EP2906532A1 - Verfahren zur herstellung von formamidinen - Google Patents

Verfahren zur herstellung von formamidinen

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Publication number
EP2906532A1
EP2906532A1 EP13815150.1A EP13815150A EP2906532A1 EP 2906532 A1 EP2906532 A1 EP 2906532A1 EP 13815150 A EP13815150 A EP 13815150A EP 2906532 A1 EP2906532 A1 EP 2906532A1
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EP
European Patent Office
Prior art keywords
alkyl
formula
group
aryl
hydrogen
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
EP13815150.1A
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English (en)
French (fr)
Inventor
Thibault Cantat
Jacky POUESSEL
Olivier JACQUET
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Publication of EP2906532A1 publication Critical patent/EP2906532A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
    • C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
    • C07C257/12—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to hydrogen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/52—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing groups, e.g. carboxylic acid amidines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/13—Amines
    • A61K31/155—Amidines (), e.g. guanidine (H2N—C(=NH)—NH2), isourea (N=C(OH)—NH2), isothiourea (—N=C(SH)—NH2)
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/395—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins
    • A61K31/41—Heterocyclic compounds having nitrogen as a ring hetero atom, e.g. guanethidine or rifamycins having five-membered rings with two or more ring hetero atoms, at least one of which being nitrogen, e.g. tetrazole
    • A61K31/4164—1,3-Diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine

Definitions

  • the present invention relates to a process for the one-step preparation of formamidines by catalytic hydrosilylation of organic ureas.
  • Formamidins are basic molecules in the chemical industry. They are used in various industries, and in particular for their applications as:
  • the present invention also relates to a method of manufacturing insecticides, pesticides, fungicides, pharmaceuticals and catalysts comprising a step of preparing formamidines according to the method of the invention.
  • Formamidines can also be used as intermediates for the synthesis of N-heterocyclic carbenes (Chem Rev., 2011, 11, 2705-2733, Org Lett, 2009, Vol 11, No. 4, 1019-1022). or for the synthesis of alkaloids used in therapeutic chemistry (J. Org., Chem., 1996, 61, 573-580).
  • the present invention relates to a process for synthesizing formamidines of formula (I) by reducing ureas of formula (II) with silanes of formula (III), according to the following reaction:
  • Formamidines can also be obtained by reducing the corresponding ureas. This method may seem attractive insofar ureas can be readily prepared by condensation of flames with C0 2j carbon dioxide which are stable and easy to store molecules. Synthesis formamidines then requires the use of strong reductants such as L1AIH 4, NaBH 4, triethyl orthoformate ((EtO) 3 CH) (J. Am. Chem. Soc, 1955, 77, 5872-5877) or a mixture dimethylamineborane / trichlorophosphate (Synthesis-Stuttgart, 1986, No. 3, 226-228).
  • strong reductants such as L1AIH 4, NaBH 4, triethyl orthoformate ((EtO) 3 CH) (J. Am. Chem. Soc, 1955, 77, 5872-5877) or a mixture dimethylamineborane / trichlorophosphate (Synthesis-Stuttgart, 1986, No. 3, 226-228
  • the inventors have succeeded in developing a process for synthesizing formamidines in a single step, via a single reaction that is unknown to date.
  • hydrosilanes as reducing agents, the latter being known to be stable, low in toxicity and tolerated by numerous functional groups.
  • the invention firstly relates to a process for the preparation of formamidines of formula (I): R 3
  • R, R and R independently of one another, hydrogen, alkyl, alkenyl, alkynyl, aryl, hconvergeroaryie, a heterocycle, a silyl group, siloxy or amino, said alkyl alkenyl, alkynyl, aryl, heteroaryl, heterocycle, silyl, siloxy and amino being optionally substituted, or
  • n is an integer ranging from 1 to 20000
  • n - 1 and Y represents a single bond
  • - R 4 , R 5 and R 6 represent, independently of one another, a hydrogen or halogen atom, a hydroxyl group, alkyl, alkenyl, alkynyl, aryl, alkoxy, a silyl group, siloxy or amino, said alkyl, alkenyl, alkynyl, aryl, alkoxy, silyl, siloxy and amino groups being optionally substituted, or
  • R 6 is as defined above and R 4 and R 5 taken together with the silicon atom to which they are bonded form an optionally substituted silylated heterocycle, or
  • R 4 represents a hydrogen or halogen atom, an alkyl or alkoxy group
  • R 5 represents a silyl group of formula -Si (X) 3 in which each X, independently of one another, is chosen from a hydrogen or halogen atom, an alkyl or alkoxy group,
  • R 6 represents a siloxy group of formula -O-Si (X) 3 in which each X, independently of one another, is chosen from a hydrogen or halogen atom, an alkyl or alkoxy group.
  • the method of the invention has the advantage of allowing the synthesis of formamidines with a good yield (of the order of 30 to 100%), and a very good selectivity.
  • the yield is calculated relative to the amount of urea of formula (II) introduced initially, on the basis of the amount of formamidine of formula (I) isolated:
  • the selectivity relates to the nature of the products formed from the urea of formula (II).
  • alkyl means a linear, branched or cyclic carbon radical, saturated or unsaturated, optionally substituted, comprising 1 to 12 carbon atoms.
  • saturated alkyl linear or branched, there may be mentioned for example the methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecanyl and their branched isomers.
  • cyclic alkyl there may be mentioned cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicylco [2, 1, 1] hexyl, bicyclo [2.2, 1] heptyl.
  • cyclic alkyls unsaturated there may be mentioned for example cyclopentenyl and cyclohexenyl.
  • Unsaturated alkyls also referred to as "alkenyl” or "alkynyl” respectively contain at least one double or one triple bond.
  • the alkyl group within the meaning of the invention including the alkenyl and alkynyl groups, may be optionally substituted by one or more hydroxyl groups; one or more alkoxy groups; one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms; one or more nitro groups (-NO 2 ); one or more nitrile groups (-CN); one or more aryl groups, with the alkoxy and aryl groups as defined in the context of the present invention.
  • aryl generally refers to a cyclic aromatic substituent having from 6 to 20 carbon atoms.
  • the aryl group may be mono- or polycyclic.
  • the aryl group may be optionally substituted by one or more hydroxyl groups, one or more alkoxy groups, one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms, one or more nitro groups (-NO 2 ) , one or more nitrile groups (-CN), one or more alkyl groups, one or more aryl groups, with the alkoxy, alkyl and aryl groups as defined in the context of the present invention.
  • heteroaryl generally refers to a mono- or polycyclic aromatic substituent having 5 to 10 members of which at least 2 are carbon atoms, and at least one heteroatom selected from nitrogen, oxygen or sulfur.
  • the heteroaryl group can be mono or polycyclic.
  • furyl benzofuranyl, pyrrolyl, indolyl, isoindolyl, azainoyl, thiophenyl, benzothiophenyl, pyridyl, quinolinyl, isoquinolyl, imidazolyl, benzimidazolyl, pyrazolyl, oxazolyl, isoxazolyl, benzoxazolyl, thiazoyl, benzothiazolyl, isothiazolyl, pyridazinyl groups.
  • heteroaryl group may be optionally substituted with one or more hydroxyl groups, one or more alkoxy groups, one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms, one or more nitro groups (-NO2), one or more nitrile groups (-CN), one or more aryl groups, one or more alkyl groups, with alkyl, alkoxy and aryl groups as defined in the context of the present invention.
  • alkoxy means an alkyl group, as defined above, bonded through an oxygen atom (-O-alkyl).
  • heterocycle refers to a saturated or unsaturated 5- to 10-membered mono- or polycyclic substituent containing from 1 to 4 heteroatoms selected independently of one another from nitrogen, oxygen and the like. sulfur.
  • heteroatoms selected independently of one another from nitrogen, oxygen and the like. sulfur.
  • the heterocycly may be optionally substituted by one or more hydroxyl groups, one or more alkoxy groups, one or more aryl groups, one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms, one or more groups. nitro (-NO 2 ), one or more nitrile groups (-CN), one or more alkyl groups, with the alkyl, alkoxy and aryl groups as defined within the scope of the present invention.
  • halogen atom is meant an atom chosen from fluorine, chlorine, bromine or iodine atoms.
  • sil group is meant a group of formula -Si (X) 3 in which each X, independently of one another, is selected from a hydrogen atom; one or more halogen atoms selected from fluorine, chlorine, bromine or iodine atoms; one or more alkyl groups, one or more aryl groups, one or more alkoxy groups; with the alkyl, aryl, alkoxy groups as defined in the context of the present invention.
  • sioxy group is meant a silyl group, as defined above, linked by an oxygen atom ⁇ O-Si (X) 3 .
  • silated heterocycle means a mono- or polycyclic substituent, comprising from 5 to 15 members, saturated or unsaturated, containing at least one silicon atom, and optionally at least one other heteroatom chosen from nitrogen, oxygen or sulfur.
  • Said heteryl ring may be optionally substituted with one or more hydroxyl groups; one or more alkyl groups, one or more alkoxy groups; one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms; one or more groups aryls, with the alkyl, alkoxy and aryl groups as defined in the context of the present invention.
  • silacycîo-3-pentene 1- or l-methyl-l-dihydrido-2,3,4 May 5-tetraphenyl-l- silac clopentadiène the formulas below -
  • methyl siloxane 1-phenyl-1-silacyclohexane, 1-sila-bicyclo [2.2.1] heptane, 1-methyl-1-silacyclopentane, 9,9-dihydro-5-sil
  • the silylated heterocycles of the invention may be commercially available or may, if desired, be prepared by known synthetic methods such as, for example, those described by CL, Smith et al, J. Org. Chem., 1974, 81, 33-40; GD Homer, J. Am. Chem. Soc., 1973, 95:23, 7700-7707; L. Spialter et al., J. Am. Chem. Soc., 1971, 93:22, 5682-5686; R. West, J. Am. Chem. Soc., 1954, 76, 6015-6017.
  • Those skilled in the art are able to implement and adapt the known methods to the synthesis of the different silyl heterocycles which it needs.
  • amino group is meant a group of formula -NR 7 R 8 , in which:
  • R and R represent, independently of one another, a hydrogen atom, an alkyl group, alkenyl, aicynyl, aryl, heteroaryl, a heterocycle, a silyl group, siloxy, with the alkyl, alkenyl or aicynyl groups, aryl, heteroaryl, heterocycle, silyl, siloxy, as defined in the context of the present invention; or
  • R 7 and R 8 taken together with the nitrogen atom to which they are bonded, form a heterocycle optionally substituted by one or more hydroxyl groups; one or more alkyl groups; one or more alkoxy groups; one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms; one or more nitro groups (-NO 2 ); one or more nitrile groups (-CN); one or more aryl groups; with the alkyl, alkoxy and aryl groups as defined in the context of the present invention,
  • the groups R 1 , R 2 and R 3 of the urea of formula (II) represent, independently of one another, a hydrogen atom, a C 1 -C 4 alkyl group; -C 7 linear or branched, a C 5 -C 6 heterocycle> an aryl group selected from phenyl or benzyl, a heteroaryl group chosen by imidazolyl or benzimidazolyl, said alkyl, heterocyclic, aryl or heteroaryl groups being optionally substituted by one or more hydroxyl groups; one or more alkyl groups; one or more alkoxy groups; one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms; one or more nitro groups (-NO 2 ); one or more nitrile groups (-CN); one or more aryl groups; with the alkyl, alkoxy and aryl groups as defined in the context of the present invention.
  • R 4 represent, independently of one another, a hydrogen atom, a aikyle, aryl, alkoxy, silyl or siloxy group, said alkyl, aryl, alkoxy, silyl and siloxy groups being optionally substituted, and preferably 4 , R 5 and R 6 represent, independently of one another:
  • each X independently of one another, is chosen from a hydrogen or halogen atom, an alkyl or alkoxy group,
  • each X independently of one another, is chosen from a hydrogen or halogen atom, an alkyl or alkoxy group.
  • N> 1 advantageously n varies from 1000 to 5000, and Y is an oxygen atom, and
  • R 4 is chosen from a hydrogen atom or a methyl group
  • R 5 represents a silylated group of formula -Si (X) 3 in which each X, independently of one another, is chosen from an atom hydrogen or halogen, an alkyl or alkoxy group,
  • R 6 represents a siloxy group of formula -O-Si (X) 3 in which each X, independently of one another, is selected from a hydrogen or halogen atom, an alkyl or alkoxy group.
  • the silane compound of formula (III) is a polymeric organosilane (n> 1)
  • the latter may be, for example, polymethylhydroxysiloxane (PMHS).
  • the number of equivalents introduced into the reaction medium is given relative to the number of hydrides introduced, and consequently to the number of monomers introduced relative to the urea of formula (II).
  • catalyst within the meaning of the invention is meant any compound capable of modifying, in particular by increasing, the speed of the chemical reaction in which it participates, and which is regenerated at the end of the reaction.
  • This definition encompasses both catalysts, that is, compounds that exert their catalytic activity without the need for any modification or conversion, and compounds (also called pre-catalysts) that are introduced into the medium. and converted therein to a catalyst.
  • the catalysts may be chosen from organic catalysts or metal catalysts, the metal catalysts being chosen from salts or metal complexes.
  • Organic catalysts have the advantage of overcoming the toxicity problems generally observed for metal catalysts and cost problems associated with the use of precious metals.
  • the catalyst is preferably a metal salt used in the presence or absence of a ligand.
  • organic catalysts are, in general, organic bases chosen from:
  • nitrogenous bases such as, for example, secondary or tertiary amines selected from triazabicyclodecene (TBD); N-methyltriazabicyclodecene (MeTBD), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU), trimethylamine, triethylamine, piperidine, 4-dimethylaminopyridine (DMAP), 1,4 diazabicyclo [2.2.2] octane (DABCO), proline, phenylalanine, a thiazolium salt, N-diisopropylethyl amine (DIPEA or DIEA); or
  • alkyl and aryl phosphines selected from triphenylphosphine, 2,2'-bis (diphenylphosphino) -1,1-binaphthyl ( ⁇ ), triisopropylphosphine; alkyl and aryl phosphonates selected from diphenylphosphate, triphenylphosphate (TPP), tri (isopropylphenyl) phosphate (TIPP), cresyldiphenylphosphate (CDP), tricresylphosphate (TCP); alkyl and aryl phosphates selected from di-n-butyl phosphate (DBP), tris- (2-ethylhexyl) phosphate, triethylphosphate;
  • alkyl and aryl phosphines selected from triphenylphosphine, 2,2'-bis (diphenylphosphino) -1,1-binaphthyl ( ⁇ ), triisopropyl
  • the carbon bases for which the protonation takes place on a carbon atom such as, for example, an N-heterocyclic carbene such as a carbene obtained from an imidazolium salt chosen from sels, 3-bis (2.6 diisopropylphenyl) -1H-imidazol-3-ium, 1,3-bis (2,6-diisopropylphenyl) -4,5-dihydro-1H-imidazol-3-ium, 1,3-bis (2,6-diisopropylphenyl) -4,5-dihydro-1H-imidazol-3-ium; bis (2,4,6-trimethylphenyl) -1H-imidazol-3-ium, 1,3-bis (2,4,6-trimethylphenyl) -4,5-dihydro-1H-imidazol-3-ium, 4 5-dichloro-1,3-bis (2,6-diisopropylphenyl) -1H-imidazol-3-ium, 1,3
  • oxygenated bases such as for example hydrogen peroxide; benzoyl peroxide; an alcoholate selected from methanolate, ethanolate, propanolate, butanolate, pentanolate, hexanolate, sodium or potassium.
  • the organic catalyst is chosen from triazabicyclodecene (TBD), N-methyltriazabicyclodeene (MeTBD), 1,8-diazabicyclo [5A0] undec-7-ene (DBU).
  • TBD triazabicyclodecene
  • MeTBD N-methyltriazabicyclodeene
  • DBU 1,8-diazabicyclo [5A0] undec-7-ene
  • the catalyst when it is a metal catalyst, it may be chosen from the salts or complexes of:
  • metals selected from boron, silicon, aluminum, gallium, tin, indium;
  • alkali metals selected from sodium and potassium; alkaline earth metals selected from magnesium and calcium; transition metals selected from nickel, iron, cobalt, zinc, copper, rhodium, ruthenium, platinum, palladium, iridium; rare earths selected from lanthanum, cerium, praseodymium, neodymium.
  • the metal catalyst is a salt or transition metal complex selected from nickel, iron, cobalt, zinc, copper, rhodium, ruthenium, platinum, palladium, iridium, and more. more preferentially among iron, zinc, copper, ruthenium.
  • the metal catalyst may be chosen from the following salts or complexes:
  • metal complex an organometallic or inorganic coordination compound in which a metal ion is attached to an organic or inorganic ligand.
  • An organometallic or inorganic complex may be obtained by mixing a metal salt with a ligand, which ligand binds to the metal by phosphorus, carbon, nitrogen, oxygen, hydrogen or silicon atoms, for example.
  • a ligand of the phosphine or amine type such as, for example, tris [(2-diphenylphosphino) ethyl] phosphine (PP 3 ), tricyclohexylphosphine, acetate (AcO), acetylacetonate (acac), 1,2-bis-diphenylphosphinoethane (dppe), ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-ethylenediamine (TMEDA), N, N'-bis (2,6) diisopropylphenyl) ⁇ -diketiminate (BDI), 1,2-bis (diphenylphosphino) ethane (dppb), or pyridine.
  • a ligand of the phosphine or amine type such as, for example, tris [(2-diphenylphosphino) ethyl] phosphine (PP 3 ), tricyclohexylphosphin
  • the metal catalyst is:
  • the catalysts may, where appropriate, be immobilized on heterogeneous supports in order to ensure easy separation of said catalyst and / or its recycling.
  • Said heterogeneous supports may be chosen from supports based on silica gel or on plastic polymers such as, for example, polystyrene; carbon supports selected from carbon nanotubes; silica carbide; alumina; or magnesium chloride (MgCl 2 ).
  • the reaction temperature can be between 20 and 150 ° C, and preferably between 75 and 125 ° C.
  • the reaction may be carried out for a period of from 1 to 72 hours, and preferably from 1 to 48 hours.
  • the process of the invention in particular the reaction between the different reactants, may take place in one or more solvents chosen from:
  • ethers and preferably diethylether or THF; hydrocarbons, and preferably benzene or toluene;
  • nitrogenous solvents and preferably pyridine or acetonitrile
  • sulfoxides and preferably dimethylsulfoxide; alkali halides, and preferably chloroform or methylene chloride.
  • the molar ratio between the urea of formula (II) and the silane compound of formula (III) is from 0.5 to 5, and preferably from 1 to 3.
  • the amount of catalyst is from 0.001 to 1 molar equivalent, preferably from
  • the various reagents used in the process of the invention are, in general, commercial compounds or compounds which can be prepared by any method known to those skilled in the art.
  • Another subject of the invention relates to a process for preparing insecticides, pesticides, fungicides, pharmaceuticals and catalysts comprising a step of preparing formamidines of formula (I) according to the process of the invention.
  • the invention also comprises other arrangements which will emerge from the additional description which follows, which relates to examples of synthesis of formamidines of formula (I) according to the method of the invention.
  • the urea of formula (I) (1 equivalent), the catalyst (from 0.001 to 1 equivalent), the silane (1 to 3 equivalents) and the solvent are introduced into a Schlenk tube which is then sealed by a J. Young valve ®, La urea and silane concentration in the reaction mixture is about 0.5 mol L "1 (based on the concentration of the introduced volume of solvent).
  • the tube Schlenk is then heated to a temperature of 100 ° C until the total conversion of the urea (24 hours of reaction).
  • the mixture is acidified with an aqueous solution of hydrochloric acid IN and the The aqueous phase is washed 3 times with ether, potassium hydroxide pellets are then added to the aqueous phase to basic pH, and the mixture is then extracted 3 times with ethyl acetate. anhydrous magnesium sulphate ethyl acetate is evaporated under pressure r pick and pure formamidine is obtained as a white solid. In case of presence of other organic by-products, formamidine can be purified by chromatography on silica gel. The use of a dichloromethane / methanol mixture as an ester makes it possible to obtain analytically pure formamidine.
  • phenylsilane and polymethylhydrosiloxane Two different sources of reducing agents were used: phenylsilane and polymethylhydrosiloxane (PMHS).
  • PMHS polymethylhydrosiloxane
  • the silane being a polymer
  • the number of equivalents introduced is given relative to the number of hydrides introduced and thus to the number of monomers introduced relative to urea.
  • the introduction of 3 equivalents of PMHS corresponds to the introduction of 3 equivalents of hydride, and thus 3 equivalents of PMHS monomers relative to urea.

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EP13815150.1A 2012-10-12 2013-10-11 Verfahren zur herstellung von formamidinen Withdrawn EP2906532A1 (de)

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FR1259757A FR2996846B1 (fr) 2012-10-12 2012-10-12 Procede de preparation de formamidines
PCT/IB2013/059304 WO2014057466A1 (fr) 2012-10-12 2013-10-11 Procede de preparation de formamidines

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CN109111375B (zh) * 2018-10-17 2021-03-09 沅江华龙催化科技有限公司 一种α-氧代乙酰脒的合成方法
CN109111374B (zh) * 2018-10-17 2021-03-09 沅江华龙催化科技有限公司 一种以芳香胺和酰胺为氮源由铜盐催化芳基酮合成α-氧代乙酰脒的方法
CN117003663A (zh) * 2023-07-28 2023-11-07 浙江大学 催化加氢反应以及锰基催化剂的应用

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FR2996846B1 (fr) 2014-11-28
FR2996846A1 (fr) 2014-04-18
US9663452B2 (en) 2017-05-30
US20150266813A1 (en) 2015-09-24

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