EP1301275A1 - Zusammenstellung und verbindung auf grund von metallsalzen und säure mit einem sulonyl-substituierten perhalogenierten kohlenstoff und ihre verwendung als lewissäure - Google Patents

Zusammenstellung und verbindung auf grund von metallsalzen und säure mit einem sulonyl-substituierten perhalogenierten kohlenstoff und ihre verwendung als lewissäure

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Publication number
EP1301275A1
EP1301275A1 EP01954096A EP01954096A EP1301275A1 EP 1301275 A1 EP1301275 A1 EP 1301275A1 EP 01954096 A EP01954096 A EP 01954096A EP 01954096 A EP01954096 A EP 01954096A EP 1301275 A1 EP1301275 A1 EP 1301275A1
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EP
European Patent Office
Prior art keywords
formula
perhalogenated
function
anions
advantageously
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP01954096A
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English (en)
French (fr)
Inventor
Nicolas Roques
Jacques Dubac
Christophe Le Roux
Sigrid Repichet
Jean-Marie Bernard
Jean-Pierre Maestro
Thierry Vidal
Magali Peyronneau
Alexandre Picot
Stéphane MAZIERES
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
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Rhodia Chimie SAS
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Publication date
Priority claimed from FR0009213A external-priority patent/FR2811592B1/fr
Priority claimed from FR0017310A external-priority patent/FR2818980B1/fr
Priority claimed from FR0109213A external-priority patent/FR2827195A1/fr
Application filed by Rhodia Chimie SAS filed Critical Rhodia Chimie SAS
Publication of EP1301275A1 publication Critical patent/EP1301275A1/de
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0222—Sulfur-containing compounds comprising sulfonyl groups
    • B01J31/0224—Sulfur-containing compounds comprising sulfonyl groups being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0215—Sulfur-containing compounds
    • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
    • B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0237—Amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0252—Nitrogen containing compounds with a metal-nitrogen link, e.g. metal amides, metal guanidides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/06—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing halogen atoms, or nitro or nitroso groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
    • C07C45/46—Friedel-Crafts reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B01J2231/341—1,2-additions, e.g. aldol or Knoevenagel condensations
    • B01J2231/342—Aldol type reactions, i.e. nucleophilic addition of C-H acidic compounds, their R3Si- or metal complex analogues, to aldehydes or ketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type

Definitions

  • the present invention relates to a new category of catalysts reacting like a Lewis acid.
  • catalysts based on Lewis acid which are used to carry out numerous reactions and, in particular, to carry out so-called Friedel and Crafts reactions or for alkylating aromatic rings. These catalysts generally favor the formation of cations and, in particular, of carbocations.
  • the most commonly used catalysts are trivalent atoms, generally of metallic nature, and which have an electronic gap capable of capturing leaving groups which then constitute anions or entities which it is usual to write in the form of anions.
  • one of the aims of the present invention is to provide a new family of catalysts which have properties similar to the salts of triflic acid without having the cost thereof.
  • trivalent cations require the presence of three triflate anions to ensure the electrical balance of the molecule, or of the salt. Mutatis mutandis the problem is the same for polyvalent cations, in particular tetra and pentavalents and for imides.
  • Another object of the present invention is to find a process allowing the use of these new catalysts.
  • Another object of the present invention is to provide a process for easily reaching the catalysts according to the present invention.
  • Another object of the present invention is to provide new compounds capable of acting as catalysts according to the present invention.
  • the halogens in particular chlorine and fluorine, are perhalogenated so that the chloro- and fluorine anions sulphonic are covered by the definition of sulphonate ions above.
  • these sulfonates can hydrolyze, so we usually prefer to use perhalogens on carbon.
  • the cations targeted by the present invention are essentially those of rare earths (scandium, yttrium, lanthanum and lanthanide) and the square metals of the periodic table of the elements formed by gallium, germanium, arsenic, indium, l , antimony, thallium, lead and bismuth.
  • the catalysts according to the present invention give good results even if they are hydrated and this up to hydration rates of up to 12 H 2 0 ( by element M).
  • the limit is more linked to the hydrolyzable nature (stricto sensu) of the substrates than to the water sensitivity of the compounds according to the present invention.
  • the strength of the Lewis acid according to the invention generally decreases with hydration. It is thus preferable to limit hydration to 3 H 2 0, hydration ranging from! _> To 3 H 2 0 per atom of element M generally constitutes a good compromise for non-aqueous and / or anhydrous media.
  • the other anion or the other anions are organic or mineral anions, preferably monoanions.
  • these anions noted Y " , the sulfonates, the monoalkyl sulfates (when the latter are stable in the medium), the carboxylates, the halides, the halogenates (when the latter are not too oxidizing for the medium) , phosphates, phosphonates and phosphinates; pyrophosphates can be envisaged in environments where they are stable; carbonates and bicarbonates; O " functions as in oxides (O " ), even hydroxides, can give highly active compounds.
  • the aromatic carbanions are however to be avoided because the loss of activity is significant.
  • the charge is carried by a nitrogen, and in particular in the case of imides, the loss of activity is low.
  • the preferred compounds according to the present invention correspond to the formula: - where M represents an ⁇ -valent element and at least trivalent in cationic form, preferably known to give Lewis acids;
  • Y is an anion or a monovalent anionic function
  • ⁇ " represents an anion, or an anionic function, carrying a sulfonyl function carried by a perhalogenated atom, preferably perfluorinated, more preferably a perfluoromethylene group (-CF 2 -);
  • q is an integer advantageously chosen from the closed interval (including the limits) going from 1 to ( ⁇ -1) (that is to say 1 or 2 when ⁇ is 3).
  • the compounds according to the present invention can be used alone or as a mixture and, in particular, as a mixture with one another. They can be mixed with the starting product and with the compound of formula M ⁇ ⁇ which would correspond to complete electrical neutrality given by the single ⁇ " .
  • compositions used can have fractional values.
  • M ⁇ + is the at least trivalent cation and if we denote by
  • Y " anions other than ⁇ " the compounds according to the present invention correspond to the formula MY ⁇ . q ⁇ q , with q equal to 1; 2; ⁇ -2 and / or ⁇ -1.
  • q can become fractional and, in particular, be between 0.1 and ⁇ -0.1, (that is to say between 0.1 and 2.9 when M is trivalent), advantageously from 0.5 to ⁇ - 0.5 (0.5 to 2.5 when M is trivalent), preferably from 1 to ⁇ -1 (from 1 to 2 when M is trivalent), the limits being understood.
  • anions other than perhalogenated sulfonates are not chelating.
  • the pKa of the acid associated with these anions is at most equal to approximately 10, preferably to approximately 5, more preferably to approximately 2.
  • the acid associated with these anions is not more acidic than the hydrohalic acids. It is also preferable that these anions are not complex anions (that is to say resulting from the complexation of a cation with simple anions in sufficient quantity to obtain an anionic complex) too bulky (such as BF 4 " , PF 6 " , ... because these anions are both large and capable of dissociating).
  • the cations of these new catalysts are, as has been mentioned, cations of nature, advantageously trivalent and are preferably chosen from the periods of the Mendeleev periodic table at least equal to the third, preferably to the fourth. Mention may be made, as a cation of particular interest, of those already mentioned, namely gallium, germanium, arsenic, indium, tin, antimony, thallium, lead and bismuth, the most interesting are those which have a trivalent state and the preferred state is the trivalent state. Thus, according to the present invention, gallium III, indium III, antimony III, and even arsenic III are preferred, as well as bismuth and rare earths, including scandium and yttrium.
  • the anions carrying a sulfonyl function carried by a perhalogenated atom are the anions whose charge is carried by the atom directly linked to the sulfonyl function;
  • the sulfone group (SO2) of the sulfonyl is linked on one side to the perhalogenated atom and on the other to the atom carrying the anionic charge or hydrogen when the anion is in the form of its associated acid.
  • Z represents an atom of the nitrogen column or a chalcogen
  • R1 represents an electron-withdrawing radical, advantageously chosen from those of formula (II):
  • Rf and Rf independently represents a fluorine, a carbon radical whose carbon linked to sulfur is perfluorinated or a halogen atom heavier than fluorine; with the condition that, when Z represents a chalcogen, Ri, does not exist.
  • Z is advantageously nitrogen or oxygen.
  • R1 may be an aryl (such as benzene sulfonyl) or aliphatic sulfonyl group (such as a sulfonic alkane, for example mesylate).
  • aryl such as benzene sulfonyl
  • aliphatic sulfonyl group such as a sulfonic alkane, for example mesylate.
  • This invention is of essential economic interest because, on the one hand, it is extremely difficult to obtain these pure triflates, the exchange with the usual salts being very difficult to complete; indeed, it is quite common to use acetates to make the triflates by moving the acetic anion by the triflic anion, the first acetic is generally quite easy to move, the second is already more difficult, as for the third the techniques become extremely delicate, especially if you want to obtain an anhydrous salt. Examples of a difficulty in producing these salts are provided in the patent application filed in the name of the applicant published under the number EPA 0 877726.
  • triflic acid and the triflates which result from it are particularly expensive.
  • the fact of having shown that it was possible to have cases of catalytic properties with usual anions neutralizing the trivalent cation with the triflates is of very great interest.
  • GEA- (CX 2 ) P - - X similar or different, represent a fluorine or a radical of formula C n F 2n + ⁇ , with n integer at most equal to 5, preferably 2;
  • - p represents zero or an integer at most equal to 2, with the condition that when p represents zero, GEA is chlorine and especially fluorine;
  • - GEA represents a hydrocarbon group, that is to say bearing hydrogen and carbon, such as alkyl or aryl preferably having at most 15 carbon atoms or rather an electron-withdrawing group (that is to say say whose Hammett constant ⁇ p is greater than 0, advantageously 0.1, preferably 0.2) whose possible functions are inert under the conditions of the reaction, advantageously fluorine or a perfluorine residue of formula C n F 2n + ⁇ , with n integer at most equal to 8, advantageously 5.
  • p is, the more the salts are soluble in organic solvents which are not very miscible with water (solubility of said solvents less than or equal to 1% by mass) so it is preferable that p is at least equal to 1, and even to 2, when it is desired to work in environments which are hardly miscible with water.
  • the total number of carbons of R f is advantageously between 1 and 15, preferably between 1 and 10.
  • GEA can be or carry a sulfonyl function, including a sulfonic acid of the type described above or its anion. GEA can also form a link with a polymer network, although this is not preferred.
  • sulfonic acids having two sulfonic functions, both of which are carried by a perhalogeno group, preferably perfluoroethylene or perfluoromethylene.
  • the distance between two sulfonic functions is then advantageously less, by the shortest path, to 10, preferably to 5, more preferably to 4 links.
  • the compounds according to the present invention can be used alone or as a mixture and, in particular, as a mixture with one another. They can be mixed with the starting product and with the sulfonate which would correspond to complete electrical neutrality given by the sulfonates according to the present invention.
  • compositions used can have fractional values.
  • M ⁇ + is the at least trivalent cation
  • sulfonate perhalogenated by R x -S0 2 -0 "
  • Y anions other than the sulfonates carried by a perhalogenated carbon
  • q can become fractional and, in particular, be between 0.1 and ⁇ -0.1, (that is to say between 0.1 and 2.9 when M is trivalent), advantageously from 0.5 to ⁇ - 0.5 (0.5 to 2.5 when M is trivalent), preferably from 1 to ⁇ -1 (from 1 to 2 when M is trivalent), the limits being understood.
  • sulfonates comprising two or more sulfonate functions carried by a perhalogenated carbon atom
  • q will imply the number of equivalents of sulfonate functionality carried by perhalogenated carbon atoms.
  • These compounds can be used as Lewis acids as mentioned above and in reactions where Lewis acids are used as catalysts. They can in particular be used to functionalize aromatic nuclei by reactions using nucleophilic cations. In particular, it is possible to carry out reactions with acid halides or acid anhydrides which give a cation such as the sulfonylium cation or the acylium cation.
  • this reaction does not generally require strong catalysts, this reagent can also be used for alkylation reactions.
  • these catalysts constitute Lewis acids which are particularly capable of forming nucleophilic cations in particular from acid anhydrides, whether they are symmetrical or asymmetrical.
  • acid chlorides are a form of asymmetric acid anhydride, one of the acids being a hydrohalic acid.
  • these acid chlorides in the case of sulfonylations, although they are reputed to be less active than the symmetrical ones, give excellent yields when they are used concomitantly with the catalysts according to the invention.
  • these compounds are likely to be very good neutral reaction catalysts, such as for example aldolization or ketolization reactions.
  • These catalysts can be made in situ in the case of rare earths (scandium, yttrium, lanthanum and lanthanide) and elements of the square of the periodic table of the elements formed by gallium, germanium, arsenic, indium, l , antimony, thallium and lead.
  • the case of bismuth is more complex, due in particular to the difficulty in synthesizing bismuth trifluoromethylsulfonates by simple action of triflic acid (TfOH).
  • TfOH triflic acid
  • rare earths scandium, yttrium, lanthanum and lanthanide gallium, germanium, arsenic, indium, tin, antimony, thallium and lead
  • the amount of acid eg triflic or sulfonimide
  • anions including oxide [O " ] and hydroxide anions, ensuring the initial neutrality of said salt; when they are not oxides, or hydroxides
  • Displacement of oxygenated anions oxide, hydroxide, or carbonate leaves in the middle of the formation water which does not alter if significantly catalysis.
  • the divalent anions count for two.
  • a Lewis acid catalyst a composition comprising at least one of the salts chosen from the group of rare earth salts (scandium, yttrium, lanthanum and lanthanide) of gallium, germanium, arsenic, indium, tin, antimony, thallium and lead and an ⁇ H acid, (such as sulfonic acids, i.e.
  • the salts chosen from the group of rare earth salts (scandium, yttrium, lanthanum and lanthanide) of gallium, germanium, arsenic, indium, tin, antimony, thallium and lead and an ⁇ H acid, (such as sulfonic acids, i.e.
  • sulfonic acids whose sulfonic function is carried by a perhalogenated atom above, the sulfonimides of which a sulfonyl function is carried by a perhalogenated atom, and if appropriate their mixture, but the mixtures are not preferred); that is to say acids having a sulfonyl group (s) carried by a perhalogenated atom, preferably perfluorinated, more preferably a perfluoromethylene group (-CF 2 ).
  • a composition can comprise, inter alia, solvents and water when the agent generating the cation is not sensitive to hydrolysis under the operating conditions.
  • the present invention provides a reagent useful for electrophilic aromatic substitutions (such as the Friedel and Crafts reactions) which comprises:
  • At least one ⁇ H acid such as sulfonic acids, that is to say sulfonic acids whose sulfonic function is carried by a perhalogenated atom above, the sulfonimides of which a sulfonyl function is carried by a perhalogenated atom and, where appropriate mixing them, but mixtures are not preferred); that is to say acids having a sulfonyl group (s) carried by a perhalogenated atom, preferably perfluorinated, more preferably a perfluoromethylene group (-CF 2 );
  • Said ratio is advantageously at most equal to ⁇ - 0.1, preferably to ⁇ - 0.5; more preferably at ⁇ - 1.
  • Said composition can also comprise a solvent, which can moreover be a possible excess substrate.
  • the acids may be polyacids and the halides, polyacid polyhalides, and in particular the mono- and di-halides of sulfur-based acids.
  • the salts according to the present invention correspond to the formula (that is to say that in the preceding formula, Z is oxygen and consequently Ri does not exist): MY ⁇ . q (R x S0 2 -0-) q,
  • M is an element in an at least trivalent cationic form, which element being advantageously chosen from rare earths (scandium, yttrium, lanthanum and lanthanide) and the square metals of the periodic table of elements formed by gallium, germanium , arsenic, indium, tin, antimony, thallium lead and bismuth;
  • ⁇ represents the charge of the cation corresponding to M
  • Y represents anions other than perhalogenated sulfonates on the carbon carrying said sulfonate function
  • q represents an integer chosen from the closed interval ranging from 1 to ⁇ -1; q can in particular take the values 1, 2, ⁇ -2 and / or ⁇ -1; and can be made in situ (except for bismuth) or prepared in isolation.
  • salts in particular allow catalysts in environments where too high an acidity can be harmful (acidity corresponding to an acidity which, if the salt was in an aqueous medium, would correspond to a pH between 2 and 8, advantageously between 4 and 7) .
  • the salts themselves are not acidic and can be used in a neutral medium (acidity corresponding to an acidity which, if the salt was in an aqueous medium, would correspond to a pH between 2 and 8, advantageously between 4 and 7). This aspect of things allows the use in a neutral medium of a Lewis acid catalyst which is both powerful and does not significantly modify the neutrality of the medium.
  • the salts according to the present invention correspond to the formula (that is to say that in the preceding formula, Z is nitrogen): MY ⁇ . q (R x S0 2 -N (R 1 )) q , with Rx having the value of Rf and R 1 (being an electron-withdrawing group, advantageously an aromatic or aliphatic sulfonyl radical, and preferably a sulfonyl radical carried by a perhalogenated atom as defined in the beginning of this description;
  • M is an element in an at least trivalent cationic form, which element being advantageously chosen from rare earths (scandium, yttrium, lanthanum and lanthanide) and the metals of the square of the periodic table of elements formed by gallium, germanium , arsenic, indium, tin, antimony, thallium lead and bismuth;
  • ⁇ represents the charge of the cation corresponding to M
  • Y represents anions other than perhalogenated sulfonates on the carbon carrying said sulfonate function
  • salts in particular allow catalysts in environments where too much acidity can be harmful (acidity corresponding to an acidity which, if the salt was in aqueous medium, would correspond to a pH between 2 and 8, advantageously between 4 and 7).
  • the salts themselves are not acidic and can be used in a neutral medium (acidity corresponding to an acidity which, if the salt was in an aqueous medium, would correspond to a pH between 2 and 8, advantageously between 4 and 7). This aspect of things allows the use in a neutral medium of a Lewis acid catalyst which is both powerful and does not significantly modify the neutrality of the medium.
  • Rx has the value defined previously and advantageously 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 x and Ri 'can be linked together,
  • - k is equal to 1 or 2, with k preferably being equal to 2 when Ri 'represents a fluorine atom,
  • - Ri ' is an organic carbon radical advantageously containing at most 30 carbon atoms [when it is not polymeric (that is to say does not constitute a bond of attachment to a polymer)] or a group such as defined for R x , and the Value k advantageously being 2.
  • the formula of the salts targeted by the invention can be: with:
  • the anions Y " advantageously a carboxylate group, such as acetate or sulfonate, or a halogen atom, preferably chlorine, bromine and iodine;
  • phenyl groups optionally substituted by one or more substituents electron alkyl type to C 4 linear or branched, such as methyl, ethyl, propyl, type -alkoxy-C 4, such as methoxy, ethoxy, propoxy, phenoxy or C 1 to C 4 thioether type.
  • substituents electron alkyl type to C 4 linear or branched such as methyl, ethyl, propyl, type -alkoxy-C 4, such as methoxy, ethoxy, propoxy, phenoxy or C 1 to C 4 thioether type.
  • the two groups R 3 are identical.
  • the anion of formula (I) corresponds to the formula (Ha) or (Mb):
  • k 1 or 2, and preferably 2.
  • x has the value 1.
  • the compounds, as defined above, prove to be particularly effective as Lewis acids. It therefore follows an increased catalytic activity of said promoter.
  • the salts of elements of valence ⁇ , targeted by the present invention generally have particularly advantageous Lewis acid properties.
  • the claimed catalyst promoters have thus been found to be particularly effective in catalyzing reactions of the Diels-Alder reactions, carbonyl allylations, ene reactions and Prins reactions.
  • the present invention also relates to the use of a promoter comprising at least one anion of formula (I) as defined above and a cation of formula (III):
  • - A symbolizes the remainder of a cycle forming all or part of a carbocyclic or heterocyclic, aromatic, monocyclic or polycyclic system: said cyclic residue being able to carry a radical R representing a hydrogen atom or one or more substituents, identical or different ,
  • - n represents the number of substituents on the cycle.
  • the invention is particularly applicable to aromatic compounds corresponding to formula (I) in which A is the residue of a cyclic compound preferably having at least 4 atoms in the optionally substituted ring and representing at least one of following cycles:
  • a optionally substituted represents the remainder: 1) Of an aromatic, monocyclic or polycyclic carbocyclic compound.
  • polycyclic carbocyclic compound is meant:
  • heterocyclic polycyclic compound we define:
  • alkylene or alkylidene radical having from 1 to 4 carbon atoms, preferably a methylene or isopropylidene radical
  • Ro Ro in these formulas represents a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, a cyclohexyl or phenyl radical.
  • cycles under 1) to 3 there may be mentioned:
  • an aromatic compound of formula (I) is preferably used in which A represents a benzene ring.
  • the aromatic compound of formula (I) can carry one or more substituents.
  • the number of substituents present on the cycle depends on the carbon condensation of the cycle and on the presence or not of unsaturations on the cycle.
  • a hydrogen atom • an alkyl radical, linear or branched, having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, dry -butyl, tert-butyl,
  • Ri represents a valential bond or a divalent, linear or branched, saturated or unsaturated hydrocarbon radical, having from 1 to
  • radicals R 2 identical or different, represent a hydrogen atom or an alkyl radical, linear or branched, having from 1 to 6 carbon atoms;
  • X symbolizes a halogen atom, preferably a chlorine, bromine or fluorine atom.
  • radicals R and the 2 successive atoms of the aromatic ring can be linked together by an alkylene, alkenylene or alkenylidene radical having from 2 to 4 carbon atoms to form a saturated, unsaturated or aromatic heterocycle having 5 to 7 carbon atoms.
  • One or more carbon atoms can be replaced by another heteroatom, preferably oxygen.
  • the radicals R can represent a methylene dioxy or ethylene dioxy radical.
  • the present invention is particularly applicable to aromatic compounds corresponding to formula (!) In which: - the radical (s) R represents (s) one of the following groups:
  • - n is a number equal to 0, 1, 2 or 3.
  • m represents a number equal to 0, 1 or 2 and the symbols R, which are identical or different, and n, having the meaning given above, a compound consisting of a chain of two or more monocyclic aromatic carbocycles corresponding to formula (Ib):
  • alkylene or alkylidene radical having from 1 to 4 carbon atoms, preferably a methylene or isopropylidene radical,
  • Ro in these formulas, Ro represents a hydrogen atom or an alkyl radical having from 1 to 4 carbon atoms, a cyclohexyl or phenyl radical.
  • - R represents a hydrogen atom, a hydroxyl group, a _CHO group, a group -N0 2 , a group -NH 2 , a linear or branched alkyl or alkoxy radical having from 1 to 6 carbon atoms, preferably from 1 with 4 carbon atoms or a halogen atom, - B symbolizes a valential bond, an alkylene or alkylidene radical having from 1 to 4 carbon atoms or an oxygen atom,
  • - m is equal to 0 or 1
  • - n is equal to 0, 1 or 2
  • the compounds of formula (I) are chosen in which R represents a hydrogen atom, a hydroxyl group, a methyl radical, a methoxy radical or a halogen atom.
  • - aromatic compounds such as benzene, toluene, chlorobenzene, dichlorobenzenes, trichlorobenzenes, fluorobenzene, difluorobenzenes , chlorofluorobenzenes, chlorotoluenes, fluorotoluenes, bromobenzene, dibromobenzenes, bromofluorobenzenes, bromochlorobenzenes, trifluoromethyl-benzene, trifluoromethoxybenzene, trichloromethylbenzene, trichloromethyethylenomethylenobenzene
  • - monoethers such as anisole, ethoxybenzene (phenetole), butoxybenzene, Pisobutoxybenzene, 2-chloroanisole, 3-chloroanisole, 2-bromoanisole, 3-bromoanisole, 2-methylanisole, 3 -methylanisole, 2-ethylanisole, 3-ethylanisole, 2-isopropylanisole, 3-isopropylanisole, 2-propylanisole, 3-propylanisole, 2-allylanisole, 2-butylanisole, 3-butylanisole, 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-ethylbenzen
  • - diethers such as veratrole, 1, 3-dimethoxybenzene, 1, 2-diethoxybenzene, 1, 3-diethoxybenzene, 1, 2-dipropoxybenzene, 1, 3-dipropoxybenzene, 1, 2-methylenedioxybenzene, 1, 2-ethylenedioxybenzene,
  • Triethers such as 1, 2,3-trimethoxybenzene, 1, 3,5-trimethoxybenzene, 1, 3,5-triethoxybenzene.
  • the compounds to which the process according to the invention applies are benzene, toluene, phenol, anisole and veratrole.
  • the reagent works all the better as the substrate is rich in electrons which, in the case of homocyclic 6-membered nuclei, corresponds to a sum of the Hammett constants ⁇ p of the possible substituents, less than About 0.5.
  • the reagent according to the present invention comprises a catalyst according to the present invention, whether it is a composition or a compound and an acid anhydride which, preferably, is an acid halide and most often for economic reasons chlorides d 'acid.
  • the reagent can comprise a sulfonyl halide of formula (II) R 3 S0 2 X '.
  • R 3 is aryl, in particular phenyl or naphthyl optionally substituted by an organic radical such as an alkyl group C ⁇ -C 8 -alkyl, C ⁇ -C 8, nitro, or one or more halogen atoms, in particular chlorine.
  • R 3 can also be an alkyl radical.
  • X ' represents a halogen atom, preferably a chlorine or bromine atom, or else a residue of another acid to form a leaving group. It is simpler to use symmetrical anhydrides, sulfonyl halides.
  • the reagent can also comprise an acylation reagent, in which case it corresponds to the formula R 3 CO-X where R 3 and X 'have the same values as above.
  • R 3 represents:
  • cycloaliphatic radical saturated, unsaturated or aromatic, monocyclic or polycyclic, having from 4 to 12 carbon atoms
  • halogen atom preferably a chlorine or bromine atom
  • R - a radical -O-CO-R4, with R, identical or different from R 3 , having the same meaning as R 3 .
  • cyclic substituent is preferably meant a saturated, unsaturated or aromatic carbocyclic ring, preferably cycloaliphatic or aromatic, in particular cycloaliphatic, comprising 6 carbon atoms in the ring or benzene.
  • R 3 represents an alkyl radical, linear or branched, having from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms: the hydrocarbon chain can possibly be interrupted by a heteroatom (for example oxygen) , by a functional group (for example _CO_) and / or carrying a substituent (for example a halogen or a group CFa).
  • a heteroatom for example oxygen
  • a functional group for example _CO_
  • a substituent for example a halogen or a group CFa
  • R 3 preferably represents an alkyl radical having from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl.
  • the radical R 3 also preferably represents a phenyl radical which may be optionally substituted. It is necessary that this radical is more deactivated than the aromatic compound because, otherwise, there would be acylation of the acylating agent itself.
  • an alkyl radical linear or branched, having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,
  • alkoxy radical linear or branched, having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, such as the methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert- butoxy,
  • halogen atom preferably a fluorine, chlorine or bromine atom.
  • the preferred acylating agents correspond to formula (II) in which X 1 represents a chlorine atom and R 3 represents a methyl or ethyl radical.
  • the preferred compounds correspond to formula (II) in which R 3 and R 4 are identical and represent an alkyl radical having from 1 to 4 carbon atoms.
  • acylating agents corresponding to formula (II), there may be mentioned more particularly: - acetyl chloride,
  • reaction can be carried out in a solvent, or in the absence of a solvent, in which case one of the reagents can be used as reaction solvent provided that it is placed at a temperature where these reagents are melted.
  • a preferred variant of the process of the invention consists in carrying out the reaction in an organic solvent.
  • a solvent for the starting substrate is preferably chosen and, more preferably, an organic, aprotic, polar solvent.
  • linear or cyclic carboxamides such as N, N-dimethylacetamide (DMAC), N, N -diethylacetamide, dimethylformamide (DMF), diethylformamide or 1-methyl-2-pyrrolidinone (NMP); nitro compounds such as nitromethane, nitroethane, 1-nitropropane, 2-nitropropane or their mixtures, nitrobenzene; alphatic or aromatic nitriles such as acetonitrile, propionitrile, butanenitrile, isobutanenitrile, benzonitrile, benzyl cyanide; dimethyl sulfoxide (DMSO); tetramethylsulfone (sulfolane), dimethylsulfone, hexamethylphosphotriamide (HMPT); dimethyl ethylene, dimethyl propylene, tetramethyl urea;
  • DMAC N-dimethylacetamide
  • DMF dimethylformamide
  • NMP diethylformamide
  • the preferred solvents are: nitromethane, nitroethane, 1 -nitropropane, 2-nitropropane. It is also possible to use a mixture of organic solvents.
  • the amount of catalysts used is determined so that the ratio between the number of moles of catalysts and the number of moles of acylating or sulfonylating agents, or any other agent capable of forming a cation, is less than 1 , advantageously 0.5, preferably 0.2. In general, the minimum quantity corresponds to a ratio at least equal to 0.001, advantageously at least equal to 0.02, preferably 0.05.
  • the reactions are carried out at atmospheric pressure or under pressure higher than atmospheric pressure for reasons of simplicity.
  • the reaction temperature is between 20 ° C and 200 ° C, preferably between 40 ° C and 150 ° C.
  • Another aspect of the invention relates to a process for preparing the catalyst or promoter compound according to the invention.
  • R 3 representing • a phenyl group, where appropriate, substituted by one or more electron donor substituents of C1 to C 4 alkyl type, linear or branched, such as for example methyl, ethyl, propyl, of C 1 to C alkoxy type 4 , such as methoxy, ethoxy, propoxy, phenoxy or of C1 to C thioether type 4 .
  • a carboxylate group such as acetate or sulfonate; or
  • halogen atom preferably chlorine, bromine and iodine
  • the compound of general formula (V) is used in an amount of at most one equivalent.
  • an excess of compound of general formula (V) is used.
  • the R 3 groups present on the bismuth atom are therefore preferably chosen so as to confer on it a charge at least equivalent to that conferred by three tolyl groups. More preferably, the three substituents R 3 are identical and represent a tolyl group.
  • 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.
  • a haloalkane type solvent such as dichloromethane, dichloroethane, or a solvent of acetonitrile or toluene type and under an inert atmosphere.
  • the expected promoter is then isolated.
  • This operating mode can be transposed for the compounds according to the invention
  • Example 1 Preparation and isolation of the mixed BiCI derivative (QTf) 2
  • BiCI (OTf) 2 Preparation of BiCI (OTf) 2
  • Into a 100 ml schenck flask 9.11 g (28.89 mmol) of bismuth (III) chloride are introduced and add 60 ml of anhydrous toluene. Then 10.5 g (70 mmol) of triflic acid are added when cold.
  • the suspension is stirred magnetically, the flask is connected to an oil bubbler and heated to 110 ° C. using an oil bath for 1 h 30 min. At the end of this time, more HCl is observed in the bubbler.
  • the mixture is cooled and the toluene is removed using a syringe.
  • IR analysis (cm 1 ): 1326 (m), 1271 (m), 1232 (m), 1201 (s), 1032 (m), 1022 (m), 1001 (m) Raman analysis: 1303, 1293, 1250, 1213, 1175, 1154, 1054, 781, 654, 584, 518, 365, 351, 337, 308.
  • the aromatic tested is brought into contact with mesyl chloride in an equimolar ratio 1.
  • the catalyst is then introduced and the reaction is then carried out for 24 hours at a temperature of 105 ° C.
  • the catalyst is introduced at a rate of 10 mol% relative to the amount of substrate introduced. The results are collated in the table below.
  • Bismuth (inferred formula BiCI 2 (NTf 2 )) gives after 5 hours approximately the same yield as Bi (NTf 2 ) 3 for an identical amount of bismuth, namely approximately 35%.
  • Example 10 Activation of the carbonyl with a Lewis acid and addition on an unsaturation such as enol
  • the rare earth triflate (TfO) or triflimide (TfSI) (0.04 mmol) is diluted in a THF / water mixture (2 ml / 1 ml) at room temperature in a Schott tube 40 ml. To this solution are successively added benzaldehyde (0.4 mmol) and silylated enol ether (0.4 mmol). The mixture is stirred at 20 ° C for 17 h, then analyzed by CPL with external calibration.

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EP01954096A 2000-07-13 2001-07-13 Zusammenstellung und verbindung auf grund von metallsalzen und säure mit einem sulonyl-substituierten perhalogenierten kohlenstoff und ihre verwendung als lewissäure Withdrawn EP1301275A1 (de)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
FR0009213 2000-07-13
FR0009213A FR2811592B1 (fr) 2000-07-13 2000-07-13 Composition et compose a base de sel(s) de metaux et de sulfonate(s) porte(s) par un carbone perhalogene et leur utilisation comme acide de lewis
FR0017310 2000-12-29
FR0017310A FR2818980B1 (fr) 2000-12-29 2000-12-29 Promoteur de type bis-amidure de bismuth
FR0109213 2001-07-11
FR0109213A FR2827195A1 (fr) 2001-07-11 2001-07-11 Composition et compose a base de sel(s) de metaux et de sulfonate(s) porte(s) par un carbone perhalogene et leur utilisation comme acide de lewis
PCT/FR2001/002289 WO2002005954A1 (fr) 2000-07-13 2001-07-13 Composition et compose a base de sel(s) de metaux et d'acide presentant un groupe sulfonyle porte par un carbone perhalogene et leur utilisation comme acide de lewis

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DE102011011881A1 (de) 2011-02-21 2012-08-23 Thyssenkrupp Uhde Gmbh Verfahren zur Beseitigung von N2O und NOX aus dem Prozess zur Salpetersäureherstellung

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WO2007114073A1 (ja) 2006-03-31 2007-10-11 Adeka Corporation シアニン化合物及び光学記録材料
JP5078386B2 (ja) 2006-05-08 2012-11-21 株式会社Ａｄｅｋａ 新規化合物、該化合物を用いた光学フィルター及び光学記録材料
JP5475244B2 (ja) 2007-03-30 2014-04-16 株式会社Ａｄｅｋａ シアニン化合物、該化合物を用いた光学フィルター及び光学記録材料
JP2012506428A (ja) * 2008-10-24 2012-03-15 グルオウセステル プハルマセウトイカルス ガンの療法
IN2013CN05909A (de) 2011-02-18 2015-09-04 Adeka Corp
JP2012208465A (ja) 2011-03-16 2012-10-25 Adeka Corp 光拡散性樹脂組成物及びこれを用いた光拡散シート
US9881745B2 (en) 2013-08-29 2018-01-30 Adeka Corporation Dye sensitized solar cell
EP3556811A4 (de) 2016-12-19 2020-09-23 Adeka Corporation Lösung mit schichtstoff und verfahren zur herstellung davon
KR20210133236A (ko) 2019-02-28 2021-11-05 가부시키가이샤 아데카 신규 화합물, 그 화합물을 포함하는 조성물, 자기 수복 재료, 표면 코트제, 도료, 접착제, 전지용 재료 및 경화물

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DE102011011881A1 (de) 2011-02-21 2012-08-23 Thyssenkrupp Uhde Gmbh Verfahren zur Beseitigung von N2O und NOX aus dem Prozess zur Salpetersäureherstellung
WO2012113516A1 (de) 2011-02-21 2012-08-30 Thyssenkrupp Uhde Gmbh Verfahren zur beseitigung von n2o und nox aus dem prozess zur salpetersäureherstellung und dafür geeignete anlage
US10899617B2 (en) 2011-02-21 2021-01-26 Thyssenkrupp Industrial Solutions Ag Method for removing N2O and NOx from the nitric acid production process, and an installation suitable for same

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