EP2064219A2 - Aromatische sulfinate und sulfonylhalide sowie ihre herstellung - Google Patents

Aromatische sulfinate und sulfonylhalide sowie ihre herstellung

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Publication number
EP2064219A2
EP2064219A2 EP07823294A EP07823294A EP2064219A2 EP 2064219 A2 EP2064219 A2 EP 2064219A2 EP 07823294 A EP07823294 A EP 07823294A EP 07823294 A EP07823294 A EP 07823294A EP 2064219 A2 EP2064219 A2 EP 2064219A2
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European Patent Office
Prior art keywords
cfr
group
groups
nmr
mmol
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EP07823294A
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English (en)
French (fr)
Inventor
Jean-Yves Sanchez
Bernard Langlois
Maurice Medebielle
Fabien Toulgoat
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Eras-Labo
Universite Claude Bernard Lyon 1 UCBL
Institut Polytechnique de Grenoble
Eras Labo SAS
Original Assignee
Eras-Labo
Universite Claude Bernard Lyon 1 UCBL
Institut Polytechnique de Grenoble
Eras Labo SAS
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Publication of EP2064219A2 publication Critical patent/EP2064219A2/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/78—Halides of sulfonic acids
    • C07C309/79—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms
    • C07C309/81—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C313/02—Sulfinic acids; Derivatives thereof
    • C07C313/04—Sulfinic acids; Esters thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/14—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/64—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/64—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton
    • C07C323/66—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton containing sulfur atoms of sulfo, esterified sulfo or halosulfonyl groups, bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring

Definitions

  • the present invention relates to a process for the preparation of sulfonyl fluorides, as well as to new sulfonyl fluorides obtained by said process.
  • the sulfonyl halides are useful compounds for obtaining sulfonylimides and sulfonates used for the constitution of electrolytes, especially for lithium batteries and for fuel cells.
  • the sulfonyl halides are prepared either by the action of a halogenating agent (for example PCl 5 ) on the corresponding acid, or from the corresponding sulfinates.
  • a halogenating agent for example PCl 5
  • 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.
  • sulfinates are very hygroscopic compounds and insufficiently thermally stable to be easily dehydrated. Their isolation is therefore a source of moisture supply in the halogenation reaction medium, which greatly affects the formation yield of sulfonyl halides.
  • the invention provides a process for the synthesis of sulfonyl fluorides in which a sulfinate which forms as intermediate product is not necessarily isolated before being converted into sulfonyl fluoride.
  • the process of the invention is intended for the preparation of a sulfonyl fluoride Ar-Z- (CF 2 ) n -CFR f -SO 2 F (I), and it is characterized in that it involves reacting a sulfinate of formula [Ar-Z- (CF 2 ) n -CFR f -SO 2 ] m M (H), with a fluorinating agent chosen from fluorine F 2 , xenon difluoride XeF 2 , potassium fluorosulfate KSO 4 F, N-fluorobenzenesulfonimide (PhSO 2 J 2 NF, N-fluoropyridinium heptafluorodiborate, N-fluoropyridinium trifluoromethanesulfonate, N, N '-difluorinated bis-tetrafluoroborate, 2, 2'-bipyridinium and 1-chloromethyl-4-fluoro-1,4
  • Z represents a carbonyl, sulphide, sulfinyl, or sulphonyl group; n is 0 or 1;
  • R f is F or a linear or branched perfluoroalkyl group having 1 to 8 carbon atoms
  • Ar is an aromatic group selected from the group consisting of monocyclic aromatic groups; polycyclic aromatic groups having fused or non-condensed rings; and heterocyclic, bicyclic aromatic groups with condensed or non-fused rings, or monocyclic rings;
  • M is a cation whose valence m is 1 or 2, chosen from alkali metal or alkaline earth metal cations, and ammonium or phosphonium organic cations.
  • An aromatic group Ar can be part of a repeating unit of a polymer chain.
  • F-TEDA is particularly preferred as a fluorinating agent.
  • An aromatic group Ar may carry one or more substituents selected from the group consisting of: o halogen atoms, Cl-CH 2 -, and ⁇ -O-CH 2 - groups in which Q 1 is H, a group alkyl or an acyl group; a protected hydroxyl group in the form of a Q 2 -O- ether, in the form of a carboxylic ester Q 2 C (O) O- or in the form of a sulfonate Q 2 -SO 2 -O-, Q 2 representing an alkyl group or an aryl group, [e.g.,
  • a Z group of the carbonyl, sulphide, sulphinyl or sulphonyl type is represented respectively by the formulas -C (O) -, -S-, -S (O) - or -S (O) 2 -
  • the following compounds can be cited as examples of sulfonyl fluorides according to the present invention: the compounds Ar-CO- (CF 2 ) n -CFR f -S ⁇ 2 F which are hereinafter designated by Ico; the compounds Ar-S- (CF 2 ) n -CFR f -S ⁇ 2 F which are designated hereinafter by I 3 ; the compounds Ar-SO- (CF 2 ) n -CFR f -S ⁇ 2 F which are hereinafter denoted by I 3 O; the compounds Ar-SO 2 - (CF 2 ) n -CFR f -S ⁇ 2 F which are hereinafter denoted by I S0 2-
  • Ar represents a phenyl group without a substituent, or a phenyl group carrying a halogen substituent (for example
  • a particular family of compounds includes compounds having the formula Ar-CO- (CF 2 ) n -CFR f -SO 2 F wherein Ar is an aromatic group without ring hetero atoms and (CF 2 ) n -CFR f is CF 2 or C (CF 3 ).
  • Another particular family of compounds includes compounds having the formula Ar-CO- (CF 2 ) n -CFR f -SO 2 F wherein Ar is a heteroaromatic group, and (CF 2 ) n -CFR f is CF 2 or (CF 2 ) 2.
  • a third family of compounds comprises compounds having the formula Ar-Z- (CF 2 ) n -CFR f -SO 2 F wherein Z is S, SO or SO 2 , and Ar is an aromatic or heteroaromatic group bearing no no perhaloalkyl substituent.
  • the sulfinate cation M is chosen from alkali metal (in particular Cs or K) or alkaline earth metal (in particular Mg) cations, and ammonium or phosphonium organic cations in which all the groups borne by N or P are hydrogen atoms, or at least one of said substituents is different from H and selected from: • alkyl groups; Monocyclic aromatic groups and aromatic heterocyclic groups in which the heteroatom is a nitrogen atom.
  • Ammonium or phosphonium cations bearing alkyl groups are particularly preferred.
  • (C 4 Hg) 4 N + , (CH 3 ) 4 N + and tetraphenylphosphonium Ph 4 N + may be mentioned.
  • the sulfinates which form as intermediates in the synthesis of sulfonyl fluorides may furthermore constitute radical generators useful in various processes for the synthesis of chemical compounds.
  • a sulfinate [Ar-S- (CF 2 ) n -CFR f -SO 2 ] m M (hereinafter referred to as Ils) in which Ar, - (CF 2 ) n -CFR f -, M and m have the meaning given above can be obtained by a process comprising: a first step of reducing a halide Ar-S- (CF 2) n -CFR f -X wherein X is Br or Cl, with an excess of magnesium in the presence of trimethylsilyl chloride (TMSCl) to obtain a compound Ar-S- (CF 2 ) n -CFR f -Si- (CH 3 ) 3 ; a second step in which the compound Ar-S- (CF 2 ) n -CFR f -Si- (CH 3 ) 3 ;
  • Step 1 Ar-S- (CF 2 ) n -CFR f -X + Mg + TMSCl ⁇ Ar-S- (CF 2 ) n -CFR f -Si (CH 3 ) 3 + MgClX
  • Step 2 m Ar-S- (CF 2) n -CFR f -Si (CH 3) 3 + MF + SO 2 ⁇ II S + (CH 3 J 3 SiF the era
  • the step is preferably carried out in THF, and preferably the 2 nd step in MeCN, so it is not necessary to isolate the resulting sulfinate, before being reacted to convert it into sulfonyl fluoride.
  • a compound Ar-S-type (CF 2 ) n CFR f -Br used as starting material for the sulfinate may be obtained by reacting the thiol Ar-SH with a dibromide Br (CF 2) n -CFR f -Br using dibromide in excess.
  • a sulfinate [Ar-SO- (CF 2 ) n -CFR f -SO 2 ] m M (hereinafter referred to as IIso) or a sulfinate [Ar-SO 2 - (CF 2 ) n -CFR f -SO 2 ] m m (hereinafter referred to by IISO 2) can be obtained by a process comprising the step of reducing era a Ar-S- halide (CF 2) n -CFR f -X wherein X is Br or Cl, by an excess of magnesium in the presence of trimethylsilyl chloride (TMSCl) to obtain an Ar-S- (CF 2 ) n -CFR f - Si- (CH 3 ) 3 compound; a 2 nd step in which the oxide compound Ar-S- (CF 2) n -CFR f -Si (CH 3) 3 using benzoic directivechloroper- acid (m-CPBA) in excess, the quantity
  • Ar-CO-CFR f -X halides useful as starting materials for the preparation of C 2 sulfinates are commercially available.
  • Ph-C (O) -CF 2 Cl and the following compounds, marketed in particular by Aldrich, Acros and Oakwood:
  • the sulfinate [Ar-C (O) -CF 2 -SO 2 -CFR f] mM can be obtained by a process comprising the following steps: the step of age to protect the carbonyl group of Ar -C (O) -CF 2 CF 2 Br in the form of 1,3-dioxolane- or 1,3-dioxane-Ar-C (OR) 2 -CF 2 CF 2 Br, [C (OR) 2 representing a ring -O-CH 2 CH 2 -O or -OCH 2 CH 2 CH 2 -O-]; a 2nd step consisting in reducing Ar-C (OR) 2 -CF 2 CF 2 Br to magnesium in the presence of Me 3 SiCl to obtain Ar-C (OR) 2 - CF 2 CF 2 -SiMe 3 ; a 3 rd step of reacting Ar-C (OR) 2 -CF 2 CF 2 - SiMe 3 with a fluoride
  • the last stage of the process is advantageously carried out with, as deylation agent, an MF fluoride in which M is an alkali or alkaline earth metal cation, or an ammonium cation. .
  • M is an alkali or alkaline earth metal cation
  • ammonium cation is advantageously carried out with, as deylation agent, an MF fluoride in which M is an alkali or alkaline earth metal cation, or an ammonium cation.
  • a sulfinate of a different cation can then be obtained if necessary by cation exchange.
  • MF fluoride may be chosen for example from
  • the desilylating agent may further be (C 4 Fg) 4 NSi (Ph) 2 F 2 and (C 4 F 9 ) 4 NSn (Ph) 2 F 2 .
  • the procedures for implementing the step of obtaining a sulphonyl fluoride from a sulfinate depend on the sulphonyl fluoride targeted, in particular on the nature of Z of the Ar-Z group that it contains. In general, the process is carried out in acetonitrile, using sulfinate in the acetonitrile solution from which it is obtained.
  • the fluorinating agents used for the fluorination of sulfinate are commercially available products. For example, 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo [2,2,2] octane bis (tetrafluoroborate) (F-TEDA)
  • Fluorine F 2 xenon difluoride XeF 2 , potassium fluorosulfate KSO 4 F, N-fluorobenzenesulfonimide (PhSO 2 ) 2NF, N-fluoropyridinium heptafluorodiborate N-fluoropyridinium trifluoromethanesulfonate
  • difluoro-2,2'-bipyridinium are marketed notably by the company Acros and the company Aldrich.
  • Sulfonyl fluoride I can be obtained by reaction of the corresponding compound II with a fluorin
  • a sulfonyl fluoride I S o or I ⁇ 0 2 can be obtained from the corresponding sulfonyl fluoride I 3 .
  • the oxidation is advantageously carried out using metachloroperbenzoic acid (J ⁇ -CPBA) in excess, the amount of acid being chosen as a function of the degree of oxidation (IV) or (VI)] that one wishes to achieve for the S atom. It is further noted that the oxidation of the group S to the SO or SO 2 group can generally be carried out on the compound
  • Said method comprises: - a ere the step of reducing the ⁇ , ⁇ , ⁇ -trifluoro-acetophenone PhCOCF 3 with an excess of magnesium in the presence of TMSCl at a temperature close to 0 0 C, to obtain the ether silyl enol which is then treated with an excess of fluoride and an excess of sulfur dioxide SO 2 to obtain a sulphinate; a 2 nd step of fluorinating the sulfinate.
  • the l st step may be represented by the following reaction scheme:
  • PhCOCF 3 _- - U * H PhCOCF 2 SO 2 M
  • 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 fluoride co I can be obtained in the 2nd stage (halogenation of sulfinate) by rea- salt sulfinate with F-TEDA at -20 ° C. and room temperature, according to the following reaction scheme:
  • Said method comprises: - a step of the era reducing a compound Ph-S- (CF 2) m Br with an excess of magnesium in the presence of TMSCl to give Ph-S- (CF 2) m -Si (CH 3 ) 3 , then reacting this intermediate with an excess of fluoride and an excess of sulfur dioxide SO 2 to obtain a sulfinate; - a 2 nd step of fluorinating the sulfinate.
  • the l st step may be represented by the following reaction scheme:
  • CsF could be replaced by a quaternary ammonium fluoride.
  • a sulfonyl fluoride ⁇ I can be obtained during the 2 SRUEI step (fluorination of sulfinate) reacting the sulfinate with the fluorinating agent, for example F-TEDA at a temperature between -20 ° C and room temperature according to the following reaction scheme:
  • a compound I and I o S S o2 can be obtained by oxidation of the corresponding compound Is-, using benzoic shortcutchloroper- acid (m-CPBA) in excess, the amount of acid being chosen according to the degree of (Oxidation (IV) or (VI)] that is desired to achieve for the S atom.
  • m-CPBA benzoic griefchloroper- acid
  • 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 refluxing dichloromethane.
  • the processes described above for the different types of compounds can be implemented by choosing the Ar-ZY starting halides corresponding to the desired final sulfonyl fluoride.
  • the Ar 'group of an existing halide can be modified on the compound Ar' -S- (CF 2 ) n -CFR f -Si (CH 3 ) 3
  • n-tetrabutylammonium 1,1-difluoro-2-oxo-2-phenylethanesulfinate was obtained from 2,2-difluoro-1-phenylvinyloxy) trimethylsilane.
  • a sulfur dioxide solution is prepared by bubbling sulfur dioxide (2.3 g, 36 ⁇ mol) in a solution of anhydrous acetonitrile (20 mL) at room temperature. This solution is added to the 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 and then brought to ambient temperature for 1 h. The reaction is monitored by TLC and 19 F NMR (CDCl 3 ) until disappearance of the enol ether. After evaporation of the solvents, the desired sulfinate is obtained in the form of a yellow oil. 19 F NMR (280 MHz, CDCl 3 ): ⁇ -112.18 (s, 2F)
  • Sulfur dioxide solution was prepared by bubbling sulfur dioxide (2.3 g, 36 mmol) in a solution of anhydrous acetonitrile (20 mL) at room temperature. This solution was added to the silyl enol ether 1 (11.2 mmol) prepared according to the method of Example 1, and stirred at -40 ° under an inert atmosphere. Anhydrous CsF (1.7 g, 11.3 mmol) is then added, with stirring, to the reaction mixture maintained at -40 ° C. for 1 h and then brought to ambient temperature for 1 h. The reaction is monitored by TLC and 19 F NMR (CDCl 3 ) 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 distillation in a baking oven.
  • the sulfonyl fluoride is obtained in the form of a colorless liquid (1.79 g, 67% yield).
  • thiophenol (10.2 mL, 100 mmol) is added dropwise within 40 min at 0 C 0 on a suspension of NaH (6 g, 150 mmol) in anhydrous DMF (100 mL). The mixture is then stirred at 0 ° C. for 30 min and then cooled to -50 ° C. The dibromodifluoromethane (27 mL, 300 mmol) is then added at -50 ° C. The mixture is then stirred for 3 hours at this temperature and then 30 min at room temperature.
  • the carbons C Ar i, C Ar 2 and C Ar 3 are determined on the 2D NMR spectra by analogy with products of the same family.
  • PhSCF 2 Br (4.8 g, 20 mmol) is added dropwise to a suspension of turnings of magnesium (960 mg, 40 mmol), trimethylsilyl chloride (10.2 mL, 80 mmol) and anhydrous THF (50 mL) cooled to 0 ° C.
  • the mixture is stirred at 0 ° C. for 1 h and then at ambient temperature for 1 h.
  • the mixture is then concentrated and the resulting solid is washed with petroleum ether.
  • the organic phase is evaporated under vacuum to provide difluoro- (phenylsulfanyl) methyl] trimethylsilane as a yellow liquid (4.3 g, 92%).
  • the carbons C Ar i and C Ar 2 are determined on the 2D NMR spectra by analogy with products of the same family.
  • a sulfur dioxide solution is prepared by bubbling sulfur dioxide (160 mg, 2.5 mmol) in a solution of anhydrous acetonitrile (2 mL) at room temperature. This solution is added to PhSCF 2 SiMe 3 (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 monitored by TLC and 19 F NMR (CDCl 3 ) until disappearance of PhSCF 2 SiMe 3 . The mixture is filtered and the solid residue washed with acetonitrile. The filtrate is evaporated and the residue washed with acetonitrile. After drying in vacuo, the cesium difluoro (phenylsulfanyl) -methanesulfinate is obtained as a white solid (0.18 g, quantitative). TLC: R f 0 (pentane)
  • CAr 1, CAr 2 and CAr 3 carbons are determined on the 2D NMR spectra by analogy with products of the same family.
  • a sulfur dioxide solution is prepared by bubbling sulfur dioxide (3.9 g, 61 mmol) in a solution of anhydrous acetonitrile (20 mL) at room temperature. This solution is added to PhSCF 2 SiMe 3 (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 monitored by TLC and 19 F NMR (CDCl 3 ) until disappearance of PhSCF 2 SiMe 3 . 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 carbons C Ar i, C Ar 2 and C Ar 3 are determined on the 2D NMR spectra by analogy with products of the same family.
  • thiophenol (10.2 ml, 100 mmol) is added dropwise (30 min) at 0 ° C. on a suspension.
  • NaH (6 g, 150 mmol) in anhydrous DMF (100 mL).
  • the mixture is then stirred at this temperature for 20 min and then cooled to -50 ° C.
  • the 1,2-dibromo-1,1,2,2-tetrafluoroethane (15 mL, 125 mmol) is then added dropwise to - 50 0 C in 10 min. The mixture is then stirred for 2 h at this temperature and then 1 h at room temperature.
  • PhSCF 2 CF 2 Br (3.7 g, 12.8 mmol) is added dropwise to a slurry of magnesium (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 and then at ambient temperature for 5 h and 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.degree. %).
  • a solution of sulfur dioxide is prepared by bubbling sulfur dioxide (0.2 g, 3.1 mmol) in a solution of anhydrous acetonitrile (5 mL) at room temperature. This solution is added to PhSCF 2 CF 2 SiMe 3 (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 monitored by TLC and 19 F NMR (CDCl 3 ) until disappearance of PhSCF 2 CF 2 SiMe 3 . The mixture is filtered and the solid residue washed with acetonitrile.
  • a sulfur dioxide solution 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 to PhSCF 2 CF 2 SiMe 3 (8 mmol) and stirred at ambient 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 monitored by TLC and 19 F NMR (CDCl 3 ) until disappearance of PhSCF 2 CF 2 SiMe 3 . F-TEDA (2.9 g, 8.2 mmol) is added to the mixture which is stirred for 1 h at room temperature.
  • CAr 1, CAr 2 and CAr 3 are determined by 2D NMR.
  • a sulfur dioxide solution is prepared by bubbling sulfur dioxide (0.5 g, 7.8 mmol) in a solution of anhydrous acetonitrile (10 mL) at room temperature. This solution is added to (C 5 H 4 N) SCF 2 CF 2 SiMe 3 (0.43 g, 1.5 mmol) and stirred at ambient 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 monitored by TLC and 19 F NMR (CDCl 3 ) until disappearance of C 5 H 4 NSCF 2 CF 2 SiMe 3 .
  • Sulfur dioxide solution is prepared by blowing sulfur dioxide (200 mg, 3.1 mmol) into a solution of sulfur dioxide. anhydrous acetonitrile (5 mL) at room temperature. This solution is added to BrC 6 H 4 SCF 2 CF 2 SiMe 3 (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 monitored by TLC and 19 F NMR (CDCl 3 ) until disappearance of BrC 6 H 4 SCF 2 CF 2 SiMe 3 . F-TEDA (355 mg, 1 mmol) is added to the mixture, which is stirred for 2 hours at room temperature.
  • Sulfur dioxide solution was prepared by bombarding sulfur dioxide (350 mg, 5.4 mmol) in a solution of anhydrous acetonitrile (5 mL) at room temperature. This solution is added to Me 3 SiC 6 H 4 SCF 2 CF 2 SiMe 3 (190 mg, 0.5 mmol) and stirred at room temperature under an atmosphere. inert. Anhydrous CsF (90 mg, 0.5 mmol) is then added to the reaction mixture which is stirred at room temperature overnight. The reaction is monitored by TLC and 19 F NMR (CDCl 3 ) until disappearance of Me 3 SiC 6 H 4 SCF 2 CF 2 SiMe 3 .
  • FC 6 H 4 SCF 2 CF 2 Br (615 mg, 2 mmol) is added dropwise to a suspension of turnings of magnesium (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 extracted with dichloromethane. The organic phases are washed with water and dried over MgSO 4 .
  • Sulfur dioxide solution 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 FCeH 4 SCF 2 CF 2 SiMe 3 (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 monitored by TLC and 19 F NMR (CDCl 3 ) until disappearance of FC 6 H 4 SCF 2 CF 2 SiMe 3 . F-TEDA (360 mg, 1 mmol) is added to the mixture, which is stirred for 2 hours at room temperature.
  • FCoH 4 SCF 2 Br (1.29 g, 5 mmol) is added dropwise to a suspension of magnesium turnings (245 mg, 10 mmol), trimethylsilyl chloride (2.5 mL, 20 mmol). ) and anhydrous THF (20 mL) cooled to -78 ° C. The mixture is then stirred for 4 h while slowly returning to ambient temperature. Water is added to the reaction mixture and the product is extracted with dichloromethane. The organic phases are washed with water and dried over MgSO 4 . After evaporation of the solvents, [difluoro- (4-fluorophenylsulfanyl) -methyl] trimethylsilane is obtained in the form of a yellow liquid (1.19 g, 95%).
  • a sulfur dioxide solution is prepared by bubbling sulfur dioxide (0.5 g, 7.8 mmol) in a solution of anhydrous acetonitrile (10 mL) at room temperature. This solution is added to FCgH 4 SCF 2 SiMe 3 (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 monitored by TLC and 19 F NMR (CDCl 3 ) until disappearance of FC 6 H 4 SCF 2 SiMe 3 .
  • F-TEDA (890 mg, 2.5 mmol) is added to the mixture at -20 ° C., which is then stirred for 2 hours at room temperature. The mixture is concentrated and the solid residue washed with ethyl ether. The filtrate is evaporated and the product purified by distillation in a baking oven. The difluoro- (4-fluorophenylsulfanyl) -methanesulfonyl fluoride is obtained as a colorless liquid (205 mg, 32%).
  • Example 4 The procedure of Example 4 was repeated, replacing PhSCF 2 Br with 5.4 mmol of P-MeOC 6 H 4 SCF 2 CF 2 Br.
  • Example 5 The procedure of Example 5 was repeated, replacing PhSCF 2 SiMe 3 with 4.87 mmol of P-MeOC 6 H 4 SCF 2 CF 2 SiMe 3 .
  • 1 H NMR 200 MHz, CDCl 3
  • 6.92-6.96 m, 2H)
  • HOC 6 H 4 SCF 2 CF 2 SO 2 F (910 mg, 2.96 mmol) is dissolved in anhydrous dichloromethane (5 mL).
  • Acryloyl chloride (242 ⁇ l, 2.96 mmol) and then diisopropylethylamine (514 ⁇ l, 2.96 mmol) are added to the reaction mixture at 0 ° C.
  • the medium is left stirring at 0 ° C. for 15 min, then the temperature is raised to ambient temperature.
  • the solution is stirred at ambient temperature for 1.5 h.
  • the mixture is concentrated and purified by chromatography on silica with diethyl ether.
  • Example 14 The procedure of Example 14 was repeated, replacing PhSO 2 CF 2 CF 2 SO 2 F with 3.2 mmol of 2- (4-) fluorine. fluorophenylsulfanyl) -1,2,2,2-tetrafluoroethanesulfonyl prepared according to Example 25.
  • NMR 19 P ⁇ 46.44 (m, 1 F, SO 2 F), -96.57 (m, 1 F, F Ar ), -106.32 (m, 2 F), -110.57 (m, 2 F) .
  • 1 H NMR ⁇ 7.39 (m, 2H), 8.10 (m, 2H).
  • the mixture is concentrated and purified by chromatography on silica with diethyl ether.
  • the trimethyl- [1,1,2,2-tetrafluoro-2- (4-vinylphenylsulfanyl) ethyl] silane is obtained in the form of a light yellow liquid, in a mixture with the
  • the overall yield is 70%, and the molar ratio ArCF 2 CF 2 SiMe 3 / ArCF 2 CF 2 H is 1/1.
  • Example 6 The procedure of Example 6 was repeated, replacing PhSCF 2 SiMe 3 with 4.3 mmol of p-vinyl-CeH 4 SCF 2 CF 2 SiMe 3 prepared according to the method of Example 38.
  • Example 13 The procedure of Example 13 was followed, replacing PhSCF 2 SO 2 F with 5 mmol PhSCF 2 CF 2 Br, and the following compound was obtained by oxidation with meta acid. -chloroperbenzoic acid, followed by extraction with dichloromethane and washing with an aqueous solution of Na 2 SOa (10%) and
  • Example 14 The process described in Example 14 was carried out, replacing PhSCF 2 CF 2 SO 2 F with 1.5 mmol of PhSCF 2 CF 2 SiMe 3 .
  • PhSCF 2 CF 2 SO 2 F By oxidation with metachloroperbenzoic acid, then extraction with dichloromethane and washing with an aqueous solution of Na 2 SO 3 (10%), then NaHCO 3 (6%), the following compound was obtained, which is another precursor of
  • NMR 19 ⁇ ⁇ -109.18 (m, 2F, SO 2 CF 2 ), -126.03 (m, 2F, CF 2 Si).

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