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AssigneeSaltigo GmbH
InventorsMatthias Gotta, Bernd Wilhelm Lehnemann, Waldemar Maximilian Czaplik, Matthias Mayer, Axel Jacobi Von Wangelin
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What is described is a process for preparing organic compounds of the general formula (I) R—R′ (I) by converting a corresponding compound of the general formula (II) R—X (II) in which X is fluorine, chlorine, bromine or iodine to an organomagnesium compound of the general formula (III) [M+]n[RmMgXkY1] (III) wherein compounds of the formula (III) are reacted with a compound of the general formula (IV) characterized in that the reaction of (III) with (IV) is performed in the presence of a) catalytic amounts of an iron compound, based on the compound of the general formula (II), and optionally in the presence of b) a nitrogen-, oxygen- and/or phosphorus-containing additive in a catalytic or stoichiometric amount, based on the compound of the general formula (II).
A process for preparing organic compounds of the general formula (I)
The process as claimed in one at least one of the preceding claims, characterized in that the allylic or vinylic R′ radical may optionally bear one or more substituents Q which may each independently be (C4-C18)-alkyl, (C4-C18)-cycloalkyl, (C4-C18)-alkenyl, (C4-C18)-cycloalkenyl, (C4-C18)-alkynyl, (C4-C18)-aryl, O—[(C4-C18)-alkyl], O—[(C4-C18)-aryl], O—Si[(C4-C18)-alkyl]n[(C4-C18)-aryl]3-n, OC(O)—[(C4-C18)-alkyl], OC(O)—[(C4-C18)-aryl], NH2, NH[(C4-C18)-alkyl], N[(C4-C18)-alkyl]2, NH[(C4-C18)-aryl], N[(C4-C18)-aryl]2, NHC(O)—[(C4-C18)-alkyl], N[(C4-C18)-alkyl]C(O)—[(C4-C18)-alkyl], NHC(O)—[(C4-C18)-aryl], N[(C4-C18)-alkyl]C(O)—[(C4-C18)-aryl], NO2, NO, S—[(C4-C18)-aryl], S—[(C4-C18)-alkyl], fluorine, chlorine, bromine, pentafluorosulfuranyl, CF3, CN, COOM, COO—[(C4-C18)-alkyl], COO—[(C4-C18)-aryl], C(O)NH—[(C4-C18)-alkyl], C(O)NH—[(C4-C18)-aryl], C(O)N—[(C4-C18)-alkyl]2, C(O)N—[(C4-C18)-aryl]2, CHO, SO2—[(C4-C18)-alkyl], SO—[(C4-C18)-alkyl], SO2—[(C4-C18)-aryl], SO—[(C4-C18)-aryl], OSO2—[(C4-C18)-alkyl], OSO2—[(C4-C18)-aryl], PO—[(C4-C18)-alkyl]2, PO—[(C4-C18)-aryl]2, SO3M, SO3—[(C4-C18)-alkyl], SO3—[(C4-C18)-aryl] or Si[(C4-C18)-alkyl]n[(C4-C18)-aryl]3-n, where M is an alkali metal or alkaline earth metal atom and n is a natural number in the range from 0 to 3, and where at least two of these substituents may form a ring system with one another.
The process as claimed in at least one of the preceding claims, characterized in that the R″ radical is an optionally branched, optionally cyclic alkyl group or an aryl or heteroaryl group, all of which may optionally bear one or more substituents which may each independently be (C4-C18)-alkyl, (C4-C18)-cycloalkyl, (C4-C18)-alkenyl, (C4-C18)-cycloalkenyl, (C4-C18)-alkynyl, (C4-C18)-aryl, O—[(C4-C18)-alkyl], O—[(C4-C18)-aryl], O—Si[(C4-C18)-alkyl]n[(C4-C18)-aryl]3-n, OC(O)—[(C4-C18)-alkyl], OC(O)—[(C4-C18)-aryl], NH2, NH[(C4-C18)-alkyl], N[(C4-C18)-alkyl]2, NH[(C4-C18)-aryl], N[(C4-C18)-aryl]2, NHC(O)—[(C4-C18)-alkyl], N[(C4-C18)-alkyl]C(O)—[(C4-C18)-alkyl], NHC(O)—[(C4-C18)-aryl], N[(C4-C18)-alkyl]C(O)—[(C4-C18)-aryl], NO2, NO, S—[(C4-C18)-aryl], S—[(C4-C18)-alkyl], fluorine, chlorine, bromine, pentafluorosulfuranyl, CF3, CN, COOM, COO—[(C4-C18)-alkyl], COO—[(C4-C18)-aryl], C(O)NH—[(C4-C18)-alkyl], C(O)NH—[(C4-C18)-aryl], C(O)N—[(C4-C18)-alkyl]2, C(O)N—[(C4-C18)-aryl]2, CHO, SO2—[(C4-C18)-alkyl], SO—[(C4-C18)-alkyl], SO2—[(C4-C18)-aryl], SO—[(C4-C18)-aryl], OSO2—[(C4-C18)-alkyl], OSO2—[(C4-C18)-aryl], PO—[(C4-C18)-alkyl]2, PO—[(C4-C18)-aryl]2, SO3M, SO3—[(C4-C18)-alkyl], SO3—[(C4-C18)-aryl] or Si[(C4-C18)-alkyl]n[(C4-C18)-aryl]3-n, where M is an alkali metal or alkaline earth metal atom and n is a natural number in the range from 0 to 3, and where at least two of these substituents may form a ring system with one another.
The process as claimed in at least one of the preceding claims, characterized in that the iron compound used is iron(II) chloride, iron(III) chloride, iron(II) acetylacetonate, iron(III) acetylacetonate, iron(II) acetate, iron(III) acetate, iron(II) bromide, iron(M) bromide, iron(II) fluoride, iron(III) fluoride, iron(II) iodide, iron(III) iodide, iron(II) sulfate, iron(II) trifluoroacetate, iron(II) trifluoromethanesulfonate, iron(ill) trifluoromethanesulfonate or iron(III) chloride-TMEDA complex.
The process as claimed in at least one of the preceding claims, characterized in that the iron compound is used in an amount of 0.01 to 50 mol %, based on the compound of the general formula (II).
The process as claimed in at least one of the preceding claims, characterized in that the optionally added nitrogen-, oxygen- and/or phosphorus-containing additive having one or more nitrogen, oxygen and/or phosphorus atoms comprises optionally substituted alkylamines, N-containing heterocycles, alkylamides, cyclic alkylamides, cycloalkylamines, cycloalkyldiamines, alkylimines, cycloalkylimines, aniline, aniline derivatives, nitrogen-containing heteroaromatics, dialkyl ethers, alkyl aryl ethers, diaryl ethers, cyclic ethers, oligoethers, polyethers, triarylphosphines, trialkylphosphines, aryldialkylphosphines, alkyldiarylphosphines and bridged bisphosphines.
The process as claimed in at least one of the preceding claims, characterized in that the nitrogen-, oxygen- and/or phosphorus-containing additive used is triethylamine, ethyldiisopropylamine, N,N,N′,N′-tetramethylethylenediamine (TMEDA), 1,4-diazabicyclo[2.2.2]octane (DABCO), sparteine, N,N,N′,N′-tetramethyldiaminomethane, 1,2-diaminocyclohexane (DACH), N-methyl-2-pyrrolidine (NMP), N,N-dimethylaniline, pyridine, phenanthroline, PEG-DME (polyethylene glycol dimethyl ether), DME (1,2-dimethoxyethane), binaphthyl dimethyl ether, 18-crown-6, triphenylphosphine, tri-n-butylphosphine, tri-tert-butylphosphine, dppf (1,1′-bis(diphenylphosphino)ferrocene), dppe (1,2-bis(diphenylphosphino)ethane), dppp (1,3-bis(diphenylphosphino)propane), dppb (1,4-bis(diphenylphosphino)butane) or dpppe (1,5-bis(diphenylphosphino)pentane).
The process as claimed in at least one of the preceding claims, characterized in that the nitrogen-, oxygen- and/or phosphorus-containing additive is used in an amount of 0 to 200 mol %, based on the compound of the general formula (II).
The process as claimed in at least one of the preceding claims, characterized in that the reaction of (II) to give (III) is performed in the presence of (IV), such that the organomagnesium compound (III) formed reacts further in situ with IV to give (I).
The process as claimed in any of the preceding claims, characterized in that the R radical in formula (I) is an aryl radical from the group of phenyl, naphthyl, anthracenyl and phenanthryl or a heteroaryl radical from the group of pyridyl, pyrimidyl, pyrazinyl, dioxinyl, furyl, (thiophen)yl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, thiadiazolyl, triazolyl and pyrrolyl, and the R′ radical in formula (I) is an allylic radical from the group of allyl, crotyl, methallyl, 1-methylallyl, cyclopent-1-en-3-yl and cyclohex-1-en-3-yl or a vinylic radical from the group of vinyl, 1-propenyl, 2-methyl-1-propenyl, cyclopent-1-en-1-yl and cyclohex-1-en-1-yl.
Dependencies are inferred from the claim text.