -CO- (CF2) n-CFRf-SO2F (Ico-F) Ar-S- (CF2) n-CFRf-SO2F (Is-F) 20 _ Ar-SO- (CF2) n-CFRf-SO2F (Iso- F) Ar-SO2- (CF2) n-CFRf-SO2F (Is02-F) Ar-OP (0) (OR1) - (CF2) n-CFRf-SO2F (IpoR-F) - Ar-P (0) ( R1) - (CF2) n-CFRf-SO2F (IpR-F) - Ar-N (R2) - (CF2) n-CFRf-SO2F (IN-F) 25 23. The method of claim 9, characterized in that it consists in preparing a sulfonyl chloride here, then reacting the sulfonyl chloride with KF in CH3CN to obtain the corresponding sulfonyl fluoride IF. 30 24. The method of claim 9, characterized in that it consists in preparing a sulfonyl halide Is_y, then subjecting it to oxidation using excess metachloroperbenzoic acid (m-CPBA), to obtain an ISO_Y or IS02_Y compound, the amount of acid being chosen according to the degree of oxidation of S in the final compound. 25. A compound of the formula [Ar-Z- (CF2) ä-CFRf- S02] mM (II), wherein Z represents carbonyl, sulfide, sulfinyl, sulfonyl, phosphine oxide, aryl phosphonate. or amino; • n is 0 or 1; • Rf is F or or a linear or branched perfluoroalkyl group having 1 to 8 carbon atoms; • Ar is an aromatic group selected from the group consisting of o monocyclic aromatic groups optionally bearing one or more substituents; o polycyclic aromatic groups having condensed or non-condensed rings, said rings optionally bearing one or more substituents; o heterocyclic aromatic groups, bicyclic with condensed or non-condensed rings, or monocyclic, and optionally bearing one or more substituents; it being understood that said aromatic group can form part of a repeating unit of a polymer chain. 26. A compound according to claim 25, characterized in that the substituents of the aromatic groups which constitute Ar are chosen from the group consisting of: o halogen atoms, Cl-CH2-, and Q1-O-CH2- groups. wherein Q1 is H, an alkyl group or an acyl group; A hydroxyl group protected in the form of an ether Q2-0-, in the form of the carboxylic ester Q2C (O) 0- or in the form of a sulfonate Q2-SO2-O-, Q2 representing an alkyl group or an aryl group; o aliphatic or aromatic groups possessing an ethylenic unsaturation which may originate from a vinyl unit (CH = CH2-), from an allyl unit (CH2 = CH-CH2-) or from an acryloyloxy unit (CH2 = CH-C (O) -O-), optionally substituted; o protected amino groups Q3-NH- in which Q3 5 represents an alkyl group, an aryl group, an arylalkyl group or an acyl group; o trialkylsilyl groups; o oxirane groups; electron withdrawing groups such as perfluoroalkyl groups, alkylsulfonyl or arylsulfonyl groups, sulfonyl halide groups, ester, nitrile, cyclic carbonate or nitro groups. 27. Compound according to one of claims 25 to 26, characterized in that Z is an aryl phosphonate group corresponding to the formula -OP (0) (OR ') - or a phosphine oxide group corresponding to the formula -P (0) (R1) -, R1 being chosen from the groups defined for Ar. 28. A compound according to one of claims 25 to 26, characterized in that Z is an amino group corresponding to the formula -N (R2) - in which R2 represents H or a linear or branched alkyl group, or an aryl group. as defined for Ar. 29. Compound according to one of claims 25 to 28, characterized in that it corresponds to one of the following formulas: Ar-CO- (CF2) n-CFRf-SO2M (IIco) Ar-S- (CF2 ) n-CFRf-SO2M (IIs) Ar-SO- (CF2) n-CFRf-SO2M (IIso) -Ar-SO2- (CF2) n-CFRf-SO2M (IIso2) 30 - Ar-OP (0) (OR1) - (CF2) n-CFRf-SO2M (IIpoR) Ar-P (0) (R1) - (CF2) n-CFRf-SO2M (IIPR) - Ar-N (R2 ) - (CF2) n-CFRf-SO2M (IIN) 30. Compound according to one of claims 24 to 28, characterized in that Ar represents a phenyl group without a substituent, or a phenyl group bearing a halogen or a trialkylsilyl group. 31. Compound according to one of claims 25 to 29, characterized in that Ar represents a heterocyclic aromatic group. 32. Compound according to one of claims 25 to 31, characterized in that Rf is F. 33. Compound according to one of claims 25 to 32, characterized in that the cation M is a cation of valence m 10 (m being 1 or 2), chosen from alkali metal or alkaline earth metal cations, and organic ammonium, phosphonium, imidazolium and pyridinium cations, said organic cation optionally carrying one or more substituents. 15 34. The method of claim 33, characterized in that the substituent (s) of the organic cation is (are) chosen from the group consisting of: • hydrogen; • the alkyl chains; • monocyclic aromatic groups; polycyclic aromatic groups with condensed or non-condensed rings; heterocyclic aromatic groups in which the heteroatom is a nitrogen atom, said heterocyclic groups being polycyclic with condensed or non-condensed rings, or monocyclic.