EP1658249A2 - Verfahren zur herstellung einer kohlenstoff-kohlenstoff bindung zwischen eine übertragbare gruppe und eine akzeptor gruppe - Google Patents

Verfahren zur herstellung einer kohlenstoff-kohlenstoff bindung zwischen eine übertragbare gruppe und eine akzeptor gruppe

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Publication number
EP1658249A2
EP1658249A2 EP04786350A EP04786350A EP1658249A2 EP 1658249 A2 EP1658249 A2 EP 1658249A2 EP 04786350 A EP04786350 A EP 04786350A EP 04786350 A EP04786350 A EP 04786350A EP 1658249 A2 EP1658249 A2 EP 1658249A2
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Prior art keywords
group
carbon atoms
aromatic
formula
radical
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French (fr)
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Johann Vastra
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Rhodia Chimie SAS
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Rhodia Chimie SAS
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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
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B37/00—Reactions without formation or introduction of functional groups containing hetero atoms, involving either the formation of a carbon-to-carbon bond between two carbon atoms not directly linked already or the disconnection of two directly linked carbon atoms
    • C07B37/04—Substitution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
    • C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
    • C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes

Definitions

  • the present invention relates to a coupling process between a transferable group and an acceptor group by creating a carbon-carbon bond in the presence of a palladocycle type catalyst.
  • organometallic nucleophiles with organic halides or sulfonates, in the presence of a catalyst based on nickel, palladium or platinum, is currently the most effective means of producing carbon-carbon bonds.
  • organosilylated derivatives lie in the fact that it is easy to prepare them from chlorosilanes. They are less expensive and more easily purified than organoboronic acids which tend to polymerize.
  • reaction effluents with organosilylates are less problematic than releases of reaction with organoboronic acids, having regard to the environment and the regulations in force.
  • Patent application WO 01/94355 discloses a carbon-carbon coupling process from silylated derivatives and from an organic electrophile in the presence of a basic anionic activator and nucleophile and of a catalyst which is a metal of the group 10.
  • the process described in this application leads to undesirable homocoupling by-products, which is detrimental to the supply of very high purity compounds for the applications defined above.
  • it is indicated that the formation of homocoupling by-products can be reduced by adding phosphine derivatives to the reaction medium.
  • Their elimination can however pose problems, both in terms of the difficulty of obtaining products of high purity, and in that of the treatment of effluents before discharge into the environment.
  • the phosphines are relatively difficult to synthesize, generally unstable and their cost is high.
  • a first objective of the present invention to provide a coupling method between a transferable group and an acceptor group by creating a carbon-carbon bond without using compounds of boronic type.
  • Another object of the present invention is to provide a method of coupling between a transferable group and an acceptor group by creating a carbon-carbon bond without using phosphine-type compounds.
  • a third objective consists in avoiding, or at least reducing, the formation of homocoupling by-products during the creation of a carbon-carbon bond in a process which aims at coupling between a transferable group and a group. acceptor.
  • a fourth objective of the present invention is to reduce the amount of catalyst necessary for the creation of a carbon-carbon bond during a coupling process between a transferable group and an acceptor group.
  • a fifth objective of the present invention consists in obtaining a coupling between a transferable group and an acceptor group by creation of a carbon-carbon bond with kinetics significantly higher than that observed with the analogous coupling reactions available in l prior art. Obtaining coupling products between a transferable group and an acceptor group by creating a carbon-carbon bond with good yields, in particular greater than those observed with similar coupling reactions available in the prior art, also represents one of the objectives of the present invention.
  • the present invention relates first of all to a process for creating a carbon-carbon bond by coupling between a transferable group and an acceptor group, comprising the steps of: a) activation of a silicon compound carrying a group transferable by an activation agent; b) addition of a derivative carrying an acceptor group; and, simultaneously or consecutively, in any order, c) addition of a palladocycle type compound acting as a catalyst for the coupling reaction between the transferable group and the acceptor group by creation of said carbon-carbon bond.
  • Step a) of activation of the silicon compound is carried out in a medium comprising a preferably polar solvent, in particular ethers among which mention may be made, by way of nonlimiting examples, of dioxane, tetrahydrofuran, anisole, dibutyl ether, methyl-te / ⁇ -butyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, di-iso-propyl ether, dioxane and anisole which are among the preferred solvents. Of course, mixtures of these solvents can be used in all proportions.
  • a preferably polar solvent in particular ethers among which mention may be made, by way of nonlimiting examples, of dioxane, tetrahydrofuran, anisole, dibutyl ether, methyl-te / ⁇ -butyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, di-iso-propy
  • the solvent of the activation step is however not limited to polar solvents, and it is also possible to use other solvents, such as for example aromatic solvents, mixtures of these solvents which can be used .
  • Toluene is a possible representative of this class of solvents. It also remains understood that mixtures of one or more solvents, chosen from polar solvents, with one or more other solvents, such as those defined for example in the preceding paragraph, can be used.
  • the activating agents commonly used, and in particular the anionic nucleophilic compounds are used. In general, this anionic nucleophilic compound is capable of releasing anions, for example hydroxyl ions (OH " ), ions of alcoholate type, etc., in the reaction medium.
  • Organic or mineral fluorides may also be suitable as activating agents. Mention may be made in this case of alkaline earth fluorides, in particular potassium fluoride, as well as tetraalkylammonium fluorides, for example tetrabutylammonium fluoride.
  • the activating agent is chosen from hydroxides of alkali and alkaline earth metals, alcoholates, carbonates, amides, as well as their derivatives.
  • the activating agent can be chosen from sodium hydroxide, lithium hydroxide, potassium hydroxide, barium hydroxide, barium oxide, the potassium salt of hexamethyldisilazane (KHMDS), etc.
  • the activating agent used is an alkali metal hydroxide, and in particular sodium hydroxide, in solid form, for example in the form of finely ground pellets, or also in the form of a solution. aqueous.
  • the reaction solvent mixtures of activating agents can be used.
  • the amount of activating agent used is such that the molar ratio of activating agent / silicon compound is generally between 1 and 8, preferably between 2 and 6, most often between 3 and 5, for example around 4.
  • the silicon compound to be activated is poured into the solvent / activating agent mixture so as to keep the reaction temperature between 40 ° C.
  • the reaction medium can be heated or cooled, as the case may be, during the pouring of the silicon compound, so that the temperature of the reaction medium remains in the range of values set out above.
  • the cooling or heating of the reaction medium can be ensured according to any conventional method known to a person skilled in the art who specializes in organic syntheses.
  • the silicon compound carrying the transferable group can be of any type, and in particular a dihalosilane corresponding to formula (I):
  • X 1 and X 2 identical or different, independently of one another, represent a halogen atom chosen from fluorine, chlorine, bromine and iodine, preferably from chlorine and bromine, more preferably X 1 and X 2 are identical and each represents a bromine atom or a chlorine atom, advantageously a chlorine atom;
  • R is chosen from the hydrogen atom, a linear or branched alkyl radical containing from 1 to 6 carbon atoms, and the radical R ⁇ defined below;
  • R ⁇ represents the transferable group and is chosen from an aryl, vinyl and allyl radical, each of which can be optionally substituted, R ⁇ preferably representing an optionally substituted aryl radical, for example an optionally substituted phenyl radical.
  • the transferable group R ⁇ can for example represent a group of formula R ' ⁇ as follows:
  • R T , R T2 and R T3 are chosen, independently of one another, from the hydrogen atom and a hydrocarbon group having from 1 to 20 carbon atoms which can be a saturated or unsaturated, linear or branched aliphatic group; a saturated, unsaturated or aromatic carbocyclic or heterocyclic group,
  • the invention does not exclude the presence of one or more other unsaturations on the hydrocarbon chain such as one or more other double bonds and / or one or more triple bonds, which can be conjugated or i5 not.
  • the hydrocarbon chain can be optionally interrupted by a heteroatom (for example, oxygen or sulfur) or by a functional group insofar as the latter does not react; there may be mentioned in particular a group such as in particular -CO-.
  • the hydrocarbon chain may optionally carry one or more substituents insofar as they do not react under the reaction conditions and mention may in particular be made, as possible substituents, of a halogen atom, a nitrile group or a trifluoromethyl group.
  • substituents of a halogen atom, a nitrile group or a trifluoromethyl group.
  • cycle is meant a carbocyclic or heterocyclic, saturated, unsaturated or aromatic cycle.
  • the acyclic aliphatic group can be linked to the ring by a valential bond, a heteroatom or a functional group such as oxy, carbonyl, carboxy, sulfonyl, etc.
  • cyclic substituents it is possible to envisage cycloaliphatic, aromatic or heterocyclic, in particular cycloaliphatic, substituents comprising 6 carbon atoms in the ring or benzenic, these cyclic substituents themselves being optionally carriers of any substituent to the extent where they do not interfere with the reactions involved in the process of the invention. Mention may in particular be made of alkyl or alkoxy groups having from 1 to 4 carbon atoms.
  • aliphatic groups carrying a cyclic substituent more particularly is aimed at aralkyl groups having from 7 to 12 carbon atoms, in particular benzyl or phenylethyl.
  • R ⁇ 1 can also represent a carbocyclic group, saturated or not, preferably having 5 or 6 carbon atoms in the ring, preferably cyclohexyl; a heterocyclic group, saturated or unsaturated, comprising in particular 5 or 6 atoms in the ring including 1 or 2 heteroatoms such as nitrogen, sulfur and oxygen atoms; an aromatic, monocyclic, preferably phenyl or polycyclic carbocyclic group, condensed or not, preferably naphthyl.
  • R T2 and R T3 they preferably represent a hydrogen atom or an alkyl group having from 1 to 12 carbon atoms, a phenyl group or an aralkyl group having from 7 to 12 carbon atoms, preferably , a benzyl group.
  • R T1 , R T2 and R T3 more particularly represent a hydrogen atom or else R T1 represents a phenyl group and R T2 and R T3 represent a hydrogen atom.
  • the transferable group R ⁇ can also represent a group of formula R " ⁇ below:
  • A symbolizes the remainder of a cycle forming all or part of a carbocyclic and / or heterocyclic, aromatic, monocyclic or polycyclic system
  • R T4 identical or different, represent substituents on the cycle
  • t represents the number of substituents on the cycle.
  • A is the remainder of a cyclic compound, preferably having at least 4 atoms in the ring, preferably 5 or 6, optionally substituted, and representing at least one of the following rings: * an aromatic, monocyciic or polycyclic carbocycle, that is to say a compound constituted by at least 2 aromatic carbocycles and forming between them ortho- or ortho- and pericondensed systems or a compound constituted by at least 2 carbocycles of which only one of them is aromatic and forms between them ortho- or ortho- and pericondensed systems; * an aromatic, monocyclic heterocycle comprising at least one of the heteroatoms chosen from oxygen, nitrogen and sulfur, or a polycyclic aromatic heterocycle, that is to say 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, or a compound consisting of at least one carbocycle and at least one heterocycle of which at least one
  • the optionally substituted residue A preferably represents the remainder of an aromatic carbocycle such as benzene, of an aromatic bicycle comprising two aromatic carbocycles such as naphthalene; a partially aromatic bicycle comprising two carbocycles, one of which is aromatic, such as tetrahydro-1, 2,3,4-naphthalene.
  • A can represent the rest of a heterocycle. More particularly, the optionally substituted residue A represents one of the following cycles: - an aromatic heterocycle corresponding to one of the following formulas: - an aromatic bicycle comprising an aromatic carbocycle and an aromatic heterocycle represented by one of the following formulas:
  • the transferable group R " ⁇ 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. The number maximum of substituents likely to be carried by a cycle, is easily determined by a person skilled in the art.
  • the group (s) R T4 preferably represent one of the following groups: - an alkyl group, 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, te / ⁇ -butyl; - an alkenyl or alkynyl group, linear or branched having from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms, such as vinyl, allyl; a linear or branched alkoxy or thioether group having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy groups, an alkenyloxy group, preferably a group allyloxy or a phen
  • R 1 represents a valential bond or a divalent, linear or branched, saturated or unsaturated hydrocarbon group having from 1 to 6 carbon atoms such as, for example, methylene, ethylene, propylene, isopropylene, isopropylidene;
  • the identical or different R 2 groups represent a hydrogen atom or a linear or branched alkyl group having from 1 to 6 carbon atoms or phenyl;
  • Z represents a hydrogen atom, an alkali metal preferably, sodium or a group R 2 ;
  • Y symbolizes a halogen atom, preferably a chlorine, bromine or fluorine atom.
  • X 1 and X 2 are identical and each represents a bromine atom or a chlorine atom, advantageously a chlorine atom;
  • R is chosen from the hydrogen atom, the radical R ⁇ defined below, and a linear or branched alkyl radical containing from 1 to 6 carbon atoms, preferably the methyl, ethyl, propyl, / so- radical propyl, butyl, te / ⁇ -butyl, sec-butyl, / so-butyl, pentyl, neopentyl and n-hexyl, more preferably the methyl or ethyl radical;
  • R ⁇ represents an optionally substituted aryl radical, for example an optionally substituted phenyl radical.
  • the compounds of formula (I) which are particularly preferred for the process of the present invention are those for which: • X 1 and X 2 each represent a chlorine atom; • R represents the methyl radical or an optionally substituted phenyl radical; and • R ⁇ represents an optionally substituted phenyl radical.
  • the compound of formula (I) defined above can be chosen from chlorosilanes, and in particular, the compound of formula (I) can be diphenyldichlorosilane, methylphenyldichlorosilane or methyltolyl-dichlorosilane.
  • the silicon compound carrying the transferable group can advantageously be chosen from silicone oils, generically called polysiloxanes.
  • R ⁇ represents a transferable group as defined above;
  • R a , b, R c , d and R e which are identical or different, are chosen independently of one another from the hydrogen atom, a linear or branched alkyl radical containing from 1 to 6 carbon atoms, and the radical R ⁇ previously defined;
  • r represents an integer between 1 and 10, limits included;
  • q represents 0 or an integer between 1 and 9, limits included;
  • q represents 0 or an integer between 1 and 9, limits included, the sum q + r + s being between 4 and 10, limits included.
  • the polysiloxanes of formula (I ′) can also be in cyclic form, that is to say in the form of a ring in which the endocyclic atoms are alternately silicon and oxygen.
  • Such cyclic polysiloxanes can be represented schematically by the following formula:
  • R ⁇ , R a , R b , Rc, d , Re, q, r and s are as defined above.
  • the silicone oils, and in particular the polysiloxanes, cyclic or not, of formula (I ′) are known compounds, and available, in particular in the silicone industries.
  • the compounds of formula (I ') can also be easily prepared by hydrolysis in buffered aqueous medium of the compounds of formula (I) defined above.
  • R a , Rb, Rc, d and R e are chosen independently of each others among the hydrogen atom, the radical R ⁇ defined below, and a linear or branched alkyl radical containing from 1 to 6 carbon atoms, preferably the methyl, ethyl, propyl, / so-propyl, butyl radical , terf-butyl, sec-butyl, / so-butyl, pentyl, neopentyl and n-hexyl, more preferably the methyl or ethyl radical; • R ⁇ represents an optionally substituted aryl radical, for example an optionally substituted phenyl radical.
  • silicone oils suitable for the process of the present invention mention may be made of those obtained by hydrolysis of the dihalosilanes of formula (I) as defined above, the alkylarylpolysiloxanes, in particular the methylarylpolysiloxanes, and for example the methylphenylpolysiloxane, sold by the company Rhodia under the name of Rhodorsil H550 ® .
  • the silicon compounds carrying a transferable group used in the process of the present invention must be activated before carrying out the actual coupling reaction. The activation time depends on the nature and amount of the compound carrying the transferable group (for example compound of formula (I) or of formula (I 1 )), the solvent used and the agent activation used.
  • This duration generally varies from a few minutes to a few days. It is most often less than a few hours, advantageously less than 3 hours.
  • R A represents a hydrocarbon group (acceptor group) comprising from 2 to 20 carbon atoms and has a double bond situated in position a of a leaving group X or a carbocyclic group and / or heterocyclic, aromatic, monocyclic or polycyclic; and X represents a leaving group.
  • R A represents an aliphatic hydrocarbon group comprising a double bond in position a of the leaving group X or a cyclic hydrocarbon group comprising an unsaturation carrying the leaving group X, or also represents a carbocyclic and / or heterocyclic, aromatic group , monocyclic or polycyclic.
  • X represents a halogen atom, a perhaloalkyl group, such as trifluoromethyl, or a sulphonic ester group of formula -OSO 2 -R ⁇ in which R 'is a hydrocarbon group.
  • R ' is a hydrocarbon group of any kind.
  • R ' is of a simple nature, and consequently advantageously represents a linear or branched alkyl group having from 1 to 4 carbon atoms preferably a methyl or ethyl group; R 'may however also represent, for example, a phenyl or tolyl group or a trifluoromethyl group.
  • the leaving group X is a triflate group
  • this corresponds to a group -OSO 2 -R ', in which R' represents the trifluoromethyl group.
  • a halogen atom is preferably chosen, in particular a bromine or chlorine atom, more preferably a chlorine atom.
  • the compounds of formula (II) targeted very particularly according to the method of the invention can be classified into two groups: - (1) those of aliphatic type carrying a double bond and which can be represented by the formula ( lia):
  • R A1 , R 2 and R A3 are chosen, independently of one another, from the hydrogen atom and a hydrocarbon group having from 1 to 20 atoms carbon which may be a saturated or unsaturated, linear or branched aliphatic group; a saturated, unsaturated or aromatic, monocyclic or polycyclic carbocyclic or heterocyclic group; a chain of aliphatic and / or carbocyclic and or heterocyclic groups as mentioned above; X symbolizes the leaving group as previously defined, - (2) those of aromatic type which are designated subsequently by "haloaromatic compound" and which can be represented by the formula (Nb):
  • D symbolizes the remainder of a cycle forming all or part of a carbocyclic and / or heterocyclic, aromatic, monocyclic or polycyclic system.
  • X represents a leaving group as previously defined, R A4 , identical or different, represent substituents on the cycle, n represents the number of substituents on the cycle.
  • R A1 preferably represents a linear or branched acyclic aliphatic group preferably having from 1 to 12 carbon atoms, saturated.
  • the invention does not exclude the presence of one or more other unsaturations on the hydrocarbon chain such as one or more other double bonds and / or one or more triple bonds, which can be conjugated or not.
  • the hydrocarbon chain can be optionally interrupted by a heteroatom (for example, oxygen or sulfur) or by a functional group insofar as the latter does not react; there may be mentioned in particular a group such as in particular -CO-.
  • the hydrocarbon chain may optionally carry one or more substituents insofar as they do not react under the reaction conditions and mention may in particular be made, as possible substituents, of a halogen atom, a nitrile group or a trifluoromethyl group.
  • the acyclic, saturated or unsaturated, linear or branched aliphatic group may optionally carry a cyclic substituent.
  • cycle is meant a carbocyclic or heterocyclic, saturated, unsaturated or aromatic cycle.
  • the acyclic aliphatic group can be linked to the ring by a valential bond, a heteroatom or a functional group such as oxy, carbonyl, carboxy, sulfonyl, etc.
  • cyclic substituents it is possible to envisage cycloaliphatic, aromatic or heterocyclic, in particular cycloaliphatic, substituents comprising 6 carbon atoms in the ring or benzenic, these cyclic substituents themselves being optionally carriers of any substituent to the extent where they do not interfere with the reactions involved in the process of the invention. Mention may in particular be made of alkyl or alkoxy groups having from 1 to 4 carbon atoms.
  • R A1 must be understood as having the same definition as that given above for R ⁇ 1 and can therefore also represent a carbocyclic group, saturated or not, preferably comprising 5 or 6 carbon atoms in the ring, preferably cyclohexyl; a group heterocyclic, saturated or unsaturated, comprising in particular 5 or 6 atoms in the ring including 1 or 2 heteroatoms such as nitrogen, sulfur and oxygen atoms; an aromatic, monocyclic, preferably phenyl or polycyclic carbocylic group, condensed or not, preferably naphthyl.
  • R 2 and R A3 having the definitions identical to those given for R T2 and R T3 defined above, they preferably represent a hydrogen atom or an alkyl group having from 1 to 12 carbon atoms, a group phenyl or an aralkyl group having 7 to 12 carbon atoms, preferably a benzyl group.
  • R A1 , R ⁇ and R A3 more particularly represent a hydrogen atom or else R A1 represents a phenyl group and R A2 and R A3 represent a hydrogen atom.
  • haloaromatic compounds corresponding to formula (llb) in which D represents the remainder of a cyclic compound having the same definition as that given for the rest of the cyclic compound A of the group R " ⁇ defined above, that is to say preferably having at least 4 atoms in the ring, preferably 5 or 6, optionally substituted, and representing at least one of the rings previously described for A, that is that is to say an aromatic, monocyclic or polycyclic carbocycle or an aromatic, monocyclic heterocycle comprising at least one of the heteroatoms chosen from oxygen, nitrogen and sulfur, or a polycyclic aromatic heterocycle.
  • an aromatic carbocycle such as benzene, an aromatic bicycle comprising two aromatic carbocycles such as naphthalene; a partial bicycle aromatic ment comprising two carbocycles, one of which is aromatic such as tetrahydro-1, 2,3,4-naphthalene.
  • D can represent the rest of a heterocycle. More particularly, the optionally substituted residue D represents one of the cycles already listed above for A of the group R " ⁇ .
  • a halogenoaromatic compound of formula (IIb) is preferably used in which D represents an aromatic nucleus, preferably a benzene or naphthalene nucleus.
  • the aromatic compound of formula (IIb) 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. The maximum number of substituents capable of being carried by a cycle is easily determined by a person skilled in the art.
  • the term "several” generally means less than 0 4 substituents R A4 on an aromatic ring. Examples of R A4 substituents are in particular those given as an example of R T4 above in the description. This list of substituents is not, however, limiting. .
  • the present invention applies very particularly to the compounds5 corresponding to the formula (llb) in which the group or groups R A4 represent: - an alkyl group, 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; - a linear or branched alkenyl group having from 2 to 6 carbon atoms, preferably 0, from 2 to 4 carbon atoms, such as vinyl, allyl; a linear or branched alkoxy group having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy groups, an alkenyloxy group, preferably an allyloxy group or a phenoxy group; 5 - a group of formula -R 1 -OH, -R 1 -
  • the amount of the compound carrying a group leaving from formula (II), preferably of formula (IIa) or (IIb), used is generally expressed relative to the amount of silicon compound carrying a group transferable.
  • the ratio between the number of moles of the silicon compound carrying a transferable group and the number of moles of the compound carrying an acceptor group generally varies between 1 and 3, preferably between 1 and 2.
  • phase transfer agent Before initiating the actual coupling reaction, it may be advantageous to add a phase transfer agent to the reaction medium.
  • the amount of appropriate phase transfer agent depends of course on the nature of the various constituents of the reaction medium and is generally between 0.01 moles and 1 mole of phase transfer agent for one mole of compound carrying the acceptor group (II). This amount is preferably between 0.01 moles and 0.1 moles, advantageously approximately 0.05 moles of phase transfer agent for one mole of compound bearing the acceptor group (II).
  • the phase transfer agent is of any type known to those skilled in the art.
  • a phase transfer agent which can advantageously be used in the process of the present invention is represented by the compounds of formula:
  • ion w ion there may be mentioned in particular halides, for example fluoride, chloride, bromide, iodide; or hydroxy anions, etc.
  • the cation A ⁇ is generally an organic cation, in particular of the onium type, in particular chosen from the ammonium, sulfonium, phosphonium, carbenium, oxonium, picolinium, pyridinium, arsonium, triazolium and iodonium cations.
  • the compounds of general formulas (111-1) and (II1-2) are particularly preferred: (111-1) (HI-2) in which: - E is chosen from the nitrogen, phosphorus ⁇ or arsenic atom; - G is chosen from the sulfur, oxygen, selenium and carbon atom; - Y 1 , Y 2 , Y 3 and Y 4 , identical or different, are chosen from:. an alkyl radical, linear or branched, having 1 to 16 carbon atoms and optionally substituted by one or more phenyl, hydroxyl, halogen, nitro, aikoxy or aikoxycarbonyl groups or atoms, the aikoxy groups having 1 to 4 carbon atoms; .
  • an alkenyl radical linear or branched, having 2 to 12 carbon atoms; . an aryl radical having 6 to 10 carbon atoms, optionally substituted by one or more alkyl groups or atoms having 1 to 4 carbon atoms, aikoxy, aikoxycarbonyl, the aikoxy radical having 1 to 4 carbon atoms, or halogen; . two of said radicals Y 1 to Y 4 can together form an alkylene, alkenylene or alkadienylene radical, linear or branched having from 3 to 6 carbon atoms.
  • the quaternary ammonium derivatives are particularly advantageous, in particular tetra-alkylammonium, trialkylbenzylammonium, dialkyldiphenylammonium and alkyltriphenylammonium.
  • the compounds of formula A ⁇ , w ⁇ mention may be made of the following compounds: tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetramethylammonium bromide, cetyltrimethylammonium bromide, Bu 4 NSCN, Bu 4 NOCN, Bu 4 NCN, E NCN, KCN,
  • phase transfer agents which are particularly preferred for the process of the present invention, there may be mentioned in particular tetrabutylammonium iodide, tetrabutylammonium chloride, bromide tetrabutylammonium, tetramethylammonium bromide and cetyltrimethylammonium bromide.
  • the presence of a phase transfer agent is not essential for the process of the invention.
  • the coupling reaction optionally in the presence of a phase transfer agent as it has just been defined, is carried out at a temperature generally between room temperature and 150 ° C, preferably between 50 ° C and 110 ° C, for a period usually between a few minutes and 4 hours, most often around 15 minutes to 1 hour and 30 minutes.
  • the coupling reaction can even be almost instantaneous, even instantaneous, or even last more than 1 hour and 30 minutes, or even more than 4 hours.
  • the solvent for the actual coupling reaction (step b) is, in general, identical to that used in the step for activating the halogenosilylated compound (step a). This is generally the case when the reaction product from step a) is not isolated and is directly used in step b). It may however prove useful to add solvent before engaging in step b) the reaction product of step a), whether the latter has been isolated or not.
  • the solvent of step b) will advantageously be chosen from the possible solvents defined for step a) and as described above.
  • the amount of solvent used in the coupling step is such that the concentration of the compound with an acceptor group of formula (II) is between 0.01 M and 2 M, preferably between 0.1 M and 1 M.
  • the coupling step b) is further characterized by the addition (step c) of a catalyst of the palladocycle type, before, during or even after the addition of the compound carrying an acceptor group of formula (II) as defined above.
  • a catalyst of the palladocycle type catalyst is meant a cyclic compound comprising in the cycle a carbon-palladium bond.
  • This carbon-palladium bond generally results from a carbopalladation reaction, in particular substitution, by a palladium atom, of a hydrogen atom carried by a sp 2 hybridization carbon atom, for example an aromatic carbon atom, or by a sp 3 hybridization carbon atom.
  • * Q represents a group of formula (Q-1) or a group of formula (Q-2):
  • Y 3 and Y 4 may together form an alkylene, alkenylene or alkadienylene radical, linear or branched having from 3 to 6 w carbon atoms; . Y 3 or Y 4 can form, with R 4 or R 4 ' , and with the atoms to which they are linked, an unsaturated or totally or partially unsaturated ring comprising 5 or 6 members; .
  • one of Y 3 or Y 4 may also represent hydrogen, the other being as defined above; - Y 3 can also form a bond with R 3 (or R 3 ' ) when E represents the nitrogen atom, and in this case Y 4 can also represent the hydroxy group;
  • * T represents a counterion usually understood as such by a person skilled in the art and is generally chosen from anions of the following groups: -F, -Cl, -Br, -I, -CN, -OCN, -SCN, -CF 3 , -OCF 3 , -SCF 3 , -ONO, -ONO 2l -OSO 2 N (R 6 ) (R 7 ), -SO 2 R 8 , -OSO 2 R 8 , -O (O) CR 8 , -SR 8 , -N 3 and -OR 8 ; * R 3 , R 4 , R 3 ' and R 4' , identical or different, are chosen from the hydrogen atom
  • R 3 , R 4 , R 3 ' and R 4' represent the hydrogen atom or the methyl radical, more preferably the hydrogen atom;
  • R 3 , R 4 , R 3 ' or R 4' can also form, with Y 3 and or Y 4 and / or R 5 , together with the atoms to which they are linked, an unsaturated or totally or partially unsaturated ring comprising 5 or 6 links;
  • R 5 identical or different, represent substituents on the ring, preferentially one of the groups chosen from an alkyl group, linear or branched, having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, Phone as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, te / f-butyl; a linear or branched alkenyl or alkynyl group having from 2 to 6 carbon atoms, preferably from 2 to 4 carbon atoms, such as vinyl, allyl; a linear or branched aikoxy or thioether group having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy groups, an alkenyloxy group, preferably an allyloxy group or a phenoxy group; a cyclohexyl, pheny
  • the palladocycle of formula (IV) can also be in dimeric form.
  • * Q represents a group of formula (Q-1): in which: - E represents the nitrogen atom; - Y 3 and Y 4 , identical or different, represent an alkyl radical, linear or branched, having 1 to 16 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably the methyl radical; one of Y 3 or Y 4 may also represent hydrogen, the other being as defined above; - Y 3 can also form a bond with R 3 (or R 3 ) when E represents the nitrogen atom, and in this case Y 4 can also represent the hydroxy group;
  • * T represents a halogen, preferably -F, -Cl, -Br, or -I, more preferably -Cl, or else the triflate group, or the acetate group; * R 3 , R 4 , R 3 and R 4 ', identical or different
  • a palladocycle of formula (IV) is a palladocycle, in dimer form, of the following formula (IV-1):
  • R 5 is as defined above.
  • R 5 represents hydrogen or a halogen, fluorine or chlorine atom for example.
  • Palladocycles in dimer form, which are particularly preferred are the following palladocycles P1 and P2:
  • any other palladocycle such as those presented in the disclosures of the prior art, for example the articles cited above, may be suitable for the method of the present invention.
  • R 4 , R 5 , Y 3 , Y 4 and p can for example take the values defined for formula (IV) above.
  • the palladocycles type catalysts used in the process of the present invention are in liquid or solid form.
  • the catalyst can be introduced directly into the reagent, or after dilution in a suitable solvent, for example the solvent used in steps a) or b), and as defined above.
  • the process of the present invention shows that the reaction product is almost free of homocoupling product, without the need for recourse to addition of phosphines.
  • the yields observed are significantly better than those obtained with the coupling methods described hitherto in the prior art, and the reaction times generally shorter than those known in the prior art.
  • Another very advantageous characteristic of the process of the invention lies in the very small amount of catalyst necessary to give very good results, both in terms of quality and in terms of quantity.
  • the amounts of catalyst used in the process of the present invention are generally between 0.0005% and 2%, preferably between 0.01% and 1% in moles relative to the compound carrying the acceptor group of formula (II).
  • the process of the invention has been shown to be quite suitable and efficient with quantities of catalysts of less than 0.1 mol% (1000 ppm) relative to the compound carrying the acceptor group of formula (II).
  • the compounds of formulas (I), (I '), (II), (III) and (IV) are either available directly commercially, or easily prepared according to conventional procedures known to those skilled in the art, procedures available for example in scientific literature, in patents and patent applications, summaries of "Chemical Abstracts" and via Internet.
  • the reaction product is separated from the reaction medium, isolated and purified, according to techniques known to those skilled in the art, or according to known procedures easily accessible from from the sources cited above.
  • the reaction product of the process according to the invention is a compound which can be represented schematically by the following formula (V), when it is obtained by coupling of a compound carrying a transferable group and a compound bearer of an acceptor group as defined above,: R T R A (V) compound in which R ⁇ and R A are as defined above.
  • V formula (V)
  • the compounds (V) find quite interesting applications in very many fields, such as for example those of agrochemistry, pharmacy, electronics and performance products entering for example in the development of liquid crystals, etc.
  • the following examples are intended to illustrate the process of the present invention, without however making any limitation.

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EP04786350A 2003-08-28 2004-08-24 Verfahren zur herstellung einer kohlenstoff-kohlenstoff bindung zwischen eine übertragbare gruppe und eine akzeptor gruppe Withdrawn EP1658249A2 (de)

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FR0310259A FR2859206B1 (fr) 2003-08-28 2003-08-28 Procede de creation d'une liaison carbone-carbone par couplage entre un groupe transferable et un groupe accepteur
PCT/FR2004/002186 WO2005023735A2 (fr) 2003-08-28 2004-08-24 Procede de creation d'une liaison carbone-carbone par couplage entre un groupe transferable et un groupe accepteur

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