FR2818980A1 - Novel compositions and compounds comprising metal salts with sulfonyl attached to perhalogenated carbon forming Lewis acids, useful as catalysts for reaction of electrophilic cations - Google Patents

Abstract

The use of salts of elements of valency mu (with mu = 3 or more) as catalysts , the co-anions comprising at least one and no more than ( mu -1) anions with a sulfonyl function attached to a perhalogenated atom, preferably perfluorinated and more preferably a perfluoromethylene group. Independent claims are also included for the catalytic compositions and compounds and their preparation, and reactants including the catalyst and an agent providing a carbocation.

Description

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 The present invention relates to new derivatives of bismuth amides, their application as Lewis acid, in particular for acylation reactions of aromatic compounds, and a corresponding preparation process.

 The acylation reactions of aromatic compounds, known as the Friedel and Crafts type, represent an important industrial issue. To date, ASC'3 remains the most widely used promoter in the industry for this type of reaction.

However, the need to use it in at least stoichiometric amounts has the major drawback of causing significant production of waste (aluminum hydroxides and hydrochloric acid). Consequently, industrial interest remains for new, more efficient catalysts.

 The present invention aims more particularly to propose the catalytic use of new bismuth (III) salts.

 BiCI3, a weak Lewis acid, is already available today for the acylation of activated aromatics. Its derivative, bismuth tris-triflate (Bi (OTf) 3), for its part, has an improved catalytic activity compared to that of BiCI3 and rare earth triflates. Indeed, it is capable of carrying out the aroylation of aromatic compounds which are not activated or deactivated.

 The present invention is based more precisely on the demonstration that it is advantageous to combine in a bismuth salt, a ligand of the Tf2N- type. These bismuth salts indeed show catalytic activities superior to their trifiate type counterparts. This is how they prove to be effective for carrying out the benzoylation and sulfonylation reactions of Friedel and Crafts. These two reactions are in fact known to be particularly difficult to carry out with conventional catalysts. In addition, on the industrial implementation plan, the amide derivatives of bismuth have the clear advantage of manifesting a higher inertia than the catalysts mentioned above, in particular derived from aluminum, vis-à-vis common solvents, in particular vis opposite ethers.

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 Consequently, the first object of the present invention is a promoter of the bismuth bis-amide type.

 It aims in its second object to propose the use of this type of promoter as a Lewis acid catalyst and in particular for carrying out benzoylation and sulfonylation reactions of the Friedel and Crafts type.

 Finally, it provides a useful process for preparing the promoters according to the present invention.

dans laquelle : - R2 représente un atome de fluor ou avantageusement un radical carboné organique, le cas échéant substitué par un ou plusieurs atomes d'halogène et dont le carbone porteur de la fonction sulfonique est perhalogéné, de préférence perfluoré, avec R, et R2 pouvant être liés entre eux, - n est égal à 1 ou 2 avec n étant de préférence égal à 2 lorsque R1 représente un atome de fluor, - Ri est un radical carboné organique contenant avantageusement au plus 30 atomes de carbone [lorsqu'il n'est pas polymérique (c'est-à-dire ne constitue pas un lien de rattachement à un polymère)] ou un groupement tel que défini pour R2, et # au moins un cation de formule (II) : (R3) xBi (3-x)# (II) More specifically, the present invention firstly relates to a promoter, characterized in that it comprises:. at least one anion of formula (1):

in which: - R2 represents a fluorine atom or advantageously an organic carbon radical, optionally substituted by one or more halogen atoms and whose carbon carrying the sulfonic function is perhalogenated, preferably perfluorinated, with R, and R2 can be linked together, - n is equal to 1 or 2 with n preferably being equal to 2 when R1 represents a fluorine atom, - Ri is an organic carbon radical advantageously containing at most 30 carbon atoms [when n is not polymeric (that is to say does not constitute a bond of attachment to a polymer)] or a group as defined for R2, and # at least one cation of formula (II): (R3) xBi ( 3-x) # (II)

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C4 comme méthoxy, éthoxy, propoxy, phénoxy ou de type thioéther en Ci à C4 ; un groupement carboxylate comme l'acétate ou le sulfonate ; ou un atome d'halogène, de préférence le chlore, le brome et l'iode ; avec de préférence, lorsque x est égal à 2, les deux groupements R3 étant identiques. with: - x representing the integer 1 or 2, and - the identical or different R3 groups representing: + a phenyl group, optionally substituted by one or more electron donor substituents of C, to C4 alkyl type, linear or branched as for example methyl, ethyl, propyl, of C1 to alkoxy type

C4 as methoxy, ethoxy, propoxy, phenoxy or of C1 to C4 thioether type; a carboxylate group such as acetate or sulfonate; or a halogen atom, preferably chlorine, bromine and iodine; preferably with, when x is equal to 2, the two groups R3 being identical.

ou

avec, dans le cas de la formule (lb), R1 et R2 devant représenter une chaîne hydrocarbonée en accord avec les définitions proposées ci-dessus pour R, et R2. According to a preferred variant of the invention, the anion of formula (1) corresponds to formula (la) or (Ib):

or

with, in the case of formula (lb), R1 and R2 having to represent a hydrocarbon chain in accordance with the definitions proposed above for R, and R2.

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préférence à 2, avec la condition qu'au moins un des X soit un atome de fluor, - p représente un entier au plus égal à 2, - GEA représente un groupement électroattracteur, c'est-à-dire dont le sigma p est supérieur à 0, avantageusement à 0,1 et de préférence à 0,2, et dont les éventuelles fonctions sont inertes dans des conditions de mise en oeuvre du promoteur, avantageusement un atome de fluor ou un reste perfluoré de formule Cn"F2n"+1 (Rf) avec n"étant un entier au plus égal à 8, avantageusement à 5, le nombre total de carbone de Rf étant avantageusement compris entre 1 et 15, de préférence entre 1 et 10. According to a preferred embodiment of the invention, the anion corresponds to the general formula (Ia) and R2 is a fluorine atom or corresponds to the formula GEA- (CX2) p- where: - the similar or different X represent an atom of fluorine or a radical of formula Cn, F2n '+ 1 with not being an integer at most equal to 5, of

preferably 2, with the condition that at least one of the X is a fluorine atom, - p represents an integer at most equal to 2, - GEA represents an electron-withdrawing group, that is to say of which the sigma p is greater than 0, advantageously 0.1 and preferably 0.2, and the possible functions of which are inert under conditions of implementation of the promoter, advantageously a fluorine atom or a perfluorinated residue of formula Cn "F2n" + 1 (Rf) with n "being an integer at most equal to 8, advantageously 5, the total number of carbon of Rf advantageously being between 1 and 15, preferably between 1 and 10.

 According to a preferred embodiment of the invention, the cation of formula (tut) is represented by the formula (R'3) Bi (3-X) + with R'3 representing a phenyl group or a tolyl group.

avec n représentant 1 ou 2 et de préférence 2. As regards the anion of formula (1), it preferably corresponds to the formula:

with n representing 1 or 2 and preferably 2.

 It is understood that the compounds of general formulas (1) and (II) are present in said promoter in stoichiometric quantities sufficient to ensure the electrical neutrality of the promoter.

 Thus, in the case where x of the formula (II) represents an integer equal to 1, a molecule of the corresponding compound of formula (II) is associated with two molecules of the compound of formula (I).

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On the other hand, in the case where x has the value 2, a molecule of the compound of formula (in), namely (R3) 2Bi + is associated with a molecule of the compound of formula (1).

 According to a preferred embodiment of the invention, x has the value 1.

c'est-à-dire de formules (1) et (11), zelle peut être de nature ionique ou non. Regarding the association between the two types of molecules,

that is to say of formulas (1) and (11), zelle can be of ionic nature or not.

Thus the promoter can contain said compounds of general formulas (1) and (II) in the form of a metal salt in the ionic state, of type:

le tétrahydrate est un dimère [Bi (OTf) 3, 4 H2O]2 dans lequel chaque atome de bismuth est relié à 4 molécules d'eau et à trois groupements triftates, l'un d'entre eux assurant un pont avec l'autre atome de bismuth. Although it is not intended in the sense of the invention to be limited to a particular chemical structure for the promoter, it is likely that, like the other bismuth (III) derivatives comprising electronegative atoms (CI, OTf), the structure of the claimed promoter is of polymeric structure, the amide groups ensuring the bridges between the bismuth atoms. In this hypothesis, each bismuth atom is linked to 3 nitrogen atoms and to several oxygen atoms by coordination S = O-7Bi. Indeed, in the case of bismuth (III) triflate which exists in several hydrated forms (Bi (OTf) 3, n H2O with n = 2,4, 9, it appears that

the tetrahydrate is a dimer [Bi (OTf) 3, 4 H2O] 2 in which each bismuth atom is linked to 4 water molecules and to three triftate groups, one of them ensuring a bridge with the other bismuth atom.

 The promoters as defined above prove to be particularly effective as Lewis acids. Presumably, the amide ligand induced by its highly electron-withdrawing character a significant increase in the Lewis acidity, at the level of the atom.

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bismuth auquel il est associé. Il s'ensuit donc une activité catalytique accrue dudit promoteur.

bismuth with which it is associated. It therefore follows an increased catalytic activity of said promoter.

 As a representative of the promoters claimed according to the invention, mention may more particularly be made of BiPh (NTf2) 2 and BiPh2 (NTf2).

 A second aspect of the invention relates to the use of a promoter as defined according to the invention as Lewis acid.

 The Lewis acidity of a reagent is the property defined quantitatively by measuring the equilibrium constant of formation of the Lewis adduct with a base taken for reference. Without binding to a specific mechanism, it seems that bismuth would use the three 6p electrons to form three bonds, thus giving its most stable degree of oxidation (+3), while the two 6s electrons would intervene in the highest degree of 'oxidation (+5). As for the other heavy elements, the presence of vacant 6d orbitals would then be responsible for the Lewis acidity of the bismuth (III) derivatives, that is to say their ability to complex Lewis bases as functions carbonyl or sulfonyl.

 The promoters claimed thus prove to be particularly effective in catalyzing reactions of the Diels-Alder reactions, carbonyl allylations, ene reactions and Prins reactions.

 More particularly, the present invention also relates to the use of a promoter comprising at least one anion of formula (1) as defined above and a cation of formula le (III): (R3) x, Bi (3- x ') (i3 with: - Rg being as defined above; and - x'representing 0 or an integer having the value 1 or 2 with in the case where x is equal to 2, the groups R3 can be identical or different ,

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 as a Lewis acid catalyst for acylation reactions such as benzoylation and sulfonylation reactions of the Friedel and Crafts type.

 As is apparent from the examples below, the catalysts corresponding to the definition according to the invention make it possible to effectively carry out this type of reaction known to be particularly difficult.

 Furthermore, it has been noted that the promoters comprising as a cation a derivative of formula (R3) Bi ++ have a reactivity almost equivalent to that manifested by a promoter comprising as a counter-cation of the compound of general formula (1) be Bi +++ cation. This equivalence in terms of reactivity is particularly advantageous in industrial terms, since the anions of general formula (1) are fairly expensive compounds.

The Bi promoters (NTf2) prove to be particularly advantageous for the claimed use. BiPh2 (NTf2) and BiPh (NTf2) 2 '
The promoters are generally directly introduced into the reactions to be catalyzed.

 Generally, these reactions are carried out in solvents such as aromatic hydrocarbons such as toluene and benzene and haloalkanes. Of course, these solvents must remain inert under the reaction conditions.

 Thus with Bi (NTf2) 3, satisfactory yields of o-, m- and p-methylbenzophenone are obtained by acylation of toluene.

 Of course, the promoter is used as a Lewis acid catalyst in an amount sufficient to start the expected reaction.

 By way of non-limiting example of the invention, it can be used at a rate of 0.5% to 100 mol% expressed relative to the substrate to be transformed.

 More preferably, it is present in an amount of 5 to 20% and more particularly in an amount of about 10%.

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The invention applies more particularly to the functionalization of optionally substituted aromatic compounds, and having at least one of the following cycles:. an aromatic, monocyclic or polycyclic carbocycle,. an aromatic, monocyclic or polycyclic heterocycle comprising at least one of the heteroatoms 0, N and S,
It will be specified, without however limiting the scope of the invention, that this optionally substituted aromatic compound may represent: 1 - an aromatic, monocyclic or polycyclic carbocyclic compound.

 By "polycyclic carbocyclic compound" is meant:. a compound consisting of at least 2 aromatic carbocycles and forming between them ortho-or ortho-and pericondensed systems,. a compound consisting of at least 2 carbocycles of which only one of them is aromatic and forming between them ortho-or ortho-and pericondensed systems.

 20-tun aromatic, monocyclic or polycyclic heterocyclic compound.

 By "polycyclic heterocyclic compound", we define:. a compound consisting of at least 2 heterocycles containing at least one heteroatom in each cycle of which at least one of the two cycles is aromatic and forming between them ortho-or ortho-and pericondensed systems,. a compound consisting of at least one hydrocarbon ring and at least one heterocycle of which at least one of the rings is aromatic and forming between them ortho-or ortho-and pericondensed systems.

 3-of a compound constituted by a chain of cycles, as defined in paragraphs 1 and / or 2 linked together:. by a valential link,. by an alkylene or alkylidene radical having from 1 to 4 carbon atoms, preferably a methylene or isopropylidene radical,

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. par l'un des groupes suivants : - O-,-CO-,-COO-,-OCOO- -S-, -SO-, -SO2-,

dans ces formules, Rr. représente un atome d'hydrogène ou un radical alkyle ayant de 1 à 4 atomes de carbone, un radical cyclohexyl ou phényle.

. by one of the following groups: - O -, - CO -, - COO -, - OCOO- -S-, -SO-, -SO2-,

in these formulas, Rr. represents a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, a cyclohexyl or phenyl radical.

As examples of cycles under 1 to 3, we can cite:
1 - benzene, toluene, xylene, naphthalene, anthracene,
2 - furan, pyrrole, thiofen, isoxazole, furazanne, isothiazole, imidazole, pyrazol, pyridine, pyridazine, pyrimidine, quinoline, naphthyridine, benzofuran, indole,
3 - biphenyl, 1, 1'-methylenebiphenyl, 1, isopropylidenebiphenyl, 1, 1'-oxybiphenyl, 1, 1'-iminobiphenyl.

 In the process of the invention, a benzene compound is preferably used.

 The aromatic compound can carry one or more substituents. Mention may in particular be made, as representative of these substituents. an OH group,. a linear or branched alkyl radical having from 1 to 6 carbon atoms,. a linear or branched alkenyl radical having from 2 to 6 carbon atoms,. a linear or branched alkoxy radical having from 1 to 6 carbon atoms,. a group-CHO,. an acyl group having from 2 to 6 carbon atoms,

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. un groupe-COOR2 où R2 a la signification donnée précédemment, . un groupe-NO, . un groupe-NH2' . un atome d'halogène, de préférence, de fluor, de chlore, de brome, et . un groupe-CF.

. a group-COOR2 where R2 has the meaning given above,. a group-NO,. an NH2 'group. a halogen atom, preferably fluorine, chlorine, bromine, and. a group-CF.

By way of illustration of these aromatic compounds, it is possible to mention more particularly: fluorotoluenes, bromobenzene, dibromobenzenes, bromofluorobenzenes, bromochlorobenzenes, trifluoromethylbenzene, trifluoromethoxybenzene, trichloromethylbenzene, trichloromethoxybenzene, trifluoromethylthienebenzenes, such as phenol, o-cresol, guaiacol, monoethers such as anisole, ethoxybenzene (phenetole), butoxybenzene, isobutoxybenzene, 2-chloroanisole, 3-chloroanisole, 2- bromoanisole, 3-bromoanisole, 2-methylanisole, 3-methylanisole, 2-ethyl anisole, 3-ethylanisole, 2-isopropylanisole, 3-isopropylanisole, 2-propylanisole, 3-propylanisole, 2-allylanisole, 2-butylanisole, 3butylanisole, 2-tert-butylanisole, 3- tert-butylanisole, 2-benzylanisole, 2-cyclohexylanisole, 1-bromo-2-ethoxybenzene, 1-bromo-3-ethoxybenzene, 1-chloro-2-ethoxybenzene, 1-chloro-3-ethoxybenzene, 1-ethoxy-2-ethylbenzene, 1-ethoxy-3-ethylbenzene, 2, 3dimethylanisole, 2, 5-dimethylanisole,

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 - diethers such as veratrole, 1, 3-dimethoxybenzene, 1, 2diethoxybenzene, 1, 3-diethoxybenzene, 1, 2-dipropoxybenzene, 1, 3-dipropoxybenzene, 1, 2-methylenedioxybenzene, 1, 2-ethylenedioxybenzene, - triethers such as 1,2, 3-trimethoxybenzene, 1,3, 5trimethoxybenzene, 1,3, 5-triethoxybenzene.

 A third aspect of the invention relates to a process for preparing a promoter according to the invention.

caractérisé en ce que : e l'on fait réagir au moins un composé de formule (IV) : (R3) 3Bi (IV) avec R3 représentant - un groupement phényle, le cas échéant substitué par un ou plusieurs substituants électrodonneurs de type alkyle en C1 à C4, linéaire ou ramifié comme par exemple méthyle, éthyle, propyle, de type alkoxy en C1 à

C4 comme méthoxy, éthoxy, propoxy, phénoxy ou de type thioéther en Ca à C4. More specifically, it relates to a process for the preparation of a promoter comprising at least one anion of formula (I) as defined above and a cation of formula e (III): (R3) XIBi (3-x ') ( i with: - R3 being as defined above; and - x'representing 0 or an integer having the value 1 or 2 with in the case where x is equal to 2, the groups R3 can be identical or different,

characterized in that: e reacting at least one compound of formula (IV): (R3) 3Bi (IV) with R3 representing - a phenyl group, optionally substituted by one or more alkyl type electron substituents in C1 to C4, linear or branched such as for example methyl, ethyl, propyl, of C1 to alkoxy type

C4 as methoxy, ethoxy, propoxy, phenoxy or thioether type in Ca to C4.

- a carboxylate group such as acetate or sulfonate; or - a halogen atom, preferably chlorine, bromine and iodine;

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avec Rl, R2 et n étant tels que définis précédemment et en ce que l'on récupère ledit promoteur. with the groups R3 possibly being identical or different and preferably being identical, with at least one compound of formula (V):

with R1, R2 and n being as defined above and in that said promoter is recovered.

 Of course, the stoichiometry between the two components is adjusted according to the degree of deprotometallation sought.

 If it is desired to carry out a mono-deprotometallation of the compound of general formula (IV), the compound of general formula (V) is used in an amount of at most one equivalent.

 On the other hand, if it is desired to carry out at least two deprotometallation reactions at the level of the compound of general formula (IV), an excess of compound of general formula (V) is used.

 Furthermore, in the particular case where it is desired to carry out successively three deprotometallation reactions at the level of the compound of general formula (IV), it is advantageous to choose the groups R3 so as to increase the electron density at the level of the bismuth atom.

 Indeed, the fact that two groups of general formula (1) are already fixed on the bismuth atom strongly deactivates the last group R3 present on this same atom. Consequently, the presence of an electron-rich ligand linked to the bismuth atom overcomes this effect induced by the two groups of general formula (1) and helps to carry out the last deprotometallation reaction. In this particular case, the R3 groups present on the bismuth atom are therefore preferably chosen so as to confer on it a charge at least

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 equivalent to that conferred by three tolyl groups. More preferably, the three substituents R3 are identical and represent a tolyl group.

ajoute progressivement le sel de bismuth au composé de formule générale (V) préalablement solubilisé dans le solvant refroidi. The syntheses of the promoters are generally carried out in a haloalkane type solvent such as dichloromethane, dichloroethane, or a solvent of acetonitrile or toluene type and under an inert atmosphere. We

gradually add the bismuth salt to the compound of general formula (V) previously dissolved in the cooled solvent.

 The expected promoter is then isolated.

 The examples appearing below are presented by way of illustration and without limitation of the subject of the present invention.

5% phénylpolysiloxane). L'évolution des réactions est suivie à l'aide de tétradécane comme étalon interne. MATERIAL AND METHOD
The GC analyzes were performed on a Hewlett-Packard GC 6890 chromatograph (BPX capillary column 5.25 mx 0.22 mm, film

5% phenylpolysiloxane). The progress of the reactions is monitored using tetradecane as an internal standard.

 The CPG-MS is a Hewlett-Packard set made up of the 5890 &commat; and mass spectrometer 59890.

 The measurements are carried out on Brucker AC 80, 300 and 400 MHz spectrometers. The chemical shifts are expressed in unit 8 (ppm) relative to the TMS for 1 H and 13 C NMR and relative to the trifluoroacetic acid for 19 F NMR. The coupling constants are expressed in Hz. The solvent used is acetone-d6.

 IR spectrometry was carried out on a Perkin Elmer model 1760-X spectrometer (5000-400 cm-1) using an AgCI slide cell.

 The solvents used (toluene, dichloromethane) are dried according to the usual methods. Benzoyl, toluoyl, benzenesulfonyl chlorides and benzoic anhydride are commercial products.

The bis (trifluoromethanesulfonyl) amide (Tf2NH) was supplied by the company

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 FINE ORGANIC RHODIA. It is stored and handled in a glove box. The bis (trifluoromethanesulfonyl) silver amide (AgNTf2) was prepared according to the method described in the literature [Vij A, Zheng YY, Kirchmeier RL, Shreeve J, Inorg Chem (1994) 33, 3281] as well as the tris-p -tolylbismuth [Gilman H, Yale HL, J Chem Soc (1941) 281].

BiPh, (NTfJ
Dans un Schlenck de 100 ml purgé à l'argon, on introduit Tf2NH (0,281 g ; 1 mmol) dans 10 ml de CH2Cl2 distillé. Le Schlenck est refroidi à 0 C. On rajoute à la seringue une solution de BiPh3 (0,44 g ; 1 mmol) dans 10 ml de CH2Cl2. Le mélange prend une couleur jaune orangée et un composé insoluble dans le dichlorométhane apparaît. On ramène le Schienck à température et l'agitation est maintenue pendant trois heures. La totalité du dichlorométhane est évaporée et le résidu est séché sous vide. On obtient une poudre blanche de BiPh2 (NTf2) (0,60 g ; 0,94 mmol ; Rdt 94%). EXAMPLE 1:

BiPh, (NTfJ
In a 100 ml Schlenck purged with argon, Tf2NH (0.281 g; 1 mmol) is introduced into 10 ml of distilled CH2Cl2. The Schlenck is cooled to 0 C. A solution of BiPh3 (0.44 g; 1 mmol) in 10 ml of CH2Cl2 is added to the syringe. The mixture takes on an orange-yellow color and a compound insoluble in dichloromethane appears. The Schienck is brought back to temperature and the stirring is maintained for three hours. All of the dichloromethane is evaporated and the residue is dried under vacuum. A white BiPh2 powder (NTf2) is obtained (0.60 g; 0.94 mmol; Yield 94%).

RMN'H (400, 13 MHz) : : 7, 50 (para ; 1H ; Hx ; tt ; J (H,Hm) = 7, 5 Hz ; J (H. HJ = 1, 2Hz) ; 7, 89 (méta ; 2H ; Hm ; dd ; J (HHJ=7, 5Hz ; J (HJ-L) =7, 8 Hz) ; 8, 52 (ortho ; 2H ; Ha ; dd ; J (HaHm) =7, 8 Hz ; J (HaHx) = 1, 2 Hz). Spectroscopic characteristics of BiPhNTf2):

1 H-NMR (400, 13 MHz):: 7.50 (para; 1H; Hx; tt; J (H, Hm) = 7.5 Hz; J (H. HJ = 1.2Hz); 7.89 ( meta; 2H; Hm; dd; J (HHJ = 7.5Hz; J (HJ-L) = 7.8Hz); 8.52 (ortho; 2H; Ha; dd; J (HaHm) = 7.8Hz ; J (HaHx) = 1.2 Hz).

"F NMR (376, 48 MHz): singlet at = = -1.79 ppm.

13 C NMR (100.62 MHz): #: 121.0 (q; J = 321 Hz; CF3); 131.3 (s; CH); 133.7 (s; CH); 186.6 (s; CH); Cq ipso of the aromatic cycle not visualized by NMR.

EXAMPLE 2: BiPh (NTf
It is the same process as that described for BiPh2 (NTf2) from 2 mmol of Tf2NH and 1 mmol of BiPh3. We get a white powder of

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BiPh (NTf2) (0, 76 g, 0, 9 mmol, 90%).

BiPh (NTf2) (0.76 g, 0.9 mmol, 90%).

Spectroscopic characteristics of BiPh (NTf: 1 H NMR (400, 13 MHz): ô: 7.60 (para; 1H; Hx; tt; J (H, Hm) = 7.5 Hz; J (H, HH) = 1.2 Hz); 8.32 (meta; 2H; Hm; dd; J (H) = 7.5 Hz; J (HmHa) = 8.3 Hz); 9.21 (ortho; 2H; Ha; dd ; J (H, HJ = 8.3 Hz; J (H, H) = 1.2 Hz).

19F NMR (75, 393 MHz): singlet at = = -2.1 ppm.

13C 13C NMR (75, 469 MHz):: 120.5 (q; J = 321 Hz; CF3); 130.7 (s; CH); 135, 1 (s, CH); 138.8 (s; CH); Cq ipso of the aromatic cycle not visualized by NMR.

Tf2NH (0, 85 g ; 3 mmol) dans 10 ml de CH2CI2. Le Schlenck est refroidi dans un bain de glace et on rajoute à la seringue une solution de Bi (Tolyl) 3 (0,48 g ; 1 mmol) dans 10 ml CH2CI2. Le mélange prend instantanément une couleur jaune orangée et un composé insoluble apparaît. Après une nuit d'agitation à température ambiante, les solvants sont évaporés sous vide. EXAMPLE 3: Bi (NTf,:
In a Schlenck of 100 ml, a solution of

Tf2NH (0.85 g; 3 mmol) in 10 ml of CH2Cl2. The Schlenck is cooled in an ice bath and a solution of Bi (Tolyl) 3 (0.48 g; 1 mmol) in 10 ml CH2Cl2 is added to the syringe. The mixture instantly takes on an orange-yellow color and an insoluble compound appears. After stirring overnight at room temperature, the solvents are evaporated in vacuo.

1.01 g of a pale yellow powder of Bi (NTf2) 3 is thus recovered, ie a yield of 96%. This product is stored and handled in a glove box.

Spectroscopic characteristics of Bs -INTf2) 3 1 H NMR (300.13 MHz): Absence of peaks.

 "F NMR (376.47 MHz): singlet at 8 = -1.77 ppm.

13C NMR (75.469 MHz): #: 120.4 (q; J = 321 Hz; CF3).

 IR (CCl4) # (cm-1): 1451 (very strong), 1305 (shoulder), 1231 (very strong), 1132 (very strong), 894 (shoulder), 855 (very strong), 650 (strong), 608 (very strong), 573 (shoulder), 502 (very strong).

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EXAMPLE 4 Catalytic benzoylation of toluene.

 All handling is done under argon. Toluene (4.6 g; 50 mol), tetradecane (0.496 g;) are successively introduced into a 50 ml two-necked flask fitted with a condenser and containing Bi (NTf2) 3 beforehand (0.525 g; 500 mol); 2.5 mmol) and 5 mmol of the acylating agent chosen (benzoic anhydride or benzoyl chloride). The reaction mixture with stirring is placed in an oil bath at 110oC. The progress of the reaction is monitored by CPG by withdrawing with a syringe a small part of the reaction mixture in order to determine the change in the yield of methylbenzophenone (ortho, meta and para). This analysis is completed by a comparison of the chromatogram and the mass spectra (CPG / MS) obtained on samples of pure o-, m-, p-methylbenzophenone [Aldrich; 15,753-8, 19,805-6, M2, 955-9].

 Percentage of ortho / meta / para isomers: 16/4/80 (from benzoyl chloride), 20/4/76 (from benzoic anhydride).

- CPG: Analysis condition: Initial temperature = 125 C
Final temperature = 300 C
Slope = 20 C / min
Retention time: ortho: 6.1 min; meta: 6.4 min; para: 6.6 min.

 - CPG / MS [m / z (%)]: o-methylbenzophenone: 196 (ist, 60), 195 (100), 119 (24), 105 (55), 91 (41), 77 (89). p-methylbenzophenone: 196 (tvr. 57), 181 (12), 119 (100), 105 (43), 91 (41), 77 (61).

Sulfonylation catalytique du toluène. EXAMPLE 5:

Catalytic sulfonylation of toluene.

 It is the same process as that described for benzoylation.

This analysis is also supplemented by a comparison of the chromatogram and mass spectra (CPG / MS) obtained on

<Desc / Clms Page number 17>

échantillons d'o-, m-, p-méthyidiphénylsufone purs.

samples of pure o-, m-, p-methyidiphenylsufone.

- CPG: Analysis condition: Initial temperature = 125 C
Final temperature = 300 C
Slope = 20 C / min
Retention time: ortho: 7.8 min; meta: 7.9 min; para: 8.1 min.

 Percentage of ortho / meta / para isomers: 34/6/60 (from benzenesulfonyl chloride).

p-méthyldiphénylsulfone : 232 (M+, 65), 139 (75), 125 (52), 107 (67), 91 (48), 77 (100).- CPG / MS [m / z (%)]: o-methyldiphenylsulfone: 232 (M +, 25), 214 (45), 166 (72), 137 (33), 91 (35), 77 (100).

p-methyldiphenylsulfone: 232 (M +, 65), 139 (75), 125 (52), 107 (67), 91 (48), 77 (100).

Claims (20)

 in which: - R2 represents a fluorine atom or an organic carbon radical, optionally substituted by one or more halogen atoms and whose carbon carrying the sulfonic function is perhalogenated, with R1 and R2 being able to be linked together, - n is equal to 1 or 2, - Ri is an organic carbon radical or a group as defined for R2, and. at least one cation of formula (II): (R3) XBi (3-x) # (II) with: - x representing the integer 1 or 2, and - the identical or different R3 groups representing: * a phenyl group, optionally substituted with one or more electron or substituent substituents of C1 to C4 alkyl type, linear or branched, of C1 to C4 alkoxy type or of C1 to C4 thioether type; # a carboxylate group; or # a halogen atom;

 CLAIMS 1. Promoter, characterized in that it includes:. at least one anion of formula (1): 2. A promoter according to claim 1, characterized in that the anion of formula (1) corresponds to the formula (la) or (alb): <Desc / Clms Page number 19>

 or

 in which R1, R2and n are as defined in claim 1.

 3. A promoter according to claim 1 or 2, characterized in that the anion corresponds to the general formula (la) with R2 representing a fluorine atom or corresponding to the formula GEA- (CXJp- in which: - the similar X or different represent a fluorine atom or a radical of formula Cn '+ 1 with not being an integer at most equal to 5, with the condition that at least one of the X is a fluorine atom, - p represents an integer at most equal to 2, - GEA represents an electron-withdrawing group whose sigma p is greater than 0, preferably chosen from a fluorine atom or a residue

 perfluorinated of formula e CFi (Rf) with n "being an integer at most equal to 8, the total number of carbon of Rf being between 1 and 15.  4. Promoter according to one of the preceding claims, characterized in that the anion corresponds to the formula:

 with n representing 1 or 2. <Desc / Clms Page number 20>

5. Promoter according to one of the preceding claims, characterized in that the cation is represented by the formula (R'gBP 'with R'3 representing a phenyl group or a tolyl group.  6. Promoter according to one of the preceding claims, characterized in that it associates a molecule of a compound of formula (II) in which x is equal to 1, with two molecules of the compound of formula (1).  7. Promoter according to one of claims 1 to 5, characterized in that it associates a molecule of the compound of formula (II) in which x has the value 2, with a molecule of the compound of formula (1).  8. Promoter according to one of the preceding claims, characterized in that it is in the form of a metal salt in the ionic state of formula:

 with R3, x, n, R1 and R2 being as defined in claims 1 to 5.  9. Promoter according to one of the preceding claims, characterized in that it is chosen from BiPh (NTf2) 2 and BiPh2 (NTf2).  10. Use of a promoter as defined in claims 1 to 9 as Lewis acid.  11. Use of a promoter comprising at least one anion of formula (1) <Desc / Clms Page number 21>  with: - Rg being as defined in claim 1; and - x'representing 0 or an integer having the value 1 or 2 with, in the case where x is equal to 2, the groups R3 may be identical or different, as catalyst of Lewis acid type for reactions of Friedel and Crafts type acylation and sulfonylation.

 (R3) x Bi (3- (111)

 and a cation of formula (III):

 in which: R2 represents a fluorine atom or an organic carbon radical, optionally substituted by one or more halogen atoms and the carbon carrying the sulfonic function of which is perhalogenated, with R1 and R2 possibly being linked together, - n is equal to 1 or 2, - Ri is an organic carbon radical advantageously containing at most 30 carbon atoms or a group as defined for R2,

 12. Use according to claim 11, characterized in that the anion of formula (1) is as defined in claims 2 to 4.

13. Use according to claim 11 or 12, characterized in that the promoter is chosen from BiPh2 (NTf2), BiPh (NTf2) 2 and Bi (NTf2) 3 ' <Desc / Clms Page number 22> 14. Use according to one of claims 11 to 13, characterized in that the promoter is used at a rate of 0.5% to 100 mol% expressed relative to the substrate to be transformed.  15. Process for the preparation of a promoter comprising at least one anion of formula (1):

 in which: - R2 represents a fluorine atom or an organic carbon radical, optionally substituted by one or more halogen atoms and whose carbon carrying the sulfonic function is perhalogenated, with R, and R2 being able to be linked together , - n is equal to 1 or 2, - R1 is an organic carbon radical advantageously containing

 at most 30 carbon atoms or a group as defined for R2, and a cation of formula (III):

 (R3) x-Bi (3 (! (1 1)

 with: - the same or different groups R3 representing: * a phenyl group, optionally substituted by one or more electron-donor substituents of the linear or branched Ca-C4 alkyl type, of the C1 to C4 alkoxy type or of the C1 thioether type to C4; * a carboxylate group; or * a halogen atom; <Desc / Clms Page number 23>  with R ,, R2 and n being as defined above and in that said promoter is recovered.

 - x'representing 0 or an integer having the value 1 or 2 with in the case where x is equal to 2, the groups R3 can be identical or different, characterized in that: 'at least one compound is reacted of formula (IV): (R3) 3Bi (IV) with R3 as defined above, with at least one compound of formula (V):  16. The method of claim 15, characterized in that one uses at most one equivalent of compound of general formula (V) for a compound of general formula (IV).  17. The method of claim 15, characterized in that an excess of compound of general formula (V) is used relative to the compound of general formula (IV).  18. Method according to one of claims 15 to 17, characterized in that the compound of general formula (IV) has as substituent R3 radicals making it possible to obtain at the level of the bismuth atom an electronic charge at least equivalent to that conferred by three tolyl groups. <Desc / Clms Page number 24>  19. Method according to one of claims 15 to 18, characterized in that the reaction is carried out under an inert atmosphere.  20 Method according to one of claims 15 to 19, characterized in that the compound of formula (IV) is gradually added to the compound of formula (V).